Redox behaviors of iron by absorption spectroscopy and redox potential measurement

Abstract

This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ~ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III).