Overlimiting Current and Shock Electrodialysis in Porous Media

Most electrochemical processes, such as electrodialysis, are limited by diffusion, but in porous media, surface conduction and electro-osmotic flow also contribute to ionic fluxes. In this paper, we report experimental evidence for surface-driven over-limiting current (faster than diffusion) and deionization shocks (propagating salt removal) in a porous medium. The apparatus consists of a silica glass frit (1 mm thick with 500 nm mean pore size) in an aqueous electrolyte (CuSO$_4$ or AgNO$_3$) passing ionic current from a reservoir to a cation-selective membrane (Nafion). The current-voltage relation of the whole system is consistent with a proposed theory based on the electro-osmotic flow mechanism over a broad range of reservoir salt concentrations (0.1 mM - 1.0 M), after accounting for (Cu) electrode polarization and pH-regulated silica charge. Above the limiting current, deionized water ($\approx 10 \mu$ $M$) can be continuously extracted from the frit, which implies the existence of a stable shock propagating against the flow, bordering a depleted region that extends more than 0.5mm across the outlet. The results suggest the feasibility of "shock electrodialysis" as a new approach to water desalination and other electrochemical separations.Comment: 39 pages, 9 fig

An overview of the oil-brine interfacial behavior and a new surface complexation model

Abstract The few existing surface complexation models (SCM) for the brine-oil interface have important limitations: the chemistry of each crude oil is not considered, they cannot capture the water/non-polar hydrocarbons surface charge, the interactions between Na+ and the acid sites are not included, and the equilibrium constants for the adsorption reactions are not validated against experimental data. We address the aforementioned constraints by proposing an improved diffuse-layer SCM for the oil-brine interface. The new model accounts for the chemistry of crude oils by considering surface sites linearly dependent on the TAN (total acid number) and TBN (total base number). We define weak sites to account for the negative surface charge observed for non-polar hydrocarbons in water. We optimize the parameters of our model by fitting the model to reported zeta potential measurements of oil in aqueous solutions. When we validate the optimized model against different experimental data sets, it generally shows a good performance in predicting the surface charge of oil in different brines with different pHs. We show that the acid and base numbers are only useful as a qualitative estimation of the distribution of polar groups at the oil surface, and more sophisticated analysis is necessary to quantify the chemistry of the oil-brine interface