Estimation of rate constants for hydrogen atom abstraction by OH radicals using the C-H bond dissociation enthalpies: Haloalkanes and haloethers
Estimation of rate constants for hydrogen atom abstraction by OH radicals using the C-H bond dissociation enthalpies: Haloalkanes and haloethers
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DOI：
10.1002/kin.10110
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发表时间：
2003-03-01
影响因子：
1.5
通讯作者：
Sekiya, A
中科院分区：
文献类型：
--
作者：
Chandra, AK;Uchimaru, T;Sekiya, A
我们提出了一个半经验的方法来估计OH自由基与卤代烷和卤代醚的氢原子提取反应的速率常数。我们的方法源自基于碰撞理论的动力学方程，该方程最初由Heicklen（Int. J. Chem. Kinet.，1981，13，65 1）。该方程提供了从每个潜在的氢原子提取位点的C-H键解离焓中提取氢的速率常数的估计。我们重新参数化的方程，然后将此程序应用到一系列的卤代烷和卤醚分子。新方程的计算结果是令人满意的。此外，我们还报告了六个环境重要的卤醚分子（CH_2FOCH_2F，CHF_2CF_2 OCH_2CF_3，CF_3CH_2 OCH_2CF_3，CF_3CF_2CH_2 OCHF_2，CHF_2 OCF_2CHF_Cl，和CHF_2 OCH_ClCF_3）的C-H键解离能谱的高度可靠的计算值。(C)2002 Wiley Periodicals，Inc.
We propose a semiempirical procedure for the estimation of the rate constants for hydrogen atom abstraction reactions of OH radicals with haloalkanes and haloethers. our procedure is derived from the collision theory based kinetic equation, which was originally proposed by Heicklen (Int. J. Chem. Kinet. 1981, 13, 65 1). This equation provides the estimates for the rate constants of hydrogen abstraction from the C-H bond dissociation enthalpy for each potential hydrogen atom abstraction site. We reparameterized the equation and then applied this procedure to a series of haloalkane and haloether molecules. The results obtained from the new equations are found to be quite satisfactory. In addition, we also report highly reliable calculated values of the C-H bond dissociation enthalpies for six environmentally important haloether molecules (CH2FOCH2F, CHF2CF2OCH2CF3, CF3CH2OCH2CF3, CF3CF2CH2OCHF2, CHF2OCF2CHFCl, and CHF2OCHClCF3). (C) 2002 Wiley Periodicals, Inc.