Electrochemical physico-chemical models, describing isothermically surface coverage dependency with electrode potential of underpotentially deposited Cu adlayers (Cu-UPD) as well as successive surface-limited redox replacement (SLRR) reactions between Cu-UPD and PtCl62-, to form multilayered Pt deposits on crystalline Au, have been explored. Modelling of such phase formation phenomena take into account heterogeneity effects and extent of adatom interactions within the adlayers on the base Au substrate and gradually formed Pt multilayered deposits. Insights on exchanged electrons, phenomenological reaction kinetics and Gibbs free energy variations during various deposition stages involving SLRR reactions are divulged. (C) 2014 Elsevier Ltd. All rights reserved.