期刊
JOURNAL OF FLUORINE CHEMISTRY
卷 178, 期 -, 页码 79-85出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jfluchem.2015.07.005
关键词
Fluoroesters; DFT; Isodesmic reactions; Bond dissociation enthalpy; Atmospheric lifetime
资金
- Council of Scientific and Industrial Research (CSIR), New Delhi [09/796(0038)/2012-EMR-I]
- University Grants Commission, New Delhi [F.6-6/2014-15/EMERITUS-2014-15-GEN-4309/(SA-III), F. 13-696/2012(BSR)]
The reaction mechanism of OH-initiated hydrogen abstraction reactions of CF3C(O)OCH2CH3, ethyl trifluoroacetate (ETFA) were investigated by performing DFT calculations. The optimized geometries, frequencies and minimum energy path were obtained at MPWB1K in conjunction with 6-31+G(d,p) basis set. The single-point energy calculations were further refined by using high level G2(MP2) method. Two conformers of ETFA have been located and considered for kinetic calculations. The rate constants of the two reactions are determined for the first time in a wide temperature range of 200-450 K. The evaluated rate constant (2.43 x 10(-13)) at 298 K is found to be in good agreement with the available experimental data [(2.64 +/- 0.59) x 10(-13)]. The standard enthalpies of formation for species are evaluated by using a series of isodesmic reactions. The OH-driven atmospheric life time are also estimated and compared with literature values. Based on mechanistic and kinetics studies, we suggest that the H abstraction from -CH2 group is more favorable than the -CH3 group. (C) 2015 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据