Cyclic voltammetry resistance

Figure 10. Cyclic voltammetry (top) and in situ electronic resistance (bottom) of poly(3-methylthiophene) from parallel-band electrode [Fig. 9(A)] experiments in S02(1) containing 0.1 M Bu4NPF6.37 (Reprinted with permission from J. Am. Chem. Soc. 112, 7869-7879, 1990. Copyright 1990, American Chemical Society.)...

The ohmic drop effect we are discussing deals only with the Ru portion ofthe cell resistance (Figure 1.5c). Indeed, the action of the potentiostat makes the working electrode potential independent not only of the possible shift of the counter electrode potential as the current varies, but also independent of the ohmic drop in the Rc portion of the cell resistance. In the case of cyclic voltammetry, the equation above becomes... 

In particular, from the analysis in the very low frequency region, the limiting capacitance Q can be evaluated (via the limiting resistance R ). Practical cases have given values of Cj, of about 20mFcm (Panero et al, 1989), i.e. values of the same order as those obtained by cyclic voltammetry, thus confirming the validity of the charge saturation model. 

Stripping is the most sensitive form of voltammetry. In anodic stripping polarography, analyte is concentrated into a single drop of mercury by reduction at a fixed voltage for a fixed time. The potential is then made more positive, and current is measured as analyte is reoxidized. In cyclic voltammetry, a triangular waveform is applied, and cathodic and anodic processes are observed in succession. Microelectrodes fit into small places and their low current allows them to be used in resistive, nonaqueous media. Their low capacitance... 

When using microelectrodes to obviate resistance problems, it is convenient to develop a procedure to determine what conditions are required to reduce the error to an acceptable level. The results of such a procedure applied to disk electrodes are shown in Figure 16.6 [45]. In this and the remaining discussion, the technique of cyclic voltammetry is considered, as it is one of the most widely used voltammetric methods. The region of practical working conditions of electrode radius and scan rate is defined by the area set off by lines A, B, and C. 

The introduction of ultramicroelectrodes in the field of voltammetric analysis offers access to cyclic voltammetry experiments that are impossible with conventionally sized macroelectrodes. In addition to analyses in small volumes or at microscopic locations, microelectrodes allow measurements in resistive media and make it possible to perform high scan rate voltammetry [9,10]. 

Fig. 2.19. (A) The effect of potential on the observed electrocatalytic response obtained at poly(aniline)/poly(vjnylsu fonate) electrode (geometric area 0.38 cm2, Q, 150 mC) rotated at 9 Hz in 0.1 mol dm-2 citrate/phosphate pH 7 buffer solution. Responses have been recorded at four different concentrations of NADH ( ) 0.12 mmol dm- ( ) 0.3 mmol dm"3 ( ) 0.6 mmol dm-3 and (O) 0.8 mmol dm"3. (B) Cyclic voltammetry of an identical poly(aniline)/poly(vinylsulfonate) electrode in 0.1 mol dm" 3 citrate/phosphate pH 7 buffer scanned at 5mVs , superimposed on this trace is the measured resistance for the same...

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