Significance of Mixed Potentials in Eh Measurements with Platinum Electrodes

The influence of dissolved oxygen and the Pt - Pt-O reaction on the measurement of redox potentials in solutions containing ferrous-ferric couple was examined. Current-potential curves were used to illustrate the shift in measured potentials toward the oxygen potential in oxygenated and deoxygenated systems at low concentrations of ferrous and ferric ions. The ranges of concentrations of the ferrous-ferric couple, in which the interference from oxygen and the platinum-oxygen reactions becomes significant, are illustrated through the mixed potential mechanism.