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Review of Hydrolysis Behavior of Ions in Aqueous Solutions*

Published online by Cambridge University Press:  28 February 2011

R. E. Mesmer  and
C. F. Baes Jr
R. E. Mesmer
Affiliation:
Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831
C. F. Baes Jr
Affiliation:
Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831
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Abstract

The word “hydrolysis,” literally “water splitting,” refers here to those reactions of metallic ions with water that liberate protons and produce hydroxy or oxy complexes in solution and precipitate hydroxide or oxide solids. Over the wide range of pH available in water, the strong tendency of hydroxide to bond to and bridge among cations leads to a multitude of species for many of the metals. Properties of the metal ion such as “hardness” and, especially, charge and size, determine the strength of these interactions and the species formed by each. Over 200 mononuclear species have been identified that predominate in dilute solutions across the pH scale. It is the stability of these species that largely determines the pH dependence of the solubility of the oxide or hydroxide solid formed. Both the tendency of the variety of polynuclear species (those containing more than one metal ion) to form and the solubility of the hydrolytic solid correlate with the stability of the first mononuclear species. Other correlations allow one to predict the enthalpy and entropy of a variety of hydrolysis reactions, and therefore the dependence of the stability of hydrolysis products on temperature.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 180: Symposium A – Better Ceramics Through Chemistry IV , 1990 , 85
Copyright
Copyright © Materials Research Society 1990

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Footnotes

*

Research sponsored by the Division of Chemical Sciences, Office of Basic Energy Sciences of the U. S. Department of Energy under contract DE-AC05–840R21400 with Martin Marietta Energy Systems, Inc.

References

REFERENCES

1. Baes, C. F. Jr. and Mesmer, R. E., The Hydrolysis of Cations, (John Wiley and Sons, New York, 1976;Google Scholar
1a second printing, Krieger, Robert E., Malabar, FL, 1986).Google Scholar
2. Baes, C. F. Jr. and Mesmer, R. E., Am. J. Science, 281, 935 (1981).Google Scholar
3. Johansson, C., Acta Chem. Scand., 14, 771 (1960).Google Scholar
4. Muha, G. M. and Vaughan, P. A., J. Chem. Phys., 33, 194 (1960).Google Scholar
5. Enderby, J. E., Cummings, S., Herdman, G. J., Nielson, G. W., Salmon, P. S., and Skipper, N., J. Phys. Chem., 91, 5851 (1987).Google Scholar
6. Robinson, R. A. and Harned, H. A., Chem. Rev., 28, 419 (1941).Google Scholar
7. Mesmer, R. E. and Baes, C. F. Jr., Inorg. Chem., 8, 618 (1969).Google Scholar
8. Bond, A. M. and Hefter, G. T., IUPAC Chem. Data Ser. 27, 1 (1980).Google Scholar
9. Shannon, R. D. and Prewitt, C. T., Acta Cryst., B25, 925 (1969).Google Scholar
10. Enüstün, B. V. and Turkevich, J., J. Amer. Chem. Soc., 82, 4502 (1960).Google Scholar
11. Schindler, P., “Heterogeneous Equilibria Involving Oxides, Hydroxides, Carbonates, and Hydroxide Carbonates,” Advances in Chemistry Series No. 67, p 196 (1967).Google Scholar
12. Sillen, L. G., “Polynuclear Complexes in Solution,” in Coordination Chemistry, ed. Martell, A. E., Vol. 1, 491–541 (1971).Google Scholar
13. Palmer, D. A. and Wesolowski, D. J., The Solubility of Gibbsite in Aqueous Sodium Chloride Solutins, “Proceedings of the 11th International Conference on the Properties of Steam, Prague, Czechoslovakia (1989).Google Scholar
14. Mesmer, R. E. and Baes, C. F. Jr., Inorg. Chem. 10, 2290 (1971).Google Scholar
15. Aveston, J., J. Chem. Soc., 4438 (1965).Google Scholar