Kinetics and chemiluminescence in the reaction of N atoms with O2 and O3

Abstract

Room-temperature rate constants for the reactions N + O₂→ NO + O (1), N + O₃→ NO + O₂(2), have been measured using the discharge flow chemiluminescence technique. Values obtained are, k₁=(8.8 ± 0.4)× 10^–17 cm³ molecule^–1 s^–1, k₂=(1.0 ± 0.2)× 10^–16 cm³ molecule^–1 s^–1. Visible and near-i.r. emissions were observed on adding O₂ or O₃ to a flow of N atoms, but neither reaction (1) nor reaction (2) appears to be the source of the chemiluminescence. Further experiments were conducted to elucidate the excitation mechanisms. Chemiluminescence from electronically excited NO and O₂ was observed and mechanisms for the formation of these species are proposed.