Abstract
The ion-molecule reactions occurring in mixtures of CH 3SH with CH 3CHO, CH 2 CH 2 O ︹ , C 2H 5CHO, (CH 3) 2O, (CH 3) 2S, and (CH 3) 2CO have been studied using a trapped-ion technique. Particular emphasis has been paid to the rates and equilibria for proton-transfer reactions of CH 3SH + 2. Apparent equilibria have been observed for the proton-transfer reaction: CH 3SH + 2 + M ⇄ CH 3SH+MH +, when M CH 3CHO, C 2H 5CHO, and (CH 3) 2O. The results lead to a proton affinity of 186 kcal mole −1 for CH 3SH. The rate for the forward reaction increases from ca. 30% of the calculated collision rate for thermoneutral reactions to ca. 100% (unit collision efficiency) for reactions ⩾ 10 kcal mole −1 exothermic.
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