Theory of square wave voltammetry of amalgam forming ions at spherical electrodes

•Square wave voltammetry on microelectrodes.•Spherical diffusion within mercury drop.•Dependence of net peak current on frequency and electrode radius.

A theoretical model of reversible reduction of amalgam forming ion on stationary mercury drop electrode is developed for square wave voltammetry. The dependence of dimensionless net peak current on the dimensionless inverse electrode radius is investigated. This relationship is not linear, but it is a curve with two asymptotes. These results apply to electroanalytical measurements at spherical microelectrodes.