Surface tension of electrolyte interfaces: Ionic specificity within a field-theory approach

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Abstract

We study the surface tension of ionic solutions at air/water and oil/water interfaces by using field-theoretical methods and including a finite proximal surface-region with ionic-specific interactions. The free energy is expanded to first-order in a loop expansion beyond the mean-field result. We calculate the excess surface tension and obtain analytical predictions that reunite the Onsager-Samaras pioneering result (which does not agree with experimental data), with the ionic specificity of the Hofmeister series. We derive 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 salt concentrations for different monovalent ions using one fit parameter per electrolyte and reproduces the reverse Hofmeister series for anions at the air/water and oil/water interfaces.

Original languageEnglish
Article number044702
JournalJournal of Chemical Physics
Volume142
Issue number4
DOIs
StatePublished - 28 Jan 2015

Funding

FundersFunder number
Israel Science Foundation438/12

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