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Reaction of hydrogen atoms with dimethyldisulfide
Author(s) -
Ekwenchi M. M.,
Jodhan A.,
Strausz O. P.
Publication year - 1980
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550120608
Subject(s) - disproportionation , chemistry , methanethiol , yield (engineering) , hydrogen , hydrogen sulfide , radical , ethylene , sulfur , physics , organic chemistry , catalysis , thermodynamics
Hydrogen atoms, generated by the mercury ( 3 P 1 ) sensitization of H 2 , were allowed to react with dimethyldisulfide in the temperature range of 25–155°C. The only retrievable product is methanethiol, formed in the primary metathetical reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm CH}_3 {\rm SSCH}_3 {\rm CH}_3 {\rm SH} + {\rm CH}_3 {\rm S} $\end{document} . The intermediacy of thiyl radicals was clearly demonstrated in experiments carried out in the presence of ethylene where one of the major products detected was ethyl methyl sulfide, formed via CH 3 S + C 2 H 5 → CH 3 SC 2 H 5 . The major fate of the CH 3 S radical is recombination and disproportionation, and the yield of methanethiol formed via disproportionation contributes less than 5% to the total thiol yield. The rate coefficient of step 1, from competition with the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm C}_{\rm 2} {\rm H}_5 $\end{document} , is k 1 = (5.7 ± 1.2) × 10 12 exp[(100 ± 100)/ RT ] cm 3 /mol sec.