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.