ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Hydrogen atoms, generated by the mercury (3P1) sensitization of H2, 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} $\end{document}. The intermediacy of thiyl radicals was clearly demonstrated in experiments carried out in the presence of ethylene where one of the major products detected was ethyl methyl sulfide, formed via CH3S + C2H5 → CH3SC2H5. The major fate of the CH3S radical is recombination and disproportionation, and the yield of methanethiol formed via disproportionation contributes less than 5% to the total thiol yield. The rate coefficient of step 1, from competition with the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm C}_{\rm 2} {\rm H}_5 $\end{document}, is k1 = (5.7 ± 1.2) × 1012 exp[—(100 ± 100)/RT] cm3/mol sec.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550120608
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