Theoretical investigation on the reaction of n-C3H7O2 with Cl

Organic peroxy radicals (RO2) are important in the tropospheric degradation of hydrocarbons and other volatile organic compounds (VOCs). N-propyl peroxy radical (n-C3H7O2) is one of the key intermediates during propane oxidation. The reaction of n-C3H7O2 with halogen species Cl was studied using quantum chemistry methods in this work. Result shows that addition-elimination, substitution and abstraction mechanisms were located, with n-C3H7O2Cl, n-C3H7O + ClO, C2H5CHO + HOCl, C2H5CHO + HClO formed. The most feasible product is the direct adduct n-C3H7O2Cl, and the subdominant product is C2H5CHO + HClO. And the formation of C2H5CHO + HOCl might make certain contribution in high-temperature conditions. In the reactions of RO2 (R = H, CH3, C2H5, n-C3H7) with Cl atom, the substitution effect of n-alkyl groups will increase the reactivity of HO2 to formation of RO2Cl and the stability of RO2Cl.