A numerical study on the influence of electroosmotic flow on analyte preconcentration by isotachophoresis ( ITP) is made. We consider that the double layer induced electroosmotic flow ( EOF) counterbalance the electrophoretic velocity and a stationary ITP stacked zones results. We solve the Navier-Stokes equations coupled with the Nernst-Planck equations to determine the local convective velocity and the preconcentration dynamics of ions. Our numerical algorithm is based on a finite volume method along with a secondorder upwind scheme. The present numerical algorithm can capture the the sharp boundaries of step-changes ( plateau mode) or zones of steep gradients ( peak mode) accurately. The convection of ions due to EOF reduces the resolution of the ITP transition zones and produces a dispersion in analyte zones. The role of the electrokinetic parameters which induces dispersion is analyzed. A one-dimensional model for the area-averaged concentrations based on the Taylor-Aristype effective diffusivity is found to be in good agreement with the computed solutions.
We have studied the migration of a charged permeable aggregate in electrolyte under the influence of an axial electric field and pressure gradient. The migration of the positively charged aggregate leads to a deformation of the anionic cloud around it. The hydrodynamics of the aggregate is governed by the interaction of electroosmotic flow in and around the particle, hydrodynamic friction and electric force experienced by the aggregate. We have computed the non-linear Nernest-Planck equations coupled with the Dracy- Brinkman extended Navier-Stokes equations and Poisson equation for electric field through a finite volume method. The permeability of the aggregate enable the counterion penetration. The penetration of counterions depends on the volume charge density of the aggregate and ionic concentration of electrolytes at a fixed field strength. The retardation effect due to the double layer polarization increases the drag force compared to an uncharged aggregate. Increase in migration sped from the electrophretic velocity of the aggregate produces further asymmetry in charge cloud and reduces the electric body force exerted on the particle. The permeability of the particle have relatively little influence on the electric body force when Double layer is relatively thin. The impact of the key parameters of electrokinetics on the hydrodynamics of the aggregate is analyzed.