Kinetic studies for diatomic free radicals using mass spectrometry. Part 3.—Elementary reactions involving BrO X2Π radicals

Abstract

Elementary reactions involving BrO X²Π radicals have been studied at 298 K in a discharge-flow system linked to a mass spectrometer with collision-free sampling. Detection of BrO was made directly by means of the BrO⁺ ion current, calibrated in terms of absolute BrO concentrations using the rapid reaction (1), NO + BrO [graphic omitted] NO₂+Br.(1) Rate constants at 298 K (cm³ molecule^–1 s^–1) are reported for the second order decay reaction (2), BrO + BrO [graphic omitted] 2 Br + O₂(2) as well as for reaction (1): k₁=(2.2 ± 0.4)× 10^–11; k₂=(6.4 ± 1.3)× 10^–12 cm³ molecule s^–1. In addition, the rate constant k₃ for reaction of Br ²P_3/2 atoms with O₃(3), has been determined at 298 K: Br + O₃ [graghic omitted] BrO + O₂(3), k₃=(1.2 ± 0.2)× 10^–12 cm³ molecule^–1 s^–1.