The dynamics of the gas release at thermal oxidation of the two-phase systems of 30% solution of tri-n-butyl phosphate (TBP) in isoparaffinic diluent Isopar M – aqueous solution of 4.3, 8.2 and 12 mol/L of HNO3 has been investigated within the temperature range from 70°C to 110°C. The effect of pre-irradiation of the system TBP–Isopar-M–HNO3 on the kinetics of its thermolysis has been determined. All of the samples were irradiated with an electron accelerator at a dose rate of 10 kGy/h up to integrated doses of 0.5, 1 and 2 MGy. The parameters of heat and gas emission during thermolysis of the tested extraction system in an open apparatus have been determined experimentally. It has been demonstrated, that there are no conditions for extension of autocatalytic oxidation under heat treatment of two-phase extraction systems in open vessels.