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