By Donald Bethell
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Additional info for Advances in Heterocycling Chemistry. Vol. 32
1995) Compton and Dryfe (1994) Compton et al. (1993b) Von Stackelberg et al. 7 ϫ 10Ϫ5 J. C. EKLUND ET AL. 20 may migrate and contribute to the migration current. The total migrative ﬂux (Jm) is related to the sum of the migration ﬂuxes for each charged species. For all the charged species, i, present the migration ﬂux due to a potential gradient (ѨE/Ѩx) is given (see for example; Bard and Faulkner, 1980) by (14), Jm ϭ ѨE Ϫzi F Di[i] Ѩx RT all species i (14) or more generally for multi-dimensional transport by (15), Jm ϭ Ϫzi F Di[i](ٌE) RT all species i (15) where z is the charge on the electroactive species, i.
For all the charged species, i, present the migration ﬂux due to a potential gradient (ѨE/Ѩx) is given (see for example; Bard and Faulkner, 1980) by (14), Jm ϭ ѨE Ϫzi F Di[i] Ѩx RT all species i (14) or more generally for multi-dimensional transport by (15), Jm ϭ Ϫzi F Di[i](ٌE) RT all species i (15) where z is the charge on the electroactive species, i. Obviously, for a neutral species, migration may be neglected. For charged species the magnitude and sign of the migration current are determined by the charge on the ion, zi.
E ϩ Ϫ mer → ← mer ϩ e (43) At very high scan rates the fac0/facϩ couple appears to be reversible, with red ϩ 0 Iox P ϭ ϪIP ; concomitantly, the mer /mer couple disappears. Thus, at very ϩ ϩ short time domains, the fac /mer isomerization step is outrun and the oxidation process becomes a single one-electron transfer process. MODERN VOLTAMMETRY 37 The kinetics of the facϩ/merϩ isomerization step can be determined quantitatively from the scan-rate dependence of the oxidation process. Both theory and experiment show that the peak potential corresponding to the oxidation of the fac0 species (Eox P ) shifts to less positive potentials as the scan rate is increased.
Advances in Heterocycling Chemistry. Vol. 32 by Donald Bethell