Kinetics of hydrogen abstraction reactions from fluoromethanes and fluoroethanes

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[1] Matsugi, Akira
[2] Shiina, Hiroumi
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Matsugi, Akira | 1600年 / Chemical Society of Japan卷 / 87期
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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;
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