Vacuum-Ultraviolet Photochemistry. VIII. Photolysis of Hydrazine–15N in the Presence of 14NO at 1470 Å

Abstract

The relative contributions of direct molecular elimination and radical disproportionation reactions to the formation of nonrandomized nitrogen in the photolysis of hydrazine and hydrazine–¹⁵N have been determined by examining the production of ³⁰N₂ in the photolysis of hydrazine–¹⁵N at 1470 Å in the presence of ¹⁴NO. The limiting value of the ratio H₂/³⁰N₂ in close to two and suggests that the mechanism of the molecular elimination processes is best represented by the sequence N₂H₄→N₂H₂ + H₂, N₂H₂→N₂ + H₂. The ratio of disproportionation to combination of radicals in the system (N₂H₃ and NH₂) is approximately five. The formation of ²⁹N₂ is attributed to the reaction of ¹⁵NH₂ with ¹⁴NO while the formation of ²⁸N₂ is discussed in terms of the reaction of atomic hydrogen with ¹⁴NO.