In this review, we present an overview of the state of the art concerning the fundamental properties of electrode polarization (EP) of interest in the measurement of high conductivity samples and its implications for both dielectric (DS) and impedance spectroscopy (IS). Initially a detailed description of what constitutes EP is provided and the problems that it induces. Then, we review some of the more popular models that have been used to describe the physical phenomena behind the formation of the ionic double layer. Following this we shall enumerate the common strategies used historically to correct its influence on the measured signals in DS or in IS. Finally we also review recent attempts to employ fractal electrodes to bypass the effects of EP and to offer some physical explanation as to the limitations of their use.

In this, the second part of our series on the dielectric spectrum symmetrical broadening of water, we consider ionic aqueous solutions. If in Part I, dipole-dipole interaction was the dominant feature, now ion-dipole interplay is shown to be the critical element in the dipole-matrix interaction. We present the results of high-frequency dielectric measurements of different concentrations of NaCl/KCl aqueous solutions. We observed Cole-Cole broadening of the main relaxation peak of the solvent in the both electrolytes. The 3D trajectory approach (described in detail in Part I) is applied in order to highlight the differences between the dynamics and structure of solutions of salts on one hand and dipolar solutes on the other hand.

Using quasielastic neutron scattering spectroscopy, we measured the averaged translational diffusion of water in solutions of biologically relevant salts, NaCl, a kosmotrope, and KCl, a chaotrope. The analysis revealed the striking difference in the influence of these ions on water dynamics. While the averaged water diffusion slows down in the presence of the structure making (kosmotrope) Na(+) ion, the diffusion becomes faster in the presence of the structure breaking (chaotrope) K(+) ion. The latter means that, despite strong Coulombic interactions introduced by the K(+) ions, their disruption of the hydrogen-bonding network is so significant that it leads to faster diffusion of the water molecules.