Theoretical study on dynamics of the gas phase reactions of CF3CF2CH2OCHF2 with OH radicals

被引：2

作者：

Wang, Li ^{[1
]}

Zhang, Ting ^{[1
]}

Wen, Jinmiao ^{[1
]}

He, Hongqing ^{[2
]}

Zhang, Jinglai ^{[1
]}

机构：

[1] Henan Univ, Coll Chem & Chem Engn, Inst Environm & Analyt Sci, Kaifeng 475004, Henan, Peoples R China

[2] Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan Ctr Magnet Resonance, Wuhan 430071, Peoples R China

来源：

JOURNAL OF FLUORINE CHEMISTRY | 2014年 / 168卷

基金：

中国国家自然科学基金;

关键词：

H-abstraction; CF3CF2CH2OCHF2; Direct dynamics; Rate constants; TRANSITION-STATE THEORY; RATE CONSTANTS; CL ATOMS; DECOMPOSITION KINETICS; ATMOSPHERIC CHEMISTRY; THERMAL-DECOMPOSITION; ALKOXY RADICALS; HYDROFLUOROETHERS; DEGRADATION; DENSITY;

D O I：

10.1016/j.jfluchem.2014.08.024

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A theoretical study on the mechanism and dynamics properties of the gas-phase reaction of CF3CF2CH2OCHF2 + OH is performed by using BMK method with the 6-311+G(d,p) basis set. The energy is further refined by the BMC-CCSD theory on the basis of the optimized structures. There are two kinds of H-abstraction channels and two displacement channels. The reactivity of displacement and H-abstraction reaction is compared from both the thermodynamic and kinetic viewpoints. The contributions from displacement channels are negligible. For both H-abstraction channels, the H-abstraction from -CH2- site is more favorable than that from -CHF2 site. The rate constants of title reaction are firstly determined by theoretical method in a wide temperature range. (C) 2014 Published by Elsevier B.V.

引用

页码：25 / 33

页数：9

共 52 条

[1] Atmospheric chemistry of CF3OCF2CF2H and CF3OC(CF3)2H:: Reaction with Cl atoms and OH radicals, degradation mechanism, global warming potentials, and empirical relationship between k(OH) and k(Cl) for organic compounds [J].