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Inorganic Chemistry. 603 View Article Online / Journal Homepage / Table of Contents for this issue INORGANIC CHEMISTRY. 603 Inorganic Chemistry. Intensifying (" Activirende ") Action of Reducing Agents, Colloidal Noble Metals, Alkaloids, and other Basic Substances on Oxidising Agents. By EDUARDSCHAER (Annalen, 1902, 323, 32--82).-The intensifying action of sulphurous acid, hydrogen per- oxide, colloidal gold and platinum, alkaloids and insoluble carbonates on certain oxidising agents has been studied, using the oxidisable sub- stances potassium iodide, guaiacum, indigo-carmine pyrogallol, guaiacol, p-phenylenediamine, and aloin as indicators. A description of the experiments made on cupric salts has already been published (this vol., ii, 140). Hydrogen peroxide, like sulphurous acid (Abstr., 1901, ii, 603), intensifies the oxidising action of ferric salts on indigo, and, in addition, promotes the oxidation of guaiacum, potassium iodide, 13-phenylene- diamine, and guaiacol. Colloidal platinum, although not inducing any action on indigo, renders the oxidising agent more active towards the other oxidisable substances. Sulphurous acid does not intensify the action of mercuric chloride, and hydrogen peroxide does so only in the case of aloin, Colloidal platinum induces the oxidation of guaiacum and pyrogdlol by this reagent, and both this metal and colloidal gold promote the develop- ment of the guaiacol coloration. Pyrogallol is oxidised both by mer- curic chloride and ferric salts in the presence of insoluble carbonates and alkaloids. Silver nitrate oxidises indigo and aloin in the presence of hydrogen peroxide, whilst the guaiacum and guaiacol colorations are developed in the presence of the colloidal noble metals, Published on 01 January 1902. Downloaded 31/10/2014 10:47:34. Hydrogen peroxide intensifies the action of chromic acid on all the oxidisable substances under examination (compare Bach, this vol., ii, 251). Sulphurous acid promotes the oxidation of indigo, guaiacum, and aloin, whilst colloidal gold and platinum render the oxidising agent more active towards pyrogallol, p-phenylenediamine, and potass- ium iodide. Hydrogen peroxide intensifies 'the action of hypochlorous acid on p-phenylenediamine ; the colloidal metals promote the oxidation of guaiacum and aloin by this acid. Chloric acid and the chlorates are rendered more generally active by sulphurous acid, but are not affected by hydrogen peroxide or the colloidal metals. Sulphurous acid has a less marked effect on bromic acid and the bromates; pyrogallol and p-phenylenediamine are attacked by these reagents in the presence of the colloidal metals, which also induce a slight oxidation of aloin. Iodates oxidise indigo, pyrogallol,. p-phenylenediamine, and guaiacol under the influence of sulphurous acid, hydrogen peroxide promotes the oxidation of pyrogallol and p-phenylenediamine ; this effect is likewise produced by colloidal platinum, which also intensifies the action of the oxidising agent on guaiacol and aloin. Nitric acid and the nitrates readiIy oxidise indigo and guaincum View Article Online 604 ABSTRACTS OF CHEMICAL PAPERS, under the influence of sulphurous acid ; hydrogen peroxide promotes the decomposition of indigo and potassium iodide, whilst the action on pyrogallol, p-phenylenediamine, guaiacol, and the iodide is intensified by the presence of colloidal platinum. Permanganates act more energetically on potassium iodide and p-phenylenediamine in the presence of hydrogen peroxide ; sulphurous acid induces the oxidation of indigo, whilst guaiacum and p-phenylenediamine are oxidised under the influence of colloidal platinum, aloin being also affected by colloidal gold. Benzoic peroxide is rendered more active towards indigo, guaiacum, and guaiacol by the presence of sulphurous acid ; hydrogen peroxide promotes the oxidation of indigo, especially in warm solutions, it also produces a similar effect in the case of p-phenylenediamine. Colloidal platinum also influences the oxidation of indigo in warm solutions, and causes the development of a faint coloration with aloin. Quinone is rendered more active by hydrogen peroxide and colloidal platinum, the first agent promotes the oxidation of indigo, potassium iodide, and guaiacol, whilst the second intensifies the action on guaiacum, pyrogallol, and aloin. The last of these substances and leucaniline are also oxidised by quinone in the presence of sulphurous acid or colloidal gold. G. T. M. Crystallised Hydrogen Peroxide. By WILHELMSTAEDEL (Zeit. angew. Chevn., 1902, 15, 642--643).-When a concentrated solution of hydrogen peroxide is cooled, it solidifies and the crystals melt at -29 A 90-95 per cent. solution remains liquid at -20°, but solidifies in a freezing mixture of ether and carbon dioxide. The eutectic point lies between - 20" and - 23". The crystals, which are anhydrous, are colourless and prismatic. The best method of obtaining anhydrous hydrogen peroxide is by this freezing out process. When Published on 01 January 1902. Downloaded 31/10/2014 10:47:34. a trace of platinum sponge or manganese dioxide is thrown on to the anhydrous preparation, an explosive decomposition takes place ; a mixture of powdered carbon or magnesium with a trace of manganese dioxide inflames when dropped on to it. When a 90-95 per cent. solution of hydrogen peroxide is added to a concentrated solution of cadmium chloride, silky crystals separate which contain 23 per cent. of hydrogen peroxide. J. McC. Preparation of Sulphuryl Chloride. ALFREDWOHL & OTTORUFF (D.R.-I?. 129862).-The transformation of chlorosulphonic acid into sulphuric acid and sulphuryl chloride in molecular proportion is readily effected by boiling the compound with mercury or mercuric sulphate. If the apparatus is fitted with a reflux condenser at 70", the sulphuryl chloride distils over in quantitative yield, The process is continuous and other metallic salts, such as those of tin and antimony, may be employed as catalysts; sulphur dichloride and iodine mono- chloride also produce the same effect. G. T. M. The Lead Chamber Process in the Light of Physico-chemical Theories. By E. HAAGN(Zeit. arzgew. Chem., 1902, 15, 583-585). -The author believes that the lead chamber process can best be explained by physic0 -chemical theorier on the assumption that View Article Online INORGANIC CHEMISTRY. 605 nitrosylsulphuric acid is formed as an intermediary product. Since this substance has a very low vapour tension, it is removed from the reaction mixture and thus the reaction is accelerated. J. McC. Theory of the Lead Chamber Process. By GEORGLUNGE (Zeit. angew. Chem., 1902, 15, 581-583. Compare this vol., ii, 315).-A reply to Th. Meyer (Zeit. angew. Chem., 1901, 14, 1245; 1902, 15, 278) and Riedel (this vol., ii, 450). J. McC. Selenium. 11. By JULIIJSMEYER (Zeit. anorg. Chem., 1902, 31, 391--400).-A full account of the determination of the atomic weight of selenium (see this vol., ii, 392). Selenium can be completely reduced and separated in the elementary condition from an acid solution of a selenite by hydrazine. J. McC. Direct Hydrogenation of Nitrogen Oxides by Contact Action. By PAULSABATIER and JEANB. SENDERENS(Compt. rend., 1902, 135, 278--281).-When a mixture of nitrous oxide and hydrogen is passed over reduced nickel, a reaction takes place at the ordinary temperature with a large development of heat, and in presence of excess of hydrogen the oxide is completely reduced without any formation of ammonia. If the oxide is in excess, the front part of the metal becomes incan- descent, higher nitrogen oxides appear in the cooler part of the tube, and a little ammonia is formed, Reduced copper behaves in the same way as nickel, but reduction does not take place below 180'. Mixtures of nitric oxide with excess of hydrogen are not reduced by nickel below 180°, but above this temperature water, ammonia, and nitrogen are formed. With excess of nitric oxide, the metal becomes incandescent. Copper behaves in the same way as nickel. With nitrogen peroxide and hydrogen, the phenomena are similar, but if the proportion of the Published on 01 January 1902. Downloaded 31/10/2014 10:47:34. peroxide is increased, ammonium nitrite and nitrate are formed as well as ammonia, and when the proportion exceeds a certain limit the metal becomes incandescent and an explosion usually occurs. Mixtures of nitric acid vapour and hydrogen are reduced in a similar manner. C. H. B. Reactions in the Formation of Calcium Carbide. By G. GIN (Zeit. Elektrochem., 1902, 8, 397).-Free oxygen is found in the gases formed in the hottest portions of a calcium carbide furnace, whilst calcium vapour is found in cooler portions of the furnace. The author suggests that these substances may be formed by the reactions 2Ca0 + 4C = 3CaC, + 0, and CaCz + 2Ca0 = 3Ca + 2C0, the tern- pernture in the hottest zones of the furnace being higher than the dissociation temperature of carbon monoxide. T. E. Separation of Beryllium. By GREGOIREN. WYROUBOFF(Bull. Xoc. Chim., 1902, [iii], 2'7, 733-734).-For the purpose of separating beryllium from aluminium and iron, which generally accompany it in minerals, the author takes advantage of the fact that beryllium oxalate is very sparingly soluble, whereas the oxalates of aluminium and of iron are comparatively soluble in waber. A. F. VOL. LXXXII. ii. 41 View Article Online 606 ABSTRACTS OF CHEMICAL PAPERS. Properties and Constitution of Zinc Peroxides. By ROBERT DE FORCRAND(Compt. rend., 1902, 135, 103--106).-The zinc per- oxides Zn305,2H,0, Zn30,,3H,0, Zn,O7,4H,0: and 2Zn0,,5H20 (this vol., ii, 322) are stable in moist or dry air with the exception of the last, which at the ordinary temperature gradually changes into Zn30,,2H,0. At 1004 the compound Zn40,,4H,O is gradually con- verted into Zn,0,,3H20, but both the hydrates of the oxide Zn305are stable at this temperature. The compound Zn30,,3H,0 at 190' and the compound Zn30,,2H,0 at 210' suddenly lose water and oxygen and are converted into the monoxide, All of them dissolve in dilute sulphuric acid without liberation of oxygen, yielding a solution which behaves like a mixture of zinc sulphate and hydrogen peroxide.
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