On the Rate Constant for NH₂+HO₂ and Third-Body Collision Efficiencies for NH₂+H(+M) and NH₂+NH₂(+M)

In low-temperature flash photolysis of NH₃/O₂/N₂ mixtures, the NH₂ consumption rate and the product distribution is controlled by the reactions NH₂ + HO₂ → products (R1), NH₂ + H (+M) → NH₃ (+M) (R2), and NH₂ + NH₂ (+M) → N₂H₄ (+M) (R3). In the present work, published flash photolysis experiments by, among others, Cheskis and co-workers, are re-interpreted using recent direct measurements of NH₂ + H (+N₂) and NH₂ + NH₂ (+N₂) from Altinay and Macdonald. To facilitate analysis of the FP data, relative third-body collision efficiencies compared to N₂ for R2 and R3 were calculated for O₂ and NH₃ as well as for other selected molecules. Results were in good agreement with the limited experimental data. Based on reported NH₂ decay rates in flash photolysis of NH₃/O₂/N₂, a rate constant for NH₂ + HO₂ → NH₃ + O₂ (R1a) of k_1a = 1.5(±0.5) × 10¹⁴ cm³ mol^-1 s^-1 at 295 K was derived. This value is higher than earlier determinations based on the FP results but in good agreement with recent theoretical work. Kinetic modeling of reported N₂O yields indicates that NH₂ + HO₂ → H₂NO + O (R1c) is competing with R1a, but perturbation experiments with addition of CH₄ indicate that it is not a dominating channel. Measured HNO profiles indicate that this component is formed directly by NH₂ + HO₂ → HNO + H₂O (R1b), but theoretical work indicates that R1b is only a minor channel. Based on this analysis, we estimate k_1c = 2.5 × 10¹³ cm³ mol^-1 s^-1 and k_1b = 2.5 × 10¹² cm³ mol^-1 s^-1 at 295 K, with significant uncertainty margins.