Determination of the Rate Constants for the NH 2 (X 2 B 1 ) + NH 2 (X 2 B 1 ) and NH 2 (X 2 B 1 ) + H Recombination Reactions in N 2 as a Function of Temperature and Pressure
The recombination rate constants for the reactions NH2 + NH2 → N2H4 (reaction k1b) and NH2 + H → NH3 (reaction k2b) with N2 as a third-body have been measured as a function of temperature and pressure. The temperature range was from 292 to 533 K and the pressure range from a few Torr up to 300–400 Torr, well within the pressure falloff region. The NH2 radical was produced by 193 nm pulsed-laser photolysis of NH3 in a temperature controlled flow chamber. High-resolution time-resolved laser absorption spectroscopy was used to follow the temporal concentration profiles of both NH2 and NH3, simultaneously. The NH2 radical was monitored at 14800.65 cm–1 using the 1231 (0,7,0)Ã2A1 ← 1331 (0,0,0)$\tilde{X}$2B1 ro-vibronic transition, and NH3 monitored at 3336.39 cm–1 on the qQ3(3)s (1,0,0,0) ← (0,0,0,0) ro-vibrational transition. The necessary collisional broadening parameters for each molecule were measured in separate experiments. The pressure and temperature dependence of k1b can be represented by the Troe parameters: k0, the low-pressure three-body recombination rate constant, k0(T) = (1.14 ± 0.59) × 10–19T–(3.41±0.28) cm6 molecule–2 s–1, and Fcent, the pressure broadening parameter, Fcent = 0.15 ± 0.12, independent of temperature. The data could not be fit by three-independent parameters, and the high-pressure limiting rate constant k∞(T) = 9.33 × 10–10T–0.414 e33/T cm3 molecule–1 s–1 was taken from the high-quality theoretical calculations of Klippenstein et al. (J. Phys. Chem A 2009, 113, 10241). The pressure and temperature dependence of k2b, can be represented by the Troe parameters: k0(T) = (9.95 ± 0.58) × 10–26T(-1.76±0.092) cm6 molecule–2 s–1, Fcent = 0.5 ± 0.2, k∞ = 2.6 × 10–10 cm3 molecule–1 s–1. Again, the data could not be fit with three independent parameters, and k2b∞ was chosen to be 2.6 × 10–10 cm3 molecule–1 s–1 and fixed in the analysis.