Hostname: page-component-586b7cd67f-2brh9 Total loading time: 0 Render date: 2024-11-23T01:24:52.880Z Has data issue: false hasContentIssue false

Reaction of OH-Al Polymers with Smectites and Vermiculites

Published online by Cambridge University Press:  28 February 2024

Pa Ho Hsu*
Affiliation:
Department of Environmental Sciences Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Five montmorillonites, one hectorite, and two vermiculites were treated with OH-Al solutions containing rapid- and slow-reacting polymers of similar concentrations. With all smectites, both rapid- and slow-reacting OH-Al polymers were much more preferentially adsorbed than monomeric species. Relatively slow-reacting OH-Al polymers were more preferentially adsorbed than rapid-reacting ones. The average basicity of the adsorbed Al was 2.46, which was close to that of the OH-Al polymers in the original solution. The OH-Al polymers that enter the interlayer resemble those in original solutions.

With vermiculites, the solution concentration of rapid-reacting OH-Al polymers was much reduced after reaction. The average basicity of the adsorbed Al was 1.99, which was considerably lower than that in the original solution. It is postulated that OH-Al polymers break to monomeric Al ions and then enter the clay. The monomeric Al species that enter the clay interlayers hydrolyze and polymerize in situ and become fixed. The H+ ions released from hydrolysis convert the rapid-reacting OH-Al polymers to monomeric Al in solution. Limited amounts of slow-reacting polymers were adsorbed because of their resistance to acid depolymerization.

Type
Research Article
Copyright
Copyright © 1992, The Clay Minerals Society

Footnotes

New Jersey Agricultural Experiment Station Publication No. D-07425-1-91.

References

Akitt, J. W. and Farthing, A., New 27Al NMR studies of the hydrolysis of the aluminum(IIl) cation J. Magn. Reson. 1978 32 345352.Google Scholar
Akitt, J. W., Greenwood, N. N., Khandelwal, B. L. and Lester, G. D., 27Al nuclear magnetic resonance studies of the hydrolysis and polymerization of the hexa-aqua-aluminum(III) cation J. Chem. Soc. Dalton Trans. 1972 1972 604610 10.1039/dt9720000604.CrossRefGoogle Scholar
Barnhisel, R. I., Bertsch, P. M., Dixon, J. B. and Weed, S. W., Chlorites and hydroxy-interlayered vermiculite and smectites: Chap. 15 Minerals in Soil Environment 1989 2nd ed. Madison, Wisconsin Soil Science Society of America 729788.Google Scholar
Bertsch, P. M., Layton, W. J. and Bamhisel, R. I., Speciation of hydroxy-Al solutions by wet chemical and 27Al NMR methods Soil Sci. Soc. Amer. J. 1986 50 14491454 10.2136/sssaj1986.03615995005000060014x.CrossRefGoogle Scholar
Bertsch, P. M., Thomas, G. H. and Bamhisel, R. I., Characterization of hydroxy-aluminum solutions by aluminum-27 nuclear magnetic resonance spectroscopy Soil Sci. Soc. Amer. J. 1986 50 825830 10.2136/sssaj1986.03615995005000030051x.Google Scholar
Bottero, J. Y., Cases, J. M., Fiessinger, F. and Poirier, J. E., Studies of hydrolyzed aluminum chloride solutions. 1. Nature of aluminum species and composition of aqueous solutions J. Phys. Chem. 1980 84 29332939 10.1021/j100459a021.CrossRefGoogle Scholar
Brindley, G. W. and Semples, R. W., Preparation and properties of some hydroxy-aluminum beidellites Clay Miner. 1977 12 229237 10.1180/claymin.1977.012.3.05.Google Scholar
Brosset, C., Biederman, G. and Sillen, L. G., Studies on the hydrolysis of metal ions. XI. The aluminum ion, Al3+ Acta Chem. Scand. 1954 8 19171926 10.3891/acta.chem.scand.08-1917.Google Scholar
Denney, D. and Hsu, P. H., 27Al nuclear magnetic resonance and ferron kinetic studies of partially neutralized AlCl3 solutions Clays & Clay Minerals 1986 34 604607 10.1346/CCMN.1986.0340516.Google Scholar
Fripiat, J. J., High resolution solid state NMR study of pillared clays Catalysis Today 1988 2 281295 10.1016/0920-5861(88)85010-7.Google Scholar
Hsu, P. H., Heterogeneity of montmorillonite surface and its effect on the nature of hydroxy-aluminum interlayers Clays & Clay Minerals 1968 16 303311 10.1346/CCMN.1968.0160407.Google Scholar
Hsu, P. H., Mechanism of gibbsite crystallization from partially neutralized aluminum chloride solutions Clays & Clay Minerals 1988 36 2530 10.1346/CCMN.1988.0360104.Google Scholar
Hsu, P. H., Dixon, J. B. and Weed, S. W., Aluminum hydroxides and oxyhydroxides: Chap. 7 Minerals in Soil Environments 1989 2nd ed. Madison, Wisconsin Soil Science Society of America 331378.Google Scholar
Hsu, P. H. and Bates, T. F., Fixation of hydroxyaluminum polymer by vermiculite Soil Sci. Soc. Amer. Proc. 1964 28 763769 10.2136/sssaj1964.03615995002800060025x.CrossRefGoogle Scholar
Hsu, P. H. and Cao, D., Effects of acidity and hydroxylamine on the determination of aluminum with ferron Soil Sci. 1991 152 210219 10.1097/00010694-199109000-00008.CrossRefGoogle Scholar
Jardine, P. M., Zelazny, L. W. and Parker, J. C., Mechanisms of aluminum adsorption on clay minerals and peat Soil Sci. Soc. Amer. J. 1985 49 862867 10.2136/sssaj1985.03615995004900040015x.CrossRefGoogle Scholar
Johansson, G., On the crystal structures of basic aluminum sulfate, 13Al2O3 6SO3 H2O Ark. Kemi. 1963 20 321342.Google Scholar
Pinnavaia, T. J., Intercalated clay catalysts Science 1983 220 365371 10.1126/science.220.4595.365.Google Scholar
Pinnavaia, T. J., Tzou, M.-S. Landau, S. D. and Raythatha, R. H., On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum J. Mol. Catal. 1984 27 195212 10.1016/0304-5102(84)85080-4.Google Scholar
Plee, D., Borg, L., Gatineau, L. and Fripiat, J. J., High resolution solid state 27Al and 29Si nuclear magnetic resonance study of pillared clay J.Amer. Chem. Soc. 1985 107 23622369 10.1021/ja00294a028.Google Scholar
Plee, D., Borg, L., Gatineau, L. and Fripiat, J. J., Pillaring processes of smectites with and without tetrahedral substitution Clays & Clay Minerals 1987 35 8188 10.1346/CCMN.1987.0350201.CrossRefGoogle Scholar
Schutz, A., Stone, W E E Poncelet, G. and Fripiat, J. J., Preparation and characterization of bidimensional zeolitic structures obtained from synthetic beidellite and hydroxy-aluminum solutions Clays & Clay Minerals 1987 35 251261 10.1346/CCMN.1987.0350402.Google Scholar
Tsai, P. P. and Hsu, P. H., Studies of aged OH-Al solutions using kinetics of Al-ferron reactions and sulfate precipitation Soil Sci. Soc. Amer. J. 1984 48 5965 10.2136/sssaj1984.03615995004800010011x.Google Scholar
Tsai, P. P. and Hsu, P. H., Aging of partially neutralized aluminum solutions of NaOH/Al molar ratio = 2.2 Soil Sci. Soc. Amer. J. 1985 49 10601065 10.2136/sssaj1985.03615995004900040053x.Google Scholar
Turner, R. C., Effect of aging on properties of polynuclear hydroxyaluminum cations Can. J. Chem. 1976 54 15281534 10.1139/v76-220.Google Scholar
Turner, R. C., A second species of polynuclear hydroxyaluminum cation, its formation and some of its properties Can. J. Chem. 1976 54 19101915 10.1139/v76-273.CrossRefGoogle Scholar
Vaughan, D E W and Lussier, R. J., Preparation of molecular sieves based on pillared interlayered clays Proc. 5th International Conference on Zeolites 1980.Google Scholar
Veith, J. A., Selectivity and adsorption capacity of smectite and vermiculite for aluminum of varying basicity Clays & Clay Minerals 1978 26 4550 10.1346/CCMN.1978.0260105.CrossRefGoogle Scholar
Veith, J. A., Basicity of exchangeable aluminum, formation of gibbsite, and composition of the exchange acidity in the presence of exchanger Soil Sci. Soc. Amer. J. 1978 41 865870 10.2136/sssaj1977.03615995004100050010x.Google Scholar
Zelazny, L. W., Jardine, P. M. and Sposito, G., Surface reaction of aqueous aluminum species The Environmental Chemistry of Aluminum 1989 Boca Raton, Florida CRC Press Inc. 148178.Google Scholar