Dielectric exclusion, an éminence grise

Abstract

Dielectric exclusion has long been well-established as the key mechanism in membrane desalination, critical for delivering the required levels of salt rejection, also playing important role in electro-membrane processes, nanofluidics, and biomimetics. Unfortunately, its elusive nature and many features, such as dependence on the pore size, membrane hydration, and ion size and charge, make it deceivingly similar to the other ion exclusions mechanisms, steric and Donnan, which has led to much controversy and misconceptions. Starting from the Born model and the concept of self-energy, the present paper reviews and highlights the physical basis of dielectric exclusion, its main features and the ways it may be looked at. It discusses what makes the dielectric exclusion both similar and distinctly different from the other mechanism and its synergy and intimate connection with other phenomena, such as Donnan exclusion, permeability-selectivity upper-bound, and selectivity of charged membranes towards uncharged solutes. The paper also addresses subjects that still cause much controversy at present, such as appropriate measures of ionic radii and the subtle distinction between the dielectric exclusion and primary ion hydration. It also points to gaps that need to be bridged towards more complete theory. The points addressed here are important for understanding, modeling and development of various next-generation separation technologies including water purification, resource recovery and reuse, and green energy generation and storage.