Simple Reactions on Stationary Spherical Electrodes and Microelectrodes

3 Simple Reactions on Stationary Spherical Electrodes and Microelectrodes 

The basic theory of SWV at a stationary spherical electrode is explained in the Appendix (see Eqs. II.3.34, IL3.35, II.3.36, II.3.37, II.3.38, II.3.39 and IL3.40). If the electrode reaction (Eq. II.3.1) is fast and reversible, the shape of the SWV response and its peak potential are independent of electrode geometry and size [46 8]. At a spherical electrode the dimensionless net peak current is linearly proportional to the inverse value of the dimensionless electrode radius y = 

Theoretically, if an extremely small electrode is used and low frequency is applied, so that a steady-state, frequency-independent peak current should appear (A/p)ss = 2.83 [51]. However, even if the electrode radius 

The dimensionless peak current of a totally irreversible electrode reaction is a function of the variable y however, the relationship is not strictly linear. If a = 0.5, it can be described with two asymptotes A Pp = 0.11-t-0.32y(fory 0.5)and A p = 0.15-1- 0.24y (for 0.5 y 10). The slopes and intercepts of these straight lines are linear functions of the transfer coefficient a. The responses of quasi-reversible electrode reactions are complex functions of both the electrode radius and the kinetics parameter k = Hence, no linear relationship between A p and y was 

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