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.