Theoretical study on the mechanism and kinetics for the ozonolysis of vinyl propionate

Abstract

The O3-initiated oxidation of vinyl propionate is studied using quantum chemistry calculations. Detailed and complete reaction mechanisms are presented which involve the formation of the primary ozonide (POZ), the subsequent decomposition of POZ, the secondary reactions of CH3CH2C(O)OCHO2 (IM4) in the presence of H2O or NO as well as the generation of the secondary ozonide (IM6). Based on the above PESs calculations, the Multichannel Rice–Ramsperger–Kassel–Marcus theory is employed to calculate the total and individual rate constants for major product channels. The rate constants and branching ratios of main products are obtained. The total rate constants are temperature dependent over the whole study temperature range (200–2,000 K), but pressure independent over the range of 0.01–10,000 Torr. In addition, the atmospheric lifetime is estimated in accordance with rate constants.