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 reacti...

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Bibliographic Details
Published in:Canadian journal of chemistry 1981-12, Vol.59 (23), p.3226-3231
Main Authors: Ekwenchi, Mbanefo Mbonu, Safarik, Imre, Strausz, Otto Peter
Format: Article
Language:English
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Summary: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 .
ISSN:0008-4042
1480-3291
DOI:10.1139/v81-474