Theoretical Analysis of Voltammetry at a Rotating Disk Electrode in the Absence of Supporting Electrolyte

The mathematical model of Oldham J. Phys. Chem. B 2000, 104, 4703 for rotating disc electrode in an unsupported system is discussed. This article presents a new analytical method for the calculation of concentration at a rotating disc electrode controlled by diffusion, convection, and migration. This model contains a steady-state nonlinear differential equation in a three-ion system under the assumption that all the ions have the same diffusivity. The homotopy perturbation method is employed to solve the nonlinear governing equation, where the ionic concentration and current are obtained analytically, in terms of charge numbers. The comparison between the analytical results of this study and previous studies confirms that the result of the proposed method is in stronger agreement with numerical simulations than other analytical methods.