Reactions of Nitrogen Atoms. II. H2, CO, NH3, NO, and NO2

Abstract

The reactions of H₂, CO, and NH₃ with nitrogen atoms are too slow for detection either at room temperature or in the neighborhood of 250° in a low pressure ``stirred'' reactor flow system with a mass spectrometer as the analytical device, the rate constants being less than 10⁸ cc/mole, sec. The addition of these gases to active nitrogen causes no qualitative changes in the spectrum of the afterglow. In presence of ammonia the intensity of the afterglow is reduced, the inverse of the intensity being linear in the pressure of ammonia. These observations, coupled with the data in the literature, are interpreted as evidence that a transfer of electronic energy takes place between the excited nitrogen molecules, the emitters of the afterglow and ammonia molecules. Excitation of ammonia is followed by its dissociation. A modified flow apparatus, more suitable for the study of fast reactions, was used to reinvestigate the reactions of nitrogen atoms with NO and NO₂. Only the lower limit of the rate constant of the reaction N+NO=N₂+O, 5×10¹³ cc/mole, sec, could be estimated. The rate of the reaction with NO₂ was also too fast to measure, but the lower limit of the rate constant is less certain.