Journal of Electroanalytical Chemistry, Vol.500, No.1-2, 418-434, 2001
Adsorption of bromide at the Ag(100) electrode surface
The adsorption and phase formation of bromide on Ag(100) has been studied by chronocoulometry and surface X-ray scattering (SXS). With increasing electrode potential, bromide undergoes a phase transition from a lattice gas to an ordered c(2 x 2) structure (theta = 0.5). The degree of lateral disorder was estimated by comparing the SXS- and the electrochemical measurements. Based on chronocoulometric experiments, a thermodynamic analysis of charge density data was performed to describe the bromide adsorption at the Ag(100) electrode. The Gibbs surfaces excess, electrosorption valencies, Esin-Markov coefficients, and the Gibbs energy of adsorption, lateral interaction energies as well as surface dipole moments have been estimated. The experimental theta versus E- isotherms are modeled employing (i) a quasi-chemical approximation as well as (ii) the results of a recent Monte Carlo simulation. An attempt is made to discuss the structure data and thermodynamic quantities of bromide adsorption on Ag(100) on the basis of the Grahame-Parsons model of the Helmholtz layer.