Flash photolysis study of the spectra of CH3O2 and C(CH3)3O2 radicals and the kinetics of their mutual reactions and with NO

Abstract

The ultraviolet spectra of the alkyl peroxy radicals, CH₃O₂ and C(CH₃)₃O₂, have been obtained using flash photolysis with photoelectric recording. They are in good agreement with those found using molecular modulation spectroscopy. The overall rates of the “mutual” reactions: 2CH₃O₂→ products (3), and 2C(CH₃)₃O₂→ products (4) also agree very well with rates found previously.

Two other reactions of importance in low temperature oxidation have been studied. A lower limit of 10^–12 cm³ molecule^–1 s^–1 was found for the rate constants of the overall reactions of CH₃O₂ and of C(CH₃)₃O₂ with NO. The rate constant for the reaction between OH and t-butyl hydro-peroxide was found to be (3.0 ± 0.8)× 10^–12 cm³ molecule^–1 s^–1 at room temperature.