Determination of the Driving Force for the Hydration of the Swelling Clays from Computation of the Hydration Energy of the Interlayer Cations and the Clay Layer

The key feature of swelling clays such as montmorillonite, in contrast with the nonswelling clays, is their ability to adsorb water in the interlayer space. This interlayer water interacts with the interlayer cations or with the silicate layer surface inside the interlayer space, or with both. However, no direct experimental technique offers the possibility to determine separately these two contributions. In order to determine the hydration energy for interlayer alkali cations, we use a combination of electrostatic calculations of the surface energy and measurements of immersion heats in clays. The results show that Li+ and Na+ cations are characterized by a strongly exothermic hydration energy in the interlayer space, in contrast with K+, Rb+, and Cs+ which have a much lower hydration energy in the interlayer space. The extreme situation is that of Cs+, for which an endothermic hydration energy value is obtained. These trends are in good agreement with results from molecular modeling calculations and con...

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