By Wang Joseph
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Additional resources for Analytical Electochemistry. Second Edition
Been developed (9). 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).
Figure 1-9 shows a typical Morse potential energy curve for the reaction: O neÀ R, at an inert metallic electrode (with O and R being soluble). Because of the somewhat different structures of O and R, there is a barrier to electron transfer (associated with changes in bond lengths and bond angles). In order for the transition from the oxidized form to occur, it is thus necessary to overcome the free energy of activation, DGz . , the rate constant) is given by k AeÀDG z =RT 1-34 Any alteration in DGz will thus affect the rate of the reaction.
In practice, however, the current could not rise to an in®nite value due to restrictions from the rate at which the reactant reaches the surface. ) 1-2 15 FARADAIC PROCESSES FIGURE 1-8 curve. Tafel plots for the cathodic and anodic branches of the current±potential For small departures from E , the exponential term in equation (1-27) may be linearized and the current is approximately proportional to Z: i i0 nFZ=RT 1-30 Hence, the net current is directly proportional to the overvoltage in a narrow potential range near E .
Analytical Electochemistry. Second Edition by Wang Joseph