Reactions of O 3PJ atoms with halogens: The rate constants for the elementary reactions O + BrCl,O + Br2, and O + Cl2

Direct determinations of the rate constants (cm³/molec · sec) k₁, k₂, and k₃ from 298 to 299°K are reported, using atomic resonance fluorescence in discharge flow systems:

1 One standard deviation.

The rate constant k₁, which has not been determined previously, was found to possess an insignificant temperature coefficient (E_A = (0 ± 700) J/mole) in the range of 299 to 619°K. The present result for k₂ agrees well with reinterpreted values from the one previous determination. Measurements of O atom consumption rates and Br atom production rates in the O + Br₂ reaction are interpreted to give an estimate of the rate constant k₄, which has not been reported previously, at 298°K: k₃ has been measured at three temperatures between 299 and 602°K. The present and previous results for k₃ were combined to give the following rate expression: