W. C. W. Continuous Preparation of Oxygen from Bleaching Powder and Cobalt Oxide

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41s ABSTRACTS OF CHEMICAL PAPERS.

Inorganic C h e mi s t r y.

The Equations employed by Pebal in his Investigation of Euchlorine. By L. BOLTZMANN(Annulen, 232, 121-124) .-The author points out that the method used by Pebal (this Journal, 1875, 1157), in his investigation on euchlorine, does not prove that euchlorine entirely consists of a, mixture of chlorine tetroxide and clilorine. His results do not exclude the possibility that euchlorine may contain a third constituent, 0,. w. c. w. Continuous Preparation of Oxygen from Bleaching Powder and Cobalt Oxide. By A. BIDET(Bull. Xoc. Chim., 45, 81-83). -A description of a convenient form of apparatus for preparing oxygen gas, in which the gas given off in excess of t,hat actually employed is stored in a reservoir and afterwards used, whilst the generator is being recharged with cobalt oxide. This arrangement is specially adapted for combustions. A. P. Analysis of Air from Cape Horn. By A. MUNTZand E. AUBIN (Couipt. rend., 102, 421--423).-The analyses of a series of twenty samples of air collected at Cape Horn during the months of May, July, and August, give a percentage of oxygen varying between 20.97 and 20.72, the mean being 20.864. This number is slightly below the mean of Regnault’s analyses, but the difference is very small, and it is evident that the atmosphere at Cape Horn has sensibly the same composition as the atmosphere in other parts of the world. Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. C. H. B. Action of Nitrites on Ferrous Salts. By A. PICCINIand F. M. Zuco (Gazzetfu, 15, 475--479).-One of the authors has previously proposed a method of separation of the iiitrites from the nitrates, based on the complete decomposition of the former, with evolution of nitric oxide on addition of an excess of ferrous chloride, whilst the nitrate under the same conditions remains unaltered. This reaction is here more minutely examined. On the addition of equi- molecular proportions of silver nitrite to ferrous chloride, or preferably of barium nitrite to ferrous sulphate, silver chloride and barium sulphate respectively are precipitated, and the liquid turns brown ; finally an ochre-coloured powder separates, accompanied by an evolution of nitric oxide. Prom quantitative determinations of the nitric oxide evolved the authors consider that ferrous nitrite is at first formed, which decomposes into nitric oxide, ferric oxide, and a basic ferric nitrate, thus: GPe(NO,), = lONO + Pe,O, + 2Fe,0y,N20,. V. H. V. Preparation and Titration of Orthophosphoric Acid. By A. JOLY (Cnmpt. rend., 102, 316--318).--In order to prepwe phw1)horic acid, monammonium phospha;te is dissolved in warm coilcmtrated View Article Online

INORGAX'IC CHENISTRT. 419

hydrochloric acid, and the ammonium chloride which separates on cooling is removed by decantation. The liquid is concentrated by evaporation and heated with successive quantities of nitric acid, until all ammonium salts and hydrochloric acid are expelled. Commercial diammonium phosphate may be purified for this purpose by mixing it with hydrochloric acid until the liquid is slightly acid to methyl- orange, and crystallising the monammonium phosphate, which may be further purified by recrystallisation. If arsenic is present (and this element is frequently found in commercial phosphates and phosphorus) it must be removed by the usual methods. Phosphoric acid can be accurately titrated with alkalis if methyl- orange is used as indicator, but wit,h phenolphthaleh the end reaction is not sufficiently sharp, and it is still less sliarp with soluble blue, C4B (comp. Engel, this vol., p. 420). Arsenic acid gives almost identical results, but in this case the end reaction is not perfectly sharp, even with the methyl orange. The most accurate method of titrating solutions of phosphoric or arsenic acid is to mix the liquid with phenolphthale'in, and then gradually to add standard baryta solution, until a gelatinous precipitate forms. This precipitate is a tribarium salt, which rapidly changes into a c~ystallinedibarium salt. More baryta is carefully added until a gelatinous precipitate is again produced, and this process is continued until a drop of barjta solution produces a permanent intense red coloration. The alteration of the gelatinous precipitate is especially rapid in the case of arsenic. The author claims priority on the question of the behaviour of various acids with different indicators. C. H. B. New Mode of Formation of Hypophosphoric Acid and its Ethereal Salts. By A. SANGER(Anrt,aleyL, 232, 1-42).-Ethyl hypophosphate may be conveniently prepared by the action of an excess of Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. ethyl iodide on silver hypoph0sphat.e at 100". It is a colourless liquid of sp. gr. 7 -117 at 15", which decomposes on distillation. It dissolves slowly in cold water, forming ethylhypophosphoric acid and hypophosphoric acid. NethyZ hypophospliate resembles the ethylic salt. Its sp. gr. at 15" is 1.109. Thepropyl, isobufyl, and arnyl hypophosphates were also prepared. None of these compounds were obtained in the pure stat'e. They all contained silver iodide in solution, which is deposited on the addition of water. The following salts were prepared by the action of water and a metallic carbonate on alkyl hypophosphates. Calcium rnethzJZ hypophosphate, P,O,MeHCa + 5H20, and calcium ethgl hypophosph8ate, P,O,EtHCa + 5h',O, form yellow needle-shaped crystals. Barium propyl hypophosphate crystalliees with 6 mols. H20, and calcium iso- hutyl hypophosphate with 5 mols. H20. Hypophosphoric acid is formed when ammonia and silver nitrate are added to a cold solution of phosphorous acid, but the silver oxide which also results from this reaction oxidises some of the hypophosphoric acid to orthophosphoric acid. The white crystalline precipitate which is produced on tlhe addition of silver nitrate to phosphorous acid has the composition Ag2HP03. View Article Online

420 ABSTRACTS OF CHEMICAL PAPERS.

A hydrat'e of hypophosphoric acid, H4P206 + HzO, is obtained in cubical crystals, when the aqueous solution is evaporated over sulphuric acid in a vacuum. The hydrate melts between 79.5" and 81*5", and decomposes, forming a mixtnre of phosphoric and phosphorous acids. Attempts to isolate a crystalline hydrate of orthophosphoric acid were unsuccessful, althoiigh the existence of a definite hydrate is indicated by the thermic changes which accompany the admixture of orthophosphoric acid wit,h water (comp. Joly, this vol., p. 201). w. c. w. Hypophosphoric Acid. By T. SALZER(Anna7en, 232, 114- 121).-The author finds that an aqueous solution of phosphorous acid does not oxidise on exposure to the air at, the ordinary temperature. Tetrasodic hypophosphate is converted into sodium hydrogen pyrophosphate by bromine, Na4PZO6 + Br, + H20 = N&H2P2O7+ 2NaBr. Dimagnesium pyrophosphate, Mg2P206+ 12H,O, is obtained as a white, crystalline precipitate by mixing cold solutions of magnesium sulphate and sodium hypophosphate. If hot solutions are used, a gelatinous precipitate is produced, which becomes crystalline after several weeks. Jf this salt is dissolved in hypophosphoric acid, the monomagnesium hypophosphate, MglH2Pz06+ 4H20, is obtained, It is sparingly soluble in water. Magnesium ammonium hypophosphate appears to be formed when sodium hypophosphate is added to a mixture of magnesium sulphate and ammonium chloride. The mono- caZcium saZt, CaH2P,o6 + 6Hz0, is obtained by bringing together hypophosphoric acid and the dicalcium salt in exactly their molecular proportions. It cryetallises in monoclinic plates. The silver salt, Ag4P206,obtained by double decomposition, is sparingly soluble in nitric acid, and does not change at 100". w. c. w. Published on 01 January 1886. Downloaded 22/10/2014 11:29:52.

Indicators of the Relative Energies of Polybasic Acids. BY R. ENGEL(Compt. rend., 102, 262--264).-Boric acid, which ig neutral to methyl-orange, and very feebly acid to litmus, phenolphthale'in, and other indicators, is decidedly acid to Poirier's soluble blue, C4B (Abstr., 1885, 931), which even shows the tendency of boric acid to combine with a second equivalent of potash. Borax, which is alkaline to all other indicators, is acid to soluble blue. Phosphoi-ic acid is monobasic wi t,h meth yl-orange, bibasic with phenolphthalein, and tribnsic with soluble blue, but in the latter case the end reaction is gradual. Disodium phosphate is alkaline to litmus and methyl-orange, neutyal to phenolphthaleln, acid to soluble blue. Arsenic acid behaves like phosphoric acid. Phosphorous acid is monobasic with methyl-orange, bibasic with phenolphthaleih or soluble blue. Hypophosphorous acid shows only a bibasic tendency. Cnrhonic acid is bibasic with soluble blue, and alkaline bicarbonates which are alkaline to litmus and methyl-orange can be accurately titrated with potash solution if soluble blue is used as the indicator. Salicylic and lactic acids are monobasic with all indicators. Para- hydroxybenzoic acid is moiiobasic with lifmus, bibasic with soluble blue. Cd H. B. View Article Online

INORGAN1 C CBE hlISTRY. 421 Germanium, a New Non-metallic Element. By C. WINKLER ( Rer., 19, 210-2ll).-A. Weisbach lately found in the Himmelsfurst Mine, near Freiberg, a mineral which he named argyrodite. Analysis proved this mineral to consist of about 73-75 per cent. of silver, 17--18 per cent. of sulphur, and 0.2 per cent. of mercury, but the analysis always showed a deficiency of 6- 7 per cent. The author has found that this deficiency is due to the presence of a new element, for which he proposes the name Germanium (Ge) ; this closely resembles antimony, and in acid solutions gives a white sul- plhide, soluble in ammonium sulphide. When argyrodite is heated in a stream of hydrogen, it yields a black crystalline sublimate, which melts to brownish-red drops. This is principally germanium sulphide (mixed with a trace of mercury sulphide) ; it dissolves in ammonium sulphide, and is reprecipitated by hydrochloric acid as a white powder, readily soluble in ammonia. When heated in a current of air or with nitric acid, the sulphide yields a white oxide, which is not volatile at a red heat. This oxide is soluble in potash. The oxide and the sulphide can both be reduced by heating in a current of hydrogen, and yield the element as a grey moderately lustrous substance, which is only volatile (without previous fusion) at a full red heat, and therefore much less so than antimony. The volatilised element is deposited on cooling in small crystals much resembling those of iodine. When germanium or its sulphide is heated in a current of chlorine, the easily volatile white chloride is formed, soluble in water. The author is inclined to consider germanium as the element indicated by the periodic law as probably existing between antimony and bismuth, and is now determining its atcjmic weight. L. T. T. Alkaline Hydrates. By E. J. MAUXENE(Bull. SOC.Chinz., 44, 578-602).-A hydrate of strontium oxide may be obtained in crystals from its aqueous solution, and after drying by the method adopted Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. for the similar barium compound (Abstr., 1883, 1052), has the com- Imsition SrO(H,O),.,,,; by melting this compound at a low red heat, z1 second hydrate, SrO( H20)o.a21,is formed. Potassium oxide forms several definite crystalline hydrates ; the first, obtained by allowing a cold aqueous solution of the oxide to crystallist., and drying the rhombic octahedral crystals formed over fused potash, has the composition represented by the formula K,O(H,O),., ; a marked reduction of temperature takes place on dissolving this compound in water. A second hydrate, having the composition K20(H20)3.133,may be prepared by pouring a concentrated aqueous solution of potassium oxide, heated to loo", into a cold porcelain dish ; rectangular crystalline plates are formed, these are dried Over fused potash ; on dissolving in water the hydrate thus obtained, a considerable rise of temperature takes place. By desiccating the hydrate K20(H20)5.2in a vacuum over fused potash, the hydrate Kt(,O(H,O)l.,,is formed. This hydrate may also be obtained by fusing potash in a silver dish at a low red heat; by raising the heat to bright redness a fifth hydrate is formed, and may be obtained in crystals by partially cooling the fused mass, and then running off the still liquid hydrate through a hole pierced in the crystalline c'ruat VOL. L. 2f View Article Online

422 ABSTRACTS OF CHEMICAL PAPERS.

formed ; thus obtained it has the composition K,O(H,O),.,, ; finally. a, sixth hydrate was obtained, but not in the crystalline. form, by heahing potash to a white heat in a platinum dish ; it has the composition K20(H20)o.7,3. Sodium oxide also forms a series of hydrates ; the first, Na20(H20)3.44, crystallises from water in transparent lamellar crystals ; by heating this hydrate to a dull redness, a crystalline hydrate, Na20(H20)1.11r, is formed, and by further heating to whiteness for about two hours, a third hydrate, N&0(H20)wr92,is obtained. The author considers that hydroxides of the formula M’HO, or M”(H0)2,never actually exist, a fact foreseen by a theory which he has enunciated ; the composition of the hydrates analysed agree almost absolutely with the proportions required by his theory. A. P.

Insolubility of Barium Chloride in Presence of Lithium Chloride. By C. N. DRAPER(Chem. News, 53,52).-A crystalline precipitate of barium chloride is obtained when a solution of that salt is added to a concentrated solution of lithium chloride, or to a less marked degree when added to a solution of sodium, pot,assium, or calcium chloride. D. A. L.

Solubility of Barium Sulphate in Hydrobromic and in Hydriodic Acid. By A. R. HASLAM(Chem. News, 53,87).-When pure barium sulphsbte is boiled for a quarter of an hour with a solution of pure hydrobromic acid (containing 40 per cent. HBr), it is dissolved to the extent of 1 in 2500 parts of acid solution ; with hydriodic acid the solubility is 1in 6000. D. A. L.

Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. Transference of Copper across a Stratum of Gas. Direct Combination of Nitrogen with Copper. By R. BLONDLOT(Co~pt. rend., 102, 210--212).-The observations recorded in this paper were made in the course of some experiments on the passage of electricity through incandescent gases. A disc of platinum and a disc of copper, each 33 mm. in diameter, were fixed vertically opposite one amother at a distance of 3-4 mm. on two platinum columns, the discs and supports being enclosed in a glazed porcelain globe with an aperture at the bottom. The globe and its contents were heated to bright redness for three hours, and it was found on cooling that the surface of the platinum disc was covered to a depth of 0.1 mm. with a layer of some substance resembling plumbago. This substance was insoluble in cold but soluble in hot nitric acid, yielding a solution which contained copper, whilst a residue of platinum black was left. In the first experiment the globe was filled with air, and the copper disc was strongly oxidised, but when the discs were heated in an atmosphere of nitrogen, a similar deposit was formed on the platinum, and the surface of the copper, although remaining bright, was dis- tinetly corroded, and showed the internal crystalline structure of the View Article Online

INORGANIC CHEMISTRY- 423

metal. If, however, the discs were heated in an atmosphere of hydrogen no deposit was formed. These facts point to the formation of a compound of nitrogen and copper which either combines as a whole with the platinum or is decomposed by it, the copper being deposited. The deposited substance is dissociated and volatilised at a very high temperahre. C. H. B. Action of Copper on Aqueous Solutions of Sulphurous Anhydride. By CAUSSE(Bull. SOC.Chim., 45, 3-5).-An aqueous solution of sulphurous anhydride acts slowly on metallic copper, forming cupric sulphite and hyposulphurous acid; if, however, a large excess of sulphurous acid is present, sulphuretted hydrogen is formed, precipitating the cupric sulphite as sulphide and coatring the metallic copper with a film of sulphide; a precipitate of sulphur also being formed. These reactions appear to take place more rapidly when the copper is exposed to an atmosphere of moist sulphurous anhydride. A. P. Behaviour of Hydrogen Phosphide with some Mercury Salts. By K. A. ASCHAN(Chern. Zeit., 10, 82 ; 102--103).-When hydrogen phosphide, prepared by boiling amorphous phosphorus with potash solution (1 : 2 of water), is passed into aqueous mercuric chloride, the precipitate is yellow at first, until all the mercury is precipitated from the solution ; it then turns reddish, and by the continued action of the hydrogen phosphide becomes darker, nl timately, after 18 hours, it consists wholly of reduced mercury, whilst the solution contains free hydrochloric acid and some phosphoric acid. In alcoholic solutions, the darker (or brown) stage is more persistent. In the above manner, three compounds of mercuric chloride with mercury phosphide have been isolated, but not pure mercury phosphide. The yellow compound, 3Hg3P2,7HgCI2,differs from that described by H. Rose (2PHgzCL,HgClz + 3H20, Ann. Phys. Chm., 40, 78) in Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. being more stable. It can be exposed to air for months without alteration, and can be dried at 105". At 110-120", however, it is decomposed, becoming moist and reddish-brown in colour, with separation of globules of mercury. It is decomposed by boiling water. The red compound, 4Hg,P2,5HgC12, is decomposed immediately in the air, but when dried in a current of hydrogen can be kept for a short time. It is decomposed by water. When freshly precipitated, agitation with alcoholic mercuric chloride converts it into the yellow compound. The brown compound, Rg-,P?,HgCl,,is decomposed by exposure to air, or in water through which air is being passed. It, can, however, be dried in a stream of hydrogen, and is not converted into either of the previous compoiinds when shaken with mercnric chloride. The author failed to obtain mercury phosphide by the action of hydrogen phosphide on gently heated mercuric chloride, as described by Rose (ibid., 24, 335). In solutions of mercuric nitrate, hydrogen phosphide produces at first a white precipitate, which becomes yellow, brown, and grey in succession. These precipitates can be dried and kept in a vacuum. When heated to 140°, the white and yellow compounds explode violently; the grey compound when dry explodes at 94O, or 2f2 View Article Online

424 ABSTRACTS OF GHEMICAL PAPERS. when moist turng white and explodes at 140". These compounds like- wise explode by percussion ; they appear to be mixtures of different compounds of mercury, phosphorus, and nitric acid. Hydrogen phosphide also decomposes mercurous carbonate with the evolution of car- bonic anhydride and the formation of an unstable compound, most likely 2PHg3,6Hga0,readily soluble in nitric acid, and unaltered by dilute sulphuric acid; it becomes brown-red at 120", and is decomposed at higher temperatures. D. A. L. Use of Potassium Sulphate in the Fractionation of Rare Earths. By L. DE BOISBAUDRAN(Cowpt. rend., 102, 398-399).- The usual method is to saturate with potassium sulphate a greater or less volume of liquid, according to the nature of the earth which it is required to separate. It is, however, difficult to separate in this way the earths which are most soluble in potassium sulphate. The author prefers to add to the somewhat dilute solution ft certain quantity of potassium sulphate solution either saturated or non-saturated. Any precipitate of double salt which may form is collected, and the liquid is then fractionally precipitated by the addition of successive qnan- tities of dilute alcohol. C. H. B. Oxides of Cerium in Practical Use. By J. R. STROHECKER (J.pr. Chem. [2], 33,260-264; comp. this vol., p. 314).-The varying colours (orange-red to leather colour) of bricks made from the red Hainstadt clay (Zoc. cit.), depend partly on the temperature at which the bricks are burnt; this is shown by the fact that cerium hydroxide (precipitated from a concentrated solution by alkali) when dried and heated acquires a leather colour, whilst orange-red cerium oxide is obtained at a red heat. The lemon colour of bricks made from the clay containing lignite is due to a lower oxide, Ces04,formed by the reduction of cerium oxide by the carbon present, in the clay. Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. These bricks are very rare, but some houses in Frankfort are built of bricks made from the different clap. It will be possible to obtain brilliant colours for painting from the didymium oxide present in the clays; of which a considerable amount can be got in the preparation of large quantities of cerium oxide. The sky-blue cerium oxide, CeO, is also readily obtained. The oxides of cerium have a further interest with regard to the chemical substitution of isomorphous bases in plants, Their medical properties are being investigated. N. H. M.

Equivalent of Terbia. By L. DE BOISBAUDRAN(Compt. rend., 102, 395-398) -By fractionatlion, at first with ammonia and afterwards with potassium sulphate, the author has obtained a specimen of terbia considerably deeper in colour than any which he has previously prepared. This terbia gives the spectra of ZZ, ZP, and Zy, and contains a small quantity of holmium and minute traces of erbium and samarium. The equivalent of the moat deeply coloured fraction was found to be 124.9, and that of the palest fraction 123%; these values give 163.1 and 1G1.4 respectively, as the mean atomic weight of the metals contained in the two fractions. These equivalents are con- View Article Online

ISORGAXIC CHEJITSTRY. 425

siderably higher than those of previously prepared specimens of terbia. Some details respecting the intensities of the spectra of these and three other samples of terbia are given in the original paper. C. H. B. Manganites of the Alkaline Earths. By G. ROUSSEAU(Compt. rejid., 102, 425--428).-A mixture of manganese chloride and calcium oxychloride heated for six hours by means of a Bunsen flame (comp. Abstr., 1885, 1114) yields slender, black needles of a trimanganite, Ca0,3Mn02, and this result confirms the author's supposition that at low temperatures the manganese oxide becomes polymerised. Mixtures of manganese chloride with strontium oxychloride yield the manganite when heated at a temperature below 1000" or above llOOo, but between these temperatures the product is a dimanganite, Sr0,2Mn02, which is only stable between these limits. Barium behaves in a precisely similar manner, but the phenomena are not so distinct. On the other hand, if the calcium trimanganite is heated, it gradually decomposes until at a white heat it is converted into ,z bibasic manganite, Mn02,2Ca0. The mangauese oxide under the influence of heat undergoes isomeric modifications similar to those observed in the case of certain volatile metallic chlorides. Strontium dimanganite crystallises in slender, black needles ; barium manganite and dimanganite in brilliant, black lamellze. C. H. B. Action of Hydrogen Chloride on Iron. By F. ISAMBERT (Covzpt. rend., 102, 423-425).-Hydro,aen chloride acts on metallic iron with formation of ferrons chloride and liberation of hydrogen, but hydrogen will also act on ferrous chloride producing the reverse change, and the object of the experiments described in this paper was to ascertain the condition of equilibrium. Dry hydrogen chloride was passed over finely divided iron heated in a porcelain tube to Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. which manometers were attached. The results show that the pro- portion of hydrogen which is liberated is lower the higher the temperature; for example, the mixture of hydrogen chloride and hydrogen which has no action on iron at a dull red heat, contains 89-91 per cent. of hydrogen, whilst the mixture which has no action at a bright red heat contains only 67-69 per cent. The action of hydrochloric acid, therefore, proceeds in the same way as the action of aqueoiis vapour, and this result is probably due to the fmt that the heat of formation of hydrogen chloride increases as the temperature rises, whilst the heat of formation of ferrous chloride probably varies in the reverse direction. The pressure of the gas seems to be without influence on the results. The ratio of the pressures of hydrogen and hydrogen chloride is constant, whatever the total pressure at a given temperature, a, result which is analogous to the law of dissociation. The iron seems to rolatilise and distil from tjhe cold to the warm parts of the tube. The gaseous mixture which removes ferrous chloride at a somewhat low temperature becomes a reducing agent at a higher temperature, and the iron is deposited in the metallic state. This action may take part in the formation of minerals, C. H, B. View Article Online

42 6 ABSTRACTS OF CHEXICAL PAPERS. Behaviour of Phosphorus with Iron and Slags. By A. BRACKELSBERG(Dingl. polyt. J., 258, 364--370).-1n order to deter- mine the behaviour of phosphorus towards iron and slag in the process of reducing iron compounds, a series of trials was made, in which the precipitate obtained by adding ferrous sulphate to sodium phosphate, and consisting of 55 per cent. of ferrous phosphate, 35 per cent. of ferric phosphate, and 10 per cent. of ferric oxide, was heated strongly in a crucible filled with coke. The bright iron regulus obtained was very brittle, and contained 75.45 per cent. of iron and 24.55 per cent. of phosphorus, whilst from the phosphate employed a, metal containing 27.4 per cent. of phosphorus should have been obtained. From the results of a further series of experiments, in which slag was added to the charge in the crucible, it is in- ferred that the presence of slag prevents rather than favours the absorp- tion of phosphorus by iron. This is due probably to the simultaneous presence of silicon in the metal, and the powerful action of silica on the metallic phosphate. It is shown also that sulphur is expelled from iron compounds by phosphorus. On heating a mixture of calcium phosphate (11 parts) and ferric oxide (2.5 parts) with coal, a metal containing 264 per cent. of phosphorus was obtained (although it was expected to contain 74 per cent. of phosphorus), so thibt iron does not appear to absorb more than about 26 per cent. of this element. Brackelsberg concludes that the same results are obtained whether the phosphoric acid is in combination with ferric oxide or lime, a circumstance easily explained by the great affinity which iron has for phosphorus. The iron phosphide (ferro-phosphor) obtained in these trials had a sp. gr. varying between 6.3 and 7.2. It was not very hard, its fracture varied considerably, and it was un- affected by strong mineral acids, aqua regia acting only yery slowly, whilst dilute sulphuric acid had no action in the cold. D. B.

Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. Double Potassium and Ammonium Manganese Chromates. By C. HENSGEN(Rec. Trav. Ohim., 4, 212-220).-I'otassium manganese chroiiiate, K2Cr04,2MnCr04+ 4H20, is precipitated on mixiug solutions of potassium chromate and manganese sulphate, and can be recrystnllised from chromic acid solut'ion. It rorma blackish-blue, highly refractive crystals, resembliiig iodine. By varying the proportions of the two salts, substances of intermediate composition are obtained. The corresponding nnmoniurn salt, (NH4)2Cr04,2MnCr04+ 4&0, resembles in appearance the above compound; it decomposes at 200", and the change is accompanied by a slight explosion when the salt is quickly heated. V. H. V. Complex Inorganic Acids. By W. GIBHS(Amer. Chem. J., 7, 313-338 ; coaip. this vol., p. 205) .--Arsenoso-tungstutes.-The alkaline salts are obtained by boiling arsenious oxide wi6h strong solutions of acid tungstates. They are colourless or pale-yellow, and are only easily oxidised in alkaline solution. The following are described :- 2As2O3,l8WO3,7(NH4>,O+ 18H20,almost colourless prisms ; As20,,9W03,4Ba0 + 21H,O, white, crystalline precipitate ; 8As203,16W03,9Naz0+ 55H20, large, colourless prisms. View Article Online

ISORGANIC CHEMISTRY. 427

Arsenoso-moZybdates are obtained in manner similar to the preceding. 2As203,8Mo03,3Ba0+ 13H,O, very pale greenish crystals ; 5As,03,12Mo03,3(NH,),0 + ‘24H,O, colourless crystals ; 3As20j,6MoOj,2Mn0 + 6H20,bright orange octahedra. The zinc and copper salts correspond exactly in composition and form. Another manganese salt, 3Asz03,6iMo03,2Mn0+ 15H20,is a canary-yellow precipitate. Phosphoroso-tunystates are readily formed by the action of phosphorous and hydrochloric acids on the higher metatnngstates ; they are generally better defined than the corresponding phosphoroso- molybdates. 4H3P03,22W03,6(NH&O + 25H20, crystalline powder ; 16H3P03,32W03,5K,0 + 46H20, colourless and crystalline ; 8H3P03,22WOs,2Na20 + 85Hz0,yello w, granular crystals. Phosphoroso-molybdates.--The preparation of an ammonium salt before described has been repeated, and its composition confirmed, except that the new salt, 4H3PO3,24Mo0,4(NH&0 + 25H20, contains 8 mols. H20more. Antimonoso-tzLrzgstates are obtained in manner similar to the arsenoso- compounds ; freshly precipitated antimony oxide must be used. The salts of the alkalis are very soluble, forming oily liquids or gummy masses. Addition of barium chloride throws down an indistinctly crystalline salt, 3Sb20,,2Ba0,11W03 + 18H20. Antimonoso-mol~bdates are obtained by boiling antimonious oxychloride with an acid molybdate ; a partial reduction of the molybdate always occurs. 3Shz03,17Mo03,6(NH4),0 + 21H20, forms greenish- yellow, granular crystals. Its preparation is rather uncertain. Phosphoroso-phospho-tungstates.-The salt, 2H3P03,P,05,24W0,5KZ0 +3H20, is obtained by adding potassium bromide to a mixture of Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. phosphorous and orthophosphoric acids and 12 : 5 sodium tungstate. Phosphoroso-phos~ho-mo1ybdates.--By adding phosphorous acid to ammonium phosphomolybdate (10 : 2 salt) a greenish-yellow, crystalline precipitate is obtained of the formula 2H3P03,.3P205,72M003,9(NH*)20+ 38HzO. Phospho- hypop hosp ho-tungstate, 4P20,,2 H3P02,26W03,9Kz0,Na20 + 43H20, is a white, crystalline precipitate. Arsenoso-phospho-tuizgstates are obtained by boiling arsenious oxide with a phospho-tungstate, or by adding an orthophosphate to an arsenio-tungstate. 14As203,3P20,,32 W 03,10K20 + 28H20, forms minute greenish-yellow crystals ; 2Asn03,2Pz05,12W03,5 K20,Na20 + 15H20, a yellow oil, drying to a pale-yellow, gummy, transparent mass ; Asz03,4Pz05,60W03,7Kz0+ 55H20, pale-yellow crystals. Arsenoso-arsenio-t ungstrrtes are formed in manner similar to the preceding salts. As,O~,~AS~O,,~~W~~,~~K~O+ 26H,O, forms a white c vystalline precipitate. H. B. Crystals of Thorium. By W. C. BR~GGER(Juhrb. f. Min., 1886, L, lief., 25--26).-The metal prepared by L. F. Nilson (Abstr., 1833, View Article Online

428 ABSTRACTS OF CHEMICAL PAPERS. 152, 553) was a fine grey powder. The separate grains, only 0.0001 to 0*0002gram in weight, prove to be thin bent plates produced from the regular and irregular growth of numberless small tabular hexa- gonal crystals, each apparently exhibiting a combiuation of two rhombohedra with the basal plane. From the angular measurements, however, it would seem probable that the crystals of thorium are regular, and exhibit a combination of the octahedron and cube. This view is supported by the nature of the twin crystals, the plane of twinning being an octahedral plane. B. H. 1-3. Extraction of Vanadium from Magnetite ; the Behaviour of several Vanadium Compounds towards Reagents ; the Quanti- tative Determination of Vanadium and its Separation from Chromium. By E. CLAASSRN(Amer. Chem. J., 7, 349-353).- Magnetite is treated with hydrochloric acid ; the residue is decomposed by igniting with nitre and soda, The two portions are then mixed, more nitre and sodium carbonate added, and tbe whole fused; the aqneous solution of the fused mass contains all the vanadium and chromium. Vanadium oxide is not entirely soluble in ammonium sulphide. By igniting it with sulphur and sodium carbonate a mass is obtained soluble in water. The whole of the vanadium caniiot be precipitated from such a solution by treatment with an acid. Before precipitating a solution of a vanadate with ammonium chloride it must be made slightly alkaline wit,h ammonia; the filtrate from the ammonium metavanadate should be precipitated by alcohoi, when a small additional amount of metavanadate is obtained. Lead vanadate may be decomposed by hydrochloric acid and alcohol. Barium vanadate is not entirely decomposed by dilute sulphuric acid, but is by ignition with potassium pyrosulphate. A solution containing a hypovanadate is not completely precipitated by Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. mercuric chloride and ammonia. A iiiixture of vanadium and chromium oxides may be separated by fusion with sulphur and sodium carbonate ; the chromium remains as oxide ; the vanadium goes into solution as a sulpho-salt. H. B. Solubility of Antimonic Oxide in an Alkaline Solution of Glycerol, and a New Mordant for Cotton Dyeing. By H. KOHLER(Dingl. polyt. J., 258, 520--525).-1t has been shown by Morawsky, Puls, and Schottlander that different metallic oxides are dissolved by alkaline solutions of glycerol, such as the oxides of iron, manganese, copper, and bismuth. The author finds that antimonic oxide behaves in a similar manner. It was proved by experiment that the solubility of the oxide depends on the presence of glycerol and not on the alkali employed. The alkalinity of the solution, however, in- fluences the solubility of the oxide, the ratio increasing until a compound is obtained consisting of equal m.olecular weights of caustic soda, glycerol, and oxide. Caustic potash gave less favourable results, whilst ammonia does not dissolve even a trace of the metallic oxide. The solution of sodio-antimonic glyceride has a strongly alkaline reaction, and may be saturated with an acid to a certain limit, but beyond View Article Online

INORGASIC CHEMISTRY. 429

this, antimonic oxide separates in the form of a thick precipitate soluble in an excess of the acid. When exposed to the action of the atmosphere, the solution becomes turbid, and deposits a white mass of microscopic crystals which are insoluble iii water, and correspond in composition with the formula Na,Sb,O,. The solution of sodio- antimonic glyceride can be used with advantage as a mordanting agent in dyeing. Care should, however, be taken to remove antimony sulphide, almost invariably present in commercial antimonic oxide, otherwise red antimony sglphide will be deposited on the fibre by the tannin, leading to the production of colours lacking in brightness and intensity. D. B.

Antimony Sulphide. By A. DITTE (Compt. rend., 102, 212- 214) .--The double sulphides of antimony and potassium previonsly described (this vol., p. 309), can also be obtained from anhydrous antimony sulphide, if it is finely powdered and digested with a concentrated solution of the alkaline sulphide. A highly concentrated solution deposits yellow needles of the composition KzS,2Sb,S3 ; a moderately concentrated solution at first deposits the same compound, and afterwards 2KzS,Sb2S3. The conditions of equilibrium between antimony snlphide, antimony chloride, hydrogen sulphide, and hydrogen chloride (see Berthelot, this vol., p. 308), are materially modified by changes of temperature. If the liquid is heated, the hydrates of hydrogen chloride are more easily dissociated, whilst at the same time less and less hydrogen sulphide remains dissolved in the liquid, and a point is eventually reached at which hydrated antimony sulphide can no longer exist, and crystals of the anhydrous sulphide are formed. This is well seen when the hydrated sulphide is boiled with moderately dilute hydrochloric acid. At tirst there is only a slight evolution of hydrogen sulphide, but as the liquid evaporates and the solution becomes more Published on 01 January 1886. Downloaded 22/10/2014 11:29:52. concentrated, decomposition of the antimony sulphide takes place more rapidly, and at a certain temperature the action of the dissolved hydrogen sulphide on the antimony chloride also in solution produces anhydrous antimony sulphide, which separates in shining grey needles. If the boiling is continued, the hydrated sulphide is still more easily attacked, whilst the reverse action produces only tile anhydrous sulphide, until at last the whole of the antimony sulphide remaining undissolved is converted into grey anhydrous needles with a metallic lustre. The formation of the grey crystals begins when the solution contains about 54 grams of anhydrous hydrogen chloride per litre, a part being in the state of antimony chloride. Hydrated antimony sulphide is not attacked by sulphuric acid unless the latter is concentrated and boiling, but the phenomena are strictly analogous to those observed in the case of hydrochloric acid. The sp. gr. of natmal grey antimony sulphide is 4-6-47; that of the fused sulphide obtained by the direct union of sulphur and antimony, 4.892; that of the anhydrous sulphide prepared in the wet way, 5.012. The mean sp. gr. of the sulphide calculated from the sp. gr. of its constituents is 3982 or 4.095, according as the View Article Online

430 ABSTRACTS OF CHEMICAL PAPERS.

sp. gr. of sulphur is taken as 1.97 or 2.07. The formation of antimony snlphide is therefore accompanied by considerable contraction, and this fact corresponds with its high heat of formation. Puchs stated tihat if the sulphide is fused and poured into water, its sp. gr. diminishes, and the cooled amorphous substance yields an orange-red powder. The author finds that when the antimony sul- phidc is treated in this way its sp. gr. does diminish, but it yields a black powder similar to that of the ordinary compound. Hydrated antimony sulphide after prolonged drying over sulphuric acid has the composition Sb& + 2H20. If heated above loo", it loses water, and acqnires a, metallic grey colour. C. H. B.

New Solvents of Anhydrous Auric Chloride. By L. LINDET (Budl. SOC.Chim., 45,149-151).-Anhydrous auric chloride dissolves in arsenious chloride (22 per cent. dissolving at 160" and 2.5 per cent,. at 15"), and is soluble to a similar extent in antimonic chloride. It also dissolves in stannous and titanous chlorides, but is much less soluble, only 4 per cent. being dissolved at 150". Silicon tetrachlo- ride dissolves only a trace, even at a high temperature. It crystallises from these solvents in triclinic prisms of a fine dark-red colour. A. P. Published on 01 January 1886. Downloaded 22/10/2014 11:29:52.