B4b Ultramicroelectrodes

The model in Table 11.2 using the exponential background term has also been applied to electrochemical catalysis using steady state microelectrode voltammetry. Here, the shape of the wave remains the same at low scan rates irrespective of full kinetic control or pseudo-first-order conditions. The value of id estimated by the regression analysis was used to obtain kx

Figure 11.13 Linear sweep voltammogram at a Hg-drop electrode at 0.2 V s 1 for the reduction of 4,4'-dichlorobiphenyl (DCB) in 0.1 M tetrabutylammonium iodide in DMF: (a) with 0.1 mM anthracene as catalyst and 4 mM DCB; (b) direct reduction of 4 mM DCB; (c) catalytic component of curve in (a) computed from regression parameters obtained using the model in Table 11.2 with exponential background. (Reproduced with permission from [16], copyright by the American Chemical Society.)

Figure 11.13 Linear sweep voltammogram at a Hg-drop electrode at 0.2 V s 1 for the reduction of 4,4'-dichlorobiphenyl (DCB) in 0.1 M tetrabutylammonium iodide in DMF: (a) with 0.1 mM anthracene as catalyst and 4 mM DCB; (b) direct reduction of 4 mM DCB; (c) catalytic component of curve in (a) computed from regression parameters obtained using the model in Table 11.2 with exponential background. (Reproduced with permission from [16], copyright by the American Chemical Society.)

via computation of theoretical curves relating the catalytic limiting current to log k\ by digital simulation. The reader is referred to the original literature for details [18],

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