Kinetic and mechanistic study of the atmospheric oxidation by OH radicals of allyl acetate

Abstract

Acetates are emitted into the atmosphere by several anthropic and natural sources. To better evaluate the environmental impact of these compounds, OH-induced oxidation kinetic and mechanism of allyl acetate (CH3C(O)OCH2-CH=CH2) have been investigated at room temperature and atmospheric pressure using three environmental chambers: an indoor Teflon-film bag (LISA, Créteil), an indoor Pyrex photoreactor (LISA, Créteil), and the outdoor Smog chamber EUPHORE (Valencia). Rate constant of the reaction of allyl acetate with OH radicals was determined by relative rate technique in the indoor Teflon-film bag. It is (30.6 +/- 3.1) x 10(-12) cm3 molecule-1 s-1. Mechanistic experiments were performed in the indoor photoreactor and in the outdoor Smog chamber EUPHORE. The main oxidation products observed by FTIR in both chambers were acetoxyacetaldehyde and formaldehyde. From these data, a mechanism was developed to describe the OH-induced oxidation of this acetate in the presence of NOx. Finally, atmospheric impact of allyl acetate emissions was evaluated using kinetic and mechanistic results.