Mass Spectrometric Studies of Atom Reactions. II. Vibrationally Excited N2 formed by the Reaction of N Atoms with NO

Abstract

A mass spectrometric method was used to show that 75±5% of the nitrogen formed by the reaction $$\mathrm{N}+\mathrm{NO}\to {\mathrm{N}}_2^{*}+\mathrm{O}$$ has more than the 24 kcal/mole of excess energy required to decompose ozone. The rate constant for the reaction $${\mathrm{N}}_2^{*}+{\mathrm{O}}_3\to {\mathrm{O}}_2+\mathrm{O}+{\mathrm{N}}_2$$ was found to be (5.4±1.1)×10^—13 cm³ molecule^—1 sec^—1. The rate of collisional deactivation of N₂^* to vibrational levels below the fourth was found to be 3.5×10^—16 cm³ molecule^—1 sec^—1 with unexcited N₂ and 1.3×10^—15 cm³ molecule^—1 sec^—1 with N₂O as the collision partners. If loss of vibrational energy occurs mainly by single quantum jumps, the measured deactivation rate constant is less than that for a single quantum jump by the ratio of the number of molecules in the fourth level to those in all levels above the third.