Theory of microelectrode voltammetry with little electrolyte

Abstract

General theoretical relationships are derived that apply to steady-state voltammetry at hemispherical microelectrodes for any electrode reaction and any solution composition. These relationships are then applied to two typical systems: the oxidation of ferrocene and the reduction of a quinone. The effect of electrolyte concentration on these two systems is examined in detail. This study demonstrates why, in certain circumstances, small amounts of electrolyte behave as “excess supporting electrolyte.”