期刊
JOURNAL OF CHEMICAL PHYSICS
卷 142, 期 4, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4905954
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资金
- Israel Science Foundation (ISF) [438/12]
- U.S.-Israel Binational Science Foundation (BSF) [2012/060]
- ARRS [P1-0055]
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. (C) 2015 AIP Publishing LLC.
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