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Article << Previous     |     Next >>   Contents Vol 12(1)

Ligand- and oxygen-isotope-exchange pathways of geochemical interest

William H. Casey A

Department of Chemistry and Department of Geology, University of California, 1 Shields Lane, Davis, CA 95616, USA. Email: whcasey@ucdavis.edu

Environmental Chemistry 12(1) 1-19 http://dx.doi.org/10.1071/EN14043
Submitted: 28 February 2014  Accepted: 27 May 2014   Published: 7 January 2015


 
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Environmental context. Most chemical processes in water are either ligand- or electron-exchange reactions. Here the general reactivity trends for ligand-exchange reactions in aqueous solutions are reviewed and it is shown that simple rules dominate the chemistry. These simple rules shed light on most molecular processes in water, including the uptake and degradation of pesticides, the sequestration of toxic metals and the corrosion of minerals.

Abstract. It is through ligand-exchange kinetics that environmental geochemists establish an understanding of molecular processes, particularly for insulating oxides where there are not explicit electron exchanges. The substitution of ligands for terminal functional groups is relatively insensitive to small changes in structure but are sensitive to bond strengths and acid–base chemistry. Ligand exchanges involving chelating organic molecules are separable into two classes: (i) ligand substitutions that are enhanced by the presence of the chelating ligand, called a ‘spectator’ ligand and (ii) chelation reactions themselves, which are controlled by the Lewis basicity of the attacking functional group and the rates of ring closure. In contrast to this relatively simple chemistry at terminal functional groups, substitutions at bridging oxygens are exquisitely sensitive to details of structure. Included in this class are oxygen-isotope exchange and mineral-dissolution reactions. In large nanometer-sized ions, metastable structures form as intermediates by detachment of a surface metal atom, often from a underlying, highly coordinated oxygen, such as μ4-oxo, by solvation forces. A metastable equilibrium is then established by concerted motion of many atoms in the structure. The newly undercoordinated metal in the intermediate adds a water or ligand from solution, and protons transfer to other oxygens in the metastable structure, giving rise to a characteristic broad amphoteric chemistry. These metastable structures have an appreciable lifetime and require charge separation, which is why counterions affect the rates. The number and character of these intermediate structures reflect the symmetry of the starting structure.



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