Radiolytic decomposition of methanesulfonyl chloride in liquid cyclohexane. A kinetic determination of the bond dissociation energies D (ME‐SO 2 ) and D ( c ‐C 6 H 11 ‐SO 2 )

The gamma radiation induced decomposition of MeSO 2 Cl in cyclohexane (RH) was studied between 60 and 150°C. Throughout this temperature range the reaction proceeds by a free radical chain mechanism. Its propagation is described by the following reactions:The kinetic analysis of the results of the experiments with added SO 2 , which were carried out in the temperature range of 80 to 150°C, gives 14.94 ± 0.92 and 11.91 ± 0.82 kcal/mole for D (Me‐SO 2 ) and D (c‐C 6 H 11 ‐SO 2 ), respectively. These bond dissociation energies are considerably lower than the gas‐phase values, and the possible cause of this difference is discussed. Present results also seem to indicate that D (MeSO 2 ‐H) does not exceed 95 kcal/mole. Competitive experiments with added tetrachloroethylene result in\documentclass{article}\pagestyle{empty}\begin{document}$$\log k_{2{\rm a}} (1./{\rm mole} \cdot {\rm sec}) = 9.07 \pm 0.17- (4.92 \pm 0.21)/\theta $$\end{document} where θ = 2.303 RT in kcal/mole.