Mass Spectrometric Study of the Kinetics of Nitrogen Afterglow

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Abstract
Lewis‐Rayleigh afterglow in nitrogen has been examined by simultaneous observation with a mass spectrometer and a photomultiplier. Afterglow intensity was found to be proportional to the square of the ground‐state nitrogen atom concentration under a variety of conditions. The proportionality constant was essentially unaffected by small oxygen addition, but was somewhat increased with admixture of noble gases. Evidence is presented for a linear dependence of afterglow intensity on total pressure of nitrogen. Addition of nitric oxide to the afterglow results primarily in the production of nitrous oxide. From a rough calibration of the atomic concentration (ca 1%) and the afterglow radiation intensity, (1013 photons/cc‐sec) a termolecular rate constant of 2×10—33 cc2‐molecule—2‐sec—1 is obtained. The experimental data point to a termolecular reaction involving two 4S nitrogen atoms. The detailed mechanism probably involves the intermediate formation of the 5Σg+ molecular state, followed by a collision‐induced, radiationless transition into the 3πg state.

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