By Donald Bethell
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Extra info for Advances in Heterocycling Chemistry. Vol. 32
In these experiments, the potential at the working electrode is swept at a ﬁxed scan rate () from an initial value of E1 to a second potential E2. On reaching E2, the direction of the sweep is reversed and, when the potential returns to E1, the scan may be halted and again reversed or allowed to continue to a third potential E3. A typical potential–time proﬁle is illustrated in Fig. 13(a), and Fig. 13(b) shows the coordinate system used to describe a cyclic voltammetric experiment. The scan rate is represented by the magnitude of the slope of the potential–time plot; by convention is always said to be positive.
C. EKLUND ET AL. 30 Table 4 Boundary conditions for a simple reversible one-electron oxidation process examined by cyclic voltammetry. e. the electrode surface tϭ0 xу0 [A] ϭ [A]0 [B] ϭ 0 tϾ0 x→ϱ [A] ϭ [A]0 [B] ϭ 0 tϾ0 xϭ0 (electrode surface) DA(Ѩ[A]/Ѩt)xϭ0 ϭ ϪDB(Ѩ[B]/Ѩt)xϭ0 tϾ0 xϭ0 ln ([B]xϭ0 /[A]xϭ0) ϭ nF/RT(E Ϫ E0f ) considerably less positive than E0f to a value considerably more positive than E0f (E2), and back to E1. The shape shown in Fig. 14 arises for the following reasons. On scanning the potential from E1 to more positive values, the concentration of A at the electrode surface ([A]xϭ0) drops as A is converted into B; this results in an increased concentration gradient of A at the surface of the electrode, and thus the diffusional ﬂux of A to the electrode increases.
MODERN VOLTAMMETRY 53 Fig. 26 Voltammogram obtained for a simple reversible one-electron transfer process at a hydrodynamic electrode. ELECTRON-TRANSFER PROCESSES A reversible one-electron transfer process (19) is initially examined. For all forms of hydrodynamic electrode, material reaches the electrode via diffusion and convection. In the cases of the RDE and ChE under steady-state conditions, solutions to the mass transport equations are combined with the Nernst equation to obtain the reversible response shown in Fig.
Advances in Heterocycling Chemistry. Vol. 32 by Donald Bethell