Thermal decomposition of the ethyl radical

Abstract

The kinetics of the thermal decomposition of the ethyl radical to give an ethylene molecule and a hydrogen atom were studied over the pressure range 4 to 650 mm Hg and the temperature range 400 to 500 °C; the mercury-photosensitized decomposition of ethane was used to generate the ethyl radical. The unimolecular decomposition of the ethyl radical was found to be pressure dependent over the entire range of pressures studied, with the order of reaction varying from 1.6 for the lowest pressures to 1.4 at the highest pressures. The extrapolated high-pressure and low-pressure rate constants for the decomposition of the ethyl radical are given by [Formula: see text] [Formula: see text]A best fit of the Kassel equation to the observed pressure dependence shows that s = 8 for this reaction. The results lead to a value of 98 1 kcal/mole for the bond dissociation energy D(C2H5—H). The heat of formation of the ethyl radical was calculated to be 30.0 and 26.2 kcal/mole for 0 °K and 25 °C respectively.