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Kinetics of reactions in the thermal decomposition of tetraphenylhydrazine in the presence of a mixture of sterically hindered phenol and hydroperoxide

Research paper by V. T. Varlamov, E. T. Denisov

Indexed on: 01 Nov '86Published on: 01 Nov '86Published in: Russian Chemical Bulletin



Abstract

In the decomposition of tetraphenylhydrazine in the presence of 2,4,6-tri-tert-butylphenol and cumyl hydroperoxide (or tert-butyl hydroperoxide), both compounds are consumed with equal rates close to the rate of decomposition of tetraphenylhydrazine. Diphenylamine is formed with a rate equal to the sum of the rates of consumption of the phenol and hydroperoxide, and quinoline peroxides are formed with a rate equal to the rate of consumption of the phenol (or hydroperoxide). These mechanisms are preserved when the initial concentrations of the phenol and hydroperoxide are varied and when diphenylamine is added.The results obtained are explained and quantitatively described with a kinetic scheme which includes 11 reactions involving aminyl, aroxyl, and peroxide radicals. The reversible character of the reaction of the aminyl radical with the phenol is an important moment in the scheme.