The use of electrolyte redox potential to monitor the Ce(IV)/Ce(III) couple

Mathematical modelling of the oxidation reduction redox potential (ORP) of an electrolyte has been carried out for a batch system comprising an electrochemical reactor and an electrolyte circuit containing a redox couple. The ORP can be useful to monitor the environmental impact of chemical species in solution that represent a risk to the environment. Considerations of four fundamental equations, namely, the Nernst equation, a mass balance, Faradayʹs laws of electrolysis and a first order kinetic equation, leads to an expression for the electrolyte redox potential as a function of the batch time, the electrical charge and the redox concentration. Such an expression facilitates graphical plots which can be used to estimate kinetic parameters, current efficiency and the relative redox concentration. The Ce(IV)/Ce(III) system has been chosen as a model reaction for electrolyte redox potential measurement in a batch recycle system consisting of a pumped flow through a divided FM01-LC parallel-plate electrochemical reactor (64 cm2 projected electrode area) and a well mixed tank (3600 cm3). The differences between experimental and model predictions are discussed.