Computed Activation Energies for Reactions of O2, N2, No, N2o, NO2, CO, and CO2

摘要

A method is described for calculating the activation energies of bimolecular reactions of such multivalent gaseous compounds as O2, N2, NO, N2O, NO2, CO, and CO2. It is also applicable to the monatomic reactants O, N, and H and to the OH radical. The method uses relationships between dissociation energy, bond length, vibrational wavenumber, and bond order. It avoids the use of adjustable parameters. The agreement between calculated and experimental activation energies is very good when spin conservation in the transition state is considered in the computation procedure. A convenient rule has also been formulated that predicts the activation energy will be negligible in bimolecular reactions between radicals when the transition-state formula corresponds to that of a compound having stable bonds. No exceptions to this rule have been found. The method is applicable to computing rates needed for nonequilibrium calculations of propellant performance and of reentry behavior. (Author)