Kinetics of the Reactions of OH with C2H6, CH3CCl3, CH2ClCHCl2, CH2ClCClF2, and CH2FCF3

Article abstract of DOI:10.1021/j150650a041

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, A_th³⁰⁰ is calculated by thermochemical transition-state theory and compared with A_exp³⁰⁰, 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 A_exp³⁰⁰ on n, the temperature exponent, is calculated.Consequently, it is suggested that fitting routines be guided by theoretical considerations.