Kinetics of hydrogen abstraction reactions from fluoromethanes and fluoroethanes

被引：0
|
作者：
机构：
[1] Matsugi, Akira
[2] Shiina, Hiroumi
来源：
Matsugi, Akira | 1600年 / Chemical Society of Japan卷 / 87期
关键词：
Hydrogen abstraction reactions from hydrofluorocarbons are important reaction steps in both atmospheric and combustion chemistry. In this study; kinetics of the H-abstraction reactions from methane; ethane; fluoromethanes; and fluoroethanes by H; O; and OH radicals are investigated using the CBS-QB3//ωB97X-D quantum chemical method and transition state theory; and the site-specific reactivity of the fluoroalkanes systematically examined. The calculated rate constants for these reactions are found to accurately reproduce available experimental data for a wide temperature range; with only minor differences between experimental and theoretical barrier heights. Analysis of site-specific reactivity indicates that fluorine substitution at the β-carbon site of the fluoroalkanes systematically increases the barrier heights of H-abstraction; and the substitution effect at the α-carbon site can be interpreted by electron-withdrawing and steric effects. Fluorine substitution also decreases the pre-exponential factor for the H-abstraction reactions by O and OH radicals due to steric and electrostatic interactions between these radicals and the F atoms. © 2014 The Chemical Society of Japan;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
相关论文
共 50 条
  • [41] Theoretical kinetics of hydrogen abstraction and hydroperoxyl addition reactions of 3-hexene by hydroperoxyl radicals
    Jin, Wu
    Tang, Chaowei
    Yang, Feiyu
    Zhang, YingJia
    Li, Jianzhong
    Huang, Zuohua
    FUEL, 2020, 277
  • [42] REACTIONS OF ETHYNYL RADICAL .1. HYDROGEN ABSTRACTION FROM ALKANES
    TARR, AM
    STRAUSZ, OP
    GUNNING, HE
    TRANSACTIONS OF THE FARADAY SOCIETY, 1965, 61 (513P): : 1946 - &
  • [43] Ab initio study of the kinetics of hydrogen abstraction reactions occurring in the pyrolysis of phenethyl phenyl ether
    Beste, Ariana
    Buchanan, A. C., III
    Hathorn, Bryan C.
    Harrison, Robert J.
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2007, 233
  • [44] Modeling the kinetics of hydrogen abstraction reactions in nitrogen-containing compounds via group additivity
    Pappijn, Cato A. R.
    van de Vijver, Ruben
    Sabbe, Maarten K.
    Reyniers, Marie-Francoise
    Marin, Guy B.
    Van Geem, Kevin M.
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2024, 26 (27) : 18763 - 18775
  • [45] Mechanism and Kinetics of Diuron Oxidation Initiated by Hydroxyl Radical: Hydrogen and Chlorine Atom Abstraction Reactions
    Manonmani, G.
    Sandhiya, L.
    Senthilkumar, K.
    JOURNAL OF PHYSICAL CHEMISTRY A, 2019, 123 (41): : 8954 - 8967
  • [46] Theoretical study of the hydrogen abstraction reactions from substituted phenolic species
    Wang, Quan-De
    Sun, Mao-Mao
    Liang, Jinhu
    COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2021, 1196
  • [47] Solvent effects on hydrogen abstraction reactions from lactones with antioxidant properties
    Aliaga, C
    Stuart, DR
    Aspée, A
    Scaiano, JC
    ORGANIC LETTERS, 2005, 7 (17) : 3665 - 3668
  • [48] REACTIONS OF TRIFLUOROMETHYL RADICALS .2. HYDROGEN ABSTRACTION FROM MONOCHLOROSILANE
    ARTHUR, NL
    HARMAN, BR
    AUSTRALIAN JOURNAL OF CHEMISTRY, 1973, 26 (06) : 1269 - 1275
  • [49] HYDROGEN-ABSTRACTION REACTIONS BY ETHYL RADICALS FROM METHYLAMINES AND HYDRAZINE
    EDWARDS, DA
    KERR, JA
    LLOYD, AC
    TROTMAND.AF
    JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1966, (11): : 1500 - &
  • [50] SOME REACTIONS OF FLUOROETHANES WITH SODIUM ETHOXIDE
    TARRANT, P
    YOUNG, JA
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1953, 75 (04) : 932 - 934
12345