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Phosphorus Thiotrifluoride, PSF3

Phosphorus Thiotrifluoride or thiophosphoryl fluoride, PSF3, was first prepared by heating a mixture of phosphorus and sulphur with an excess of lead fluoride in a lead tube to 250° C. and leading over the mixture a current of dry nitrogen. The gas was purified by standing for about a day over dry lime. It was also prepared by heating arsenic trifluoride in a sealed tube with phosphorus thiotrichloride:—

AsF3 + PSCl3 = PSF3 + AsCl3

It is a transparent and colourless gas, which has no action on glass at ordinary temperatures. The formula has been established by analysis and from the vapour density. The compound is decomposed by heat, giving sulphur and fluorides of phosphorus, thus:—

PSF3 = PF3 + S
5PF3 = 3PF5 + 2P

It burns in air with a blue or greyish-green low-temperature flame. The white fumes which are produced contain P2O5. The sulphur probably burns first, leaving PF3, which combines with more oxygen, giving PF5 and P2O5, the whole reaction being summarised by the equation

10PSF3 + 15O2 = 6PF5 + 2P2O5 + 10SO2

With moist oxygen in closed vessels the reaction may proceed explosively, but it does not proceed at all when the gas and the oxygen are intensively dried. The gas was slowly absorbed and hydrolysed by water, more rapidly by alkalies, thus:—

PSF3 + 4H2O = H2S + 3HF + H3PO4
PSF3 + 6NaOH = Na3PSO3 + 3NaF + 3H2O

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