Mass-Transfer Measurements by the Limiting-Current Technique

Publisher Summary Limiting-current density refers to the maximum rate at 100% current efficiency, at which a particular electrode reaction can proceed in the steady state. This rate is determined by the composition and transport properties of the electrolytic solution and by the hydrodynamic condition at the electrode surface. It has been observed that in many cases mass transfer is not the sole cause of unsteady-state limiting currents, observed when a fast current ramp is imposed on an elongated electrode. Major conditions for valid measurement and interpretation of limiting currents include reaction characterized by slow surface kinetics, progress of the electrode position reaction, use of low concentrations of the reacting ionic species in free convection studies. This chapter outlines the underlying principles, discusses the conditions of validity, and highlights some selected applications and basic features of the limiting-current phenomenon. The chapter also illustrates a synopsis of electrochemical mass-transfer theory, to the extent required for analysis of limiting-current conditions. Various complicating factors—migration effects, the choice of appropriate diffusivity values, unsteady-state conditions, current distribution below and at the limiting current, and the effect of formation of rough metallic deposits—in the interpretation of limiting-current measurements are considered.

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