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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

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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References

Aveyard, R. and Mitchell, R. W., 1968 Heat of solution in water of the liquid methylene group at 25°C Trans. Faraday Soc. 64 1757–1762.CrossRefGoogle Scholar
Aveyard, R. and Mitchell, R. W., 1969 Distribution of n-alkanols between water and n-alkanes Trans. Faraday Soc. 65 2645–2653.CrossRefGoogle Scholar
Barrer, R. M., Papadopoulos, R. and Rees, L. V. C., 1967 Exchange of sodium in clinoptilolite by organic cations J. Inorg. Nucl. Chem. 29 2047–2063.CrossRefGoogle Scholar
Boruff, C. S., 1959 Report on fusel oil: colorimetric method for quantitative determination of fusel oil in distilled beverages J. Assoc. Off. Agric. Chem. 42 331–336.Google Scholar
Brown, G. E., Everett, D. H., Powell, A. V. and Thome, P. E., 1975 Adsorption and structuring phenomena at the solid/liquid interface Chem. Soc. Faraday Disc. 59 97–108.CrossRefGoogle Scholar
Brown, G. and MacEwan, D. M. C., 1949 The interpretation of X-ray diagrams of soil clays—II. Structures with random interstratification J. Soil Sci. 1 239–253.CrossRefGoogle Scholar
Danielsson, I. and Friberg, S., 1976 Lyotropicmesomorphism: phase equilibria and relation to micellar systems Lyotropic Liquid Crystals Washington, D.C. American Chem. Soc.Google Scholar
Ekwall, P., Mandell, L. and Solyom, P., 1971 The solution phase with reversed micelles in the cetyltrimethylammo-nium bromide-hexanol-water system J. Coll. Interface Sci. 35 266–272.CrossRefGoogle Scholar
German, W. L. and Harding, D. A., 1969 The adsorption of aliphatic alcohols by montmorillonite and kaolinite Clay Miner. 8 213–227.CrossRefGoogle Scholar
Guveli, D. E., Kayes, J. B. and Davis, S. S., 1979 Hydro-dynamic studies of micellar systems of alkyltrimethylam-monium bromides and the effect of added 1-alkanols J. Coll. Interface Sci. 72 130–139.CrossRefGoogle Scholar
Hansen, R. S. and Craig, R. P., 1954 The adsorption of aliphatic alcohols and acids from aqueous solutions by non-porous carbons J. Phys. Chern. 58 211–215.CrossRefGoogle Scholar
Hayase, K. and Hayano, S., 1978 Effect of alcohols on the critical micelle concentration decrease in the aqueous sodium dodecyl sulfate solution J. Coll. Interface Sci. 63 446–451.CrossRefGoogle Scholar
Herzfeld, S. H., Corrin, M. L. and Harkins, W. D., 1950 The effect of alcohols and of alcohols and salts on the critical micelle concentration of dodecylammonium chloride J. Phys. Colloid Chem. 54 271–283.CrossRefGoogle Scholar
Huyskens, P., Haulait-Pirson, M Cl, Hanssens, I. and Mullens, J., 1980 Fixation of water by alcohols in organic solvents J. Phys. Chem. 84 28–33.CrossRefGoogle Scholar
Kertes, A. S., Chaston, S. and Lai, W. C., 1980 Thermodynamics of microemulsion systems. 1. Enthalpies of solution in binary and ternary systems of octane, octanol and octanoic acid J. Coll. Interface Sci. 73 94–104.CrossRefGoogle Scholar
Lagaly, G., Weiss, A. and Heller, L., 1969 Determination of the layer charge in mica type layer silicates Proc. Int. Clay Conf, Tokyo Jerusalem Israel Universities Press 61–80.Google Scholar
Lagaly, G. and Weiss, A., 1969 Zur van der Waals Wechselwirkung in n-dodecylammonium-Schichtsilicaten: Z Naturforschung. 24b 1057–1058.CrossRefGoogle Scholar
Lagaly, G. and Weiss, A., 1970 Anordnung und Orientierung kationischer Tenside auf ebenen silicatoberflächen. II. Anordnung von n-Alkylammonium ionen in Schichtzwischenraum von Glimmern Kolloid Z. Z. Polym. 237 364–368.CrossRefGoogle Scholar
Lagaly, G. and Weiss, A., 1971 Schichteinlagerungsverbindungen als Modelle für Struktur und Strukturumwandlungen von monomolekularen und bimolekularen Schichten langkettiger Verbindungen. I. n-Alkylammonium-Schichtsilicate mit primären n-Alkanolen Kolloid Z. Z. Polym. 248 968–978.CrossRefGoogle Scholar
Lagaly, G., Weiss, A., Serratosa, , Sanchez, , 1972 Conformational changes of long chain molecules in the interlayer space of swelling mica-type layer silicates Proc. Int. Clay Conf., Madrid, 1972 Madrid Division de Ciencias C.S.I.C. 637–649.Google Scholar
Lagaly, G., Weiss, A. and Bailey, S. W., 1976 The layer charge of smectite layer silicates Proc. Int. Clay Conf, Mexico City, 1975 157–172.Google Scholar
Mishra, R. K., Chander, S. and Fuerstenau, D. W., 1980 Effect of ionic surfactants on the electrophoretic mobility of hydroxyapatite Colloids and Surfaces 1 105–119.CrossRefGoogle Scholar
Nery, H., Marchai, J. P., Canet, D. and Cases, J. M., 1980 NMR study of alkylammonium chlorides. 1. Proton longitudinal relaxation times and linewidths of isotropic mi-cellar medium J. Coll. Interface Sci. 77 174–181.CrossRefGoogle Scholar
Ratkovics, F. and László, M., 1973 Properties of some alcohol/amine mixtures. II. The heat of mixing n-butyl-amine with n-primary alcohols Acta Chim. Acad. Sci. Hung. 79 395–400.Google Scholar
Somasundaran, P., Healy, T. W. and Fuerstenau, D. W., 1964 Surfactant adsorption at the solid-liquid interface-dependence of mechanism on chain length J. Phys. Chem. 68 3562–3566.CrossRefGoogle Scholar
Stul, M., Maes, A. and Uytterhoeven, J. B., 1978 The adsorption of n-aliphatic alcohols from dilute aqueous solutions on RNH3-montmorillonites. I. Distribution at infinite dilution Clays & Clay Minerals 26 309–317.CrossRefGoogle Scholar
Stul, M. and Mortier, W. J., 1974 The heterogeneity of the charge density in montmorillonites Clays & Clay Minerals 22 391–396.CrossRefGoogle Scholar
Stul, M., Uytterhoeven, J. B., De Bock, J. and Huyskens, P., 1979 The adsorption of n-aliphatic alcohols from dilute aqueous solutions on RNH3-montmorillonites. II. Inter-lamellar association of the adsorbate Clays & Clay Minerals 27 377–386.CrossRefGoogle Scholar