A theoretical investigation on the kinetics, mechanism and thermochemistry of gas-phase reactions of methyl acetate with chlorine atoms at 298 K

A theoretical study on the kinetic and thermochemistry of the reactions of CH3C(O)OCH3 with Cl atoms is performed using DFT and ab initio methods. The formation of pre and post-reactive complexes indicates an indirect hydrogen-abstraction reaction. The calculated total rate coefficient value kCl = 2.61 × 10−12 cm3 molecule−1 s−1 is in good agreement with the experimental value of kCl = 2.79 × 10−12 cm3 molecule−1 s−1 at 298 K. Our calculations suggest that the H abstraction from –OCH3 group is kinetically and thermodynamically more favorable than the –CH3C(O) group. The atmospheric lifetime of CH3C(O)OCH3 is found to be 44 days.