Rovibrational internal energy transfer and dissociation of N2(1Σg+)-N(4S(u)) system in hypersonic flows

A rovibrational collisional model is developed to study energy transfer and dissociation of N(2)((1)Σ(g)(+)) molecules interacting with N((4)S(u)) atoms in an ideal isochoric and isothermal chemical reactor. The system examined is a mixture of molecular nitrogen and a small amount of atomic nitrogen. This mixture, initially at room temperature, is heated by several thousands of degrees Kelvin, driving the system toward a strong non-equilibrium condition. The evolution of the population densities of each individual rovibrational level is explicitly determined via the numerical solution of the master equation for temperatures ranging from 5000 to 50,000 K. The reaction rate coefficients are taken from an ab initio database developed at NASA Ames Research Center. The macroscopic relaxation times, energy transfer rates, and dissociation rate coefficients are extracted from the solution of the master equation. The computed rotational-translational (RT) and vibrational-translational (VT) relaxation times are different at low heat bath temperatures (e.g., RT is about two orders of magnitude faster than VT at T = 5000 K), but they converge to a common limiting value at high temperature. This is contrary to the conventional interpretation of thermal relaxation in which translational and rotational relaxation timescales are assumed comparable with vibrational relaxation being considerable slower. Thus, this assumption is questionable under high temperature non-equilibrium conditions. The exchange reaction plays a very significant role in determining the dynamics of the population densities. The macroscopic energy transfer and dissociation rates are found to be slower when exchange processes are neglected. A macroscopic dissociation rate coefficient based on the quasi-stationary distribution, exhibits excellent agreement with experimental data of Appleton et al. [J. Chem. Phys. 48, 599-608 (1968)]. However, at higher temperatures, only about 50% of dissociation is found to take place under quasi-stationary state conditions. This suggest the necessity of explicitly including some rovibrational levels, when solving a global kinetic rate equation.