Beschreibung:
<jats:title>Abstract</jats:title><jats:p>This review is concerned with the phenomenological fluid dynamics in capillary and chip electrochromatography (EC) using high‐surface‐area random porous media as stationary phases. Specifically, the pore space morphology of packed beds and monoliths is analyzed with respect to the nonuniformity of local and macroscopic EOF, as well as the achievable separation efficiency. It is first pointed out that the pore‐level velocity profile of EOF through packed beds and monoliths is generally nonuniform. This contrasts with the plug‐like EOF profile in a single homogeneous channel and is caused by a nonuniform distribution of the local electrical field strength in porous media due to the continuously converging and diverging pores. Wall effects of geometrical and electrokinetic nature form another origin for EOF nonuniformities in packed beds which are caused by packing hard particles against a hard wall with different zeta potential. The influence of the resulting, systematic porosity fluctuations close to the confining wall over a distance of a few particle diameters becomes aggravated at low column‐to‐particle diameter ratio. Due to the hierarchical structure of the pore space in packed beds and silica‐based monoliths which are characterized by discrete intraparticle (intraskeleton) mesoporous and interparticle (interskeleton) macroporous spatial domains, charge‐selective transport prevails within the porous particles and the monolith skeleton under most general conditions. It forms the basis for electrical field‐induced concentration polarization (CP). Simultaneously, a finite and – depending on morphology – often significant perfusive EOF is realized in these hierarchically structured materials. The data collected in this review show that the existence of CP and its relative intensity compared to perfusive EOF form fundamental ingredients which tune the fluid dynamics in EC employing monoliths and packed beds as stationary phases. This addresses the (electro)hydrodynamics, associated hydrodynamic dispersion, as well as the migration and retention of charged analytes.</jats:p>