Investigating alternative voltammetric methodologies to study complex formation

Abstract

Metal complexes have a wide range of applications in fields such as medicinal, industrial, environmental and so on. Determining the formations constants for metal complexes is thus essential to gather information on complexes. Conventional methods used to study complexation include spectroscopic methods and the use of voltammetric techniques such as direct current polarography using a mercury drop electrode. In this work alternative voltammetric methods to study complex formation are investigated. Bismuth complexes have important medicinal applications but not much is known about them because of the difficulties in studying them due to extensive bismuth hydrolysis and precipitation of hydrolysis products from very low pHs. The aim of this work was to investigate whether using low concentrations of bismuth (10-6 M) would prevent precipitation in nitrate solutions as predicted in literature. Differential pulse anodic stripping voltammetry (DPASV) was the technique of choice because of its low detection limit, even though it has not been widely used in complex formation studies before. The study revealed that electrochemical response for Bi3+ was not fully reversible using this technique. Additionally, even at the low concentration precipitation was observed in the acidic region (investigated via pH titration) and was suspected to be the formation of BiONO3 species. The second alternative method investigated was the use of mercury film electrodes to replace the use of the toxic mercury drop electrodes which are being phased out worldwide. This work looked at using in situ and ex situ plated films, where the in situ measurements proved more reproducible. A number of challenges were encountered, such as film degradation, peak splitting and ligand adsorption to the film electrode. Nonetheless, formation constants of lead-glycine complexes were determined under different experimental conditions and these were found to be reasonably compared to the literature values.