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Thermodynamics of the stepwise formation of metal-ion complexes in aqueous solution

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Coordinative Interactions

Part of the book series: Structure and Bonding ((STRUCTURE,volume 15))

Abstract

On the whole, the thermodynamic functions found for the stepwise formation of complexes in aqueous solution agree very well with the models proposed for complexes of different character. Thus for interactions between hard acceptors and hard donors, postulated to be mainly electrovalent, the expected stepwise decrease of δS o n generally occurs, often accompanied by a similarly expected decrease of δH o n . With interactions between soft acceptors and soft donors, postulated to be mainly covalent, virtually constant values of δH o n from step to step are often found, while in other cases values of δH o n becomes step by step less exothermic. Both modes of behaviour are compatible with the current model.

The models applied are based on evidence from several fields, both thermodynamic and non-thermodynamic (1, 2, 10, 58, 63, 83–86). The fact that many characteristics pertaining to the consecutive steps are in good agreement with the models further augments their plausibility.

The trends of δH o n and δH o n indicate changes of coordination in the systems considered. Some of these discontinuities are already well known e.g. those occurring between the second and third step in Hg2+ systems. Others have not previously been very well established, such as those taking place after the second and third steps in several systems of Zn2+ and Cd2+, respectively. In other systems, e.g. the halides of Tl (III), equilibria between complexes of different coordination are indicated for several steps.

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  1. Inorganic Chemistry 1, Chemical Center, University of Lund, Lund, Sweden

    S. Ahrland

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Ahrland, S. (1973). Thermodynamics of the stepwise formation of metal-ion complexes in aqueous solution. In: Coordinative Interactions. Structure and Bonding, vol 15. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0036786

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  • DOI: https://doi.org/10.1007/BFb0036786

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