Reactions of thiyl radicals. II. The photolysis of methyl disulfide vapor

Abstract

The photolysis of methyl disulfide vapor in the pressure range 2–25 Torr at wavelengths between 2 300 and 2 800 and at 2 288 Å has been examined and the effect of temperature, pressure, added inert gases, ethyl disulfide, and nitric oxide determined.The primary process is a direct production of two CH₃S radicals which have excess energy and which can be observed as methyl thionitrite when NO is present during the decomposition. When pure disulfide is photolyzed the major observable product is methanethiol, although this material accounts for only a small fraction of the primarily produced thiyl radicals whose principal fate is recombination in a substrate-reforming reaction producing excited disulfide molecules. The latter species are deactivated by added gases, or by the substrate itself. The mode of mercaptan formation is by abstraction of H atoms from the substrate by excited CH₃S radicals with an apparent activation energy of 1.5 kcal.