title: Computational study on the mechanisms and rate constants of the Cl-initiated oxidation of methyl vinyl ether in the atmosphere.
abstract: The Cl-initiated oxidation reactions of methyl vinyl ether (MVE) are analyzed by using the high-level composite method CBS-QB3. Detailed chemistry for the reactions of MVE with chlorine atoms is proposed according to the calculated thermodynamic data. The primary eight channels, including two Cl-addition reactions and six H-abstraction reactions, are discussed. In accordance with the further investigation of the two dominant additional routes, formyl chloride and formaldehyde are the major products. Over the temperature range of 200-400 K and the pressure range of 100-2000 Torr, the rate constants of primary reactions are calculated by employing the MESMER program. H-abstraction channels are negligible according to the value of rate constants. During the studied temperature range, the Arrhenius equation is obtained as ktot = 5.64 × 10(-11) exp(215.1/T). The total rate coefficient is ktot = 1.25 × 10(-10) cm(3) molecule(-1) s(-1) at 298 K and 760 Torr. Finally, the atmospheric lifetime of MVE with respect to Cl is estimated to be 2.23 h.
authors.affiliation: Environment Research Institute, Shandong University , Jinan 250100, People's Republic of China.
authors.forename: Dandan
authors.initials: D
authors.lastname: Han
authors.forename: Haijie
authors.initials: H
authors.lastname: Cao
authors.forename: Mingyue
authors.initials: M
authors.lastname: Li
authors.forename: Xin
authors.initials: X
authors.lastname: Li
authors.forename: Shiqing
authors.initials: S
authors.lastname: Zhang
authors.forename: Maoxia
authors.initials: M
authors.lastname: He
authors.forename: Jingtian
authors.initials: J
authors.lastname: Hu
mesh_terms: D001272:Atmosphere / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D008738:Methyl Ethers / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D002712:Chlorides; D008738:Methyl Ethers; D014753:Vinyl Compounds; C100195:vinyl ether