Collect. Czech. Chem. Commun. 1981, 46, 1071-1082

Hydrogen and electron transfer from diphenylamine in reaction with coordinated peroxy-radicals and hydroperoxides

Vlado Cholvad and Alexander Tkáč

Institute of Chemical Physics, Slovak Institute of Technology, 880 37 Bratislava


Reaction of diphenylamine with coordinated peroxy-radicals and various hydroperoxides (tert-butyl hydroperoxide, cumene hydroperoxide, tetraline hydroperoxide) has been studied in non-polar solvents by the EPR method. From this kinetic study the activation energies of H-transfer (105 ± 2 kJ/mol in the temperature range -40 to -10 °C) and e-transfer (97 ± 2 kJ/mol in the temperature range 10 to 50 °C) have been determined. From the activation energies it follows that, in a reaction mixture containing simultaneously a hydroperoxide and initiating peroxy-radicals, oxidation of diphenylamine goes by the both parallel mechanisms until the final concentration of nitroxyl radical reaches the value of about 1.7 . 1021 spin/l.