Perspective on concentration polarization effects in electrochromatographic separations

This work illustrates the appearance and electrohydrodynamic consequences of concentration polarization in the particulate and monolithic fixed beds used in capillary electrochromatography and related electrical‐field assisted processes. Key property of most porous materials is the co‐existence of bulk, quasi‐electroneutral macroporous regions and mesoporous compartments which are ion‐permselective (due to electrical double‐layer overlap) causing different transport numbers for co‐ionic and counterionic species, e.g. , background electrolyte components, or the analytes. For a cathodic electroosmotic flow the (cation) permselectivity, together with diffusive and electrokinetic transport induces depleted and enriched concentration polarization zones at the anodic and cathodic interfaces, respectively, in dependence of the mobile phase ionic strength and applied electrical fields. At high field strength a secondary, nonequilibrium electrical double layer may be created in the depleted concentration polarization zones of a material stimulating electroosmosis of the second kind. The potential of this induced‐charge electroosmosis with respect to nonlinear flow velocities and electrokinetic instability mixing (basically destroying the concentration polarization zones) is analyzed in view of the pore space morphology in random‐close packings of spherical‐shaped, porous particles and hierarchically structured monoliths. Possible applications based on a fine‐tuning of the illustrated effects emerge for microfluidic pumping and mixing, or the intensification of sample recovery in adsorption processes. With this perspective we want to focus the attention on concentration polarization in electrochromatographic systems by presenting and discussing original data acquired on relevant microscopic as well as macroscopic scales, and point towards the importance of related effects in colloid and membrane science.*