Thermally stimulated depolarization current (TSDC) technique is a powerful tool for probing dipole re-orientational motions in condensed matter. In the case of cation-exchangeable alummosilicates, it allows the assessment of the potential barrier related to the hopping mechanism of cations and, consequently, the measurement of its evolution when molecules, i.e. water, are adsorbed and interact with the cations embedded in the solid framework. Then, using suitable models based on thermodynamics, the analysis of TSDC signals obtained at various hydration states provides insights about the surface properties of the studied solid and the mechanism of adsorption at the cationic site. In this work, TSDC is used to study the first stage, i.e. when the number of adsorbed molecules is below the occurrence of the water monolayer, of water adsorption in a Na+-montmorillonite from Mostaganem (Algeria). It is shown that the hydration process follows two stages. Using the "chemical force" concept it can then be concluded that when the number of adsorbed water molecules per cation is lower than 2, cation-water interaction dominates the energetics of adsorption, whereas at higher water loading the water "chemical force" is also involved into water-water and/or water-clay framework interactions. The number of water molecules for the monohydrated state is found to be about 7. (c) 2007 Elsevier Inc. All rights reserved.