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Osmotic Coefficients and Surface Tensions of Aqueous Electrolyte Solutions: Role of Dispersion Forces

Werner KunzInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, Germany, Service de Chimie Moléculaire, CEA/Saclay, F-91191 Gif-sur Yvette Cedex, France, Laboratoire LI2C, Université Pierre et Marie Curie, Boîte no. 51, 4 place Jussieu, 75252 Paris Cedex 05, France, and Department of Physical Chemistry, University of Florence, Cagliari, and Department of Applied Mathematics, Australian National University, via della Lastrucci 3, Sesto Fiorentino, 50019 Florence, ItalyLuc BelloniInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, Germany, Service de Chimie Moléculaire, CEA/Saclay, F-91191 Gif-sur Yvette Cedex, France, Laboratoire LI2C, Université Pierre et Marie Curie, Boîte no. 51, 4 place Jussieu, 75252 Paris Cedex 05, France, and Department of Physical Chemistry, University of Florence, Cagliari, and Department of Applied Mathematics, Australian National University, via della Lastrucci 3, Sesto Fiorentino, 50019 Florence, ItalyOlivier BernardInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, Germany, Service de Chimie Moléculaire, CEA/Saclay, F-91191 Gif-sur Yvette Cedex, France, Laboratoire LI2C, Université Pierre et Marie Curie, Boîte no. 51, 4 place Jussieu, 75252 Paris Cedex 05, France, and Department of Physical Chemistry, University of Florence, Cagliari, and Department of Applied Mathematics, Australian National University, via della Lastrucci 3, Sesto Fiorentino, 50019 Florence, ItalyBarry W. NinhamInstitute of Physical and Theoretical Chemistry, University of Regensburg, D-93040 Regensburg, Germany, Service de Chimie Moléculaire, CEA/Saclay, F-91191 Gif-sur Yvette Cedex, France, Laboratoire LI2C, Université Pierre et Marie Curie, Boîte no. 51, 4 place Jussieu, 75252 Paris Cedex 05, France, and Department of Physical Chemistry, University of Florence, Cagliari, and Department of Applied Mathematics, Australian National University, via della Lastrucci 3, Sesto Fiorentino, 50019 Florence, Italy

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Annotatsiya

Osmotic coefficients of a series of 16 aqueous electrolyte solutions are described at concentrations up to about 1 M with the help of HNC calculations and solvent-averaged potentials of charged hard spheres with an additional necessary dispersion potential, omitted from all earlier treatments. The adjusted ionic radii and excess polarizabilities have values of the expected order of magnitude. Whereas the description of the bulk properties is satisfactory, the theory is not so successful in predicting the surface tensions of the corresponding solutions (Hofmeister series). The reasons for this are quite subtle and explored in the text. It is clear now how to make further progress and tackle hydration in a consistent way.

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DOI: 10.1021/jp036113x

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