26 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h e m i s t r g . Compound of Iodine with Ammonia. By F. RASCHIG (Annulen, 241, 253-255).-Iodiiie absorbs dry ammonia gas, forming a dark- blue liquid ; Bineau (Ann. Chim. Phys. [3], 15, SO) assigns to this substance the formula 3NH3,2I, but according to Millon (Annulen, 62, 54) iodine absorbs less than half the volume represented by this formula. The anthor finds that the volume of ammonia absorbed by the iodine Taries with the temperature. At 20°, the amount of ammonia absorbed corresponds with Bineau's formula, but a t 80" it carresponds with NHJ, a t 0" with I(NH3)2, and at -10' with 12(NH3)5. The liquid is decomposed by water, yielding ammonium iodide and nitrogen iodide, but it dissolves completely in alcohol Method for Decomposing Arsenical Sulphides.By . H. WARREN (ahem. News, 56, 193--194).-The cobalt speiss or arsenical alloy is digested in hydrochloric acid containing copper nitrate, and after a day or so, the insoluble portions are calcined at a low red heat with plentiful access of air ; the calcined mass is then easily dissolved by hydrochloric acid and mixed with the other solution. The copper is separated by means of metallic iron, which also removes some bismuth and arsenic ; and the iron and remaining arsenic are precipitated by adding milk of lime. The culcium salts are removed by treatment with sulphuric acid, and the solution containing nickel and cobalt is precipitated by means of sodium carbonate. The precipitate is then suspended in water and chlorine passed to saturation, when the nickel goes into solution, whilst the cobalt remains undissolved.The solu- without undergoing any change. w. c. w.INORGANIC CHEMISTRY. 27 tion is boiled, and on adding caustic soda the nickel is obtained as hydroxide, which is ignited and reduced in the usual way. D. A. L. Zinc Titanates. By L. LEVY (Compt. rend., 105, 378-380).- When a mixture of 6 grams of titanic oxide, 2.5 grams of zinc oxide, and 5 to 10 grams of anhydrous zinc chloride is heated in a glass tube, the reaction is incomplete, and a violet product is obtained which contains an excess of titanic oxide. With excess of zinc chloride, the product is yellowish. If the mixture is heated in a Perrot's furnace in a crucible brasqued with charcoal and rutile, the zinc chloride volati- lises, but if the heating takes place in a long porcelain tube closed at one end, a violet or green, crystalline mass is formed, which contains titanium, zinc, silicon, and potassium.I f a mixture of 7 grams of titanium oxide, 5 grams of zinc oxide, and a small quantity of zinc fluoride, or 7 grams of titanium oxide and 30 grams of zinc fluoride is heated under a thin layer of potassium fluoride in a graphite crucible in a Perrot's furnace for an hour and a half, washed with water, and then treated with concentrated sul- phuric acid to remove zinc oxide and titanium fluoride, beautiful violet needles are obtained. With potassium chloride in place of the fluoride, the product is a greenish mass. With a mixture of potassium and sodium chlorides the violet needles are obtained mixed with yellowish needles of potassium titanate.The violet crystals are zinc trititanate, Zn0,3TiU2, a small quantity of the zinc being displaced by iron. They are insoluble in water, alcohol, and ether, are not affected by hot dilute sulphuric, nitric, and hydrochloric acids, nor by boiling concentrated solutions of alkaline hydroxides, butl are attacked with difficulty by boiling concentrated sulphuric acid, and are decom- posed by fusion with potash. They are infusible before the blowpipe, but change to a greenish mass without loss of weight ; sp. gr. at l 5 O = 4.92. The crystals are not attacked by hydrogen at a red heat, but partially volatilise in a mixture of chlorine and hydrogen chloride. When treated with acidified hydrogen peroxide, the latter acquires a characteristic yellow colour, but decomposition is never complete. Electrolytic Method of preparing Metallic Alloys, &c.By H. WARREN (Chem. h'ews, 56, 153--154).-The following method is recommended for the preparation of alloys such as phoaphor-bronzes, silicides, &c. The metal and substance containing alloying material are placed in a deep, conical crucible, through the bottom of which passes a rod of graphite, extending about one inch within the crucible and protected on the outside by au iron tube. The metal is melted and the graphite put in connection with the negative pole, whilst the molten substance on the surface is connected with the positive pole of a battery of two large ferric chloride cells. In this manner silicon copper and silicon-eisen are easily prepared from pobassium silico- fluoride and the respective metal ; the salt being taken in sufficient quantity to form a molten layer 2 inches deep.By some slight variation in the details, phosphor-bronzes can be produced ; moreover, native cryolite can be decomposed in contact with metallic zinc, and on C. H. B.28 ABSTRACTS OF CHEMICAL PAPERS. subsequently volatilising the zinc, pure aluminium is obtained. Mag- nesium, barium, strontium, and calcium have not yielded satisfactqry alloys as yet. Process for obtaining the Rare Earths from the Ceriferous Hainstadt Clays. By J. R. STROHECKER (Chem. News, 56,175-1'76). --The author attributes the failure of other chemists to obtain cerium from these clays (compare Abstr., 1886, 678) to the fact that in the presence of more than 0.5 per cent.of iron, the cerium precipitated by oxalic acid and potassium sulphate is much contaminated with iron, the oxide prepared therefrom being so colonred by iron oxide as to be mistaken for that substance. He describes the processes by which he affirms that he has separated the various rare earths from these clays. A. J. G. Reduction of Aluminium Oxide. By G. A. FAURIE (Compt. rend., 105, 494).-Two parts of pure finely-powdered aluminium oxide is made into a paste with one part of petroleum or some other hydrocarbon, and then mixed with one part of sulphuric acid. When the masc is homogeiieous with a pale yellow tint, and begins to give off sulphurous anhydride, it is wrapped in paper and thrown into it crucible heated to above 800" in order to decompose the hydrocarbon, The compact product thus obtained is powdered and mixed with its own weight of a finely-divided metal, the mixture being then heated to a whit>e heat in a plumbago crucible.The regulus after being allowed to cool is found to contain grains of an aluminium alloy in the midst of a metallic powder. This method of reduction is applicable to silica, calcium oxide, magnesium oxide, &c. Halogen Compounds of Gold. By G. K R ~ S and F. W, SCl-TMtuT (Bey., 20: 2634--2643).--Experiments made with a view to prepare aurous chloride and bromide by the action of chlorine and bromine respectively on gold, .gave negative results. The gold is con- verted into auric compounds in both cases ; if, is difficult to complete the reaction.I t is suggested that the numbers obt'ained by Thornsen, pointing to the formula Au,C14, were obtained from a product from which the adbeling chlorine had not been removed. When gold is warmed in bromine vapour, a black compound is formed which decom- poses into its constituents when heated at loo", even when kept in bromine vapour. The product contains a large amount of unattacked gold together with auric bromide. The compound AuzBr4 is not formed. The authors conclude that Thomsen's auro-auric chloride and bro- mide (this Journal, 1877, ii, 485) do not exist. By L. HOFFMANN and G. K R ~ ~ S S (Ber., 20, 2704--8710).-Oberkampf believed that he obtained an auro-auric sulphide, Au&, by heating a solution of auric chloride with hydrogen sulphide, but the product, according to Levol and Pellenberg, had a composition varying between that of Au,Sp and Au2S3, whilst Schrotter and Priwoznik state that an auro-auric sulphide of constant composi- I>.A. L. C. H. B. N. H. M. Gold Sulphides.INORGANIC DHE MISTRY. 29 tion cannot be obtained. These results are probably to be attributed to an incomplete removal, by mere washing on a filter, of sulphur pre- cipitated simultaneously, since the authors find that to remove free sulphur from the precipitate it is necessary to wash the sulphicle by decantation with absolute alcohol, anhydrous ether, and carbon bi- sulphide successively (compare Abstr., 1887, 1019 j. When a neutral solution of auric chloride is treated with hydrogen sulphide in the cold until all colour has disappeared from the solu- tion, and the precipitate, after repeated washing with water, is washed by decantation as above, auro-auric sulphide, AuZS2, of constant com- position is obtained, and the reaction is represented quantitatively by Levol's equation, 8AuC13 + 9H2S + 4H,O = 4Au2S2 + 24HCl + H2S04.Auro-auric sulphide is a black powder in thc dry state, and when moist is also black by reflected light, but in the finely-divided state it transmits light of a reddish-brown colour. On, porcelain, it gives a black streak. When heated in a tube, sulphur begins to vola- tilise at 140°, as sulphurous anhydride, and is completely expelled at 250-270" without the intermediate formation of aurous sulphide. With the exception of aqua regia, auro-auric sulphide is insoluble in all acids.Bromine water, gradually converts it, especially on warming, into auric bromide and snlphuric acid. Alkaline monosulphides dis- solve it slowly in the cold, but readily on heating, yielding brown solutions which beoome greenish-yellow when the heating is con- tinued ; alkaline polysulphides dissolve it in the cold, and the solu- tions on heating become brown and eventually yellow; yellow sulphide of ammoniurq, however, dissolves the compound less readily than the sulphides of the alkalis. Concentrated aqueous potash does not attack it in the cold, but on heating converts it into gold, potas- sium gold sulphide, and potassium gold oxide. Potassium cyanide dissolves it readily. When heated in a currenk of oxygen, the sulphide ignites, and is converted into gold and sulphurous anhydride, whilst hydrogen sulphide is formed when the heating occurs in a current of hydrogen.By fusing gold with potassium pentasulphide, Berzelius states that he obtained a sulphide which he believed to have the composition AuZS3, although no analyses were made. The authors have endeavoured to prepare a gold sulphide of this composition in four ways :-(1) By Berzelius' method ; (2) by Obei-kampf's and by Yorke's method (this Journal, 1848, 236), which consists in precipitating a saturated solu- tion of auro-auric sulphide in sodium bisulphide with an acid ; (3) by precipitating a saturated solution of auPo-auric sulphide in sodium monosulphide with hydpochloric acid ; and (4) saturating a solution of sodium gold oxide with hydrogen sulphide and heating the normal sodium thioaurate with an acid ; the precipitates in every case were washed by decantation with alcohol, ether, and carbon bisulphide.The precipitated sulphide obtained by the first two methods, however, contained more sulphur than required for the formula Au2S3, and had not a const'ant composition; whilst that prepared by the last two methods had a composition intermediate between that of Au,S, and Au2Ss. The authors therefore conclude that auric sulphide, Au2SJ, does not exist, and show that the properties of the so-called com-30 ABSTRACTS OF CHEMICAL PAPERS. pound are those of a mixture of suro-auric sulphide and sulphur, the latter being left as an insoluble, white powder on digestion with potassium cyanide.w. P. w.26 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e m i s t r g .Compound of Iodine with Ammonia. By F. RASCHIG (Annulen,241, 253-255).-Iodiiie absorbs dry ammonia gas, forming a dark-blue liquid ; Bineau (Ann. Chim. Phys. [3], 15, SO) assigns to thissubstance the formula 3NH3,2I, but according to Millon (Annulen,62, 54) iodine absorbs less than half the volume represented by thisformula. The anthor finds that the volume of ammonia absorbed bythe iodine Taries with the temperature. At 20°, the amount ofammonia absorbed corresponds with Bineau's formula, but a t 80"it carresponds with NHJ, a t 0" with I(NH3)2, and at -10' with12(NH3)5. The liquid is decomposed by water, yielding ammoniumiodide and nitrogen iodide, but it dissolves completely in alcoholMethod for Decomposing Arsenical Sulphides. By .H.WARREN (ahem. News, 56, 193--194).-The cobalt speiss or arsenicalalloy is digested in hydrochloric acid containing copper nitrate, andafter a day or so, the insoluble portions are calcined at a low red heatwith plentiful access of air ; the calcined mass is then easily dissolvedby hydrochloric acid and mixed with the other solution. The copper isseparated by means of metallic iron, which also removes some bismuthand arsenic ; and the iron and remaining arsenic are precipitated byadding milk of lime. The culcium salts are removed by treatmentwith sulphuric acid, and the solution containing nickel and cobaltis precipitated by means of sodium carbonate.The precipitate is thensuspended in water and chlorine passed to saturation, when the nickelgoes into solution, whilst the cobalt remains undissolved. The solu-without undergoing any change. w. c. wINORGANIC CHEMISTRY. 27tion is boiled, and on adding caustic soda the nickel is obtained ashydroxide, which is ignited and reduced in the usual way.D. A. L.Zinc Titanates. By L. LEVY (Compt. rend., 105, 378-380).-When a mixture of 6 grams of titanic oxide, 2.5 grams of zinc oxide,and 5 to 10 grams of anhydrous zinc chloride is heated in a glass tube,the reaction is incomplete, and a violet product is obtained whichcontains an excess of titanic oxide. With excess of zinc chloride, theproduct is yellowish. If the mixture is heated in a Perrot's furnacein a crucible brasqued with charcoal and rutile, the zinc chloride volati-lises, but if the heating takes place in a long porcelain tube closed atone end, a violet or green, crystalline mass is formed, which containstitanium, zinc, silicon, and potassium.I f a mixture of 7 grams of titanium oxide, 5 grams of zinc oxide,and a small quantity of zinc fluoride, or 7 grams of titanium oxideand 30 grams of zinc fluoride is heated under a thin layer of potassiumfluoride in a graphite crucible in a Perrot's furnace for an hour anda half, washed with water, and then treated with concentrated sul-phuric acid to remove zinc oxide and titanium fluoride, beautifulviolet needles are obtained. With potassium chloride in place of thefluoride, the product is a greenish mass. With a mixture of potassiumand sodium chlorides the violet needles are obtained mixed withyellowish needles of potassium titanate.The violet crystals are zinctrititanate, Zn0,3TiU2, a small quantity of the zinc being displacedby iron. They are insoluble in water, alcohol, and ether, are notaffected by hot dilute sulphuric, nitric, and hydrochloric acids, nor byboiling concentrated solutions of alkaline hydroxides, butl are attackedwith difficulty by boiling concentrated sulphuric acid, and are decom-posed by fusion with potash. They are infusible before the blowpipe,but change to a greenish mass without loss of weight ; sp. gr. at l 5 O =4.92. The crystals are not attacked by hydrogen at a red heat, butpartially volatilise in a mixture of chlorine and hydrogen chloride.When treated with acidified hydrogen peroxide, the latter acquires acharacteristic yellow colour, but decomposition is never complete.Electrolytic Method of preparing Metallic Alloys, &c.ByH. WARREN (Chem. h'ews, 56, 153--154).-The following method isrecommended for the preparation of alloys such as phoaphor-bronzes,silicides, &c. The metal and substance containing alloying materialare placed in a deep, conical crucible, through the bottom of whichpasses a rod of graphite, extending about one inch within the crucibleand protected on the outside by au iron tube. The metal is meltedand the graphite put in connection with the negative pole, whilst themolten substance on the surface is connected with the positive pole ofa battery of two large ferric chloride cells.In this manner siliconcopper and silicon-eisen are easily prepared from pobassium silico-fluoride and the respective metal ; the salt being taken in sufficientquantity to form a molten layer 2 inches deep. By some slightvariation in the details, phosphor-bronzes can be produced ; moreover,native cryolite can be decomposed in contact with metallic zinc, and onC. H. B28 ABSTRACTS OF CHEMICAL PAPERS.subsequently volatilising the zinc, pure aluminium is obtained. Mag-nesium, barium, strontium, and calcium have not yielded satisfactqryalloys as yet.Process for obtaining the Rare Earths from the CeriferousHainstadt Clays. By J. R. STROHECKER (Chem.News, 56,175-1'76).--The author attributes the failure of other chemists to obtain ceriumfrom these clays (compare Abstr., 1886, 678) to the fact that in thepresence of more than 0.5 per cent. of iron, the cerium precipitatedby oxalic acid and potassium sulphate is much contaminated withiron, the oxide prepared therefrom being so colonred by iron oxideas to be mistaken for that substance. He describes the processes bywhich he affirms that he has separated the various rare earths fromthese clays. A. J. G.Reduction of Aluminium Oxide. By G. A. FAURIE (Compt.rend., 105, 494).-Two parts of pure finely-powdered aluminiumoxide is made into a paste with one part of petroleum or some otherhydrocarbon, and then mixed with one part of sulphuric acid.Whenthe masc is homogeiieous with a pale yellow tint, and begins to giveoff sulphurous anhydride, it is wrapped in paper and thrown into itcrucible heated to above 800" in order to decompose the hydrocarbon,The compact product thus obtained is powdered and mixed with itsown weight of a finely-divided metal, the mixture being then heatedto a whit>e heat in a plumbago crucible. The regulus after beingallowed to cool is found to contain grains of an aluminium alloy inthe midst of a metallic powder.This method of reduction is applicable to silica, calcium oxide,magnesium oxide, &c.Halogen Compounds of Gold. By G. K R ~ S and F. W,SCl-TMtuT (Bey., 20: 2634--2643).--Experiments made with a view toprepare aurous chloride and bromide by the action of chlorine andbromine respectively on gold, .gave negative results.The gold is con-verted into auric compounds in both cases ; if, is difficult to completethe reaction. I t is suggested that the numbers obt'ained by Thornsen,pointing to the formula Au,C14, were obtained from a product fromwhich the adbeling chlorine had not been removed. When gold iswarmed in bromine vapour, a black compound is formed which decom-poses into its constituents when heated at loo", even when kept inbromine vapour. The product contains a large amount of unattackedgold together with auric bromide. The compound AuzBr4 is notformed.The authors conclude that Thomsen's auro-auric chloride and bro-mide (this Journal, 1877, ii, 485) do not exist.By L.HOFFMANN and G. K R ~ ~ S S (Ber., 20,2704--8710).-Oberkampf believed that he obtained an auro-auricsulphide, Au&, by heating a solution of auric chloride with hydrogensulphide, but the product, according to Levol and Pellenberg, had acomposition varying between that of Au,Sp and Au2S3, whilst Schrotterand Priwoznik state that an auro-auric sulphide of constant composi-I>. A. L.C. H. B.N. H. M.Gold SulphidesINORGANIC DHE MISTRY. 29tion cannot be obtained. These results are probably to be attributedto an incomplete removal, by mere washing on a filter, of sulphur pre-cipitated simultaneously, since the authors find that to remove freesulphur from the precipitate it is necessary to wash the sulphicle bydecantation with absolute alcohol, anhydrous ether, and carbon bi-sulphide successively (compare Abstr., 1887, 1019 j.When a neutral solution of auric chloride is treated with hydrogensulphide in the cold until all colour has disappeared from the solu-tion, and the precipitate, after repeated washing with water, is washedby decantation as above, auro-auric sulphide, AuZS2, of constant com-position is obtained, and the reaction is represented quantitatively byLevol's equation, 8AuC13 + 9H2S + 4H,O = 4Au2S2 + 24HCl +H2S04.Auro-auric sulphide is a black powder in thc dry state, andwhen moist is also black by reflected light, but in the finely-dividedstate it transmits light of a reddish-brown colour. On, porcelain, itgives a black streak. When heated in a tube, sulphur begins to vola-tilise at 140°, as sulphurous anhydride, and is completely expelled at250-270" without the intermediate formation of aurous sulphide.With the exception of aqua regia, auro-auric sulphide is insoluble in allacids.Bromine water, gradually converts it, especially on warming,into auric bromide and snlphuric acid. Alkaline monosulphides dis-solve it slowly in the cold, but readily on heating, yielding brownsolutions which beoome greenish-yellow when the heating is con-tinued ; alkaline polysulphides dissolve it in the cold, and the solu-tions on heating become brown and eventually yellow; yellowsulphide of ammoniurq, however, dissolves the compound less readilythan the sulphides of the alkalis. Concentrated aqueous potash doesnot attack it in the cold, but on heating converts it into gold, potas-sium gold sulphide, and potassium gold oxide.Potassium cyanidedissolves it readily. When heated in a currenk of oxygen, the sulphideignites, and is converted into gold and sulphurous anhydride, whilsthydrogen sulphide is formed when the heating occurs in a current ofhydrogen.By fusing gold with potassium pentasulphide, Berzelius states that heobtained a sulphide which he believed to have the composition AuZS3,although no analyses were made. The authors have endeavoured toprepare a gold sulphide of this composition in four ways :-(1) ByBerzelius' method ; (2) by Obei-kampf's and by Yorke's method (thisJournal, 1848, 236), which consists in precipitating a saturated solu-tion of auro-auric sulphide in sodium bisulphide with an acid ; (3) byprecipitating a saturated solution of auPo-auric sulphide in sodiummonosulphide with hydpochloric acid ; and (4) saturating a solutionof sodium gold oxide with hydrogen sulphide and heating the normalsodium thioaurate with an acid ; the precipitates in every case werewashed by decantation with alcohol, ether, and carbon bisulphide.The precipitated sulphide obtained by the first two methods, however,contained more sulphur than required for the formula Au2S3, and hadnot a const'ant composition; whilst that prepared by the last twomethods had a composition intermediate between that of Au,S, andAu2Ss. The authors therefore conclude that auric sulphide, Au2SJ,does not exist, and show that the properties of the so-called com30 ABSTRACTS OF CHEMICAL PAPERS.pound are those of a mixture of suro-auric sulphide and sulphur, thelatter being left as an insoluble, white powder on digestion withpotassium cyanide. w. P. w