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Adsorption of n-Aliphatic Alcohols from Dilute Aqueous Solutions on RNH3-Montmorillonites. III. Interlamellar Aggregation of the Adsorbate

Published online by Cambridge University Press:  02 April 2024

Michael S. Stul  and
Jozef De Bock
Michael S. Stul
Affiliation:
Laboratorium voor Oppervlaktescheikunde, Katholieke Universiteit Leuven, Kardinaal Mercierlaan 92, B-3030 Leuven (Heverlee), Belgium
Jozef De Bock
Affiliation:
Laboratorium voor Oppervlaktescheikunde, Katholieke Universiteit Leuven, Kardinaal Mercierlaan 92, B-3030 Leuven (Heverlee), Belgium
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Abstract

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The large amount of water in the interlamellar space of alkylammonium montmorillonites in aqueous solutions is not fixed by intercalated hexanol or octanol. The hydration of the NH3+-group and the filling of the empty spaces between the carbon chains are responsible for this phenomenon. Hydrogen bonds between the alcohols and the ammonium groups reduce the enthalpy of solution of hexanol and octanol in the interlamellar region at infinite dilution to +17.6 and +12.7 kJ/mole, respectively. Self-association of the alcohols further diminishes the enthalpy of solution at higher alcohol concentration. The interlamellar fixation of the RNH3 cations prevents a micellization as has been obtained in bulk solutions. At a given alcohol concentration smectic type aggregates, i.e., double layers of alcohol molecules, appear as shown by an increase of the basal spacing of the organo-clay complexes. The aggregate formation is favored by a longer chain length of both the cation and the alcohol.

Samenvatting

Samenvatting

Het hoge watergehalte van de interlamellaire faze van alkylammonium-montmorillonie-ten in waterige oplossing is niet gefixeerd door de binnenkomende hexanol of oktanol. De hydratatie van de NH3+-groep en het opvullen van de ruimtes tussen de koolwaterstofketens zijn er verantwoordelijk voor. Bij oneindige verdunning reduceren waterstofbruggen tussen alkoholen en ammoniumgroepen de oplossings-enthalpie van respektievelijk hexanol en oktanol in de interlamellaire faze tot +17,6 en 12,7 kJ/mol. Bij hogere alkoholkoncentratie vermindert deze oplossings-enthalpie verder door associatie van de alkoholen. De interlamellaire fixatie van RNH3 kationen verhindert het micellisatiefenomeen zoals het zich in bulk oplossingen voordoet. Bij een bepaalde alkoholkoncentratie duidt een verhoging van de basisafstand van de organo-kleikompleksen het optreden aan van aggregaten van het smektiet type, d.i. een dubbellaag van alkohol molekulen. Deze aggregaat vorming wordt bevorderd door een langere keten van zowel het kation als van de alkohol.

Keywords

AdsorptionAlcoholAlkylammonium cationsIntercalationMicellizationMontmorillonite
Type
Research Article
Information
Clays and Clay Minerals , Volume 33 , Issue 4 , August 1985 , pp. 350 - 356
Copyright
Copyright © 1985, The Clay Minerals Society

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