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Mixed Phosphorus Thiotrihalides

Mixed Phosphorus Thiotrihalides, PSClBr2 and PSCl2Br, have been prepared by passing a mixture of PSCl3 and HBr over pumice at 400° to 500° C., the products being separated by fractional distillation. Amongst these is also the starting material PSCl3, which is formed in a sealed tube by the reaction:—

2PSCl2Br = PSClBr2 + PSCl3

Thioiodides may be obtained by several methods:—

  1. By the interaction of the elements, in their correct proportions, in carbon disulphide.
  2. By the action of hydrogen sulphide on heated iodides of phosphorus, thus

    2P2I4 + 3H2S = P4S3I2 + 6HI
    2PI3 + 2H2S = P2S2I2 + 4HI
These compounds are soluble in carbon disulphide, from which they may be obtained as orange or yellow crystals. They are only slightly soluble in other organic solvents such as benzene, chloroform, etc. They can be burnt in air, giving oxides of phosphorus, sulphur and iodine. They are decomposed by warm water or moist air, giving first phosphoric and hydriodic acids, then phosphoric acid and hydrogen sulphide.

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