Reactions of Gaseous Molecule Ions with Gaseous Molecules. V. Theory

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Abstract
Ion‐molecule reactions of the sort observed as secondary reactions in mass spectrometers have been treated by the methods of the modern kinetic theory; that is, the rate of reaction is expressed in terms of the velocity distribution functions of the reactants and the cross section for the reaction. The cross section, which is calculated by means of the properties of the classical collision orbits, is found to have an inverse square root dependence on energy. The ion distribution function, which is far from Maxwellian, is found by means of an explicit solution of the Boltzmann equation. A simple relation is given which relates the mass spectrometric data to the specific rate of the same reaction under thermal conditions. For the simpler molecules, this rate may be calculated completely a priori, with excellent agreement with experiment.