|Isosteric heat of water adsorption and desorption in homoionic alkaline-earth montmorillonites |
(Article) Publié: Chemical Physics, vol. 501 p.26-34 (2018)
Ref HAL: hal-01927357_v1
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The aim of the present work is to study by means of thermodynamic measurements, i.e. isotherms of adsorption and desorption of water and Infrared (IR) spectroscopy, the effect of the interlayer cations on the mechanism of adsorption-desorption of water in the case of a montmorillonite exchanged with alkaline-earth metals. For the first time, the net isosteric heat of water adsorption and desorption is determined from isotherms recorded at three temperatures. The net isosteric heat is a very useful parameter for getting more insights into the sorption mechanism since it provides information about the sorption energy evolution which can be complementary to that obtained from structural or gravimetric measurements. The homoionic montmorillonite samples are prepared from purification and cationic exchanged in aqueous solution of the raw material, i.e the reference SWy-2 Wyoming material. XRD at the dry state and elemental chemical analysis confirm that the treatment does not deteriorate the clay structure and yield the expected homoionic composition. The adsorption and desorption isotherms measured at various temperatures show that the nature of the interlayer, i.e. exchangeable, cation changes the adsorbed/desorbed amount of water molecules for a given water relative pressure. The total amount of water adsorbed at = 0.5 follows the cation sequence Ca>Mg>Ba. Although the adsorption isosteric heat also follows the cation sequence Ca>Mg>Ba, that of desorption obeys a slightly different sequence Ca~Mg>Ba. This discrepancy between the adsorption and desorption heat is due to the higher irreversibility of water sorption process in the Ca exchanged montmorillonite. Finally, analysis of the IR spectra recorded at room temperature and under a primary vacuum reveals that the amount of adsorbed water follows the same sequence as that of the isosteric heat of adsorption and shows the coexistence of liquid-like and solid-like water confined in the interlayer space.