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A theoretical model for transient and steady‐state cataphoresis is developed starting with the macroscopic equations of continuity. After a brief breakdown period, the impurity ions are assumed to be closely coupled with their neutral counterparts. The basic assumptions in the model are that after breakdown, the level of ionization of the impurity, and the axial electric field remain constant; it is demonstrated that under these conditions a system involving rapid ionization‐recombination reactions is equivalent to a system in which no reaction occurs, but in which the ``effective'' ion mobility is a product of the true ion mobility and the fraction of impurity ionization. The influence of endbulbs commonly employed in experiments is analyzed and found to influence greatly the characteristic time required to reach steady state. Agreement is found between the model and available experimental data. Particular emphasis is placed upon mass spectrometer data reported by Matveeva, and by Beckey, Groth, and Welge; these data are for mixtures of rare gases and for mixtures of hydrogen and deuterium, and involve endbulbs. The ordinary diffusion case, associated with the collapse of the steady‐state cataphoretic profile, is also analyzed for a system containing endbulbs.

A Theoretical Model for Gas Separation in a Glow Discharge: Cataphoresis