Comparison of AGNES (absence of gradients and Nernstian equilibrium stripping) and SSCP (scanned stripping chronopotentiometry) for trace metal speciation analysis

The free metal ion concentrations obtained by SSCP (stripping chronopotentiometry at scanned deposition potential) and by AGNES (absence of gradients and Nernstian equilibrium stripping) techniques have been compared and the usefulness of the combination of both techniques in the same electrochemical cell for trace metal speciation analysis is assessed. The free metal ion concentrations and the stability constants obtained for lead(II) and cadmium(II) complexation by pyridinedicarboxylic acid, by 40 nm radius carboxylated latex nanospheres and by a humic acid extracted from an ombrotrophic peat bog were determined. Whenever possible, the free metal ion concentrations were compared with the theoretical predictions of the code MEDUSA and with the free metal ion concentrations estimated from ion selective electrodes (ISE). SSCP values were in agreement with the ones obtained by AGNES, and both of them agreed reasonably with the ISE values and the theoretical predictions. For the lead(II)-humic acid, it was not possible to obtain the stability constants by SSCP due to the heterogeneity effect. However, using AGNES it is possible to obtain, for these heterogeneous systems, the free bulk metal concentration, which allows us to retrieve the stability constant at bulk conditions.

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

A lability criterion is developed for dynamic metal binding by colloidal ligands with convective diffusion as the dominant mode of mass transport. Scanned stripping chronopotentiometric measurements of Pb(II) and Cd(II) binding by carboxylated latex core-shell particles were in good agreement with the predicted values. The dynamic features of metal ion binding by these particles illustrate that the conventional approach of assuming a smeared-out homogeneous ligand distribution overestimates the lability of a colloidal ligand system. Due to the nature of the spatial distribution of the binding sites, the change in lability of a metal species with changing ligand concentration depends on whether the ligand concentration is varied via manipulation of the pH (degree of protonation) or via the particle concentration. In the former case the local ligand density varies, whereas in the latter case it is constant. This feature provides a useful diagnostic tool for the presence of geometrically constrained binding sites.

Metal speciation dynamics in colloidal ligand dispersions. Part 2: electrochemical lability

We investigate the dynamic nature of metal speciation in colloidal dispersions using a recently proposed theory [J.P. Pinheiro, M. Minor, H.P. Van Leeuwen, Langmuir, 21 (2005) 8635] for complexing ligands that are situated on the surface of the particles. The new approach effectively modifies the finite rates of association/dissociation of the colloidal metal complexes, thus invoking consideration of the two basic dynamic criteria: the association/dissociation kinetics of the volume complexation reaction (the ‘‘dynamic’’ criterion), and the interfacial flux of free metal to a macroscopic surface due to dissociation of complex species (the ‘‘lability’’ criterion). We demonstrate that the conventional approach for homogeneous systems that assume a smeared-out ligand distribution, overestimates both the dynamics and the lability of metal complexes when applied to colloidal ligands. It is also shown that the increase of lability with increasing particle radius, as expected for a homogeneous solution, is moderated for spherical microelectrodes and practically eliminated for planar electrodes.

Measurement of Donnan potentials in gels by in situ microelectrode voltammetry

This work describes the electrochemical methodology for the determination of the Donnan potential from diffusion-limited steady-state voltammograms of acrylamide gels. The technique is based upon the measurement of gel–sol systems that have reached Donnan equilibrium and contain Cd2+ as a probe ion. Au-amalgam microelectrodes are used to measure the Cd concentration in the gel phase relative to the solution phase, thus permitting comparison of the Cd voltammograms obtained in both phases. This approach yields two independent measures of the Donnan potential resulting from (i) the potential shift relative to the reference electrode, and (ii) the enhancement of the Cd2+ wave. Two suites of acrylamide gels containing 0.2% and 0.5% Na-acrylate were studied as a function of ionic strength by varying [NaNO3] and maintaining a constant concentration of the electroactive probe ion, [Cd2+] = 1 · 10 5 mol/L in the equilibrating solutions. Independent model predictions of the Donnan potential as a function of ionic strength that consider the effects of differential swelling on the charge density, the influence of a mixed electrolyte on the potential developed in the gel at the limit of low ionic strength and the effects of incomplete dissociation of the carboxylic functional groups were in agreement with the Donnan potentials independently measured by the twofold steady-state voltammetric approach.