Coupling between electroosmotically driven flow and bipolar faradaic depolarization processes in electron-conducting microchannels

A quantitative theory is proposed for the analysis of steady electroosmotically driven flows within conducting cylindrical microchannels. Beyond a threshold value of the electric field applied in the electrolyte solution and parallel to the conducting surface, electrochemical oxidation and reduction reactions take place at the two extremities of the substrate. The spatial distribution of the corresponding local faradaic currents along the bipolar electrode is intrinsically coupled to that of the electric field in solution. The nonuniform distribution of the electric field alters the double layer composition, and in particular the zeta-potential value, along the conducting surface via the occurrence of concomitant electronic and ionic double layer charging processes. The combined spatial dependencies of the lateral electric field and electrokinetic potential considerably affects the distribution of the electroosmotic velocity field in the directions parallel and perpendicular to the surface depolarized by faradaic processes. In this paper, the coupling between bipolar electrodic behavior and electroosmosis is explicitly investigated for the case of irreversible--that is, kinetically controlled--electron transfer reactions. Typical simulation results are presented and illustrate the possibility of controlling and optimizing electroosmotic flows in conducting channels by electrochemical means.