Theoretical study on the mechanisms and kinetics of Cl-initiated oxidation of methyl acrylate

被引：7

作者：

Zhang, Shiqing ^{[1
]}

Cao, Haijie ^{[1
]}

Li, Xin ^{[1
]}

Sun, Jianfei ^{[1
]}

He, Maoxia ^{[1
]}

机构：

[1] Shandong Univ, Environm Res Inst, Jinan 250100, Peoples R China

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2016年 / 1091卷

关键词：

Methyl acrylate; Cl atoms; Mechanisms; Kinetics; Products; GAS-PHASE REACTIONS; ATOMIC CHLORINE; RATE CONSTANTS; OH RADICALS; NO3; ACROLEIN; PRODUCT;

D O I：

10.1016/j.comptc.2016.07.008

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：

The atmospheric oxidation mechanism and kinetics of CI with methyl acrylate are investigated in this study. The mechanisms of MA with Cl atoms have been obtained in detail at the M06-2X/6-311++G (3df, 2p)//M06-2X16-31+G(d, p) level of theory. The reaction initiates with two kinds of reaction pathways: Cl-addition and H-abstraction. In general, Cl atoms attacking to terminal carbon (the pathway producing IM1) is more favorable. Hydrogen abstraction from the -CH3 group also plays an important role. Besides, the kinetic results are determined by MESMER program on the basis of Rice-Ramsperger-Kass el-Marcus (RRKM) theory. The calculated results show that the addition reactions predominate the initial reaction under atmospheric condition and the calculated total rate constant is 1.66 x 10(-10) cm(3) - molecule (-1) s(-1) at 298 K and 760 Torr. (C) 2016 Elsevier B.V. All rights reserved.

引用

页码：99 / 106

页数：8

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