title: Computational study on the mechanisms and rate constants of the OH-initiated oxidation of ethyl vinyl ether in atmosphere.
abstract: The hydroxylation reactions of ethyl vinyl ether (EVE) in the present of O2 and NO are analyzed by using MPWB1K/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) level of theory. According to the calculated thermodynamic data, the detailed reaction mechanisms of EVE and OH are proposed. All of the ten possible reaction pathways are discussed. The major products of the title reaction are ethyl formate and formaldehyde, which is in accordance with experimental detection. The rate constants of the primary reactions over the temperature of 250-400K and the pressure range of 100-2000Torr are computed by employing MESMER program. At 298K and 760Torr, OH-addition channels are predominate and the total rate constant is ktot=4.53×10(-11)cm(3)molecule(-1)s(-1). The Arrhenius equation is obtained as ktot=6.27×10(-12)exp(611.5/T), according to the rate constants given at different temperatures. Finally, the atmospheric half life of EVE with respect to OH is estimated to be 2.13h.
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Dandan
authors.initials: D
authors.lastname: Han
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Haijie
authors.initials: H
authors.lastname: Cao
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Jing
authors.initials: J
authors.lastname: Li
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Mingyue
authors.initials: M
authors.lastname: Li
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China. Electronic address: hemaox@sdu.edu.cn.
authors.forename: Maoxia
authors.initials: M
authors.lastname: He
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, PR China.
authors.forename: Jingtian
authors.initials: J
authors.lastname: Hu
mesh_terms: D001272:Atmosphere / Q000737:chemistry*; D005019:Ethyl Ethers / Q000737:chemistry* / Q000378:metabolism; D005557:Formaldehyde / Q000737:chemistry; D005563:Formic Acid Esters / Q000737:chemistry; D006207:Half-Life; D006878:Hydroxides / Q000737:chemistry*; D007700:Kinetics; D008962:Models, Theoretical; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics
chemical_list: D005019:Ethyl Ethers; D005563:Formic Acid Esters; D006878:Hydroxides; C510888:ethyl formate; D005557:Formaldehyde; C013333:ethyl vinyl ether; C031356:hydroxide ion
keywords: Ethyl vinyl ether (EVE); Hydroxylation reactions; Rate constants; Reaction mechanism