INFRARED CHEMILUMINESCENCE STUDIES OF THE H+NFCL(2) AND H+NFCL REACTIONS

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(v=0-4) + NFCl with a total rate constant of (1.9 +/- 0.4) x 10(-11) cm(3) molecule(-1) s(-1) and an inverted vibrational distribution of P-0-P-4 = 9:20:32:27:12. The rate constant for HF formation from H + NFCl was estimated as (0.9 +/- 0.4) X 10(-11) cm(3) molecule(-1) s(-1), and the HF vibrational distribution, P-0-P-3 = 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) cm(3) 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.