The reactions of hydrogen atoms with bis(trifluoromethyl)disulfide

The reactions of hydrogen atoms produced by the mercury‐photosensitized decomposition of H 2 with bis(trifluoromethyl)disulfide has been studied. The rate coefficient for the primary reaction, H + CF 3 SSCF 3 → CF 3 SH + CF 3 S, was determined in competition with the reaction H + C 2 H 4 S → SH + C 2 H 4 to have the value k = (3.0 ± 0.18) × 10 14 exp[‐(4560 ± 140)/ RT ] cm 3 mol −1 S −1 . The high A factor can be partially accounted for by assuming free rotation for the two CF 3 groups and the SCF 3 groups about the S—S bond in the transition state. The relatively high activation energy is attributed to inductive and orbital overlap effects. CH 3 SH, H 2 S, and CF 3 SH all react with CF 3 SSCF 3 to yield solid complexes which were not explored further.