Direct determination of free metal concentration by implementing stripping chronopotentiometry as the second stage of AGNES.

The electroanalytical technique Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) has been extended by applying stripping chronopotentiometry (SCP) as the re-oxidation stage in the determination of the free concentration of Zn(2+), Cd(2+) and Pb(2+). This new approach, called AGNES-SCP, has been implemented with screen-printed electrodes (SPE) and the standard Hanging Mercury Drop Electrode (HMDE). Clear advantages of this variant have been shown: (i) the easy resolution of the peaks of different metals present in mixtures and (ii) the sparing of blanks. A rigorous computation of the faradaic charge along the SCP stage takes into account the contribution of other oxidants, which can be efficiently measured at the end of the deposition stage of AGNES. The free Cd concentration determined in an oxalate solution at pH 6 with an HMDE as the working electrode agreed well with values obtained with a Cd Ion Selective Electrode. The free metal concentration measured using an SPE for the system Cd and nitrilotriacetic acid (NTA) at pH = 4.8 also conformed well with Visual MINTEQ results.