Reactions of radicals containing fluorine. Part 1.—Hydrogen and deuterium atom abstraction from trideuteromethanol by trifluoromethyl radicals

Abstract

The reactions of trifluoromethyl radicals with methanol and trideuteromethanol have been studied in the temperature range 84–162°C in order to determine the rate at which hydrogen and deuterium atom abstraction occurs. Over this temperature range, abstraction from the hydroxyl group is slightly favoured over abstraction from the methyl group. Substitution of deuterium for hydrogen alters the positional reactivity by an amount in accord with the zero-point energy difference.

Arrhenius parameters (based upon a value of 10^13.34 mole^–1 cm³ sec^–1 of the rate constant of combination of trifluoromethyl radicals) have been measured for the reactions : [graphics omitted] and have been calculated for [graphic omitted]

(units of A mole^–1 cm³ sec^–1 and E kcal mole^–1).