Infrared Chemiluminescence Studies of the H + NFCl2 and H + NFCl Reactions

Article abstract of DOI:10.1021/j100053a024

The primary and secondary reactions in the H + NFCl2 system have been studied by infrared chemiluminescence in a fast flow reactor at 300 K.The primary reaction is exclusively Cl atom abstraction to give HCl(ν=0-4) + NFCl with a total rate constant of (1.9 +/- 0.4) X 10^-11 cm³ molecule^-1 s^-1 and an inverted vibrational distribution of Ρ_o-Ρ₄ = 9:20:32:27:12.The rate constant for HF formation from H + NFCl was estimated as (0.9 +/- 0.4) X 10^-11 cm³ molecule^-1 s^-1, and the HF vibrational distribution, Ρ_o-Ρ₃ = 42:34:18:6, is characteristic of unimolecular HF elimination reactions.These data for the HF + NCl(a) product channel from the H + NFCl reaction are compared to earlier studies, which provided information about the HCl + NF(a) product channel.The latter seems to be the more important, and the total rate constant for H + NFCl is about 4 X 10^-11 cm³ molecule^-1 s^-1 at 300 K.The dynamics of the H + NFCl reaction are discussed and compared to the H + NF2 reaction.A small number of experiments also were done with the H + NF2Cl reaction system.