Peroxides. IX. The kinetics of the hydrogen evolution from the thermal decomposition of 1-hydroxyalkyl alkyl peroxides

The kinetics of the thermal decomposition of 1-hydroxy-n-butyl n-butyl peroxide and 1-hydroxyisobutyl isobutyl peroxide have been studied over the temperature range of 80-110 degrees by following the rate of hydrogen evolution as a means of elucidating the mechanism of the decomposition of these compounds and the corresponding hydroperoxides from which they were derived. alpha-Methylsytrene was used both as a solvent and as a trap for free-radicals. The Arrhenius energies of activation and frequency factors and the enthalpies of activation and entropies of activation were calculated from the rate data for both compounds. These data have been interpreted in terms of a concerted cyclic transitions state.