Kinetics and Products of the Reactions of Fluorine Atoms with ClNO and Br2 from 295 to 950 K.

The kinetics and products of the reactions of F atoms with Br2 and ClNO have been studied in a flow reactor coupled with an electron impact ionization mass spectrometer at nearly 2 Torr total pressure of helium and over a wide temperature range, T = 295-950 K. The rate constant of the reaction F + ClNO → products (1) was determined under pseudo-first order conditions, monitoring the kinetics of F atom consumption in excess of ClNO. The measured temperature independent rate constant, k1 = (1.29 ± 0.13) × 10-10 cm3 molecule-1 s-1 (T = 299-950 K), was found to be in excellent agreement with the only previous low temperature study which allowed to recommend the value of k1 in an extended temperature range, 228-950 K. FCl and Cl atoms were observed as the reactions products (corresponding to two reaction pathways: Cl-atom abstraction and replacement with fluorine atom, respectively) with the independent of temperature, in the range 295-948 K, yields of 0.68 ± 0.10 and 0.32 ± 0.05, respectively. Rate constant of the reaction F + Br2 (2), k2 = (1.28 ± 0.20) × 10-10 cm3 molecule-1 s-1, determined using both absolute and relative rate methods, was found to be independent of temperature at T = 299-940 K.