The present work analyzes the electrodynamic dispersion of sample streams in a free-flow zone electrophoresis (FFZE) chamber resulting due to partial or complete blockage of electroosmotic flow (EOF) across the channel width by the sidewalls of the conduit. This blockage of EOF has been assumed to generate a pressure-driven backflow in the transverse direction for maintaining flow balance in the system. A parallel-plate based FFZE device with the analyte stream located far away from the channel side regions has been considered to simplify the current analysis. Applying a method-of-moments formulation, an analytic expression was derived for the variance of the sample zone at steady state as a function of its position in the separation chamber under these conditions. It has been shown that the increase in stream broadening due to the electrodynamic dispersion phenomenon is additive to the contributions from molecular diffusion and sample injection, and simply modifies the coefficient for the hydrodynamic dispersion term for a fixed lateral migration distance of the sample stream. Moreover, this dispersion mechanism can dominate the overall spatial variance of analyte zones when a significant fraction of the EOF is blocked by the channel sidewalls. The analysis also shows that analyte streams do not undergo any hydrodynamic broadening due to unwanted pressure-driven cross-flows in an FFZE chamber in the absence of a transverse electric field. The noted results have been validated using Monte Carlo simulations which further demonstrate that while the sample concentration profile at the channel outlet approaches a Gaussian distribution only in FFZE chambers substantially longer than the product of the axial pressure-driven velocity and the characteristic diffusion time in the system, the spatial variance of the exiting analyte stream is well described by the Taylor-Aris dispersion limit even in analysis ducts much shorter than this length scale.
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