The rate of nucleation and number density of nuclei of tin and tin-silver deposits on copper and nickel substrates in acid sulfate and acid methanesulfonate baths were measured by application of a nucleation model to chronoamperometric data. Based on the dependence of nucleation rate on overpotential, the critical Gibbs free energy of nucleation and the critical nucleation size were calculated. A mechanism of alloy nucleation in the presence of thiourea is proposed. (c) 2007 The Electrochemical Society.