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the microchannel height is decreased even further to a few microns. In this regime, vortices can no longer form, as seen in Yossifon’s [118] and Nam’s [70] experiments (convection becomes negligible compared to diffusion). However, overlimiting current can still be observed, which can be explained by surface conduction, in which the current is now passed through the charged screening layer. The second class of mechanisms for overlimiting current involve the water split- ting reaction. As discussed in the review by Nikonenko et al. [77], the water splitting reaction tends to occur at the membrane-bulk interface and can contribute to overlim- iting current by adding extra charge carriers (H+ and OH−) to the solution, thereby carrying extra current. Furthermore, extra charge carriers produced at a membrane can cause the exaltation effect. The exaltation effect occurs when extra charge carri- ers at the interface disrupt the electric field, thereby causing an increase in the salt counterion transfer. For example, H+ ions generated at an anion-selective membrane would attract salt anions from the bulk into the depleted diffusion layer next to the membrane and thereby facilitate current flow and contribute to overlimiting current. In addition to these two mechanisms involving water splitting, a new mechanism was recently proposed by Andersen et al [4], who argued that taking in account membrane protonation and the fact that both salt ions and the hydronium and hydroxide ions are present in the membrane will lead to a decrease in ion-selectivity and will cause overlimiting current by current-induced membrane discharge (CIMD). He proceeds to show that CIMD will not only cause overlimiting current, but will also lead to significant gradients of pH across the system, to substantial changes in membrane protonation as the voltage changes, and to the suppression of the electro-osmotic instability. It furthermore leads to a prediction of a much smaller extended space charge layer than the traditional model (no coions in membrane and no change in membrane protonation) and to a prediction of the non-divergence of the transverse electro-osmotic mobility. 33PDF Image | Shock Electrodialysis for Water Purification and Electrostatic Correlations
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