Shock Electrodialysis for Water Purification and Electrostatic Correlations

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Shock Electrodialysis for Water Purification and Electrostatic Correlations ( shock-electrodialysis-water-purification-and-electrostatic-c )

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ranged between 3.5 Åand tens of nm depending on electrolyte and concentration (in general it decreased with increasing concentration). However, even this model struggles significantly with in modeling NaOH, a highly non-ideal electrolyte. In fact, for NaOH, the simple Debye-Huckel + Born model gives better predictions. This difficulty could be explained through the fact that the hydroxide ion is very different from the other ions that we have looked at in that not only correlations are important, but also that it interacts much more strongly with water (such as H+ hopping from hydroxide to hydroxide). Overall, this model could probably be improved even further by also taking in account water-ion interactions. One interesting question that comes up when comparing this model to the model from Chapter 5 is why did we need the first derivative to go to zero in this model, whereas it was necessary for the third derivative to go to zero in the model in Chapter 5. While we cannot currently give a definite answer, we speculate that it has to do with the underlying assumptions for the respective surfaces. The model with the third derivative going to zero has been shown to work for surface with ionic liquids that are at a constant potential [8], whereas the model with the first derivative going to zero has yielded useful results fro surface with a constant charge [89]. The model in Chapter 5 is used in conditions more akin to a surface at constant potential (varying surface charge that depends on surface potential), whereas the model in this chapter is clearly used in constant surface charge conditions. While these facts suggest what is causing the difference in boundary conditions, it is not at all clear what the physical reasons for this difference are. 6.4 Non-Aqueous Electrolytes In addition to the nice behavior of the new model for aqueous electrolyte, we have also investigated a solution of LiPF6 in a 10%/27%/63% mixture of propylene carbonate, ethylene carbonate, and dimethyl carbonate [101]. Since we did not have data for the behavior of the dielectric constant as a function of concentration, we took a somewhat different approach. We simply assumed that the correlation length is exactly the 153

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