Rates of addition of tert‐butyl and pivaloyl radicals to acrylonitrile measured by modulated ESR and μSR spectroscopy

For the rate constant of addition of tert‐butyl radicals to acrylonitrile at T = 300 K in solution modulated ESR spectroscopy and muon spin rotation yield 106 M−1 s−1 and 2.4 × 106 M−1 s−1. The addition of pivaloyl radical to acrylonitrile proceeds with Arrhenius parameters log A/M−1 s−1 = 7.7 and Ea = 11.5 kJ/ mol. The results are discussed in terms of polar effects in radical addition reactions.