The reactions of hydrogen atoms with bis(trifluoromethyl)disulfide

The reactions of hydrogen atoms produced by the mercury‐photosensitized decomposition of H2 with bis(trifluoromethyl)disulfide has been studied. The rate coefficient for the primary reaction, H + CF3SSCF3 → CF3SH + CF3S, was determined in competition with the reaction H + C2H4S → SH + C2H4 to have the value k = (3.0 ± 0.18) × 1014 exp[‐(4560 ± 140)/RT] cm3 mol−1 S−1. The high A factor can be partially accounted for by assuming free rotation for the two CF3 groups and the SCF3 groups about the S—S bond in the transition state. The relatively high activation energy is attributed to inductive and orbital overlap effects. CH3SH, H2S, and CF3SH all react with CF3SSCF3 to yield solid complexes which were not explored further.