Hydronium and hydroxide at the interface between water and hydrophobic media

Abstract

The behavior of hydronium and hydroxide ions at the water/alkane, water/vapor, and water/rigid wall interfaces was investigated by means of molecular dynamics simulations. All these interfaces exhibit a strong affinity for hydronium, which is in agreement with spectroscopic and low pH zeta-potential measurements. Except for the water/rigid wall interface, which strongly structures water and weakly attracts OH⁻, none of the other investigated interfaces shows an appreciable accumulation of hydroxide. This computational result is at odds with the interpretation of higher pH zeta-potential and titration experiments, however, it is supported by surface selective spectroscopies of the surface of water and hydroxide solutions.