Voltammetry and electrodeposition in the presence of attractive interactions: I. a mean-field approach

We present the voltammograms for electrodeposition when strong attractive interactions exist between the adsorbed atoms. Within the mean-field approximation we provide the characteristics (current density, electrode potential and electrode coverage) of the peak that appears in these voltammograms as a function of the parameters of the kinetic model. For the whole range of the electrode potential sweep rates, we compare the expressions obtained from a Frumkin equilibrium isotherm to the classical results provided by a Langmuir isotherm, i.e., disregarding the interactions. For temperatures greater than the phase separation critical temperature Tc and low sweep rates, accounting for the interactions leads to a large increase of the current density at the peak when T → Tc. For T < Tc these interactions make this dimensionless current density diverge as 1/vb when the sweep rate vb tends to 0.