Electrochemical processes potential sweep rate

The irreversibility of the reduction peak of 16 2+, combined with the appearance of a reversible peak corresponding to tetracoordinated copper, suggests that the reorganization of the rotaxane in its pentacoordinated form 16(S)+ (i.e., with the copper coordinated to terpy and to dpp units) to its tetracoordinated form (16 +, in which the copper is surrounded by two dpp units) occurs within the timescale of the cyclic voltammetry. Indeed, the cyclic voltammetry response located at -0.15 V becomes progressively reversible when increasing the potential sweep rate, as expected for an electrochemical process in which an electron transfer is followed by an irreversible chemical reaction (EC). Following the method of Nicholson and Shain, 9S the rate constant value, k, of the chemical reaction, i.e., the transformation of pentacoordinated Cu(i) into tetracoordinated Cu(i), was determined. A value of 17 s 1 was... 

The kinetic analysis of a complicated electrochemical process involves two crucial steps the validation of the proposed mechanism and the extraction of the kinetic parameter values from experimental data. In cyclic voltammetry, the variable factor, which determines the mass transfer rate, is the potential sweep rate v. Therefore, the kinetic analysis relies on investigation of the dependences of some characteristic features of experimental voltammograms (e.g., peak potentials and currents) on v. Because of the large number of factors affecting the overall process rate (concentrations, diffusion coefficients, rate constants, etc.), such an analysis may be overwhelming unless those factors are combined to form a few dimensionless kinetic parameters. The set of such parameters is specific for every mechanism. Also, the expression of the potential and current as normalized (dimensionless) quantities allows one to generalize the theory in the form of dimensionless working curves valid for different values of kinetic, thermodynamic, and mass transport parameters. 

In the presence of 6-iodo-l-phenyl-l-hexyne, the current increases in the cathodic (negative potential going) direction because the hexyne catalyticaHy regenerates the nickel(II) complex. The absence of the nickel(I) complex precludes an anodic wave upon reversal of the sweep direction there is nothing to reduce. If the catalytic process were slow enough it would be possible to recover the anodic wave by increasing the sweep rate to a value so fast that the reduced species (the nickel(I) complex) would be reoxidized before it could react with the hexyne. A quantitative treatment of the data, collected at several sweep rates, could then be used to calculate the rate constant for the catalytic reaction at the electrode surface. Such rate constants may be substantially different from those measured in the bulk of the solution. The chemical and electrochemical reactions involved are... 

The electrochemical technique used in PV is known as linear sweep voltammetry with a slow sweep rate. It can be shown [332] that under the conditions just described (a constant S) and for a reversible process, the applied potential (E) is related to the measured current ( ) by... 

The most popular electroanalytical technique used at solid electrodes is Cyclic Voltammetry (CV). In this technique, the applied potential is linearly cycled between two potentials, one below the standard potential of the species of interest and one above it (Fig. 7.12). In one half of the cycle the oxidized form of the species is reduced in the other half, it is reoxidized to its original form. The resulting current-voltage relationship (cyclic voltammogram) has a characteristic shape that depends on the kinetics of the electrochemical process, on the coupled chemical reactions, and on diffusion. The one shown in Fig. 7.12 corresponds to the reversible reduction of a soluble redox couple taking place at an electrode modified with a thick porous layer (Hurrell and Abruna, 1988). The peak current ip is directly proportional to the concentration of the electroactive species C (mM), to the volume V (pL) of the accumulation layer, and to the sweep rate v (mVs 1). 

Cyclic voltammetry is a widely used electrochemical technique, which allows the investigation of the transient reactions occurring on the electrode surface when the potential applied to the electrode is varied linearly and repetitively at a constant sweep rate between two given suitable limits. The steady-state current-potential curves or voltammograms provide direct information as to the adsorption-desorption processes and allow estimating the catalytic properties of the electrode surface. 

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