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A study of aluminum speciation in aluminum chloride solutions by small angle x-ray scattering and 27Al NMR

Published online by Cambridge University Press:  03 March 2011

Amit Singhal  and
Keith D. Keefer
Amit Singhal
Affiliation:
Department of Materials Science and Engineering, University of Cincinnati, Cincinnati, Ohio 45221-0012
Keith D. Keefer
Affiliation:
Department of Materials Science and Engineering, University of Cincinnati, Cincinnati, Ohio 45221-0012
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Abstract

Aluminum ions may exist in one of several different types of polynuclear species depending upon the degree to which it is hydrolyzed. The hydrolysis of aluminum can be explained by a metastable equilibrium among Al(H2O)3+6, Al(OH)(H2O)2+5, Al13O4(OH)24(H2O)7+12, and an oligomer. We have made small angle x-ray scattering and 27Al NMR measurements on 0.3 M aluminum chloride solutions over a range of OH/Al ratios. 27Al NMR shows two sharp peaks corresponding to the monomer Al(H2O)3+6 and the tetrahedrally coordinated aluminum in Al13O4(OH)24(H2O)7+12, and a broad peak due to the octahedrally coordinated aluminum in the oligomer. The observed radius of gyration (Rg) of the species in solution increases from 3.0 to 3.6 A, and the intensity at zero angle (which is proportional to the weight average molecular weight of the species) also increases as the OH/Al ratio increases from 1.0 to 2.2. The oligomer has an Rg of approximately 3.3 A, a hydrolysis ratio close to 2.0, and may be a six-membered ring with a structure similar to that of a gibbsite layer.

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Articles
Information
Journal of Materials Research , Volume 9 , Issue 8 , August 1994 , pp. 1973 - 1983
Copyright
Copyright © Materials Research Society 1994

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