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

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W. C. W. Continuous Preparation of Oxygen from Bleaching Powder and Cobalt Oxide View Article Online / Journal Homepage / Table of Contents for this issue 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 evolu- tion 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 phos- phorus) 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 hypo- phosphate 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 hypophos- phoric 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 hypo- phosphate, 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 hypophos- phoric acid to orthophosphoric acid. The white crystalline precipi- tate 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 sul- phuric 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 pyro- phosphate 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, phenol- phthale'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 solu- ble 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.
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