By Donald Bethell
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Extra info for Advances in Heterocycling Chemistry. Vol. 32
The form of the cyclic voltammogram is identical to that shown in Fig. 12a for a general ECE process. The ﬁnal product of this overall two-electron reduction process was found to be the radical anion of nitrobenzene as evidenced by EPR spectroscopy. A simpliﬁed form of the ECE mechanism proposed for the reduction of p-iodonitrobenzene is in (48)–(50), where HS is an H atom source. E иϪ p-NO2C6H4I ϩ eϪ → ← [p-NO2C6H4I] HS (48) C [p-NO2C6H4I]иϪ → p-NO2C6H5 ϩ IϪ (49) E иϪ p-NO2C6H5 ϩ eϪ → ← [p-NO2C6H5] (50) J.
21 Convective ﬂow proﬁle associated with a rotating-disc electrode. The crucial parameter which controls the time-scale over which electrode reactions are examined at a RDE is the electrode angular velocity, , which is related to the rotation frequency, f, by ϭ 2f. CHANNEL ELECTRODES Figure 22 shows a schematic diagram of a channel electrode (ChE), which consists of an electrode embedded in the wall of a rectangular duct through which solution is made to ﬂow under well-deﬁned laminar steady-state conditions (Compton and Unwin, 1986; Cooper and Compton, 1998).
26. A sigmoidal-shaped voltammogram is obtained, in contrast to the peak-shaped voltammetric response obtained in cyclic voltammetry. There are two critical parameters that are measured in a steady-state voltammogram: • The limiting or mass transport limited current Ilim. As soon as the potential is reached when [A]xϭ0 ϭ 0, the current reaches a ﬁxed limiting current value that is determined by the mass transport of material to the electrode surface. Under these conditions, material is continuously replenished at the electrode surface by convection, in contrast to the situation in a CV where depletion occurs and a peak-shaped response is observed.
Advances in Heterocycling Chemistry. Vol. 32 by Donald Bethell