Shock-Tube Measurements of Atomic Nitrogen Collisional Excitation in 8000–12000 K Partially Ionized Nitrogen–Argon Mixtures

We report on shock-tube experiments measuring the collisional excitation of atomic nitrogen using tunable diode laser absorption spectroscopy (TDLAS). Conditions behind the reflected shocks ranged from 8000 to 12000 K and 0.1 to 1.1 atm in mixtures of 1 or 2% molecular nitrogen (N2) in argon (Ar). Absorption from the transition between atomic nitrogen quantum states 4P to 4D at 868 nm was used to monitor the formation of electronically excited nitrogen. Population measurements of the 4P state were made at a rate of 50 kHz. In connection with these measurements, a multitemperature kinetic mechanism is proposed for nitrogen excitation. Measurements suggest a multistage process. In early test times, a period of induction due to N2 dissociation is followed by a rise via heavy particle excitation. The dominant channel causing this excitation is believed to be N + N ↔ N(4P) + N with a measured forward rate constant of 3.65 × 10–18 exp(−119892/T) [m3/s]. As test time evolves, the excitation of 4P, referred to as N*, is subsequently interrupted and then resumes, as the kinetic environment becomes increasingly electron-dominated. The most impactful reactions of the mechanism are optimized to reduce the residual between simulations and the measurements. The measured N* populations indicate strong, though indirect, sensitivity to adjacent processes, including the excitation of metastable nitrogen, and ionization channels.