Abstract: | The gamma radiation induced decomposition of MeSO2Cl 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 SO2, 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-SO2) and D(c-C6H11-SO2), 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(MeSO2-H) does not exceed 95 kcal/mole. Competitive experiments with added tetrachloroethylene result in where θ = 2.303RT in kcal/mole. |