The kinetics of ClO formation in the flash photolysis of chlorine–oxygen mixtures

The production of ClOO and ClO radicals following the flash photolysis of chlorine + oxygen mixtures has been studied. For the mechanism the following kinetic parameters were measured: k₃K = 1.3 × 10¹⁰ l²/mol²·sec; k₂/k₃ = 17; and k₃/?(ClOO; 250 nm) = 9.7 × 10⁵ cm/sec. Then k₃ = 5.9 × 10⁹ l/mol·sec, k₂ = 1.0 × 10¹¹ l/mol·sec, and ?(ClOO; 250 nm) = 6.1 × 10³ l/mol·cm. From limits established for the equilibrium constant K, ΔH°_f (ClOO) = 94 ± 2 kJ/mol.