Regensburg 2010 – wissenschaftliches Programm

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CPP: Fachverband Chemische Physik und Polymerphysik

CPP 46: Focus: Charge Effects in Soft and Biological Matter II (jointly with BP)

CPP 46.8: Vortrag

Donnerstag, 25. März 2010, 16:30–16:45, H37

Ion specificity and the Jones-Ray effect at liquid-liquid interfaces — •Markus Bier — Max-Planck-Institut f. Metallforschung, Heisenbergstr. 3, 70569 Stuttgart, Germany

The solvation shells around ions in solution are one of the key features which determine, e.g., the kinetics of electrochemical reactions and the charge transport across ion channels in biological membranes. Ion specificity of certain properties is, to a large extent, brought about by a variation of the structure or the stability of the solvation shell when considering different types of ions. In the present contribution the interfacial tension between two immiscible liquids as a function of the ionic strength is studied theoretically. For large ionic strengths the well-known linear behaviour is found, which is related to a finite size of the solvation shells. For small ionic strengths a decrease with the negative square root occurs due to an unequal partitioning of ions near the interface, which is induced by a difference of the solvation free energy contrasts between the two liquids. The crossover ionic strength between both regimes turns out to be strongly ion specific. A minimum of the interfacial tension can occur close to the crossover ionic strength, similar to the Jones-Ray effect of the electrolyte-air surface. The theoretical results are compared with experimental data and the relation to the limiting case of an electrolyte-air surface is discussed. It is argued that the dependence of the liquid-liquid interfacial tension on the ionic strength could serve as a sensitive probe to study solvation shells of various ions in various liquids.