Abstract

AbstractWe discuss the effect of electrolytes on retention of aqueous colloidal polystyrene particles in asymmetrical flow (AF‐FFF) and thermal field‐flow fractionation (ThFFF). In both FFF subtechniques, interparticle interaction leads to non‐ideal fractionation behavior, which can result in a sample load dependency. Electrostatic repulsion is reduced with increasing electrolyte concentration, resulting in a pronounced increase of retention. At higher salinities, hydrophobic interactions dominate, thus applications of AF‐FFF under physiological conditions are limited. In ThFFF, also the separation mechanism of thermophoresis is affected by ionic shielding and experimental data are in accordance with recent theoretical models of thermophoresis.

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