Surface and interfacial tensions of Hofmeister electrolytes

TL;DR

This paper introduces a quantitative theory explaining how electrolyte ions affect surface and interfacial tensions, considering ion classes, hydration, polarizability, and dispersion interactions, aligning well with experimental data.

Contribution

The theory uniquely accounts for ion-specific effects on surface and interfacial tensions, incorporating hydration, polarizability, and dispersion interactions for accurate predictions.

Findings

Kosmotropes are repelled from the interface due to hydration.

Chaotropes adsorb to the surface after losing hydration.

The model predicts strong hydronium ion surface adsorption.

Abstract

We present a theory that is able to account quantitatively for the surface and interfacial tensions of different electrolyte solutions. It is found that near the interface, ions can be separated into two classes: the kosmotropes and the chaotropes. While the kosmotropes remain hydrated near the interface and are repelled from it, the chaotropes loose their hydration sheath and become adsorbed to the surface. The anionic adsorption is strongly correlated with the Jones-Dole viscosity B-coefficient. Both hydration and polarizability must be taken into account to obtain a quantitative agreement with the experiments. To calculate the excess interfacial tension of the oil-electrolyte interface, the dispersion interactions must also be included. The theory can also be used to calculate the surface and the interfacial tensions of acid solutions, predicting a strong surface adsorption of hydronium ion.