Dispersion reduction in open-channel liquid electrochromatographic columns via pressure-driven back flow.

Application of electrokinetic forces to drive the mobile phase diminishes analyte dispersion in open-channel liquid chromatographic columns due to minimization of shear in the flow field. However, the retentive layer coating the inner walls of such devices slows down the average convective velocity of solute molecules in its vicinity, inherently causing dispersion of analyte bands. In this article, we explore the possibility of reducing such dispersion in electrochromatographic columns by imposing a pressure-driven back flow in the system. Analysis shows that although such a strategy introduces shear in the flow field, the overall dispersion in the mobile phase is reduced. This occurs as the streamline velocity in such a system is greater near the channel walls than that in the center of the conduit, thereby allowing fluid dispersion to counteract wall retention effects. For an optimally chosen magnitude of the back flow, hydrodynamic dispersion of any target species in the mobile phase may be shown to diminish by a factor of 3 and 10/3 in a circular tube and a parallel-plate geometry, respectively. A similar reduction in slug dispersion is also realized in rectangular conduits for all aspect ratios. In trapezoidal geometries with large wedge angles or isotropically etched profiles, this reduction factor may attain values of 10 or greater.