Kinetics of the Mercury-Photosensitized Decomposition of Propane. Part II. Reactions of the Propyl Radicals

Abstract

The results of the previous paper are analyzed to yield information about the reactions of the n-propyl and i-propyl radicals. The various combination and disproportionation reactions are considered. The rate of decomposition of the n-propyl radical was determined as a function of temperature and pressure, and limiting high-pressure and low-pressure kinetic parameters were obtained. The high-pressure activation energy is 32.6 kcal mol⁻¹, and this leads to a value of 24.3 kcal mol⁻¹ for the dissociation energy of the C—C bond in the n-propyl radical, to 22.2 kcal mol⁻¹ for its heat of formation, and to 99.1 kcal mol⁻¹ for the primary C—H dissociation energy in propane. Entropy changes are also calculated from the results.For the decomposition of the i-propyl E_∞ = 38.7 kcal mol⁻¹, and this leads to 37.7 kcal mol⁻¹ for the C—H bond dissocation energy in this radical and to 19.3 kcal mol⁻¹ for its heat of formation. The secondary C—H dissociation energy in propane is calculated to be 96.2 kcal mol⁻¹. Corresponding entropy changes are calculated.