Impedance aspects of anion adsorption on gold single crystal electrodes

Abstract

In order to explore the origins of the capacitance dispersion observed for single crystal electrodes, voltammetric and impedance measurements on Au(l 11) and Au(100), in the absence and the presence of specifically adsorbed anions, mostly Br −, have been carried out. Interfacial capacitances and rate coefficients characterizing the kinetics of adsorption have been evaluated from the impedance spectra. We present evidence that the double layer behaves as an ideal capacitance in the absence of specific adsorption. The approximation with a constant phase element yields an exponent larger than 0.99. The “capacitance dispersion” observed in the presence of specific adsorption is either assigned to a slow diffusion or adsorption process, or to transformations within the adlayer or the substrate surface.