The mechanism and kinetic studies for Cl-initiated oxidation of allyl acetate in troposphere

Abstract

Computational investigation on Cl-initiated oxidation of allyl acetate (AAC) including reaction mechanisms and kinetics are performed using quantum chemical method. Compared with experimental results, a more comprehensive and reasonable mechanism is proposed. For the primary reaction, seven channels (two Cl-additions and five H-abstractions) are discussed. The calculated results show that the two additional channels dominate the reaction of AAC with Cl. Further investigations of two Cl-adducts are performed in the presence of O2 and NO. The rate constants are calculated using RRKM theory by employing the MESMER program. The total rate constant (1.39×10−10cm3molecule−1s−1) is well consistent with experimental data at 298K and 760Torr, and shows negative temperature dependence in the range of 200–500K. Tropospheric half-life of AAC (τ1/2=4.6h for Cl-initiated oxidation) is estimated to evaluate the atmospheric implications.