Kinetics and Mechanism of the Reaction of NFCl2 with Hydrogen Atoms

Article abstract of DOI:10.1021/j100173a039

The reaction of gaseous NFCl2 with excess H atoms has been observed in a continuous flow reactor.The reaction produces excited singlet states (a¹Δ, b¹Σ⁺) of NF and NCl and is thougth to proceed by a two-step mechanism in which H atoms react with NFCl2 to produce primarily HCl and NFCl, followed by the H + NFCl reaction which proceeds to both HCl + NF and HF + NCl.The rate constant of the first step, H + NFCl2, is (2.6 +/- 0.2) * 10^-12 cm³ s^-1 at 298 K.The rate constant of the second step, H + NFCl, was too great to be accurately measured with our apparatus.Overall, the two-step process shows a roughly 10-fold preference for the production of NF(a¹Δ) over NCl(a¹Δ).The generation of both NF(a¹Δ) and NCl(a¹Δ) in this system results in energy pooling among these species which produces NF(b¹Σ⁺).This process is significantly enhanced by the admission of HI to the reaction medium.