Platinum as a HOI/I2 Redox Electrode and Its Mixed Potential in the Oscillatory Briggs-Rauscher Reaction

J Phys Chem A. 2017 Jan 19;121(2):429-439. doi: 10.1021/acs.jpca.6b10243. Epub 2017 Jan 5.


Pt is a common redox electrode used to follow oscillations qualitatively in the Briggs-Rauscher (BR) and the Bray-Liebhafsky (BL) reactions from the time of their discovery. Although the potential oscillations of the electrode reflect the temporal pattern of the reaction properly, there is no general agreement as to how that potential is determined by the components of the reaction mixture. In this article, first we investigate how iodine species in different oxidation states affect the potential of a Pt electrode. It was found that I(+3) and I(+5) species do not affect the potential; only I-, I2, and HOI may have an influence. Although the latter three species are always present simultaneously as participants of the rapid iodine hydrolysis equilibrium, it was found that below and above the so-called hydrolysis limit potential (HLP, where the iodide and HOI concentrations are equal) the actual potential determining redox couple is different. Below the HLP, it is the traditional I2/I- redox couple, but above the HLP, it is the HOI/I2 redox pair that determines the potential of a Pt electrode. That change in the potential control mechanism was proven experimentally by exchange current measurements. In addition, from the potential response of the Pt electrode below and above the HLP, it was possible to calculate the equilibrium constant of the iodine hydrolysis as K°H = (4.97 ± 0.20) × 10-13 M2, in rather good agreement with earlier measurements. We also studied the perturbing effect of H2O2 on the previously mentioned potentials. The concentration of H2O2 was 0.66 M, as in the BR reaction studied here. It was found that below the HLP, the perturbing effect of H2O2 was minimal but above the HLP, H2O2 shifted the mixed potential considerably down toward the HLP. In our experiments with the BR reaction, the potential oscillations of the Pt electrode crossed the HLP, indicating that from time to time the HOI concentration exceeds that of the iodide. We can conclude that although the perturbing effect of H2O2 prevents the calculation of concentrations from Pt potentials above the HLP, [I-]/[I2]1/2 ratios can be calculated as a good approximation from Pt potentials below the HLP.