Kinetic spectrophotometric study of the kinetics of direct and reverse reactions of the peroxide radical with diphenylamine

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1. A new method was developed for determining the rate constants of direct; and reverse reactions of peroxide radicals with diphenylamine based on the kinetics of accumulation of the products of the reaction between peroxide and diphenylaminyl radicals in initiator-diphenylamine-oxygen and initiator-hydroperoxide-diphenylamine-oxygen systems. The rate constants of reactions of the peroxide radical with diphenylamine (3.4 · 105 liters/mole · sec) and the reverse reaction (1.1 · 105 liters/mole · sec) in chlorobenzene at 348.5 K were determined. 2. The strength of the N-H bond in the diphenylamine molecule, equal to 365 kJ/mole, was estimated with the equilibrium constant of the direct and reverse reactions.