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Interactions of Citric Acid and Synthetic Hydroxy-Aluminum Montmorillonite

Published online by Cambridge University Press:  02 April 2024

P. Cambier  and
Garrison Sposito
P. Cambier
Affiliation:
Station de Science du Sol, Institut National de la Recherche Agronomique, Route de Saint-Cyr, 78026 Versailles Cedex, France
Garrison Sposito
Affiliation:
Department of Soil Science, University of California, Berkeley, California 94720
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Abstract

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Hydroxy-Al-montmorillonite was prepared by mixing Na-Wyoming montmorillonite with Al(OH)2.5 polycations and aging the mixture for 10 days. The reactions of this complex with citric acid at millimolar concentrations were investigated at different pHs for a 4-hr reaction time. The citrate sorption data, X-ray powder diffraction patterns of the montmorillonite adsorbent, and solubility products for Al(OH)3, estimated after computer speciation of the aqueous solution phase, suggested two reaction mechanisms, depending on pH. At 4 < pH < 5.5, the complex was stable, and only external hydroxy-Al polycations could react with citrate, yielding a sorption envelope characteristic of an acid having a low pKa. At higher pH, and particularly at pH > 7, the interlayer Al-polymers became accessible to the ligand and desorbed quickly from the montmorillonite basal planes to form a new, external, X-ray-amorphous solid phase with citrate. This reaction produced a large second peak in the sorption envelopes near pH 8, which was controlled by the increasingly negative surface charge at high pH and by the initial concentration of citric acid. This ligand accelerated, i.e., favored kinetically, the dissociation of adsorbed hydroxy-Al polymers from montmorillonite at pH > 7.

Résumé

Résumé

On prépare une smectite hydroxyalumineuse en mélangeant et en laissant en suspension 10 jours une montmorillonite du Wyoming Na et des polycations Al(OH)2.5. Les réactions de ce complexe avec l'acide citrique en concentration millimolaire et à différent pH sont analysées à partir des quantités de citrate adsorbé, de la diffraction X appliquée à des dépôts orientés de l'argile ayant réagi, du calcul du produit de solubilité Al(OH)3 et des concentrations des diverses espèces en solution. Deux mécanismes sont invoqués selon les domaines de pH. A 4 < pH < 5.5, le complexe est stable et seuls les polymères d'Al des surfaces externes peuvent réagir avec le citrate, conduisant à une fixation de citrate faible, caractérisée par des courbes en fonction du pH avec un maximum apparent. A pH plus élevé et surtout à pH >7, tous les polymères d'Al deviennent accessibles au ligand. et sont rapidement détachés des surfaces basales pour former avec le citrate une nouvelle phase amorphe en dehors des feuillets de l'argile. Cette dernière réaction se traduit par un deuxième maximum plus important dans les courbes enveloppes, vers pH 8, dont l'amplitude est limitée par l'effet de l'augmentation des charges négatives à pH élevé, et par la quantité initiale de citrate. Cet anion accélère la dissociation des polymères d'Al et de la montmorillonite à pH > 7.

Keywords

AdsorptionCitric acidHydroxy-AlMontmorilloniteX-ray powder diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 39 , Issue 2 , April 1991 , pp. 158 - 166
Copyright
Copyright © 1991, The Clay Minerals Society

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