Journal of Physical Chemistry p. 1222 - 1226 (1984)
Update date:2022-08-28
Topics:
Jeong, Kyu-Man
Hsu, Kuang-Jung
Jeffries, J. B.
Kaufman, Frederick
The rate constants of the five H-abstraction reactions are measured from about 250 to 470 K by using the discharge-flow technique.Arrhenius parameters, three-parameter fits, and modified A and E values centered at 300 K are obtained.As in earlier papers on substituted methanes, Ath300 is calculated by thermochemical transition-state theory and compared with Aexp300, giving good agreement, on average, for a C-H-O bond angle of 150 deg.Three-parameter fits are reexamined for the ten methane reactions, their usefulness is discussed, and the dependence of Aexp300 on n, the temperature exponent, is calculated.Consequently, it is suggested that fitting routines be guided by theoretical considerations.
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