Theoretical Studies on the Reaction Mechanism and Kinetics of Ethylbenzene-OH Adduct with O2 and NO2

Abstract

The OH-initiated reaction of ethylbenzene results in major OH addition, and the formed ethylbenzene-OH adducts subsequently react with O2 and NO2, which determine the components of the oxidation products. In this study, nine possible reaction paths of the most stable ethylbenzene-OH adduct, EB-Ortho (2-ethyl-hydroxycyclohexadienyl radical intermediate), with O2 and NO2 were studied using density functional theory and conventional transition state theory. The calculated results showed that ethyl-phenol formed via hydrogen abstraction was the major product of the EB-Ortho reaction with O2 under atmospheric conditions. Peroxy radicals generated from O2 added to EB-Ortho could subsequently react with NO and O2 to produce 5-ethyl-6-oxo-2,4-hexadienal, furan, and ethyl-glyoxal, respectively. However, nitro-ethylbenzene formed from NO2 addition to EB-Ortho was the predominant product of the EB-Ortho reaction with NO2 at room temperature. The total calculated rate constant of the EB-Ortho reaction with O2 and NO2 was 9.57 × 10−16 and 1.78 × 10−11 cm3 molecule−1 s−1, respectively, approximately equivalent to the experimental rate constants of toluene-OH adduct reactions with O2 and NO2. This study might provide a useful theoretical basis for interpreting the oxygen-containing and nitrogen-containing organics in anthropogenic secondary organic aerosol particles.