Hostname: page-component-cd9895bd7-jkksz Total loading time: 0 Render date: 2024-12-24T12:25:22.688Z Has data issue: false hasContentIssue false

The Nature of Polynuclear OH-Al Complexes in Laboratory-Hydrolyzed and Commercial Hydroxyaluminum Solutions

Published online by Cambridge University Press:  28 February 2024

Wei-Zi Wang
Affiliation:
State University of New Jersey—Rutgers—The Department of Environmental Sciences, Cook College, New Brunswick, New Jersey 08903-0231
Pa Ho Hsu
Affiliation:
State University of New Jersey—Rutgers—The Department of Environmental Sciences, Cook College, New Brunswick, New Jersey 08903-0231
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.

Laboratory-hydrolyzed and commercial OH-Al solutions were characterized using kinetics of Al-ferron color development, kinetics of structural OH neutralization with H+, 27Al NMR spectroscopy, and sulfate precipitation. The results showed that the Al13 complexes having the Keggin structure were dominant only in fresh, laboratory-hydrolyzed OH-Al solutions of OH/Al molar ratio = 1.8 and above. These species gradually converted to other polynuclear forms that reacted with ferron slowly, were not detectable by 27Al NMR spectroscopy, and yielded different basic Al sulfates following Na2SO4 addition. These more stable complexes can best be interpreted to have a Al(OH)3-fragment structure. In the three commercial aluminum chlorohydrate (ACH) solutions studied, Al13 complexes accounted for a small portion of the total Al present. More than 80% of the Al was present as species that were not detectable with NMR spectroscopy and resembled the slow-reacting complexes in aged, laboratory-hydrolyzed OH-Al solutions. Small portions of the slow-reacting complexes appeared to be submicron particulates that acted as nuclei for gibbsite formation or aggregates of Al13 complexes that dispersed to Al13 upon dilution. Polyaluminum chloride (PA) solution resembled the moderately aged laboratory-hydrolyzed OH-Al solutions.

Type
Research Article
Copyright
Copyright © 1994, Clay Minerals Society

Footnotes

1

New Jersey Agricultural Experiment Station Publication No. D-07424-1-93.

References

Akitt, J. W., and Farthing, A., (1981) Aluminum-27 nuclear magnetic resonance studies of the hydrolysis of aluminum(III). Part 4. Hydrolysis using sodium carbonate: J. Chem. Soc. Dalton Trans. 1981, 16171623.CrossRefGoogle Scholar
Bersillon, J., Hsu, Pa Ho, and Fiessinger, F., (1980) Characterization of hydroxy-aluminum solutions: Soil Sci. Soc. Amer. J. 44, 630634.CrossRefGoogle Scholar
Bertsch, P. M., (1987) Conditions for Al13 polymer formation in partially neutralized Al solutions: Soil Sci. Soc. Amer. J. 51, 825828.CrossRefGoogle Scholar
Bertsch, P. M., (1989) Aqueous polynuclear aluminum species: in The Environmental Chemistry of Aluminum, Sposito, G., ed., CRC Press Inc., Boca Raton, Florida.Google Scholar
Bertsch, P. M., Thomas, G. H., and Barnhisel, R. I., (1986) Characterization of hydroxy-aluminum solutions by aluminum-27 nuclear magnetic resonance spectroscopy: Soil Sci. Soc. Amer. J. 50, 825830.CrossRefGoogle Scholar
Buffle, J., Parthasarathy, N., and Haerdi, W., (1985) Importance of speciation methods in analytical control of water treatment processes with application to fluoride removal from waste waters: Water Res. 19, 723.CrossRefGoogle Scholar
Denney, D., and Hsu, Pa Ho 1986() 27Al nuclear magnetic resonance and ferron kinetic studies of partially neutralized AlCl3 solutions: Clays & Clay Minerals 34, 604607.CrossRefGoogle Scholar
Hesterberg, D., and Reed, M., (1991) Volumetric treatment efficiencies of some commercial clay stabilizers: SPE Prod. Eng. 6, 5762.CrossRefGoogle Scholar
Hsu, Pa Ho 1988() Mechanism of gibbsite crystallization from partially neutralized aluminum chloride solutions: Clays & Clay Minerals 36, 2530.Google Scholar
Hsu, Pa Ho 1989() Aluminum Hydroxides and Oxyhydroxides: in Minerals in Soil Environments: 2nd ed., J. B. Dixon and S. W. Weed, eds., Soil Science Society of America, Madison, Wisconsin, 331378.Google Scholar
Hsu, Pa Ho 1992() Reaction of OH-Al polymers with smectites and vermiculites: Clays & Clay Minerals 40, 300305.CrossRefGoogle Scholar
Hsu, Pa Ho and Cao, Dan-Xia 1991() Effects of acidity and hydroxylamine hydrochloride on the determination of aluminum with ferron: Soil Sci. 152, 210219.CrossRefGoogle Scholar
Johansson, G., (1960) On the crystal structures of some basic aluminum salts: Acta Chem. Scand. 14, 771773.CrossRefGoogle Scholar
Johansson, G., (1963) On the crystal structures of basic aluminum sulfate, 13Al2O3 6SO3 H2O: Ark. Kemi. 20, 321342.Google Scholar
Pinnavaia, T. J., (1983) Intercalated clay catalysts: Science 220, 365371.CrossRefGoogle ScholarPubMed
Pinnavaia, T. J., Tzou, Ming-Shin Landau, S. D., and Raythatha, R. H., (1984) On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum: J. Mol. Catal. 27, 195212.CrossRefGoogle Scholar
Reed, M., (1972) Stabilization of formation clays with hydroxy-aluminum solutions: J. Pet. Tech. 24, 860864.CrossRefGoogle Scholar
Teagarden, D. L., Kozlowski, J. F., White, J. L., and Hem, S. L., (1981) Aluminum chlorohydrate I. Structure studies: J. Pharma. Sci. 70, 758761.CrossRefGoogle ScholarPubMed
Tsai, Ping Ping and Hsu, Pa Ho 1984() Studies of aged OH-Al solutions using kinetics of Al-ferron reactions and sulfate precipitation: Soil Sci. Soc. Amer. J. 48, 5965.CrossRefGoogle Scholar
Tsai, Ping Ping and Hsu, Pa Ho. 1985 () Aging of partially neutralized aluminum solutions of NaOH/Al molar ratio = 2.2: Soil Sci. Soc. Amer. J. 49, 10601065.CrossRefGoogle Scholar