Interactions between Small Inorganic Ions and Uncharged Monolayers on the Water/Air Interface.

The interaction of several simple electrolytes with uncharged insoluble monolayers is studied on the basis of tensiometric and potentiometric data for the surface electrolyte solution|air. The induced adsorption of electrolyte on the monolayer is determined via a combination of data for equilibrium spreading pressure and surface pressure versus area isotherms. We show that the monolayer-induced adsorption of electrolyte is not only strongly ion-specific but also surfactant-specific. The comparison between the ion-specific effects on a carboxylic acid monolayer at low pH and an ester monolayer shows that the anion series follows the same order while the cation series reverses. The effect of the electrolyte on the chemical potential of the monolayer shows attraction between the surfactant and the ions at low monolayer densities, but at high surface densities, repulsion seems to come into play. In nearly all investigated cases, a maximum of monolayer-induced electrolyte adsorption is observed at intermediate monolayer densities. This suggests specific interactions between the surfactant headgroup and the ions. The Volta potential data for the monolayers are analyzed on the basis of the equations of quadrupolar electrostatics. The analysis suggests that the ion-specific effect on the Volta potential is due to the ion-specific decrement of the bulk dielectric constant of the electrolyte solution. Moreover, we present evidence that in most cases the effect of the electrolyte on the orientation of the adsorbed dipoles cannot be neglected. Instead, the change in the ion distribution in the electric double layer seems to have a small effect on the Volta potential.