Reaction of hydrogen atoms with diethylsulfide

Abstract

In the reactions of H atoms, generated by the Hg(3P1)-sensitized decomposition of H2, with C2H5SC2H5 the primary reaction has been established to be [Formula: see text] with k1 = (4.7 ± 0.9) × 1013 exp [−(3797 ± 152)/RT] cm3 mol−1 s−l relative to the rate constant of the H + C2H4 → C2H5 reaction. The mechanism postulated explains adequately all the experimental observations. The entropy of activation for the primary reaction, −22.1 eu is close to the value obtained for the H + CH3SCH3 reaction, suggesting a transition state with similar structure. H atoms do not abstract hydrogen from diethylsulfide, but the ethyl radicals from reaction [1] do with a rate coefficient of k = (7.4 ± 0.5) × 1013 exp [−(6860 ± 98)/RT] cm3 mol−1 s−1.