Hydration sequence of swelling clays: Evolutions of specific surface area and hydration energy

In order to identify the key steps and the driving force for the hydration process of swelling clays, the water adsorption isotherms and enthalpies were measured on mono-ionic montmorillonite samples saturated with alkali or calcium ions, and on bi-ionic samples saturated with a sodium-calcium mixture. The specific surface area evolution along the hydration process was determined using a recent interpretation of the experimental adsorption isotherms of swelling solids. Results are interpreted in structural terms. Compared with additional data from sample-controlled thermal analysis (SCTA), the results confirm experimentally that the hydration of Li- and Na-montmorillonite is mainly a cation-controlled process, in contrast with the hydration of Cs samples in which the cation contribution to hydration is negligible, as we have already demonstrated using electrostatic calculations or conductivity measurements. (authors)