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

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 02 and NO. The rate constants are calculated using RRKM theory by employing the MESMER program. The total rate constant (1.39 x 10(-10) cm(3) molecule(-1) s(-1)) is well consistent with experimental data at 298 K and 760 Torr, and shows negative temperature dependence in the range of 200-500 K. Tropospheric half-life of AAC (tau(1/2) = 4.6 h for Cl-initiated oxidation) is estimated to evaluate the atmospheric implications. (C) 2016 Elsevier B.V. All rights reserved.