Theoretical Studies on the Reaction Mechanism and Kinetics of Ethylbenzene-OH Adduct with O<sub>2</sub> and NO<sub>2</sub>
Tingting Lu,
Mingqiang Huang,
Xin Lin,
Wei Zhang,
Weixiong Zhao,
Changjin Hu,
Xuejun Gu,
Weijun Zhang
Affiliations
Tingting Lu
Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, College of Chemistry & Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, China
Mingqiang Huang
Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, College of Chemistry & Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, China
Xin Lin
Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, College of Chemistry & Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, China
Wei Zhang
Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, College of Chemistry & Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, China
Weixiong Zhao
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China
Changjin Hu
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China
Xuejun Gu
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China
Weijun Zhang
Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China
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.
