title: Theoretical study for OH radical-initiated atmospheric oxidation of ethyl acrylate.
abstract: OH radical-initiated atmospheric oxidation of ethyl acrylate (ethyl 2-propenoate, EA) has been investigated by performing density functional theory (DFT) calculations. Optimizations of the reactants, intermediates, transition states and products were carried out at the MPWB1K/6-31+G(d,p) level. Single-point energy calculations were performed at the MPWB1K/6-311+G(3df,2p) level of theory. The detailed oxidation mechanism was presented and discussed. The results show that the OH addition is more energetically favorable than the H abstraction. Rice-Ramsperger-Kassel-Marcus (RRKM) theory was used to predict the rate constants over the possible atmospheric temperature range of 180-370 K. The Arrhenius expression adequately describes the total rate constant: k(EA+OH)=(1.71×10(-12))exp(805.42/T)cm(3) molecule(-1) s(-1). At 298 K, the atmospheric lifetime of ethyl acrylate determined by OH radicals is about 16.2h. In order to find out the effect of alkyl substitution on the reaction activity, rate constants for the reactions of methyl acrylate, methyl methacrylate and butyl acrylate with OH radicals were also discussed. Calculation results show that the reaction activity may increase with the increased electron-donating substitution for electrophilic addition reaction.
authors.affiliation: Environment Research Institute, Shandong University, 27 Shanda Nanlu, Jinan 250100, PR China.
authors.forename: Yanhui
authors.initials: Y
authors.lastname: Sun
authors.affiliation: Environment Research Institute, Shandong University, 27 Shanda Nanlu, Jinan 250100, PR China. Electronic address: zqz@sdu.edu.cn.
authors.forename: Qingzhu
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: Environment Research Institute, Shandong University, 27 Shanda Nanlu, Jinan 250100, PR China.
authors.forename: Jingtian
authors.initials: J
authors.lastname: Hu
authors.affiliation: Environment Research Institute, Shandong University, 27 Shanda Nanlu, Jinan 250100, PR China.
authors.forename: Jianmin
authors.initials: J
authors.lastname: Chen
authors.affiliation: Environment Research Institute, Shandong University, 27 Shanda Nanlu, Jinan 250100, PR China.
authors.forename: Wenxing
authors.initials: W
authors.lastname: Wang
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry; D007700:Kinetics; D008956:Models, Chemical; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D000179:Acrylates; D017665:Hydroxyl Radical; C032490:n-butyl acrylate; C040833:ethyl acrylate; C035956:methyl acrylate
keywords: Ethyl acrylate; Kinetic parameters; OH radicals; Quantum chemical calculation; Reaction mechanism