We present an experimental and numerical investigation of electrokinetic instability (EKI) in microchannel flow with streamwise conductivity gradients, such as those observed during sample stacking in capillary electrophoresis. A plug of a low-conductivity electrolyte solution is initially sandwiched between two high-conductivity zones in a microchannel. This spatial conductivity gradient is subjected to an external electric field applied along the microchannel axis, and for sufficiently strong electric fields an instability sets in. We have explored the physics of this EKI through experiments and numerical simulations, and supplemented the results using scaling analysis. We performed EKI experiments at different electric field values and visualised the flow using a passive fluorescent tracer. The experimental data were analysed using the proper orthogonal decomposition technique to obtain a quantitative measure of the threshold electric field for the onset of instability, along with the corresponding coherent structures. To elucidate the physical mechanism underlying the instability, we performed high-resolution numerical simulations of ion transport coupled with fluid flow driven by the electric body force. Simulations reveal that the non-uniform electroosmotic flow due to axially varying conductivity field causes a recirculating flow within the low-conductivity region, and creates a new configuration wherein the local conductivity gradients are orthogonal to the applied electric field. This configuration leads to EKI above a threshold electric field. The spatial features of the instability predicted by the simulations and the threshold electric field are in good agreement with the experimental observations and provide useful insight into the underlying mechanism of instability.
Electric-field-based Poisson-Boltzmann theory: Treating mobile charge as polarization