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Mechanism of Adsorption and Desorption of Water Vapor by Homoionic Montmorillonite: 3. The Mg2+, Ca2+, Sr2+ and Ba2+ Exchanged Forms

Published online by Cambridge University Press:  28 February 2024

J. M. Cases ,
I. Bérend ,
M. François ,
J. P. Uriot ,
L. J. Michot  and
F. Thomas
J. M. Cases
Affiliation:
Laboratoire Environnement et Minéralurgie et UA 235 du CNRS, BP 40, 54501 Vandœuvre Cedex, France
I. Bérend
Affiliation:
Laboratoire Environnement et Minéralurgie et UA 235 du CNRS, BP 40, 54501 Vandœuvre Cedex, France
M. François
Affiliation:
Laboratoire Environnement et Minéralurgie et UA 235 du CNRS, BP 40, 54501 Vandœuvre Cedex, France
J. P. Uriot
Affiliation:
Centre de Recherches Pétrographiques et Géochimiques (CNRS-UPR 9046), BP 20, 54501 Vandœuvre Cedex, France
L. J. Michot
Affiliation:
Laboratoire Environnement et Minéralurgie et UA 235 du CNRS, BP 40, 54501 Vandœuvre Cedex, France
F. Thomas
Affiliation:
Laboratoire Environnement et Minéralurgie et UA 235 du CNRS, BP 40, 54501 Vandœuvre Cedex, France
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Abstract

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The swelling of some well-defined Mg-, Ca-, Sr- and Ba- homoionic montmorillonites was studied in the domain of water relative pressures lower than 0.95. This involves the expansion of the crystal lattice itself, commonly known as the “interlamellar expansion” or “inner crystalline swelling”. The initial freeze-dried clays were characterized by nitrogen adsorption-desorption volumetry and controlled transformation rate thermal analysis. The evolution of the structural and textural properties of these different clays at different stages of hydration and dehydration was investigated using water adsorption gravimetry, immersion microcalorimetry at different precoverage water vapor relative pressures and X-raydiffraction (XRD) under controlled humidity conditions. Large textural variations are observed in the dry state depending on the exchangeable cations. The 2-layer hydrate exhibits the most ordered layer stacking. Water is mainly adsorbed in the interlamellar space. With increasing water pressure, each homoionic species leads to a 1-layer hydrate and, with the exception of Ba-montmorillonite, to a predominant 2-layer hydrate. The relative pressure corresponding to the formation of the 2-layer hydrate decreases with increasing hydration energy of the interlayer cation. For Ca-, Sr- or Mg-montmoriHonites, simulation of XRD patterns leads to the definition of successive homogeneous states corresponding to the 2-layer hydrate. Furthermore, it yields the water filling ratio corresponding to the different hydration states during adsorption and desorption of water vapor.

Keywords

AdsorptionDesorptionEarth-Alkaline CationsImmersion MicrocalorimetryMontmorilloniteRelative HumiditySurface AreaX-ray Diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 1 , February 1997 , pp. 8 - 22
Copyright
Copyright © 1997, The Clay Minerals Society

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