Kinetics of three reactions involving the azide radical: H + HN3, thermal decomposition of N3, and N3 + HN3

Abstract

Reactions were studied computationally using quantum chemistry, transition state theory, master equation / RRKM, and literature data on potential energy surfaces: H + HN3 → Products (1), N3 → N + N2 (2), and N3 + HN3 → N2H + 2 N2 (3). The previously neglected abstraction channel in reaction 1 is important, resulting in greater production of N3 in flames of hydrogen azide decomposition. Thermal decomposition is an important channel of N3 destruction, whereas reaction 3 is negligible. This likely results in greater importance of the chemistry of singlet 1NH biradical produced the reaction of N3 with the H atoms.