By Joseph Wang
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Analytical applications of ECL relying on the linear dependence of the ECL intensity and the reactant concentration have also been realized (39). 2-2 SPECTROELECTROCHEMISTRY 45 Additional spectroscopic techniques can be used for probing the molecular structure of electrode-solution interfaces, as desired for understanding the fundamentals of electrode surfaces. The focus of these surface techniques is the correlation of the surface structure with electrochemical reactivity. Such surfacesensitive analytical tools can be classified as in-situ or ex-situ.
By recording linear scan voltammograms at different scan rates (using the supporting electrolyte solution), and plotting the charging current (at a given potential) versus the scan rate, one obtains a straight line with slope corresponding to Cdl A. Measurements of the double-layer capacitance provide valuable insights into adsorption and desorption processes, as well as into the structure of film-modified electrodes (6). Further discussion of the electrical double layer can be found in several reviews (5,7-11).
Figure 2-2 illustrates the expected response of a reversible redox couple during a single potential cycle. It is assumed that only the oxidized form O is present initially. Thus, a negative-going potential scan is chosen for the first half-cycle, starting from a value where no reduction occurs. As the applied potential approaches the characteristic E° for the redox process, a cathodic current begins to increase, until a peak is reached. After traversing the potential region in which the reduction process takes place (at least 90/« mV beyond the peak), the direction of the potential 28 2-1 29 CYCLIC VOLTAMMETRY Cycle 1 —| -E f i n c o 4-< O D.
Analytical Electrochemistry by Joseph Wang