Rate constants for the decarboxylation of the t‐butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR

Rate constants of various simultaneous reactions of t‐butoxicarbonyl and t‐butyl radicals generated by photolysis of t‐butylpivalate in n‐heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t‐BuOĊO → t‐Bu. + CO2 obeys log )K/S−1( = 13.8−49.0/θ where θ = 2.303 RT/kJ . mol−1. The self‐ and cross‐termination of the radicals are diffusion limited.