Decrease of permittivity of an electrolyte solution near a charged surface due to saturation and excluded volume effects

The dipole moment of a water molecule in liquid water differs from that of an isolated one because each molecule is further polarized by the electric field of its neighbours. In this work a formula for the spatial dependence of the relative permittivity of an electrolyte near a highly charged surface is obtained in which the mutual influence of the water molecules is taken into account by means of the cavity field. The orientational ordering of water dipoles is considered in the saturation regime. It is predicted that the relative permittivity of an electrolyte solution near the highly charged surface (i.e. in saturation regime) may be substantially decreased due to orientational ordering of water (saturation effect) and depletion of water molecules (excluded volume effect) due to accumulation of counterions.

► Theoretical consideration of an electrolyte solution near a highly charged surface. ► Orientational ordering of water dipoles in the saturation regime. ► Depletion of water near the charged surface due to accumulation of counterions. ► Analytical expression for spatial dependence of relative permittivity. ► Decrease of relative permittivity of the electrolyte solution near the charged surface.