Complexation by natural heterogeneous compounds: Site occupation distribution functions, a normalized description of metal complexation

Details Complexation by natural heterogeneous compounds: Site occupation distribution functions, a normalized description of metal complexation Complexation by natural heterogeneous compounds: Site occupation distribution functions, a normalized description of metal complexation

Jun 1990

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1990gecoa..54.1535b&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 54, Issue 6, pp.1535-1553

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This paper presents a new conceptual approach to interpreting titration curves of metal complexation by physically and chemically heterogeneous natural complexants such as humic acids, clays, complete soils, or sediments. The physico-chemical and analytical difficulties encountered with such systems are reviewed by comparison with a system containing only a few simple ligands, followed by discussion of the new approach on the same basis. It is shown that interpretation of heterogeneous complexant properties necessitates a preliminary transformation of experimental raw data into a function sufficiently normalized so as to allow comparison of results obtained under different conditions. A normalized function called a Site Occupation Distribution Function (SODF) and its potential usefulness is described here. The SODF is a readily computable function which relates the complexation buffer intensity of the system to the differential free energy of the complexation sites present. Its major interest is that it enables one to obtain both a rigorous mathematical description of the complexant properties (even when highly heterogeneous) at the macroscopic level and, in certain cases, an estimation of the molecular-scale behavior of particular site types. The relationship of the SODF to other distribution functions proposed in the literature is discussed and applications are exemplified using simulated and real natural systems. In particular, its utility is discussed in detail for 1. (1) discriminating between different site types (major, minor, dominant, background), 2. (2) evaluating the degree of heterogeneity of an unknown complexant system, 3. (3) estimating the nature and true thermodynamic constants of complexes, and 4. (4) yielding a rigorous definition of "complexation capacity."

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