Reactions of N(4<i>S</i>) atoms with NO and H2

Abstract

Reactions of N(4S) atoms with NO and H2 have been investigated using direct detection of N atoms by the atomic resonance absorption technique in a shock tube apparatus, where N(4S) is generated by photodecomposition of NO by 193 nm laser radiation behind reflected shock waves. The rate constant of the reaction, N+NO→N2+O (1) has been determined using pseudo first-order kinetic analysis to be k1=(1.3±0.3)×1013 (cm3 mol−1 s−1) over 1600–2300 K temperature range, which agrees very well with the estimation by Baulch et al. [Evaluated Kinetic Data for High Temperature Reactions (Butterworths, London, 1973), Vol. 2]. No (or very small) activation energy of this process was confirmed. Also, the rate constant of the reaction, N+H2→NH+H (2) has been decided by adding H2 to NO–Ar mixtures; it is k2=(2.8±0.2)×1014 exp(−Ea/RT) (cm3 mol−1 s−1), where Ea =33±7 kcal/mol. A quantum mechanical calculation performed in order to determine the mechanism of this reaction suggests that the reaction N(4S)+H2→NH+H proceeds via a direct abstraction of H atom from H2, and it gives calculated activation energy which is in good agreement with the present experiment.