Estimation of excitation energy of diatomic molecules in expanding nonequilibrium flows

The energy contained in the highly excited vibrational and rotational states in a diatomic gas in a thermochemical nonequilibrium state during expansion is estimated. The estimation is made on the assumption that the populations of the vibrational and rotational states, when normalized by their respective equilibrium values, are describable by simple functions containing no more than four arbitrary parameters. A cubic polynomial, a logarithmic-cubic polynomial, and a bimodal step function are used for this purpose. The four parameters are determined by imposing conditions known at the ground state and the dissociation limit and the mass conservation law. The energy in excess of that accounted for by assuming a Boltzmann distribution of these states, defined here as excess excitation energy, is calculated for N2, O2, NO, CO, OH, and H2. A calculation made for a typical nozzle flow shows that the excess energy may reach 6 percent of the total enthalpy of the flow, and that the flow velocity may decrease by as much as 4 percent due to the nonequilibrium excitation phenomenon.