TY - JOUR
T1 - Surface tension of electrolyte interfaces
T2 - Ionic specificity within a field-theory approach
AU - Markovich, Tomer
AU - Andelman, David
AU - Podgornik, Rudi
N1 - Publisher Copyright:
© 2015 AIP Publishing LLC.
PY - 2015/1/28
Y1 - 2015/1/28
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84923795654&partnerID=8YFLogxK
U2 - 10.1063/1.4905954
DO - 10.1063/1.4905954
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:84923795654
SN - 0021-9606
VL - 142
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 4
M1 - 044702
ER -