INORGANIC OEEMISTRY. 43 I n o r g a n i c C h e m i s t r y. Action of Thionyl Chloride on Inorganic and Organic Acids and Aldoximes. By C. MOIJREIJ (Compt. rend., 1894, 119, 337--340).-When pure sulphuric acid is niixed with excess of thionyl chloride, a mixture of sulphurous anhydride and hydrogen chloride, in molecular proportion, is evolved without appreciable development of heat, and the residue is a mixture of chlorosulphonic acid, SOzC1*OH, and pyrosulphuric chloride, S2O,CIz. With nitric acid, thionyl chloride acts violently, with development of heat and formation of nitroxyl chloride, sulphurous anhydride, and hydrogen chloride. Nitrogen oxides and sulphuric acid are also formed, in consequence of secondary actions between the hydrogen chloride, the excess of nitric acid, and the sulphurous anhydride.Phosphoric, metaphosphoric, and boric acids are at once attacked by thionyl chloride, but with metaphosphoric acid the action is incomplete, whilst phosphoric and boric acids form chlorinated con- densation products, which are not further attacked by the thionyl chloride. Thionyl chloride, even at its boiling point, has no action on oxalic acid, but sodium, mercury, and silver oxalates yield a metallic chloride, sulphurous anhydride, and carbonic oxide and carbonic anhydride.44 ABSTRACTS OF CHEMICAL PAPERS. In order to moderate the action, the thionyl chloride must be dis- solved in ether or benzene. No trace of oxalic chloride, C202C1,, was formed. Anhydrous formic acid yields carbonic oxide, hydrogen chloride, and sulphurous anhydride, no liquid being left when the action is complete.Aldoximes are violently attacked by tliionyl chloride, but in pre- sence of benzene the action proceeds regularly. The thionyl chloride acts ag a dehydrating agent, and converts the aldoximes into the cor- responding nitriles, RCH:NOH + SOC1, = SO, + 2HC1 + RCN. With benzaldoxime the yield of nitrile is 70 per cent., with isovaler- aldoxime 48 per cent., and with oenanthaldoxime 62 per cent. C. H. B. Secondary Products containing Nitrogen formed during Combustion in Air. By L. ILOSVAY DE NAGY ILOSVA (BUZZ. SOC. Chim., 1894, [3], 11, 272-280).-See this vol., ii, 61. Schuller's Yellow Modification of Arsenic. By H. MCLEOD (Chem. News, 1894, 70, 139).-The author obtained the yellow modi- fication of arsenic, first discovered by Schnller, by heating arsenic in carbonic anhydride or in a vacuum.It reverts spontaneously to ordinary arsenic, the change commencing at the warmer part of the deposit, and extending gradually but rapidly to the cooler portion. D. A. L. Hydrate of Carbonic Anhydride : Composition of Gaseous Hydrates. By P. VILLARD (Compt. rend., 1894, 119, 368-371).- The hydrate of carbonic anhydride discovered by Wroblewski (Abstr., 1882, 1026) is analogous in its mode of formation and decomposition to the hydrate of nitrous oxide (Abstr., 1894, ii, 278). Combination between the gas and water takes place under simple pressure, and neither hydrate decomposes below 0" under ordinary pressure, except in presence of liquid water. Both hydrates have the same crystalline form, and neither of them acts on polarised light.Analyses of the hydrate of carbonic anhydride by thc method used for the hydrate of nitrous oxide gave results varying betwesn C02,6-2H20 and co2,5*9H2o, and the author concludes that the exact composition is C02,6H20, and hence the compound is strictly analogous to the nitrous oxide hydrate. The heats of formation of the two compounds are the same, + 15.0 Cal., from gas and from liquid water. The heat of dissolution under pressure is, in both cases, practically identical with the heat of fusion of the combined water. A crystalline hydrate of sulphurous anhydride formed at 0" gave results varying between S02,6*1H20 and 8O2,6.0H20, and a hydrate of methylic chloride gave resnlts between MeC1,6.3H20 and MeC1,5*9H20.It would seem, therefore, that the two hydrates have, respectively, the formulae S02,6H20 and MeC1,6H20. In both cases the crystals are without action on polarised light, and seem to have the same form as the hydrates of nitrous oxide and carbonic an- hydride. These results render it very probable that the hydrates of all gases,INORGANlC CHEMISTRY. 45 except the hydracids, have the same constitution and are represented by the general formula M,6H20. Triammonium Orthophosphate. By P. SCHOTTLANDER (Zeif. anorg. Chem., 1894, 7, 343-344).-See this V O ~ . , ii, 64. Colloidal Silver. By E. A. SCHKEIDER (Zeit. anorg. Chem., 1894, 7, 339-340).--The organosol Ag (EtOH) (Abstr., 1892, 775), when treated with organic solvents, either remains in solution or coagu- lation takes place, and the production or absence of coagulation shows the existence or otherwise of an organosol with the organic solvent employed.No coagulation is observed with propylic, isobutylic, tertiary butylic, or cetylic alcohol, ethylene glycol, glycerol, or phenol. Coagulation takes place after a few hours with trimethylamide and pyridine. Coagulation takes place at once with isopropylic, normal and secondary butylic alcohols, trimethylcarbinol, heptylic, cetylic or allylic alcohol, erythrol, octane, amylene, formaldehyde, cenant,h- aldehyde, acetone, ether, acetic acid, benzene, benzylic alcohol, meta- cresol, triethylamine, dimethylamine, diethylamine, and quinoline. The solutions in which coagulation did not take place were observed for some months.With phenol, coagulation commenced after 14 days and gradually increased ; and after one month coagulation was ob- served in the case of propylic and tertiary butylic alcohols. After two months, coagulation had taken place in all the solutions. The organosol Ag (Et.OH) was coagulated by ether, the pre- cipitate washed with absolute ether and dried over sulphuric acid in a, vacuum. It has a greenish, metallic lustre, loses 4.5 per cent. in weight when heated, and when allowed to remain i n a damp atmo- sphere increases in weight to the extent of 15.82 per cent. The dry colloid is entirely soluble in water. Basic Calcium Salts. By TASSILLY (Cornpt. rend., 1894, 119, 371--373).-When three parts of calcium oxide is added in successive small portions to a solution of 100 parts of calcium bromide in 75 parts of hot water, the filtered liquid, on cooling, deposits acicular crystals of the oxybromide CaBr,,SCnO + 16HZ0, which may be washed with a 25 per cent.aqneous solution of calcium bromide. The oxyiodide previously described (Abstr., 1894, ii, 92) may be more advantageously prepared in the same way as the oxybromide. The oxybromide and oxyiodide are decomposed by water, alcohol, carbonic anhydride, and the stronger acids. The hydracids and very dilute nitric acid dissolve them readily, and sulphuric acid converts them into sulphates. C. H. B. E. C. R. CaBr,,3Ca0,16H20 + 6HBr dil. . . . . develops + 63.55 Cal. and hence CaBr, + 3Ca0 + 16H20 liquid .. . . . 97 +98-85 ,, CaBr, + 3Ca0 + 16H20 solid.. .. . . 19 +76-45 ,, Further Ca12,3C'a0,16H20 + 6HI dil.. . . . . . . 9 , +63*4 1946 ABSTRAOTS OF CHEMIOAL PAPERS. hence Car, + 3Ca0 + 16H20 liquid.. . . . . . It is noteworthy that the heat of dissolution of the oxy-salt in the corresponding hydracid is practically identical in the three cases, but the heat of formation from the proximate constituents increases with the atomic weight of the halogen. develops + l o 2 9 Cal. CaT, + 3Ca0 + 16H20 solid . .. . . . . ,7 + 79.3 ?9 C. H. B. Action of Phosphorus Trichloride on Magnesium Nitride. By E. A. SCHNEIDER (Zeit. anorg. Chew, 1894, 7, :358).-When phos- phorus trichloride i8 passed over magnesium nitride by the aid of a current of nitrogen, a violent action takes place at a red heat, and large quantities of phosphorus distil over.The residue consists o€ magnesium chloride and a bright, brown powder, which contains 19.26 per cent. of magnesium together with phosphorus and nitrogen. Stability of Aqueous Solutions of Mercuric Chloride. By E. BURCEER (Compt. rend., 1894, 119, 340--342).-Aqueous solutions containing 1 part of mercuric chloride and 1.14 parts of hydrogen chloride per litre of ordinary water (containing calcium carabonatej undergo only trifling alteration when exposed to air and light, and no alteration at all when kept in well-closed vessels in the dark. 0.5 gram of tartaric acid per litre has the same effect (compare Abstr., 1894, ii, 93 and 381). Indigo-calamine has no decomposing effect on solations of mercuric chloride i n distilled water acidified with tartaric acid, even when they are exposed to light.Fhe Molecular State of Mercurous Chloride Vapour. By V. MEYER (Bey., 1894, 27, 3143-3145 ; compare Harris and Meyer, Abstr., 1894, ii, 353).-The author adheres to the conclusion already drawn (Zoc. cit.), and referring to the experiments of Fileti (Abstr., 1894, ii, 449), points out that no amalgamation occur^ when a cooled gold surface is immersed in the mixed vapourv of mercury and mer- curic chloride ; the evidence of the stability of mercurons chloride adduced by Fileti is, therefore, no longer valid. Double Salts of Higher Chlorides of Manganese and Copper. By G. WEUMANN (Monatsh., 1894, 15, 489--%94).-The compound (NH4),MnC15 is obtained" when manganese dioxide is allowed to remain for a considerable time in contact with concentrated hydro- chloric acid, kept cool by immersion in a freezing mixture of ice and d t , and saturated with hydrogen chloride and chlorine ; the brown solution thus obtained, when filtered and treated with a cold solution of ammonium chloride, yields the compound in violet-brown crystals. It is readily decomposed, the violet-brown aqueous solution, even when kept cool, becoming turpbid from sepalsation of manganese di- oxide.In a, precisely similar manner, the double potassium tnanganese chloride, K2kI.nCI5, is obtained. The formation of these compounds confirms the results obtained. by Pickering (Trans., 1878, 654), and E. C. R. C. H. B. M. 0. I?.INORQANIO OHEMISTRY. 47 disprove8 Fisher’s statement that a tetrachloride of manganese is formed (Trans., 1878, 409).On passing a mixture of hydrogen chloride and chlorine into a well- cooled solution of cupric chloride, glistening, red needles, which quickly change to green, are obtained. These have the formula CuH3Clb, whereas on passing hydrogen chloride into a well-cooled Rolution of cupric chloride, Engel (Abstr., 1888, 558) obtained a salt to which he ascribed the formula CuHCI,, and Sabatier (Abstr., 1888, 1036, 1037) stated that t.he product formed was CnH2C14, Cuprous chloride, free from cupric salt, Fives with hydrogen chloride the compound CuHC12, which crystalhses in pearly-grey needles. The two compounds MnK,Cl, and CuH3C15 are of interest on account of their illnstrating the heptad nature of manganese and the octrtd nature of copper respectively. Constitution of Cobalt, Chromium, and Rhodium Bases.By S. If. J~RGENSEN (Zeit. anorg. Chem., 1894, 7,289-330 ; Abstr., 1894, ii, 50).-Aquotetraminexanthocobalt salts are obtained from chloro- nitrotetraminecobalt chloride (Abstr., 1894, ii, 50), which is easily pre- pared by heating croceocobalt sulphate with concentrated hydrochloric acid. Aquotetraminexanthocobalt chloride, N02*Co( 0H2,C1) (NH,),Cl, is obtained by warming the above chloride with water and a few drops of acetic acid, and allowing the solution to crystallise over sulphuric acid. If treated with concentrated hydrochloric acid, it is recon- verted into the anhydrous chloride, and after drying in the air gives up its water when allowed to remain over sulphuric acid. Aquotetraminexanthocobalt hydrate, N02*Co( OH2,0 El) ( NH3),CI, is obtained when the anhydrous chloride is.treated with dilute am- mpni? in the cold. It crystallises in deep red prisms, is converted into the auhydrous chloride by concentrated hydrochloric acid, and gives with silver nitrate a mixture of silver chloride and silver oxide. The formation of this basic salt shows that the two chlorine atoms in aquotetraminexanthocobalt chloride, although they behave in the same way towards silver nitmte, are combined in a totally different manner, namely, the one to the ammonia chain, the other to the radicle OH,. When the anhydrous chloride is shaken with f reshly-prepared silver oxide, it yields a yellowish-brown filtrate, which is stzongly alkaline, liberates ammonia from ammonium salts, and no doubt con- tains aqnotetraminexanthocobalt hydrate.The preparation and properties of the following salts are described. The bromide, N02*Co(OH2, Br) (NB3)IBr ; the nitrate, G. T. M. NOz*Co(OH2,h’03) (NH,),NO, ; the sukhate, N02*Co< (OH’) > SO4 ; the platinosochloride, w 3 3 ) 4 NOZ*Co(OH,,Cl) (NH,),Cl,PtCI, ; the auroc7doride, NO2-Co( OH2,C1) (NH3)4C1,AuC13 ; the diaminecobalti- nitrite, NO2.Co(OH2) (NH3),[ (NO&(NH&CO(NOJ~]~ ; aud the oxa- late, NO2*Go( OH2)( NH3)&O4.48 ABSTRACTS OF CHEMICAL PAPERS. Preparation of dinitrotriaminecobalt salts.-Dinitrotriaminecobalt nitrite is obtained by the oxidation of an ammoniacal mixture of cobalt chloride, sodium nitrite, and ammonium chloride, employed in the proportions represented by the following equation, CoC12 + 3NHdN02 + 2NH3 + $0 = ZNHICl + gH20 + (NO~)~CO(NH~)~*NOZ.The reaction varies, however, Tery considerably, according to the pro- portions of ammonium salt and ammonia employed, and under these varying conditions ammonium cobalt nitrite, ammonium diamine- cobalt nitrite, croceocobalt chloride, xanthocobalt chloride, or croceo- diaminecobalt nitrite is obtained. The triamine nitrite is also obtained by heating the ammoniiim diamine nitrite with water and concen- trated ammonia on the water bath, also by boiling an aqueous solu- tion of ammonium diamine nitrite and the flavonitrate with a few drops of acetic acid. Dinitrotriaminecobalt chloride, (N02)2Co(NH3)3Cl, is obtained by heating the triamine nitrite with hydrochloric acid. It cry stallises in red tablets, yields all its chlorine as silver chloride when treated with silver nitrate, is converted into the triamine nitrite by sodium nitrite, and into the dichrochloride when warmed with concentrated hydrochloric acid.When warmed with ammonium nitrate and ammonia, and then treated with dilute nitric acid, it yields flavocobalt nitrate, whence the author concludes that the constitution of this salt is represented by the formula (N02)2Co*NH3*NH3*N*H3*C1. The dinitrotriamine bromide, (N02)2Co (NH3),Br, and dinitrotri- amiiie sulphate, [(N02)2C~*( NH3)3]2S04,2H20, are also described. The last part of the paper deals with the views put forward by A. Werner (Zeit.physika1. Chem., 1894,14, SOS), and the structure of the ammonio-cobalt salts. E. c.a. Molybdamide. By H. FLECK and E. F. SMITH (Zeit. anorg. Chewt., 1894, 7, 351-357) .-When freshly-prepared molybdic chloride, MoO,Cl,, is treated with sodium ethoxide in ethereal solution, a, precipi- tate of sodium chloride is obtained ; the filtrate, on evaporation, yields a blue, amorphous compound, which is converted into ammonium molybdate when dissolved in alcohol and treated with ammonia. Nolybdamide, OH*Mo02*NH2, is obtahed when molybdic chloride dissolved in chloroform is treated with dry gaseous ammonia or shaken with aqueous ammonia. A black precipitate is obtained which is probably the diamide; it is, however, very unstable, and when extracted with alcohol is converted into the monamide; the latter is a brownish-red, amorphous powder. Molybdic chloride forms more stable compounds with ethylamine than with ammonia, a mono- or di-ethylamide being formed accord- ing t o the amount of ethylamine employed.The monethgEamide, OH*MoO,*NHEt + QH20, is a white powder, which gradually turns reddish-brown on exposure to air ; it is soluble in water, and yields ethylamine when treated with alkalis. The diethylamide, Mo02(NHEt),, is a reddish-brown powder, which gives off ethylamine on exposure to air, and gradually becomes white ;BfINERALOGICAL CHEMISTRY. 49 it yeacts violently wihh nitric acid, yields ethylnmine when treated wit.h alkalis, and gives a deep blue solution with concentrated sul- phuric acid. E. C. R. Thorium Metaoxide and its Hydrate. By J. LOCKE (Zeit. a72org. Chenz., 1894, 7, 345--350).-Thorium metaoxide, which is obtained by heating the osalate, is found to hare the composition Th305. It is also obtained when the normal thorium oxide contain- i n g iron is heated in a current of steam, or when the pure normal oxide is heated in hydrogen. A quantitative determination of tho water formed by the last method of reduction gave numbers agree- ing with those required for the reduction of Tho, to Th3O5. Thorium metahydroxide is prepared by evaporating the meta- oxide to dryness with hydrochloric acid, dissolving the residue in hot water and precipitating with ammonia. It is a pure white precipi- tate, and has the composition Th,O,,'LH,O; when dried at 100' it loses 1H,O. The metahydroxide, Th305,H20, is also obtained when the metaoxide is treated with hydrochloric acid, but if prepared by this method it forms a brownish residue resembling varnish. Vanadium in Commercial Caustic Soda. By H. L. ROBINSON (Qhem. Nezos, 1894, 70, 199).-A solution of caustic soda became deep purple in colour when saturated with washed hrdrogen sulphidc, but on exposure to light with access of air the colour slowly faded, the liquid becoming yellowish, and a brown precipitate being formed ; this was found t o be due to the presence of vanadium, but tbis element apparently is not present as a vanadate. E. C. R. D. A. L.