Reaction Rates of t-Butyl and Pivaloyl Radicals in Solution

The rate constants of the unimolecular decomposition of the pivaloyl radical (k_D) and of the bimolecular self terminations of pivaloyl (k₁) and t-butyl radicals (k₂) in liquid methylcyclopentane are determined by ESR.-spectroscopy: The viscosity dependence of (k₂) is analysed with respect to diffusion control of the reaction. Comparison of (k_D) values of different acyl radicals reveals a strong dependence of the activation energies on radical structure.