Analytical Electochemistry. Second Edition by Wang Joseph

By Wang Joseph

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Hence, as illustrated in Figure 2-6, i is the ratio of the rate constant (of the chemical step) to the scan rate, which controls the peak ratio. Most useful information is obtained when the reaction time lies within the experimental time scale. 2 180 120 60 0 180 (E – EV2)n (mV) FIGURE 2-6 Cyclic voltammograms for a reversible electron transfer followed by an irreversible step for various ratios of chemical rate constant to scan rate, k/a, where a ˆ nFv=RT . 1±1000 ms. 4) offer the use of much faster scan rates and hence the possibility of shifting the upper limit of follow-up rate constants measurable by cyclic voltammetry (3).

Large negative potentials accelerate the movement of charge in the cathodic direction, and also decelerate the charge movement in the opposite direction. As a result the anodic current component becomes negligible and the net current merges with the cathodic component. 5. Similarly, no cathodic current contribution is observed at suf®ciently large positive potentials. When E ˆ Eeq , no net current is ¯owing. This situation, however, is dynamic, with continuous movement of charge carriers in both directions, and equal opposing anodic and cathodic current components.

In particular, the high sensitivity of molecular vibrations to the chemical environment has led to the widespread use of vibrational spectroscopies, such as surface enhanced Raman scattering (SERS), for monitoring the surface composition before, during, and after the electrochemical experiment. In these experiments, a small fraction of the photons exchange energy with the sample and are inelastically scattered, with a change of their wavelength characteristic of the energy change. Such Raman scattering effect can be enhanced by factors of up to 108 when the compound is adsorbed on the metallic surface (40).

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