CH3CHOH与HO2抽氢反应机理及动力学的理论研究  

Theoretical study on the mechanism and kinetics of hydrogen abstraction reaction of CHCHOH with HO

作　　者：陈旭 文明杰 柴广 付峻锋 郭西明 穆茹雪 王睿[1] CHEN Xu;WEN Ming-jie;CHAI Guang;FU Jun-feng;GUO Xi-ming;MU Ru-xue;WANG Rui(Shaanxi Key Laboratory of Catalysis,College of Chemical Environment Science,Shaanxi University of Technology,Hanzhong 723000,China)

机构地区：[1]陕西省催化基础与应用重点实验室,陕西理工大学化学与环境科学学院,陕西汉中723000

出　　处：《分子科学学报》2020年第6期497-503,I0005,共8页Journal of Molecular Science

基　　金：陕西省科技厅资助项目(2019JQ-880);陕西省教育厅资助项目(18JK0147);陕西理工大学研究生创新基金项目(SLGYCX2022);陕西省大学生创新创业训练计划资助项目(S202010720050)。

摘　　要：采用CBS-QB3和B3LYP方法对CH3(β)CH(α)OH与HO2反应的单、三重态抽氢反应势能面进行了研究,并计算了各通道的速率常数.计算表明,CH3(β)CH(α)OH+HO2反应在单、三重态势能面上均存在HO2中端基O原子分别抽取CH3CHOH中(HO)H原子、(α-C)H原子、(β-C)H原子以及CH3CHOH中α-C原子抽取HO2中H原子等4类抽氢反应.其中,生成产物为3CH3COOH+H2O和CH3CH2OH+3O2的三重态通道能垒仅为6.4~9.6 kJ·mol-1,是CH3CHOH+HO2抽氢反应的优势通道.进一步的速率常数及其分支比研究表明,在200 K^1000 K温度范围内,生成3CH3COOH+H2O的通道速率常数比其他通道大1~3个数量级,是CH3CHOH+HO2抽氢反应的主通道.The mechanism and rate constant of the singlet and triplet hydrogen abstraction reactions between HO2 and CH3(β)CH(α)OH is investigated at the CBS-QB3 and B3 LYP level.The calculated result shows that both singlet and triplet CH3CHOH+HO2 reaction involves four kinds of hydrogen abstraction routes,wherein the terminal O atom of HO2 respectively extracts the H atom of—HO,α-C andβ-C in CH3CHOH,as well as theα-C atom in CH3CHOH extracts the H atom of HO2.The triplet channels of the formation of 3CH3COOH+H2O and CH3CH2OH+3O2 are favorable with energy barrier only of 6.4~9.6 kJ·mol-1.Further studies on the rate constants and their branching ratios show that the rate constants of the channels for the formation of 3CH3COOH+H2O are 1~3 orders of magnitude larger than those of other channels in the temperature range of 200 K^1000 K,which is the main channel for the dehydrogenation of CH3CHOH+HO2.

关 键 词：CH3CHOH HO2 反应机理 速率常数 

分 类 号：O643[理学—物理化学]