Abstract
The ion—molecule reactions occuring in CH 3SH, CD 3SH and CH 3SHCD 4 mixtures have been studied using the ion-trapping technique and rate coefficients measured. The predominant reaction product is CH 3SH 2 + although the fragment ion CSH 3 + reacts in part (22%) to produce C 2H 5S +. In CD 3SH the molecular ion reacts to produce CD 3SH 2 + and CD 3SHD + in the ratio 23:1; this ratio appears to depend on the internal and/or kinetic energy of the reactant ion. The CD 3SHD + ion transfers a proton to CD 3SH. The rate coefficient for this “symmetrical” proton transfer reaction is less than the calculated collision rate coefficient and increases as the internal energy of the reactant ion increases. The CD 5 + and C 2D 5 + ions product from CD 4 transfer a D + to the mercaptan with essentially unit collision efficiency.
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