Surface tension of electrolyte interfaces: ionic specificity within a field-theory approach.
J Chem Phys
; 142(4): 044702, 2015 Jan 28.
Article
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| MEDLINE
| ID: mdl-25637998
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.
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MEDLINE
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En
Revista:
J Chem Phys
Año:
2015
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Article
País de afiliación:
Israel