Cyclic voltammetry electrode geometry

According to Eq. (27), Stromme et al.125,126 developed systematically the peak-current method to determine the fractal dimension of the electrode surface by using cyclic voltammetry. It must be recalled that this method is valid when the recorded current is limited by diffusion of the electroactive species to and away from the electrode surface. Since the distribution of the reaction sites provides extensive information about the surface geometry, the fractal dimension of the reaction site distribution may agree with the fractal dimension of the electrode surface which is completely electrochemical-active. In addition, it is well known that this method is insensitive to the IR drop in the electrolyte.126... 

DDPV curves is shown for spherical and disc electrodes and different AEf values. As can be seen, independently of the electrode size, a peak-shaped response is obtained with the same peak potential and width (see the superimposed A/pDPV/ A/[, 5 pyk — E curves in the inserted Figures) since these responses are independent of the electrode geometry (see Eqs. (4.173) and (4.176)). This is a notable advantage over Cyclic Voltammetry where sigmoidal curves are obtained when small electrodes are employed which makes data analysis more difficult and less... 

Cyclic Staircase Voltammetry and Cyclic Voltammetry at Electrodes and Microelectrodes of Any Geometry... 

In this section, the general analytical expression for the current-potential response (Eq. (6.15)) is particularized for the electrochemical techniques Cyclic Staircase Voltammetry (CSCV) and Cyclic Voltammetry (CV). Thus, the expression for the CSCV and CV currents of multi-electron processes at electrodes of any geometry and size is... 

In the case of Cyclic Square Wave Voltammetry (CSWV), the SWV curve obtained in the second scan is a mirror image to that of the first scan whatever the electrode geometry if the diffusion coefficients of species O and R are assumed as equal. In the contrary case, although the peak potentials of both scans are coincident, differences in the peak heights are observed for nonplanar electrodes. 

Linear and cyclic voltammetry is widely used both for analytieal application and for investigating the mechanisms and kinetics of various electrochemical systems [1-4]. In order to study electrochemical behavior of a redox couple, different parameters determined the view of voltammetric response, may be changed (e.g. sweep rate, bulk concentrations, hydrodynamic conditions, geometry and size of the utilized electrode, and so on). Meanwhile,... 

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