Abstract
Ions in the negative glow and positive column of a dc glow discharge in nitrogen have been examined at a pressure of 0.4 mm and a current density of 0.03 mA/cm2. Mixtures of nitrogen with hydrogen (0.9%) and with oxygen (0.5% and 20%) were also used. In addition to N2+ and N+, the ions N3+ and N4+ are prominent in the negative glow in pure nitrogen. They appear to be formed by N++2N2→N3++N2, N2++2N2→N4++N2, both of which proceed to an extent dependent on field strength. With added hydrogen the ions N2H+ and NH4+ become important. N2H+ appears to be formed by at least two processes. The concentration of NH4+ is greatest in the tail of the negative glow where vibrational excitation is a possible factor and the residence time of ions is relatively long. In the presence of oxygen the ions NO2+ and N2O+ appear, as well as O2+, but the most prominent oxygen-containing ion is NO+. The mechanism of formation of these ions is not definitely assigned but charge-transfer reactions may be important, as well as ion-molecule reactions which depend to some extent upon vibrational excitation, or upon residence time in the discharge.
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