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trends can at least to some extent be explained by the nature of the ions involved. The Hofmeister series predicts that potassium ions are more kosmotropic than mag- nesium ions and that the same is true for chloride ions when compared to nitrate ions [14, 124], which means that KCl is the most kosmotropic electrolyte among the elec- trolytes investigated in this study. Kosmotropic salts generally exhibit better salting in and higher solubility of macromolecules, which might explain the larger thickness of the polymer layer observed and hence the lower background charge density. Fur- thermore, since the polymer is not as closely packed, the effective concentration of polyelectrolyte is lower, which means that the dielectric constant would probably be lower. However, this conclusion is confounded by the fact that electrolytes can affect the effective charge on a polymer chain and hence how much polymer adsorbs to the surface and that the size of polymer chains also plays a role, since this conclusion is not supported by the data in KCl for different polymer chain molecular weights shown previously. Tighter packing; however, would explain the decrease in correla- tion length. All these trends would then also explain why ∆φs is higher for more chaotropic salts, since the behavior near the surface is more dominated by dense and long polymer chains and there is less capacity for "charge inversion" through the simple electrolyte. Making a direct comparison between KNO3 and MgCl2 is more difficult, since it is not clear which electrolyte is more kosmotropic and which one is more chaotropic. However, the fact that for MgCl2 ∆φs changes signs at a lower concentration may well be due to the fact that the concentration of the more kos- motropic chloride ions is always twice the electrolyte concentration; which may also explain why MgCl2 appears to behave more kosmotropically than KNO3. 5.3.4 Modification of Model using Pincus Relation In all of the previous curves, the polymer layer thickness (L) was treated as a constant and independent of the bulk electrolyte concentration. However, it is well know that polymer layers do change thickness as a function of concentration [44]. Hence, we modified the polymer layer thickness with the Pincus relation (L ∼ c−1/3), where 0 we assumed that the chain area density remains constant. In addition to modifying 130PDF Image | Shock Electrodialysis for Water Purification and Electrostatic Correlations
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