Reactions of thiyl radicals. XII. Triplet mercury photosensitized decomposition of ethyl sulfide in the gas phase

Abstract

CONRAD S. SMITEI and ARTHUR R. KNIGHT. Can. J. Chem. 54, 1290 (1976. The triplet mercury photosensitized decomposition of ethyl sulfide vapour has been studied at 25 "C. The reaction products include C2H4 (90 = 0.075), C2H6 (90 = 0.013), C4HI0 (90 = 0.011), C,H5SH ( @ = 0.068), 4-methyl-3-thiahexane ( @ = 0.01 l), and C2H5SSC,H5 (90 = 0.175). The overall decomposition q~~a n t u m yield is 0.38 at high sulfide pressures. The initial decomposition gives principally ethyl radicals and ethylthiyl radicals; a second step which yields ethylene and ethanethiol may account for up to 20' ;;; of the primary process. Comparison of the direct and sensitized decompositions indicates that both likely originate in the triplet manifold of ethyl sulfide.Primary decomposition quantum yields have been accurately redetermined for the direct. [Traduit par le journal]