The electrodeposition of bismuth on a gold electrode consists of an underpotential deposition (UPD) and an overpotential deposition (OPD) of bulk bismuth which follows nucleation on the UPD. Mathematical modelling and numerical simulations have been compared with experimental data to propose a mechanism for the deposition and stripping of bulk bismuth on a Au(111) electrode from a 1 mM Bi3+/0.1 M HClO4 solution. This mechanism has first order kinetics with respect to the concentration of Bi3+ and a chemical rate determining step that likely involves the change in solvation. of a Bi+ intermediate. (c) 2008 Elsevier B.V. All rights reserved.