Entropic contributions to the stability of electrochemically adsorbed anion layers on Au(111): a microcalorimetric study

Abstract

We measure the entropy of formation of the interface upon anion adsorption (Cl⁻, Br⁻ I⁻ and SO₄²⁻) on Au(111) as an important indicator for the structure, order and composition of the interface. The entropy of formation of the interface exhibits a rather universal behaviour for all anions with a steep decrease upon initial adsorption followed by a shallow minimum at intermediate anion coverages and a strong increase close to the completion of the adsorbate adlayer. The strong variation of the entropy signals significant entropic contributions to the free enthalpy of the adsorption process and thus the stability of the adsorbed phase. At low anion coverages, close to the potential of zero charge, we attribute the entropy variations to the rearrangement of the interfacial water structure. At intermediate and high anion coverages, a comparison with the results of a lattice-gas model, considering pairwise repulsive interactions within the quasi-chemical approximation, shows that the entropy changes upon anion adsorption can be explained by the configurational entropy of the adsorbed phase. Thus, entropic contributions from both the solvent and the adsorbate are important for the stability of surface phases, particularly for disordered systems.