Abstract
The bimolecular reaction rate constant of ion—molecule gas phase reactions is calculated using the assumption that ions and molecules have Maxwell-Boltzmann velocity distributions including different effective temperatures T I and T M of ions and molecules, respectively (two-temperature model). Three cases may be distinguished depending on the mass ratio of the reactants: m I/ m M = 1; <1; >1. Some ion-polar molecule reactions are discussed to demonstrate the effects of several mass and temperature ratios. Taking into account molecular hard core effects the two-temperature rate coefficient differs from that of a one-temperature model even if ion—permanent dipole interactions are neglected. The two-temperature model of ion—molecule reactions in an electric field is investigated. Our “effective” two-temperature parameter Θ is in accordance with Rebentrost's “effective” temperature, T 1, in the case where the thermal ion energy is equal to the energy gained by an ion in the electric field between successive collisions.
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