Hydrogen and deuterium atom abstraction from methanol and trideuteromethanol. Reaction of methoxy radicals with methane

Abstract

The reactions of trideuteromethyl radicals with methanol and trideuteromethanol have been studied in order to determine the position and rate of hydrogen and deuterium atom abstraction. Over the temperature range studied (130–250°C) the rate of abstraction from the methyl and hydroxyl groups is similar. Substitution of deuterium for hydrogen alters the positional reactivity by an amount in agreement with zero-point energy difference.

Rate constants at 182°C and Arrhenius parameters (based on a value of 10^13.34mole^–1cm³sec^–1 for the recombination rate constant of methyl radicals) have been measured for the reactions:[graphic omitted] and have been calculated for [graphic omitted]Units k and A mole^–1 cm³ sec^–1, E kcal mole^–1.