Computational study on the mechanism and kinetics of NO3-initiated atmosphere oxidation of vinyl acetate

被引：10
作者：
Cao, Haijie [1 ]
Li, Xin [2 ]
He, Maoxia [2 ]
Zhao, X. S. [1 ,3 ]
机构：
[1] Qingdao Univ, Sch Mat Sci & Engn, Inst Mat Energy & Environm, Qingdao 266071, Peoples R China
[2] Shandong Univ, Environm Res Inst, Jinan 250100, Shandong, Peoples R China
[3] Univ Queensland, Sch Chem Engn, Brisbane, Qld 4072, Australia
来源：
COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2018年 / 1144卷
基金：
中国博士后科学基金; 中国国家自然科学基金; 澳大利亚研究理事会;
关键词：
Vinyl acetate; Mechanism; Kinetics; Atmospheric oxidation; Quantum chemical method; VOLATILE ORGANIC-COMPOUNDS; OH-INITIATED DEGRADATION; GAS-PHASE REACTIONS; TROPOSPHERIC CHEMISTRY; NO3; RADICALS; PRODUCTS; AEROSOL; O-3;
D O I：
10.1016/j.comptc.2018.09.012
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
It is known the NO3 radical contributes to the oxidation of volatile organic compounds in the atmosphere in the night, leading to the formation of carbonyl compounds and organic nitrates. The mechanistic and kinetic properties of NO3-initiated oxidative degradation of vinyl acetate (VAC), a typical unsaturated ester, have been studied using density functional method. According to the computational results, two types of primary reactions were identified: NO3-addition and H-abstraction. The NO3-addition reaction especially the C-beta-addition pathway dominates the entrance channel of NO3 into VAC while the H-abstraction reaction is negligible. Further reactions of the two adducts were discussed in the presence of O-2/NOx. The rate constants were estimated by using the MultiWell software. The overall rate constant of NO3-initiated oxidation of VAC was about 7.30 x 10(-15) cm(3) molecule(-1) s(-1) at 298.15 K and atmospheric pressure, in good agreement with the experimental value of (7.30 +/- 1.8) x 10(-13) cm(3) molecule(-1) s(-1). The atmospheric lifetime of VAC reacting with NO3 radicals (5.0 x 10(8) molecule cm(-3)) is about 76.1 h under atmospheric conditions.
引用
收藏
页码：18 / 25
页数：8
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