Ions in mixed dielectric solvents: density profiles and osmotic pressure between charged interfaces


  Dan Ben-Yaakov [1]  ,  David Andelman [1]  ,  Daniel Harries [2]  ,  Rudi Podgornik [3]  
[1] Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv University, Ramat Aviv, Tel Aviv 69978, Israel
[2] Institute of Chemistry and The Fritz Haber Research Center, The Hebrew University, Jerusalem 91904, Israel
[3] Department of Theoretical Physics, J. Stefan Institute, and Department of Physics, Faculty of Mathematics and Physics, University of Ljubljana, 1000 Ljubljana, Slovenia

The forces between charged macromolecules, usually given in terms of osmotic pressure, are highly affected by the intervening ionic solution. While in most theoretical studies the solution is treated as a homogeneous structureless dielectric medium, recent experimental studies concluded that for a bathing solution composed of two solvents (binary mixture), the osmotic pressure between charged macromolecules is affected by the binary solvent composition. By adding local solvent composition terms to the free energy, we obtain a general expression for the osmotic pressure, in planar geometry and within the mean-field framework. The added effect is due to the permeability inhomogeneity and non-electrostatic shortrange interactions between the ions and solvents (preferential solvation). This effect is mostly pronounced at small distances and leads to a reduction in the osmotic pressure for macromolecular separations of the order 1-2nm. Furthermore, it leads to a depletion of one of the two solvents from the charged macromolecules (modeled by us as planar interfaces). Lastly, by comparing the theoretical results with experimental ones, an explanation based on preferential solvation is offered to recent experiments on the osmotic pressure of solutions of DNA molecules.