摘要:

THE QUARTERLY JOURNAL OF THE CHEMICAL SOCIETY OF LONDON. -VOL. I. THE QUARTERLY JOURNAL OF THE CHEMICAL SOCIETY OF LONDON. EDITED FOR THE SOCIETY BY EDMUND RONALDS PH.D. LECTURER ON CHEMXSTRY AT THR MIDDLESEX HOSPITAL-VOL. I. Ir 0N D0N HIPPOLYTE BAILLIERE PUBLISHER 219 REGENT STREET. PARIS J. B. BAILLIERE 13 RUE DE L’GCOLE DE M~DECINE. 1849. LON DON Printed by Schiilze and Co. 13 Poland Street. PREFACE. IN order to promote the more speedy and regular circulation of the communications made to the Society amongst its members the Council has resolved to publish the Memoirs and Proceedings which up to this time have appeared at irregular intervals in the form of a QUARTERLY JOUBNAL.It has been resolved that Notices and Abstracts of the more important papers upon Chemical Subjects which may appear in foreign Journals shall be appended to each number of this Quarterly Journal and that the January Number for each year shall contain an alphabetical list of the heads of all Chemical Papers which have appeared during the year both at home and abroad up to the time of publication of the Journal. DECEMBER 30 1848. PROCEEDINGS OF THE CHEMICAL SOCIETY UP TO THE TIME OF PUnLICATION OF THE JOURNAL. Nov. 20 1848.-The following papers were read ‘‘On the Ashes of Esculent Vegetables,” by John T. Herapath Esq. ‘‘ Analyses of Black-Ash Soda-Ash &c.” by Frederick Mus-pratt Esq. A Note on the paper of Mr.Vaux “As to the Presence of Traces of Copper and Lead in Coal,’’ by J. Yhilips Esq. December 4 1848.-“ On a Balance Galvanometer,’’ by W. S. Warde Esq. “Analysis of the Water supplied to the Highgate district,” by W. A. Mitchell Esq. ‘‘On the Action of Barytes on Salycilic Ether,” by G. Baly Esq. December 18 1848.-John Thomas Cooper Vice-president in the Chair. A paper was read by Dr. -Hofmann IC On the Volatile Or-ganic Bases,” Part IV.

ISSN:1743-6893    

DOI:10.1039/QJ84901FP001

出版商:RSC    

年代:1849

数据来源: RSC

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If2 MR. ADIE’S EXPEEIMENTS WITH VOLTAIC COUPLES. 11. An account oj some experiments with Voltaic Couples immersed in pure water and in oxygenated water by MR. RICHARDADLE of Liverpool. In the present communication it will be my endeavour to trace alittle further the line of demarcation between water and oxyge- nated-water-voltaic actions the existence of which was proved in the paper submitted by me last session for the consideration of the Society; an attempt will also be made to prove that where a voltaic current is developed by two similar pieces of an oxidizable metal the negative plate in such an arrangement is in reality the oxide of the metal. In the trials described in the former paper when zinc and iron acted as the positive elements of couples excited by boiling water the galvanometer showed that the difference between them was only one of degree.With zinc after long boiling the galvanometer was deflected 20°,and with iron 7O from which I was led to think that although iron was usually held incapable of rusting in pure water it might like zinc possess the power of slowly decomposing water but that the quantity of oxide formed in this manner was so small that it had heretofore escaped notice,-a view which is strengthened by a remark often made by other observers that decomposition of water probably occurred during the ordinary rusting of iron because ammonia was always found in the rust or hydrated oxide. The experiment in which zinc and copper elements decomposed water in a hermetically sealed tube occupied so long a time that I despaired of obtaining any notable effect with iron unless.a large surface was brought into action. For this purpose some iron was reduced from the red oxide by a stream of hydrogen; the precautions necessary for obtaining the metal in the state of greatest subdivision (the pyrophoric form) were carefully observed and to prevent the spontaneous combustion to which I found the iron liable the tube in which the metal had been reduced was filled with water as soon as the temperature would permit Iron subdivided in this manner was placed with distilled water in two tubes of hard glass; these tubes were then heated to the boiling temperature and her- metically sealed. A third tube was .similarly prepared in which a surface of 45 inches of bright polished iron wire was substituted for the pyrophoric iron.The woodcut Fig. 1 represents the form of the tubes employed. A is the tube filled with water and iron BC is a capillary portion MR. ADIdS EXPEKINENTS WITH VOLTAIC COUPLES. drawn out by the blow-pipe after the metal is inserted and is sealed at c. FIG. 1. When the tubes are closed the water on cooling leaves a space which at first is only filled with aqueous vapour ; but should any gas be generated a portion of it will collect in that part. After three days had elapsed from the date of sealing part of the atmosphere of the space left by the cooling of the water was driven into the capillary termination BC where after resting for some hours its bulk was registered by a mark at B with a view to use this as a gauge for indicating change of pressure in the interior of the tube.The experiment was conducted in a room with a northern aspect where the temperature was very steady about 60° F. At the end of ten days the gauges of the two tubes containing pyrophoric iron gave decided evidence of an increase of pressure; and shortly after- wards the gauge in the tube containing iron wire gave a similar indication. From this time the pressure in all the three tubes continued regu- larly to increase and at the expiration of a month one of them containing pyrophoric iron was opened and the gas having been transferred to a detonating tube was exploded with oxygen. At the end of two months the gas from the cell containing the iron a wire was likewise detonated with oxygen.A portion of the finely divided iron was now taken from the hard glass tube and having been repeatedly washed was placed with pure water in a tube of ordinary flint glass. A second portion of the iron had a plate of platinized platinum associated with it in another tube. Both the gauges exhibited after a few days indications of a gradual disengagement of gas. These experiments clearly establish the fact that iron is capable of slowly decomposing water at ordinary temperatures. I believe if iron and water could be brought together perfectly free from oxide of the metal or from oxygen gas dissolved in the water that no decomposition could ensue ; but this is a condition that cannot be attained in practice.Where iron forms the positive element of a couple excited by rain water the oxygenated-water action and the JIB ADIE’S EXPERIMENTS WITH voL‘r2iIC COUPLES. decomposition-of-water action will exist together the first of thesc being by far the more active. If we ascend the scale of metals towards those which are less oxidizable voltaic elements can be formed from one metal which give rise in oxygenated water to a notable voltaic action. With copper as a positive element I expected to get an effect due solely to oxygenated water but I thought it better to subject the copper in the first place to the same series of experiments in which both iron and zinc had decomposed water. A pair of copper and platinum plates in oxygenated water at a temperature of 60’ F.deflected the needle of the galvano- meter . 5O On heating the water nearly to the boiling point the deflec- tion amounted to . 50° After 1+hours’ boiling it was only . . lo In this experiment after thorough boiling there remained merely a trace of voltaic action. Some copper was precipitated in a subdivided form by a battery from solutions of the chloride and sulphate and the metal after having been thoroughly washed was placed with pure water in sealed tubes of flint glass in the same manner as has been already detailed in the case of iron. After the tubes had been kept for three months at ordinary temperatures their respective. gauges showed no trace of the disengagement of gas.One of the tubes containing copper precipitated from the sulphate was then digested for three weeks at a temperature approaching that of boiling water. There was no appearance of action upon the copper nor was there any gas evolved but the water and the constituents of the flint-glass had undergone an extensive alteration. The water though still transparent was strongly alkaline to test-paper and even to the skin. The glass was quite opaque in consequence of the formation of a thick coating of white enamel and deeply corroded in parts where the enamel was scraped off. The enamel tested by the blow-pipe gave evidence of lead but none of copper. In the same bath were pieces of flint-glass filled with oils and wax also hermetically sealed and in these the glass appeared unchanged at the end of three years’ digestion.At the same time that the tubes containing copper were prepared similar tubes containing lead tin bismuth and antimony were tried ; they however have given no signs of the evolution of gas. These results accord with the prevalent opinion that copper does MR. ADIE’S EXPERIRIENTS WITH VOLTAIC COUPLES. not possess the power of deconiposing water. Yet two similar pieces of this metal act as a voltaic couple when the one is more rapidly oxidized than the other. Two lengths of copper wire of the same dimensions as the zinc and iron wires represented at Fig. 2of the last set of experiments were placed in a stream of water during summer at a period when thc weather was steady and the surface- level of the stream was nearly stationary.The circuit between the plates was completed in the usual manner with a small decom- posing cell intervening containing copper poles and a solution of sulphate of copper. In this case I found a steady precipitation of metallic copper which at the end of three weeks made a difference between the weight of the poles of +th of a grain or the weight of metal precipitated was &th of a grain. In my first communication I referred to the sheathing of a ship as proof that the pieces of metal in a stream waste away in propor- tion to the rapidity of the current. With two pieces of copper in a stream the analogy is yet more close In still water I found the surface of the metal covered with large stains of black oxide while on the nietal exposed to the current there was a general covering of a very thin film of a dull green colour.In sheathing ships copper of three degrees of thickness is applied to the same hull; the places in the fore part of the vessel are sheathed with the stoutest plates and about the stern with the thinnest; experience having long ago shown that thinner metal on the parts about the stern where the water is comparatively still will endure as long as the stout metal on those parts where the water exerts greater friction. Connected with this subject it may be further worthy of remark that when the difference between the relative parts of the sheathing of a ship which developes a notable voltaic action is wanting the copper fails com- pletely to preserve the ship’s bottom frorn fouling.This I have seen practically proved in the case of the light ships anchored near the entrance to the channels of the port of Liverpool where they are exposed to the action of the tides and to the agitation of the Irish Sea. On one of these vessels brought into dock for repair the whole surface of the copper was covered to a thickness of two inches with marine plants and animals. From this it would appear that the voltaic action such as I have noticed in the experiment with copper wire in a stream performs a part in preventing vegetation on the ship’s bottom. On examining the sheathing of a vessel just returned from a voyage and noticing the dark red hue of the copper on those parts which are exposed to the currents of water produced by the sailing MR.ADIE’P EXPERIMENTS WITH VOLTAIC CotwLEs. of the ship as contrasted with portions so placed as to be in compaya- tively still water and which are coated with the green-coloured carbonate of the oxide of copper few would hesitate to say that the bright part acted as a negative or platinode element and corres-ponded with a piece of metal in the rapid part of a stream. In looking at copper in this state I have hitherto considered that it owed its platinode action to its clean metallic surface; but this view I now believe can be shown by experiment to be incorrect ; the active platinode is an oxide of copper of which there is a continuous supply in the nascent state on the surface of the metal when exposed to a current of oxygenated water.I selected silver as the metal best suited for the examination of the nature of the active platinode surface in oxygenated-water-voltaic actions. In the Edin. Phil. Journal vol. XXXIX p. 330 I have detailed some experiments with silver plates to which I again returned. Two pieces of pure silver foil placed in a horizontal position and connected with a delicate galvanometer gave no action when immersed in oxygenated water ;with oxide of silver strewed on one of the plates a notable current sufficient to precipitate metallic silver was obtained. The oxide acted as a negative pole and became coated with a film of a lilac or blueish leaden hue; but the tendency to this change was much modified by conditions attending its prepa- ration such as the temperature at which the oxide was washed and dried.When pale coloured oxide of silver is long boiled in pure water the colour darkens and I have gencrally found this dark coloured oxide most active as a platinode. Oxide of silver enclosed with pure water in a glass tube undergoes no change; exposed in the tube to the sun’s rays it darkens in the same manner as if it were exposed to the atmosphere. After being darkened by light the pale lilac colour appeared in a slight degree during night on the surface of the oxide in a hermetically sealed tube although no change could be perceived until the rays of the sun had been employed. When the sun’s rays fall on the oxide of silver while it forms the negative portion of a voltaic couple the needles of the galvanometer recede and the colour of the oxide darkens rapidly ;on the positive plate the sun has little influence.In the arrangement for obtaining a voltaic action from silver elements it was necessary to add some of the ready-formed oxide of the metal which gradually changed colour on the surface exposed to the oxygenated water and formed the negative element of the couple. The nature of this change appeared to me to be of MR. AUIE’S EXPERIMENTS WITH ’VOLTAIC COUPLES. importance for shewing the action of metallic oxides as negative elements. The question I sought to determine was whether the alteration noticed on the surface of the negative element was due to the oxide of silver absorbing or parting with oxygen.The action of the sun’s rays on the negative plate covered with oxide of silver diminished the voltaic effect and as the solar light tends to reduce silver from its oxide I inferred that the change observed on the surface of the negative element could not arise from a reduction of the oxide for had it been so the sun’s rays should have increased the action of the couple. Again in order to ascertain whether the oxide of silver in assuming a pale hue was absorbing oxygen some oxide of silver was placed on filter-paper and a jet of steam made to play on its surface for thirty minutes without producing any change of’ colour. A jet of dry oxygen gas was directed in a similar manner on to dry oxide of silver without altering it.Then a jet of oxygen was made to play on moistened oxide of silver when a light coloured stain appeared round the spot where the oxygen struck the oxide ; careful washing so as not to intermingle the particles of the oxide did not remove the stain. The experiment was several times repeated and a lapse of from ten to fifteen minutes was fonncl sufficient to produce the stain which was obtained both on the pale and darker coloured oxide It is upon this experiment that I rely for proof that the change to a light colour on the surface of the oxide of silver is due to the production of a higher state of oxidation; and as the sun’s rays rapidly destroy the light colour and at the same time check the action of the plate as a negative element of a couple I infer that it is this compound on the surface (4the brown oxide which is the real negative part of the arrangement while on the positive side there is a slow oxidation of the bright silver.To test the view of the oxide of a metal acting as a platinode a piece of zinc was cut into two halves one of these was roasted till its surface was covered with oxide and then formed into a couple with the bright piece; on immersing these in water the galvanometer indicated the oxidized surface to be negative. Similar results were obtained with couples of iron formed of bright iron associated with a rusted piece or a portion oxidized by heat ; also from bright and oxidized copper and from lead. In still water the effect from these couples is as might be expected of short duration; oxide in a nascent state is soon developed on the bright surface to counter- balance the oxide opposite; but the development of a current can be made continuous if means be taken to form oxide more rapidly on one surface than on the other of which the several esperirnents VOL.I. NO. I. C 18 DR. ANDREWS ON THE SPECIFIC HEAT OF BROMINE. stated afford examples the plate most rapidly oxidized being negative. I have always looked on oxygenated-water-voltaic couples and the well known gas battery of Mr. Grove as similar in their nature the hydrogen of the gas battery supplying the place of the positive element; if we may hold that in an oxygenated-water action the negative element is the oxide of a metal and that the action is of longer duration where there is a continuous supply of the oxide on the negative side in a nascent state the extension of this principle to the gas battery would give nascent water as the negative element in Ah.Grove’s arrangement. Should the view I have been led by the experiment on oxide of silver to adopt stand the test of time it will reconcile the action of couples formed of oxidizable metals with a general principle which was suggested to me in examining thermo-electric actions ;namely that in all electrical arrangements the current passes from the side which is changing towards that which is the more stationary. Where there are exceptions to this law among the more com- plicated batteries I am now inclined to hope that they when fully examined will like the oxygenated-water actions become recon-cilable to it; for at one time 1 looked on the metal in a stream wasting away through rapid oxidation and yet acting as a negative element as in direct contradiction to this law; but now the experiments show that it is is not the metal that is the platinode but a compound formed on its surface; and the more rapid the formation of the oxide on the negative side by a supply of oxygen as in Grove’s battery or by a very swift streani of surface water then the action of the couple increases in like proportion.Nov. 15 1847. The President in the chair. Resolved having been proposed by the Council at the previous meeting in accordance with Law 6 that an admission fee of &2 be required from members elected into the Society after the 30th day of March 1848.Taylor’s Calendar of the Meetings of Scientific Bodies for 1847 and 1848 were presented by the Editor. The Hon. and Rev. S. W. Lawley was elected a member of the Society. The following communications were read On the Specijc Heat of Bromine by THOMAS M.D. M.R.I.A. ANDREWS -Bromine being the only liquid member at ordinary temperatures of the class of bodies to which it belongs it appeared important to ascertain .J. MITCHELL ON THE DETERMINATION OF NITROGEN IN ANSLYSIS. 19 its specific heat with reference to the law of Dulong and Petit. The low temperature at which bromine boils and its feeble specific heat rendered the determination of the latter difficult.The method adopted was to heat bromine contained in a small glass flask to about 10' C. (18' F.) below its boiling point by means of a water-bath which was maintained at a very steady temperature. It was then quickly transferred into a glass tube which had been previously immersed in a copper vessel filled with water and the increment of temperature in the water was carefully observed. The details of the experiment are the same as those usually followed in such investigations. The bromine employed was carefully purified and its purity tested by ascertaining its atomic weight from the silver salt previous to the experiment. It boiled at a temperature of 58' C. (137'5O F.) under a pressure of 29.9 inches. In the experiments the temperature of the air was about 11 Co.(52' F.) and the bromine was heated to about 45O C. (1 13' F.). Br. represents the weight of the bromine ; T the increment or gain of heat of the water ; TIthe heat lost by the bromine ; and Sp. H. the specific heat. 1. XI. 111 IV. V. Br. 25-08grms. 26-13grms. 24.98 grms. 24.69grms. 24.48 grrcs. T 1"-208(C.) 1'-315 (C.) 1O.263 (C.) 1O.213 (C.) 1O.184 (C.) rr' 320 32' 32O-7 31"*9 3 2O.4 Sp.H.0-1053 0.1097 0.1083 0°1075 0.1044 Mean specific heat 0.1071. Dr. Andrews concludes from these results that in accordance with the views of Berzelius the atomic weight usually ascribed to bromine in this country as also those of the elements of the class to which it belongs should be halved in which case silver being taken at 1350 bromine from the author's experiments would be 999.4 'Oo0, -or nearly -and 2 a 5x 0.1071 = 53.55 would represent the atomic heat of bromine.2 According to the experiments of M. Regnault however the atomic heats of the simple bodies vary between the limits of 38 and 42 and bromine would thus form an exception to the law of Dulong and Petit as its atomic heat is about one-fourth higher than that required by theory. This discrepancy is attributed by Dr. Andrews to the specific heat being necessarily determined in the liquid state and he considers that bromine would agree with the law of Dulong and Petit and its specific heat be about 0.08 if this could be ascertained with the solid substance. On the determination of Nitrogen in analysis by JOHNMITCHELL, ESQ.-Mr. Mitchell recommends a further modification of Will and Varantrapp's process based upon that proposed by Peligot,* for rendering the estima- * Comptes Rendus March 29 1847. c2 MR. DrlRBY ON BICHROJZATE OF AMRIONIA tion of nitrogen more expeditious. The latter consists in using a solution of sulphuric acid of known strength in the bulbous tube in place of the muriatic acid of the original process and in ascertaining by means of a solution of lime in sugar also of definite strength what proportion of the acid has been saturated by the ammonia produced in the combustion with soda-lime. Mr. Mitchell objects to the use of lime dissolved in sugar on account of the tendency which it has to undergo spontaneous decompo-sition and also to form carbonate with the carbonic acid of the air and become altered in strength ; he substitutes therefore a weak solution of caustic soda (sp gr.l.OlS) and the quantity of this which is consumed in any experiment he prefers to weigh from a Schuster’s alkalimeter instead of measuring by a burette. For neutralizing the acid with greater accuracy than can be obtained by the use of litmus a decoction of logwood is recommended a few drops of which impart a yellowish-brown colour to the acid liquid and this is converted into a distinct blackish blue by the minutest possible excess of the alkaline solution. The accuracy of the process as compared with that of Will and Varrantrapp was verified by two experiments with Hyson tea. The original process yielded 5.81 nitrogen The modified process . . 5.80 ,

ISSN:1743-6893    

DOI:10.1039/QJ8490100012

出版商:RSC    

年代:1849

数据来源: RSC

摘要:

MR. DrlRBY ON BICHROJZATE OF AMRIONIA HI. Analysis of Bichromate of Ammonia and some double salts of Chromic Acid. By MR. STEPHEN DARBY. 1. Bichromate of Ammonia-This salt as is well known may readily be prepared by partially saturating a solution of chromic acid with ammonia and crystallizing to remove any adhering sulphate of ammonia. As no analysis of the salt has hitherto been published it was of interest to determine whether the animonia in combination with the acid was anhydrous or analogous to potash. The following are the results of my experiments. It has already been shown by Hayer and Biittger that this salt is deconiposed on the application of heat giving off water whilst pure oxide of chromium remains in appearance bearing a great resemblance to tea.On heating it in a tube the escape of free undecomposed ammonia is perceived sufficient in fact to cause a loss of 2 per cent in the water when the substance is heatedper se. The temperature at which it is decomposed I found to be 200° C. (392OF.). The following arc the results of the analyses of pure bichromate of ammonia dried in the air AND SOME DOUBLE SALTS OF CHROIUIC ACID. I. 0.349 grni. gave 0,224 ox. chromiuni=84-96 per cent chromic acid. 11. 0.208 gave 0.135 chromic oxide = 85.2 per cent chromic acid 111. 0.736 grm. heated alone gave 0.154 water=ZO.9 per cent. IV. 0.555 grin. heated with chromatelead gave 0.128 grammes of water =23.0 per cent. At the end of each combustion the point of the tube was broken off and the remaining vapour drawn into the chloride of calcium tube.Thus the following formula is deduced from my analysis Calc. per cent. Pound. I. 11. 1 at Ammonia NH . . 17.0 14.4 13.14 14.4 2 , Chromic acid 2Cr 0 100.6 85.5 84.96 85.2 NH 2Cr 0,=117.6 99.9 98.10 99.6 The three atoms of hydrogen being oxidised by half the oxygen of the acid form 23 per cent of water; if oxide of ammonium coni- posed the base of the salt (NH 0,2Cr O,,) the required per centage of water would be 28.6. On the addition of caustic potash to the salt ammoniacal vapours were instantly given off; it also yielded a precipitate with chloride of platinum thus differing from anhydrous sulphate of ammonia. The neutral chromate of ammonia consists according to Kopp of NH 0 Cr 0, containing one atom of water ; analysis yielded me 47.0 per cent of water thus agreeing with the formula assigned it.2. Double salt of the Bichromate of Ammonia with Chloride of Mercury .-On dissolving equivalent quantities of biehromate of am- monia and corrosive sublimate in water deep-red crystals were obtained by evaporation which gave on analysis the following results I. 0.728 grm. gave 0-224oxide of chromium. 11. 0.680 grm. gave 0.212 oxide of chromium. Calc. per cent. Found. I. 11. 2 at. Chromic acid . . . 100.6 39.7 40.4 40.8 1 , Ammonia . . . . 17.0 1 , Corrosive sublimate . 135.4 253.0 agreeing with the formula NH, 2Cr 0,+Hg C1. 3. Double salt of Bichromate of Potash with Chloride of Mer-cury.-On evaporating a solution containing equivalent quantities of bichromate of potash and chloride of mercury the double salt 22 Mfc.DARBY ON BICHROMATE OF ARlRIONIA is obtained in beautiful red pointed crystals which are anhydrous and have the formula KO 2Cr 0 + Hg C1. I. 1.699 grni. of the salt gave 0.722 sulphide of mercury and 0.448 oxide of chromium. 11. 0.181 grm. gave 0.109 chloride of silver or Calc. per cent. Pound. 1 equiv. Potash . . . 47.12 J YY 2equivs. Chromic acid . 100.6 35.5 34-55 1 equiv. Chlorine . . . 35.4 12.5 14.80 1 , Mercury . . . 100-0 35.0 36.60 KO 2Cr 0 + Hg C1= 283.2 The excess of chlorine is accounted for by a portion of the chromic acid being precipitated which even hot nitric acid would not entirely dissolve.This salt was previously described by Millon,% who assigns it the same constitution. 4. Double salt of Neutral Chromate of Potash with Chloride of Mercury.-On mixing a solution of neutral chromate of potash with one of corrosive sublimate a brick-red precipitate of basic chromate of oxide of mercury is formed which has also been described by mill on.^ My analysis agrees with the formula 3Hg 0+ Cr 0,. I. 0.285 grm. of the salt dried over sulphuric acid gave 0.030 oxide of chromium. 11. 0.521 grm gave 0.054 oxide of chromium or Calc. per cent. Found. 1. 11. 3 equiv. Oxide of mercury. 324 86.5 1 , Chromic acid . . 50.3 13.5 13.8 13.6 3Hg 0 Cr 0,=374*3 100.0 On evaporating the solution filtered from the above precipitate small crystals are formed of a pale-red colour which readily dissolve in water ,yielding a yellow solution.The analysis of these yielded the following results I. 0.638 grm. gave 0.065 oxide of chromium and 0.157 sulphate of potash. 11. 0,342 grm. gave 0.205 sulphide of mercury and 0.077 sul-phate of potash. 111. 0.370 grm. gave 0.038 oxide of chromium. IV. 0.198 gmi. gave 0.171 chloride of silver. * Berzelius Jahresbericht ssv,p. 293. t Alznales de Cltim. et de Phys. xviii. p. 333. AND SOME DOUBLE SALTS OF CHROMIC ACID. 23 V. 0.274 grm. gave 0,236 chloride of silver. Calc. per cent. Found. I. 11. 111. 1 equiv. Potash . . . 47.2 12.6 13.3 12.1 1 , Chromic acid . 50.3 13.4 13.3 13-4 13.8 2equivs.Mercury . . 200.0 53.6 , 51.2 2 , Chlorine .. 70.8 20.4 21.3 21.1 I--KO Cr 03+2Hg Cl=368*3 100.0 The same salt may be directly prepared with equivalent quan- tities of chromate of potash and chloride of mercury or with two of the latter and one of the former to which just sufficient hydrochloric acid is added to dissolve the precipitate formed 011 inixing them; the salt which crystallizes has the same composition as the preceding one. 5. Double salt of Neutral Chromate of Potash with Cyanide of Mercury .-This salt has been previously described by Caillot and Podevin,s and by Rammelsberg.? The former assign it the formula KO Cr O,+ 2Hg Cy which is given by L. Gmelin ;$ according to Rammelsberg however the formula is 2K0,Cr 0 + 3Hg Cy ; and it is with the latter that the results of my analysis agree.The salt is formed by evaporating together solutions of equivalent parts of chromate of potash and cyanide of mercury; it yields fine laminated crystals of a clear yellow colour readily soluble in water. I. 0.383 grm. gave 050 oxide of chromium. 11. 0.255 grm. gave 0.159 sulphide of mercury. 111. 0,305 grm. gave 0.108 sulphide of mercury and 0.041 oxide of chromium. IV. 1.363 grm. gave 0.805 sulphide of mercury 0.188 oxide of chromium 0.415 sulphate of potash. Calc. per cent. By experiment. I. It. 111. 2equivs.Potash . . 94.4 16.7 , 9 16-40 2 , Chromicacid 100.6 17.5 17.07 17.60 18.09 3 , Mercury . 300.0 52.2 52.47 50.80 50.80 3 , Cyanogen . 78.0 , , 9 J 2K0 Cr 0 + 3Hg Cy = 573.0 Rammelsberg found in 100 parts 17.28 potash 17-60chromic acid and 51.14 mercury numbers nearly in accordance with the above analysis.* Compt. Rend. xxiii. p. 766. t. Pogg. Anitalen xlii. p. 131. L. Gmelin Hmdbuch iv. p. 24 MIC. DAILBY ON BICHROhZATE OF ADZMONIA &C. 6. Double salt of Chromate of Silver und Cynnide of Mercury.-On adding nitrate of silver to a solution of the salt just described as long as a precipitate is formed and then heating the mixture almost to the boiling point with just as much nitric acid as is required to dissolve the whole beautiful red needle-shaped crystals are formed on cooling which are scarcely soluble in cold but more readily so in hot water. They contain neither nitric acid nor potash are decomposed on heating with strong nitric acid and explode at a high temperature.Analysis assigns them the formula Bg 0,2Cr 0,+2Hg Cy. I. 0.704 grni. gave 0.219 chloride of silver and 0.116 oxide of chroniiuni. 11. 0.682 grm. gave 0.215 chloride of silver and 0.112 chromic oxide-Calc per cent. Found. I. 11. 1 equiv. Oxide of silver . . 116.0 24.7 25.1 25.5 2equivs.Chromic acid . . 100.6 21-3 21.6 21.6 2 , Mercury . . . 200.0 2 , Cyanogen . . . 52.0 Ag 0 2Cr 03+21-IgCy=468.6 7. Neutral Suhchromate of Mercury.-On mixing a solution of subnitrate of mercury with neutral chromate of potash a precipitate as is well known of subchromate of mercury is formed which according to the analysis of Godon and L. Gnielin,* consists of 4 equivalents of suboxide of mercury and 3 equivalents of chromic acid.On boiling this precipitate with dilute nitric acid it is converted into a crystalline powder or when corrosive sublimate or nitrate of mercury is added to a solution of the yellow salt (2K0,Cr 0,+3Hg Cy) with a small quantity of nitric acid as much as will exactly dissolve the precipitate and this solution is heated almost to the boiling point the chromate of mercury is precipitated on cooling as a sub-salt in a fine red crystalline powder. The whole of the mercury in this salt is precipitated by hydrochloric acid from the solutioii in nitric acid. Ammonia and potash both give black precipitates with this salt. The analyses were as follows I. 0.246 grm. of the salt prepared directly gave 0,036 oxide of chromium. 11.0.383 grm. of thc salt prepared from the double salt gave 0.057 oxide of chromium. * Hand6uch iii. 11. 572. Utt. GREGORY ON THE PREPARATION OF CBEATINE. 111. 0.453 grni. of t.he salt prepared froiii the double salt gave 0.067 oxide of chroniiuni. Calc. per cent. Found. I. 11. 111. 1 equiv. Chromic acid . . 50.3 19.14 19.2 19.5 19.1 1 J> Subox. of inercury 208.0 Hg 0 +Cr 0,=258.3 Dec. 6 1847. The President in the chair. NI. Dumas was elected a foreign member and S. E. Churchill Esq. Chemist to the Royal Agricultural Society of Jamaica a non-resident member of the Society. ‘The following communications were read On the preparation of Creatine and on the proportions of that substance contained in diferent kinds of $eJ and fish by WILLIAM M.D., GREGORY F.R.S.E.-The process followed by the author in the preparation of crea-tine from the flesh of birds and quadrupeds is that described in Baron Liebig’s work “ On the Chemistry of Food,” translated by Dr.Gregory ; but as a cheap source of this sparingly disseminated substance the flesh of cod or skate is recommended which although yielding a two or three times lesser amount of creatine is nevertheless five times more economical and the facility afforded by it in the preparation of the substance is greater. The only fish from which creatine was obtained by Liebig was the pike; and he found a difficulty in submitting the hacked flesh to pressure which obliged him to obtain the latter portions of the fluid by displacement with water on a strainer ; this is not found to be the case with cod or haddock from which the fluid portion can be more completely expressed than from fowl or butcher-meat; less water is consequently necessary in the operation and more of the flesh can be employed at once.The chopped fish is mixed with an equal weight of water or at most with 4 parts of water to 3 of fish and a second extraction is found unnecessary for the fish may be pressed nearly quite dry. When after coagulating the albumen the barytes is added the liquid from fishis apt to remain turbid part Df the precipitate not subsiding and passing at first even through the filter. This precludes the possibility of ascertaining when the proper amount of barytes has been added but the use of turmeric paper (which in all cases is preferred to litmus by Dr.Gregory) imme- diately shows when a sufficiency of barytes has been employed. As was the case in Liebig’s experiments with pike so with cod skate and haddock the liquid when finally concentrated to a certain point gelatinizes on cooling and in this jelly the crystals of creatine are formed. DR. GREGORY ON THE PREPARATION OF CREATINE. When the evaporation has not been carried too far the addition of cold water readily liquifies the jelly and causes the crystals to collect at the bottom of the vessel the liquid may then be decanted off with facility. The crystals thus obtained are in a state of great purity and hardly require re-crystallization. In the haddock alone the creatine was mixed with a good deal of another substance soluble in water and alcohol the nature of which the author has not pet further examined.The following are the quantities of creatine obtained by Liebig and by the author from different sources. 100 parts of the flesh of Liebig. Gregory. Fowl yielded of creatine . . 3.2 ::} i::; ox , . .0.697 Horse ..0.72 2 Ox-heart , No. 1 1.375 .. {, 2:) 1,418 Pigeon ........ 0.825 , { ::* Skate 1) * ' ' 0,607 i:} 0*050? 0.935 ::8:) 1.741 Cod ....{ Goose ........ 0.895 3 Haddock , ........ 0.614 Brill > ........ 0.7 Herring ,) ........ 1.324 The quantities of creatine obtained from cod at different times stated in the table as Nos. 1 and 2 clearly show that the proportion of this substance varies in the same kind of flesh as the same process was followed in both cases without the occurrence of any apparent differences during the operation.The two results obtained from skate also prove this and in the second experiment No. 2 noticed with a point of interrogation in the table no crystals were deposited even when the liquid had been evaporated to the consistence of a thick jelly but on boiling the jelly with alcohol a small despoition of crystals ensued which when re-crystallized from water appeared as fine slender prisms evidently quite distinct from creatine as they were not altered by a temperature of 212' F. It appeared as if the creatine in this case were replaced by one or more different compounds although on reboiling the jelly with alcohol a very small crop of crystals of creatine was obtained.In the experiment with haddock the addition of barytes caused a distinct disengagement of ammonia and the creatine obtained was less pure than in any other instance being accompanied by another substance the nature of which was not ascertained. In neither of the two last kinds of fish named in the table did the concentrated liquid gelatinize as in pike skate and cod It ratber DR. ANDREW ON THE LATEST HEAT OF VAPOURS. assumed the thick syrupy consistence of the liquid from fowl or beef. In the case of the brill as in that of the haddock ammonia was given off on the addition of the barytes; and during the evaporation the liquid acquired an offensive smell at first somewhat resembling that of putres- cence but afterwards becoming exactly similar to the fcetor of the evacua- tions in dysentery and other diseases of the mucous membrane of the intestines.It is important to observe that in the decomposition thus indicated the creatine did not d&appear and that the liquid continued neutral. Liebig has found that creatine disappears in the putrefaction of urine probably in consequence of the presence of free ammonia. The author did not succeed in obtaining creatinine from the syrupy liquid which deposited the first crop of crystals of creatine but from the mother liquids left on the recrystallization of creatine perfectly neutral chloride of zinc produced Pettenkofer's compound which is a mixture of creatine with chloride of zinc and creatinine. Dr. Gregory is therefore inclined to think that the creatinine is formed from the creatine during the process and is not as Liebig supposes a constant ingredient in the juice of flesh.

ISSN:1743-6893    

DOI:10.1039/QJ8490100020

出版商:RSC    

年代:1849

数据来源: RSC

摘要:

DR. ANDREW ON THE LATEST HEAT OF VAPOURS. ANDREWS, IV. On the Latent Heat of Vapcurs. By THOMAS M.D. M.R.I.A. SINCE the period when Black first explained his celebrated doctrine of Latent Heat and showed the general method of measuring the quantities of heat evolved or abstracted during the changes of bodies from one physical state to another the subject has attracted the attention of several distinguished inquirers both in this country and on the continent It would be foreign to my present purpose to enter into a detailed account of their methods or results which is indeed the less necessary as a very complete history of the subject accompanied by critical remarks will be found in an able Memoir published a few years ago in Poggendorff’s Annalen,* by Dr.Brix of Berlin More recently two important communications on this subject have been made to the Academy of Sciences of Paris; one by M. Regnault on the Latent Heat of Steam when generated under different pressures; the other by MM. Favre and Silbermann on the Latent Heat of the Vapours of several Organic Liquids. My object in entering upon this inquiry was not to attempt a new determination of the latent heat of aqueous vapour but to extend the investigation to the vapours of other bodies differing widely from one another in chemical composition with the view principally of ascer- taining whether any fixed relation exists between the latent heat and * Bd. LV. s. 341. DE. ANIIREWS ON THE LriTENT HEAT OF VAPOURS. the other physical properties of vapours.In this inquiry I have been preceded by Ere Despretz Brix and Fabre and Silbermann. Their results are for the most part remarkable for accuracy but with the exception of those of the last-named experimentalists extend only to a very small number of substances. Even their experiments how- ever only embrace compounds of oxygen hydrogen and carbon. By employing a very delicate glass xpparatus 1have been enabled to supply in some measure this deficiency and to extend the inquiry to one simple substance and a small number of inorganic com-pounds . The apparatus employed in these experiments is represented in Fig. 1. The fluid to be converted into vapour is placed in a FIG. 1. small glass flask the iieck of which has a very short bend as shown in the figure.Into this the end of the rccciver is inserted by means DR. ANDREWS ON THE LATENT HEAT OF VAPOURS. of a small cork. The form of the receiver is shown in Fig 2. It consists of a very thin bulb of German glass terminating in a spiral tube of the same material. The glass receiver is fixed by a cork in a light copper vessel (Fig. 3) from which it 'can be FIG. 3. easily removed at the end of the experiment. The copper vessel which is open above is filled with water cooled from loto 2O C. (lo%-3'*6F.) below the temperature of the air. The whole is surrounded by an outer vessel of tin-plate fitted with a moveable lid in which are three openings one for the thermometer another for the extremity of the spiral tube of the receiver and a third for the stirrer which is formed of a very light and hollow glass tube.An additional screen as shown in the figure is interposed between the lamp by which the liquid is heated and the rest of the apparatus. The thermometer employed is very delicate and the greatest pains were taken to insure its accuracy. The diameter of the reservoir is not greater than that of a thin thermometer tube and it occupies the entire depth of the calorimeter. It is attached to an arbitrary metallic scale divided into fiftieth parts of an inch. The errors of calibre were determined by two distinct measurements of columns of mercury of different lengths ; the freezing point was ascertained by direct observation and another point situated near 25O C.(770F.) by comparison with an accurate thermometer constructed by Greiner. It was easy from these data to prepare a table showing the degree corresponding to each arbitrary division of the scale and also the multiplier required to reduce an increment observed at any part of the scale into true degrees. Two independent tables were constructed from the separate measurements and they were found to differ nowhere more than OO.01 C. (0".018F.). Within the ordinary limits of atmospheric temperature the difference of the expansion of a metallic or glass scale for increments of a few degrees is so slight that it may be neglected. The correction for the mercury in the stem of the thermometer is more important. The multipliers for the divisions of the arbitrary scale were corrected accordinply.DR. ANUREWS ON THE LATENT HEBT OF VAPOUILS. The increments of temperature as obtained by observation were carefully corrected for the cooling and heating influence of the surrounding air. From one to two minutes were occupied in raising the liquid to the point of ebullition; and during this period the thermometer remained nearly at the same point. While the ebullition continued the t,hermometer rose very steadily and uniformly but it did not attain the maximum point till about two minutes after the ebullition had ceased. For the heat gained and lost during these periods a correction deduced from direct experiments with the calorimeter alone was applied. The agitation was continued for five minutes after the thermometer had reached the maximum and the difference between the loss of heat observed and that indicated by calculation was added as a further correction to the result.This last is frequently omitted in inquiries such as the present but it generally amounts to an appreciable quantity and in accurate experi- ment ought never to be neglected. To prevent the mercurial column from becoming heated by the person of the observer the divisions were read through a powerful magnifier which was fixed on a moveable support. In addition to the causes of error already referred to others exist of' not less importance but the effect of which it is much more difficult to estimate. If the liquid be boiled too slowly a portion of the vapour will be condensed in the tube of the receiver just before it enters the calorimeter and a considerable loss of heat will occur.On the other hand if the ebullition is carried on very rapidly an undue pressure will be produced in the interior of the retort the tempera- ture of the vapour will be raised above the ordinary boiling point and too large an increment finally obtained. A portion of uncon-densed but partially cooled vapour will also escape particularly at the commencement of the operation before the air has been expelled. On this part of the subject an elaborate mathematical investigation will be found in the memoir of Dr. Brix to which reference has already been made; but it may be doubted whether the experimental data are yet sufficiently precise to admit of the useful application of formulas derived from the higher branches of analysis.To ascertain as far as possible the limits of error to which the apparatus now described is liable I made two series of experiments with water and alcohol; in the first the ebullition occupied from one and a half to two minutes; in the second from three and a half to five minutes. In order to complete the operation in the shortest period the liquid was made to boil very violently and there can be no doubt that the vapoiir was generated under a higher pressurc than that of the DR. ANDREIT'S ON THE LATENT HEAT OF VAPOURS. atmosphere. In the other case the ebullition proceeded at a gentle rate and all the causes of error tended to render the results too low.The mean number given by the experiments of the first series for the latent heat of water was 541O.4 C. (1038@*5 ) ;and by those of the F second 532O.7 C. (1023"F.). The mean of the whole was 535O-9 C. (1030"*75F.). This latter number agrees very closely with the mean of the results obtained by Despretz Dulong and Brix and is almost identical with that recently arrived at by 34. Regnault.* From these observations it follows that when the operation was purposely so performed as to exaggerate to the utmost the errors occasioned by the apparatus the result does not diverge more than Ath part from the true number The experiments with alcohol lead to the same conclu- sion; the mean of the series in which the ebullition occupied the shortest period being 205O.O C.(401' F.) and of that in which it occupied the longest period 202O.4C. (396"3 F.); so that the diffe- rence here was even less than in the experiments with water. In deter- mining the latent heat of other bodies the fluid was made to boil as fast as was possible without producing increased pressure on the interior of the apparatus. In the case of a few liquids it was found difficult to complete the vaporization in the ordinary time and hence the results expressing their latent heats are probably a little below the true numbers. This remark applies particularly to the iodic and oxalic ethers and to the iodide and acetate of methyl. The weight of the condensed vapour was ascertained by weighing the glass receiver (Fig.2) at the end of the experiment and deducting the weight of the same when empty. The boiling points of all the liquids operated on were determined with great care. This is often attended with considerable difficulty and even distinguished chemists have committed serious mistakes in examining the boiling points of volatile fluids. The numbers given in this paper were obtained by heating the liquid with a very small spirit flame in a glass retort the thermometer being immersed in the vapour at a short distance above the surface of the liquid. A quantity of mercury was placed in the retort except in the case of liquids which attacked that metal. The results given by observation were corrected for the portion of mercury in the stem of the thermo- meter which was not heated in the rapour and also for the variations of the barometer.In making the latter correction it was assumed as a sufficient approximation that the boiling points of other liquids were raised or depressed to the same extent as that of water by the same changes in the height of the barometer. * Their numbers are 531 Despretz ; 543 Diilong; 540. Brix ; 536.4 Regnaiilt. 32 DR. ANDREWS ON THE LATENT HEAT OF VAPOURS. The specific heats of several of the liquids were deteriiiiiied by direct experiment. The liquid raised to the boiling point was quickly int,roduced into a thin glass tube immersed in water and the gain of heat of the latter observed. The results in general agreed very closely with those of Regnault.In other cases I have employed the numbers given by the same accurate observer which were in general deter- mined by observing their rates of cooling. A slight error may thus be produced in consequence of the specific heat of the liquid not being the same at different temperatures but for the liquids actually employed this difference is probably unimportant. Finally every precaution was taken to operate on perfectly pure chemical substances. This is of much more importance in such inquiries as the present than even in analytical investigations from the great differences in the specific heats of the same weight of different liquids. Thus the presence of only ,&th part by weight of aqueous vapour would induce an error of +th part in the determi- nation of the latent heat of the vapour of ether.The weight and thermal value in ternis of water of the different parts of the apparatus were as follows Copper vessel 49.5 grms. x 0.095 4-7grms. Glass receiver 13.7 x 0.183 25 Thermometer stirrer and cork . . . 0-5 -Thermal equivalent of apparatus . . . 7.7 grnis. In stating the results I have used the following abbreviations Bar. the height of the barometer reduced to 0. Air the temperature of the air in centigrade degrees. Ex. the excess of the final temperature of the water in the calori- meter above the air. Inc. the increment of temperature as obtained by observation. T the time of ebullition. Ti the time from the observation of the initial temperature till the thermometer attained its maximum.V the weight of condensed vapour. W the weight of the water in the calorimeter exclusive of the thermal value of the vessels. L.H. the latent heat corrected. PVuter.-Specific heat 1*OO. Boiling point under a pressure of 29.92 inches at 100" C. (212' F.). FIRST SERIES. I. 11. 111. Bar. 29.52 in. 30.43 30.14 DR. ANDREWS ON THE LATENT HEAT OF VAYOVRS* I. 11. 111. I\-. Air. 6O.50 8O.60 9”*90 Ex. 2O.69 aO*oo 10.97 Inc. 4O-083 3”*411 3O.761 T 1’,20” 1’,35” 1I 50” T 3’,45” 3’,30” 5’,0 V 1.860 gm. 1.573 gm. 1.766 gin. W 2792.2grms. 282.3grms. 286.2 grim. L.H. 542.9 543.4 537.9 Mean latent heat 541.4. SECOND SERIES. I. 11. 111. IV. V. Bar. 29.70 in. 30.10 in. 30.10 in. 30.15 in. 30.09 in.Air. 11O.30 100.10 1OO-44 90.55 10°*20 Ex. 2O.08 lo-87 2O.20 10.83 10.78 Inc. 3O.772 3O.833 4O-078 4O.039 3O.822 T. 4,35” 4’,0” 3’,15” 3’,35” 5’,0 T. 7’,10” 6’,15” 5’,45” 5’,40” 6’,55‘ V. 1.780 gm. 1.829 gm. 1.980 gm. 1.921 gm. 1.833gin. W. 285.1 grms. 287.8 grms. 293.8 grms. 287.7 286.7grms. L.H. 536.8 531.9 533.2 531.6 530.8 Mean latent heat 532.7. Mean of whole series 535.9. Alcohol.-The alcohol was purified by repeated distillations from lime in a vapour-bath. It was deprived of essential oil by charcoal. It boiled at 78O.3 C. (173O.O F.) under a prsssure of 30.3 in.; and hence its true boiling point under a pressure of 29.9 in. is 77’9 C. (172O.3 F.). The mean of three experiments gave for its specific heat 0.617. FIRST SERIES.I. 11. 111. Bar. 29.75 in. 29.75 in. 29.73 Air. 14O-20 14O.95 14O.55 Ex. 1O.50 20.00 2-29 Inc. 3O.467 30.367 3.633 T. 1’,55” 2’,0” 1’,45” T. 4’,25” 4’,40” 4’,40’’ V. 4.202 gms. 4.167 gms. 4.418 gms. w. 286-0 , 289-4 , 286.8 L.H. 204.8 203.9 206.2 Mean latent beat 205.0. VOL. I. NO. I. D DR. ANDREWS OX THE LATENT HEEAT OF VAPOURY. SECOND SERIES. I. 11. 111. I\’. v. Bar. 29.90 in. 29-90 in. 29.91 29.91 29.90 Air. 1lo.1O 1l0*1O 10°*80 10O.70 10°.60 Ex. 2O.38 10.90 1O.56 1O.92 1O.72 Inc. 4O.417 3O.833 3O.533 3O.878 3O.567 T. 4‘,25” 4’,35” 3’,40” 3’,50” 4’,25” T’. 6’,401’ 6’,45” 4‘ 55” 5’,25’’ 6’,0” V. 5.381 gms. 4.785 gms. 4.402 gms. 4.830 gms. 4.430 gms. TIr. 286.3 , 292.2 , 293.0 , 291.4 , 289.5 L.H.201.7 201.4 201.5 199.7 199.7 Mean latent heat 200.8. Mean of whole series 202.4. Brornine.-Pure bromine according to my experiments boils under a pressure of 29.9 in. at 58O C. (136O.6 F.) and its specific heat is 0*107.* I. 11. 111. IV. Bar. 30-01in. 29.99 in. 29.70 in. 29-70 in. Air. 6O.30 6O-50 5O70 5O-70 Ex. 1O.33 lo-28 1O.33 1O.55 Inc. 2O.659 2O.708 2O.568 2O.975 T. 2‘,45” 3’,30” 3’,55// 2’,55” T. 5’,30” 6’,30” 6’,45” So 15” V. 14.983 gms 15.291 gms. 14.638 gms. 16.910 gms. W. 279.8 , 279-2 , 279.3 , 279.2 , L.H. 45-95 45.62 45.28 45.56 Mean latent heat 45.60. Protochloride of Phosphorus.-The protochloride was prepared by the action of dry chlorine gas on phosphorus. It was afterwards digested for several days with an excess of phosphorus and purified by repeated distillations.It was perfectly limpid and colourless. and under a pressure of 30.20 in. it boiled at 78O-5 C. (173~4~ F.) I have taken Regnault’s number (0.209) for its specific heat. I. 11. 111. Bar. 29.54 in. 29.29 in. 29.49 in. Air. 4O.90 7O.16 1OO.33 Ex. 1O.67 20.I 1 2O.21 7 Inc. 2O556 3n*0.1 3.733 T. 2’,30” 2’,35” 3’,5” * See present number p. 19. Dlt. ANDREWS ON THE LATENT HEAT OF VAPOURS. I. 11 111. T’ 5’,30” 5’,30” c,’ 0” V. 11.245 gms. 13.122 gms. 16.531 gins. W. 280.0 , 276.5 , 278.0 , L.H. 51.11 51.77 51-39 Mean latent heat 51.42. Bichloride of Tin.-This compound was prcpared by the action of dry chlorine on tin and after being deprived of the excess of chlorine by digestion with tin filings was purified by repeated distillations.It boiled at ll2O.5 C. (233O.9 F.) under a pressure of 29.60 in. Its specific heat was assumed to be 0.148. I. 11. 111. Bar. 30.12 in. 30.12 in. 30.17 in. Air. 6O.10 6O.10 6“40 Ex. 1O.64 1O.55 1O.28 Inc. 2O-578 3O.006 2O.700 T. 2‘ 15’’ 2’,0” 2’,45” T 6,30” 5’,30’’ 6’,0” V. 16.232 gms. 18.555 gins. 16.924 gms. W. 278.8 , 278.8 , 278.8 L.H. 30-37 31-02 30.21 Mean latent heat 30.53. Su(~7zuretof Carbon.-This liquid was digested with chloride of calcium and distilled It boiled under a pressure of 30.30 in. at 46O.2 (115O F.) Specific heat assumed to be 0.319 (Regnault). I. rr. 111. Bar. 29.92 in. 30.27 in. 30.27 in. Air. 9O.10 9O.05 8O.94 Ex.2O.83 3O.00 P44 Inc. 4O.422 4O.467 4O.761 T. 3’,30” 3‘,0“ 3’,45 ’ T‘. 535“ 5’,30“ 6’,25” V. 13.465 gms. 13.618 gms. 14.548 gms. W. 276.7 , 276% , 277.1 , L.H. 86.72 86-56 86-72 Mean latent heat 86.67 Subhuric Ether.-This ether was purified in the usual manner. It boiled under a pressure of 29-61 in. at 34O.9 C. (94O.73 F.) Specific heat 0.517. D2 DR ANDREWS ON THE LATENT HEAT OF VAPOURY. I. 11. 111. Bar. 30.18 in. 30.16 in. 30.16 in. Air. 2O.30 8@*10 8O.10 Ex. lo-78 lo*% 2O.11 Inc 3O.783 3O.5 72 3O.806 T. 4/>15” 3‘,50” 3/,50” T’. 6’,25” 6’ 10” 6’,20” V. 10.477 gms. 9.812 gins. 10.473gms. W. 277.0 , 277.1 , 2765 , L.H. 89.89 90.94 90.50 Mean latent heat 90.45. Iodic Ether.-This ether was prepared by taking 14 gms.phos-phorus and 70 gms. alcohol sp. gr. 0.816 and adding in small portions 46 gms. iodine waiting between each addition of iodine till the liquid became clear. It was then distilled at a gentle heat washed with water and allowed to digest for forty-eight hours with an excess of chloride of calcium. It was again didlled at a tempera-ture of from 70° to 75O. (1d8°-1670 F.) The purification was finally completed by another digestion with chloride of calcium and distillation. Its boiling point was found to be 71O.3 (160O.36 F.) under a pressure of 29.9 in. I. 11. 111. IV. Bar. 29-53in. 29.39 in. 29.40 in. 29-40 in. Air. 7O-70 7O.05 7O.90 8@*05 Ex. 2O.39 1O.72 2O.28 2O.44 Inc. 3O.939 3O.294 3O.717 4O.256 T. 5’,35” 6’,5” 6/,0” 6’,0” T!.8’,20” 9’,20” 8’ 55” 9/,30” V. 20974 gms. 17-504gms. 19.590 gms. 22.170 gms. W. 289.6 , 292.1 , 285.2 , 283-7 L.H. 46.94 46.78 46.83 46.94 Mean latent heat 46-87. OxaZic Ether.-The oxalic employed in the following experiments boiled at 184.4 (396O F.) under a pressure of 30.7 in. Specific heat 0-45 7. 1. 11. m. Bar. 30.66 in. 30.60 in. 30.60 in. Air. 6O.20 7O.50 7O.60 Ex. 2O.89 1O.50 2O.89 Inc. 4O.744 3O.772 4O.333 T. 3’,10” 5/,35” 3’,15‘‘ DR. ANDREWS ON THE LATENT HEAT OF T‘APOURS. 37 1 11. 111. T’. 7’,25” 9’ 5 0” 8’,30” V. 9.177 gms. 7.335 gms. 8.4161 gms. W. L.H. 284.3 73-33 , 288.5 72.61 , 284.8 72.22 , Mean latent heat 72-72. Acetic Ether.-This ether carefully purified was found to boil at 74O.6 (166O.36 F.) under a pressure of 30 in.Its specific heat in two trials was found to be 0-471 and 0.477 ; mean 0.474. I. 11. 111. IV. Bar. 29.92 in. 29.90 in. 29.90 in. 29-89 in. Air. 1O”20 10”*50 1OO.90 11O.10 EX. 2O.33 1O.94 1O-56 1”-78 Inc. 4°*500 4O.012 3O.967 3O.711 T. 5’,5”’ 3’,50” 3’,10” 3’,35” T. 8’,35” 6,45” 5‘,45“ 6’,30’’ V. 10.804 gms. 9-524 gms. 9,468 gms. 8.761 gms. w. 283.0 , 283.7 , 281.3 , 279.6 , L.H. 92-22 93.72 92.00 92.78 Mean latent heat 92.68. Formic Ether.-The easiest method of procuring formic acid for the preparation of this ether is by distilling rapidly hydrated oxalic acid. On neutralizing the acid liquid which passes over with carbo- nate of soda the greater part of the oxalic acid precipitates in the form of oxalate of soda and by evaporation the formiate of soda mixed with a little oxalate is obtained.This may be etherified without further purification as the formic ether is easily and com- pletely separated from the oxalic by distillation. Formic ether thus obtained probably furnishes the easiest means of procuring formic acid and its salts in a state of purity. Formic ether boils under a pressure of 30 in. at 54O.3 (2290.9 F.). In three experiments its specific heat was found to be 0.485 0.437 and 0.490; mean 0.485. I. 11. 111. IV. Bar. 29-83 in. 29.57 in. 29.57 in. 29.57 in. Air. 11”.05 9’-20 9O.67 9”-55 Ex. 1”*94 2”OO 1O.78 2O.28 Inc. 4°*006 3O.572 3O.439 4O.061 T. 2’,45” 3’,50” 3’,55” 1’,40” T’. 5’,30” 6’,20” 6’,25” 4’ 10” V.9.323 pis. 8.508 gnis. 8-092pis. 9.379 gins. DH. ANDREWS ON THE LATENT HEAT OF VA4POUBS. 1. 11. 111. IV. W. 281.9 gms. 2884 giiis. 283.6 gins. 282.6 gnis. L.H. 105.3 105.0 104.2 106.7 Mean latent heat 105.3 Methylic Acohol.-The pyroxylic spirit of commerce was rectified several times over a water-bath from an excess of lime the first and last portions being rejected. It was afterwards combined with chloride of calcium and purified according to the method of Kane. It boiled at 65O.8 (150O.72 F.) under a pressure of 30.2 in. In two experiments the numbers obtained for its specific heat were 0.611 and 0.615 ;mean 0.613. 1. 11. 111. Bar. 29-72 ill. 29.72 in. 29.71 in. Air. 1l0.1O 11”*90 l2“20 Ex. 2”50 1’0.61 2’%1 Inc. 4“.059 4O.539 4’*800 T.4/,5” 3’,15” 2’,35” T’. 6’,3 5” 5’,50” 4’,55” V. 4.039 gms. 4.451 gms. 4.743 gms. W. 281.5 , 281.3 , 282*4 , L.H. 264.0 262.4 264.6 Mean latent heat 263.7. Iodide of Methyl.-This compound was prepared by taking 50 gms. of purified wood-spirit and 10 gms. of phosphorus and adding iodine in small quantities as long as it was dissolved. The quantity of iodine taken up by the liquid was about 69 grammes. The liquid was then distilled at a temperature varying &om 70° to 90° (158O -196O F.) the distillate washed with ice-cold water and added to a large excess of chloride of calcium with which it was allowed to digest for three days. It was afterwards rectified three times from chloride of calcium. It boiled at 42O-2 (108O F.) under a pressure of 29.6 in.Specific heat assumed to be 0.158. I. 11. 111. IV. Bar. 29.71 in. 29-70 in. 29.81 in. 29.81 in. Air. 9O.50 9”-45 8”80 9’-20 Ex. 2O.06 2’*33 1”-56 1O.83 Inc. 3O.689 3”%83 3’-417 3O.761 T. 5’ 15” 4’,50’’ 4’,50” 5’,55” T’. 7’,40” 7’,20” 7‘,25” 8’,30” v. 21.465 gms. 22.446 gms 20.011 gms. 21.460 gms. I. 11. 111. IV. W. 288-0gms. 286.9 pis. 291.0 gnis. 282.0 pis. DR. ANDREWS ON THE LATENT HEAT OF VAYOUHS. L.H. 46.06 46.39 46.00 45-83 Mean latent heat 46-07. Acetate of Methyl.-The impure acetate of methyl obtained by distilling a mixture of purified wood-spirit acetate of soda and sulphuric acid was digested with milk of lime and chloride of calcium afterwards added in excess.After allowing the mixture to stand for twenty-four hours the ether was decanted and digested for several days with chloride of calcium and finally distilled in a water- bath whose temperature never exceeded 65O (149O F.). It boiled under a pressure of 30 in. at 55' (131' F.). Specific heat assumed to be 0.47. I. 11. 111. Bar. 29.77 in. 29.78 in. 29.78 in. Air. 10°~OO lO"~10 10"*60 Ex. 1'4 2O.06 1'-94 Inc. 3"*806 3O.633 3O.5 78 T. 4/,35/' 4',40/' 4',35" T'. 7/,35/( 8/,5/' 7',25" v. 8.485 gms. 8.158 pis. 8.040 pis. W. 283.8 , 284.2 , 284.1 , L.H. 110.0 110.3 110.2 Mean latent heat 110.2. Furmiate of Methyl.-It was prepared and purified by a process analogous to that last described. It boiled at 32'0.9 (91'-2 F.) under a pressure of 2'3.6 in.Specific heat assumed to be 0.47. I. IT. 111. IV. Bar. 30.07 in. 30.07 in. 30.06 in. 30.06 in. Air. 12O.70 13"-05 13'*00 13O.30 Ex. 1O-17 1'028 0°*94 lO.40 Inc. 2O.289 2O.272 f2O.417 fJ"739 T. 3',45" 3 10" 3 15" 3/,20/' T. S',5" 5' 15" 5',25/' 5/,30" V. 5.380 pis. 4.090 gnis. 5,736 gms. 6.272 gms. w. 289.0 , 291.4 , 294.5 , 282.7 ,, L.H. 116.7 116.7 117-7 117.3 Mean latent heat 117-1. I have collected the foregoing results in the following table. The first column contains the latent heat for 1 gramme of each vapour; 40 DR. ANDREWS os THE LATENT HEAT OY viwouits. the second for 1 liter taken at the temperature of the point of ebul-lition of the vapour and under the mean barometric pressure at which the experiments were performed.For 1 gramme. For 1 liter. Bromine . . 45.60 269.6 Protochloride of phosphorus 51.42 244.4 Sulphuret of carbon . 86.67 254-9 Bichloride of tin . . 30.53 253.5 Water . . 535.90 318.3 Sulphuric ether . . 90.45 268.2 Alcohol . . 202.40 324.2 Methylic alcohol . . 263.70 303.5 Iodic ether . . 46.87 254.7 Iodide of methyl . . 46.07 252% Acetic ether . . 92.68 2287.9 Acetate of methyl . . 110.20 303.6 Formic ether . . 105.30 290.3 Formiate of methyl . . 117.10 282% Oxalic ether . . 72-72 2914 It is obvious from a cursory inspection of this table that there exists some general relation between the volume of the vapour and its latent heat but many other elements would require to be taken into consideration before the precise nature of this relation can be determined.It has indeed been concluded from a comparison I believe of the latent heats of water and alcohol that the latent heat of equal volumes of different vapours is the same; but the experimental results now obtained do not support so very simple and general a relation. It is not improbable however that under certain physical conditions the proposition may be correct but until these are realized and the result established by direct experiment we cannot be justified in drawing so general a conclusion. It may be well to remark that in the above table the latent heats of equal volumes of each vapour taken at the respective boiling points of the fluids are compared; but in order to make the comparison more perfect it would have been necessary to have examined equal volumes of t,he vapours taken at the same temperature.This could not it is obvious have been done without operating under very different pressures and thus introducing another source of complication into the results. Another circumstance to which I may also refer as connected with this subject is the uncertainty that prevails as to the molecular constitution of some vapours near the tcmperatures at MR FERGUSON ON THE CHARRING ACTION OF STEAM. 41 which they condense. The recent experiments of Cahours leave it is true little doubt that the densities of the vapours of the alcohols and of most of the compound ethers correspond with theory at all temperatures but the singular anomalies presented by the acetic formic and sulphuric acids and by the perchloride of phosphorus and some essential oils show with what circumspection we must adopt the theoretical number as truly representing the density of any vapour near its point of condensation.Some of the irregularities in the results now given may perhaps be traced to this cause. Dec. 20 1847. Thomas Graham Esq. Vice-president in the chair. Professor Dana presented a copy of his memoir On certain laws of cohesive attraction,” to the Library. Messrs. Charles W. Swaisland J. C. Stevenson Henry Watts B.A. Edward Frankland William Payne Robert Galloway and W. E. Heathfield were duly elected members of the Society. The following communications were read On the power of low pressure steam in charring animal and vegetable matter and on the reducing power of charcoal at that temperature by FERGUSON, WILLIAM EsQ.-An unsound steam-engine boiler having been covered with patent felt to prevent radiation from its surface the felt was observed at the expiration of five or six months to have become charred wherever the steam made its escape through the cracks of the boiler whilst those parts of the felt which remained dry although exposed to the same heat were perfectly unaltered.The boiler was worked under a pressure of 6 lbs. which corresponds with a temperature of 232’ F. but the temperature of the escaping steam and of those parts of the felt in contact with it was 212O F. Another instance in which wood had been charred was observed in the float-gauge of a brewing-copper which had been exposed during five years to the vapour and the saccharine solution at a temperature not exceeding 215’ or 216’ F.The charcoal in this case was permeated by a soluble salt of copper and the interstices were filled with octahedral and dedocahedral crystals of metallic copper. The author concludes from the odour of pyroligneous acid which was perceptible that acetic acid was formed by the decomposition of the wood and that this united with the copper to form an acetate which even at the temperature of 216O F. was partially reduced to the metallic state whilst in intimate contact with the porous charcoal.

ISSN:1743-6893    

DOI:10.1039/QJ8490100027

出版商:RSC    

年代:1849

数据来源: RSC

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42 MESSRS. WILLIAM AND THORNTON J. HElChYATH ON THE V. On the artificial formation of Crystalline Ogide of Zinc. By MESSRS.WILLIAMand THORNTON J. HERAPATH. It is to Mr. Cox of the Patent Lime Works Bristol that we are indebted for the discovery of the remarkable and beautiful substance which forms the subject of the present paper. Mr. Cox fouiid it lining and partially filling up the anterior extremity of one of the earthenware retorts which had been used for the distillation of zinc at his manufactory. It occurred as an aggregation of brilliant prismatic needle-shaped crystals having a vitreous semi-metallic lustre when viewed by reflected light but transparent and colourless when examined by transmitted light. These crystals were so completely studded over with tubercles of various shapes and sizes that it was only at the apices of a few of the larger ones that any traces of angles could be perceived from which to judge of their original form.From these however it appeared that their form (as well as could be determined from such irregular crystals) was a four-sided rectangular prism. Figs. 1 and 2 are illustrative of the appearance which they exhibited FIG. 1. FIG. 2. under a magnifier of about 3 diameters. Occasionally a sword-shaped crystal was met with having numerous smaller irregular crystals proceeding from it at right angles to the edge and plane with the surface of the crystal Fig. 3. The specific gravity of the larger and most perfect crystals was 5,5298. ARTIFICIAL FORMATION OF CHYSTALLINE OXIDE OF ZINC.43 FIG. 3. They were exceedingly brittle and the bro- ken surfaces had a very perfect conchoidal frac- ture. Their hardness was about 4-25. They remained unaltered in appearance even at a white heat and did not lose in weight. The crystals hssolved in nitric hydrochloric and dilute sulphuric acid without effervescence leaving a small quantity of a brilliant crystalline residue which when examined by a microscope of high power was found to consist of transpa-rent colourless crystalline fragments possessing a very perfect conchoidal fracture amongst which were scattered a few unbroken and very perfect rectangular prisms. When analysed in the usual way by solution in nitric acid &c. the crystals yielded TI.111. IV. j I I. i !89.40'91.84/92.OL Protoxide of zinc . . . 88.45 Crystalline residue . . . 11.55 10.60 I 8.16 7.95 These analyses show that they are not perfectly uniform in com- position. The crystalline residue being insoluble in all the mineral acids and also in a boiling solution of caustic alkali was analysed by the following process. It was fused for about half an hour with an excess of caustic potash in a silver crucible at a bright red heat. The fused mass was then extracted with boiling water the solution treated with an excess of nitric acid and the whole evaporated to dryness. Upon re-solution in dilute nitric acid a quantity of peroxide of tin remained undissolved; this was collected on a filter washed ignited and weighed.The solution was then boiled with.an excess of carbonate of potash the precipitated carbonate of zinc collected on a filter well washed with hot water reduced to oxide by ignition in a platinum capsule and weighed. Four analyses of this residue gave the follow-ing composition in 100 parts 44 MR. NESBIT ON THE ESTIMATION OF PHOSPHORIC ACID. Found by experiment. Calculated. I I IV. Mean. At0ms.l _I___-Stannic acid . . 66.265 65.373 64.912 Protoxide of zinc . 33.735 34-627 -35.088 1 Stannate of zinc . I 100*000I 100~000I 100~000 100~000 1 100*000 This substance may therefore be viewed as consisting of crystals of pure oxide of zinc to which the smaller crystals of stannate of zinc acted as nuclei. The crystals were probably produced by the slow percolation of atmospheric air either through a small crack in the retort or perhaps through the porous sides of the retort itself; the oxygen of the air gradually combining with the red hot vapour of the zinc formed a non-volatile oxide which being very slowly deposited assumed the crystalline form.Jan. 17 1848. The President in the chair. Messrs Herapath presented specimens of the crystals of oxide of zinc which had formed the subject of their paper to the Society's Museum. Dr. Daubeny presented his work on Volcanoes to the Library. Messrs. William Odling Robert Beavan and Benjamin Cooper were elected members of the Society. The following papers were read On the quantitative estimation of phosphoric acid and on its presence in some of the mark of the upper green sand formation by J.C. NESBIT, EsQ. F.G.S.-The methods proposed by Fresenius for estimating the quantity of phosphoric acid in a solution containing iron and alumina have been tested by Mr. Nesbit upon the occasion of the analysis of these marls. The ammonio-magnesian phosphate precipitated by a mixture of sulphate of magnesia chloride of ammonium and caustic ammonia (phosphoric acid test) from the solution of the phosphates of iron and alumina in hydrochloric acid ammonia and tartaric acid was frequently found contaminated with a variable quantity of alumina and oxide of iron which appeared to depend upon the degree of concentration of the liquid and upon the amount of tartaric acid which it contained.The author succeeded in avoiding this source of error by diluting the solution of the phosphates until it assumeda light straw colour and by employing a large quantity of tartaric acid and a very considerable excess of ammonia. The appearance of the precipitate on the addition of the phosphoric acid test may also in some measure be DR. MUSPRATT ON HYPOSULPHATHYLIC ACID &C. 4+5 taken as a guide ; for if the precipitate at the expiration of twenty-four hours during which time it should always be allowed to stand be either flocculent or gelatinous instead of crystalline the presence of iron or alumina may generally be predicated in it. When the foregoing precau- tions were observed the results were found to be very nearly accurate and iron could only be detected in the precipitate by sulphocyanide of potassium.In cases where doubt may arise as to the purity. of the precipitate it should be re-dissolved with the addition of a little tartaric acid and again precipitated by ammonia. The other plan for the estimation of phosphoric acid recommended by Fresenius according to which the solution of the phosphates of iron and alumina in hydrochloric acid is mixed with ammonia until a precipitate begins to form when the whole is boiled with acetic acid and acetate of soda in excess (or in cases where no iron is present in the solution with the addition of perchloride of iron) is found by the author to be inappli- cable when phosphate of alumina is contained in the solution.All the phosphoric acid contained in the solution is precipitated in combination with iron and alumina on boiling the above mixture and by the addition of ammonia and hydrosulphuret of ammonium to the solution of the precipi- tate in hydrochloric acid the iron and alumina are separated leaving according to Fresenius the whole of the phosphoric acid in combination with ammonia in the filtrate. When alumina is present Mr. Nesbit finds that phosphoric acid is kept back in the precipitate formed by ammonia and hydrosulphuret of ammonium and cannot be obtained in the filtrate ; he therefore rejects the process as fallacious except in those cases where alumina is absent. The marl examined is remarkable for containing a large amount of phosphoric acid the average quantity deduced from the experiments being 2.31 per cent.

ISSN:1743-6893    

DOI:10.1039/QJ8490100042

出版商:RSC    

年代:1849

数据来源: RSC

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DR. MUSPRATT ON HYPOSULPHATHYLIC ACID &C. 4+5 VI. On Hyposulphathylic Hyposu@hamethylic Bisubhithylic and Bisulphimethylic Acids produced by the action of nitric acid upon the Xulphocyanides and Bisulphides of Ethyl and Methyl +c. By SHERIDAN PH.D. MUSPRATT The action of nitric acid upon mercaptan and the bisulphide of ethyl has been studied by Lowig Weidmann and Kopp who found that the same acid was produced from the two substances. In the former an atom of hydrogen was removed and four of oxygen entered into combination ; while with the latter the hydrogen re- mained intact and four atoms of oxygen were assumed Mercapt an . . . . . . . c4 H6 s2 Bisulphide of ethyl . . . . c4 H5 s,* Bisulphithylic acid . . . . C H5 S 0 46 DR. MUSPRATT ON HYPOSULPHATHYLIC HTPOSULPHAMETHYLIC Bisulphithylic acid gives crystallizable salts with all the bases which are described in the interesting memoirs* of the above-cited chemists.The action of nitric acid upon the sulphocyanogen compounds of ethyl and methyl has been up to the present time unknown and it was possibly this circumstance that induced my much esteemed preceptor and friend Baron Liebig to suggest the investigation to me. A careful examination of the subject has led to the discovery of two new acids which are formed in a very remarkable manner. When a new acid is obtained in the ethyl series we may with a degree of certainty assume the existence of a corresponding one in the methylic class of bodies; and although the latter series is not as yet so extended as the former still the analogues of all the sulphur and oxygen compounds of the ethyl combinations will I am con- vinced before long be brought to light and vice vwsd; and as soon as this is the case more definite conclusions may be drawn by chemists with regard to the basyles and salt radicals upon which the whole fabric of chemical theory is at present based.Preparation of subhocyanide of ethyl.-It is very difficult to obtain this body in large quantities. The best method of preparing it is by distilling in a retort equal measures of strong solutions of sulphovinate of lime and sulphocyanide of potassium. The capacity of the retort must be twelve times that of the space occupied by the mixture so as to prevent any of the solution passing over into the receiver which it is very apt to do owing to a violent intumescence that occurs at intervals.The decomposition which takes place may be represented by the annexed equation C H 0 SO, CaO SO KC,N S Sulphovinate of lime sulphocyanide of potassium yield C,H S N “3 and CaO SO, 52-sulphocyanide of ethyl’ sulphate of potash’ sulphate of lime’ Sulphocyanide of ethyl discovered by Liebig and studied by Cahours,? is an oily and very dense liquid possessing an odour of garlic. The latter chemist states in his Treatise that “pretty-concentrated nitric acid dissolves it wit,h the aid of heat; but that upon cooling it separates again completely.” I cannot imagine how so accurate an investigator as M. Cahours could have made this mistake.Rather strong nitric acid decomposes the sulphocyanides * Lowig’s Organic Chemistry 1701. 11. p. 427 and Poggendorff’s Ann. der Phys. und Chem. Bd. XLVII. p. 153. j-Ann. der Pharm. 61-2 p. 99. R ISULPH ITH Y LI C AND BISULPH IMET HTLTC AC II)S. of ethyl and methyl with great rapidity affording acids which will be subsequently described. Process for obtaining hyposubhathylic acid-About an ounce and a half of sulphocyanide of ethyl and the same quantity of tole-rably concentrated nitric acid were introduced into a retort connected with one of Liebig's condensers. A slight heat was applied to the retort during the whole process. At first the action was very brisk and attended by the evolution of nitrous fumes carbonic acid and nitric oxide.Sulphuric acid was also formed during the operation; the quantity however depended upon the concentration of the acid employed. If weak nitric acid is used traces only of sulphuric acid can be detected in the liquid. The distillate was repeatedly returned to the retort so that very little loss of oil was sustained. The men- struum after four or five distillations was poured into a porcelain basin and evaporated in c?. water-bath until the last trace of nitric acid was expelled. A fluid like oil of vitriol remained possessing a slight alliaceous odour. This was diluted with water in which it readily dissolved saturated with carbonate of barytes and filtered to remove the excess of carbonate and any sulphate of barytes. The filtrate when evaporated very slowly afforded large crystals of hypo- sulphathylate of barytes.These crystals were dissolved in water precipitated by an excess of absolute alcohol and re-crystallized. The acid may be obtained in a state of purity by precipitating the barytes with sulphuric acid from the aqueous solution of the salt filtering digesting the filtrate with carbonate of lead re-filtering and decomposing the solution containing the lead salt by hydro- sulphuric acid. When the sulphide of lead is separated and the filtrate evaporated in a water-bath the acid is left in a pure state. Properties of the acid-When the acid is fused with potash and the residue treated with sulphuric or muriatic acid large quantities of sulphurous acid are evolved.It withstands a very high tempe-rature before suffering decomposition ;fumes of sulphuric acid first escape and then sulphurous acid is eliminated The taste of the acid is most disagreeable and acrid and of this the salts all of which are soluble also partake. The acid is miscible with water and alcohol in all proportions and is very persistent. Hyposu&hathylate of barytes.-This salt is so very soluble in water that it can only be obtained in fine rhombohedra1 prisms by allowing a concentrated solution to evaporate slowly. It is also very soluble in spirits of wine and ether but insoluble in alcohol which throws it down in beautiful satiny crystals. It parts with its water at 212". The dried crystals when heated with soda-lime gave no 48 DR.MUSPRATT ON HYPOSULPHATHYLIC HYPOSULPHAMETHYLIC indications of ammonia; fused with potassium and tested with iron solutions the absence of nitrogen was fully proved; and this is the most remarkable feature with regard to the acid. In what form was the nitrogen of the sulphocyanide of ethyl eliminated? Not as ammonia for no trace of this alkali could be detected. It must have passed off in the form of nitric oxide or nitrous acid. No instance of similar decomposition has hitherto been observed i. e. an acid containing no nitrogen has never yet been produced by the action of one nitrogenous body upon another. I. 0.4140 grms. of the salt dried at 212O and burned with chromate of lead afforded 0,2090 grms. carbonic acid and 0.1200 grms. of water.11. 0.4763 grms. of the salt gave 0.2300 grms. carbonic acid and 0*1310grms. of water. I. 0.2560 grms. of the salt gave 0-1665grms. sulphate of barytes = 0.1093 grms. barytes. 0.4190 grms. of the salt treated with potash and nitre gave 0.5495 grms. sulphate of barytes = 0,0753grms. sulphur. 11. 0.4160 grms. of the salt gave 0.2750 sulphate of barytes = 0.1800 grms. barytes. 0.2340 grms. of the salt gave 0*3000grms. sulphate of barytes = 0 0411 grms. sulphur. Centesimally represented Theory. Experiment. r-*- I. 11. Mean. 4 eq. Carbon . . 24.00 13.52 13-76 13.16 13.46 5 , Hydrogen . 5.00 2.81 3.21 3.05 3-13 2 , Sulphur . . 32.00 18.01 17.99 17.56 17-77 5 , Oxygen . . 40.00 22.54 22.35 22.97 22-66 1 , Barytes . . 76-60 43.13 42.69 43.26 42.98 177.60 100*00 100*00 100.00 100~00 The following formulze agree very well with the above results Ba0 C H 8 05 BaO E S 0,.The decomposition that takes place when nitric acid acts upon sulphocyanide of ethyl may therefore be represented by the annexed equation B I SULP H I T H YLI C ,AND BI SULP H IM ETH Y L I C A CI DS . C,H S N +5NO, p-5p sulphocyanide of ethyl yield '2H5 '2 '5 hyposulphathylic acid + 4N02 +2N0 +ftco,. 0.7270 grm. salt dried at 212O gave 0-0365 grm. water which is equivalent to Theory. Exp'. 1 eq. hyposulphathylate of barytes 177.60 95-16 1 ,,water ....... 9.00 4-84 5.02 186.60 100*00 Formula BaO C H S 0 +aq. The barytes salt when heated in a tube blackens and gives off fumes possessing a most stifling smell.Hyposu@hathyZaie of lead.-This salt crystallizes from a hot con- centrated solution in beautiful colourless plates which are extremely soluble in water spirits axid alcohol. They intumesce when heated and the residue contains sulphide of lead. 0.2790 grm. of dried salt gave 0.2000 grm. sulphate of lead = 0.1472 grm. ox. lead corresponding to Theory. Expt. 1eq. hyposulphathylic acid . . 101.00 47.41 1 ,,oxide of lead .....ll2*00 52.59 52-76 213.00 The preceding results agree with the formula PbO C H S 0,. 0.6110 grm. dried over sulphuric acid and heated at 212' gave 0.0250 grm. water corresponding to Theory. Expt. 1 eq. hyposulphathylate of lead 213*00 9598 ' 1 ,,water .......9.00 4.02 4.09 222.00 100.00 Formula Pb 0 C2 H S O, +aq. Hyposulphathylate of copper.-It is very difficult to obtain this salt in well-defined crystals on account of its great solubility in water and spirits. When the crystals are heated in a tube they intumesce and as soon as they blacken vapours are evolved possessing a most disagreeable odour. 0.2020 grm. of this salt dried over sulphuric acid yielded 0.0970 grm. carbonic acid and 0*0880grm. water. VOL. I. NO. 1. E 50 DR. MUSPRATT ON HYPOSULPHATHYLIC HYPOSULPHAMETHYLIC 0.6170 grm. of the salt gave 0-1338grm. oxide of copper which centesimally represented is equivalent to Theory. Expt. 4 eq. Carbon . . . . . . 24.00 12-90 13.11 Hydrogen . . . . . 10.00 5.37 4.84 Sulphur.. . . . 32.00 17.20 Oxygen . . . . . . 80.00 43-03 Oxide of copper . . . 40.00 21.50 21.68 186.00 100.00 The annexed formula agrees with the above numerical results CuO C H S 0,+ 5 aq. I thought it would be very interesting if by acting upon the sulphocyanide of ethyl with chlorate of potash the same acid as the one just described could be produced When sulphocyanide of ethyl is gradually added to a mixture of chlorate of potash and hydrochloric acid a very violent action takes place which is sometimes so brisk as to inflame the volatile products. As soon as the oil had entirely disappeared the liquid was placed in a water-bath and evaporated to dryness in order to get rid of the excess of hydrochloric acid. The residue was then treated with absolute alcohol in which medium the chloride of potassium and any sulphate of potash are insoluble.When this solution was filtered and the filtrate evaporated on a water-bath an oily acid was left which was saturated with car-bonate of barytes and the whole again filtered. The solution that passed through gave beautiful silky crystals with absolute alcohol possessing all the appearance of the hyposulphathylate of baryta. There was not enough of the salt for a combustion; I consequently only made a determination of the barytes 0.1060 grm. of salt dried at 212O gave 0.0685 grm. of sulphate of barytes = 00450grm. barytes. The above result affords 4.2,45 per cent of barytes and the formula BaO C H S 0 requires 43.13 per cent. I have therefore no doubt that the acid is the same as that produced by the action of nitric acid upon the sulphocyanide of ethyl.One equivalent of sulphocyanide of ethyl three equivalents of chlorate of potash and seven equivalents of hydrochloric acid contain the elements of one equivalent of hypo-sulphathylic acid two equivalents of carbonic acid one equivalent of nitric oxide three equivalents of chloride of potassium seven equivalents of water and seven equivalents of free chlorine. The sulphocyanide of ethyl is readily acted upon by chlorine gas. I3 I SUL P H ITH YLIC A N D BISULP HI BI ETH Y LI C A C 1DS . 51 When a stream of the gas is passed through it for some time large quantities of chloride of cyanogen are formed and there subsides a heavy yellow oil which disappears when repeatedly washed.I have not further investigated this reaction. When a cold alcoholic solu- tion of potash is mixed with sulphocyanide of ethyl and the mixture is allowed to stand for some days in a corked vessel decomposition takes place. The liquid becomes blood-red and acquires a most singular odour; but there are no indications of the presence of ammonia. The results of the above decompositions will be embraced iu a treatise on the action of chlorine bromine potash &c. upon the sulphocyanides of ethyl and methyl. Before commencing the correspondiiig reactions in the methyl series I prepared Lowig's acid from the bisulphide of ethyl. The combustion of its copper salt dried at 212O afforded me the following results 0.3765 grm.salt burned with chromate of lead gave 0.2000 grm. carbonic acid and 0.1730 grm. water numbers agreeing per- fectly with Lowig's formula C, H S 0 + 4 ago' as may be seen from the annexed centesimal table Lowig and Theory. Weidmann. Muspratt. 4 eq. Carbon . . . 24.00 14.20 14.78 14.48 9 , Hydrogen . . 9-00 5-33 5-65 5-10 8 , Oxygen . . . 64.00 37.94 36.47 2 , Sulphur . . . 32.00 18.93 19.82 1 , Oxide of copper . 40.00 23.60 23.28 169.00 100*00 100*00 Thus we possess two more sulphur acids belonging to the ethyl series; the one that of Lowig obtained from the bisulphide of ethyl and the other by the action of nitric acid upon the sulpho- cyanide of ethyl. Is it not probable that the series may be still more extended and that compounds may be produced correspond- ing with the whole sulphur series of acids? i.e. by acting upon the higher sulphides of ethyl with oxidizing agents. In the following formulae the known ethyl and sulphur acids are repre- sented collaterally with those that are required to complete the series. Ethyl series. Sulphur series. Sulphathylic acid C H S 0 Sulphuric acid s 03 Hyposulphathylic acid C H S 0 Hyposulphuroiis acid S 0 E'2 52 DR. MUSPRATT ON HYPOSULPHATHYLIC HYPOSULPHARIETHYLIC Ethyl series. Bisulphithylic acid C H S 0 Sulphur series. Bisulphurous acid S O,? Hyposulphathylicacid C H S 0 Hyposulphuric acid S 0 Tetratrionathylic acid C H S O,?Tritrionathylic acid C H S 0 ? Tetratrionic acid Tritrionic acid S 0 83 0 Yentatrionathylic acid C H S O,? Pentatrionic acid S 0 Preparation of sulphocyanide of methyl.-This body is prepared in a similar manner to the ethyl compound.I distilled together equal quantities of strong solutions of sulphate of methyl and lime and sulphocyanide of potassium. The same precautions were observed as those described under sulphocyanide of ethyl. Sulphocyanide of methyl is a heavy oil possessing a disagreeable alliaceous smell. It is very readily decomposed by strong nitric acid yielding an analo- gous compound to the hyposulphathylic acid. The acid possesses no smell and is not easily decomposed by heat. Hyposul$hamethylate of baryta.-The same course was followed for procuring this salt as with its analogue.It is very soluble in water but is precipitated from that solvent in fine needles by spirits of wine and alcohol. 0.3640 grm. of the salt dried at 212' and burned with chromate of lead gave 0.0965 grm. carbonic acid and 0*0500grm. water. 0.3385 grm. of the salt gave 0.5200 grm. sulphate of barytes = 0,071 grm. sulphur. 0.2430 grm. of the salt gave 0.0730 grni. sulphate of barytes = 0.1136 grm. barytes. Centesimally represented Theory. Expt. 2eqs. Carbon . . . . 12.00 7.34 7.23 3 , Hydrogen . . . 3.00 1-24 1.58 2 , Sulphur . . . 32.00 19-56 19.80 5 , Oxygen . . . 40.00 25.04 24-65 1 , Baryta . . . . 76.60 46-82 46.74 163.60 100.00 100.00 The preceding numerical results agree perfectly with the formula BaO C H S 0,. Hyposulphamethylate of barytes behaves like its analogue when heated in a test-tube; water first passes off and is followed by sulphuric and sulphurous acid fumes.0.5325 grm. salt dried over sulphuric acid and heated at 212O for two days gave 0.Q278grm water corresponding to B ISULP H I TH Y LI C AN D R I SULPH 1bl ETH Y LI C A C I I) S. Theory. Espt. 1eq. Hyposulphamethylate of barytes 163.60 94-78 1 ,,Water ........-5.22 5.25 9.00 172.60 100.00 Formula :BaO C H S 0 +aq. Hyposu&hamethyZate of lead.-This salt crystallizes in fine rhombic prisms from an aqueous solution. When heated it gives off water with intumescence. 0.5745 grm. of the crystals gave :0-0245 grm. water. 0.1755 grm. of the crystals gave :0.1250 grm. sulphate of lead = 0.0921 grm.oxide of lead. The composition in 100 parts is therefore 1 eq. Hyposulphamethylic acid 87.00 1 ..Oxide of lead ....112-00 1 ..Water ...... 9.00 Theory. 41-86 53-84 4.32 Expt. 53.39 4-27 208.00 100°OO These numbers correspond with the formula PbO C H S 0 +aq. Hyposulphamethylate of copper.-This salt is obtained in very fine crystals by slowly evaporating the aqueous solution It is remark-ably soluble. 0,2514 grm. of the salt dried over sulphuric acid and burnt with chromate of lead gave :0.0640 grm. carbonic acid and 0.1130 grni. water which numbers correspond with Theory. Expt. 2 eq. Carbon .....12.00 6-98 6.94 8 ,,Hydrogen .... 8.00 4.65 4.99 2 ,,Sulphur ....32.00 18.60 10 ,,Oxygen .....80.00 46.41 1 ,,Oxide of copper ..40.00 23.25 172.00 100.00 This salt also agrees in composition with its analogue; the two being represented by the annexed formulze C H S O, CaO +5 aq.or M S O, CuO +5 aq. C H S 0, CuO +5 aq. or E S 0, CuO +5 aq. Previously to concluding my investigations on this subject wished to ascertain the composition of the acid resulting from the bisulphide of methyl which has not hitherto been given. Cahours DR. MUSPRATT ON HYPOSULPHATHYLIC &C. states* that tolerably concentrated nitric acid acts briskly upon the bisulphide of methyl affording sulphuric acid collaterally with a peculiar acid which yields crystals with potash barytes &c. In the preparation of the acid I proceeded in the manner previously described.I remarked on evaporating the decomposed solution in the water-bath that the fumes passing off were most stifling and productive of lachrymation. The smell is similar to that of horse-radish but much more disagreeable and pungent. Bisulphimethylate of lead.-This salt crystallizes in fine rhornbic prisms. When heated penetrating vapours are expelled accompa- nied by some water. 0.6960 grm. of the salt dried over sulphuric acid gave 0.1498 grm. carbonic acid and 0.1265 water 0.4040 grm. of the salt gave 0.2980 grm. sulphate of lead = 0.2195 grm. oxide of lead. Calculated per cent Theory. Expt. 2 eq. Carbon . . . 12.00 . 6.00 5.87 4 , Hydrogen . . . 4-00 2.00 2.01 2 , Sulphur . . . 3200 16.00 5 , Oxygen . . . 40-00 20.00 1 , Oxide of lead .. 112-00 56-00 54-33 200.00 100.00 The annsxed formula may be deduced from the above I PbO C H S 0,+ aq. Here then we possess another instance of the remarkable similarity which exists between the ethyl and methyl series of compounds; for the above acid is the analogue of the bisulphithylic. Before closing this memoir I shall place some of the salts of the four acids in a tabular form with the view of displaying the striking similarity existing between the two series Bisulphithylate of baryta C H S 0, BaO + aq. Bisulphithylate of lead C H S 0, PbO + aq. Bisulphithylate of copper C H S 0,CuO + 5 aq. Hyposulphathylate of baryta C H S 0,,BaO + aq. Hyposulphathylate of lead C H S 0, PbO + aq. Hyposulphathylate of copper C H S 0, CuO + 5 aq.Bisulphimethylate of baryta C H S 0, BaO + aq. ? Bisulphimethylate of lead C H S 0, PbO + aq. * Ann. de Pharm. 61-2 p. 93. DR. ANDERSON ON THE PHOSPHATES OF THE OBGANIC ALKALIES. 55 Bisulphimethylate of copper C N,S 0, CuO + aq. ? Hyposulphamethylate of baryta C H S 0, BaO + aq. Hyposulphamethylate of lead C H S 0,,PbO + aq. Hyposulphaniethylate of copper C H S 0, CuO + 5 aq. I hope that I shall soon be enabled to present this Society with another treatise upon these compounds.

ISSN:1743-6893    

DOI:10.1039/QJ8490100045

出版商:RSC    

年代:1849

数据来源: RSC

摘要:

DR. ANDERSON ON THE PHOSPHATES OF THE OBGANIC ALKALIES. 55 VII. Note on the constitution of the phosphates of the Organic Alkalies. By THOMAS M.D . Lecturer on Chemistry, ANDERSON Edinburgh. The following observations were made a considerable time since with the view of clearing up the apparent anomaly in the results obtained by Regnault* in the analysis of the phosphate of strychnine which he inferred to consist of single equivalents of phosphoric acid and strychnine without any basic water except the atom required by the organic base. As this result was entirely incompatible with the known constitution of tbe inorganic phosphates it appeared to me desirable to ascertain its correctness ;and it was my intention to have further extended the inquiry to the complete investigation of the phosphates of the organic alkalis but subjects of more interest having intervened the analyses were laid aside until I should have leisure for extending and completing them and they had almost escaped my memory when my attention was recalled to them by the publica- tion of a paper upon the constitution of the phosphates of aniline by Mr.Nicho1son.t At the conclusion of that paper the author having stated his intention of further pursuing the subject and investi- gating the phosphates of the other alkaloids I again laid my analyses aside in order that he might have the opportunity of com-pleting what he had begun. As however more than a year and a half have now elapsed since Mr. Nicholson’s paper was read to the Chemical Society without the appearance of any further researches by that gentleman I have resolved to publish my analyses as a small addition to our knowledge of these salts.Phosphate of strychnine with one equivalent of strychnine.-This salt is readily obtained by digesting a moderately dilute solution of tribasic phosphoric acid upon strychnine at a gentle heat so long as it is freely dissolved. On allowing the solution to cool the salt is leposited in groups of long radiated needles with truncated extre-* Annales de Chimie et de Physique vol. 68 p. 150. -/-Memoirs of the Chemical Society of London Part 19 p. 227. DR. ANDERSON ON THE CONSTITUTION mities which are easily obtained half an inch long even from very small quantities of the solution.These crystals are acid to teet- paper and like all the salts of strychnine excessively bitter to the taste. They dissolve in five or six times their weight of cold water and in a much smaller quantity of hot. The analysis gave the following results. I. 0.3228 grm. dried at 260° gave 0.699 grm. carbonic acid and 0.1735 irm. water. 11. 0.4535 grm. dried at 260° gave 0.9765 grm. carbonic acid and 0.2435 grm. water. Which correspond with the following numbers per cent. : - Experiment. Calculation. r- r-L- Y I. 11. Carbon . . 59.05 58.72 59-27 C, 3300.0 Hydrogen . . . 5.97 5.96 5-84 H26 325.0 Nitrogen . . . , , 6-28 N 350.0 Oxygen . . . . ,J >> 12.58 0 700.0 Phosphoric acid . , , 16.03 PO 892.3 100.00 5567.3 The formula of the salt is therefore (C44 H, N 0 HO) 2H0,PO,.0.7516 grammes of crystallized phosphate of strychnine heated to 260° lost 0.0598 = 7.95 per cent corresponding to 4 equivalents of water the calculated result for which gives 7.42 per cent and the formula of the crystallized salt is (C, H23 N 0 HO) 2H0 PO 4-4H0. Phosphate of strychnine with two equivalents of strychnine.-I f a solution of the salt just described be digested for a long time with an excess of etrychnia in fine powder an additional equivalent of the base is dissolved and a new salt produced which is deposited in crystals as the solution cools. In order to obtain it however very long continued digestion is necessary and I have never succeeded in entirely converting the former salt into the latter a considerable quantity of the acid salt always remaining in the solution.The separation of the two compounds is readily effected by two or three crystallizations the acid salt being more soluble than that containing two equivalents of base. The latter is deposited from its solutions in the form of rectangular tables often of considerable size and sometimes so thin as to be beautifully iridescent. It is not acid to test-paper The following are the results of the analysis OF THE PHOSPHATES OF THE ORGANIC ALKALIES. 0.2798 grm. dried at 260° gave 0.6805 grm. carbonic acid and 0.1649 grm. water. Experiment. Calculation. r--L- Carbon . . . . . 66-31 66 64 C88 6600.5 Hydrogen . . . . 6-54 6-18 H49 612.5 Nitrogen .. . . , 7.06 N4 700.0 Oxygen . . . . . 9 11-10 01 1100.0 Phosphoric acid . . 9 9.02 PO 892.3 0-795 grammes of the salt dried at 212O at which temperature the whole of its water of crystallization is expelled lost 0,143 = 17-6 per cent corresponding exactly to 18 HO the calculated result for which is likewise 17.6 per cent. These analyses give for the formula of the crystallized salt 2(C44H, N 0 HO) HO PO + 18HO. The foregoing analyses sufficiently prove that the phosphates of strychnine agree in constitution with the inorganic salts of the acid and enable us to explain the source of error in Regnault’s analysis. He obtained for his phosphate of strychnine Carbon . . . . 59.85 Hydrogen . . . . 5.85 in which result the excess of carbon is no doubt due to his having analysed the acid phosphate mixed with a small quantity of the last described salt which owing to the long continued digestion necessary for its production in quantity might easily escape detection unless actually sought for.I endeavoured to prepare a double phosphate of strychnine and soda by digesting strychnine in a solution of acid phosphate of soda; but did not succeed in obtaining it. Phosphate of brucine with two equivalents of brucine.-When tri-basic phosphoric acid is digested upon brucine rapid solution takes place; and on concentrating and cooling the solution the salt in question is deposited in short thick prisms which have in general a somewhat yellowish colour. The salt is moderately soluble in cold water and in all proportions in hot.It is neutral to test-paper. The crystals contain a large quantity of water of crystallization which they lose by efflorescence in the air. When suddenly heated to 212O they melt in their water and then solidify into a resinous-looking mass from which it is difficult to expel the remainder of the water. DR. ANDERSON ON THE CONSTITUTION It is advisable therefore to remove the greater part of the water over sulphuric acid and then to complete the drying at 212O. The analysis gave the following results 0.3545 grm. dried at 212'' gave 0.8065 grm. carbonic acid and 0.208grm water. Experiment. Calculation. Carbon . . . . . 62.05 82-53 CSS 6600-0 Hydrogen Nitrogen . . . . . . 6.51 , 6.27 6-63 H53 N* 662-5 700.0 Oxygen .. . . , 16-12 01 1700-0 Phosphoric acid . . , 8.45 PO5 892.3 100~00 '105548 corresponding to the formula 2 (C44H, N 0,HO) HO PO,. A double phosphate of brucine and soda is readily prepared by digesting brucine with acid phosphate of soda. It crystallizes in short opaque prisms. I was unable to obtain it perfectly pure but the analysis gave results approximating to the formula (C44H, N 0 HO) NaO HO YO,. Phosphate of quiniiae with three equivalents of quinine.-&uinine dissolves with great rapidity in warmphosphoric acid and on cooling the fluid becomes a solid mass of minute needle-shaped crystals. If the solution be more dilute it deposits the salt in the form o€ radiated tufts of silky needles which are exceedingly thin and soft and matt together into a mais as they become dry.The salt is perfectly neutral to test-paper. Analysis gave the following results 0.334 grm. dried at 212O gave 0.7576 grm. carbonic acid and 0.205grm. water. Experiment. Calculation. A -Carbon . . . . . 61.85 6lG C60 4600*5 Hydrogen . . . . 6.81 6.68 H39 487.5 Nitrogen . . . . , 7-18 N3 525*0 Oxygen . . . . , 12.32 09 900.0 Phosphoric acid . , 12.22 PO 892.3 ~ ioo.oo 7304.8 The formula of the dry salt is therefore 3 (CQ0H, NO HO) PO,. 0.648 grm. of the crystallized salt heated to 250° lost 0.0415 = 7.57 per cent; 0.4775 grm. heated to 2500 lost 0.0375 = 7.85 per OF THB PHOSPHATES OF THE ORGANIC ALKALIES. cent ; six equivalents of water of crystallization correspond to -517 per cent which gives for the crystallized salt the formula 3 (C2,,H, NO HO) PO + 6H0.On another occasion 1 obtained a salt the characters of which did not materially'differ from those above described but which lost by a heat of 250° 15.3 per cent of water ;this agrees with 12 equivalents of water the calculation for which gives 15.6 per cent. It is probable therefore that two different hydrates of this salt exist. The analyses of these salts are sufficient to establish in a satis- factory manner the general constitution of the phosphates of the organic alkalis and to show that they agree with the inorganic salts of that acid as well as with the phosphates of aniline described by Nicholson. They contain however water of crystallization which is absent in the phosphates of the latter base; and in this respect its salts correspond exactly with those of ammonia while the phosphates of the fixed organic alkalis are more closely analogous to those of the inorganic bases.This peculiarity adds one to the numerous points of relationship subsisting among the volatile bases and seems at the same time to point to some peculiarity of constitution distinguishing them from the non-volatile members of the class which may perhaps be of more importance than it at first sight appears. It has always been considered that the organic bases formed an extremely well- marked natural family agreeing perfectly in their fucctions and constitution ;but this opinion has been arrived at principally from the observation of their general properties and scarcely anything has been done in the way of minutely examining their compounds with the view of classifying them or ascertaining the individual peculiarities of their constitution.The most minute attention has been paid to the examination of the salts of every new acid with the inorganic bases and their constitution established with very great care but the discoverer of a new organic base generally contents himself with the analysis of the platinum compound required to determine its atomic weight and a few observations sometimes very loose on the charac- ters of its other salts. It is true that the rarity of many of these substances and the difficulty and expense o€ obtaining them in suffi- cient quantity almost preclude the possibility of a complete inves- tigation; I apprehend however that if the same care which has been bestowed upon the salts with the view of characterizing their acid were extended to them in relation to their basic constituent it would afford an important means of classification and even of indirectly determining the nature of their constitution.The possibility of this is illustrated by the analyses detailed MESSRS. KOLBE AND FRANKLAND ON THE PRODUCTS above; for it so happens that the bases whose salts I have ex-amined may be considered as representing three different classes according to the number of equivalents of the alkaloid which unite' with phosphoric acid to form what may be called its normal salt.Thus if three portions of phosphoric acid be taken and digested under similar circumstances with quinine brucine and strychnine three two and one equivalent of the respective bases will be dissolved. Quinine therefore which replaces at once three equiva- lents of basic water may be compared to oxide of lead or the oxides of the heavy metals generally. Brucine may represent the inorganic alkalis which replace two equivalents in their normal compound while strychnine which under ordinary circumstances replaces only a single equivalent of water belongs to a class which has no analogue among the series of inorganic bases. Feb. 7,1848. The President in the chair. Messrs. T. A. Malone and J. B. Edwards were duly elected members of the Society. The following papers were read

ISSN:1743-6893    

DOI:10.1039/QJ8490100055

出版商:RSC    

年代:1849

数据来源: RSC

摘要:

MMESSRS. KOLBE AND FRANKLAND ON THE PRODUCTS VIII. On the products qf the action of Potassium on Cyanide of Ethyl. By H. KOLBE,PH.D. and E. FRANKLAND, Esq. Professor Bunsen in his investigation on the iiolation of Cacodyl,* points out two important conditions which in the separation by means of metals of the organic radicals from their liquid combina- tions it is essentially necessary to observe. Firstly the decom-position must be effected at a lower temperature than that at which the substance to be decomposed boils; and secondly the metallic compound produced must not be insoluble in the newly-formed radical. These remarks induced us to make an experiment upon the separa- tion of ethyl from its cyanide by means of potassium as we conceived that this metal would exert its affinity for cyanogen at a temperature below the boiling point of that liquid.This expectation appeared to be fully realized. For not only did the potassium act energetically upoi the cyanogen compound even at ordinary temperatures but the cyanide of potassium which was formed in large quantity was so completely dissolved in the sur-* Anrialen der Chemie Bd. 42 S. 45. OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. rounding liquid that the metal retained a bright surface to the last. At the same time an inflammable gas insoluble in water and pos- 9essing a faint ethereal odour was evolved. We at first imagined this gas to be the radical sought and we therefore resolved to follow out the investigation. We employed the following apparatus Fig 1 for the preparation of FIG.1. the gas. In the flask A which was capable of containing about 60 cubic centimetres was placed a number of small pieces of potassium previously freed from the adhering rock oil; the neck was fitted with a cork through which were inserted on the one side the gas-deliver- ing tubep and on the other the tube a having a bulb blown upon it the lower end being recurved and drawn out to a capillary orifice; the upper extremity was connected by a caoutchouc joint with the stop-cock b. The bulb served to contain the cyanide of ethyl which by the cautious opening of the stop-cock b could afterwards be allowed to fall in drops upon the potassium. For the collection of the gas the receiver B inverted in the glass cylinder C C was employed its lower edge resting upon two strips of glass.The gas-delivering tube g proceeding from the tubulure of the bell-jar was slightly drawn out at x and then connected by caoutchouc joints with the wider tubes eA which served to contain the gas for eudiometric purposes. To the extremity of the last of these was attached a caoutchouc tube h containing a piece of glass rod by means of which the aperture could be perfectly closed. Immediately before the experiment and previous to the gas-deli- vering tube d being introduced under the bell-jar B a quantity of boiled water still warm was poured into the outer cylinder CC and suction being applied to the open extremity at h the entire system of tubes from B to h was filled with it.The caoutchouc tube MESSRS. KOLBE AND FRANKLAND ON THE PRODUCTS surrounding the small piece of glass rod above mentioned was then rendered perfectly air-tight by being tied with silk cord. The first few drops of cyanide of ethyl which by the momentary opening of the stop-cock b were allowed to fall upon the potassium exhibited generally a very violent action which was not unfrequently attended by flashes of light and accompanied especially at the com- mencement by a very rapid evolution of gas which soon expelled all atmospheric air from the apparatus. As soon as the last traces of air had been displaced from the apparatus the conducting tube d was inserted under the edge of the receiver B which then became slowly filled with gas as the pieces of potassium gradually disap- peared on the addition of cyanide of ethyl and were converted into a tenaceous mass of a yellowish colour.Towards the end of the pro- cess the decomposition was promoted by the application of a gentle heat. "he experiment was interrupted BSsoon as the evolution of gas perceptibly diminished the potassium being then in most instances quite consumed. It appeared desirable to allow the gas collected in the bell-jar to stand over water for several hours or even for a whole day that the vapour of cyanide of ethyl with which it was still contaminated might be perfectly absorbed; we therefore took the precaution to cover the outer surface of the water with a layer of oil in order to prevent the possibility of diffusion taking place between the enclosed gas and the atmosphere.The cylinder was afterwards quite filled with water and the caoutchouc tube at h opened until all the water was expelled from the system of tubes and its place was occupied by the gas acting under the pressure of the outer column of water. The caoutchouc connectors h s,and r were then tied with silk cord the two last doubly and these being cut through between the liga- tures the tubes e andfwere taken asunder. To make the four ends perfectly gas-tight they were immersed in melted wax; by taking this precaution gases may be preserved for a twelvemonth without any diffusion taking place; this method was preferred to fusing them before the blow-pipe as it was to be feared that the heat necessary in the latter case might decompose the gas.The rest of the gas was employed for the determination of its specific gravity and for combustion with oxide of copper. For the first purpose we used a glass flask containing about 200 cubic centi- metres the neck of which was contracted before the blow-pipe until its diameter was reduced to that of a stout straw. This could be closed air-tight by means of a small ground-glass stopper. In order to dry the gas several pieces of fused potash were intro- OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. duced and fixed to the bottom of the flask by a gentle heat; it was then filled with mercury inverted in the vessel D containing the same metal and its open mouth held over the extremity of the gas- delivering tube previously cut off at the point x.To overcome the pressure of t,he mercury the gas in the receiver B was more strongly compressed by pouring a proportionate quantity of quicksilver into the outer cylinder. The gas was allowed to pour into the flask until the mercury in the neck stood only about lommabove that in the vessel; thk flask was then brought with its mouth still immersed in the liquid metal into a room of a constant temperature where it was allowed to remain for upwards of an hour. Whilst the gas assumed the temperature of the surrounding air which was ascertained by a delicate thermometer it was at the same time per- fectly dried by means of the pieces of fused potash. The height of the internal column of mercury was measured by a pair of com-passes and determined in millimeters.The flask was then carefully stopped under mercury and weighed without bringing the hand in contact with it; it was afterwards filled with dry air and lastly with mercury the weight being taken after each operation. The following results were obtained Temperature of room . . . . . . . . . 19*7OC. Height of barometer . . . . . . . . . 748.0m. m. Height of mercury in flask above that in outer vessel 17.2m. m. . . . . . . 53.591 grms. Weight of flask filled with gas Temperature in balance case . . . . . . 20*3OC. Weight of flask filled with dry air . . . . . 53.5775 grms. Temperature of balance case . . . . . 20*9OC. Capacity of flask .. . . . . . . . 210*2c. c. From which the specific gravity was calculated at 1.075. For ascertaining the relative proportions of carbon and hydrogen we allowed an indefinite volume of the gas to stream over ignited oxide of copper contained in a combustion tube which was connected at one extremity with a chloride of calcium tube and potash appa- ratus both previously weighed and at the opposite end with another chloride of calcium tube connected with the gas apparatus B by the caoutchouc tube c. Thus the gas was freed from moisture before passing over the ignited oxide of copper. By carefully depressing the receiver B a perfectly regular stream of gas was obtained the velocity of which was indicated by the liquid in the potash apparatus.When a sufficient quantity of water and carbonic acid had been formed the caoutchouc tube c was hided and the gases remaining in the combustion tube were drawn through the potash bulbs by MESSRS. KOLBE AND FRANKLAND ON THE PRODUCTS suction in the usual manner. On re-weighing the chloride of calcium tube it was found to have increased by 0.1794 grms.; the weight of the potash apparatus had increased 0,2915 grms. The gas consequently contained 0.0795 parts by weight of carbon to 0.0199 parts of hydrogen ; numbers which closely correspond with the proportion C H = 2 3. The eudiometric analysis should confirm this result and at the same time indicate the degree of condensation. For this purpose the gas contained in one of the tubes ef was employed filled as before described and transferred under mercury into the eudiorneter and exploded with oxygen.For the details of the methods of obser- vation in eudiometrical researches and the precautions necessary to be used we refer to the “Handworterbuch der Chemie,” article Eudiometrie,” vol. 11. p. 1050. I. Height of mer- Corrected vol. Observed Temp. cury above at Oo C. and vol. C. that in trough. Barom. 1” pressure. Volume of gas used (moist) . . . . 117.2 15O.7 456.5“” 743.9mm 30-37 After admission of 0 (moist) . . . . 348.9 15O-7 216.3 , 743.5 , 169.55 After combustion (moist) . . . . 224.5 16O.1 286.1 , 743.1 , 94-00 After absorption of CO (dry) . . . 121.6 16O.2 451.5 , 744.4 , 33.74 After admission of H (dry) .. . . 323-3 16O.3 241.4 ,) 744.0 , 153.37 After combustion (dry) 167.4 16O.1 404.0 ) 744-9 , 53-90 11. Volume of gas used (moist) . . . . 68.7 15O.2 500.7 , 744.1 , 15.00 After admission of 0 (moist) . . . . 331.9 15O.3 229.1 , 743.6 , 157.65 After combustion (moist) . . . . 281.6 15O.3 280.9 , 744.1 ) 120-07 After absorption of CO,(dry) . . . 231.6 15O.3 333.1 , 747.7 , 90.92 After admission of H (dry) . . . . 539.0 15O.4 21.5 , 746.8 ) 370.05 After combustion (moist) . . . . 247.2 15O.4 316.7 , 7425.5 , 97.30 OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. It appears froin the above analyses that 1 volume of the gas requires 34 volumes of oxygen for combustion and generates 2 volumes of carbonic acid.Volume of gas used. Oxygen consumed. Carb. acid generated. I. 30.37 106.02 60-26 --1 3-49 1-99 11. 15.00 51-74 29-15 - 1 3.45 1-94! The above facts prove that the unknown gas has the composition and the state of condensation of the hitherto hypothetical radical methyl. The determination of its specific gravity already detailed gave the number 1.076 which agrees sufficiently near with the calculated specific gravity (1.037) when we consider that the gas at the time the experiment was made probably contained a little of the comparatively heavy cyanide of ethyl vapour. 1 vol. Carbon vapour = 0.82922 3 vols. Hydrogen = 0.20730 1 vol. Methyl gas = 1.03652 By experiment 1.076 Methyl is a colourless gas not condensible at a temperature of 18' C.(65O.5 F.) insoluble in water and possessing a slight ethereal odour. One volume of alcohol absorbs 1-13 volumes of this gas; agitated with an equal volume of previously boiled alcohol over mercury it disappeared with the exception of a small bubble which did not amount to + per cent. Concentrated sulphuric acid had no action upon methyl nor did it combine with sulphur or iodine when those elements were heated in the gas. It appeared important to ascertain whether methyl like hydro-gen would combine immediately with chlorine to form chloride of methyl. For this purpose we again filled some dried tubes similar to those marked in the figure ef and joined them with flexible connectors; to these a chloride of calcium tube was attached connected with the caoutchouc tube c which last was dosed by a silken cord while the receiver B was being filled with gas ; the ligature was then loosed and by pressing down the bell-jar the gas was driven through the system of tubes.As the volume of gas in the receiver amounted to nearly twenty times the capacity of the tubes to be filled we took for granted that all atmospheric air had been expelled from the apparatus The tubes were then taken T'OL. I. NO. I. F MESSRS. KOLRE AND FRANKLAND ON THE PRODUCTS asunder at the caoutchouc connections in the manner before described. Another tube of the same dimensions as one of those above mentioned was now filled with dry chlorine and then connected as quickly as possible by a strong india-rubber joint with a similar tube containing methyl and the two gases were thus allowed to communicate with each other.After remaining for twenty-four hours carefully preserved from the light they perfectly inter-mingled but were otherwise unchanged. On exposure to diffused daylight the coloiir of the chlorine gradually disappeared a proof that combination had taken place After twenty-four hours more the two tubes were hermetically sealed before the blow-pipe and reserved for further experiments. On breaking off the end of one of the tubes under mercury it did not appear that any condensation had taken place yet the new product could not be chloride of methyl since a few bubbles of the gas which were allowed to escape contained a large quantity of hydrochloric acid.To determine the quantity of hydrochloric acid present we trans- ferred the gas into a small eudiometer and after carefully noting the volume a ball of tribasic phosphate of soda was introduced and afterwards one of caustic potash which was allowed to remain until all traces of hydrochloric acid were absorbed; the volume was again read off and the residual gas transferred to a large eudio- meter furnished in the usual manner with platinum wires in which it was then exploded with oxygen and yielded the following results. ESTIMATION OF HYDROCHLORIC ACID. Height of mer-Corrected vol. Observed Temp. cury above at 00 C.and volume. C. that in trough. Barorn. lm pressure. Volume of gas used (dry) . . . . 103.6 18"9 47.2"" 752.5mm 68.35 After absorption of HC1 (dry) .. . 55.1 18"8 95*0, 755.1 , 34.00 EXAMINATION OF THE GAS FREED FROM HYDROCHLORIC ACID. Gas used (moist) . . 116.1 18".8 439.2 , 755.0, 32-50 After admission of 0 (moist) . . . . 362.5 19".0 186.6, 754*8, 187.05 OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. Height of mer- Corrected vol. Observed Temp. cury above at 00 C. and volume. C. that in trough. Barom. lmpressure. After explosion* (moist) 281.5 19O-1 269.8 , 753.7 , 123.00 After absorption of CO (dry) . . . 186.1 19O.8 367.3 , 753.2 , 66.95 After admission of H (dry) . . . . After explosion (moist) 462.3 240.2 20"O 86.5 , 200*031 1.6 , 752*4, 286.90 752.0 , 9470 Owing to the great difficulty of obtaining the tubes for the methyl and chlorine of precisely the same size and further as in connecting them together it is impossible to prevent a small quantity of atmo-spheric air from being included absolute correctness cannot be * The heat developed by the explosion was so great that a portion of mercury was volatilized and the interior of the eudiometer was partially covered with a black film of the metal.At the same time a large quantity of free chlorine was evolved which caused the residual gas to assume a deep yellow colour ; it was however rapidly and perfectly absorbed by the mercury converting the black film above mentioned into white bichloride of mercury. According to Bunsen (Annalen der Chemie Bd. 46 S. 33) the hydrogen of combustible gases containing chlorine should not be estimated by explosion with oxygen since the hydrochloric acid evolved is partially decomposed with the separa- tion of chlorine.If as the results prove a complete combustion has taken place in the above analysis then the cause of this phenomenon unquestionably depends upon the high temperature accompanying the explosion of the gas. The following eudio- metrical experiments show how very much the combustibility of hydrochloric acid is augmented by an increase of the heat developed during combustion ; in these experi- ments hydrochloric acid was exploded with a mixture of oxygen and hydrogen procured from the decomposition of water by voltaic agency and free oxygen in different proportions. FIRST EXPERIMENT. Height of mer- Corrected vol.Observed Temp. cury above at 00 C. and vol. C. that in trough. Barom. lmpressure. Oxygen gas (dry) . . 172.3 21O.2 382.4"" 748*9mn1 63.1 After admission of the gases composing water (dry) . 285.5 81O.2 265.9 , 748.0 , 137.6 After admission of H C1 (dry) 362.2 21°*2 187.4 , 746.9 , 202.7 After explosion (moist) . 237.7 21O.2 316.5 , 746.9 , 102-3 After admission of water (moist) . . . . 170.0 367.0 , 746.9 , 61.2 The explosion by means of the electric spark was in the above instance very slight and the small quantity of chlorine separated could scarcely be distinguished by the colour it imparted to the gas. In the next experiment where a smaller volume of Fa MESSRS. KOLBE AND FRANKLAND ON THE PRODUCTS expected in the above analysis.The results however furnish data which enable us safely to fix the atomic constitution of the new chlorine compound. It follows then that the mixture consisted of equal volumes of hydrochloric acid gas and of the other product. The explosion of the gas remaining after the absorption of carbonic acid with hydrogen showed that it contained 2.8vols. of nitrogen the conversion of which into nitric acid during the explosion must have reduced the observed volume; the quantity of atmospheric air due to the above amount of nitrogen is 3.5 vols. which being deducted from 32-50,leaves 29.0 vols. of the true combustible gas; this according to the analysis consumed 99.5 vols. oxygen forming with it 56.0 vols. carbonic acid. Thus it has been shown that 1 vol.of methyl gas with 1 vol. of chlorine is decomposed into 1 vol. of hydrochloric acid (= 6 vol. H + $ vol. Cl) and into 1 vol. of another gas; the last must therefore evidently consist of 4vol. chlorine and 1 vol. methyl minus 4 vol. hydrogen and its specific gravity must be 2.226. hydrochloric acid gas was ignited with a much larger volume of the elements of water and less excess of oxygen than before the explosion was attended with a much greater development of heat ; there was at the same time a sublimation of the mercury and a copious separation of chlorine. SECOND EXPERIMENT. Height of mer- Corrected vol. Observed Temp. cury above at Oo C. and vol. C. that in trough. Barom. 1" pressure. Constituents of water (dry). 305.4 210.4 251.2"" 746.8"" 140.4 After admission of 0 (dry) .353.0 After admission of H C1 (dry) 405.6 21O.5 21O.4 199.8 , 146.1 , 746.2 , 745.8 , 178.8 225.6 After explosion (moist) . 119.6 21O-5 435.2 , 742.9 , 32-0 After admissioii of water (moist) . . . . 111-1 21O.5 419.8 ,,.+-2"" = 26"" 742.9 , 31.3 (pressure of water) Although no absolutely exact results could be expected from these experiments on account of the last reading being performed over water yet they sufficiently demonstrate the point above alluded to. By the first experiment in which 65.1 vols. of hydrochloric acid were burnt with 74.5 vols. of the elements of water and 63.1 vols. of oxygen only 1.9 vols.'of this last disappeared. There were thus only 7.6 out of 65.1 vols. of hydrochloric acid decomposed.In the second experiment 46.8 vols. of hydrochloric acid were mixed with 140.4 vols. of the constituents of water and 38-4 vols. of oxygen. On the explosion taking place 7.1 vols. of oxygen disappeared. Out of 46-8 vols. of hydrochloric acid only 18.4 vols. escaped decomposition. In the first instance scarcely -& ; in the second above 4 of the volume of the acid gas was consumed. OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. 69 1 vol. Carbon vapour . . #82922 2; vols. Hydrogen . . . 017270 4 vol. Chlorine . . . . 1.22445 Condensed to 1 vol. = 2.22637 This is the composition and state of condensation of chloride of ethyl 1vol. of which according to calculation requires 3.25 vols of oxygen for complete combustion and generates 2 vols.of carbonic acid ;the above analysis sufficiently coincides with this calculation 3.15 vols. of oxygen being consumed and 1.93 vols. of carbonic acid generated by 1vol. of the combustible gas. Although this gas agrees closely with chloride of ethyl in its composition in the state of condensation of its elements and conse- quently in its specific gravity yet it is not the same body but a compound isomeric with it. For whilst chloride of ethyl becomes liquid at lfJ0 C. and crystallizes at -18' C. this gas freed from hydrochloric acid by a ball of phosphate of soda and from moisture by one of potash retains its gaseous condition unchanged at the latter temperature. The two bodies also differ though less decidedly in their relative solubility in water which takes up an equal volume of chloride of ethyl but absorbs at a temperature of 19O C.and a pressure of $m nearly twice its volume of this gas. It can scarcely be doubted that this isomerism in a body having the rational composition of chloride of ethyl is caused by the anomalous grouping of its atoms. It is possible that the new gaseous body is a conjugate compound of one atom of methyl with another atom of the same gas in which 1 eq. of hydrogen is replaced by chlo- rine C H + C (H2)c1 . But how far this hypothesis is correct further investigations must determine. On the other hand this gas exhibits several points of agreement with chloride of ethyl; it possesses a similar odour burns with a green flame generating hydrochloric acid vapour and by exposure to sunlight with excess of chlorine it is transformed like that compound into a substance resembling camphor which is without doubt sesqui- chloride of carbon C Cl,.Owing to the want of material we have not further studied its properties. PYANETHINE. When 1 atom of methyl is obtained from 1 atom of cyanide of ethyl the elements C H Cy remain and must evidently be contained 3IESSRS. KOLBE AND FRANKLAND ON THE PRODUCTS in the tenaceous yellow mass which in the preparation of methyl is left in the place of the potassium. We have not however yet succeeded in ascertaining the combina- tion into which this body or at least the group C H enters. When the residue is treated with water a large quantity of cyanide of potassium is dissolved and a white insoluble substance remains which as the following observations show has no connection with the compound sought for.This insoluble substance which on account of its remarkable rela- tions to cyanide of ethyl had the first claim upon our attention was freed from cyanide of potassium and cyanide of ethyl by washing with cold water and then dissolved in boiling water. On cooling small crystalline scales of a pearl-like lustre were deposited ; these dried at looo C. exhibited the following composition. I. *3557grms. burnt with oxide of copper* gave *856grms. carbonic acid and ,300grms. water. II.*2055grms. gave 0495grms. carbonic acid and -171 grms. water. The determination of the nitrogen was effected according to Bunsen’s method by igniting an indefinite quantity of the substance with oxide of copper and metallic copper in a hermetically sealed glass tube previously freed from nitrogen and exhausted.By this process the following data were obtained Height of mer- Corrected vol. Observed Temp. cury above at 00 C.and vol. C. that in trough. Barom. lmpressure. Volume of mixed gases CO,+N (moist) . 185.1 20O.9 370.4mm 753.9mm 62.81 After absorption of CO (dry) . . . 40.8 20°08 517.4 , 755.8 , 9.04 Hence it follows that the proportion of carbonic acid to nitrogen = 6 1.009. Per centage composition (C = 75 ; H = 12.5). * In this and the following analysis after the termination of the combustion a stream of oxygen was led over the reduced copper ; this gas was furnished by heating a small quantity of fused perchlorate of potash placed at the posterior end of the combus- tion tube and separated from the oxide of copper by about Q of an inch of recently ignited asbestos.Perchlorate of potash answers the purpose better than the chlorate since the evolution of gas from the former is more regular and less rapid on the first application of heat. The potash apparatus was also furnished with a small tube contain- ing a stick of fused potash to absorb the aqueous vapour imbibed by the bubbles of gas in their passage through the potash ley; both were weighed together. Lastly the OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. C Calculated. . . . 65.5 Experiment.++ 65.6 65.6 H .. . 9.1 9.3 9.2 N . . . . 25.4 25.5 25.5 100.0 100-4 100-3 The compound analyzed has therefore the composition of cyanide of ethyl; it is however far from participating in any of its qualities. It dissolves in all acids with ease forming with them in some cases beautiful crystallizable salts which are soluble in water and alcohol ; from these it is precipitated unchanged by potash ammonia and the alkaline carbonates; in short it is an organic base We propose to call it kyanethine on account of its derivation from cyanide of ethyl. The formula of cyanide of ethyl does not however express the atomic constitution of kyanethine but must be trebled in order to do SO as is proved by the analyses of its salts. One atom of the base therefore consists of C, H, N,.Kyanethine is when pure a white volatile substance inodorous and almost tasteless ;it melts at about 190°C (376O F.) and begins to boil at about 280° C. (536O F,) undergoing at the same time partial decomposition. It is soluble in alcohol in almost all proportions; it is very slightly soluble in cold but tolerably so in hot water ; from the latter it sepa-rates as was stated by slow cooling in small shining crystalline scales. The solution in warm water shows a slight but distinct alkaline reaction. This base can be boiled with potash ley without suffering the decomposition of cyanide of ethyl or undergoing any other change. When the ley containing it is evaporated to dryness and the mass fused in a silver crucible the greater part of the base sublimes without the separation of carbon.Most of the salts of kyanethine have a bitter astringent taste and are all soluble in alcohol and water. Nitrate of kyanethine C, H, N + HO NO, prepared by digest- potash apparatus was detached from the chloride of calcium tube and the oxygen which might possibly be still retained in the former was displaced by atmospheric air. Many compounds rich in carbon are not perfectly burnt by oxide of copper without the assistance of oxygen. Benzole naphthaline and similar volatile bodies give on an average 3 per cent. carbon too little ; but by the simultaneous use of oxygen an extreme degree of accuracy is attained The loss appears to be occasioned by the formation of a carburet of copper. MESSRS.KOLBE AND FRANKLAND ON THE PRODUCTS ing the base in dilute nitric acid crystallizes by spontaneous evapora- tion in large colourless prisms ;after re-crystallization it exhibits a perfectly neatral reaction. The analysis of this salt dried at loooC. gave the following numbers 0401grms. gave 0699grms. carbonic acid and *256grms. water. Two determinations of nitrogen according to Bunsen's method yielded the following results I. Height of mer-Corrected vol. Observed Temp. cury above at 00 C. and vol. C. that in trough. Barom. 1" pressure. Volume of mixed gases CO,+N (moist) . 132.0 2lO.2 134-6mm 74609"~ 72.74 After absorption of cog (dry) . 28.2 21O.2 236*8, 746.9 ) 13-30 11. Volume of mked gases (moist) . .1341.7 18O.4 130.0, 745.3 I 75.76 After absorption of CO (dry) . . . 285 17"*9 235.0, 750.9, 13.80 Hence the proportion of carbonic acid to nitrogen I 45 1.007 u. 4-5 1.002 Composition in 100 parts Calculated. Experiment. c, . . 47-4 47.5 H, . . 7.0 7.0 N4 . . 24.5 24.6 0 . . 21.1 100*0 Sulphate and chloride of kyanethine are very soluble in water and uncrystallizable. The acetate loses acetic acid by evaporation even in vacuo and is changed into an insoluble basic compound. The oxalate obtained by neutralizing oxalic acid with an excess of the base gives large well-formed prismatic crystals by spontaneous evaporation of the filtered liquor. The chlorocarbohyposulphate of kyanethine also shows a strong disposition to crystallize.OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. 73 Like ammonia and the organic bases chloride of kyanethine forms with chloride of platinum a double salt of remarkable beauty which separates in the form of a yellowish red crystalline precipitate when concentrated solutions of both salts are mixed. It is soluble in alcohol as well as in a mixture of alcohol and ether; in water it is difficultly soluble and crystallizes by the slow evaporation of its watery solution in large ruby-red octohedrons. The alcoholic solu- tion undergoes decomposition by boiling and ammonio-chloride of platinum is subsequently formed. The above precipitate washed several times with water pressed between blotting-paper and dried at 100° C. gave on analysis the following numbers 0.797 grm.moistened with alcohol inflamed and afterwards strongly ignited left 0.209grm. platinum. 0.427grm. gave 0.456 grm. carbonic acid and 0.169 grm. water. Composition Pt C1 + C, H, N, H C1. Calculated. Found. C, . . 29.1 29.1 HI . . 4.3 44 N3. b 11.4 C13 . . 28-7 Pt . . 26.5 26.2 1000 We have in vain endeavoured to discover the conditions which determine this remarkable transformation of the elements of cyanide of ethyl into kyanethine. All attempts to form this substance by other methods than the one already mentioned have proved fruitless Even when we altered the process only so far that instead of allowing the cyanide of ethyl to fall in drops upon the potassium the latter was thrown into that liquid methyl gas was it is true formed but scarcely a particle of this base.Cyanide of ethyl underwent just as little change when it was heated to 240° C (464' I?.) in a herme- tically sealed glass tube either alone or in conjunction with anhy- drous cyanide of potassium. Lastly the quantity of the base obtained by the above method was very small; it amounted to only a trifling per centage of the cyanide of ethyl used. It is difficult to form an opinion regarding the rational compo- sition of kyanethine. But we may assume the hypothesis which has already been applied to aniline and to which we have nothing to add OF THE ACTION OF POTASSIUM ON CYANIDE OF ETHYL. viz. that it is like this substance a conjugate amide in which 2 eqs.of hydrogen are replaced by 2 eqs. of cyanogen C +NH,. The l4 CY2 truth or fallacy of this view must be decided by further researches. The above investigation was conducted in the laboratory of Prof. Bunsen the use of which he in the most friendly manner placed at our disposal during our stay in Marburg. We gladly avail our- selves of the present opportunity of expressing our warmest thanks for his uniform kindness towards us.

ISSN:1743-6893    

DOI:10.1039/QJ8490100060

出版商:RSC    

年代:1849

数据来源: RSC

摘要:

NOTICES OF PAPERS CONTAINED IN THE FOREIGN JOURNALS. On the Acids of Su$hur.*-By acting upon the perchloride of sulphur with an aqueous solution of sulphurous acid Messrs. Fordos and G6lis have succeeded in forming an acid of sulphur represented by the formula S,O,. This acid which is isomeric with hyposulphurous acid is obtained in combination with barytes when the product afforded by the mutual action of the substances named above is freed from sulphuric and hydro- chloric acids by carbonate of lead and the filtrate after the decomposition of the soluble lead-compound by sulphuric acid is treated with carbonate of barytes and precipitated by alcohol. The barytes salt which crystallizes in needles is decomposed by sulphuric acid and the new acid called by the authors pentathionic acid is separated and bears in its aqueous solution a great resemblance to the tetrathionic acid of the same chemists.The taste of the acid is slightly bitter it reddens litmus paper and under- goes the same decomposition as the barytes salt which formed the principle subject of the present investigation. The barytes salt of this acid is completely converted into sulphate of barytes by chlorine and the hypochlorites. It does not absorb iodine and is thus distinguished from hyposulphurous acid which is converted by that element into tetrathionic acid. Heated in a tube it yields sulphur sulphurous acid and sulphate of barytes and in the hydrated condition sulphuretted hydrogen gas. The solution of the salt in water is very instable but acquires stability by the presence of alcohol the last portions of which are difficultly separated from the salt when it has been used for precipitating it from an aqueous solution.The formula for the salt is BaO S,O + 2 HO. The authors obtained the same acid by the action of sulphurous acid upon protochloride of sulphur; but are disposed to think that the sulphu-rous acid plays no active part in this decomposition which is solely referable to the action of water upon the chlorides of sulphur a more detailed investigation of which they are about to publish. On the Analysis of the Oxygen Compounds of Sulphur.t-As a means of estimating the amount of oxygen in the lower oxides of sulphur (phos- phorus arsenic and antimony) and also the total amount of sulphur in * Ann.de Chim. et de Phy. XXII 66. -f Ibid XII p. 60. ANALYSIS OF THE OXYGEN COMPOUNDS OF SULPHUR mixtures of the sulphur acids Messrs. Fordos and G6lis recommend the use of a solution of an alkaline hypochlorite of known strength. The amount of liquid used or the amount of chlorine absorbed being equivalent to the quantity of oxygen required to raise the inferior oxide to the highest state of oxidation. Having found by experiment that all the lower oxides of sulphur with the exception of hyposulphuric acid are instantaneously decomposed in the cold by the hypochlorites and that it is unnecessary to use an excess of the re-agent to ensure complete oxidation the analysis is performed in the manner of a chlorometric assay.The solution of the hypochlorite is prepared by passing chlorine to saturation through a weak solution of potash or soda and diluting the product until 1 decigramme of hyposulphite of soda requires exactly 25 cub. centimeters or 50 measures of the liquid in the burette to convert it into sulphate this quantity corresponding with 0.1 14 grm. of chlorine. The authors prefer acting upon a solution of 0.1 grm. of the substance to be analysed in 100 grms. of water the solution is slightly acidulated previous to the addition of the hypochlorite and the least excess of the re-agent is then recognised by the odour of chlorine which is evolved when it ceases to be absorbed or by a solution of indigo. as in the chlorome- tric process. The quantity of sulphur in a mixture of sulphur acids is calculated from the amount of sulphuric acid produced by the action of the hyyochlorite.Analysis of the supposed double salt of Oxalate of Bislnuth and Potash.*- The product obtained by boiling oxide of bismuth with binoxalate of potash has been found by Dr. Schwartzenberg to contain a mere trace of potash and to consist of oxalate of bismuth with water of crystallization. The salt was analysed by combustion with chromate of lead and afforded I. 11. Atoms. Calculated. Carbon . . . . . 8.93 9-31 6 9.45 Hydrogen . . . . 1.01 1.01 4 1-05 Oxygen . . . . . 28.03 27.65 13 27.31 Oxide of bismuth BiO 62.03 62.03 1 62-19 100~00 1oo*oo 100 agreeing with the formula Bi03 3 C 0,+4 Aq. on Auriferous Glass.-The interesting observations of Splittgerber upon white glass containing gold,t have been verified by Henry Rose; but the remarkable changes which are produced in this glass by heat are attributed by the celebrated German chemist to other causes than those * ,4n?z.der Chern. uibd Pharm. LXIV p. 126. t Pog. Ann. vol. 61 p. 144. Ibid. vol. 72 p. 556. ON AURIFEROUS GLASS. assigned them I)y the original observer. The glass upon which the experiments of Rose were performed was prepared from a mixture of 46 lbs. of quartz 12 , borax 12 , saltpetre 1 , minium 1 , white arsenic which was moistened with the solution of 8 ducats in aqua regia and then melted. The composition of glass from this mixture only differed from that used by Splittgerber in containing no oxide of tin.The glass acquired a ruby-red colour when heated in the air or in an atmosphere of oxygen carbonic acid or even of hydrogen gas in which latter case the red tint was not so intense and the glass assumed a greyish hue evidently from the reduction of the oxide of lead. When exposed to a somewhat higher temperature produced by trans-mitting a current of oxygen gas through a spirit-lamp the glass became soft and acquired a liver colour. The flame of the oxy-hydrogen blow- pipe fused the red glass into colourless beads which could not however be re-converted into ruby glass by heat as was the case in Splittgerber’s experiments. Splittgerber expressed as his opinion with reference to the cause of these changes of colour without attaching much importance to it that the gold was contained in the colourless glass in the state of a silicate of the peroxide that the peroxide was reduced by the gentle heat to the state of oxide and this it was that exerted the powerful colouring action even when present in very minute quantity.Rose contends that although the compounds of the oxide of gold are of a more stable character than those of the peroxide yet it is highly improbable that a silicate of the peroxide should be reduced to the state of oxide by a lower degree of temperature than that at which it was formed and more particularly as this is found to occur in an atmosphere of oxygen gas. He is therefore led to infer that the colour is produced in the previously colourless glass by the separation at a low temperature of a portion of the oxide of gold which had been combined at the higher temperature in the form of a neutral or acid silicate.This opinion is borne out by the analogy presented by the oxides of copper. The ruby glass produced by means of the suboxide of copper is also colourless when first prepared and the colour is brought out by re-heating at a temperature below the softening point. That the glass does not become opaque by the separation of the oxide of gold isexplained by the minute quantity of the colouring oxide just as very small quantities of suspended sulphuret of iron or sulphuret of lead will colour a liquid green or brown respectively without impairing its transparency. The resolution of the red into a liver-coloured glass at a higher tempera- CHEMICAL EXAMINATION OF WINES ture which however is not sufficiently high to fuse the glass is obviously the result of reduction and this could not be effected even at the heat of fusion so long as the oxide of gold was in combination with silicic acid Chemical examination of some specimens of Wine from the Rhingau.*-Dr.Fresenius has examined four of the most highly prized varieties of wine from the Rhingau namely 1. Hattenheimer 2. Markobrunner 3. Steinberger and 4. Steinberger Auslese all of the vintage of 1846. The specimens of wine were prepared with the greatest care upon the plan of close fermentation. The examination commenced when they were four months old ; the three former were perfectly clear ;in the last fermen- tation had not entirely ceased.The investigation was undertaken for the purpose of determining the respective amounts of alcohol sugar free acid and water which they con- tained and the total quantity of extractive matters. 1. The alcohol was separated from the wine by distillation rectified over lime and its quantity determined by the sp. gr. of the distillate. 2. The sugar remaining in the residue from distillation was deter-mined after careful evaporation by the amount of carbonic acid which it evolved when mixed with a given quantity of yeast at a temperature between 20° and 25' C. (68' to 77' F.) in the apparatus of Will and Fresenius . 3. The total amount of free acid (tartaric malic &c.) was estimated by the quantity of bicarbonate of soda decomposed by a weighed quantity of the evaporated wine in the same apparatus.4. Careful evaporation of weighed quantities of wine and complete dessication of the residue at 100' C. (212' F.) gave the total amount of extractive matters. The following were the quantities obtained from 100 parts I. 11. 111. IV. Water . . . . . . . 85.079 83.681 84.384 78.275 Total extractive matter . . 4.214 5.178 5.559 10.555 Anhydrous grape sugar . . 3'580 4.521 4.491 8.628 Free acid expressed as free tartaric acid (T,HO) . 0.556 0.533 0.497 0.424 Alcohol . . . . . . . 10.707 11.141 10.067 10.170 It may be deduced from these numbers that the juice of the grape previous to fermentation contained the following quantities of sugar in 100 parts I.11. 111. IV. Sugar anhydrous C12H1201 . 24.52 26.25 24.12 28.46 Sugar crystallized calculated (C12H,,0,+2 Aq.) . . . 26.97 28.87 26.53 31.31 * Ann. der Chem. und Pharm. LXIII p. 384. ACTION OF CHLORINE ON DUTCH LIQUID. The value set upon these wines by judges increases with the order of the specimens from I. to IV. and the following conclusions may conse- quently be drawn from the results 1. The good quality of wine is in proportion a) to the small amount of free acid ; b) to the actual quantity of sugar ; c) to the amount of extractive matter which it contains. 2. The absolute amount of alcohol in wines of similar character is not of the first moment with reference to their respective qualities.3. The specific gravity of wine is no criterion by which to estimate its quality. It appears also from the foregoing examples in which the amount of sugar varied considerably in the juice whilst the alcohol was nearly the same in all the wines that the temperature at which the fermentation is carried on exerts the greatest influence upon the amount of alcohol pro- duced. When the largest quantity of alcohol has been produced from sugar corresponding with the temperature all further action of the ferment upon the sugar is prevented by the presence of the alcohol. If the tempera- ture is again raised more alcohol is produced in proportion. The after fermentation which frequently occurs in old wine is then accounted for by the author upon the supposition that the original amount of alcohol diminishes by keeping with the formation of different compounds of ethyl (tartaric and malic ether) and thus so long as sugar and ferment exist in the wine fermentation must proceed until the amount of alcohol sets a limit to its further production.On a new member of the series resulting from the action of Chlorine upon Dutch liquid.*-M. Isidore Pierre by causing chlorine to act upon a considerable quantity of Dutch liquid has succeeded in preparing the com- pound C4 H C1 which was still wanting to complete the series resulting from the action of these bodies upon each other in order to render it perfectly analogous to that obtained by Regnault from chloride of ethyl. This substance which to use the nomenclature of M.Regnault may be called trichlorinated Dutch liquid is obtained by a series of successive distillations of the product which passes over between the temperatures of 145' and 160' C. (293'-320' I?.) until the boiling point remains constant. The compound C H C1 is liquid at a temperature of 0' (32' F.); it boils at 153O.8 C. (309' F.) under a pressure of 763""*35 30.05 inches; its specific gravity at 0' C. (32' F.) is 1.66267. It pos-sesses an agreeable odour and a sweet but hot taste although in a less degree than Dutch liquid. The combining proportion of this compound in the form of vapour is 4 volumes and the specific gravity of the vapour * Annales de Cirinaie et de Physique XXI 439. ON THE FATTY ACIDS IN CASTOR OIL.is 7.101 by experiment it was found at 7.087. With a solution of potash in alcohol it yields protochloride of carbon (C CI,) and chloride of potassium. On the Fatty Acids of Castor Oil.*-Saalmuller has re-examined the fatty acids of castor oil under the superintendence of Dr. Will and is led to believe from his experiments which however are not perfectly con- clusive that the margaritic acid discovered by Bussy and Lecanu in that oil is probably stearic acid and that the higher fusing point (130' C. 266O F.) and the difference of composition assigned it by the latter chemists were probably occasioned by a portion of potash still remain- ing in combination with the specimens which they examined. That portion of the fatty acids which on the separation of the margaritic acid remains fluid at ordinary temperatures and was considered by Bussy and Lecanu as a mixture of ricinic with elaiodic acids Saalmhller was unable to separate into two distinct acids and he therefore considers it a simple acid and has assigned it the name ricinolic acid proposed in the first instance for elaiodic acid.This acid is prepared of constant compo- sition from the residue obtained by the process proposed by Gottlieb for the purification of oleic acid after the separation of the margaritic acid. The fatty residue is saponified with an excess of ammonia and the soap is decomposed with chloride of barium. The precipitated salt of barytes is washed with water and dried at the temperature of the air upon a slab of gypsum; it is then redissolved in alcohol from which it crystallizes on cooling and is rendered perfectly pure by repeated recrystallization from the same solvent.The salt is decomposed by hydrochloric acid and the acid is washed with water containing hydrochloric acid as long as any trace of baryta is taken up. The last portions of baryta are difficult of removal and alcohol must not be applied during the decomposition as it is subsequently nearly impossible to separate it completely from the acid. The pure acid is of a light wine-yellow colour and possesses at ordinary temperatures the consistence of syrup; it is colourless in thin layers and has a powerfully acid taste but no smell. Its specific gravity is 0.94 at 15O C. (590 F.) and it solidifies at a temperature of 60-100 C.(430-500 F.) as a mass of rounded nodules. It is miscible in all propor-tions with alcohol and ether. The alcoholic solution has an acid re-action and decomposes the carbonates of the alkalies with effervescence. The acid absorbs no oxygen from the atmosphere. It is decomposed when submitted to dry distillation but like the oil itself affords no indications of the production of sebacic acid. The hydrated acid was analyzed by means of oxide of copper and an excess of oxygen gas was necessary to effect complete combustion. The result was * Ann. der Chem. und Pharm. LXIV 108. 9N CAR 13 0T HIA L D1K E . 81 I. 11. III. Calculated. Atoms. Carbon . . 73-06 73.16 73.45 '73.08 38 228 Hydrogen . 11.68 11.59 11.51 11.54 36 36 Oxygen .. 15.26 15.25 15.04 15.38 6 48- 100.00 100~00 100*00 100~00 312 Hydrated ricinolic acid C, H,O +HO. The direct determination of the water in the hydrated acid yielded in two experiments 3.6 per cent. and 2.9 per cent. mean 3.25 water per cent. These results in conjunction with the atomic weight deduced from the analysis of the barytic salt leave no doubt concerning the composition of ricinolic acid which is represented by the formula C,H,,O,. The salts of ricinolic acid with the alkaline earths and the heavy metallic oxides are nearly all crystallizable ; they are all soluble in alcohol and some are also soluble in ether. The salts do not alter by keeping ; and like the acid absorb no oxygen from the air. In addition to the salt of barytes the salts formed with strontian with lime magnesia oxide of zinc oxide of lead oxide of silver and with oxide of ethyl have been examined and described by the author.The assertion c.f Boudet that sulphurous acid is capable of converting the fatty oils and amongst these castor oil into solid bodies in the same manner as is effected by nitrous acid is not confirmed by the author who was unable to produce any change in the nature or form of castor oil by the action of that gas. The gas was absorbed by the oil but again com- pletely removed by water. On Carbot~iaZdine.*-Messrs. Red tenbacher and Liebig have examined the action of sulphide of carbon upon ammonia-aldehyde. When pure ammonia-aldehyde is dissolved in alcohol and sulphide of carbon is added to the liquid the alkaline reaction of the latter is entirely destroyed the mixture becomes warm and deposits in a few moments brilliant white crystals which when washed with alcohol are pure carbothialdine.This substance is insoluble in water and in cold ether difficultly soluble in cold but readily soluble in boiling alcohol from which it crystallizes unchanged ;it is an organic base of the weakest kind containing sulphur but no oxygen. Carbothialdine forms a colourless solution with hydrochloric acid from which ammonia and the fixed alkalies precipitate unaltered carbothialdine ; but when this fluid is allowed to stand at rest for some time it is converted into a yellowish-white gelatinous mass and this is insoluble in water ;boiled with an excess of hydrochloric acid it is decomposed into sal ammoniac sulphide of carbon and aldehyde.When oxalic acid and subsequently ether are added to a hot solution *Aw.dw Chem. wad Pharm. LXV p. 43. VOL. 1. NO. I. G ON THE PRODUCTS OF THE of carbothialdine in alcohol delicate white hair-like needles of oxalate of ammonia are immediately deposited. A solution of silver produces a greenish-black precipitate in an alcoholic solution of carbothialdine which becomes rapidly black and is converted into sulphuret of silver. Corrosive sublimate causes a thick curdy yrecipi- tate in the solution of a yellowish-white colour and copper salts afford a greenish precipitate. The analyses of this substance lead to the following composition By experiment.5 eq. Carbon . . 30 37.04 36.87 Nitrogen 14 17.28 17-16 Hydrogen . 5 6.17 6.39 Sulphur . . 32 39.5 1 39-64 81 100. 100.06 The formation of carbothialdine is therefore explained by the separation of 2 equivs. of water from the sum of the elements of ammonia-aldehyde and of sulphide of carbon 1 equiv. Ammonia-aldehyde C N H 0 1 , Bisulphide of carbon C s2 C,NH O,S 2 , Water deducted H2 02 leave C6 N H S,. =Carbothialdine On some volatile products of the decomposition of albumen fibrin casein and gelatine by means of peroxide of manganese or by chromic acid and sulphuric acid.*-An important investigation into the nature of the products of oxida- tion of casein gelatine and the constituents of the blood fibrin and albumen has been carried out by Guckelberger with a view to throw some light on the so-called proteine compounds the composition of which has given rise of late to so much discussion.It is now generally admitted that albumen fibrin and casein do not part with the whole of their sulphur when submitted to the action of potash ; that in fact protein does not exist ; and Guckelberger deduces from this fact that the sulphur is contained in these bodies in two distinct forms of combination the one of which is decomposed with the loss of its sulphur by potash whilst the other is not ; that the substances themselves are not simple compounds of a single group of atoms or radical (protein) with sulphur but are made up of several groups which must be considered as proximate constituents of the compounds.Elementary analysis is not calculated to throw light upon the constitu- tion of such complex combinations as those here under consideration and * Ann. der Chm. und Pharm. LXIV. p. 39. OYlDATlON OF CASEIN PTBRIN AND GELATlNE. recourse must be had to the study of the products of their decomposition a method which has been of such signal service in promoting our know- ledge of other less complex substances as may be instanced in the cases of amygdalin salicin &c. I. Oxidation of casein by peroxide of manganese and sulphuric acid.- Purified casein was subjected to the action of peroxide of manganese and sulphuric acid in a large glass retort ; the proportions employed were ; 1 part dried casein 3 parts peroxide of manganese 4; , oil of vitriol 30 , water The sulphuric acid was first diluted with twice its weight of water and when the mixture had cooled down to a temperature between 400 and 50' C.(1040-1220 F.) finely powdered casein was gradually added with constant agitation ; it dissolved in the course of a few hours and coloured the acid of a more or less intense brown or violet hue according to the temperature. It was found advantageous to allow the mixture to stand until the following day when it was diluted with the half of the requisite qualrtity of water and introduced into the dietillatory vessel with the man- ganese. After complete mixture had been effected the remainder of the water was added and the distillation commenced.The retort must be large as much froth is thrown up and every possible means should be employed to secure perfect condensation as even at a temperature of -1.5' (+ 5' F.) considerable loss is unavoidable. The distillate possesses at first a peculiar and very acid smell inciting cough and tears; when the half of the fluid has been distilled this diminishes and is at length replaced by an odour resembling that of oil of bitter almonds ; a very small quantity of white flocculent matter is seen swimming in the nearly clear colourless fluid which latter exhibits a powerfully acid reaction. No trace of hydrocyanic acid could be detected in the distillate upon repeated trials. To remove the acids the liquid was shaken with chalk and ahout the half of the liquid was distilled over.This product was perfectly neutral but speedily became acid by exposure to the air. With ammonia and nitrate of silver it exhibited the properties of aldehyde. Concentrnted by repeated rectification a milky liquid was at length obtained upon which a layer of yellow oil floated and this possessed the acrid smell mentioned above in the highest degree. The milky solution became clear after some time and deposited in the cold a few drops of heavy oil which was converted by exposure into a crystalline mass. a. Non-acid products.-The yellow light oil was carefully distilled from a water-bath and in order to separate the more volatile from the less volatile constituents the flask containing it was connected with a long tube bent at an angle of 120'.It began to boil at a temperature of G2 ON THE PRODUCTS OF THE 40' C. (104O F.) and a perfectly colourless very mobile liquid (I.) distilled over miscible in all proportions with water and possessing the entire choking properties of the oil. When the temperature of the water-bath had risen to 50' C. (122O F.) and the boiling had ceased the receiver was changed; between 65O and 70° C* (149°-150u F.) ebullition began again and the first portion which passed off possessed the same choking smell as the former product ; at a later period however an agreeable etherial odour became perceptible and the product was then collected in a separate vessel (11,). In the mean time the fluid in the flask had undergone an important change.The previously homogeneous liquid had separated into two which were no longer miscible with each other; the one of these com-prising about 30 per cent. of the original quantity was water and upon this the other floated in the form of a yellow oil. At the boiling tempe- rature of water a colourless oil passed over which was very little soluble in water floated on the surface and smelt not unlike acetone (HI). When no further distillate was obtained at the temperature of the water- bath the flask was exposed to an open fire and the long bent tube exchanged for an ordinary short connecting tube. The product from this operation still swam at first upon the surface of the water but a smell of bitter-almond oil becitme more and more perceptible and the receivers were changed until the globules of oil which passed over subsided to the bottom of the accompanying water (IV).The product (I) of distillation at a temperature between 40°or 50" C. (104°-1220 F.) was found to be identical both in composition and properties with aldehyde ; its formula was therefore C H 0,. The second product (11) which passed over at a temperature between 55' and 70" C. (131"-158' F.) was a colourless liquid with an agreeable etherial smell of 0.79 sp. gr. at 3-15' C. (59' F) miscible in all propor- tions with water alcohol and ether.' It was perfectly neutral to test- paper but became slowly acid when exposed to the air and more quickly under the action of platinum-black ; caustic potash produced no visible change in the liquid and no metallic mirror could be obtained from it with nitrate of silver.This latter reaction proved the entire absence of the aldehyde of acetic acid. The composition of this body deduced from experiment is best represented by the formula C H30. It is therefore isomeric with acetone; but the author is disposed to consider it the aldehyde of metacetonic acid or perhaps the hydrate of metacetone. If one equivalent of the substance is represented by 4 vol. of vapour the weight of its vapour will be = 2.0105 and its formula C H 0,. 6 vol Carbon . . 4.9920 12 , Hydrogen . 0.8316 2 , Oxygen . . 2.2186 8.3422 --2.0105 4 OXIDATION OF CASEIN FIBRIN AND GELATINE. The experimental result of the determination of the weight of the vapour gave the number 2.169.The third product of distillation (HI) is distinguished from the former two by its slight solubility in water; it boils between 68O and 73O C. (155°-1630 F.). It is a clear liquid with an etherial but penetrating smell ; its taste is burning and not unlike that of aldehyde. The specific gravity at + 15OC. (59OF.) was 0.8. It is soluble in all proportions in alcohol and ether is neutral to test-paper but becomes rapidly acid by exposure to the air. It exhibits the same reaction with alkalies and ammonia as aldehyde and produces a brilliant coating of metallic silver with a silver solution. Sulphuric acid affords a deep blood-red colour with this substance hut no precipitation of carbon is apparent.The analyses with oxide of copper led to the formula C H 0 but the constitution of the compound which it forms with ammonia as well as that of the acid into which it is resolved by oxidation clearly prove that its equivalent must be double that indicated by the formula. The amount of carbon to that of nitrogen in the ammonia compound being in the ratio of 8 1. The ammoniacal compound is very little soluble in water and thus affords a ready means of separating this substance from the other products of distillation. On mixing dilute ammonia with the distillate a milky liquid results which in a short time deposits sharp rhombic octohedral 'crystals and then becomes clear. The crystals are soluble in alcohol and ether from which they may be again separated by evaporation in a tabular form ; when once dried they are apparently inalterable in the air but in the moist state or in contact with moist air they are transformed into a brown mass and acquire an empyreumatic smell.Slowly heated the crystals melt and volatilize in the form of drops of liquid which drops solidify on cooling ; rapidly heated they are decomposed and the smell of ammonia becomes perceptible. Potash evolves no ammo~a from the crystals in the cold and acids separate the original body unchanged Analysis yielded numbers corresponding to the formula C,H21N0,, which from the numerous analogies which this body presents with ammonia-aldehyde is viewed as the ammonia compound of butyric aldehyde with water of crystallization and is then represented by the rational formula C,H,O,HO+ NH,+ 10 Aq.The composition of the liquid body itself thus corresponds with the rational formula C,H,O HO which represents butyric aldehyde and this view of its constitution is verified by the actual production of butyric acid from it by the oxygen of the air or from oxide of silver. Compared with butyral obta,ined by Chancel by the distillation of butyrate of lime and which has the same composition agreat resemblance may be observed in the properties af the two bodies but the boiling points vary and butyral does not combine with ammonia nor has butyric acid yet been directly prepared from it by oxidation. The author observed that sulphuretted hydrogen passed through an alcoholic solution of the ammoniacal compound gave rise to a disagreeable ON THE PKODUCTS OF THE empyreumatic odour resembling that of thialdine and that ether dissolved from the product an oily body containing sulphur which produced a crystalline substance with hydrochloric acid.The last product (IV) distilled over an open fire was heavier than water it smelt like oil of bitter almonds and became solid when exposed to the air. It was purified by distillation from chloride of calcium and proved to be pure oil of bitter almonds. The solid substance into which it is converted by exposure is benzoic acid. b. Acid products.-The concentrated solution containing the acid pro- ducts which had been neutralized with chalk was treated with carbonate of soda and the filtrate from the precipitate of carbonate of lime was evapo- rated in a water-bath to the consistence of syrup when a large crop of crys-tals separated on cooling which were found to consist of acetate of soda Further concentration of the mother liquor yielded an additional crop of crystals of the same salt mixed with other tabular crystals which could not be separated by water.Alcohol however left the latter undissolved and analysis proved them to be formiate of soda. On re-dissolving this salt in water and evaporating at the ordinary temperature of the room it was observed that a salt of formic acid with soda containing 6 equivs. of water of crystallization was deposited in the form of fine silky needles which deliquesced in the air and effloresced over sulphuric acid.Ordinary formiate of soda has only 3 equivs. of water. The residue after the separation of the acetate and formiate of soda no longer deposited crystals and it was treated with twice its weight of sulphuric acid diluted with 2 parts of water. Above the crystals of sulphate of soda which separated after the mixture had remained at rest for a day was a layer of an aqueous liquid and upon this floated a brown coloured oil. The latter was carefully removed with a pipette and washed several times with an equal volume of water to separate the more soluble butyric from valerianic acid the presence of which in the mixture was indicated by the smell. 'She water in which the oil had been washed was mixed with the aqueous liquid and the whole wits then saturated with carbonate of soda and evaporated to dryness in a water-bath.The dry sgline mass treated with sulphuric acid of the above-named strength yielded a layer of nearly colourless oil which commenced boiling at a few degrees above 100' C. (212' F.) but no stability was observed in the boiling point until the thermometer indicated 130' C. (266' F.). The liquid which passed over between that temperature and 140' C. (284' F.) was collected apart and lastly a small quantity of an acid was obtained that boiled between 160' and 16~5~ C. (310"-329' F.). The distillate collected between 130" and 140' C. (266" and 284' F.) might from its smell have been mistaken for acetic acid it was soluble in water although not in all proportions ; neutraiized with ammonia it produced a crystalline precipitate with nitrate of silver which dissolved in boiling water the greater portioll hou ever undergsirig decomposition ..OXIDATION OF CASEIN FIBRIN AND GELBTlME. A crystalline salt was deposited on cooling the aqueous solution and this was but slightly affected by light; exposed to the heat of a water-bath however the crystals became blackened and fused at a higher temperature with the evolution of acid vapours. The determination of the amount of silver in this compound and the fact that the salt affords a double compound with acetate of silver together with the analysis of this double compound leave no doubt that the acid in question is the metacetonic acid discovered by Gottlieb the composition of which is expressed by the formula C,H,O,.The silver salt has the formula C,H,O, Ago and the double salt with acet%te of silver the formula C4H30,,Ago +C6H503, Ago. The analysis of the last portion of acid obtained at a temperature between 160' and 165' C. (310°-3290 F.) and that of its silver salt proved the identity of this product with butyric acid C,H,03 HO. The brown-coloured oily acid separated by the pipette from the aqueous solution of the above acids and which smelt of valerianic acid was also distilled ; a nearly colourless liquid passed into the receiver possessing the nauseous smell of the volatile acids of fat and towards the end of the process a white crystalline sublimate was observed which when dissolved out with ether after the last portions had been carbonized in the retort proved to be benzoic acid.The colourless oily distillate was mixed with the residue after the separation of the metacetonic and butyric acids and saturated with hydrate of barytes. The neutral solution evaporated over sulphuric acid yielded salts of three different acids. The least soluble of these was cayroate of barytes the second valerianate of barytes and the most soluble was butyrate of barytes ; there were also indications of the presence of a fourth salt which however could not be more minutely examined. 11. Products of the action. of chromic acid upon casein.-One part of casein was distilled with 2 parts of bichromate of potash 3 parts of sulphuric acid and 30 parts of water. The product in this case had a powerful smell of hydrocyanic acid which was not entirely removed by agitating the distillate with oxide of mercury.No trace of aldehyde could be found amongst the products. After the removal of the hydrocpanic acid by oxide of mercury the liquid was neutralized with chalk and again rectified a turbid aqueous solution was at last obtained upon which a layer of colour- less oil floated ; the aqueous liquid afforded on re-distillation an additional quantity of the colourless oil and with it the last relics of the smell of hydrocyanic acid disappeared. The small quantity of residual fluid was milky and deposited in the cold a colourless oil which had a powerful smell of oil of cinnamon and a burning aromatic taste. a. Oily non-acid products.-The heavy oil could not be obtained in sufficient quantity for minute investigation it appears to bc somewhat heavier than oil of bitter almonds does not become solid on exposure to the air and cannot be distinguished by the smell or taste from oil of cinnamon.ON THE PRODUCTS OF THE The light oily liquid afforded two substances the one of which con- tained no nitrogen and was found identical with that produced by oxida- tion with manganese and has been represented by the formula C,H,O,. The other containing nitrogen passed over at a temperature between 120° and 140° C. (248O-284O F.) and by rejecting on re-distillation the first and last portions acquired a steady boiling point between 125' and 12S0 C. (257O-263O F.) its specific gravity was 0.813 at i 15' C.(5g9F.) its smell resembled that of oil of bitter almonds its taste was bitter aromatic and burning ; it was perfectly colourless mobile soluble in about four times its weight of water miscible in *all proportions with alcohol and ether and burnt with a white flame without smoke. When heated with a solution of potash this substance evolved ammonia and the alkaline liquid then saturated with sulphuric acid threw up globules of oil which when re-distilled exhibited a strong acid reaction and possessed a smell resembling that of valerianic acid. All these properties indicated a striking similarity between this substance and the valeronitrile discovered by Schlieper among the products of the oxidation of gelatine by chromic acid.The analysis of the body and the determination of the specific gravity of its vapour established its identity with valeronitrile and this indentity was still further confirmed by the direct production of valerianic acid from it by the action of acids. The formula for valeronitrile is C,,H,N. The fluid residue in the retort after the separation of valeronitrile which boiled at a temperature above 128' C. (263O F.) was evaporated and left a very small quantity of a substance that had no smell of cinnamon but became solid on exposure to the air. This from its physical properties was recognized as benzoic acid and indicated the presence of oil of bitter almonds amongst the products of oxidation. The valeracetonitrile of Schlieper could not be detected in the liquid which distilled over between the temperatures of 68O and 70°C.(155'-158' F.) although its existence appeared probable. h. Acids.-Hydrocyanic acid has already been noticed as one of the chief products of this process of oxidation and in removing this acid by oxide of mercury the reduction of a small quantity of the latter indicated the presence of formic acid. The other acids were detected nearly in the manner already described in the former process when manganese was employed. Benzoic acid was found in considerable quantity also acetic valerianic and butyric acids. The valerianic acid was contaminated with a small quantity of an acid with a higher equivalent and there were symptoms of the presence of metacetonic acid with the butyric which however could not be decidedly proved.The series of products obtained by the oxidation of casein with these two different agents are arranged in the following order for the sake of easy comparison :- OXIDATION 8P CASEIN FIBRIN AND GELATINE. With peroxide of manganese. With chromic acid. Aldehyde of acetic acid . . C,H,O HO Aldehyde of metacetonic , ,,metacetonic acid? C,H,O HO acid? . . . . . . C6H,0 HO , , butyric acid . C,H70 HO Oil of bitter almonds . . C14H502,H Oil of bitter almonds . C14H502,H small quantity. Formic acid . . . . . C,H 0,,HO Formic acid . . . . C,H O,,HOsmall quantity. Acetic acid . . . . . C.&O,,HO Acetic acid . . . . . C,H3O3,HO Metacetonic acid . . . . C6H503,H0 Metacetonic acid .. . ? Butyric acid . . . . . C,H,O,,HO Butyric acid . . . . C,H,O,,HO HO small Valerianic acid . . . . C,,H,O, €I0 Valerianic acid . . . CIOHgOI quantity. Caproic acid . . . . . C12H1103,H0 Benzoic acid with traces of caproic acid . . . ? Benzoic acid . . . . . C&,O3,HO Benzoic acid . . . . C14H503,H0 Hydrocyanic acid . . . C,NH Valeronitrile . . . . CloHgN Heavy oil with the odour of oil of cinnamon. . ? Hydrocyanic acid and valeronitrile may be viewed as the ammonia salts of formic and valerianic acids from which the elements of 3 equivs. of water have separated by the action of a high temperature. The apparent discrepancy in the nature of the products from the two agents employed is thus explained and the reaction observed with alkalies upon the residuum of distillation fully bears out this view of the subject.When the residue from the distillation of casein with peroxide of manganese and sulphuric acid is saturated with lime ammonia is evolved in such quantity as might lead to the supposition that the whole of the nitrogen in the casein is retained as ammonia in combination with sulphuric acid. The residue from the distillation with bichromate of potash and sulphuric acid on the other hand evolves hardly a trace of ammonia when saturated with lime. In the former process the sulphuric acid was so proportioned to the peroxide of manganese that about + of the acid would remain free in the liquid and if the action of sulphuric acid and oxygen upon casein is of such a character as to give rise to the formation of valerianate and formiate of ammonia the ammonia would necessarily remain in combination with the sulphuric acid and the acids would distil over.The proportion of sulphuric acid to that of bichromate of potash in the latter process was such as would just about suffice to saturate the potash and oxide of chromium. Valerianic and formic acids could therefore under these circumstances combine with ammonia and these acids would only be found in the distillate when the ammonia present was insufficient to saturate them or when the sulphuric acid was in excess. It was remarked by Schlieper in acting upon gelatine and confirmed by the author with casein that valeronitrile and hydrocyanic acid were only obtained when no excess of sulphuric acid had been used in the process.ON THE PRODUCTS OF THE The observation of Dobereiner that formiate of ammonia is converted into hydrocyanic acid and water at a temperature of 1800 C. (3560 F.) and Fehling’s experiment in which benzoate of ammonia is converted into benzonitrile and water at a high temperature are conclusive evidence as regards the production of hydrocyanic acid and valeronitrile from the formiate and valerianate of ammonia respectively. The temperature employed in the decomposition with sulphuric acid and bichromate of potash was sufficiently high to effect this change and it would therefore appear that the production of valeronitrile and hydrocyanic acid is due to the relation between the quantities of sulphuric acid and bichromate of potash aided by a high temperature and not to the nature of the oxidizing agents.The proportions of peroxide of manganese and bichromate of potash used in the experiments with an equal weight of casein were such as would afford a nearly equal amount of oxygen but the results of the action prove that there was an excess in the case of the bichromate or the aldehydes of acetic and butyric acids would also have been found amongst the products. It is not likely that valeronitrile will be obtained when manganese is employed as an oxidizing agent for its use implies the presence of an excess of sulphuric acid. Gelatine fibrin and albumen were also treated with peroxide of manga- nese and sulphuric acid in the manner already described for casein and all yielded aldehyde.In the case of gelatine the body C H 0 (aldehyde of metacetonic acid ?)was not obtained and only small quantities of it were discovered in the products from fibrin and albumen. The aldehyde of butyric acid was produced in greatest quantity from fibrin and a compara- tively small quantity only from the other two substances. All the three bodies yielded large quantities of acetic and formic acids. Fibrin afforded the most butyric and gelatine the most valerianic acid. All three yielded small quantities of benzoic acid. From fibrin metacetonic acid was distinctly produced. The presence of caproic acid in the products of distillation was rendered highly probable by the sweaty odour of the valerianic acid and by the slight excess of silver obtained in the analysis of the salts of that acid.The same bodies treated with chromic acid afforded the same products as were obtained by acting upon casein ; much hydrocyanic acid was gene- rated and also the peculiar oil smelling like oil of cinnamon although in small quantity. The benzoic and acetic acids were the most abundant acid products Fibrin yielded more butyric acid than albumen or even than casein. This most elaborate series of experiments establishes the important fact that the products of oxidation of the bodies in question are constant and not dependant upon the nature of the oxidizing agent. A certain amount of oxygen is the only indispensable condition to the completion of this interchange of the elements ; and it appears to be without influence upon the nature of the products whether the oxygen is afforded them in a shorter OXIDATION OF CASEIN FIBRIN AND GELATISE.or longer space of time. It is not assumed that the bodies enumerated are the direct products of oxidation of casein fibrin &c. but they result no doubt from the action of oxygen upon certain groups of atoms which are supposed to form the proximate constituents of this whole class of substances. If the four substances under examination are compared with reference to the amount of nitrogen which they respectively contain fibrin appears as an intermediate or transition member of the series in passing from casein and albumen on the one hand to gelatine on the other.If the respective quantities of acetic acid and aldehyde yielded by oxida- tion are made the point of comparison beginning with those which afford the least Casein and albumen again take the lead fibrin intervenes and gelatine affords those products in greatest quantity. Formic acid was also obtained most abundantly from gelatine ; and it would therefore appear as if aldehyde acetic and formic acids were derivatives of the same group of atoms The order of the series is reversed when the quantities of benzoic acid and oil of bitter almonds produced from these substances are com- pared. They then range in the following order gelatine albumen fibrin casein. Fibrin is singular as the source of the largest quantity of butyric acid and this was obtained in minimum from gelatine.Gelatine on the contrary yielded the largest proportion of valerianic acid and casein and albumen the least. Thus in three cases fibrin assumes a position inter- mediate between casein and albumen on the one side and gelatine on the other ; and it only alters its relative position when viewed with reference to the amount of butyric acid which was obtained from it in the largest proportion. The production of aldehyde from the constituents of the Llood casein and gelatine render it probable in the author’s opinion that this body should also be obtained by the restricted oxidation of fat ; ang the proba- bility is strengthened by the fact that aldehyde is actually produced when milk-sugar is distilled with bichromate of potash and sulphuric acid and also (as recorded in an experiment of Engelliardt) by the dry distillation of lactate of copper.Bearing this in mind there appears ground for assuming some non-nitrogenous group of elements as one of the proximate constituents of the bodies under examination (e.g. milk-sugar or fat) and that this under the influence of oxygen gives rise to aldehyde. Further when the production of albumen fibrin and gelatine is con- stantly observed during the growth of a young animal from milk-sugar casein some fat and inorganic substances which constitute the whole of its food we are almost led to believe that these bodies must be derived from casein by the addition of the elements of milk-sugar ; or as this does not enter into the composition of blood by the addition of fat or lactic acid into which milk-sugar is easily convertible.Judging from the quantities of aldehyde obtained from the four substances albumen would be the first product from casein fibrin would then follow and the last CHE&IICA L EXARL IN A T10N would be gelatine. It is not supposed that these substances are the direct product of the union of casein with fat &c. as in that case the amount of nitrogen in fibrin must be less than in albumen or casein and this is not the fact. But again this may be explained by the assumption that on the addition of the elements of fat to those of casein another group of elements and that group namely which gives rise to the formation of benzoid acid and oil of bitter almonds simultaneously separates from combination.Casein afforded as stated above the largest proportion of oil of bitter almonds and gelatine the least. The uniformity in the proportions of carbon and hydrogen in casein albumen and fibrin and their slight variation in gelatine would thus be accounted for and at the same time the large amount of nitrogen in fibrin and gelatine. ChenzicaE Ezamination of the Bile of the Ox.*-The account of an elabo- rate investigation of the bile of the pig was puldished a short time since by Drs. Strecker and Grundelach in which the chief ingredient of that secretion was represented as the soda salt of a new acid termed by the authors hyocholinic acid. Dr. Strecker has since extended his researches to the bile of the ox and has arrived at very different conclusions respect- ing its nature to those deduced from the experiments of former analysts.The first experiments were made with ox-bile purified and crystallized in the manner described by Platner and subsequently by Verdeil; but notwithstanding the great uniformity in the amounts of carbon hydrogen and sulphur obtained from different analyses the substance when examined under the microscope was found to consist obviously of a mixture of crystals with an amorphous body and all further analytical investigation of it was consequently abandoned. The same crystallized bile which still contained t:aces of alcohol and ether was then treated with water and sulphuric acid until the latter produced a slight turbidity ; in the course of a few hours needles grouped in a stellar-form appeared and continued to increase in quantity until after twelve hours the whole fluid was intersected by them and converted into a white mass which when thrown upon a filter and washed with cold water was very much diminished in bulk.These crystals were boiled in water when the greater portion dissolved and was again deposited on cooling. The soluble portion possessed all the pro- perties of Gmelin’s cholic acid ; 1000 parts of cold water dissolved 3.3 parts of the acid and 8.3 parts were taken up by the same quantity of boiling water. Under the microscope the crystals appear to consist of exceedingly minute needles which dry up on the sides of the paper filter and line it with a thin silky layer.The cold aqueous solution has a sweet and some- what bitter taste reddens litmus-paper and exhibits no reaction with acids with acetate of lead with bichloride of mercury or with nitrate of silver ;basic acetate of lead produces a slight precipitate with the acid. The acid is very soluble in alcohol which when evaporated from a water- * Ann. der Chem. und Pharm.. LXV p. 1. OF THE BILE OF THE OX. bath leaves it as a syrupy or resinous mass and this as was observed by Platner cannot be re-converted entirely into the crystalline form Spon-taneous evaporation of the alcohol from a watch-glass leaves the acid in the form of resinous rings which are converted by a few drops of water into groups of needles; when water is added to the alcoholic solution until a troubled appearance is produced and the mixture is allowed to stand annular crystals appear in the course of twelve hours and the liquid becomes perfectly clear.The acid is very little soluble in ether but a considerable quantity of ether is required to precipitate it from an alcoholic solution. Ether containing a little alcohol dissolves it more freely and crystals are formed by the spontaneous evaporation of the solvent. Con-centrated cold sulpliuric acid dissolves the acid readily as do also hydro-chloric and acetic acids and from the latter it can again be obtained in crystals. The solutions of cholic acid in concentrated mineral acids are rendered turbid by heat and oily drops quickly subside. Aqueous solutions of ammonia potash and soda dissolve cholic acid in large quantity as does also water of barytes.On the addition of acids to these solutions a resinous precipitate is formed which resolves itself on standing into crystals resembling wavellite in form. Ether facilitates this assumption of the crystalline form. The neutral salts of the acid exhibit the following reactions with salts of the metallic oxides. Lime barytes strontian and magnesia cause no precipitate in the aqueous solution of the acid; a flocculent precipitate is caused by acetate of lead and subsequently a fresh precipitate is produced by the basic acetate but in very much less abundance. The fluid filtered from the latter contains a little oleic acid. Salts of copper produce blueish-white and the chlorides of iron yellow flakes in the solution which are readily soluble in alcohol; nitrate of silver produces a voluminous gelatinous precipitate in a solution contain- ing 1 per cent of cliolic acid which is partially dissolved by heating the liquid and is again deposited in the cold.A slow process of cooling separates the salt in crystalline needles ; a more rapid process causes it to subside in the gelatinous form which however is rendered crystalline by a few drops of ether. The precipitate becomes blackened by exposure to light but little or not at all in the dark even when boiled. All the salts of cholic acid are soluble in alcohol. The substance that remained insoluble in boiling water exhibited under the microscope crystalline lamin= with a lustre of mother-of-pearl some of which were perfect six-sided tables.With the exception of their insolubility and crystalline form no difference could be observed in the physical or chemical properties of this body from cholic acid ; and indeed when dissolved in alcohol and the solution treated subsequently with water needle-like crystals of cholic acid separated. The author conse- quently considers this substance as a modification of cholic acid and assigns it the name of Paracholic acid. The salts of the two acids exhibit no reactions calculated to establish a distinction between them. Both CHEMICAL EXAM INA‘PI0N acids exhibit with sugar and sulphuric acid Pettenkofer’s test for bile in z1 very marked manner and Dr. Strecker finds that acetic acid may be con- veniently substituted for sugar in that reaction.It was still necessary to show that these acids were not products of decomposition caused by the process of evaporation or by the sulphuric acid used in preparing them and for this purpose the bile fresh from the gall-bladder was precipitated with neutral acetate of lead ; the precipitate was washed with cold water dissolved in a small quantity of boiling alcohol and sulphuretted hydrogen passed through the solution ; the alcoholic solu- tion from the sulphuret of lead was mixed with a large quantity of water previously used in washing the precipitate and when it began to pass milky through the filter the mixture was set aside and at the expiration of twelve hours a crystalline mass was obtained consisting of the two modifi- cations of the acid which could be separated in the manner already indicated.The author obtained in this manner 13.5 grms. (208.5 grains) of cholic and paracholic acids from the contents of ten gall-bladders. This latter process is preferable as absolute alcohol and ether are dispensed with in the preparation of the acids. It thus appears that cholic acid is contained ready formed in the bile and is chiefly contained in the precipi- tate produced by neutral acetate of lead. The precipitate subsequently obtained with basic acetate however also yielded a small quantity of cholic acid. The analysis of these acids and the atomic weight deduced from the soda and barytes salts led to the following composition in 100 parts Equivs.Calculated. Mean of experiments Carbon . . . 52 312 67.10 67*13 Hydrogen . . 43 43 9.25 9.31 Nitrogen . . . 1 14 3.01 2.98 Oxygen . . . 12 96 20.64 20.58 465 100- 100. The formula for the acid is consequently C, H, N 01,, whilst that con- tained in the salts is represented by C, H N Oil. Dr. Strecker prepared and analyzed cholate of soda which perfectly resembles crystallized bile in appearance ; it is however very difficultly obtained in a crystalline form. The analysis of this salt yielded Calculated. Mean of experiments. C 52 31264106 63-82 H 42 42 8.62 8.74 N1 14 2-87 0 11 88 18-09 NaO 1 31 6.36 6-17 The amounts of carbon and hydrogen in this salt are considerably higher than those found by Theper and Schlosser in purified bile the mean of their experiments yielding 57.7 per cent carbon and 8.3 per cent hydro- OF THE BILE OF THE OX.gen although the amounts of nitrogen and soda in both substances nearly coincided. There must consequently be another susbtance associated with cholate of soda in bile containing the whole of the sulphur more carbon and hydrogen than the cholate and which yields with acids a resin taurine and ammonia. This is no doubt choleate of soda. Cholate of ammonia (CS2H NO,, NH 0) is prepared by passing dry ammoniacal gas into an alcoholic solution of cholic acid as long as crys-talline needles are formed. Cholate of barytes (C52Hd2Nil Ba 0) is an amorphous substance obtained by evaporating a solution of cholic acid in water of barytes after the removal of the excess of barytes by carbonic acid.An account of the products of decomposition of cholic acid is promised by the author as the subject of a future paper; and it is merely stated at present that when cholic acid is boiled with concentrated acids it appears to yield nitrogenous acids with the loss of successive atoms of water. If ebullition is kept up for a length of time with hydrochloric acid the residue becomes insoluble in alcohol. Concentrated alkali gradually eliminates ammonia and a carbonaceous matter whilst a non-nitrogenous acid remains identical in composition with the cholic acid of Demarqay and which is called cholalic acid by the author. Dr. Strecker concludes the present investigation by stating the details of two experiments instituted for the purpose of ascertaining the quantity of the bilin of Berzelius contained in bile.The result yielded 2 per cent of bilin in dry bile which is conclusive evidence that this substance is not the chief ingredient of bile. The bilin obtained in the manner prescribed by Berzelius left an ash on incineration ; and it is the author’s opinion that if the mode of separating the whole of the bases in the preparation of bilin were absolutely accurate not a trace of this substance would be obtained. That portion of the bile which is not precipitated by salts of lead (the bilin of Berzelius) has been stated by Theyer and Schlosser to possess the same composition as the bile itself and Dr.Strecker has confirmed the opinion of the latter chemists. The bile cannot therefore be constituted of two distinct substances ; the one of which is precipitated by salts of lead and the other not. On the contrary the precipitate with neutral acetate of lead has been shown to be a lead-salt of an acid containing nitrogen but no sulphur whilst that produced by basic acetate of lead contains a portion of the former mixed with an acid containing sulphur and the bile is thus shown to be a mixture of the soda salts of these acids. If the presence of these two acids ready formed in the bile is admitted all the phenomena described with reference to this secretion are easily explained. The choleic acid containing sulphur is not precipitated by acids and its presence impedes the precipitation of cholic acid by weak or even by strong acids.But in the presence of much cholic acid some choleic is also precipitated by acids as the precipitate contains sulphur although in variable proportions and the tendency which these two acids ON THE BILE OF THE OX. exhibit to accompany each other in all cases has been erroneously con- sidered a ground for supposing them to be in conjugate combination although it is much more probable that the precipitates containing both acids are mere mechanical mixtures. The author opposes the view of Berzelius and Mulder that the acids of the bile are conjugate compounds of the acids with bilin by proving from Mulder’s analysis that the proportion of bilin in the salts of bilifellinic acid is never constant and that simple treatment with ether is sufticient to separate the supposed conjuncts.Additional evidence in favour of the acid character of the constituent containing the sulphur in bile is afforded by the same experiments of Mulder which show that the saturating power of the fellinic and cholinic acids is rather increased than diminished by the assumption of the bilin as a conjunct whilst all experience tends to prove that the saturating power of an acid is diminished when a conjunct enters into combination with it unless the conjunct itself possess an acid character; and even in that case the saturating power is not always augmented. It appears therefore that the bile of all animals contains a mixture of a nitrogenized acid freed from sulphur and an acid comprising both sulphur and nitrogen amongst its elements both of which are chiefly in combina- tion with soda.That the relative quantity of both substances is pretty much the same in the same class of animals as is evinced by the uniform results obtained from the bile of the ox but varies exceedingly in different classes of animals ; this is proved by the variable quantities of sulphur obtained from the bile of different animals. In the bile of the serpent (boa anaconda) 6.3 per cent* of sulphur was discovered whilst little or none was found in that of the pig. The substance containing the sulphur of the bile is probably the same in all cases (pig’s bile excepted) as taurine can always be obtained from it.Adifference however is observed in the nature of the other constituents of pig’s and ox-bile which are the only two that have yet been carefully examined. The acid of pig’s bile (hyocholinic acid) is expressed by the formula C, H, N Ole that of ox-bile (cholic acid) C, HMN O12. If two atoms of water are deducted from the elements of the latter formula there remain C, H41N Ole which formula differs from that expressing the composition of hyochlolinic acid by C H, or by the elements of the carbo-hydrogen which constitute the distinction between the volatile fatty acids having the formula (CH) 04. These two atoms of water are in fact separated on boiling cholic acid with hydrochloric acid and the resulting resinous body exhibits great similarity to hyocholinic acid.* Ann. der Chem und Pharm. LX. 109.

ISSN:1743-6893    

DOI:10.1039/QJ8490100075

出版商:RSC    

年代:1849

数据来源: RSC

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TITLES OF CHEMICAL PAPERS IN BRITISH AN*D FOREIGN JOURNALS. A. Acid Anilk.-On the action of chlorine on anilic acid by J. Stenhouse. Phil. Mag. xxxiii 231. Arsenic.-On a new method of estimating arsenic acid by G. Werther. Journ. fur prackt. Chem. xliii 321. Arsenious.-Vegeto-physiological studies made with arsenious acid by M. Ad. Chatin. Ann. de Chim. et de Phy. xxiii 105. Bisulphithy1ic.-On bisulphithylic and bisulphimethylic acids by Sheridan Muspratt. Journ. of Chem. SOC.i 45. Butyric.-On butyric acid by Dessaignes and J. Chautard. Journ. de Pharm. et de Chim. xi 244. Carbonic.-Contributions to the methods of estimating carbonic acid by H. Vohl. Ann. der Chem. und Pharm. lxvi 247 & 377. Cholic (bile).-Note on the resolution of cholic acid into glycicoll and non-nitrogenous acids by Ad.Strecker. Idem. lxv 130. Chrysammic.-On some products of the decomposition of chrysammic acid by Dr. Schunck. Idem. 234. .. On chrysammic acid by M. Mulder. Ann. de Chim. et de Phy. xxii 122. Chryso1epinic.-On the identity of picric chrysolepinic and nitrophenissic acids by R.F. Marchand. Journ. fur prackt. Chem. xliv 91. Cyanic.-On the preparation of cyanate of potash and urea by C. Klemm. Ann. der Chem. und Pharm. lxvi. 382. Dithionic.-On some salts of dithionic acid by F. Kessler. Pogg. Ann. lxxiv 274. Fu1minic.-On the constitution and nomenclature of the fulminates by J. Fritzsche. Journ. fur prackt. Chem. xliv. 150. Hyposulphathy1ic.-On hyposulphathylic and hyposulphamethylic acids by Sheridan Muspratt.Journ. of Chem. SOC.i 45. Lactic.-On the difference between the lactic acid obtained by the fermen- tation of sugar and that contained in the liquids of flesh by H. Engelhardt. Ann der Chem. und Pharm. lxv. 359. Ma1ic.-On neutral malate of lime by Dessaignea and J. Chautard. Journ. de Pharm. et de Chim. siii 243. Mel1itic.-On metlliic acid by 0. L. Erdmann and R. F. Marchand. Journ. fur prackt. Chem. xliii 129. Mel1itic.-On mellitic acid and its products of decomposition by Dr. H. Schwartz. Ann. der Chem. und Pharm. lxvi 46. TITLES OF CHEMICAL PAPERS Acid Nitrophenissic.-On the identity of picric chrysolepinic and nitrophenissic acids by R. F. Marchand. Journ. fur prackt. Chem. xliv. 91. Nitrous.-On the nitrites by N.W. Fischer. Pogg. -4nn. lxxiv 115. Pe1oyic.-On the specific gravity of pelopic acid by H. Rose. Idem. Ixxiv. 85. Phosphoric.-On the combinations of ordinary phosphoric acid with protoxide of manganese by W. Heintz. Idem. lxxiv 449. .. on extraction of pure from bones and on a new anomalous phosphate of magnesia by W. Gregory M.D. Trans. Roy. SOC. Ed. xvi 47. Picric.-Note on the identity of picric and chrysolepinic acids by E. Robi-quet. Journ. de Pharm. et de Chim. xiv 179. .. On the identity of picric chrysolepinic and nitrophenissic acids by R. F. Marchand. Journ. fur prackt. Chem. xliv 91. Po1ythionic.-On the polythionic acids by F. Kessler. Pogg. Ann. lxxiv 249. Prussic.-On Liebigs new test for prussic acid by A. Taylor. Med.Gaz. xxxix $65. Pyrophosphoric.-Notice on the double salts of pyrophosphoric acid by Fleitmann and Henneberg. Ann. der Chern. und Pharm. IXV 387. .. .. Examination of the pyrophospates by Ad. Schwarzen-berg. Idem. lxv 133. .. On the double salts of pyrophosphoric acid by J. Persoz, 0. Idem. Irv 163. Pyrotartaric.-On yyrotartaric acid by A. E. Arppe. Idem lxvi 73. Aqueous.-On the condensation of the atoms of water in the aqueous acids by C. Fr. Naumann. Journ. fur prackt. Chem. xliii 1. Silicic.-On a native hydrate of silicic acid from Algeria by M. Salvetat. Ann. de Chitu. et de Phy. xyiv 348. Sulphovinic-On the stability of the sulphovinates by R. F. Marchand. Journ. fur prackt. Chem. xliv 122. 8ulphuric.-On the combination of sulphuric acid with water by A.Bineau. Ann de Chim. et de Phy. xxiv 337. Su1phuric.-Investigation of the reactions of iron and zinc with sulphuric acid and its compounds by A. d’Heureuse. Pogg. Ann. lxxv 255. Sulphurous.-On a combination of sulphurous acid with water by Dop- ping Journ. fiir prackt. Chem. xliv 255. .. .. Note on sulphurous acid and on its combination with water by J. Isidore Pierre. Ann. de Chim. et de Phy. xxiii 416. Tannic.-On the tannic acid of coffee by Dr. Rochleder. Ann. der Chem. und Pharm. Ixvi 35. Tartaric.-On the application of tartrate of potash and magnesia in medi- cine by Guerard and Garot. Journ. de Pharm. et de Chim. xiii 252 & 346. Tanta1ic.-On the specific gravity of tantalic acid by H. Rose. Pogg. Ann. lxxiv 285.Uric.-On the neutral salts of uric acid by Dr. James Allan and Dr. Aug. Bensch. Ann. der Chem. und Pharm. lxv 184. .. On the oxidation of uric acid by means of ferridcyanide of potas-sium by Ad. Schlieper. Idem. lxvii 214. IN BRITISH AND FOREIGN JOURNALS. Acid Vanadic -On the occurrence of vanadiate of copper at Friedrichsrode in Thuringia by H Credner. Pogg. Ann. lxxiv 546. Aesculus hippocastanurn.-Comparative chemical investigation of the mineral substances contained in different parts of the horse-chestnut tree by Dr. Emil Wolff. Journ. fur prackt. Chem. xliv 385. Affinity.-Observations on the principle of vital affinity as illustrated by the recent discoveries in organic chemistry by W. P. Allison M.D. Ed. Phil. ‘I’rans. xvi 165.Aga1matolite.-Analysis of agalmatolite by Schneider. Idem. xliii 316. Air.-Determination of the weight of a liter of air and the density of mercury by V. Regnault Pogg. Ann. lxxiv 202. Albumen.-On the soluble albumen of fishes by Dr. V. Blumhauer. Journ. fur prackt. Chem. xlv 120. Album graecuin -Analysis of album grmum by Vohl. Ann. der Chem. und Pharm. lxv 266. Alcoholates -On nitrate of magnesia and the combinations called “Alcoho-lates,” by Paul Einbrodt. Idem. In 115. Aldehyde.-On some products of the action of acids and alkalies on aldehyde by Dr. H. Weidenbusch. Idem. lxvi 152. Alkalies.-Note on the constitution of the phosphates of the organic alkalies by Thos. Anderson. Journ. of Chem. SOC.i 55. -On the action of oxalic acid on the alkaline chlorides by A.G.Anderson. Idem 231. Alkaloids.-On the chlorinated and brominated alkaloids by Aug. Laurent. Ann. de Chim. et de Phy. xxiv 302. Alumina.-On the spontaneous cohesion of the particles of alumina by R. Phillips. Phil. Mag xxxiii 35.7. on the specific gravity of alumina by H. Rose. Pogg. Ann. lxxiv 429. Aluminum.-On aluminum as a conductor of electricity and a magnetic body by P. Riess. Idem. lxxiii 619. Amalgam -Analysis of an amalgam of gold by Schneider. Journ. fur prackt. Chem. xliii 317. Amber.-On the action of potash on amber by M. Reich. Journ. de Pharm. et de Chim. xiii 33. Amidogea-On the amidogen-aeids and sugar of gelatin by M.A. Laurent. Ann. de Chim. et de Phy xxiii 110. Amiduline -On amiduline by F. Schulze.Journ. fur prackt. Chern. rliv 178. Ammonia.-On native bicarbonate of ammonia by G. L. Ulex. Ann. der Chem. und Pharm. hi 44. Ammonium.-On some isomorphus double salts of chloride of ammonium with metallic chlorides belonging to the magnesian class by 0s. Hautz. Idem. lxvi 280. Arnygda1in.-On the action of acids on amggdalin by F. Wahler. Idem. hi 238. Amy1.-Note on the existence of two bodies belonging to the amilic seris by 0.Henry Jua. Journ. de Pharm. et de Chim. xiv 247. -Researches on the amyl series by H. Medlock. Journ. of Chem. SOC. i 368. Analysis.-On the use of sal-ammoniac in chemical analysis by H. Rose. Pogg. Ann. lxxiv 562. VOL. I. NO. IV. Pp’ TITLES OF CHEMICAL PAPERS Analytical chemistry.-On the application of sal-ammoniac in analytical che -mistry by H.Rose. Idem. lxxiv 562. Ani1ides.-Researches on the anilides by Aug. Laurent and Ch. Gerhardt. Ann. de Chim et de Phy. xxiv 163. Aniline.-On chlorocyanilide and iome other anilides by M. Aug. Laurent. Idem. xxii 97. Animal oils.-On the products of the destructive distillation of animal sub- stances by Th. Anderson Ed Phil. Trans. and Phil. Mag. xnxiii 174. Antimony.-On a new method for the quantitative estimation of antimony by H. Rose. Pogg. Ann. lxxiii 582. -On the separation of aritirnony from arsenic. Ann. der Chem. und Pharm. lxvi 236. Aphthonite.-Analysis of aphthonite by Svanberg. Journ. fur prackt. Chem. xliii 313. Aposepidine.-On the composition of aposepidine or leucine by A. Laurent and Ch.Gerhardt. Ann. de Chim. et de Phy. xxiv. 321. Apparatus.-Description of a bellows adapted for chemical laboratories by Franz Schulze. Journ. fur prackt. Chem. xliii 368. Aqua-regia.-Memoir on aqua-regia IJY Gay-Lussac. Ann de Chim. et de Phy. xsiii 203. Arsenic.-On the separation of antiniony from arsenic. Ann. der Chem. und Pharm. hi 236 -On a new method for the quantitative estimation of arsenic by H. Rose. Pogg. Ann. lxxiii 58.2. -On arseniate of uranium and copper by Werther. Journ. fur prackt. Chem xliv 127. Asbestos.-Analysis of the asbestos from Zoblitz by E. Schmidt. Idem. xlv. 14. Ashes -Supplementary remarks to the paper ‘‘On the quantitative determina- tion of the constituents of ashes,” by W. Heintz.Pogg Ann. lxxiii 455. Asparagine.-On asparagine by Dessaignes and J. Chautard. Journ. de Pharm. et de Ciiim. xiii 245. -Researches into the chemical constitution of asparagine and aspartic acid by M. R. Piria. Ann de Chim. et de Phy. xxii 160. Atomic volume.-Researches on atomic volume and specific gravity by J. P. Joule and Lyon Playfair. Journ. of Chem SOC.i 121. -Observations on the atomic volumes and boiling points of analogous organic liquids by W. A. Miller. Idem. 363. Attraction.-On some phenomena of capiliary attraction observed with chloro- form bisulphuret of carbon and other liquids by G. Wilson. Idem. 174. B. Barometer.-On the aneroid barometer by Poggendorff. Pogg Ann. lxxiii 620. Base organic.-On a new organic base in opium by G.Merck. Ann. der Chem. und Pharm. lxvi 125. Bases organic.-Researches into the combinations of some organic bases with sulphocyanhydric ferrocyanhydric and ferricyanhydric acids by C.Dollfus Idem. xlv 212. IN HRITISII AND POREIGN JOURNALS. 427 Bases Researches on the volatile bases by A. W. Hofinann. Journ. of Chem. Soc. i 159 269 285. Beer.-An inquiry into the amount of inorganic constituents contained iu ale and porter by Thomas Dickson Phil. Mag. xxxiii 341. Berberine.-Berberine in the root of Columbo. Ann. der Chem. und Pharm. hi 384. Bile.-Bensch on the amount of sulphur in the bile of different animals. Idern. IXV 194. -On the constitution of the bile of the ox by Adolph Strecker. Idem 1x17 1. and lxvii 1. Bismuth.-On lactate of bismuth by H.Engelhardt. Idem. lxv 367. Blood.-Analysis of the ash of the blood of the fowl by W. Henneberg. Idem. luvi 112. -Analysis of blood by Pogiale and Mauhal de Calvi. Compt. Rend. xxvi 143. -Chemical investigatioii of the blood by Poggiale. Idem. xxv 110 & 198. -Miscellaneous observations on blood by J. Davy. Trans. Roy. SOC. Ed. xvi 53. -Metals in the blood by E. Millon Pogg. Ann. lxxiv 284. -On the absence of copper and lead in the blood by M. Melsens. Ann. de Chirn. et de Phys. xxiii 358. -On the presence of several metals in the human blood in a normal state by M. Millon. Journ. de Pharm. et de Chim. xiii 86 -On the presence of several metals in the norinal blood of man and on the analysis of the fixed salts contained in that liquid by M.E. Millon. Ann. de Chim. et de Phys. xxiii 372 & 508. -Researches on the blood by MM. Roucher and Coulier. Idem. xxiii. 377. Uodenite -On the chemical composition of bodenite by Th. Kerndt. Journ. fur prackt. Chem. xliii 219. Bromine.-On the specific heat of bromine by Th. Audrews. Journ. of Chem. soc. i 18. Brucine.-On the action of nitric acid upon brucine by S. G. Rosengarten. Ann. der Chem. und Yharm. lxv 11I. Brucine.-on the ferrocyanides of strychine and brucine by I). Brandis. Idem. Iavi 257. on the action of nitric acid on brucine by Aug. Laurent. Ann. de Cbim. et de Phys. xxii 463. c. Cadmium.-On the crystallized rnonohydrates of zinc and cadmium. Ann. de Chim. et de Phy.xxii 31. Calcareous spar.-Anal ysis of calcareous spar by Hochstetter. Journ. fur prakct. Chem. xiiii 316. Camphor.-Researches on the combinations of camphor by M. A Bineau. Ann. de Chim. et de Phys. xxiv 326. Capillary attraction.-On certain phenomenon of capillary attraction exhibited by chloroform the fixed oils and other liquids ; with an inquiry into some of the causes which modify thc form of the mutual surface of two immiscible'liquids in contact with the walls of the vessel in which they are contained by Will. Swan. Phil. Mag. xxxiii. 36. 1' F 2 TITLES OF CHEMlC.4L PAPERS Carbon.-Note on the deportment of vegetable charcoal towards chlorine bro- mine iodine chloride of lime and hyponitric acid by C. F. Schiin-bein Pogg.Ann lxxiii 326. -On the preparation of sulphuret of carbon by M. Chandelon. Journ. de Pharm. et de Chim. xiv 167. Carbonates.-On the solubility of the carbonates of the earths and metallic oxides in water containing carbonic acid by J. L Lassaigne. Journ. de Chim. Med. 1848 Juin 312. Carbonization.-Memoir on the carbonization of wood by the vapour of water by M. Violette. Ann. de Chim. et de Phy. xxiii 475. Carbothia1dine.-On carbothaildine by I. Redtenbacher and J. Liebig. Ann. der Chem. und Pharm. lxv. 43. Cerium.-Chemical composition of mecromontite a new mineral containing cerium from the -neighbourhood of Mauersberg in Saxony by Th. Kerndt. Journ. fur prackt. Chem. xliii 258. -On the chemical composition of the Oligoklase containing cerium from Boden near Marienberg in the Saxon Erzgebirge by Th.Kerndt. Idem. 214. Chabasite.-Analysis of Chabasite by €I. Engelhardt. Ann. der Chem. und Pharm. Ixv 370. Cha1colite.-Examination of Chalcolite by G. Werther. Journ. fur prackt. Chern. xliii 321. Chemico-geological -Remarks upon certain objections to several views on the caemico-geological phenomena of Iceland by R. Bunsen. Ann. der Chem. und Pharm lxv. 70. Cherry-laurel.-Experiments to illustrate the chexnico-pharmaceutical history of the leaves of the cherry-laurel of the water distilled from them and of that from bitter almonds by P. H. Lepage. Journ. de Pharm. et de Chim. xiv 190. Chinoidine.-Copper in Chinoidine. Arch. der Pharm. liv. 159. Chinon.-Notice on the composition of chinon.Ann. der Chem. und Pharm. h,349. Cbio1ite.-On the chemical composition of chiolite by C. Rammelsberg Pogg. Ann. lxxiv 314. Chlorine.-Researches on the action of perchloride of phosphorus on organic bodies by Aug. Cahours. Ann. de Chiin. et de Phy. xxiii 327. Chloroform.-Note on the preparation of chloroform by M. Kessler. Journ. de Pharm. et de Chim. xiii 161. -On the composition properties and methods of preparing chloroform. Rev. Scien- Fe'v. 1848 p. 223. -On the preparation of chloroform by Pierloz-Feldmann. Journ. de Chim. Med. 1848 Juin. _I_ .. . . by M. Godefrin. Journ. de Pharm. et de Chim. xiii 101. -.. .. by MM. Larocque and Huraut. Idem. xiii 97. -Preparation of chloroform by Meurer and Erdmann. Journ. fur prackt.Chem. xliii 397. c- .. .. by Huraut and Laracque. Compt. Rend. xxvi. 104. IN BRITISH AND FOREIGN JOURNALS. Chloroform.-Test for absence of alcohol in chloroform by Cattd. Journ. de Chim Med. 1845 257. Chloropa1.-On chloropal by Fr. v. Kobell. Journ. fur prackt. Chem. xliv. 95. Chloropicrine -On chloropicrine by J. Stenhouse. Phil. Mag. xsxiii 53. Chromium.-On protoxide of chromium by A. Moberg. Journ fur prackt. xliii 114. -On the salts of protoside of chromium by A. Moberg Idem. xliv 322. -On the preparation of some compounds of chromium by Dr. M. Trau1)e. Ann. der Chem. und Pharm. lsvi 87 & 165. -Analysis of bechromate of ammonia and some double salts of chronic acid by St. Darby. Jour. of Chem. SOC.vol.i 20. Cholesterin -On the chemical constitution of cholesterin by C. Zwenger. Ann. der Chem. und Pharm. hi 5. Coal.-Ultimate analysis of some varieties of coal by F. Vaux. Joar. of Chem. Society i. 318. Cobalt.-On the separation of nickel from cobalt by J. Liebig Idem. Ixv. 244. Cocoa-nut oil. -On the solid volatile fatty acids of cocoa-nut oil by Arthur Gorgey Idem. lxvi. 290. Condurrite.-On the composition and origin of condurrite by J. Blyth. Journ. of Chem. SOC.i. 213. Conferva-On the development and cornposition of the Confervae by Mitscher- lich. Journ. fur pracktish. Chein. xliii 15% Coniine.-On the composition of coniine and its products of decomposition by J. Blyth Journ. of Chem. SOC. i 345. Collodion. -On collodion by Souberian.Journ. de Pharm. et de Chim. xiv 263. Colouring matter.-On the red colour from Harmala by J. Fritzsche Journ. fur prakt. Chem. xliii 155. Copper on the alloy of manganese and copper from Friedrichsrode by C Rarnmelsberg. Pogg Ann. lxxiv 559. -On the copper contained in animal and vegetable textures and juices by M. Deschamps. Journ. cle Pharm. et de Chim. xiii 88. -On the occurrence of an alloy of manganese and copper at Friedrichsrode in Thuringia by H. Crudner. Pogg. Ann Ixxiv 546. -Researches on some varieties of Chinese copper by H. Onnen. Journ. fur prackt. Chem. xliv 242. Creatine.-Contributions to the knowledge of creatine and creatinine by W. Heintz. Pogg Ann. lsxiv 125. -On the crystalline form of creatine compared with that of creatinine by W.Heintz. Idem. lxsiii 595. -The existence of creatine proved in the human muscles by Dr. Schloss-berger. Ann. der Chem. und Pharm. hi 80. -On the preparation of creatine &c. by W. Gregory. Jour. of Chem. Sac. i 25. Crystallization.-Memoir upon a new method of obtaining crystalline combina- tions by fusion and on its applicability to the reproduction of mine-rals by H. Ehelman. Ann. de Chim. et de Phy. xxii. 21 1. Crystallography:-Crystallographic notice concerning a crystal with 6 times 8 faces by N.v Kokscharow. Pogg. Ann lxxiii 188. TITLE8 OF CHEMICAL PAPERS Crystallography.-Crystallographic researches by M J. Xickles Ann. de Chim. et de Phy. xxii 28. Cumidine.-On cumidine a new organic base by E.C. Xcholson. Jour of Chem. SOC.i 2. Cyanide of lead.-Analysis of cyanide of lead by L. Kugler. Ann. der Chem. und Pharm. Ixvi 63 Cyanogen compounds.-On the effect of a high temperature upon the cyanides and double cyanides by C. Rammelsberg. Pogg. Ann. lssiii 80. -Upon a new double cyanide of potassium and copper by C. Rarnmelsberg. Idem. Ixxiii 80. D. Dammar-resin.-% Dammar-resin by Dr. -4.Dulk. Journ. fiir prackt. Chem. xlv 16. Deiambra.-A new narcotic. Journ de Pharm. et de Chim. xiv 201. Dimorphism.-Researches on dimorphism by L. Pasteur. Ann de Chim. et de Yhy. xxiii 267. Dolomite.-On dolomite by A. v. Morlot. Pogg. Ann. lxxiv 591 E. Epidote.-On Epidote by R. Hermann. dourn. fur prackt. Chem. xliv 204. Ergot of rye -On the ergot of rye by M.Guibourt. Journ. de Pharm. et de Chim. xiii 267. Ether -On two new compounds of phosphoric acid with ether by F. Voegeli Yoga. Ann. lxxv 282. Ethyl -On the neutral sulphate of oxide of ethyl and the products of its decomposition hy water by K. M. Wetherill Ann der Chem und Pharm lxvi 117. -On the products of the action of potassium on cyanide of ethyl by II. Kolhe and E. Frankland. Jour. of Chern. SOC.i 60. Excrement.-Upon the composition of the ashes of solid animal excrements by J. R. Rogers. Idem. Ixv. 85. F Fah1erz.-On the pseudomorphous crystals of Fahlerz by C. Volger. Yoga-Ann. lxxiv. 25. Fe1site.-On the chemical compositjon of Felsite by Th. Kerndt. Journ. fur prackt. Chem. xliii 207. Ferrocyanides.-On ferrocyanide of copper and ferrocyanide of copper and potassium by C.Rammelsberg. Pogg. Ann. lxxiv 65. Fluorine.-On the solubility of fluoride of calcium in water and its relation to the occurrence of fluorine in minerals in recent and fossil plants and animals by Geo. Wilson M.D Ed. Phil. Trans. xvj 145. Fruits.-Memoir on the ripening of fruits by E. Fremy. Ann. de Chim. et de Phy. xxiv 5. Furfuro1.-Note on furfurol by Aug. Cahours. Idem. xxiv 277. G. Gas battery.-On the action of oxygen in Groves’s gas battery by C. F. Schijn-bein. hgg. Ann lyxiv 241. IN BRITISH AND FOREIGN JOURNALS. 431 Gas.-For illumination.-On the purification of gas for illumination. Compt. Rend. xsvi 549. Gelatin vegetable -Reply to some assertions recently advanced on the proper- ties and composition of the gelatinous substances of vegetables by E.Fremy. Ann. de Chim. et de Phy. xxiv 45. Germination.-On the action of water in the process of germination by M. Cap. Journ. de Pharm. et de Chim xiv 105. G1ucina.-On the specific gravity of Glucina by H. Rose. Pogg. Ann. lxxiv 429. Guaiacum resin.-On the guaiacum resin by C. F. Schonbein. Idem. lxxiii 439. Gun cotton.-On gun cotton. Journ fur prackt. Chem. xliii 242. Gutta percha -Notice on gutta percha (Isonandra gutta) by M. Vogel. Jun. Journ de Pharm. et de Chim. xiii 333. H. 1Iaschych.-On haschych (Indian hemp) by M. F. Foy. Journ. de Pharm. et de Chim. xiii 350 & 427. Heat.-Memoir on the radiation of heat by de la Provostaye and Ed. Desaignes Ann.de Chim. et de Phy. xxii 385. -On the conducting power for heat in crystalline bodies by %H.de Se- narmont. Pogg. Ann. lxxiii 191 and lxxv 50. -On the heat disengaged during metallic substitutions by Th. Andrews. Phil. Trans Jan. 20th 1848 p. 91 Phil. Mag. xxxii 392. -On the latent heat of fusion by C. C. Person. Ann. de Chim. et de Phy. xxiv 129 & 265. -On the effect of heat in lessening the affinities of the elements of water by the Rev. 'I' R. Robinson D 1). Trans. Roy. Jrish Acad. xxi 311. -Account of some experiments on the temperature of the earth at different soils near Edinburgh by James Forbes F.R.Y. Ed. Phil. Trans. xvi 189. -Specific.-on specific heats by A. c.Fvoetzyn. Idem. xxiii 295. -On the specific heat of some liquids by H.Kopg. Pogg. Ann. lxxv 93. -On the specific heat of bromine by 'l'h. Andrew. Journ. of Chem Soc i 18. -On the latent heat of vapours by 'rh. Andrew. Jour. of Chern. SOC.i 27. Hemp Indian.-On haschych by M.Foy. Journ. de Pharm. et de Chitn. xiii 350 & 427. Honey.-On the falsification of honey and sugar with starch-sugar and glucose by M. Guiboui t Idem. xiii 263. Horse-chesnut tree.- Comparativr chemical investigation of the mineral sub-stances contained in different parts of the horse-chesnut tree by Dr. Emil Wolf€'. Journ. fur yrackt Chem. xliv 385. Hydrates.-On the condensation of the atoms of water in the hydrated acids by C. F. Naurnann. Journ fiir prakt. Chem. xliii 1. researches on the hydrates by M.E Fremy. Ann. de Chim. et de Phy. xxiii 385 I Ilex Paraguayensis.-On the acid of the leaves of the Ilex Paraguapensis by Dr. Rochleder. Ann. der Chem. und Pharm. lxvi 39. TITLES OF CHEMICAL PAPERS Ilrnenium.-On ilmenium. by H. Rose. Pogg. Ann. Ixxiii 449. Iodine.-Iodine in Jungerrnannia albicans by Van der Marck. Journ. de Chim. Med. 1845 Juin 310. -Reaction of iodine with the oils of anise and fennel by H. Will. Ann. der Chern. und Pharm. 1x17 230. €ran.-On the crystalline structure of iron by E. F. Glocker. Pogg. Ann. lxxiii 332. -Analyses of some specimens of hot and cold blast iron by C. F. Wrightson. Jour. of Chem. SOC.i 330. -Investigation of the reactions of iron and zinc with sulphurk acid and its compounds by A.d’laeureuse. Pogg Ann. IYXP 255. Isomorphism.-Notice of a paper by M. Laurent entitled ‘‘On isomorphism and crystalline types by L Pasteur. Ann. de Chim. et de Phy. xxiii 294. -Upon certain points in the domain of polymeric isomorphism which have been questioned by Messrs. Naumann Haidinger Blurn and Ram- melsberg by Th.Schemer. Pogg. Ann. lsxiii 155. K. Kermes.-Report on the preparation of kermes by the process of M. Lisnce by M. Dublanc. Journ. de Pharrn. et de Chim. xiii 22. Kreittonite -On Kreittonite a new spinel1 from Bodenmais by v. Kobell. Journ. fur prackt Chern. xliv 99. L. Lava.-Examination of the lavas from the Hekla in Iceland by Dr. F. A. Geuth. Ann. der Chem. und Pharm. Ixvi 13. Lead.-Analysis of cyanide of lead by L.Kugler. Idem. lxvi 63. -Upon the union of oxide of lead with ordinary phosphoric acid by W. Heintz. Pogg. Ann. lxxiii 122. Leucine.-On the composition of aposepidine or leucine by Laurent and Gerhardt. Ann. de Chim. et de Phy. xxiv 321. Lichen -Examination of the proximate principles of the lichens by J. Stcn-house. Phil. Trans Feb. 10 1848 Phil. Mag. xxxii 300. Liebigite.-Analysis of Liebigite by L. Smith. Ann. der Chem. und Pharm. hi 253. Light.-Upon the action of light on iodide of lead-starch by C. S. Schonbein. Pogg. Ann lxxiii 136. M. Madder -Chemical investigation of the root of the madder by H. Debus. Ann. der Chern. und Pharm lxvi 351. 7 Examination of madder by Dr. Schunck. Idem lxvi 174. -On a new adulteration of the alizari of commerce and on the alizari and madder of Auvergne by J.Girardin. Journ. de Pharm. et de Chim. xiii 334 -On the colouring matters of madder by J. Higgin. Phil. Mag. xxsiii. 282. Magnesia.-On acetate of magnesia by Guerard and Garot Journ de Pharni- et de Chim. xiii 260 & 346. IN BRITISH AND FOREIGN JOURNALS. Magnesia -On the separation of magnesia from the alkalies by carbonate of silver. by F. Sonnenschein. Pogg. Ann. Ixxiv 313. -On t,he specific gravity of magnesia by H. Rose. Idem. lxxiv 429. Magnesium.-Upon a new method of separating magnesia from the alkalies by C. Rammelsberg. Idem. lxxiii 119. -Upon the estimation of magnesia by phosphate of soda and that of phos-phoric acid by magnesia by R. Weher. Idem. lxxiii 137.Magnetic iron ore.-On the chemical composition of magnetic iron ore by Cr. Rose. Idem. lxxiv. 291. Magnetism.-On the supposed influence of magnetism on chemical action by R. Hunt. Phil. Mag. xxxii 252. Malakone.-On the crystalline form of malakone by M. Descloizeaux. Ann. de Chim. et de Phy. xxiv 9-1. Manganese.-Experiments on the production of salts of the deutoxide of man-ganese by R. Hermann. Pogg. Ann. lxxiv 303. -On the alloy of manganese and copper from Friedrichsrode by C. Ram-melsberg Idetn. lxxiv 559. protoxide.-On the combination of ordinary phosphoric acid with pro- toxide of manganese by W. Heintz Idem. lxxiv 44% -On the manganese-copper ore of Friedrichsrode by C. Rammelsberq. Idem. lxxiv 559. -On the occurrence of a deposit of native earthy carbonate of manganese in Ireland by Sir R.Kane. Phil Mag. xxxii 37. -On the occurrence of an alloy of manganese and copper at Friedrichsrode in Thuringia by H. Crudner. Pogg. Ann. lsuiv. 546. Mannite.-On the application and production of pure mannite by Ruspini. Ann. der Chem. und Pharm. lxv 203. Matter.-On Wollaston's argument from the limitation of the atmosphere as to the finite durability of matter by Geo. Wilson M.D. Ed. Phil. Trans. Vol. mi 7'3. Medjidite.-Analysis of medjidite by L. Smith. Idem. lxvi 253. Mercury.-Determination of the density of mercury by V. Regnault. Pogg. Ann. lxxiv 202. -On the congelation of mercury and on its latent heat of fusion by C. C. Person. Ann. de Chim. et de Phy.xxiv. 257. -On the preparation of the black sulphuret of mercury by M. C. Vogler. Journ de Pharm. et de Chim. xiv 188 Metals.-On chemical combinations of the metals by Dr. J. H. Croockewit. Journ. fur prackt. Chem. xlv 97. -On the colour of the metals by M. 3. Jamin. Ann. de Chim. et de Phy. xxii 311. Meteoric iron.-Chemical composition of the meteoric iron from Seelasgen by A. Duflos. Pogg. Ann lxxiv 61. -On the chemical composition of the meteoric iron of Seelasgen by C. Ramnielsberg. Idem. lxxiv 442. -On the meteoric iron of Seelasgen near Schwiebus by W. G. Schneider. Idem. lxxiv 61. Meteoric stones -Conclusion of the investigation of the meteoric iron from Braunau by N. W. Fisher. Idem. lxxiii 590. -On the composition of the meteoric stone from Juvenas and on the phos- TITLES OF CHEMICAL PAPERS phoric and titanic acids which it contained by C.Rammelsberg. Idem. lxxiii 585. Meum.-On the action of alkalies on the resin of the root of meum by M. Reinsch. Journ. de Pharm. et de Chim. xiii 27. Mica.-On the crystalline form of rhombic mica by G. A. Kenngott. Pogg. Ann. lxxiii 601. Milk.-On the amount of carbonic acid in milk by R. F. Marchand Journ. fur prackt. Chem. xliv 250. -Miscellaneous obeervalions on by J Davy Ed. Phil. Trans. Vol. xvi p 53. -On the mode of testing milk by Schirz. Idem. xliv 90. -On the specific gravity of milk by E Brucke. Idem. xliv 88. Mineral -Analysis of a new mineral from Helsingfors by Pipping.Idem. xliii 314. Mineralogical.-C)n mineral species by Dr. Fiichs Idem. xlv. I. -On the mineralogical and chemical nature of the rocks of the Vogesen mountains by A. Delesse. Idem. xliii 417 -On the significance of certain limiting surfaces of a crystal with reference to the oxidation of the hydrated hydrolites by G Suekow Idem. xliii 401. Minerals.-Examination of Rnssian minerals by R. Hermann. Idem xliii '35 81 and xliv 193. -Researches upnn some mineral specimens by 'I' A Genth. Ann. der Chem und Pharm. lxvi 270. Mineral water.- Observations on the chemical composition of several springs of Vichy (Allier) and some reflections on the mode of viewing the composition of mineral waters by 0 Henry. Journ. de Pharm. et de Chim.xiii Ti. -Analysis of the mineral water from Mondorff near Lunemburg by Dr. J. P. Kerckhoff. Journ. fur prackt. Chem. xliii 350. -Comparative examination of the principal saline mineral waters of Germany and France with reference to their chemical composition and therapeu- tical action by L. Figuier and L. Mialhe. Journ. de Pharm et de Chim. xiii 401. -Note on the presence of iodide of sodium in different specimens of rock-salt and its correlation with the formation of certain natural mineral waters by M. 0.Henry Idem. xiv 245. -On the mineral waters of Cheltenham by F A. Abel and 'rhos. H. Rowney. Journ. of Chem. Soc. v 193. -Researches on the presence of arsenic in mineral waters and in their deposits by A. Chevallier and Th. Gobley. Idem.xiii 321. Molybdenum.-On some compounds and on the atomic weight of molybdenum by Svanberg and Struve. Journ. fur prackt. Chem. xliv. 257. -On the quantitative estimation of molybdenum by H. Rose. Pogg Ann. Ixxv 319. Morphine.-On the derivatives of morphine and narcotine by Aug. Laurent and Ch. Gerhardt. Ann. de Chim. et de Phy. xxiv 112. M ber ry Tree.-On the cornposilion and distribution of the inorganic sub-stances in the different organs and component parts of the mulberry tree by T. J. Herapath. Journ. of Chern. SOC.i i03. IN BRITISH AND FOREIGN JOURNALS. Muromontite.-Chemical composition of muromontite a new mineral contain- ing cerium from the neighbourhood of Mauersberg in the Saxon Erzgebirge by Th. Kerndt. Journ. fiir prackt.Chem. sliii 2 19. Muscle.-On the composition of the muscular tissue of fishes by Dr. V. Baum-hauer. Idem. xlio 506. N. Nickel.-Hydrated oxide of nickel a new mineral by B. Silliman J tin. Pogg. Ann lxxiii 154. -On the separation of nickel from cobalt by J. Liebig. Ann. der Chem. und Pharm. lxv 244. Nickel-speise.-Analysis of nickel .speise by Schneider. Journ. fur prackt. Chem. xliii 3 17. Niobium.-On the effect of temperature upon the specific gravity of niobic acid by H. Rose. Pogg. Ann. Ixxiii 313. Nitrate of silver.-On the decomposition of nitrate of silver by heat by M. J. Persoz. Ann. de Chim. et de Phy. xsiii 48 Nitrogen.-On the function of nitrogen in respiration by R. F. Marchand. Journ. fur prackt. Chem. xliv 1. -On a new method for the quantitative determination of nitric acid and other compounds of nitrogen by J.C. Nesbit. Jonrn. of Chem. SOC.i 28 I. -On the determination of nitrogen in analysis by J. Mitchell. Journ. of Chem. SOC. Vol. i 19. -On the methods of estimating nitrogen in analysis by C. Nollner. Ann. der Chem. und Pharm. hi 314. -On the origin of nitrogen in plants by Boutigny. Journ. de Pharm. et de Chirn. xiii 321. Nitrous acid -On the nitrites by N. W. Fisher. Pogg. Ann. lxxiv 115. 0. (Enanthal -On cmanthal its compounds and the products of its decomposi- tion by F. G Tilley. Phil. Mag. xxxiii 81. CEnanthe.-On a new substance in the enanthe fistulosa by Gerding. Journ. fur prackt. Chem. xliv 175. (Enanthol.-On cenanthol and the products of its decomposition by 'lh.G. Tilley. Phil. Mag; xxxiii 8 I. Ann. der Chem. und Pharm. lxrii 105. Oil.-Essential oil of matricaria parthenium by Dessaignes and J. Chautard. Journ de Pharin et de Chim. xiii 241. -essential.-Researches on the essential oils by Ch. Gerhardt. Ann. de Chim. et de Phys. xxiv 96. -of anise and fennel.-On the action of iodine upon the oils of anise and fennel by Will. Ann. der Chern. und Pharrn. Ixv 230. -of bitter almonds -On the volatile oil of bitter almonds by M. Grindley. Journ. de Pharm. et de Chim. xiii 119. -of potatoes.-On the action of nitric acid on potatoe-oil by M. P. Wilhem Hoffrnann. Ann. de Chim et de Phy. xxiii 374. -volatile.-On the action of volatile oils on the sulphates by W.Bastick. Journ. de Pharm. et de Chirn. xiii 120. 0ligoklase.-Analysis of Oligoklase hy Svanherg. Journ. fur prackt. Chem. diii 314. TITLES OF CHEMICAL PAPERS Opium.-On the culture of opium in Armenia by M. Gaultier de Clauhry. Journ. de Pharm. et de Chim. xiii 105. -Process for detecting the presence of small quantities of opium by M. Heusler. Idem. xiv. 187. Orcirie -On alpha and beta-orcine by J. Stenhouse. Phil. Mag. xxxiii I. -On the composition of orcine and its derivatives by Aug. Laurent and Ch. Gerhardt. Ann. de Chim. et de Phy. xxiv 315. Organic bases.-Researches on the combinations of some of the organic bases with hydrosulphocyanic hydroferrocyanic and hydroferridcyanic acids by Dollfus. Ann. der Chern. und Pharm. Ixv 212.0rthite.-On Orthite by R. Hermann Journ. fur prackt. Chem. xliv. 204. Oxide of iron -On the specific gravity of oxide of iron by H. Rose. Pogg. Ann. lxxiv 429. Oxygen.-On the action of free oxygen in the voltaic circuit by W. Beetz. Idem. 381. -On the action of oxygen in Grove's gas battery by C. F. Schonbein. Idem. 241. P. Papaverhe.-A new organic base by G. Merck. Ann. der Chem. und Pharm. Ixvi 1'2 5. Peganum Harma1a.-Examination of the seeds of Peganum harmala by J. Fritzsche. Journ. fur prackt. Chem. xliv 144 and 370. Pelopic acid -On the specific gravity of pelopic acid by H. Rose. Pogg. Ann. lxxiv 85. Phosphates.-On the phosphates of lead by Ch. Gerhardt. Ann. de Chim. et de Phys xxii 505. -On proto-phosphate of manganese by W.Heintz. Pogg. Ann. lxxv 174. Phosphoric acid.-On the phosphates by FIeitmann and Henneberg Ann der Chem und Pharm lxv 304. -On the phosphoric acid and fluorine contained in different geological strata by J. C. Nesbitt. Journ. of Chem SOC.i 233. -On the quantitative estimation of phosphoric acid and on its presence in some of the rnarls of the upper green sand formation by C. J. Nesbitt Jour. of Chem. SOC.i 44. -On two new compounds of phosphoric acid with ether by C. Vopgeli. Pogg Ann. Ixxv 282. Phosphorus.-Memoir on the fusion of phosphorus by Ed. Desaignes. Ann. de Chim et de Phy. xxii 432. -Researches on the action of perchloride of phosphorus on organic bodies by Aug. Cahours. Idem. xxiii 327. Photography.-On some peculiar properties of iodine phosphorus and nitric acid by M Nie'xe de Saint-Victor.Idem xxii 85. -On the actions exerted by solar radiations on plates of iodide chloride and bromide of silver when the rays are modified by red orange and yellow glasses and also by the vapours in the atmosphere by M. A. Claudet. Idem. 332. Picoline -On the constitution and properties of picoline a new organic base from coal tar by Th Anderson M.D. Ed. Phil. Trans. Vol. xvi 1'. 123. IN BRITISH ,4ND FOREIGN JOURNALS. 437 Picquotiane.-On a new alimentary plant collected by M. Lamare-Picquot in South America and called by the name of Picquotiane by M. Gaudi-chaud. Journ. de Pharm. et de Chim. xiii 273. Pinus -On the acids from the genus Pinus by Aug. Laurent.A4nn. de Chim. et de Phy. xxii 459. Pistomesite.-Analysis of pistomesite by Fritzsche. Journ. fur prackt. Chem. xliii 315. Platinum.-Sote on the combinations of platinum with cyanogen by Bernhard Quadrat. Ann. der Chem. und Pharrn. lxv 249. -On the extensive distribution of platinum and on its occurrence in all silver coin containing gold by Pettenkofer. Pogg. Bnn. lxxiv 316 -Researches upon the various compounds of platinum derived from the green salt of magnus by M. Raewsky. Ann. de Chim. et de Phy. xxii 278. Poisons.-Researches on the principal metallic poisons by M. Abreu. Journ. de Pharm. et de Chim. xiv 241. Pollen.-On the chemical composition of pollen by Th. J. Herapath. Journ. of Chem. SOC.Vol i p. 1. Proteine.-On proteine by G.J. Mulder. Journ. fur prackt. Chem. zliv 488. -On the proteine compounds in the vegetable kingdom by G. J. Mulder. Idem. 503. -On the proteine of flesh by G.J. Mulder. Idem. 505. Prussian blue -On the preparation of the Prussian blue generally known as “Turnbull’s Blue,” by R. Warington. Journ. of Chem. SOC.i 117. Prussic acid -On Liebig’s new test for prussic acid. Ann. der Chem. und Pharm. lxv 203. Pyroxene.-Analysis of pyroxene by Gruner. Compt. Rend xxiv 794. Pyrophosphates.-Researches on the pyrophosphates by Schwartzenberg. Ann. der Chem. und Pharm. lxv 133. -On some combinations of pyrophosphoric acid by W. Baer. Pogg. Ann. Ixxv 152. -On the double salts of pyrophosphoric acid by Persoz. Idem. 163. Q.Quartz.-On the lammeilar structure of quartz by G. A. Kenngott. Pogg. Ann. lxxiii 602. Quinidine.-A new alkaloid from quinquina by M. Winckler. Journ. de Pharm. et de Chim. xiv 279. Quinine.-Analysis of hyposulphite of quinine by C. M. Wetherill. Ann. der Chem. und Pharm. lxvi 150. -On the methods of distinguishing sulphate of cinchonine from sulphate of quinine by Calvert. Journ. de Pharm. et de Chim. xiii 341. -Process for detecting the presence of sulphate of cinchonine in sulphate of quinine by M. Henry. Journ. de Pharm. et de Chim. xiii 102. Quinquina -Note on the coloration of wines with quinquina by E. Soubeiran. Idem. xiii 342. -Syrup of aqueous quinquina by F. Cadet-Gassicourt. Idem. 341. TITLES OF C.HEMICAL PAPERS R.Respiration.-On the function of nitrogen in respiration by R. F. Marchan d. Journ. fur prakt. Chem. lxiv 1. -On the phenomena of respiration in the different classes of animals by Regnault Reiset and Millon Compt. Rend. xxvi 4 -On the respiration of animals by MM. Hegnault and Reiset Journ. de Pharm. et de Chim xiii 81. Rhubarb.-What constituents of rhubarb pass away unchanged by the urine by Dr. Schlossberger. Ann. der Chem. und Pharm. lxvi 38. Ricinus.-On the seeds of ricinus by M. Calloud. Journ. de Pharm. et de Chim. xiv 189. Rocella tinctoria. -Some remarks on the substances discovered by Mr. Sten- house in the Rocella tinctoria and Evernia prunastri by Edw. Schunk. Phil. Mag. xxxiii 249. Rock salt.-Note on the presence of iodide of sodium in different specimens of rock salt by 0.Henry. Journ. de Pharm. et de Chim. xiv 245. Rubiacea-On the family of the Rubiaceae by Dr. Rochleder. Ann. der Chem. und Pharm. lxvi 28. S. Sal-arnmoniac-On the use of sal-ammoniac in chemical analysis by 13. Rose. Pogg. Ann. lxxiv 562. Salts.-On the argument for the binary theory of salts derived from the non- action of the anhydrous oxygen acids on organic colours by G. Wilson. Journ. of Chem. SOC.i 332. Selenium.-Analysis of the liqriid chloride of selenium by M. Suce. Ann. de Chirn. et de Phy. xxiii 124. -On the specific gravity of selenium by Schaffgotsch. Journ. fur prackt. Chem. xliii 308. Silica.-Further experiments on the distribution of silica in the animal king- dom by Dr.Gorup-Besanez. Am. der Chem. und Pharm. lxvi 321. Si1icium.-Researches on the compounds of silicium by J. Pierre. Ann. de Chim. et de Phy. xxiv 286. Silver.-On the decomposition of nitrate of silver by heat by Persoz. Ann. der Chem. und Pharm. lxv 177. -On the methods of reducing chloride of silver by Dr. Mohr. Idem. lxvi 65. -On the specific gravity of the alloys of silver the hydrostatic test for silver and on the wear of silver coin during circulation by Karmarsch. Journ. fiir prakt. Chem. xliii 193. Slag.-Contributions to the knowledge of the slags from iron-smel ting furnaces by C Kammelsberg. Pogg. Ann. lsxiv. 93. Snow.-On the fall of red snow in the valley of Puster by Meister. Pogg. Ann. lxxiii 607. Soda.-On the manufacture of crude soda ash by Bodo Unger.Ann. der Chem. und Pharm lxvii 78. SGdiuin (brine) .-Analysis of the brine-spring the mother-liquor and the pan- stone from the salt-works at Werl in Westphalia by Fred. Deneke. Idem. Ixv 100. IN BRITISH AND FOREIGN JOURNALS. Specific gravity.-Oil a new method of determining the specific gravity of some gases and on the density of oxygen carbonic acid carbonic oxide and sulphurous acid gases by R. F. Marchand. Journ. fur prackt. Chern. xliv 38. -Researches on atonic volume and specific gravity by J. P. Joule and Lyon Playfair. Jour. of Chem SOC.i 121. -On the determination of the specific gravity of solid bodies by G. Osann. Pogg. Ann. lxxiii 605. -On the specific gravity of magnesia alumina glucina and oxide of iron by H.Rose. Idem. Ixxiv 429. -Upon the sources of error which arise in the determination of the specific gravities of bodies when they are weighed in the state of the most minute division by Gustav Rose. Ibid. lxxiii 1. Specific heat.-On the abnormal specific heat of certain alloys and their spon- taneous evolution of heat subsequent to solidification by C. C. Person. Idem. 472. Spinel1 -On kreittonite a new spinell from Bodenmais by V. Kobell. Journ. fur prackt. Chem. xliv 99 Stearn.-On the power of low pressure steam in charring animal and vegetable matter and on the reducing power of charcoal at that temperature by vlr. Ferguson. Journ. of Chern. SOC. i 41. Stoneware.-Analysis of some varieties of stoneware by M.Salvetat. Ann de Chim. et de Phy. xxiii 249. Strychnioe.-Note on one of the reagents for strychnine by M. E. Marchand. Journ. de Pharm. et de Chim. xiii 251. -On a combination of hydrochlorate of strychnine with cyanide of mercury by D. Brandis. Ann. der Chem. und Pharm lsvi 263. -On the ferrocyanides of strychnine and brucine by D. Brandis. Idem 257. Struvite.-On struvite by G. L Ulex. Idem. 41. Sugar.-Means of ascertaining the adulteration of cane-sugar with starch and grape-sugar by G. Reich. Journ. fur prakt. Chem. xliii 7 1. -Of ge1atine.-On the amidogen acids and on sugar of gelatine by M. Aug. Laurent. Ann. de Chim. et de Phy. xxiii 110. Su1phates.-On the nature and composition of the mixed sulphates of com-merce by M.J. Lefort. Idem. 95. Sulphur.-Determination of the proportions in which sulphur in its two different states is found in organic bodies containing- both sulphur and nitro- gen by 'I'h. Fleitmann. Ann. der Chem. und Pharm. hi 380. -Memoir on the sulphur acids by MM. Fordos and Gt5lis. Ann. de Chim. et de Yhy. xxii 66. -Note on the analysis of the oxygen compounds of sulphur by MM. Fordos and Ge'lis. Idem. GO. -On the crystallization of sulphur by L Pasteur. Pogg. Ann. lxxiv 91 Sulphurets.-On the auro-sulphurets of sodium and potassium by Col. P. Yorke. Jour. of Chem. SOC i 236. rr. Tar.-Researches on coal tar by C. B. Mansfield. Jour. of Chem. SOC.i 244. Taurin.-Upon the constitution of taurin and of a body isomeric with it by J.Redtentacher. Ann der Ch9m. und Pharm. lxv 37. TITLES OF CHEMICAL PAPERS Tantaliurn.-Continuation of the researches on the composition of the minerals belonging to the tantaliurn group by R. Hermann. Journ. fur prackt. Chem. xliv 207. Time.-On the influence exerted by time in the formation of chemical com- pounds. by J. Liebig Idem. 350. Tin -On the isomeric states of oxide of tin by H. Rose. Pogg. Ann. lxxv 1. Train oil.-On the oil of the balaena rostrata or Hyperodon by E. A. Schar-ling. Idem. xliii 257. Transsudatior1.-On transsudation in the animal body by C Schmidt. Ann. der Chem. und Pharm. lxvi 342. U. Uranite.-Examination of uranite by G. Werther. Journ. fur prackt Chem. xliii 321. Uranium -On the compounds of phosphoric and arsenic acid with oxide of uranium by G.Werther. Idem. xliii 321. Urea.-Urea contained in the fluid of the eye. Ann. der Chem. und Pharm. lxii 128. -Artificial formation of urea from fulinimic acid by J. H. Gladstone. Journ. of Chem. SOC.i. 22s. -On a new product from the decomposition of urea by G. Wiedemann. Pogg. Ann. Ixxiv 67 and Journ. fur prackt. Chem lxiii 27 1. -On the preparation of cyanate of potash and urea by C. Klemm. Ann. der Chem. und Pharm. lxvi 382. -On the quantitative estimation of urea by R. Bunsen Idem. lxv 375. Uric acid.-On the neutral salts of uric acid by Allan and Bensch. Idem. lxv 1s1 Urine.-On a new substance contained in the urine of a man suffering under softening of the bones by H.R Jones M.D. Idem. Ixvii 97. On the amount of carbonic acid in urine by R. F. Marchand. Journ. fur prackt. Chem. xliv 250. 7On the changes which organic bodies suffer in their passage into the urine by Wiihler and Frerichs. Ann. der Chem. uiid Pharm. lxv 333. V. Va1eramide.-On valeramide by Dessaignes and J. Chautard. Journ. de Pharm. et de Chem. xiii 244. Vanadium.-Analysis of vanadiate of copper and lead by Domeyko. Compt . Rend. xxiv 793. -On the occurrence of vanadiate of copper and manganese-copper near Fried- richsrode in Thuringia by H. Credner. Popg. Ann. lxxiv 546. Vegetables.-Memoir on the proximate principles of vegetables their nature arid the manner of obtaining them by M. Lebourdais. Ann. de Chim. et de Phy. xxiv 58. Vegetation -Observations upon certain phenomena connected with vegetation by J.Persoz. Ann. der Chem. und Pharm. lxv 126. Volaic electricity.-An account of some experiments with voltaic couples immersed in pure water and in oxygenated water by R Adie. Journ. of Chem SOC.i 12. Volatile bases.-(Sce bases). -. IN BRITISH AND FOREIGN JOURNALS. 441 Volume.-On the disappearance of the volume of the acid and in some cases of the volume of the base in the crystals of highly hydrated salts by Lyon Playfair and J. P. Joule Journal of Chem. SOC. i 139. -(See atomic volume). W. Water.-Analysis of the deposits from several ferruginous springs by M. Fil-hol. Journ. de Pharm. et de Chim. xiii 23. -Analysis of the Thames water by G. F. Clark.Journ. of Chem. SOC.i 153. -Analysis of the water of the artesian wells Trafalgar Square by F. A. Abel and Thos. A. Rowney. Journ. of Chem. SOC.i 97. -Analytical researches on the composition of potable waters by Sainte- Claire Deville. Ann. de Chim. et de Phy. xxiii 32. -Chemical analysis of the waters which feed the public fountains of Paris by Boutron Charlard and O’Henry. Journ. de Pharm. et de Chim. xiv 161. -Examination of the water of the Kochbrunnen at Wiesbaden by Dr. F. Lade. Ann. der Chem. und Pharm. lxvi 170. -On the mineral waters of Cheltenham by F. A. Abel and Thos. H. Rowney. Journ. of Chem. SOC.i 193. -On the presence of arsenic and copper in a ferruginous spring in the park at Versailles and on the chemical action of the organic matters con- tained in ferruginous waters of sedimentary deposits by M.Ad. Chatin. Ann. de Chim. et de Phy. xxii 327. -On the use of chloride of gold for appreciating the presence of organic matter in water by M. Dupasquier. dourn. de Pharm. et de Chim. xiii 164. -The apparatus of Briet for the fabrication of gaseous waters by M. Sou-bsiran. Idem. xiii 19. Wax.-Chemical researches on the nature of wax by B. C. Brodie. Phil. Trans. March 30th 1848. Phil. Mag. xxxiii 62 64 217 & 378. -Notice on the products of distillation of bees’-wax and on a resinous body from vegetable parasites by Th. Poleck. Ann. der Chem. und Pharm. lxvii 174. Wine.-On a means of removing acid from stored wines by J. Liebig. Idem. lxv 352.-On a new vegetable production discovered in the wine of Bordeaux by M. Guibourt. Journ. de Pharm. et de Chim. xiv 193. -Treatise on the wines of France by P. Batalliat. Idem. xiv 107. Wood.-On a new product from the dry distillation of wood by E. Schweitzer. Journ. fur prackt. Chem. xliv 129. Z. Zinc.-Investigation of the reactions of iron and zinc with sulphuric acid and its compounds by A d’Heureuse. Pogg. Ann. Ixxv 253. -On a new method for the quantitative estimation of zinc by H. Rose. Pogg. Ann. lixxii 582. VOL. I. NO. IV. GG TITLES OF CHEMICAL PAPERS &C. -On the artificial formation of crystalline oxide of zinc by W. and Th. J. Herapath. Journ. of Chem. SOC.i 42. -On the crystalline form of metallic zinc by M.J. Nickles. Ann. de Chim. et de Phy. xxii 37. -On the crystallized monohydrates of zinc and of cadmium by M. J. Nickles. Idem. xxii 31. -White-lead replaced by oxide of zinc. Compt. Rend. xxvi 361. Zirconium-Notice and analysis of a crystalline hydrosilicate of zirconia found in the department of Haute-Vienne by A. Dumour. Ann. de Chim. et de Phy. xxiv 87. Zircon -Specific gravity of zircon by Svanberg. Journ. fiir prackt. Chern. xliii 313.

ISSN:1743-6893    

DOI:10.1039/QJ8490100423

出版商:RSC    

年代:1849

数据来源: RSC