Staff Publications

Staff Publications

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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

    Full text documents are added when available. The database is updated daily and currently holds about 240,000 items, of which 72,000 in open access.

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Record number 362359
Title Impact of ligand protonation on eigen-type metal complexation kinetics in aqueous systems
Author(s) Leeuwen, H.P. van; Town, R.M.; Buffle, J.
Source The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment, & General Theory 111 (2007)11. - ISSN 1089-5639 - p. 2115 - 2121.
Department(s) Physical Chemistry and Colloid Science
Publication type Refereed Article in a scientific journal
Publication year 2007
Keyword(s) deposition potential sscp - stripping chronopotentiometry - dissociation kinetics - speciation analysis - planar diffusion - lability - association - cadmium - ions - thermodynamics
Abstract The impact of ligand protonation on metal speciation dynamics is quantitatively described. Starting from the usual situation for metal complex formation reactions in aqueous systems, i.e., exchange of water for the ligand in the inner coordination sphere as the rate-determining step (Eigen mechanism), expressions are derived for the lability of metal complexes with protonated and unprotonated ligand species being involved in formation of the precursor outer-sphere complex. A differentiated approach is developed whereby the contributions from all outer-sphere complexes are included in the rate of complex formation, to an extent weighted by their respective stabilities. The stability of the ion pair type outer-sphere complex is given particular attention, especially for the case of multidentate ligands containing several charged sites. It turns out that in such cases, the effective ligand charge can be considerably different from the formal charge. The lability of Cd(II) complexes with 1,2-diaminoethane-N,N'-diethanoic acid at a microelectrode is reasonably well predicted by the new approach.
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