A theoretical investigation on the kinetics, mechanism and thermochemistry of gas-phase reactions of methyl acetate with chlorine atoms at 298 K

被引：20

作者：

Deka, Ramesh Chandra ^{[1
]}

Mishra, Bhupesh Kumar ^{[1
]}

机构：

[1] Tezpur Univ, Dept Chem Sci, Tezpur Nappam 784028, Assam, India

来源：

CHEMICAL PHYSICS LETTERS | 2014年 / 595卷

关键词：

ATMOSPHERIC OXIDATION; RATE CONSTANTS; NONCOVALENT INTERACTIONS; OH RADICALS; CL ATOMS; ESTERS; TEMPERATURE; PRESSURE; ETHERS; SERIES;

D O I：

10.1016/j.cplett.2014.01.049

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：

A theoretical study on the kinetic and thermochemistry of the reactions of CH3C(O)OCH3 with Cl atoms is performed using DFT and ab initio methods. The formation of pre and post-reactive complexes indicates an indirect hydrogen-abstraction reaction. The calculated total rate coefficient value k(Cl) = 2.61 x 10(-12) cm(-3) molecule(-1) s(-1) is in good agreement with the experimental value of k(Cl) = 2.79 x 10(-12) cm(3) molecule(-1) s(-1) at 298 K. Our calculations suggest that the H abstraction from -OCH3 group is kinetically and thermodynamically more favorable than the -CH3C(O) group. The atmospheric lifetime of CH3C(O)OCH3 is found to be 44 days. (C) 2014 Elsevier B.V. All rights reserved.

引用

页码：43 / 47

页数：5

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