Kinetics of Hydrogen Abstraction Reactions from Fluoromethanes and Fluoroethanes

• Akira Matsugi

• Hiroumi Shiina

抄録

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.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 87 (8), 890-901, 2014-08

  Tokyo : Chemical Society of Japan

キーワード

• General Chemistry

詳細情報

• CRID: 1520854805442326656
• NII論文ID: 130004059135
• NII書誌ID: AA00580132
• ISSN: 00092673
• ISSN: 13480634
• DOI: 10.1246/bcsj.20140101
• NDL書誌ID: 025633314
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I025633314
• Web Site: https://academic.oup.com/bcsj/article-pdf/87/8/890/56277127/bcsj.20140101.pdf
• 本文言語コード: en
• NDL 雑誌分類:
  • ZP1(科学技術--化学・化学工業)
• データソース種別:
  • NDL
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