title: Platinum as a HOI/I2Redox Electrode and Its Mixed Potential in the Oscillatory Briggs-Rauscher Reaction.
abstract: 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/I2redox 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) × 10-13M2, in rather good agreement with earlier measurements. We also studied the perturbing effect of H2O2on the previously mentioned potentials. The concentration of H2O2was 0.66 M, as in the BR reaction studied here. It was found that below the HLP, the perturbing effect of H2O2was minimal but above the HLP, H2O2shifted 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 H2O2prevents the calculation of concentrations from Pt potentials above the HLP, [I-]/[I2]1/2ratios can be calculated as a good approximation from Pt potentials below the HLP.
authors.affiliation: Department of Physics, Budapest University of Technology and Economics , H-1521 Budapest, Hungary.
authors.forename: Gábor
authors.initials: G
authors.lastname: Holló
authors.affiliation: Department of Physics, Budapest University of Technology and Economics , H-1521 Budapest, Hungary.
authors.forename: Kristóf
authors.initials: K
authors.lastname: Kály-Kullai
authors.affiliation: Department of Physics, Budapest University of Technology and Economics , H-1521 Budapest, Hungary.
authors.forename: Thuy B
authors.initials: TB
authors.lastname: Lawson
authors.affiliation: Department of Physics, Budapest University of Technology and Economics , H-1521 Budapest, Hungary.
authors.forename: Zoltán
authors.initials: Z
authors.lastname: Noszticzius
authors.affiliation: Department of Physics, Budapest University of Technology and Economics , H-1521 Budapest, Hungary.
authors.forename: Maria
authors.identifier: http://orcid.org/0000-0003-2612-8478
authors.initials: M
authors.lastname: Wittmann
authors.affiliation: Department of Physics, Budapest University of Technology and Economics , H-1521 Budapest, Hungary.|Department of Physical Chemistry, Babes-Bolyai University , RO-400028 Cluj-Napoca, Romania.
authors.forename: Norbert
authors.initials: N
authors.lastname: Muntean
authors.affiliation: Penn State Berks College, The Pennsylvania State University , Reading, Pennsylvania 19610, United States.
authors.forename: Stanley D
authors.initials: SD
authors.lastname: Furrow
authors.affiliation: Faculty of Applied Sciences, Université Libre de Bruxelles , CP165/63, Av. F. Roosevelt 50, 1050 Brussels, Belgium.
authors.forename: Guy
authors.initials: G
authors.lastname: Schmitz