Voltammetry is a powerful method for interrogating electrochemical systems. A voltage is applied to an electrode and the resulting current response analysed to determine features of the system under investigation, such as concentrations, diffusion coefficients, rate constants and thermodynamic potentials. Here we will focus on ac voltammetry, where the voltage signal consists of a high frequency sine-wave superimposed on a linear ramp. Using multiple scales analysis, we find analytical solutions for the harmonics of the current response and show how they can be used to determine the system parameters. We also include the effects of capacitance due to the double-layer at the electrode surface and show that even in the presence of large capacitance, the harmonics of the current response can still be isolated using the FFT and the Hanning window.
