Chemistry

Analytical Electochemistry. Second Edition by Wang Joseph

By Wang Joseph

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It occurs when a potential is applied across the double layer, or when the electrode area or capacitances are changing. Note that the current is the time derivative of the charge. Hence, when such processes occur, a residual current ¯ows based on the differential equation iˆ dq dE dA dCdl ˆ Cdl A ‡ Cdl …E À Epzc † ‡ A…E À Epzc † dt dt dt dt …1-48† where dE=dt and dA=dt are the potential scan rate and rate of area change, respectively. The second term is applicable to the dropping mercury electrode (discussed in Section 4-2).

Such simulated voltammograms can be compared with and ®tted to the experimental ones. The new software also provides movie-like presentations of the corresponding continuous changes in the concentration pro®les. 3 Study of Adsorption Processes Cyclic voltammetry can also be used for evaluating the interfacial behavior of electroactive compounds. Both the reactant and the product can be involved in an 2-1 37 CYCLIC VOLTAMMETRY adsorption±desorption process. Such interfacial behavior can occur in studies of numerous organic compounds, as well as of metal complexes (if the ligand is speci®cally adsorbed).

Of iron porphyrin complexes) occurring after electron transfer represent another example of such a mechanism. , adjusting the experimental time scale). In particular, the scan rate controls the time spent between the switching potential and the peak potential (during which the chemical reaction occurs). 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.

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