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A view of reactions at mineral surfaces from the aqueous phase

Published online by Cambridge University Press:  05 July 2018

W. H. Casey
W. H. Casey*
Affiliation:
Department of Land, Air and Water Resources, Department of Geology, University of California, Davis, CA 95616, USA
*
*E-mail: whcasey@ucdavis.edu
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Abstract

The processes by which a metal–oxygen bond dissociates in aqueous complexes are discussed and the reactions related to more complicated pathways of mineral dissolution. The dissolution of oxide minerals, and in fact many other classes of surface reactions, can be viewed as a ligand-exchange reaction because the bridging oxygens that link the metal to the mineral are progressively replaced by non-bridging functional groups. These ligand-exchange reactions are accelerated by protonations, hydroxylations and ligand substitutions that modify the lability of surface oxygens, but always at specific sites. Molecular information is important because reactions at some sites retard rates while reaction at other sites enhance them. Virtually all of the important variables that affect these reaction rates are local.

Keywords

dissolutionligand-exchangeoxide mineralsmineral surfaces
Type
Research Article
Information
Mineralogical Magazine , Volume 65 , Issue 3 , June 2001 , pp. 323 - 337
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2001

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References

Burgess, J. (1988) Ions in Solution: Basic Principles of Chemical Interactions. Ellis Horwood, Chichester.Google Scholar
Casey, W.H. (1991) On the relative dissolution rates of some oxide and orthosilicate minerals. J. Coll. Interf. Sci., 146, 586–9.CrossRefGoogle Scholar
Casey, W.H. and Phillips, B.L. (2001) Kinetics of oxygen exchange between sites in th e GaO4Al12(OH)24(H2O)12 7+(aq) molecule and aqueous solution. Geochim. Cosmochim. Acta, 65, 705–14.CrossRefGoogle Scholar
Casey, W.H. and Sposito, G. (1992) On the temperature dependence of mineral dissolution rates. Geochim. Cosmochim. Acta, 56, 3825–30.CrossRefGoogle Scholar
Casey, W.H. and Westrich, H.R. (1992) Control of dissolution rates of orthosilicate minerals are controlled by divalent metal-oxygen bonds. Nature, 355, 157–9.CrossRefGoogle Scholar
Casey, W.H., Phillips, B.L., Karlsson, M., Nordin, S., Nordin, J.P., Sullivan, D.J. and Neugebauer-Crawford, S. (2000) Rates and mechanisms of oxygen exchanges between sites in the AlO4Al12(OH)24(H2O)12 7+(aq) complex and water: Implications for mineral surface chemistry. Geochim. Cosmochim. Acta, 64, 2951–64.CrossRefGoogle Scholar
Cotton, F.A. and Wilkinson, G. (1988) Advanced Inorganic Chemistry. Wiley-Interscience.Google Scholar
Crimp, S.J., Spiccia, L., Krouse, H.R. and Swaddle, T.W. (1994) Early stages of the hydrolysis of chromium(III) in aqueous solutions. 9. Kinetics of water exchange on the hydrolytic dimer. Inorg. Chem., 33, 465–70.CrossRefGoogle Scholar
Furrer, G. and Stumm, W. (1986) The coordination chemistry of weathering: I. Dissolution kinetics of δ-Al2O3 and BeO. Geochim. Cosmochim. Acta, 50, 1847–60.CrossRefGoogle Scholar
Hachiya, K., Sasaki, M., Ikeda, T., Mikami, N. and Yasunaga, T. (1984) Static and kinetic studies of adsorption-desorption of metal ions on a γ-Al2O3 surface 2. Kinetic study by means of pressure-jump technique. J. Phys. Chem., 88, 27–31.CrossRefGoogle Scholar
Margerum, D.W., Cayley, G.R., Weatherburn, D.C. and Pagenkopf, G.K. (1978) Kinetics and mechanisms of complex formation and ligand exchange. Amer. Chem. Soc. Monograph, 174, 1–220.Google Scholar
Murmann, R.K. (1980) Studies of the rates of isotopic oxygen exchange between aquated molybdenum(V) and solvent water. Inorg. Chem., 19, 1765–70.CrossRefGoogle Scholar
Nordin, J.P., Sullivan, D.J., Phillips, B.L. and Casey, W.H. (1998) An 17O-NMR study of the exchange of water on AlOH(H2O)5 2+(aq). Inorg. Chem., 37, 4760–3.CrossRefGoogle Scholar
Nordin, J.P., Sullivan, D.J., Phillips, B.L. and Casey, W.H. (1999) Mechanisms for fluoride-promoted dissolution of bayerite [β-Al(OH)3(s)] and boehmite [γ-AlOOH]: 19F-NMR spectroscopy and aqueous surface chemistry. Geochim. Cosmochim. Acta, 63, 3513–24.CrossRefGoogle Scholar
Phillips, B.L., Casey, W.H. and Karlsson, M. (2000) Bonding and reactivity at oxide mineral surfaces from model aqueous complexes. Nature, 404, 379–82.CrossRefGoogle ScholarPubMed
Richens, D.T. (1997) The Chemistry of Aqua Ions. Wiley, New York.Google Scholar
Richens, D.T. (1989) Crystal structure of and mechanism of water exchange on [Mo3O4(OH2)]4+ from X-ray and oxygen-17 NMR studies. Inorg. Chem., 28, 1394–402.CrossRefGoogle Scholar
Sparks, D.L. (1989) Kinetics of Soil Chemical Processes. Academic Press, London.Google Scholar
Springborg, J. (1988) Hydroxo-bridged complexes of chromium(III ), cobalt (III ), rhodium(III) and iridium(III). Adv. Inorg. Chem., 32, 55–169.CrossRefGoogle Scholar
Stone, A.T. (1997) Reactions of extracellular organic ligands with dissolved metal ions and mineral surfaces. Pp. 309–43 in: Geomicrobiolo gy: Interactions between Microbes and Minerals (Banfield, J.F., and Nealson, K.H., editors). Reviews in Mineralogy, 35. Mineralogical Society of America, Washington, D.C. CrossRefGoogle Scholar
Stumm, W. (1992) Chemistry of the Solid-Water Interface. Wiley-Interscience, New York.Google Scholar
Stünzi, H. and Marty, W. (1983) Early stages of the hydrolysis of chromium(III) in aqueous solution. 1. Characterization of a tetrameric species. Inorg. Chem., 22, 2145–50.CrossRefGoogle Scholar
Sullivan, D.J., Nordin, J.P., Phillips, B.L. and Casey, W.H. (1999) The rates of water exchange in Al(III)- salicylate and Al(III)-sulfosalicylate complexes. Geochim. Cosmochim. Acta, 63, 1471–80.CrossRefGoogle Scholar
Wirth, G.S. and Geiskes, J.M. (1979) The initial kinetics of dissolution of vitreous silica in aqueous media. J. Coll. Interf. Sci., 68, 492–500.CrossRefGoogle Scholar