Sample dispersion in isotachophoresis with Poiseuille counterflow

A particular mode of isotachophoresis (ITP) employs a pressure-driven flow opposite to the sample electromigration direction in order to anchor a sample zone at a specific position along a channel or capillary. We investigate this situation using a two-dimensional finite-volume model based on the Nernst-Planck equation. The imposed Poiseuille flow profile leads to a significant dispersion of the sample zone. This effect is detrimental for the resolution in analytical applications of ITP. We investigate the impact of convective dispersion, characterized by the area-averaged width of a sample zone, for various values of the sample Péclet-number, as well as the relative mobilities of the sample and the adjacent electrolytes. A one-dimensional model for the area-averaged concentrations based on a Taylor-Aris-type effective axial diffusivity is shown to yield good agreement with the finite-volume calculations. This justifies the use of such simple models and opens the door for the rapid simulation of ITP protocols with Poiseuille counterflow.

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