Dithionite oxidation kinetic limitations

Both stopped-flow and rapid freeze quench kinetic techniques show that the substrate reduces the flavin to its hydroquinone form at a rate faster than catalytic turnover Reoxidation of the flavin hydroquinone by the oxidized Fe4/S4 center leads to formation of a unique spin-coupled species at a rate which appears to be rate limiting in catalysis. Formation of this requires the substrate since dithionite reduction leads to flavin hydroquinone formation and a rhombic ESR spectrum typical of a reduced iron-sulfur protein . The appearance of such a spin-coupled flavin-iron sulfur species suggests the close proximity of the two redox centers and provides a valuable system for the study of flavin-iron sulfur interactions. The publication of further studies of this interesting system is looked forward to with great anticipation. 

From what is described in this section, it can be concluded that the kinetics of the oxidation reaction of sulphite and dithionite at a platinum electrode in alkaline solution are strongly affected by the nature of the platinum surface. This is important when a platinum electrode is used for a quantitative investigation of the kinetics of the oxidation of sodium dithionite and/or sulphite or as electrode material in the development of a sensor for the measurement and/or control of dithionite and/or sulphite concentrations. However, for sodium dithionite, it has no serious consequences because the limiting-current at 0.45 V vs. SCE does not change as a function of scan number. However, this oxidation is still irreversible (no return peak observed) which means that, in the onset of the voltammetric wave, the current is controlled by charge-transfer kinetics. Therefore, it is possible to investigate and obtain the mechanism of the oxidation of sodium dithionite, which is explained in the next section. 

In the first region, the current is completely independent of rotation rate of the electrode and increases exponentially, which means that in this region the current (or reaction rate) is mainly controlled by electron transfer and not by transport phenomena. This allows a study of the kinetics and the mechanism of the electron-transfer reaction of the oxidation of dithionite. The third region shows a well-defined limiting-current plateau. This indicates that in this region, electron transfer is so fast that the overall reaction rate is controlled by transport only. This is confirmed by a linear relationship between limiting-current and square root of the rotation rate of the electrode. In this region, it is not possible to study the kinetics and the mechanism, but such conditions are suitable for electroanalytical purposes and sensor development (see sections 6.5 and 6.7). 

The second region is the mixed kinetic transport-controlled region, and the most negative part of it can also be used for kinetic and mechanistic studies of the electron-transfer reaction after the experimental currents have been compensated for transport limitations. Finally, a second wave is observed at potentials higher than 0.5 V vs. AglAgCl, which can be attributed to the oxidation of sulphite to sulphate. However, this wave is not further considered because the oxidation mechanism of sulphite showed poor reproducibility (see section 6.3), and sulphite detection in dyeing processes is not of great importance compared with dithionite detection. 

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