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reaction as shown in Eq. (9.2). As discussed in detail by Gattrell et al.284, this reaction is a multi-step reaction in which oxygen transfer (a chemical step) may precede or follow an electron-transfer step, denoted in modern terminology as a CE or EC mechanism. Such reactions usually have current-potential relations which differ significantly from the ideal Butler-Volmer form, and that is the case here. Table 9.1 – Kinetics parameters for redox reactions used in flow batteries. Redox couple α Fe3+/Fe2+ 0.59 0.55 Cr3+/Cr2+ 0.5 VO2+/VO2+ 0.42 0.3 V3+/V2+ 0.5 Ce4+/Ce3+ 0.5 Br2/Br- 0.35 0.46 9.1.3 K0 / cm s-1 2.2 x 10-5 1.2 x 10-5 2 x 10-4 3.0 x 10-7 1-3 x 10-6 4 x 10-3 1.6 x 10-3 1.7 x 10-2 5.8 x 10-4 Electrode Reference Multistep mechanisms The foregoing sections have concentrated on the potential dependences of the forward and reverse rate constants governing the simple one-step, one-electron electrode reaction. By restricting our view in this way, we have achieved a qualitative and quantitative understanding of the major features of electrode kinetics. But we must now recognize that most electrode processes are mechanisms of several steps. For example, the important reaction (2.7) clearly must involve several elementary reactions. The hydrogen nuclei are separated in the oxidized form, but are combined by reduction. Somehow, during reduction, there must be a pair of charge transfers and some chemical means for linking the two nuclei. Consider also the reduction (9.32) Is it realistic to regard two electrons as tunneling simultaneously through the interface? Or must we consider the reduction and oxidation sequences as two one- electron processes proceeding through the ephemeral intermediate Sn3+. Another Au(poly) 285 Au(111) 286 Hg 287 Graphite 284 Carbon 59 Hg 287 Pt 288 Pt(poly) 289 Vitreous C 290 223PDF Image | Redox Flow Batteries Vanadium to Earth Quinones
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