Analysis of the square wave voltammetry for reversible metal deposition on a foreign substrate – Experimental study of silver deposition on gold

The behaviour of square wave voltammetry for a reversible metal deposition was investigated through a model involving underpotential adsorption of metal ions. A quantitative description of the response was performed using three dimensionless key quantities. It was found that the IR-drop can play an important role even in very conductive media. The half-width at half-height of the peak in the overpotential range was approximated by a simple expression leading to the determination of the number of electrons exchanged. On this point, a critical assessment of the method based on an analogy with the case of soluble redox species was presented. A very good correlation was obtained between model predictions and experimental data for the silver deposition on a polycrystalline gold disc electrode from HNO3 and NaNO3 solutions.