Mass-Spectrometric Study of the Reactions of Deuterium and Hydrogen Atoms with Nitric Oxide

Abstract

The details of the reactions of deuterium and hydrogen atoms with nitric oxide in D2—NO and H2–NO mixtures (less than 1% NO) have been studied by a mass-spectrometric method. Nitroxyl is produced as the primary product and rapidly attains a steady-state concentration. Further reaction of nitroxyl with nitroxyl produces nitrous oxide and water with a rate constant of 6.7±2.2×10−16 cm3 molecule−1·sec−1. The reaction of nitroxyl with hydrogen atoms produces small amounts of hydroxylamine, and proceeds, at the highest pressure employed (70 torr), with a rate about 1/70 of the rate of formation of nitrous oxide. From considerations of the effect of total pressure on the steady-state level of nitroxyl, the rate constant for the deuterium-atom abstraction of deuterium from DNO is estimated to lie between 10−13 and 10−12 cm3 molecule−1·sec−1. The vessel surfaces play no part in the reaction, other than to adsorb the products, water and hydroxylamine.