ABSTRACTS OF CHEMICAL PAPERS. Inorganic C hem i s tr y. Behaviour of Ozone with Water and Nitrogen. By L. CARIUS(Ann. Chem. clxxiv 1-30). CONTRAD~CTORY statements on this subject having been put forth by various able investigators the author has carried out a new series of researches with the view of determining these questions. By prefer-ence he obtained the ozone for his experiments by Soret's method of electrolysing dilute sulphuric acid at a low temperature ; but for com- parison he also used Houzeau's and von Babo's apparatus for producing ozone by silent electric discharges in air or oxygen. Contrary to the generally received statement he has found that ozone is soluble in water that liquid quickly acquiring from its own bulk of a gas con- taining 2 per cent.of ozone its odour and characteristic properties. Even when the gas contained orjly 1 per cent. of ozone the solution produced a powerful effect on potassium iodide and starch but dimi- nution of the proportion of ozone leads very rapidly to an extreme weakening of the solution. Ozone mixed with oxygen gas obeys in fact that law of gaseous absorption which makes the quantity dissolved proportional to that fraotion only of the total pressure due to the quantity of the gas itself which may be present in t)he mixture. Taking this law into account the author has from a series of experi- ments obtained a set of numerical results which show a very satisfac- tory accordance and furnish a mean of 0.834 as the co-efficient ot absorption for ozone at 1"and under 760 mm.pressure. For certain reasons however he believes this somewhat below the true value. The strong aqueous solution of ozone has an odour easily distinguish- able from thak of chlorine chlorous acid &c. It bleaches litmus- paper decolorises indigo changes tinct3ure of guaiacum to deep blue and precipitates thallium oxide from its solutions. The formation of silver peroxide by the action of the solution does not take place with certainty. No trace of the production of hydrogen peroxide by the action of ozonised oxygen on water could be detected either when these bodies alone were in contact or when nitrogen was also present. Nor after leaving in contact for weeks oxygen containing 2 per cent. of ozone water and nitrogen could the author discover by the most delicate tests the presence of any acids of nitrogen.He therefore emphatically asserts that nitrogen is not oxidised by ozone in the presence of water at ordinary temperatures. But when the ozone was prepared by electric discharges in oxygen containing even a very small percentage of nitrogen tthe presence of nitric acid was easily recognised. The wid is here the result not of the oxidation of nitrogen by the ozone but of the oxidation by the ozone of the nitrous acid produced by the electric discharges. Hence while electrolytically prepared ozone admits of being accurately estimated by potassium iodide the formation of nitrous acid in the other process forbids the use of this reagent with the ozone so produced.The gradual conversion of ozone into ordinar,y IXORGANIC CHEMISTRY. oxygen in presence of water which was observed by Andrews has been found by the author to be greatly influenced by temperature and at 0" it takes place so slowly that its effect did not require to be taken into account in the puthor's experiments which were conducted at about this temperature. R. R. Preparation of Crystalline Hypophosphorous Acid. By J. THOMSEN (Deut. Chem. Ges. Ber. vii 994). HYPOPHOSPHOROUS acid is generally stated to be an uncrystallisable syrup. The author has obtained it as a snow-white crystalline mass fusible at 17.4". The dilute solution obtained by decomposing the barium salt with sulphuric acid is first boiled down rapidly in a porce-lain dish and the evaporation completed in a platinum dish without ebulition.The bulb of a thermometer is immersed in the liquid and the temperature allowed to rise gradually to 105" at which tempera- ture most of the water can be driven off. The liquid is then filtered hot and the heating continued gradually up to 130". After ten minutes at this temperature the acid is transferred to a bottle and cooled below 0". It exhibits strongly the phenomenon of superfusion but crystal- lises when touched with a glass rod or more readily by the addition of a crystal of the same acid. M. J. S. Formation and Decomposition of Metallic Sulphides. By K. HEUMANN (Ann. Chem. clxxiii 21-39>. CONSIDERING it probable that the formation of crystalline cuprous sul- phide when copper remains in contact with yellow ammonium sulphide is due to the action of copper on the red crystalline substance CU~(NH~)~S,, the author allowed copper to remain in contact with a solution of the above-mentioned red salt but no cuprous sulphide was produced the red salt remaining unaltered.The double salt CU,(NH~)~S,, can be obtained abundaiitcly but in a slight,ly impure stake by adding cupric sulphate to concentrated ammo- nium pentasulphide. It is as might be expected decomposed by heat or strong acids and it is insoluble in water but soluble in ammonium sulphide the addition of an acid to this solution causing the precipi- tation of a mixture of sulphur and cupric sulphide. Copper causes the evolution of hydrogen not only from yellow ammonium sulphide but also from the hydrosulphide and the piire sulphide crystalline cuprous sulphide being formed in each case.The reactions are probably as follows :-Nz) s + CUP= CUPS+ NH + €3,. The crystals of cuprous sulphide obtained by the above reactions consist of thin ihombic needles which slowly oxidise in moist air and ABSTRACTS OF CHEMICAL PAPERS. are gradually dissolved by hot hydrochloric acid but are not acted on by sulphuric acid. Strong nitric acid acts violently on the crystals oxidising half the sulphur and leaving pseudomorphs of cupric sulphide. Dilute nitric acid dissolves the crystals sulphur being separated ; while yellow sulphide of ammonium converts them into cupric sulphide and ammonium pentasulphide transforms them into the substance Cu2(NH&S7.Silver nitrate decomposes the crystalline cuprous sul- pliide with production of a crystalline mixture of silver sulphide and metallic silver. Cupric oxide acts energetically on ammonium sulphide a mixture of cupric sulphide and cuprous sulphide being formed while sulphur is liberated and remains in solution. Metallic silver simply removes the excess of sulphur from yellow ammonium sulphide no gas being evolved. Copper reacts on an ammoniacal solution of arsenic sulphide with production of a yellowish-brown precipitate containing copper arsenic and sulphur ; while the action of copper on an ammoniacal solution of antimony sulphide leads to the production of a brown-black precipitate containing copper sulphur and antimony.These products will be investigated and the action of copper on solutions of antimony sulphide and arsenic sulpbide in ammonium sulphide will also be studied. Action of Light on Cilznabcw.-men cinnabar which has been pre- pared either in the wet or dry way is suspended in an alkaline liquid such as ammonium sulphide potash or ammonia and exposed to sun- light the outer layers become dark brown. This change takes place most readily with cinnabar prepared in the moist way. It does not take place when the cinnabar is suspended in an acid solution and only with extreme slowness when pure water is employed. Cinnabar prepared in the wet way contains metallic mercury and treatment with nitric acid partly removes this but a portion is con- verted into a white substance which is doubtless a basic nitrate.Ammonia blackens cinnaba'r containing this basic nitrate but a second treatment with nitric acid restores the red colour and renders the cinnabar pure. A sample thus purified was blackened by exposure to light and after the change it yielded no mercury to nitric acid. Hence t'he author concludes that the blackening is a molecular change and is not due to a decomposition of the cinnabar. Zinc and copper partially reduce moist cinnabar with production of metallic mercury or of a black substance from which nitric acid extracts mercury cinnabar remaining. Zinc in presence of hydrochloric acid reduces cinnabar more readily hydrosulphuric acid being evolved and other sulphides may be reduced in a similar way.Copper sulphide when treated with zinc and an acid yields a black powder which is probably cuprous sulphide this latter sulphide being very difficult to decompose by zinc a8nd an acid. T. B. INORGANIC CHEMISTRY. New Sulphur-salts. By R. Sc H N E ID E R (Pogg. Ann. cli 437-450). Potassium-nickel S~~lpl~ide.-lpart of nickel sulphate is fused for 8 or 10 minutes at a red heat with 9 parts of pure potassium carbonate and 9 parts of sulphur and the fused mass is t'reated with cold water deprived of air whereby the excess of potassium sulphide and nickel sulphide is removed and the new conipound remains in the form of brilliant crystalline plates which are further washed with water and lastly with absolute alcohol.This salt is readily decomposed by contact with air and water; the analyses agree with the formula E;i 1NiS, which is analogous with the double palladium-potassium sulphide already described KS 1Pd&. Potassium-cobaZt Su 2p 7~ide.-By fusing cobalt or cobaltous chloride with potassium carbonate and sulphur a substance is formed which the author believes to be the cobalt double salt corresponding with the above-described nickel-compound but he has not been able to obtain it in the pure state. If 1part of cobaltous chloride be fused with 6 parts of soda and 6 parts of sulphur for ten minutes at a full red heat and the fused mass be treated with water light iron-grey crystals of cobalt sesquisulphide COZS~ remain. Sodium-naaizg~~zese Szdphide.-B y fusing manganous oxide with soda and sulphur the author has prepared the two salts NaZS.2MnS and Na2S.3MnS.In attempting to prepare the corresponding potassium salts he found that considerable quantities of minute green needles were produced consisting of manganous sulphide MnS. M. M. P. M. On the Constitution of the Lead-chamber Crystals. By A. MICHAELIS (Deut. Chem. Ges. Ber. vii, and 0. SCHUMANN 1075-1078). INorder to test the validity of the formula SO generally given Yo to the lead-chamber crystals the authors have prepared the compound by the action of sulphurous acid on concentrated nitric acid and sub-mitted it to the action of phosphorus pentachloride. The decompo- sition proceeds according to the equation Towards the end of the distillation a small quantity of a crystalline body boiling at about 360° passes over presenting the characters of the anhydride S205(N02)2.Some metaphosphoric acid remained in the retort. The anhydride thus produced is the result of the action of heat on the sulphate experiments described by the authors leading to the conclusion that this decomposition takes place in accordance with the equation 4i02{gz= 250 { gg + S,O,(NO,) + N,O,. W. A. T' ABSTRACTS OF CHEMICAL PAPERS. Sodio-ferrous Sulphate. By E. B I LTZ (Zeitschr. Anal. Chem. 1874 124-128). THEauthor draws attention to the salt Na2S0414H20 which is if FeS04 properly prepared very stable and of much use #in standardised per- manganate solutions &c.instead of iron wire. This salt is best pre- pared by dissolving pure crystallised ferrous sulphate in its own weight of warm water which contains 2 per cent. of dilute sulphuric acid ; an equivalent amonnt of sodium sulpha,te is added and the liquid evapo- rated by gently boiling it until a considerable quantity of crystals is formed. The liquid is now allowed to cool with gentle stirring the salt collected on a filter pressed between paper dried in a warm air chamber and finally brought into the water-bath where it quickly becomes thoroughly dry. M. M. P. M. Ultramarine. By E. Bu c H N E R (Deut. Chem. Ges. Ber. vii 989-993). IN order to ascertain whether the presence of silica was absolutely necessary to the formation of artificial ultramarine two mixtures were made as follows :-I.A12Na60,+ 6s + 3c 11. A1zNa606 f 6s + 3c + 2Sio2 and submitted to the ordinary process for preparing ultramarine. The second mixture gave a deep blue ; the first however also gave a pale blue which was accounted for by the presence of 10 per cent. of silica subsequently found in the aluminate. Silica appears therefore to be necessary. Contrary to the statements of Unger the author finds nitrogen absent from and sodium invariably present in ultramarine. The excess of sodium is removed by washing as sulphide not as sulphate. When a mixture of clay and soda is heated in a stream of hydrogen sulphide or carbon disulphide vapour a green mass is obtained which by heating in a current of air or with sulphur or ammonium chloride is converted into blue.A similar result is obtained by heating natrolite first in carbon disulphide then in sulphur dioxide. The author regards Scheffer’s red and yellow ultramarine as the products of partial decomposition since he finds that they are obtained when ultramarine is heated in oxygen before the action has been cayried far enough to yield a white residue. Finally he shows that R. Hoff-mann’s ultramarine crystals are only quartz. They are found both in the clay employed and in the residue of the decomposition of ultra-marine by acids. M. J. S.