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Photolysis of, and the Reactions of H-Atoms With, t-Butanethiol

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A detailed investigation of the photolysis of t-C4H9SH has been carried out in the absence and presence of the inert gas, C2H6. A mechanism consisting of three primary photochemical steps: t-C4H9SH → t-C4H9S + H (1), t-C4H9SH → t-C4H9 + SH (2), t-C4 Hg SH → i-C4H8 + H2S (3), six hot and seven thermal reaction steps, adequately explains all the experimental observations. As in the case of hot H* atoms, both the H-atom abstraction H + t-C4H9SH → H2 + t-C4H9S (7), and the SH-displacement reactions, H + t-C4H9SH → H2S + i-C4H8 (8), occur with thermalized H-atoms. The Arrhenius expression of the rate constant ratio, k7/k8 for the latter reactions has been determined over the temperature range 25-14°C to be: ln(k7/k8) = (0.3 ± 0.1) + (420 ± 80)/RT.

Affiliations: 1: Department of Chemistry University of Alberta Edmonton, Alberta, Canada T6G 2G2


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