On the driving force of cation exchange in clays: Insights from combined microcalorimetry experiments and molecular simulation

We study the origin of the ionic exchange enthalpy in montmorillonite clays using microcalorimetry measurements and molecular simulation. We first determine the standard reaction enthalpy for well-defined interlayer water contents. We then show by a detailed analysis based on thermodynamic cycles that replacing Na(+) ions by Cs(+) in the interlayer of montmorillonite clays is an endothermic process, and that the overall exchange is exothermic only because it is dominated by the exothermic replacement of Cs(+) by Na(+) in the aqueous phase. This conclusion from ionic exchange enthalpies supports the one of a recent study of the ionic exchange free energy by Teppen and Miller [Teppen B.J. and Miller D. M. (2006) Hydration energy determines isovalent cation exchange selectivity by clay minerals. Soil Sci. Soc. Am. J. 70(1), 31-40] and contradicts long-held views on the role of ion-clay interactions in determining the ionic exchange thermodynamics. This calls for a paradigm shift for the origin of this exchange: The driving force is the hydrophobicity of Cs(+) compared to Na(+) and not its affinity for clay surfaces. (c) 2009 Elsevier Ltd. All rights reserved.