Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
In this study, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X• + HCR3 → XH + •CR3; X = Cl•, HO•, and Br); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3•. In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3•) = 0.0251(ΔrH) + 0.96(ΣF) 0.56(ΣR) – 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3, may depend on the nature of the substituents.
- Research Organization:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- Grant/Contract Number:
- AC05-00OR22725
- OSTI ID:
- 1263858
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 26; ISSN 1089-5639
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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