The Jones-Ray effect reinterpreted: Surface tension minima of low ionic strength electrolyte solutions are caused by electric field induced water-water correlations

Abstract

The surface tension of electrolyte solutions exhibits a minimum at millimolar electrolyte concentrations and then rises with increasing concentration. This minimum, known as the Jones-Ray effect, has been hotly debated over the past ∼80 years. If not considered as an artifact, it is typically ascribed to a phenomenological rare binding site for ions or ion pairs. Here, we propose an alternative underlying mechanism, namely that the hydrogen bond network of water responds to the collective electrostatic field of ions by increasing its orientational order, supported by recent surface tension measurements of NaCl solutions in H2O and D2O, and second harmonic scattering experiments in combination with ion resonant second harmonic reflection experiments. Recent thermodynamic and purely electrostatic treatments of the surface tension provide support for this interpretation. In addition, concerns related to possible artifacts influencing the measurements are quantified experimentally.