Adsorption of monovalent and divalent cations on planar water-silica interfaces studied by optical reflectivity and Monte Carlo simulations

Maria Porus (1) , Christophe Labbez (2) , Plinio Maroni (1) , Michal Borkovec (1)

1 Department of Inorganic, Analytical and Applied Chemistry
2 ICB - Laboratoire Interdisciplinaire Carnot de Bourgogne

Adsorption on planar silica substrates of various monovalent and divalent cations from aqueous solution is studied by optical reflectivity. The adsorbed amount is extracted by means of a thin slab model. The experimental data are compared with grand canonical Monte Carlo titration simulations at the primitive model level. The surface excess of charge due to adsorbed cations is found to increase with pH and salt concentration as a result of the progressive dissociation of silanol groups. The simulations predict, in agreement with experiments, that the surface excess of charge from divalent ions is much larger than from monovalent ions. Ion-ion correlations explain quantitatively the enhancement of surface ionization by multivalent cations. On the other hand, the combination of experimental and simulation results strongly suggests the existence of a second ionizable site in the acidic region. Variation of the distance of closest approach between the ions and surface sites captures ion specificity of water-silica interfaces in an approximate fashion.

Mots clés: adsorption; Monte Carlo methods; pH; silicon compounds; surface ionisation; water

Domaines: Chimie-Physique [physics.chem-ph]

Maria Porus, Christophe Labbez, Plinio Maroni, Michal Borkovec. Adsorption of monovalent and divalent cations on planar water-silica interfaces studied by optical reflectivity and Monte Carlo simulations. Journal of Chemical Physics, 2011, 135, pp.064701. ⟨10.1063/1.3622858⟩. ⟨hal-00650049⟩