Barium chlorate iodate

MRH Barium chlorate 5.06/83, calcium chlorate 5.61/77, potassium chlorate 6.07/76, sodium bromate 4.98/80, sodium chlorate 7.32/75, zinc chlorate 6.11/76 Dry finely divided mixtures of red (or white) phosphorus with chlorates, bromates or iodates of barium, calcium, magnesium, potassium, sodium or zinc will readily explode on initiation by friction, impact or heat. Fires have been caused by accidental contact in the pocket between the red phosphorus in the friction strip on safety-match boxes and potassium chlorate tablets. Addition of a little water to a mixture of white or red phosphorus and potassium iodate causes a violent or explosive reaction. Addition of a little of a solution of phosphorus in carbon disulfide to potassium chlorate causes an explosion when the solvent evaporates. The extreme danger of mixtures of red phosphorus (or sulfur) with chlorates was recognised in the UK some 50 years ago when unlicenced preparation of such mixtures was prohibited by Orders in Council. 

H. Klinger made the di-iodate by mixing 20 grms. of potassium chlorate, 21 grms. of iodine, and 100 c.c. of water in a half-litre tubulated retort with a thermometer fitted in the tubulure, and the neck directed upwards. The mixture is heated by a small flame. The liquid becomes yellow, and violet vapours condense in the neck of the retort. The materials begin to react at about 85°, and the reaction is complete at about 95°. Only a little chlorine is evolved when the liquid is heated up to its b.p. When the colourless liquid is cooled, crystals of the di-iodate separate, and these can be purified by recrystallization from hot water. The yield is over 70 per cent. Some barium di-iodate can be recovered by adding barium chloride to the mother-liquid. 

These two groups include chlorates, bromates, iodates, perchlorates, and periodates. Of these, only potassium chlorate and potassium F>erchlorate are of pyrotechnic importance because they are the most stable nonhygroscopic salts in this class. Barium chlorate is found in fireworks but has been abandoned for military purposes ammonium perchlorate is rarely found but is important in propellants. 

Impact sensitivities of mixtures of red phosphorus with various oxidants were determined in a direct drop-ball method, which indicated higher sensitivities than those determined with an indirect striker mechanism. Mixtures with silver chlorate were most sensitive, those with bromates, chlorates and chlorites were extremely sensitive, and mixtures with sodium peroxide and potassium superoxide were more sensitive than those with barium, calcium, magnesium, strontium or zinc peroxides. Mixtures with perchlorates or iodates had sensitivities comparable to those of unmixed explosives, such as lead azide, 3,5-dinitrobenzenediazonium-2-oxide etc. 

Intimate mixtures of chlorates, bromates or iodates of barium, cadmium, calcium, magnesium, potassium, sodium or zinc, with finely divided aluminium, arsenic, copper carbon, phosphorus, sulfur hydrides of alkali- and alkaline earth-metals sulfides of antimony, arsenic, copper or tin metal cyanides, thiocyanates or impure manganese dioxide may react violently or explosively, either spontaneously (especially in presence of moisture) or on initiation by heat, friction, impact, sparks or addition of sulfuric acid [1], Mixtures of sodium or potassium chlorate with sulfur or phosphorus are rated as being exceptionally dangerous on frictional initiation. 

The rare earths furnish soluble chlorates and bromates, and sparingly soluble iodates. The chlorates and bromates of the rare earths were prepared by C. F. Rammelsberg and J. C. G. de Marignac by covering barium bromate with water on a water-bath, and gradually adding with constant stirring-the neutral rare earth sulphate. The barium sulphate is removed by filtration, and the bromate VOL. II. 2 A... 

Potassium iodide can also be obtained from the aq. extract of kelp or from the mother liquid remaining after the separation of sodium chloride and potassium sulphate from sea-water by evaporation. In E. Allary and J. Pellieux process,8 the liquid is evaporated to dryness and roasted in a special furnace so as to avoid a loss of iodine. The product is fractionally extracted with cold water, when a soln. is obtained which on evaporation gives a residue with 50 per cent, of alkali iodide. This product is extracted.in a special digester with 50 per cent, alcohol. The solvent dissolves little more than the iodides. The alcohol is distilled off, and on evaporation a residue containing about 34 per cent, of potassium iodide, and 66 per cent, of sodium iodide is obtained. To convert the latter into potassium iodide, the proper quantity of a soln. of potassium carbonate is added and carbon dioxide passed into the liquid whereby sodium bicarbonate is precipitated. The precipitate is separated by a filter press, and the small amount of sodium bicarbonate remaining in the soln. is separated by the addition of a little hydrochloric acid and the sodium chloride and potassium iodide separated by fractional crystallization. In E. Sonstadt s process, the mother liquid is treated with chlorine mixed with potassium chlorate or permanganate so as to convert the iodine into iodate. A soln. of a barium salt is added, and the barium iodate treated with potassium sulphate. Barium sulphate is precipitated, and the soln. of potassium iodate is evaporated to dryness and calcined to convert the iodate to iodide. The latter is purified by crystallization. 

See Carbon dioxide, above Ammonium nitrate Metals Barium peroxide Metals Dinitrogen tetraoxide Metals Hydrogen peroxide Metals Lead(IV)oxide Metals Nitric acid Metals Oxygen (Liquid) Metals Potassium chlorate Metals Potassium perchlorate Powdered metals Sodium iodate Metals Sodium nitrate Magnesium See Halogens etc., above See Metal oxides, above See Metal oxosalts, above See Sulfur, etc., below... 

Metal Halogenates. Dry, finely divided mixtures of red or white phosphorus and chlorates, bromates, or iodates of barium, calcium, magnesium, potassium, sodium, or zinc explode when subjected to friction, impact, or heat. Mixtures of potassium iodate with white or red phosphorus react violently or explosively on addition of a small quantity of water.16... 

Oxygen may also be obtaiued by heating the chlorates of other metals, notably barium,1 calcium,2 strontium,3 lead,4 and silver,5 or by decomposition of metallic bromates and iodates.6... 

IV.21 IODATES, IO3 Solubility The iodates of the alkali metals are soluble in water those of the other metals are sparingly soluble and, in general, less soluble than the corresponding chlorates and bromates. Some solubilities in g -1 at 20° are lead iodate 0 03 (25°), silver iodate 0-06, barium iodate O 22, calcium iodate 3-7, potassium iodate 81-3, and sodium iodate 90 0. Iodic acid is a crystalline solid, and has a solubility of 2,330 g t 1 at 20°. 

Barium chloride solution white precipitate of barium iodate (difference from chlorate), sparingly soluble in hot water and in dilute nitric acid, but insoluble in alcohol (difference from iodide). If the precipitate of barium iodate is well washed, treated with a little sulphurous acid solution and 1-2 ml carbon tetrachloride, the latter is coloured violet by the liberated iodine, and barium sulphate is precipitated ... 

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