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.

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.