摘要:

THE QUARTElILY JOURNAL OF THE CHE~I~AL SOCIETY OF LONDON. EDITED BY HENRY WATTS BA FCS LONDON IIIYPOLYTE BAILLIERE 219 REGENT STRBET AND 169 FULTON STREET &ICW-YORb U S. PARIS J B. RAILLI~RE RUE HAUTEFLUILLF MADRID RAILLY BAILLIERE CALLE DCL PRIhCIPE 1831 LONDON Printed by Schulze and Co. 13 Poland Street.

ISSN:1743-6893    

DOI:10.1039/QJ85103FP001

出版商:RSC    

年代:1851

数据来源: RSC

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ACTION OF SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS. 5 Dec. 17 1849. The PRESIDENT in the Chair. The following presents were announced cc The Pharmaceutical Journal,” for December from the Editor. ‘c The Journal of the Franklin Institute,” for October from the Insti- tute. A. Volker Ph. I). was duly elected a Fellow of the Society. The following Papers were read ‘‘ On Titanium,” by Professor Wohler (Vol. 11. p. 352). II.-On the Action of Sutphur upon the Pentachloride of Phosphorus. BY J. H. GLADSTONE, YH. D F.C.S. The object of the present communication is to describe a substance which was first noticed by me during my researches upon the com- pounds of the halogens with phosphorus but on account of its very distinct character was reserved for separate consideration.found that when sulphur and pentachloride of phosphorus are mixed together and heat applied combination takes place; a mass of colourless crystals is formed which if the heat be continued are converted into a yellow liquid that may be distilled and obtained pure by repeating the distillation This liquid contains phosphorus chlorine and sulphur but differs from the sulphochlorides of phos- phorus already known both in physical and chemical properties. Attempts to analyze the new substance by oxidizing it with nitric acid failed because the heat evolved during the reaction volatilized part of the liquid. The results however appeared to indicate that the sulphur and phosphorus were in the proportion of 4 to 1 ; and this led me to the best method of preparing the compound which is as follows.Three parts of pentachloride of phosphorus are mixed in a small retort with 1 part of sulphur; that is 1 equiv. of the former to rather more than 4 equivs. of the latter and combination is deter- DR. GLADSTONE ON THE ACFlON OF mined by heating the mixture till it begins to fuse. There are then formed in the retort a yellow liquid and a mass of trans- parent colourless crystals differing in appearance from the penta- chloride of phosphorus. A gentle heat must be maintained until this transformation has taken place throughout the whole mass when the crystalline body will be found gradually to disappear and the liquid to increase in quantity. Qn cooling the crystals are repro- duced; but if the liquid be briskly boiled a distillate will be o5tained from which only a small quantity of crystals separates.A transformation has thus been effected; for the whole liquid may be distilled over the thermometer which at first indicated about llOo C. (230OF.) gradually rising; and nothing remains in the retort except perhaps a small quantity of a pecdiar dark-coloured viscid matter which will be immediately described. If a smaller proportion of sulphur be employed the same products result; but unaltered pentachloride of phosphorus is found in the retort after distillation. If on the contrary a larger proportion of sulphur be mixed with the pentachloride of phosphorus both substances are likewise pro-duced; but during the distillation of the yellow liquid it assumes a deep colour and there remains *in the retort a dark brown mass.This is a mixture of sulphur with another substance which may be distilled by the heat of a spirit-lamp. It is of a viscid consistence; water has no effect upon it but alkalis appear to separate some chlorine. I believe it to be a secondary product resulting from the action of sulphur upon the new liquid itself at an elevated temperature. Under no circumstances have I remarked the least trace of dichlo-ride of sulphur free chlorine or any other product accompanying the reaction just described. The crystalline and the liquid body are found in various proportions and sometimes there remains scarcely any amount of crystals. Thus it would appear that the liquid at least is formed by the direct combination of sulphur with the penta- chloride of phosphorus.LIQUID COMPOUND. No method of rectifying the liquid compound with perfect accu-racy has presented itself to me. The crystalline body will rise in vapour along with it ; but an approximate separation may be effected by decanting the liquid from the crystals and submitting it to gentlc SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS. distillation. That which passes over first must be redistilled until a product is obtained which boils uniformly at a temperature not exceeding 125O C. (257O F.). The substance thus prepared is a clear mobile liquid of rather high refracting power heavier than water of a pale yellow colour and possessing an odour somewhat acid but not powerful.It evapo- rates at ordinary temperatures and shows great disposition to rise in vapour when heated. This and other causes have combined to prevent my determining its boiling point within a degree or two but it is about 118O C. (244~4~ F.). It showed no disposition to fuse when immersed in a mixture of ice and common salt at a tempera- ture of -17O C. (1*4O F.). It is capable of dissolving a large amount of sulphur when hot which it deposits again in crystals of the form of rhomboidal octohedrons or sometimes in needles. It also dissolves phosphorus alunost to an unlimited extent when hot and deposits that substance also on cooling in a crystalline form. The same may be said of the peiitachloride of phosphorus.The new liquid under consideration dissolves iodine imparting a deep red colour to the solution as is the case with most of these liquid com- pounds of phosphorus and the halogens. It mixes with bisulphide of carbon. Strong sulphuric acid has no action upon it at least in the cold ; and instead of dissolving in ether alcohol or oil of turpen-tine it violently attacks these organic solvents. The new liquid is not affected by hydrogen gas either at the ordinary or boiling temperature; but if a stream of hydrosulphuric acid be passed over it sulphur separates bubbles of gas rise through the liquid and another liquid compound remains. Metals decompose the substance under consideration in some cases with in other cases without the assistance of heat.It is violently oxidized by nitric acid. When it is brought into contact with water decomposition instantly commences ; the characteristic odour of sulphochloride of phosphorus is perceptible; and after a few hours there remains a quantity of sulphur contaminated with some sulpliide of phosphorus and in solution hydrochloric sulphuric phosphoric and perhaps phos- phorous acid together with another acid containing both phos-phorus and sulphur and giving a brown precipitate with nitrate of silvcr not soluble in dilute nitric acid but slightly so in ammonia. I believe this to be the sulphoxyphosphoric acid described by Wurt z,* notwithstanding the remark of that chemist that the silver-salt is * Ann. Chim. Ph!s. [3] XX 372. s DR.GLADSTONE OW THE ACTION OF too unstable to be prepared. The same decomposition results only more rapidly wheu solutions of the alkalis are employed; in that case however the liquid before being entirely destroyed assumes a dark red coloui* and the sulphur which separates is mixed at first with flocculent masses of an orange tint. A remarkable circumstance attending this reaction is the total absence of hydrosulphuric acid among the numerous resulting compounds unless the solution be boiled in which case it probably arises from decomposition of the sulphoxyphosphoric acid. It appeared to me that this decomposition by water might be taken advantage of for the ultimate analysis of the compound provided means could be devised for completely separating the phos- phorus sulphur and chlorine existing under so many different forms.The following process I found effectual :-The liquid having been weighed was decomposed by a dilute solution of ammonia in a corked flask so as to prevent loss of the liquid by evaporation. When the decompositiou was complete nitrate of silver was added which produced a dark brown precipitate and rendered the ammo- niacal solution of an inky appearance. This was boiled briskly for some minutes until the precipitate completely separated leaving a clear supernatant liquid. The black precipitate was then collected well washed with ammonia and afterwards oxidized by means of strong nitric acid. If pure sulphur separated it was collected by itself. The nitric acid solution thus obtained was added to the previous ammoniacal solution ; the chloride of silver was recovered by completely acidifying the liquid by additional nitric acid if neces- sary and the sulphuric and phosphoric acids were estimated by baryta.It was found necessary to continue the boiling of the ammoniacal solution for several minutes or the whole amount of chlorine was not converted into silver-salt. I. 0.3765 grm. of the new liquid yielded 0.988 grm. of chloride of silver 0.059 grni. of free sulphur 0.222grm. of sulphate of baryta and 0.1047grm. of phosphoric acid. 11. 0.1882grm of a separate preparation yielded 0.253 grm. of sulphate of baryta and 0.0494 grm. of phosphoric acid besides 0-010grm of free sulphur. 111. 09"78grm. of a separate preparation having a somewhat higher boiling-point yielded 2.041 grnis.of chloride of silver 1*001of snlphate of bnryta and 0,068 grm. of phosphoric acid hesides 0.130 gnu. of free sulphur which proved however to con-tain phosphorus. SULPHUR UPON THE PENTACHLORIDE OP FHOSPHORUS. 9 IV 0.254 grm. of the new liquid was analyzed in a totally different manner. It was poured into a flask containing reduced copper which was corked up until the odour of the liquid had entirely disappeared The resulting mass was exhausted with hot water and afterwards oxidized by nitric acid. Owing to the formation I imagine of dichloride of copper the chlorine was in a great measure contained in that portion which was subjected to the action of nitric acid ;hence an almost inevitable loss.However it yielded 0.6265 grm. of chloride of silver equivalent to 60.84 per cent of chlorine. The sulphate of baryta obtained was 0.451 grm. V. 0.4175 grm. was analyzed in the same manner as the last iron being employed in place of copper. The application of heat was necessary to effect the decomposition. 0.521 grm of sulphate of baryta wqs obtained and 0.031 grm. of free sulphur. These results reckoned to 100 parts are I. 11. 111. IV. V. Phosphorus . . 12.3 11.7 I Sulphur . . . . 23.8 23.8 { 37'8 } 24.5 24*6 Chlorine . . . 64.7 -63.9 -These numbers accord sufficiently with these deduced from the formula PS C15. Phosphorus . . . 11.70 Sulphur . . 23.40 Chlorine . . 64-90 1oo*oo Several views may be taken of the rational constitution of this new liquid compound.It may be considered as a double chloride of phosphorus and sulphur; thus P Cl, 2 (S Cl) ;but the action of water upon the substance appears to assimilate it to those compounds in which phosphorus is combined with five atoms of halogen two of them being easily replaceable by sulphur or oxygen. We may regard it therefore as P C1 S, 2 (S Cl) and suppose the sulpho- chloride set free by the decomposition of the chloride of sulphur ;-or as pentachloride of phosphoriis in direct combination with four atoms of sulphur ;P C1 S,. This is the view I prefer and I shall accord- ingly designate the new liquid as sulpho-perchloride of phosphorus. The manner in which water acts upon this compound will then appear DIt.GLADSTONE ON THE ACTION OF analogous to its mode of action upon the pentachloride of phos- phorus itself; that is two atoms of hydrogen remove two of the five atonis of chlorine ;but the two atoms of oxygen thus liberated instead of entering into the composition of the new substance combine in this case with two of the atoms of sulphur leaving the other two still to form part of the phosphorus compound. P Clj+2HO=2HCl+PC1 0, and P CZ S,+2 HO=2 H Cl+P Cl S,+S 0,. The existence of hyposulphurous acid in the solution is hypo-thetical ;and I must remark that where a considerable amount of water was employed I never observed sulphurous acid among the products even when the decomposition was effected by means of dilute acid.But unless in large quantity the odour would be masked by that of the sulphochloride and there are many conceivable ways in which the sulphurous acid might be immediately reduced or oxidized. Yet upon adding a very small quantity of water to a portion of the liquid in a corked tube a strong pungent odour was observed when the cork was removed and the gas prodnced a blue colour when suffered to fall upon a mixture of starch and solution of iodate of potash. We may therefore conclude that sulphurous acid was evolved. I may here observe that sulphochloride of phosphorus prepared in the manner described by Serullas and decomposed by water or solu- tions of alkalis without the aid of beat gives the acid formerly referred to which yields a brown silver-salt and not a trace of hydro- sulphuric acid.The view which regards the liquid just examined as a direct com- pound of sulphur with the pentachloride of phosphorus receives additional support from the discovery of Kremers who has recently shown* that sulphurous acid combines directly with pentachloride of phosphorus Fiving rise to two liquids each resolvable by water into sulphurous acid with phosphoric and hydrochloric acids. These he terms sulphites of the pentachloride of phosphorus with the formulze P Cl, 2 SO, and P Cl, 3 SO,. Rose’s sulphate of the pentachloride of phosphorus is a substance about which too little is accurately known to warrant us in drawing any deductions from it. * Am. Cli. l’harm JLIII~, 18-19.SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS f 1 In order to ascertain whether another compound of different formula could be obtained from the liquid under examination by merely collecting that which rose first in vapour I subjected a portion for some time to a temperature not exceeding looo C. The portion which evaporated condensed into a clear yellow liquid apparently identical with that formerly examined. 0.385 grm. analyzed as above yielded 1-020grms. of chloride of silver ;the estimation of sulphur and phosphorus was unfortunately lost. This number reckoned to 100 parts gives. Chlorine = 65.35 per cent; a result sufficient to prove the identity of this liquid with the previously- described sulpho-perchloridc of phosphorus. Through the kindness of Messrs.Watts and Russell I am enabled to add a determination of the specific gravity of the vapour of sulpho-perchloride of phosphorus. The details of the experiment are as follows Weight of globe filled with air at temp. 1405~ C. 944.10 grs. (58~1~ F.) ;bar. press. 29-64inches. 1 Weight of globe filled with vapour at temp. 203O C. 951,60 grs. (39744O I?.) ;bar. press. 29-87inches. I Capacity of globe . . 29.15 cub. in. Volume of residual air at temp. 13O C. (55*4OF.) ;} 9.82 bar. press. 29.77 inches. in. The specific gravity of the vapour calculated from these numbers is 5.5. Now if we suppose 6 voluines of the vapour of pentachloride of phosphorus to unite with 4 volumes of sulphur vapour without condensation we obtain the theoretical density 5.552.This would therefore appear to be the specific gravity of the vapour in question. CRYSTALLINE COMPOUND. It has already been observed that the first distillates in the prepa- ration of sulpho-perchloride of phosphorus deposit crystals on cooling. These will often not appear till after the lapse of several hours or even days. In such a case they are usually perfectly transparent and well dcfincd having the forrn of two octagonal pyramids placed base to base and the projecting angle at the point of juncture truncated SO as to form hcsagons. The crystals thus obtained unquestionably 12 ACTION OF SULPHUR UPON THE PENTACHLORIDE OF PHOSPHORUS. sometimes contain pentachloride of phosphorus ;but they comport themselves in contact with water in a manner similar to the liquid compound just described.I. 0.2945 grm. of well-defined crystals drained and exposed for awhile to a current of dry air having been analyzed according to the process formerly described yielded 0.964 grm. of chloride of silver and 0.110 grm. of sulphate of baryta. 11. 0.1945 grm. of a separate crystallization also well-defined and uniform which was drained and dried by means of asbestos yielded 0.6415 grm. of chloride of silver and 0.058 grm. of sulphate of baryta. These numbers reckoned to 100 parts are I 11. Phosphorus (by difference) 14.1 14.6 Chlorine . 80.7 81-3 Sulphur . 5.2 4-1 The proportion between the phosphorus and chlorine is evidently as 1:5 which would require r.rr. Phosphorus . . 14.6 14-7 Chlorine . 80.7 81.3 We can scarcely suppose these crystals to be anything else than pentachloride of phosphorus contaminated with a small quantity of the sulpho-perchloride (P C1 S,) which could not be easily removed. Yet in other analyses where the crystals were so well defined I have found a larger amount of sulphur; in one instance as much as 16.6 per cent. This leads me to believe either that a crystalline compound of sulphur with the pentachloride of phosphorus does exist or that the sulpho-perchloride has itself a great tendency to cohere to the pentachloride of phosphorus. It is on this account alone that I have specially described the crystalline body. EXPERIMENT ON THE GASES GENEEATED IN A SEWER.13 Remarks on the use of the AZkaZine Carbonates for the preventiofi of Incrustation in Steam Boilers. By MR. ALFRED ANDERSON. The author gave the results of his experience that the addition of carbonates of soda and potash prevent incrustations in boilers as Kuhlmann and others had previously observed. He states that the addition of organic matters such as rice-meal was also found advantageous. Detail of some Experiments on the Gases generated in a Sewer. MAURICESCANLAN By MESSRS. AND ALFRED ANDERSON The experiments by the authors were made upon the sewer in Friar Street Southwark. The sewer was in a very foul state being 5 feet from the floor to the roof and containing between 3 and 4 feet of deposit which evolved a gas of a most powerful and filthy odour.To collect it the authors used a circular funnel of tin-plate which was inverted in the sewage matter of the sewer and there kept floating at the surface by a board ; to the top of this funnel was connected a gutta-percha delivering tube from which the gas was obtained. The pressure of the gas was capable of overcoming that of 4 inches of water. The greatest amount collected in 24 hours amounted to 34 cubic inches from an area of one square foot. The chief circumstance of chemical interest connected with this subject upon which very little has as yet been done is the probable existence of the bisulphide of carbon in this sewer at the time of the experiments. Being however a very difficult substance to detect at any time and more particularly when mixed with so many other compounds the observations as to its positive existence are not to be considered as conclusive.At times its peculiar odour was strongly developed. Alcohol through which the gas had passed acquired a peculiar odour resembling that of onions. In distilling this solution results were obtained confirming to a certain extent the existence of sulphide of carbon. The mixture of gas was found to consist of sulphuretted hydrogen carbiiretted hydrogen carbonic acid and phosphuretted hydrogen ; of the two latter a considerable proportion. A few minutes’ exposure to the gas was sufficient to produce headache and nausea. The quantitative examination of the gases was not made.

ISSN:1743-6893    

DOI:10.1039/QJ8510300005

出版商:RSC    

年代:1851

数据来源: RSC

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EXPERIMENT ON THE GASES GENEEATED IN A SEWER. 13 Remarks on the use of the AZkaZine Carbonates for the preventiofi of Incrustation in Steam Boilers. By MR. ALFRED ANDERSON. The author gave the results of his experience that the addition of carbonates of soda and potash prevent incrustations in boilers as Kuhlmann and others had previously observed. He states that the addition of organic matters such as rice-meal was also found advantageous. Detail of some Experiments on the Gases generated in a Sewer. MAURICESCANLAN By MESSRS. AND ALFRED ANDERSON The experiments by the authors were made upon the sewer in Friar Street Southwark. The sewer was in a very foul state being 5 feet from the floor to the roof and containing between 3 and 4 feet of deposit which evolved a gas of a most powerful and filthy odour.To collect it the authors used a circular funnel of tin-plate which was inverted in the sewage matter of the sewer and there kept floating at the surface by a board ; to the top of this funnel was connected a gutta-percha delivering tube from which the gas was obtained. The pressure of the gas was capable of overcoming that of 4 inches of water. The greatest amount collected in 24 hours amounted to 34 cubic inches from an area of one square foot. The chief circumstance of chemical interest connected with this subject upon which very little has as yet been done is the probable existence of the bisulphide of carbon in this sewer at the time of the experiments. Being however a very difficult substance to detect at any time and more particularly when mixed with so many other compounds the observations as to its positive existence are not to be considered as conclusive. At times its peculiar odour was strongly developed. Alcohol through which the gas had passed acquired a peculiar odour resembling that of onions. In distilling this solution results were obtained confirming to a certain extent the existence of sulphide of carbon. The mixture of gas was found to consist of sulphuretted hydrogen carbiiretted hydrogen carbonic acid and phosphuretted hydrogen ; of the two latter a considerable proportion. A few minutes’ exposure to the gas was sufficient to produce headache and nausea. The quantitative examination of the gases was not made.

ISSN:1743-6893    

DOI:10.1039/QJ8510300013

出版商:RSC    

年代:1851

数据来源: RSC

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14 ∈. JOHN f). EDWARDS ON THE ACTION OF Jan. 14 1850. The PRESIDENT in the Chair. The following presents were announced ‘‘ Ofversigt af Kongl. Vertenskaps-Academiens.” Forhandlingar 184s. “An Introductory Lecture on the importance of the study of Chc-mistry,” and the (‘Arsberattelse om framstegen i Kemi,” under iir I84 7 af L. F. Svanberg. The January number of the “ Pharmaceutical Journal,” presented bj the Editor. cc On the Nitro-prussides by Lyon Play fair Ph.D.” (Phil. Trans. 1849 p. 477) from the Author. The November number of the cc Jouriial of the Franklin Institute,” from the Institute The following papers were read 111.-On the action of Arsenious Acid upon Albumen. Bg JOHNB. EDWARDS, F.C.S. The attention of the Liverpool Chemists’ Association has been recently directed to the above subject by Dr.Brett in two Lectures upon Arscnic; and feeling interested in it I have since made several experiments with a view of determining whether arsenious acid com-bines with albumen in atomic proportion as believed by Professor Liebig,* or whether such a compound is not a mere mechanical mixture of the two substances. Liebig states that 100 grs. of albumen combines with lt grs. of arsenious acid and that it is in virtue of the powerful affinity existing between these bodies that life is destroyed when they are brought together in the living organism. I shall not notice on this occasion the physiological and patholo- gical objections to this view which were ably urged by Dr.Brett on the occasions referred to but proceed to detail my experiments and notice the objections arising therefrom to the cc Chemical Theory.” * Animal Chemistry p. 3G1 ARSENIOUS ACID UPON ALBUMEN. I took 1 gr. of opaque arsenious acid in perfect solution in water and 100 grs of the glairy albumen of eggs thoroughly mixed them by trituration and coagulated by heat ;the filtrate contained a con-siderable quantity of arsenious acid The coagulate was well washed with distilled water and the washing gave a deposit of arsenic on copper by Reinsch’s test; 4 oz. of the same gave by Marsh’s apparatus a number of large stains on porcelain which gave evidence of being arsenic by the silver copper and sulphide of hydrogen tests. The coagulate was well washed and bruised in a mortar till the filtered liquid gave no indications of arsenic by Reinsch’s test ; the coagulate was then destroyed by sulphuric acid neutralized and tested by the same method; not the slightest deposit could be ob- tained though boiled for half an hour but on the addition of a solution containing -i-ij-$8th part of a grain of arsenious acid the copper was immediately stained No combination therefore could have taken place for the whole of the acid was removed by patient trituration with hot water.This leads me to think that other expe- rimenters who have not detected arsenic in their washings have neglected thoroughly to break up the mechanical network of the coagulate. I repeated this experiment six times varying the propor- tions and the circumstances; but in each case my result was the same.In one experiment in which I used 100grs. of albumen and 8 gr. only of arsenious acid I detected arsenic in five or six washings and afterwards failed to detect it in the coagulate when decomposed. In another case I whisked the albumen with water for some minutes in order to destroy the organic structure and then digested for two hours at 98O F. before coagulating ;boiling water soon dissolved the whole of the arsenious acid and none could be detected in the washed coagulate. I then took warm sheep’s blood before congelation 960 grs. ; arsenious acid in solution 2grs.; digested at 98O for three hours and then coagulated. In this case also the whole of the acid was removed by boiling water.I next took 1000 grs. blood and.5 grs. arsenious acid ;digested at 9S0,as before for two hours then coagu- lated; by repeated boiling I extracted the whole of the acid the residue giving no trace by Reinsch’s test; I then evaporated the washings to dryness at a low temperature redissolved in hot water and through the filtered solution passed a current of hydrosulphuric acid gas. I collected the tersulphide of arsenic thus formed washed and dried by a water-bath ;the precipitate weighed 5.8 grs. ON THE ACTlON OF ARSENIOUS ACID UPON ALBUMEN. According to theory 5 grs. of ursenious acid would be equivalent to 6.22 of the tersulphide. The correspondence of the abovcx result proves that the whole of the acid was removed by boiling water.0 I took the coagulate obtained from 2 grs. acid and 200 grs. albu- men washed it with cold water and gave it to a healthy young rabbit; it was violently purged and died in about ten hours. Upon examination the stomach was found infl anied with extia-vasation of blood in patches amounting in one or two spots to positive ulceration,-also considerable vascularity of the trachea bron- chial tubes and intestines. The coagulate was found in the stomach undigested the rabbit being a herbivorous animal; the acid had been simply dissolved by the juices of the stomach without decom- position of the albumen. I then offered the same quantity to a remarkably fine healthy guinea-pig; it refused to take the whole and I suppose about I.$ grs.of arsenious acid was actually taken. It was purged frothed at the mouth and died in about sixteen hours. The stomach and other organs were found mizch more violently inflamed than those of the rabbit probably on account of its living longer. iVo coayailate was found in the stomach; it was therefore digested this being an omnivorous animal. The soft organs of the rabbit were examined by Dr. Brett. He found arsenic in each. After finding a large quantity in the mucous coat of the stomach he submitted that organ to a continuous stream of water for some time; when he could no longer detect arsenic in the washings he decomposed the tissue with nitric acid neutralized and boiled for a considerable time with Reinsch’s test but was unable to detect arsenic.I examined several organs and muscles of the guinea-pig and found arsenic in each I also treated the stomach of this animal in the same manner and removed the whole of the arsenic by hot water. Whatever objections may be raised to the first experiments with albumen I think the facts proved by the latter are weighty argu- ments against Liebig’s views. If water so readily extracts arsenious acid both from the compounds formed in the laboratory and from those which nature has prepared surely we may conclude that its retention is simply mechanical and affords no ground for the theory which that eminent chemist has raised upon it.

ISSN:1743-6893    

DOI:10.1039/QJ8510300014

出版商:RSC    

年代:1851

数据来源: RSC

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ON THE COMPOSITION OF ZIESITILOLE. 1V.-On the Composikion of Afesititote. (Letter of M. A. CAHOURSto DR. A. W. HOFMANN). In the July number of “The Quarterly Journal of the Chemical Society of London,”* you have communicated the results of some researches on mesitilole which have induced you to assume the expression Cl HI for this compound whose composition Kane had originally repre- sented by the formula C6 H*J which subsequently had been changed into in consequence of my determination of the vapour-density of the body in question. In concluding your memoir you remark that all the facts hitherto observed with regard to mesitilole are in perfect accordance with the new formula the only exception being my determination of its vapour-density ; and you leave it undecided whether the specific gravity of the mesitilole vapour is subject to variations similar to those which have been observed with acetic butyric and valerianic acid or whether the molecule of mesitilole is actually represented by 6 volumes of vapour,-an unusual mode of condensation which would explain the difference exhibited by the properties of this body and those of cumole which like the other hydrocarbons contains 4 volumes of vapour.In preparing the mesitilole for the determination of its vapour-density made at a coinparatively early period I had followed as accurately as possible the directions of Kane who states that this body boils at 135OC. I have since found as you have yourself observed that the boiling point of mesitilole is much higher ;and I have therefore repeated the determinations with a product carefully purified by several rectifications and a final distillation from an-hydrous phosphoric acid.It boiled regularly between 162O and 164O and exhibited exactly the composition of mesitilole. In two determinations made respectively at 74O and 88O higher #. Vol. 11. p. 104. VOL III.-NO* IX. c DR. SHERIDAN MUSPRATT ON THE IDENTITY OF than the boiling point of the hydrocarbon the following numbers were obtained I. XI. Temperature of the air . . . . l7O 200 Yf , vapour. . . . 236O 250° Excess of weight of balloon. . . Capacity of balloon . . . . . 0.396 grm.216 C.C. 0-478grm.275 C.C. Barorrieter . . . . . . . . O"T60 0"*763 Residual air . . . . . . . 0 1 D = 4345 D = 4282 The theoretical vapour-density of mesitilole assuming this body to contain 4 volumes of vapour is 4146. Thus the formula c, H, resulting from your researches on mesitilole and confirmed by Mr. Man le's analysis of nitromesidine,* is in perfect accordance with the specific gravity of the vapour of this compound which ceases moreover to form an exception to the mode of condensation as yet generally observed with carbohydrides. I beg you to communicate these results to the Chemical Society of London.

ISSN:1743-6893    

DOI:10.1039/QJ8510300017

出版商:RSC    

年代:1851

数据来源: RSC

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DR. SHERIDAN MUSPRATT ON THE IDENTITY OF W,-On the identity of ~ i ~ ~with~~~~~ ~ to ~~~ Acids and of Bisulphimethylic with Hyposulphamethylic acids. Bg SHERIDAN Ph. D. F.C.S. MUSPRATT In my paper on the ‘<Action of Nitric Acid upon the Sulpho-cyanides of Ethyl and Methyl,’’ I described acids containing no nitrogen which is interesting as they are produced by the action of one nitrogeneous body upon another. The following were the formuh given for the two acids.* Hyposulphethylic acid HO C 13 S 0,. Hyposulphamethylic acid HO. C HI S 0;. Since my results were published others have entered upon a similar field of research aniong whom I may mention Mr. Medlock who was induced to undertake the preparation of acids in the amyl series. By the action of nitric acid upon the sulphocyanide of amyl * Chem.SOC.Qu. Journ. 11 116. f-Chem. SOC.Qu. Journ. I 45. BISULPHETHYLIC WITH HYPOSULPHETHYLIC ACIDS. he procured a compound analogous in every respect to those above- mentioned. Appended to his paper is a note by Dr. Hofmann stating that the acid prepared by Xlr. XIedlock is evidently identical with the compound which &M.Gerathewohl and Erdmann ob- tained as a product of the decomposition of the bisulphide of amyl by means of nitric acid although these chernists adopt a different formula for that compound. The formula which they give for the baryta-salt of their acid is Ba. C, H, S 0 HO = Ba. C, EIp3 S O, differing from Mr. &ledlock’s formula Ba C, H, S O, by one equivalent of hydrogen.In four hydrogen determinations however a deficiency was found oscillating between 0.2 and 0.4 per cent while Meillock’s analysis generally gave a slight excess. A similar objection may be made to the analysis of several salts of the acid obtained by the ection of nitric acid on the bisulphide of ethyl. It would be interesting to repeat the analysis of the baryta-salt on which the formula H. C H R 0, assigned to this acid is principally founded. I have intended for some time to recur to the bisulphethylic acid considering that its description and properties correspond very closely with those of my acid; yet I have not until now had an opportunity to decide the question as to their identity moreover the repulsive qualities of bisulphide of ethyl are almost a sufficient reason to debar any one from preparing the compound.It is extremely difficult with acids containing a small per centage of hydrogen to arrive at its exact amount even when the greatest accuracy is exercised; consequently I was determined to prepare the baryta-salt of Lowig’s acid and to ascertain the exact amount of baryta; and if that amount corresponded with the quantity of baryta in the salt obtained by the action of nitric acid upon the sulphocyanide of ethyl the identity of the two would be proved and the correctness of my formula established. PREPARATION OF BISULPHIDE OF ETHYL. It is extremely difficult to obtain this body in large quantities and unless the materials employed are well prepared the stench is insuffer- able my clothes have retained it for weeks.The best mode of procedure appears to be to distil equal portions of concentrated solutions of sulphovinate of lime and tersulphide of potassium in a retort having a capacity ten times the volume of the mixture to prevent any of the solution passing over into the receiver which it is apt to do owing to violent intumescence that occurs. As c2 DR. SHERIDAN MUSPRATT ON THE IDENTITY OF the mass becomes viscid the oil that drops over must be repeatedly washed with distilled water and then rectified several times over chloride of calcium. It has a most disgusting smell when crude but after rectification the smell is only slightly alliaceous. It is sparingly soluble in water but is copiously dissolved by alcohol and ether it burns with a blue flame giving sulphurous acid.In the air it is unchanged but potash slowly decomposes it. PREPARATION OF THE ACID. Equal parts of bisulphide of ethyl and tolerably strong nitric acid were introduced into a retort adapted to a Liebig’s condenser. A gentle heat was applied during the process. The action was most violent nitrogen carbonic acid and nitrous acid passing off sul-phuric acid was also produced during the operation but I found the quantity depended upon the strength of the acid employed. The distillate was repeatedly returned to the retort to decompose all the oil. When the elimination of gas had ceased the liquid was evaporated over a water bath to expel the least trace of nitric acid.A fluid like oil of vitriol remained possessing a slight alliaceous odour. This was dissolved in water saturated with pure carbonate of baryta and filtered to remove the excess of carbonate and any sulphate of baryta. The filtrate on slow evaporation afforded large rhom-bohedral crystals of hyposulphethylate of baryta. These crystals were dissolved in water and precipitated by an excess of absolute alcohol and recrystallized. Tbe following is an analysis of the salt dried at loo0C. 0.1212grms. of substance gave 0.0797 grrns. of sulphate o€balyta = 0*0524grms. of baryta = 43.23 per cent. From a pretty considerable quantity of the salt I precipitated the baryta by sulphuric acid and filtered. I digested the filtrate with carefully prepared carbonate of lead refiltered and decomposed the lead solution by sulphide of hydrogen separated the sulphide of lead and evaporated the filtrate on a water bath.A portion of it left in a cold place over sulphuric acid in vucau afforded colourless needles extremely deliquescent and having a feeble odour of garlic. The deliquescent mass was mixed with water and carbonate of baryta filtered and the filtrate evaporated. Very fine crystals of the rhombohedra1 system settled down which were dried over sulphuric acid. BISULPHETHYLIC WITH HYPOSULPHETHYLIC ACIDS. ANALYSIS OF THESE CRYSTALS. 0*801grms. of the crystals dried at loooC. gave -0386 grms. of water. These results agree exactly with the annexed formula BaO. C H S 0 + aq.Centesimally represented Theory. Found. Hyposulphethylate of baryta . . . Water . . . . . . . . . . 178 9 95-19 4.81 >> 4% 1 100.00 This salt when dried at loooC. yielded the following numbers 0.410 grms. of salt burnt with chromate of lead gave 0.204 grms. of carbonic acid and 0.111 grms. of water. 0.1701 grms. of salt treated with potash and nitrate of potash gave 0.2210 grms. of sulphate of baryta = 0.0302 grms. of sulphur. 0,2399 salt dried at looo C. gave 0.1580 grms. of sulphate of baryta = 0,1039 grms. of baryta. Centesimally represented Theory. Pound. I---the Ba- ofAnd1ysls ryta-salt of the acid produced by the ac- tion of nitric acid ryta-salt of the acid produced by the dC-tion of nitric acid on the Ilisulphide of Ethyl.on the Sulphocy-anide of Ethyl. 4 eq. Carbon . . 24 13-49 13.53 13.16 5 , Hydrogen . 5 2.82 3-00 3.06 2 , Sulphur . . 5 ’ Oxygen . . 32 40 17.97 22.47 17.75 22-42 17.56 22.9‘7 1 , Baryta . . 77- 43.25 43.30 - 43.26- c_- 178 100.00 100*00 100*00 On referring to the preceding analysis there is every ground for asserting that the baryta-salt of the acid produced by the action of nitric acid on the bisulphide of ethyl is identical with the baryta-salt of the acid produced by the action of nitric acid on the sulphocyanide of ethyl. Lowig’s baryta-salt yields theoretically 3-36per cent of hydrogen; mine gives 2.82per cent. Analysis gives me 3.00and 3.05 per cent. Kopp found in the baryta-salt of the acid produced by DR. SHERIDAN MUSPRATT O’u’ THE IDENTITY OF the action of nitric acid upon the bisrilphide of ethyl 43.66 per cent of baryta while Lowig gives 44.83 per cent of baryta in the same salt a difference sufficiently accounting for the formula which the latter assumed.Appended are the four determinations that have been made Baryta in the acid from the bisulphide of ethyl . . 43.66 per cent-Kopp*. Baryta in the acid from the same source 43.23 , , -Muspratt. Second determination . . 43.30 , , -Ditto. Baryta in the acid produced from the sulphocyanide of ethyl by the action of nitric acid. . . 43.26 , , -Muspratt. PREPARATION OF THE ACID FROM BISULPHIDE OF METHYL. The bisulphide of methyl was treated similarly to the ethyl com-pound. I remarked on evaporating the decomposed bisulphide on the water bath that a most stifling vapour passed off which excited a flow of tears.This however was not the case when the purified bisulphide of methyl was employed. PREPARATION OF THE BARYTA-SALT. The acid was mixed with an excess of carbonate of baryta filtered and the filtrate precipitated by absolute alcohol. Very fine splendent needles were deposited which when dried at looo C. gave the annexed quantities of baryta First determination; 0.2140 grms. of salt gave 0.1520 grms. of sulphate of baryta equivalent to 0*1000grms. of baryta = 46.72 per cent. Second determination; 0.2310 grms of salt gave 0.1650 grms. of sulphate of baryta equivalent 0.2085 grms. of baryta = 46.97 per cent. f shall append the above two determinations collaterally with the one I previously made with the baryta-salt obtained from the acid produced by the action of nitric acid on the sulphocyanide of methyl.Baryta-salt of the acid obtained by the action of nitric acid on the bisulphide of methyl. * Lowig’s Chemie der organischen Verbindungen. TI. Rand S. 427. BISULPHETHYLIC WITH HYPOSULPHETHYLIC ACIDS. Centesimally represented I. . 46.72 baryta. I1 . . 46.97 , Baryta-salt of the acid obtained by the action of nitric acid on the sulphocyanide of methyl I. . . 46.74 per cent of baryta. The following formula agrees perfectly with the above BaO. C H S 0, and yields 46.95 per cent-baryta by theory ; a sufficient proof of the identity of the two methyl-acids.Having obtained such satisfactory results with regard to the identity of the two ethyl acids with each other and of the two methyl acids with each other I did not think it necessary to prepare the bisulphide of amyl so as to ascertain whether the acids of Erdmann and Medlock were identical. When identity is proved in the ethyl series with regard to two acids we may with a degree of certainty assume identity in corresponding series such as those of methyl and aniyl; and although the latter series are not so extended as the former still the analogues of all the sulphur and oxygen compounds of the ethyl combinations will I am convinced be disco- vered long before. When this is the case mom decided conclusions may be drawn with regard to the basyles and salt radicals upon which the whole fabric of chemical theory is at present based.Although the number of compounds in Organic Chemistry is very great yet I feel convinced that a repetition of old investigations by skilful hands will tend to reduce their number ; for with regard to the accurate determination of a formula very much depends upon the perfection of the apparatus employed and the accuracy of the manipulator. I shall in conclusion give the formulE for the two acids which have been discussed Hyposulphethylic acid H. C H S O, or HO. C H S 0, Hyposulphamethylic acid H. C H S O, or HO. C H S 0,.

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MR. GRAHAM ON ETHERIFICATION. Feb. 4 1850. WILLIAMALLENMILLER,MI). V.P. in the Chair. Mr. George ,Made was elected a Fellow of the Society. The following Preseiits were announced c‘ The Pharmaceutical Journal,” for February from the Editor. “ Proceedings of the Philosophical Society of Glasgow,” Vol. 111 No. 1. “ Experimental Investigation into the amount of water given off by Plants during their growth,” and ‘(On Agricultural Chemistry,” by J. B. Lawes presented by J. H. Gilbert Ph. D. ‘‘ Address delivered at the Anniversary Meeting of the Geological Society oi’ London on the 16th of February 1849 by Sir Henry T. De la Beche C.B. F.R.S.,” presented by the Author. “ On Benzole,” by C. B. Mansfield from the Author. The following Papers were read “ On some of the Salts of Carbonic Acid,” by Mr.N. Samuelson. VI.-Observations on EtheriJcaiion. By THOMAS GRAHAM,F.R.S. F.C.S. &c. In the ordinary process of etherizing alcohol by distilling that liquid with sulphuric acid two distinct chemical changes are usually recognized ; namely first the formation of sulphovinic acid the double sulphate of ether and watcr ; and secondly the decomposition of the compound named and liberation of ether. The last step or actual separation of the ether is referred to its evaporation in the circumstances of the experiment into an atmosphere of steam and alcohol vapour assisted by the substitution of water as a base to the sulphuric acid in the place of ether. The observation however of M. Liebig that ether is not brought off by a current of air passing through the heated mixture of sulphuric acid and alcohol is subver- sive of the last explanation as it deuionstrates that the physical agency of evaporation is insufficient to separate ether.Induced to try whether ether could not be formed without distillation I obtained results which appear to modify considerably the views which can be taken of the nature of the etherizing process. The spirits of wine or alcohol always employed in the following experiments was of density 0.841 or contained 83 per cent of absolute alcohol. Ezpt. 1. One volume of oil of vitriol was added to four volumes of alcohol in a gradual manner 50 as to prevent aiiy considerable rise MR. GRAHABI ON ETHERIFICATION.of temperature. The mixturc was sealed up in a glass tube 1 inch in diameter and 6.6 inches in length of which the liquid occupied 5.2 inches a space of 1.4 inch being left vacant to provide for expansion of the liquid by heat. The tube was placed in a stout digester containing water and safely exposed to a temperature ranging from 284O to 352O (140O to l78O C.) for one hour. No charring occurred but the liquid measured on cooling 5.25 inches in the tube and divided into two columns the upper occupy- ing 1.75 inches and the lower 3-5 inches of the tube. The former was perfectly transparent and colour1ess and on opening the tube was found to be eiher so entirely free from sulphurous acid that it did not affect the ycllow colour of a drop of' the soluiion of bichro-mate of potash.The lower fluid had a slight yellow tint but was transparent. It contained some ether but was principally a mixture of alcohol water and sulphuric. acid. The salt formed by neutralizing this acid fluid with carbonate of soda did not blacken when heated from which we may infer that little or no sulphovinic acid was present. The principal points to be observed in this experiment are its entire success as an etherizing process without distillation without sensible formation of sulphovinic acid and with a large proportion of alcohol in contact wilh the acid namely iwo equivalents of the former nearly to one of the latter. When the proportion of the alcohol was diminished the results were not so favourable. Expt. 2.A mixture of one volume of oil of vitriol and two volumes of alcohol sealed up in a glass tube was heated in the same manner as the last. The liquid afterwards appeared of an earthy-brown colour by reflected light and was transparent and red by transmitted light. Only a film of ether was sensible after twenty-four hours floating upon the surface of. the dark fluid. Expf.3. With a still smaller proportion of alcohol namely one volume of oil of vitriol with one volume of alcohol which approaches the proportions of the ordinary etherizing process a black opaque liquid was formed at the high teniperature thick and gummy without a perceptible stratum of ether after standing in a cool state. Crystals of bisulphate of soda containing a slight excess of acid were found to etherize about twice their volume of alcohol in a sealed tube quite as effectually as the first proportion of oil of vitriol when heated to the same tempetature.The two liquids found in the tube were colourless no sulphurous acid appeared and only a niinute quantity of sulphovinic acid. Crystals of bisufphate of soda which were formed in an aqueous solution and without an MR. GRAHAM ON ETHERIFICATION. excess of acid had still a sensible but much inferior etherizing power. Expt. 4. A mixture was made of oil of vitriol with a still larger proportion of alcohol namely 1volume of the former and 8 of the latter or nearly 1 equivalent of acid to 4 equivalents of alcohol This mixture was sealed up in a tube and heated for an hour between 284O and 317O (140"and 158O C.) which appeared sufficient for etheriz-ingit.A second exposure for another hour to the same temperature did not sensibly increase the ether product. The column of ether measured 1.25 in the tube and the acid fluid below 2.5 inches. Both fluids were perfectly colourless. It thus appears to be unnecessary to exceed the temperature of 317O (158O C.) in this mode of etherizing and that the proportion of alcohol may be increased to eight times the volume of the oil of vitriol without disadvantage. Expt. 5. The proportions of the first experiment were again used namely 1 volume of oil of vitriol with 4 volumes of alcohol and the mixture heated as in the last experiment to 317O (158O C.) The upper fluid or ether measured 1.1 inch in the tube the lower fluid 2.65 inches.The latter had a slight yellow tint like nitrcus ether but only just perceptible. It gave when neutralized by chalk Sulphate of lime . . 83.11 grains Sulphovinate of lime . . 4.91 , The last salt was soluble in alcohol and crystallized in thin plates. Here again the formation of sulphovinic acid in a successful etherizing prccess is quite insignificant. New results at 317O from the other proportions of 1 volume of oil of vitriol with 1 and 2 volumes of alcohol were quite similar to those obtained in experiments 2 and 3 at the higher temperature of 352O. In none of these experiments did there appear to be any formation of olefiant gas and the tubes could always be opened when cool without danger.Neither glacial phosphoric acid nor crystallized biphosphate of soda etherized alcohol to the slightest degree when heated with that substance in a sealed tube to 360° (182O C.). Even chloride of zinc produced no more at the same temperature than a trace of ether perceptible to the sense of smell. Expt. 6. To illustrate the ordinary process of ether-making a mixture was prepared as usually directed of 100 parts of oil of vitriol 48 , of alcohol (0.841) 18.5 , of water. MR. GRAHAM ON ETHERIFICATION. This liqyid was sealed up in a glass tube and heated to 290' (143O C.) for one hour. It became of a dark greenish-brown colour and opalescent with a gummy looking matter in small quantity. No stratum of ether formed upon the surface of the fluid.The tube was opened and the fluid divided into two equalportions. One of the portions was mixed with half its volume of water and the other with half its volume of alcohol and both sealed up in glass tubes and exposed again to 290° for one hour. It would be expected on the ordinary view of water setting free ether from sulphovinic acid that much ether would be liberated in the mixture above to which water was added. The ether which separated however amounted only to a tshin film after the liquid had stood for several days. In the other liquid on the contrary to which alcohol was added the formation of ether was considerable a column of that liquid appearing which somewhat exceeded balf the original volume of the alcohol added.In fact the srdphovinic acid was nearly incapable of itself of yielding ether even when treated with water. But it was capable of etherizing alcohol added to it in the second mixture like bisulphate of soda or any other acid salt of sulphuric acid. The conclusions which I would venture to draw from these experi- ments are the following. The most direct and normal process for preparing ether appears to be to expose a mixture of oil of vitriol with from four to eight times its volume of alcohol of 83 per cent to a temperature of 320° (160O C.) for a short time. Owing to the volatility of the alcohol this must be done under pressure as in the sealed glass tube. The sulphuric acid then appears to exert an action upon the alcohol to be compared with that which the same acid exhibits when mixed in a small proportion with the essential oils.Oil of turpen-tine mixed with one-twentieth of its volume of sulphuric acid undergoes an entire change being chiefly converted into a mixture of two other hydrocarbons terebene and colophene one of which has a much higher boiling point and greater vapour-density than the oils of turpentine. This hydrocarbon does not combine with the acid but is merely increased in atomic weight and gaseous density without any further derangement of composition by a remarkable polymeriz- ing action (as it may be termed) of the sulphuric acid. So of the hydrocarbon of alcohol; its density is doubled in ether by the same polymerizing action. Chloride of zinc effects with alcohol at an elevated temperature a polymeric catalysis of the latter of the same MR.GRAHAM ON ETHERIFICATION. character but in which hydrocarbons are formed of even greater density and free from oxygen. This view of etherification is only to be considered as an expression of the coutact-theory of that process which has long been so ably advocated by 31.Mitscherlich. The formation of sulphovinic acid appears not to be a necessary step in the production of ether ;for we have found that the etheriz- ing proceeded most advantageously with bisulphate of soda or with sulphuric arid mixed with a 1arg.e proportion of alcohol and water which would greatly impede the production of sulphovinic acid. It appears indeed thai the Combination of alcohol with sulphuric acid in the form of sulphovinic acid greatly diminishes the chance of the former being afterwards etherized; for when the proportion of oil of vitriol was increased in the preceding experiments which would give much sulphovinic acid the formation of ether rapidly diminished.The previous conversion of alcohol into sulphovinic acid appears therefore to be actually prejudicial and to stand in the way of its subsequent transformation into ether. The operation of etherizing has attained a kind of technical perfec- tion in the beautiful continuous process now followed. The first mix- ture of alcohol and sulphuric acid is converted into sulphovinic acid the sulphate of ether and water which acid salt appears to be the agent which polymerizes all the alcohol afterwards introduced into fluid.Bisulphate of soda with a slight excess of acid acts upon alcohol in the same manner and its substitution for the acid sulphate of ether would have a certain interest in a theoretical paint of view although a change of no practical importance in the preparation of ether. Sulphuric acid does not appear to be adapted for the etherizing of amylic alcohol. M. Balard by distilling these substances together obtained a variety of hydrocarbons some of them of great density but no ether. The polymerizing action of the sulphuric acid appears to advance beyond the ether stage I have varied the experiment by heating amylic alcohol in a close tube to 350° (176O C.) with oil of vitriol to which 1 2 3 4 and even 6 equivalents of water had been added without obtaining anything but the hydrocarbons of Balard. The formation of these was abundant even with the most highly hydrated acid and with a very moderate colouration of the fluid.

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ON A NATURAL ALLOY OF SILVER AND COPPER. VIL-On a Natural Alloy of Silver and Copperfrom Chile. By MR. FREDERICK FIELD. The alloy was taken from a mine about twenty leagues east of Coquirnbo and six from the Cordillera of the Andes. It was perfectly free from oxygen sulphur &c. and other sub- stances usually found combined with metals in nature having exactly the appearance of an artificially smelted product from a copper furnace. 100 grs. taken from the centre ofa large mass was found to contain on analysis Copper . 98.91 Silver . 1.09 100~00 The quantity of silver however was very variable. One portion of the alloy had almost a whitish appearance and on being separated by the chisel and analysed gave Copper . . 92.40 Silver . 7.60 100*00 I have a large specimen weighing more than a pound which I hope to have the pleasure of sending to the Society’s Museum by the first opportunity. Feb. 18 1850. The PRESIDENT in the Chair. The Rev. Bath Power and H. Yates Finch Esq. were elected Fellows of the Society. The following Papers were read ‘‘ On some Salts of Chromic Acid,’’ by Mr. J. Danson.

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DR. E. FRANKLAND ON THE VIII.-Researches 0% the Organic Radicals ;Part 11 AMMYL. By E. FRANKLAND, PH.D. F.C.S. PROFESSOR OF METALLURGY IN THE COLLEGE FOR CIVIL ENGINEERS PUTNEY. In studying the decomposition of iodide of ethyl by zinc7* I obtained in addition to ethyl and zinc-ethyl two bodies as secondary products having the empirical formulz C H and C H,; the furmer agreeing exactly so far as its reactions were followed out with olefiant gas and the latter having the same composition and specific gravity as methyl; but as both these bodies are permanent gases it was difficult to prove their complete identity with olefiant gas and with the methyl procured in the decomposition of cyanide of ethyl by potassium,+ and by the electrolysis of acetic acid;$ owing however to the much higher atomic weight and vapour-density of the amyl compounds it appeared highly probable that if the iodide of this radical be similarly decomposed by zinc the secondary products of decomposition corresponding to the two bodies above- named will exist at ordinary temperatures as liquids the re-actions and physical character of which would lead to the discovery of their rational constitution as well as that of the two gaseous bodies before alluded to.These considerations induced me to attempt next the isolation of the hitherto hypothetical radical arnyl in preference to any of the other members of ihe same series. For the preparation of the iodide of amyl which served for the experiments detailed in the following pages a modification of the process described by Cahourst was employed.Four parts of iodine were dissolved at intervals in seven parts of pure ftisel-oil and between each addition of iodine a stick of phosphorus was suspended in the liquid until the latter became nearly colourless. The fluid thus obtained had an oily consistence and emitted copious fumes of hydriodic acid when exposed to the air ;on being submitted to distillation in an oil-bath a colourless liquid containing much free hydriodic acid and unchanged fusel-oil passed over into the receiver whilst a non-volatile thick oily fluid insoluble in water * Chem. Soc. Qu. Journ. II. 265. t Chem. Soc. Qu. Journ. I 60. $ Chem. Soc. Qu. Journ. 11 173. Ann. Ch. Phys. LXX 95. ORGANIC RADTCALS.and re-acting strongly acid remained in the retort.* The distillate was washed with a small quantity of water to remove the hydriodic acid and after standing twenty-four hours over chloride of calcium was redistilled it began to boil at 120° C. (the boiling-point of iodide of amyl as given by Cahours) ;but the thermometer gradually rose to 146O C. at which teniperature the last 8 of the fluid distilled over and was collected in a separate receiver. If the whole of the hydriodic acid had not been removed by the previous washing with water the liquid generally became coloured violet by free iodine during this second distillation ;but the coloration was easily removed by a subsequent rectification over mercury and the iodide was then quite pure.The first 3of the distillate which pass over between l2OO and 146O C. also contaiiis much iodide of amyl and may be advantageously employed for the preparation of a further quantity by adding more iodine and phosphorus in the relative proportions -already given. Iodide of amyl is a colourless and transparent liquid refracting light strongly possessed of a weak ethereal odour and a sharp biting taste :it boils at 146O C. under a pressure of 175"" and not at l2Oo C. as stated by Cahours its specific gravity is 1.51113 at 11.5 C. Burnt with oxide of copper 0.3600grm. gave 0.4003 grm. carbonic acid and 0.1797 grm. water; numbers which give the following per centage composition Calculated. Found. C, ........30.36 30.32 H, ........ 5.55 5.55 I .........64.09 - 100~00 Some preliminary experiments shewed that iodide of arnyl is acted upon.by zinc with much more difficulty than the corresponding ethyl compound which seems to be principally owing to the very sparing solubility of iodide of zinc in the surrounding liquid and also to the comparatively low temperature at which iodide of amyl heated alone as well as with zinc is decomposed into free hydriodic acid and other gaseous products which I have not as yet more closely investigated. In consequence of these difficulties it requires a very nice management of the temperature to effect anything like a perfect *This fluid which is formed in large quantity and probably contains a compound of an acid of phosphorus with oxide of amyl merits closer investigation.DR. E. FRANKL4ND ON THE decomposition of the iodide by zinc alone. This led me to employ an anialgani of that metal which answered the purpose admirably; for on being subsequently heated with the liquid iodide the pasty metallic mass becomes perfectly fluid and owing to the agitation of the boiling liquid continually presents a fresh and bright surface. This amalgam acts considerably upon the iodide at the ordinary boiling-point of the latter but exposed to a temperature about loo C. higher in a sealed tube it undergoes decomposition with tolerable rapidity no gases are evolved but on distilling the resulting liquid the variation of the boiling-point from 30° C. to 160° C. shews the liquid to be a mixture of at least two bodies.For the purpose of submitting the iodide of amyl to the action of zinc-amalgam under pressure I employed strong glass tubes about 3 inch in diameter and 14inches long closed at one end and having the other drawn out to about Q inch in diameter and 3 inches long. Each of these tubes was filled to the height of 1.5 in. with zinc-amalgam of a pasty consistence above which was placed a layer of granulated zinc 2 inches deep which afterwards gradually dissolved in the mercury as the amalgam became diluted by the action of the liquid iodide. From 2 oz. to 1 oz. of the iodide of amyl being then introduced the open end oP the Lube was drawn out to a fine orifice which a€kr boiling the included Auid lor z1 moment to expel the air was hermetically sealed with 8 mouth-blowpipe.The tube was then immersed in an oil bath to ihe depih ol about 3 inches and main- tained at a temperature varying from 160° to 180° C. for several hours. Subsequently and after being allowed to cool so much of the drawn-out extremity was broken off as admitted of the intro- duction of from 1 to 2 grms. of potassium and the tube being again hermetically closed was subjected to the same temperature as before for about an hour. When perlectly cool the upper part was again cut off and a cork and bent tube adapted to the orifice. The bent tube led to a receiver which was kept cool by a freezing mixture of dilute sulphuric acid and snow; the decomposition tube was now immersed to nearly its whole length in a water-bath the temperature of which never exceeded 80" C.; about Q of the liquid contents of the tube distilled over J the receiver was then changed and the water-bath being removed the decomposition tube was carefully heated by means of a spirit-lamp until the remaining fluid had come over. As valyl according to Kolbe,* boils at 108O C. and the addition of the elements C H to the same volume of vapour must necessarily cause a considerable elevation of the boiling-point it appeared highly * Chem. SOC. Qu. J. 11 161. 0RGdN IC RA I)I CA LS. probable that the amyl if separated as such would be €oonud in the less volatile liquid which supposition was also strengthened by the analogous decomposition of iodide of ethyl ; I therefore first submitted the last-obtained product to investigation.This liquid which was colourless and possessed of a peculiar penetrating odour was not in the least acted upon by potassium even at its boiling point the fused metal remaining at the bottom of the fluid like a globule of mercury and presenting a surface of remarkable brilliancy. On being distilled its boiling point rapidly rose to 155O C. and remained nearly constant at this temperature uiitil the whole had passed over. The fluid which distilled at 155* C. was collected separately and submitted to analysis. I 0.1757 grm. burnt with oxide of copper”t’ gave 0.5426 grm. carbonic acid and 0.2433 grm. water. 11 0.2000 grm. gave 0.6207 grm. carbonic acid and 0.2732 grm. mater. 111. 0*1101grm. gave 0.1523 grm water.These numbers agree closely with those calculated from the formula of the hitherto unisolated radical amyl Cl %a* Calculated. Found. I-* .-> r-A-.-7 I. 11. 111. MEAN. C, . . . . . 60 84.5 84.2 84.6 84*4 H, . . . . 11 15.5 15.4 15.2 15.4 15.3 71 100.0 99-6 99.8 99.7 A determination of the specific gravity of its vapour yielded the following results confirmatory of the above formula Weight of liquid used . . *1670grm. Observed vol. of vapour . . 46.5 cbc. Temperature . . 19005~ C. Height of barometer . . . 738.1”“ , , inner column of mercury. 10*omm From which the specific gravity was calculated to be 48989. Amy1 is a colourless pellucid liquid possessing a slight ethereal dour and a burning taste ; exposed to a cold of‘ -30° C.it becomes * At the conclusion of each analysis a stream of oxygeii evolved from perchlorate of potash placed at the further e5d of the combustion tube was led over the reduced oxide of copper until the latter was completely reoxidized. The material used in analysis No. 11 was a separate preparation. VOL. IXI,-NO. IX. 1) DR. E. I~llANKLANI) ON THE thick and oily but does not solidify; its specitic gravity in the liquid form is 0.7704 at 1loC.,'that of its vapour 4,9062. According to the above determination of tlie specific gravity of its vapour this radical contains 5 vols. carbon vapour and 11 vols. hydrogen con- densed to 1vol. and is thus in this respect perfectly analogous to methyl ethyl and valyl. 5 vol.carbon vapour . . 4.1461 11vol. hydrogen . . 0.7601 -~ 1 vol aniyl vapour . * . 4.9062 Found by experiinent . . 4,8989 Amy1 boils at 155O C. at a pressure of 728n1lll; it does not ignite at ordinary temperatures ;but on being heated its vapour burns with a white smoky flame. It is insoluble in water but miscible in all proportions with alcohol and ether. It is not affected by fuming sulphuric acid aiid is but very 'slowly oxidized by boiling fuming nitric acid or by a niixture of nitric and sulphuric acids. During this oxidation the liquid acquires the odour of valerianic acid. The action of chlorine aiid bromine as well as of oxidizing agents upon aniyl aiid the two bodies noticed below will be described in a future conirnunication.It still remained to exaiuine the very volatile liquid which had distilled over €mm the decomposition tube at a tcrnperature not exceeding SOo C. This liquid possessed a very PO ~vcri'ui,penetrating and rather disagreeable odour much resembling that of the body C €I8 evolved during the electrolysis of valerianic acid and a taste at first rather sweet but aftei'mdrds iiameous and tar-like. It was so volatile that when the thin glass vessel containing it was held in the hand it imrnecliately entered into ebullition. To ascertain the relative quantities of carbon and hydrogen con-tained in this liquid and thus obtain some clue to its composition a portion of it was burnt with oxide of copper. 0.1577 grui. yielded 0.41870 grm. carbonic acid and 0.2260grm.water numbers which indicate the following per centage com-position Carbon . . 84.2 Hydrogen . . 15.9 lor~'l Since in tLe decomposition of iodide of ethyl by zinc a portion of the separated radical is transformed into equal volumes of C H and ORGAXIC RADICALS. C H3,* it was not improbable that a similar decomposition of aniyl had here taken place and that this volatile liquid contained the products which would in fact yield an analytical result similar to the one just given. To ascertain if this were the case I availed myself of the property which anhydrous sulphuric acid seems to possess of combining with carbo-hydrogens of the form C H, and leaving unacted upon those of the form C + H(n+v;and as the liquid was easily converted into a temporary gas I submitted it to the following experiment which at the same time gave the specific gravity of its vapour.A sinall and very thin glass bulb was filled as perfectly as possible with a weighed quantity of the fluid hermetically sealed and then introduced into a short eudiometer filled with quicksilver and inverted in an iron trough containing the same metal to which heat could be conveniently applied. A long glass Eylinder open at both ends was then lowered perpendicularly over the eudiometer and immersed to the depth of about 2 inches in the mercury; it was then filled to such a height with water that the enclosed eudiometer was conipletely beneath the surface. Heat being afterwards applied below the mercury trough the glass bulb in the eudiorneter soon burst and the enclosed Auid became converted into vapour.When the water in the glass cylinder had boiled for some time the volume of the vapour was accurately noted as well as the height of the barometer and the elevation of the column of mercury in the eudiorneter above that in the trough outside the glass cylinder. The water and cylinder were then removed and the whole apparatus allowed to cool until the vapour had again assumed the liquid form the temperature at which this took place was only a very few degrees above that of the surrounding atmosphere. A coak bullet saturated with a solution of anhydrous sulphuric acid in Nordhausen acid was then introduced on coming in contact with the carbo-hydrogen a quantity of vapour equal to about half the original volume was rapidly formed and maintained the gaseous condition at the temperature of the surrounding air although it was immediately condensed by cooling the tube a few degrees,--a proof that the body not absorbed by sulphuric acid has its boiling point near to but lower than that absorbed by the acid.Although the action of the sulphuric acid appeared to be nearly instantaneous yet in order to be sure that the absorption was quite complete the coak bullet was allowed to remain in the vapour for half-an-hour and the temperature of the mercury was raised loo or l2O C. before its withdrawal in order * Cliem. SOC. Qu. J. vol. 11 p. 281. D2 D11. E FRANKLAND ON THE to ensure the complete volatilization of the body left unabsorbed by the acid.On coming in contact with moist air the bullet still funied strongly which was a proof that the acid had been present in excess. A ball of hydrate of potash was now introduced and left in the vapour until every trace of sulphurous acid and vapours of sulphuric acid had been absorbed-in fact until the moment before the volume of the remaining vapour was read off which was effected along with the collateral observations after the glass cylinder and water had been replaced-and the whole heated to 42O C. R higher temperature was considered undesirable lest the elasticity of the vapour of the sulphuric acid compound traces of which still adhered to the sides of the eudiometer should introduce inaccuracy into the obsemation.The following results were obtained I. Cor. vol. at Diff. of mer-Barom. Oo C. and Ahstl. vol. Temp. C. cury Ievel 'i60mmpress. Vol. of vapour (dcy) 18.7 cbc. looo 109.2"" 756*Imfn11.65 Vol. after action of sulph. acid (dry) 8.9 , 42.09 142.2 , 752.2 , 6.20 11. Weight of liquid used . . 0.0356 grm. Observed vol. of vapour . . 18.7 cbc. Height of barometer . . . 760-3"" Difference of mercury level . . 109*2, Temperature * 1oooc. Specific gravity of vapour . . 2.4179 According to experiment No. I. it follows that 11-65 vols. of the vapour- contained 5.45 vol. absorbable by sulphuric acid and 6.20 vol. unabsorbable by that acid ; or 100 vols. consisted of Vapour absorbable by SO . . 46-78 Vapour unabsorbable by SO .. 53.22 100~00 These results are exactly analogous to those yielded by the gases produced by the transformation of ethyl into equal volumes of C €3 and C H3,* and indicate that a portion of the * Chem. SOC. Qu. J. 11 277. ORGANIC RADICALS. amyl has been similarly transformed into equal volumes of the hitherto unknown carbo-hydrogens having the empirical formuh and The specific gravity of the vapour of a mixture containing thcse two bodies in the proportions indicated by experiment No. I. would be 2.45533 as shewn by the following calculation 24~01s.carbonvapour=2.07305 CH{ 5 vols. hydrogen ==0*34550 Condensed to 1vol. == 2.41855 x 46.78 =113*140 24vols.carbonvapour =2*07305 6 cH{6 vols. hydrogen =0*41460 Condensed to 1vol.=2*48765 x 53*22=133.393 245.533 =2.45533 100 A number which closely corresponds with that found by direct experiment No. 11. (2.4179). It now only remained to separate one of these compounds in a state of perfect purity to prove the existence of both. To effect this the mixture of the two fluids was cooled to -looC. and mixed with an excess of a saturated solution of anhydrous sulphuric acid in Nordhausen acid. After standing for several hours and being repeatedly shaken no diminution in the volume of the ethereal fluid seemed to have taken place; but on distilling the mixture in a water-bath at a gentle heat about one half only of the clear colourless liquid floating upon the sulphuric acid distilled over ; the remaining portion which was volatile only at a very high temperature I have not further examined ; it consisted probably of the conjugate sulphuric acid homologous with that produced by the action of anhydrous sulphuric acid upon olefiant gas.The distillate was placed over pieces of caustic potash until every trace of sulphurous acid had been removed. It had now entirely lost the unpleasant smell which it possessed before treatment with sulphuric acid and emitted a very agreeable odour resembling chloroform. Burnt with oxide of copper 0.1237 grm. yielded 0,3779 grm. car- I>R. E. PltANICLiND ON THE bonic acid and 0.1856 grm. water nun1bers which exactly corn*- spond with the formula C H,. Calculated. Found. c5 ' r-7 . 30 83-33 83-32 H6 - .6 - 16.67 16.67 36 100~00 99.99 A determination of the specific gravity of its vapour gave thc following result Weight of liquid employed .. 0,0863 grm. Observed vol. of vapour . . 39.8 cub. c. Temperature . * 1000 c. Height of barometer . . 733.8"" Difference of mercury level . . 31.0"" Specific gravity of vapour . . 2*4657 This result shows that the body in question contains 2$ vols;. carbon vapour and 6 vols. hydrogen condensed to 1 vol.; for on this supposition the specific gravity ought to be 2.4876 a number which closely corresponds with that found. The composition of the body absorbed by sulphuric acid is also determined by the foregoing experiments which prove that it has a constitution homologous with olefiant gas but an atomic weight 2& times greater; for according to the vapour analysis 100 vols.consisted of Vapour absorbed by SO . . 46.78 Vapour not absorbed by SO . + 53.22 100*00 or by weight Vapour absorbable by SO . . 46.08 Vapour unabsorbable by SO . . 53.92 100*00 If then from the results of the combustion of the mixcd liquids by oxide of copper (page 34);the weight of carbon and hydrogen cor- responding to 53.92per cent of the body C H be deducted the remaining numbers give the proportion by volume C H =1 :2.10 which corresponds sufficiently near with the voluminal proportion C H = 1 2 when we consider how difficult it is to preserve the ORGANIC RADICALS. constant composition of a mixture of two such volatile fluids as those in question during a series of experiments in which the vessel con- taining them has frequently to be unstopped.With reference to the true constitution of the two bodies last described two views may be taken; for they may be regarded either as products of the splitting of 1eq. amyl into 1 eq. C5 H5 and 1 eq. c5 H,. or as resulting from the transformation of 2 eq. amyl into 1 eq. C, H, and 1 eq. C, H, Before giving preference to either of these views it appeared of importance first to ascertain whether iodide of amyl in presence of zinc and water undergoes a decomposition analogous to that of iodide of ethyl under similar circumstances and if so whether the resulting carbo-hydrogen is identical with the body C H or C, H, just described.I therefore submitted iodide of amyl mixed with rather more than an equal volume of water to the actioii of zinc in an apparatus similar to that already described. In this case the zinc was not previously amalgamated as it was fouiid that the unamalgamated metal effected the decomposition with great rapidity at a moderate temperature (about 140° C). As soon as the action appeared com- plete the tube was allowed to cool and after being cut off at the drawn-ocrt extremity was connected with a well-cooled receiver and then partially immersed in a water-bath heated to about 60 C. The colourless limpid ethereal fluid which rapidly distilled over in considerable quantity was placed over pieces of fused potash for twenty-four hours and then rectified in a water-bath at 35O C.The residue remaining in the decomposition tube consisted of oxy-iodide of zinc water and a trace of undecomposed iodide of amyl. Burnt with oxide of copper 0-1813grm. of the ethereal fluid gave 0.5540 grm. carbonic acid and 0.2702 grm. water corresponding to the following per centage composition and the empirical formula c H6. Calculated. Found. r--h---? c5 * .30 83.33 83.34 .6 16-67 16-56 H6 * -36 100.00 99.90 DR. E. FRANKLAND ON THE A determination of the specific gravity of its vapour gave the following numbers Weight of liquid employed . . 0.0965 grms. Observed vol. of vapour Temperature . . . . 44.3 cbc. loooc. Height of barometer . . 758.4'"" Difference of mercury level .. 62.0mm Specific gravity of vapour . . 2.4998 That this body is perfectly identical with that formed during the decomposition of iodide of amyl by zinc without the presence of water and to which we have assigned the empirical formula C5 H, the following comparison of their chemical and physical properties proves beyond all doubt. Body prodaced in the decom- Body produced in the decom- position of iodide of amyl by zinc position of iodide of arnyl by zinc without the presence of water. with the presence of water. Results of combustion with oxide of copper. Results of combustionwith oxide of copper. Carbon . . 83.32 Carbon . . . 83.34 Hydrogen . . 16.67 Hydrogen . . 16-56 -99.99 ~ 99.90 Specific gravity of liquid. Specific gravity of liquid.0.6385 at 14*2OC. 0.6413 at 11~2~ C. Specific gravity of vapour. Specific gravity of vapour. 2.4657 2.4998 Boiling point. Boiling point. 30° C. at 734"" pressure. 30° C. at 758"" presswe. 1 Further both bodies are equally unacted upori by fuming sulphuric acid and only with great difficulty by the most powerful oxidizing menstrua; they both possess the same odour and are perfectly similar in every respect. The decomposition of iodide of amyl by zinc in presence of water is perfectly analogous to that of iodide of ethyl under similar circum- stances and may be expressed by the following simple equation When TVC consider thc abovc facts in conncction with thc cxistcncc ORGANIC RADICALS. and products of decomposition of zinc-methyl and ziuc-ethyl in which the zinc is so evidently replaced by hydrogen and there can scarcely be a doubt that the rational constitution of thc body in question is Cl H,l and I therefore propose for it the name HYDRURET OF AMYL.Hydruret of amyl is a transparent colourless and exceedingly mobile fluid possessing an agreeable odour resembling chloroform. It is insoluble in water but soluble in alcohol and ether from the former of which it is again separated by the addition of water it is the lightest liquid known its specific gravity being only 0.6385at 149O C. Hydruret of amyl retains its fluidity at -24O C. ; it boils at 30° C. ; its vapour is easily inflammable and burns with a brilliant white flame; placed in a glass flask having its neck drawn out to a fine orifice and held in the hand a constant jet of gas issues which on being ignited gives a pure white light of surpassing brilliancy and devoid of smoke until the enclosed fluid is entirely evaporated.In accordance with two determinations of the specific gravity of its vapour it contains 1 vol. amyl vapour and 1vol. hydrogen united without condensation or 5 vols. carbon vapour and 12 vols. hydrogcn condeiised to 2 vols. 5 vols. Carbon vapour . . 4.1461 12 vols. Hydrogen . . 08292 2 vols. Hydruret of Amy1 . . 4.9753 49753 1 vol. of which therefore weighs -== 2.4876 2 Found by experiment 24657 24.998k* :: { Hydruret of amyl is not in thc least affected by prolouged contact with fuming sulphuric acid; it is a remarkably stable compound and IS only acted upoii with great difficulty by the most powerful re-agents.DR. E. FRANKLAND ON THE It can scarcely be doubted that this body was present in the liquid obtained by Reichenbach* in acting upon wood-tar with sulphuric acid and to which he gave the name Eupione as the boiling point of this liquid varied from about 47" C. to 260°C. it was evidently a mixture of several compounds. Reichenbach says that the niost volatile portion boiled at 47O C. or even lower; had a specific gravity 8.633;and formed a clear colourless and very mobile fluid of a some-what agreeable odour resembling narcissus flowers he states that the formula is either C 13 or some multiple of this or else one nearly approaching to such a multiple as C H,.It is highly probable that the liquids described by Reichenbach under the name of eupione consisted of a whole series of bodies having the form C H (n+2) and differing from each other by C H, commencing with hydrnret of amyl and terminating with the hydrurets of the radicals of the wax- alcohols described by Brodie ;+ and as the gases evolved by the destructive distillation of wood and of coal are already known to contain hydruret of methyl (light carburetted hydrogen) there can be little doubt that the other members of the series intermediate between this last body and hydruret of amyl will also be found in them viz. Hydruret of ethyl . * c H, H , butyl * cfj H,> , valyl . C H, H 3 I Probably the illuminating power of coal gas depends to a great extent upon the presence of these bodies especially the hydrurets of butyl and valyl.That the methods hitherto employed in the analysis of coal- gas have not led to the discovery of these bodies will cease to create surprise when we consider that they are probably all unacted upon by fuming sulphuric acid and perchloride of antimony and that 1 vol. hydrogen with 1 vol. hydruret of ethyl 2 vols. hydrogen with 1 vol. hydruret of butyl and 3 vols. hydrogen with 1vol. hydruret of valyl give mixtures all of which have the same specific gravity as hydruret of methyl (light carburetted hydrogen) and further contain in the same volume the same relative and absolute quantities of carbon and hydrogen and would therefore yield on combustion with oxygen precisely the same eudiometrical results as hydruret of methyl.If however coal-gas after behg freed from the bodies of the form C H by being passed through fuming sulphuric acid or * Sehweigger Seidel's Journal LXVIII 117 atid hiin. Pharm. VIII 217. i-Ann. Ch. Pharni. 71. 14l. ORGAXIC RADIC.1LS. perchloride of antimony were allowed to stream through alcohol the compounds in question would no doubt be absorbed and could be afterwards separated in the gaseous form by the addition of water or by ebullition. The careful examination of wood and coal tars in connection with the gases evolved during their formation would certainly lead to highly interesting results as is indeed already rendered evident by Mansfield's late discovery of large quantities of hydruret of phenyl (benzole) in coal-tar naphtha.The great difficulty attending such investigations has hitherto consisted chiefly in the impossibility of separating the mixed hydrocarbons by fractional distillation. The cause of this difficulty and its remedy seem to be indicated by the foregoing experiments taken in connection with the boiling points of ethyl butyrene (c H,) and the amylene of Cahours; for taking the formulae expressing equal volumes of vapour we have the following series 'y-iF'$:)p:grl Boiling points. Differences Butyrene (C H,) . * c4 H4 -17*8O C*} 5.2n c. Ethyl . c4 H5 -23.0' , Valerene* (Clo HlO) C H 35:0° jf } 5.00 ,, Hydruret of amyl (CloH12) C H 30 Oo , Amylene (Go H20) ' ' Cl HI0 160:Oo 1 } 5.00 ,, Amy1 .ClO Hll 155 Oo , Thus it appears that a carbo-hydrogen having the formula C H, and its companion C H(n+lldiffer in their boiling points by only 5O C. or in other words the addition of 1 eq. hydrogen without increase in the volume of vapour depresses the boiling point 50 C. thus rendering the separation of two such bodies by distillation alone inipossible ; but by the employment of anhydrous sulphuric acid all the compouncis having the form C, H would in all probability be removed and as the bodies C Hcn+l)and C!n421H(,,+3),lying next to each other in the remaining series have boiling points differing so far as is yet known by at least 47O C. their separation by frac- tional distillation could be easily effected.Further it is not impossible that by regulating the temperature at which the destructive distillation of wood and coal is carried on considerable quantities of hydruret of amyl might be cheaply ob-tained which as illuminating material would surpass almost every other in convenience and brilliancy. * Thc body produced fioni amql simultaneously with liydruret of amyl. (See belotv.) DR. E. FRANKLAND ON THE VALERENE. The same reasons which led me to adopt the formula C, H, H for one of the products of the transformation of amyl point also to C, H, as the rational formula of the second; for if from 2 ey. amyl 1 eq. hydrurct of aniyl be deducted the elements C, H, remain and fill a vacant space in the olefiant gas series 2 eq.Amy1 . . . . - c20 H, 1eq. Rydruret of amyl = C, H,, -1 eq. Valerene . . = C, H, Our knowledge of the rational constitution of the whole series of bodies having the formula C H in which n is an even number is much too limited to allow of permanent names being given to any of them. I have named the body under consideration Valerene in accordance with the names given to the other known members of the same series; but without any reference whatever to its true constitution. Valerene is a colourless and transparent liquid possessed of a peculiar penetrating and hsagreeable odour much resembling butyrene (C H,) so far as these properties can be judged of from its mixture with hydruret of amyl. Its boiling point is about 35O C.It is rapidly and perfectly absorbed by anhydrous sulphuric acid and by perchloride of antimony with which last it no doubt forms the coni-pound analogous to the oil of olefiant gas Cl hl c12 On the supposition that it contains 5 vols. carbon vapour and 10 vols. hydrogen condensed to 2 vols. the specific gravity of its vapour would be 2.41855. 5 vols. Carbon vapour . . 4.1461 10 , Hydrogen . . 0.6910 2 , Valerene vapour . . 41.8371 48371 1 vol. of which therefore weighs -= 2.41855 2 The specific gravity as calculated from that of the mixture of valerene and hydruret of aniyl is 2.3863 which agrees sufficiently well with the theoretical number. I have not studied its properties further. In addition to tshc bodies above-dcseribed iodide of aniyl whcn ctccomposed by zinc yields zinc-arnyl a body h~in p propties quite 0RGANIC 11ADICALS .analogous to those of zinc-ethyl and zinc-methyl. The complete history of these compounds will be given in a future communication. The foregoing experiments show that the decomposition of iodide of amyl by zinc gives rise to four new bodies viz. Amy1 . . Cl HI Hpdruret of amyl . * CIO HI17 H Zinc-amyl . GI0 Hll Zn Valerene . * CIO HI0 Iodide of amyl is also decomposed by potassium with great rapidity when the fluid is heated to the fusing point of the metal; the results of the decomposition are precisely the same as those obtained by zinc except that no compound containing potassium analogous to zinc-amyl is formed.This process cannot however be conveniently employed for the preparation of amyl because the iodide of potassium assumes such a bulky form as to render necessary the distillation of the fluids from this salt at least five or six times before the decomposition can be completed which is attended with great loss. Perhaps no class of compounds within the whole range of chemistry has been so closely investigated and at the same time the subject of such difference of opinion as the bodies termed alcohols and their derivatives the ethers ; the well-marked properties and reactions of the whole series so far as its individiial members are known and the theoretical as well as practical interest connected with the subject make the development of the true constitution of these compounds one of the most important problems of chemical science.Gay-Lussac was the first to throw out a suggestion upon the possible rational composition of alcohol and ether which he hinted might be regarded as compounds of olefiant gas and water but still preferred to view them as ternary compounds of carbon hydrogen and oxygen. The former view was soon after taken up by Dumas and Bodlay,* and worked out into their well known theory in which they assume alcohol and ether to be hydrates of olefiant gas the oxalic acetic &c. ethers as compounds of the first hydrate of that body with the respective oxygen acids and the ethereal bodies formed by the hydrogen acids as compounds of these acids with olefiant gas.This hypothesis was principally borne out by the theta received views * ilnn. Chim. Phys. LXX 95. of the coiistitution of sulphovinic acid and oxande together with the belief then prevalent that sulphuric acid by the absorpiion of olefiant gas was converted into sulphovinic acid. D unias and Boullay regarded ether alcohol acetic and hydrochloric ethers as having the following rational constitution Ether . . C 13 + HO Alcohol . . C H + 2NO Acetic ether . * (C H + HO) + c H 0 Hydrochloric ether . . C H t H Cl. The subsequent development of the true constitution of oxamide and sulphovinic acid abstracting as they did the principal support of this theory led to the views of Kane Berzelius and Liebig being very generally adopted at least in England and Germany.Berzelius* proposed to regard ether as the oxide of a compound radical ethyl (C H5),tand alcohol as the oxide of the radical (C 14J; in this view so far as ether is concerned he was soon after supported by Liebig who however regarded alcohol as the hydrate of the oxide of ethyl; and these views he confirmed and illustrated by his beautiful researches on the constitution of the oxamidef procured by the action of ammonia on oxalic ether and on the process of etherification 11 which led hiin to the following conclusions :§ 1. “That the views of Dumas and Boullay on the constitution of ether according to which this body is the hydrate of olefiant gas are not supported by any single fact.” 2. “That the only consistent view which is contradicted by no fact but which on the contrary satisfactorily explains all phenomena connected with its compounds consists in regarding ether as the pro-toxide of a compound radical C H,.0.” The same chemist adds further ‘(1have no doubt that the radical of ether viz. the carbo-hydrogen C H,-will be obtained free from every other body.” The isolation of four of the compound radicals belonging to the alcohol series now excludes every doubt of their actual existence and fixrnishes a complete and satisfactory proof of the correctness of the * Pogg. Ann. XXVIII 626; and Annnal Report presented to the Acaderny of Sciences at Stockholm March 31st 1833. -f Kane was the first to regard ether as the protoxide of a cornpound radical C IS, which he named Ethereum (Diih.Jour. of Med. Science Jan. 1833). $ Ann. Chem. Pharm. IX 6 129. 11 Idem. KSX 129 j SXIII 12. 5 Idem. IX 15. ORGANIC RAD ICILS. 47 theory propounded by Kane Berzelins and Liebig fifteen years ago. The radicals already known in their free state-viz. methyl ethyl valyl and amyl-are suEcient to enable us to judge of the chemical relations of the whole series. As might have been predicted from their behaviour in combination they present in their free state the closest relations to hydrogen and the noble metals; like these elements they are when uncombined almost perfectly indifferent and withstand the niost powerful oxidizing influences whilst in statu” nascenti they readily pass from one state of combination to another and the con- stitution of the vapours of these compounds is always perfectly analogous to that of the corresponding.compounds of the simple radical hydrogen ; the following examples may suEce as illustrations 1 vol. hydrogen combines with Q vol. oxygen and forms 1 vol. watery vapour. I 1 , methyl ,) *7 a I? r ,) 1 , oxide of methyl. -1 1 , ethyl 1 , ether vapour. I? ,f 2 9 9) 17 1 1 , ainyl ?I 11 li 17 I? ?? 1 , oxide of amyl vapnur. 1 vol. H combines with I vol. C1 and forms 2 vols. I1 C1 7 I? 1 ? c H 9 1 77 c1 ,? 29 2 c H Cl 9 ,f 1 I c H , 1 1 c1 , , 2 c 11 c1 97 99 77 ?9 $9 1 c10 Hl 1 ? c1 2 ,I c,o H, c1 The conipounds of bromine iodine fluorine and cyanogen are also perfectly analogous to the above indeed so complete is the homology of the compound radicals methyl ethyl and amyl with hydrogen that even their haloid compounds present the closest relations to hydracids as is strikingly exemplified in the behaviour of their iodides for although these bodies do not possess the pro- perty of reddening litmus-paper yet this is probably owing to the insolubility of the colouring matter in these liquids; for even hydriodic acid gas itself when perfectly dry has not the slightest action upon dry litmus paper.It may be further objected that aqueous hydrochloric and hydriodic acids rapidly dissolve zinc at ordinary temperatures whilst the iodides of methyl ethyl &c. have no action upon that metal until aided by heat. To ascertain how far this objection is well-grounded I allowed dry hydrochloric acid gas to stream over commercial zinc freshly granulated ;not the slightest action took place the brilliant surface of the metal remained un- tarnished and the escaping gas was perfectly absorbed by water until the temperature of the zinc was raised to about looo C.; and even then the decomposition of the acid gas was only very partial and ceased almost entirely as soon as the surface of the zinc becanie covered with chloride although the temperature was raised until the metal fused into globules.This experiment proves that even hydi 3- DR. E. FHANKLSND ON THE chloric acid itself when free froin water is acted upon by zinc only when aided by heat and even then with difficulty. The facility with which the series of bodies beginning with hydriodic acid and termi-nating with iodide of amyl are decomposed by zinc appears to be inversely as the atomic weight of the electro-positive group,--or in other words the electro-negative character of the compound de- creases as the atomic weight increases; for hydriodic acid is decom- posed at loooC.iodide of methyl at 150° C. iodide of ethyl with more difficulty between 150° and 160° C. and iodide of amyl with very great difficulty at 190GC. The cause of this phenomenoii probably lies to some extent in the more difficult solubility of the iodide of zinc in the surrounding liquid as the latter approaches more nearly to the character of an oil. Further hydriodic acid is rapidly decomposed with separation of free iodine under the simultaneous influence of atmospheric air and faint diffused daylight ; iodide of methyl presents the same phenomenon but requires to be exposed to these influences for a much longer time; iodide of ethyl placed under similar circumstances side by side with the last did not exhibit a trace of colour at the end of four months but when exposed to stronger diffused light became brown from separation of free iodine in a few hours ;whilst iodide of amyl exposed to strong daylight for a much longer time did not exhibit any trace of colour and only does so according to Cahours when exposed to direct sunlight.The decomposition of these iodine compounds and of hydriodic acid by zinc gives perfectly analogous results as is seen from the following equatioiis H I + Zn = Zn I + H (C H,) I + Zn = Zn I i-(C H ) (C H ) I + Zn = Zn I + (C H ) (Cia Eli) 1 + Zn = Zn 1 + (Cia Hii)* Again the late beautiful researches of Hofmann on the Organic Bases,* appear to me to confirm the claims of the haloid compounds of these radicals to the character of hydracids in a most remarkable manner and at the same time verify the suggestion I threw out in a former memoir,? that these radicals would be found capable of replacing hydrogen in many of the combinations of that element; for Hofmann has shewn that these compounds combine with am- monia aniline &c.with an energy inferior only to that of the * Anii. Ch. Phwni. LXXIII 91. -f Chem. Soc Qn. J. IT 299. ORGANIC RADICALS.corresponding hydracids themselves. The most simple explanation of these reactions and one which at the same time satisfactorily explains every fact connected with them appears to me to consist in regarding the ethereal body as playing the part of a hydracid. Although the subsequent decomposition by potash of the salts thus formed seems at first sight to militate against this view yet I conceive a little closer attention to the nature of the compound formed and to the modus operandi of the alkali completely sets this difficulty aside; for if we grant the existence of ammonium we must also adrnit that when hydrochloric acid combines with ammoniacal gas the chlorine in the former remains no longer united with any single atom of hydrogen but on the contrary with the group (N H,) ; so also when ammo- niacal gas unites with bromide of methyl the bromine remains no longer in combination with the methyl but is united with the whole group-with ammonium in which 1 eq.of hydrogen has been replaced by methyl The action of potash upon such a compound could easily be pre- dicted; for as the bromine is not in combination with any particular atom of hydrogen or methyl and as the alkali has a much stronger affinity for hydrobromic acid than for the bromide of methyl the nature of the decomposition is thereby determined and the products are bromide of potassium water and the new base,-which last by being again treated with bromide of methyl has by a precisely similar process the remaining atoms of hydrogen replaced by methyl.The replacement of hydrogen by methyl is also strikingly exem- plified in Paul Th6nard’s* new bases containing phosphorus which although that chemist regards them as otherwise constituted are evidently nothing else but the three phosphuretted hydrogens in which the hydrogen has been replaced by methyl; for as phosphide of calcium in contact with hydrochloric acid gives rise to the three compounds of phosphorus and hydrogen P H, P H, and Pz H so by substituting chloride of methyl for the hydracid the cor-responding compounds of this radical are produced. According to this view the rational constitution of these compounds and their * Compt. Rend. XXV 892. VOL. 111-NO. IX. E SIR. E. PRANKL-4ND ON THE complete correspondence with the three phosphuretted hydrogens may be thus expressed Hydrogen compounds.Metliyl compounds. H c2 83 I3 and P C2 H3 (,,€I3 {C2H3 As P. Thenard mentions that he has also obtained a similar series containing ethyl there can be little doubt that another containing ainyl will also be formed. The remarkable relation of these bodies to animonia and to the bases of Hofmann and Wurtz cannot be overlooked. It would be interesting to ascertain whether or not the phosphuretted hydrogens themselves are possessed of basic qualities. Indeed Rose has already shown that one of them (I? H3)bears a close relation to amixonia and forms several salts isomorphous with those of that base. The remarkable property of conibining with hydrogen to form hydrurets which seems to be possessed by the radicals of the series to which methyl ethyl &c.belong and which appears to be par- ticipated in by the allied series beginning with phenyl leads to a very simple view of the constitution of a number of compounds whose rational formulz have hitherto been considered doubtful LiSht carburetted hydrogen . . . . C IT + €I =hydruret of methyl.* The gas formed by the action of water upon zinc- ethyl and by the transformation of ethyl into I C 115 + H= , , ethyl.? C H, and C H, H . . . . . Volatile liquid described above . . . . C, H, + H = , , amyl. Phenol (benzole) . . . . . . CI3H + I3 = , ,? phenyl. (I Toluol . . . . . . . C, €1 + H= , 1 toluyl. CumoI . . . . . -. C, H, + H = ,) , cumyl.Cymol . . . . . . . -C, H, + 11 = , , cymyl. The action of chlorine upon the so-called methyl from cyanide of ethyl increases still further the probability of this hypothesis whilst the formation of nitro-compounds of phenol toluol &c. (by the * Kolbe has already proposed this as the rational formula of light carburetted hydrogen. See u Ilandworterbuch der Chemie art. Grubengas.” ? It is highly probable that the so-called methyl gas generated by the decomposi- tion of cyanide of ethyl by potassium is also hydruret of ethyl and therefore only isomeric with the true raclieal methyl produced in the electrolysis of acetic acid and in the decompnsition of iodide of methyl by zinc. ORGANIC RADICALS. 51 replacement of 1 eq. of hydrogen by NO,) yielding on reduction with sulphuretted hydrogen the bases aniline toluidine &c.taken in connection with the true constitution of these bases recently so completely and satisfactorily demonstrated by Ho fmann gives additional weight to the evidence in favour of this view which also explains the production of light carburetted hydrogen and phenol by the dry distillation respectively of acetate and benzoate of potash with hydrate of baryta in the most simple and satisfactory manner Acetate of potash . Hydrate of baryta rc, H 3-Benzoate of potash (5,'03 1 I C,,Hg > = jKOCO2 Hydrate of baryta CRaO Co2 (F2 j I am at present engaged with some experiments to ascertain whether the dry distillation of the salts of metacetonic butyric and valerianic acids with hydrate of baryta will not yield in the same manner respectively the hydrurets of the radicals ethyl butyl and valyl; and.the results of these experiments I hope to lay before the Society at an early period. The conclusions to which the foregoing remarks lead may be briefly expressed as follows 1. That the radicals of the series to which methyl ethyl amyl &c. belong possess exactly the chemical relations and character of hydro- gen than which they are however less electro-positive. 2. That these radicals can replace hydrogen in every combination in which that element plays the part of a simple radical aud is not enclosed in a group acting the part of a compound radical. 3. That the haldid compounds of these bodies may be regarded as hydracids in which hydrogen is replaced by one of these radicals ; and the organic acids of the series (C HIn + 0, as formic acid in which the conjugate atom of hydrogen is replaced in the same manner.4. That the replacement of hydrogen in ammonia by these radicals as exemplified in the bases of I-Iofmann and Wurtz renders the assumption of the hypothetical radical amidogen superfluous. 5. That these radicals in addition to the propei.ty of combining E2 RELATIONS BETWEEN THE with the electro-negative elements possess also the faculty of uniting with hydrogen to form hydrurets. To Professor von Liebig in whose Laboratory the foregoing investigation was made I take this opportunity of returning my warmest thanks for his advice and extreme kindness in affording me every facility for the execution of the requisite experiments.

ISSN:1743-6893    

DOI:10.1039/QJ8510300030

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

RELATIONS BETWEEN THE March 4 1850. ROBERTPORRETT,EsQ. Treasurer in the Chair. The followiiig Presents were laid upon the table ‘(Transactions of the Royal Society,” for 1848-9 presented by the Society. ‘‘Philosophical Magazine,” for March from the Editor. ‘(Pharmaceutical Journal,” for March from the Editor. Regnault’s (‘Trait6 de Chimie,” presented by the Author. (‘Miscellaneous Results from the Laboratory,” and on the “ Composi-tion of Linseed-oil Cake,” by J. T. Way (from the Quarterly Agricultural Journal) both presented by the Author. The following Paper was read IX.-Notice of Observations 0% the adjustment of the relations between the Artimal and Viyefuble Kingdoms by which the vital functions of both are permanently maintained. BY ROBERTWARINGTON, P.C.S.This communication will consist of a detail of an experimental investigation which has been carried on for nearly the last twelve months and which appears to illustrate in a marked degree that beautiful and wonderful provision which we see every where displayed throughout the animal and vegetable kingdoms whereby their continued existence and stability are so admirably sustained and by which they are made mutually to subserve each for the other’s nutriment and even for its indispensable wants and vital existence. The experiment has reference to the healthy life of fish preserved in a limited and confined portion of water. It was commeuced in May 1849 and the subjects chosen were two small gold-fish. These were placed in a large glass receiver of about twelve gallons capacity having a cover of thin muslin stretched over a stout copper wire bent into a circle placed over its mouth so as to exclude as much as possible the sooty dust of the London atmosphere without at the same time impeding the free passage of the atmospheric air.This receiver was ANIMAL AND VEGETABLE KINGDOMS. about half filled with ordinary spring water and supplied at the bottom with sand and mud together with loose stones of larger size of limestone tufa from the neighbourhood of Matlock and sand- stone; these were arranged so that the fish could get below them if they wished so to do. At the same time that the fish were placed in this miniature pond if I may so term it a small plant of the Vallisneria spiraZis was introduced its roots being inserted in the mud and sand and covered by one of the loose stones so as to retain the plant in its position.The Vallisneria spiralis is one of those delicate aquatic plants generally selected by the microscopist for the exhibition of the circulation of the sap in plants. It throws out an abundance of long wiry strap-like leaves of about $ inch in breadth and from 1 to 3 feet in length; these leavcs when the sun shines on them evolve a continued stream of oxygen gas which rises in a current of minute bubbles particularly from any part of the leaf which may have received an injury. The materials being thus arranged all appeared to go on well for a short time inntil circumstances occurred which indicated that another and very material agent was required to perfect the adjust- ment and which from my not having thought of at the time of commencing the experiment had not been provided against.The Circumstances I allude to arose from the internal decay of the leaves of the Yallisneria which became yellow from having lost their vitality and began to decompose ; this by accumulation rendered the water turbid and caused a growth of mucus or green slimy matter on the surface of the water and on the sides of the receiver. If this had been allowed to increase I conceive that the healthy life of the fish must have suffered and probably their vital functions hava been destroyed. The removal of these decaying leaves from the water therefore became a point of permanent importance to the success of the experiment.To effect this I had recourse to a very useful little scavenger whose beneficial functions have been too much overlooked in the economy of animal life,-I mean the water-snail whose natural food is the very green slimy growtb or mucus and decaying vegetable matter which threatened to destroy the object which was wished to be obtained. Five or six of these creatures- the HimnQa stagnalis-were consequently introduced and by their continued and rapid locomotion and extraordinary voracity soon removed the cause of interference and restored the whole to a healthy state thus perfecting the balance between the animal and vegetable inhabitants and enabling both to perform their vital functions with health and energy.54 RELATIONS BETWEEN THE ANTMAL AND VEGETABLE KINGDOMS. So luxuriant was the growth of the Vallisneria under these circumstances that by the autumn the one solitary plant that had been originally introduced had thrown out myriads of off-shoots and suckers thus multiplying to the extent of upwards of thirty fine strong plants ; and these threw up their long spiral flowering stems in all directions so that at one time more than forty blossoms were counted lying on the surface of the water. The fish have been lively bright in colour and appear very healthy and the snails also-judging from the enormous quantity of gela-tinous masses of eggs which they have deposited on all parts of the receiver as well as on the fragments of stone-appear to thrive wonderfully and besides their functions in sustaining the perfect adjustment of the series afford a large quantity of food to the fish in the form of the young snails which are devoured as soon as they exhibit signs of vitality wid locomotion and before their shell has become hardened.Thus we have that admirable balance sustained between the animal and vegetable kingdoms and that in a liquid element. The fish in its respiration consumes the oxygen held in solution by the water as atmospheric air ; furnishes carbonic acid ; feeds on the insects and young snails; and excretes material well adapted as a rich food to the plant and well fitted for its luxuriant growth. The plant by its respiration consumes the carbonic acid produced by the fish appropriating the carbon to the construction of its tissues and fibre and liberates the oxygen in its gaseous state to sustain the healthy functions of the animal life at the same time that it feeds on the rejected matter which has fulfilled its purposes in the nourish- ment of the fish and snail and preserves the water constantly in a clear and healthy condition,-while the slimy snail finding its proper nutriment in the decomposing vegetable matter and minute confervoid growth prevents their accumulation by removing them from the field and by its vital powers converts what would otherwise act as poison into a rich and fruitful nutriment again to constitute a pabulum for the vegetable growth while it also acts the important part of a purveyor to its finny neighbours.

ISSN:1743-6893    

DOI:10.1039/QJ8510300052

出版商:RSC    

年代:1851

数据来源: RSC