Kinetic Analysis of the Ion–Molecule Reactions in Nitrogen–Hydrogen Mixtures Using Ion Cyclotron Resonance

The thermal energy rate constants for the reactions N2++D2→ lim k1N2D++D, N2++H2→ lim k3N2H++H, N2++HD→ lim k4aN2H++D, → lim k4bN2D++H, have been measured using ion cyclotron resonance (icr) giving k1 = 1.15, k3 = 1.41, k4a = 0.65, and k4b = 0.69 × 10−9cm3molecule−1·sec−1. These results agree very well with the values calculated from the change-induced dipole model of Gioumousis and Stevenson. The absence of a significant isotope effect in k4a and k4b indicates these reactions proceed via a stripping mechanism as indicated by Wolfgang and co-workers and Mahan and co-workers. Energy dependence studies of k2 and the corresponding charge exchange rate constant k5 D2++N2→ lim k2N2D++D D2++N2→ lim k5D2+N2+ indicate that the decrease in k2 with increasing reactant ion energy is approximately offset by the increase in k5 as predicted by the phase-space theory of Light.