Reaction of hydrogen atoms with diethylsulfide

In the reactions of H atoms, generated by the Hg( 3 P 1 )-sensitized decomposition of H 2 , with C 2 H 5 SC 2 H 5 the primary reaction has been established to be with k 1 = (4.7 ± 0.9) × 10 13 exp [−(3797 ± 152)/RT] cm 3 mol −1 s −l relative to the rate constant of the H + C 2 H 4 → C 2 H 5 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 + CH 3 SCH 3 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) × 10 13 exp [−(6860 ± 98)/RT] cm 3 mol −1 s −1 .