Evaluation of Cyclical Voltammetry as an Electrolyte Screening Technique

Cyclic voltammetry (CV) has been evaluated as a technique for monitoring the quality of an industrial zinc sulphate electrolyte. The basis of the method involves measuring a change in the polarisation of the zinc nucleation reaction at an aluminium surface and relating this to the impurity content and/or the overall quality of the electrolyte. Specifically, the technique aims to be able to indicate and quantify detrimental synergism between impurity elements, something which traditional analytical techniques are incapable of providing. The technique has found some success with regard to monitoring glue additions in a range of metal electrolytes. It has been found that investigations by a number of workers over the past 15 years have produced variable and often misleading results due to the inadvertent use of commercial purity aluminium working electrodes. It has been shown that impurity elements in the working electrode can give rise to a range of responses that are not obtained when pure aluminium is used and that the response is variable due to the lack of surface homogeneity of commercial purity aluminium electrodes. Furthermore, it was demonstrated that previous detection limits reported in the literature were based on the presence of additional peaks in the cathodic scan and not polarisation effects. The results of this study have shown that when a pure aluminium working electrode was used, the method was incapable of detecting any change in polarisation for an electrolyte containing three common impurities (Co, Ni and Ge), at concentrations that would significantly reduce optimum electrolytic performance. A range of methods was tried to sensitise the technique, including raising the temperature and acidity, and adding antimony in order to induce some synergism. In all cases the polarisation response was unchanged. Consequently, apart from the commercialised application for monitoring additions of antimony and levelling agents such as glue, CV has very limited application as an electrolyte screening technique.