Conductivity of concentrated salt solutions

Abstract

The conductivity of concentrated salt solutions has posed a real puzzle for theories of electrolytes. Despite a quantitative understanding of dilute solutions, an analytical theory for concentrated ones remains a challenge for almost a century, although a number of parameters and effects incorporated into theories increases with time. Here we show that the conductivity of univalent salt solutions can be perfectly interpreted using a simplest model that relies on a modified mean-field description of electrostatic interactions and on a classical approach to calculating colloid electrophoresis. We derive a compact equation, which predicts that the ratio of conductivity to that at an infinite dilution is the same for all salt and depends only on a product of the harmonic mean of ion hydrodynamic radii and the square root of concentration. Our equation fits very well the data for inorganic salts (up to a few mol/l), although at a very high dilution the relaxation correction seems necessary.