A comparison between the determination of free Pb(II) by two techniques: absence of gradients and Nernstian equilibrium stripping and resin titration.

Absence of gradients and Nernstian equilibrium stripping (AGNES) is an emerging electroanalytical technique designed to measure free metal ion concentration. The practical implementation of AGNES requires a critical selection of the deposition time, which can be drastically reduced if the contribution of the complexes is properly taken into account. The resin titration (RT) is a competition method based on the sorption of metal ions on a complexing resin. The competitor here considered is the resin Chelex 100 whose sorbing properties towards Pb(II) are well known. The RT is a consolidated technique especially suitable to perform an intercomparison with AGNES, due to its independent physicochemical nature. Two different ligands for Pb(II) complexation have been analyzed here: nitrilotriacetic acid (NTA) and pyridinedicarboxylic acid (PDCA). The complex PbNTA is practically inert in the diffusion layer, so, for ordinary deposition potentials, its contribution is almost negligible; however, at potentials more negative than -0.8 V vs. Ag/AgCl the complex dissociates on the electrodic surface giving rise to a second wave in techniques such as normal pulse polarography. The complex Pb-PDCA is partially labile, so that its contribution can be estimated from an expression of the lability degree of the complex. These new strategies allow us to reduce the deposition time. The free Pb(II) concentrations obtained by AGNES and by RT are in full agreement for both systems here considered. The main advantage of the use of AGNES in these systems lies in the reduction of the time of the experiment, while RT can be applied to non-amalgamating elements and offers the possibility of simultaneous determinations.