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The oxidation of elemental phosphorus (P4) by elemental sulfur (S8) has been studied by a combination of 31P nmr and Raman spectroscopic techniques. At temperatures below the auto-ignition temperature, a molten mixture of the elements gives rise to a complex mixture of products which are dominated by phosphorus sulfides which have a high S/P4 ratio. Both the rate at which the products are formed and their distribution support the formation of a reactive P4S8 intermediate which then cascades through a series of reactions, incorporating the sulfur atoms into the phosphorus cage. Two new phosphorus sulfides (of composition P4S6 and P4S8) have been identified in these product mixtures.

EARLY EVENTS IN THE REACTION CHEMISTRY OF PHOSPHORUS (P<SUB>4</SUB>) AND SULFUR (S<SUB>8</SUB>)