Dehydration enthalpy of alkali-cations-exchanged montmorillonite from thermogravimetric analysis.

Dehydration of a series of homoionic alkali-exchanged montmorillonites is studied at different treatment temperatures by means of thermogravimetric analysis. More specifically, we investigate the last stages of dehydration when the number of adsorbed water molecules corresponds, at maximum, to a monolayer. Weight losses are measured at several constant temperatures as a function of time. Application of Van't Hoff's law yields the dehydration enthalpy. Trends and data similar to those reported from other experimental conditions are found. Comparison with X-ray data and with the dissociation enthalpy of alkali cation/water complexes shows that dehydration of weakly hydrated homoionic alkali montmorillonites results from the competition between opposite energy contributions due to (i) the cation solvation, (ii) the hydration of the silicate interlayer surface, and (iii) the structural swelling. So, depending on the balance between these various energy contributions, different behaviors are observed according to the nature of the alkali cations.

DC conductivity, cationic exchange capacity, and specific surface area related to chemical composition of pore lining chlorites.

Low resistivity in argillaceous sandstone reservoirs may be attributed either to the effect of microporosity, or to specific effects due to intrinsic clays' conducting properties or to other conducting minerals. In order to distinguish these effects, cation exchange capacity, specific surface areas, and dc conductivity of various pore lining chlorite-bearing sandstones from different hydrocarbon reservoir measurements are investigated. Cation exchange capacity and specific surface area are measured on whole rocks as well as on size-separated fractions. Both sets of values are low, in agreement with the structural and textural observations. The conductivity of these chlorites, measured in air conditions and after dehydration, is investigated by means of complex impedance spectroscopy on size-separated fractions as a function of temperature and compared to that of reference clays. The results show a large influence of moisture, applied electric field frequency, and temperature on the electrical properties. The magnitude of the dehydrated clays' conductivity is such that its influence on the conductivity of argillaceous sandstone is lower than that related to the presence of water or brine by several orders of magnitude. The dc conductivity and the related activation energy of the dehydrated samples appear to be related to the chemical composition of the clays. More specifically, a clear correlation occurs with the electrical charges of the clay network, that is to say with the location, i.e., tetrahedral or octahedral sites, of the substituting trivalent elements.

Hydration of a Na(+)-montmorillonite studied by thermally stimulated depolarization current.

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 aluminosilicates, 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.

Use of dielectric relaxation for measurements of surface energy variations during adsorption of water on mordenite.

This paper tries to assess simply and quantitatively the link between classical adsorption theories and dielectric spectroscopy, in order to demonstrate that dielectric spectroscopy can be used as a tool of determination of surface energy variations due to movements of charge carriers at the surface of solids. A simple theory is developed to analyze hops of cations at the surface of mordenite, which are detected by complex impedance spectroscopy during adsorption of water. An energy of extraction of the cation can be determined from measurements and its dependence on the quantity of water molecules adsorbed is shown and qualitatively and quantitatively explained, using relationships developed in order to interpret adsorption phenomena generally. The agreement with other determinations of the adsorption energies and solid surface energy is correct.