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Hard and Soft Acid-Base Model Applied to Bivalent Cation Selectivity on a 2:1 Clay Mineral

Published online by Cambridge University Press:  28 February 2024

M. Auboiroux ,
F. Melou ,
F. Bergaya  and
J. C. Touray
M. Auboiroux
Affiliation:
UMR CNRS-Université d'Orléans 6530, Ecole Supérieure de l'Energie et des Matériaux, Rue Léonard de Vinci, 45072 Orleans, CEDEX 2, France CNRS-Université d'Orléans, Centre de Recherche sur la Matiére Divisée, 1B Rue de la Férollerie, 45071 Orleans, CEDEX 2, France
F. Melou
Affiliation:
UMR CNRS-Université d'Orléans 6530, Ecole Supérieure de l'Energie et des Matériaux, Rue Léonard de Vinci, 45072 Orleans, CEDEX 2, France
F. Bergaya
Affiliation:
CNRS-Université d'Orléans, Centre de Recherche sur la Matiére Divisée, 1B Rue de la Férollerie, 45071 Orleans, CEDEX 2, France
J. C. Touray
Affiliation:
UMR CNRS-Université d'Orléans 6530, Ecole Supérieure de l'Energie et des Matériaux, Rue Léonard de Vinci, 45072 Orleans, CEDEX 2, France
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Abstract

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We applied the hard and soft acid-base (HSAB) model (Xu and Harsh 1990a, 1990b) to bivalent cation exchange on a purified Ca-montmorillonite. As a result, a satisfactory model is proposed to describe the gradual selectivity of exchange with Ca for 4 of the 6 metals studied (Cd, Cu, Pb, Zn). The selectivity is predicted as a function of the differences of electronegativity and softness of the metals. The deviation of Ni and Co data from the predicting model is interpreted in terms of hydration (Ni and Co being the most strongly hydrated ions). The fitting parameters of the model, α and β, are related to the electronegativity and softness characteristics of the surface, respectively. Their ratio gives information on the nature of bonding. Results suggest that covalent bonding modifies electrostatic interactions, which in turn affect selectivity, with an increasing influence of covalent bondings in the order: Pb < Cd < Zn < Cu.

To balance the lack of representativity of the model for the small molar fraction (NM), we propose to associate to the HSAB model an equation describing the variation of the Vanselow selectivity coefficient as a function of the molar fraction of metal on clay.

Keywords

Bivalent CationsCovalent BondingElectronegativityHSABMontmorilloniteSelectivity CoefficientSoftness
Type
Research Article
Information
Clays and Clay Minerals , Volume 46 , Issue 5 , October 1998 , pp. 546 - 555
Copyright
Copyright © 1998, The Clay Minerals Society

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