Surface tension of electrolyte solutions: A self-consistent theory

¹ Raymond and Beverly Sackler School of Physics and Astronomy Tel Aviv University - Ramat Aviv, Tel Aviv 69978, Israel
² Department of Theoretical Physics, J. Stefan Institute, and Department of Physics, Faculty of Mathematics and Physics, University of Ljubljana - 1000 Ljubljana, Slovenia

Received: 7 February 2014
Accepted: 25 March 2014

Abstract

We study the surface tension of electrolyte solutions at the air/water and oil/water interfaces. Employing field-theoretical methods and considering short-range interactions of anions with the surface, we expand the Helmholtz free energy to first order in a loop expansion and calculate the excess surface tension. Our approach is self-consistent and yields an analytical prediction that reunites the Onsager-Samaras pioneering result (which does not agree with experimental data), with the ionic specificity of the Hofmeister series. We obtain analytically the surface-tension dependence on the ionic strength, ionic size and ion-surface interaction, and show consequently that the Onsager-Samaras result is consistent with the one-loop correction beyond the mean-field result. Our theory fits well a wide range of concentrations for different salts using one fit parameter, reproducing the reverse Hofmeister series for anions at the air/water and oil/water interfaces.