Electron transfer kinetics cyclic voltammetry

Vitamin B 2 (cyanocob(III)alamin) is an example of a quasi-reversible redox system that exhibits slow heterogeneous electron-transfer kinetics. Cyclic voltammetry alone suggests that the reduction of vitamin B 2 is a single two-electron process at = -0.93 V vs SCE to the Co(I) redox state (Figure lOA). However, thin-layer spectroelectrochemistry using a... 

How electron transfer kinetics may be investigated by means of an electrochemical method such as cyclic voltammetry is the question we address now, starting with the case where the reactants are immobilized on the electrode surface, as in the beginning of Section 1.2. The key equations are those that relate the surface concentrations rA and rB to the current. The first of these expresses the Faradaic consumption of A and production of B as the current flows ... 

These electron transfer reactions are very fast, among the fastest known. This is the reason that impedance methods were used originally to determine the standard rate constant,13,61 at a time when the instrumentation available for these methods was allowing shorter measurement times (high frequencies) to be reached than large-amplitude methods such as cyclic voltammetry. The latter techniques have later been improved so as to reach the same range of fast electron transfer kinetics.22,63... 

As with the other reaction schemes involving the coupling of electron transfer with a follow-up homogeneous reaction, the kinetics of electron transfer may interfere in the rate control of the overall process, similar to what was described earlier for the EC mechanism. Under these conditions a convenient way of obtaining the rate constant for the follow-up reaction with no interference from the electron transfer kinetics is to use double potential chronoamperometry in place of cyclic voltammetry. The variations of normalized anodic-to-cathodic current ratio with the dimensionless rate parameter are summarized in Figure 2.15 for all four electrodimerization mechanisms. 

Cyclic voltammetry is generally considered to be of limited use in ultratrace electrochemical analysis. This is because the high double layercharging currents observed at a macroelectrode make the signal-to-back-ground ratio low. The voltammograms in Eig. 9B clearly show that at the NEEs, cyclic voltammetry can be a very powerful electroanalytical technique. There is, however, a caveat. Because the NEEs are more sensitive to electron transfer kinetics, the enhancement in detection limit that is, in principle, possible could be lost for couples with low values of the heterogeneous rate constant. This is because one effect of slow electron transfer kinetics at the NEE is to lower the measured Faradaic currents (e.g.. Fig. 8). 

The use of a potential-step technique such as cyclic staircase voltammetry represents a simple alternative to Ichise s method (j0 of obtaining information on both adsorption and electron transfer kinetics. The current decay immediately after a step is primarily capacitive while current at later times is almost totally due to electron transfer reactions. Thus, by measuring the current at several times during each step and by changing the scan rate, information on both the kinetics of the electrode process and the differential capacity can be obtained with a single sweep. 

DO Wipf, EW Kristensen, MR Deakin, RM Wightman. Fast-scan cyclic voltammetry as a method to measure rapid heterogeneous electron-transfer kinetics. Anal Chem 60 306-310, 1988. 

As discussed before in the case of nucleic acids the authors have also considered the incidence of the interfacial conformation of the hemoproteins on the appearance of the SERRS signals from the chromophores. Although under their Raman conditions no protein vibration can be observed, the possibility of heme loss or protein denatura-tion are envisaged to explain a direct interaction of the heme chromophores with the electrode surface in the case of the adsorl Mb. extensive denaturation of Cytc at the electrode appears unlikely to the authors on the basis of the close correspondence of the surface and solution spectra. Furthermore, the sluggish electron transfer kinetics measured by cyclic voltammetry in the case of Cytc is also an argument in favour of some structural hindrance for the accessibility to the heme chromophore in the adsorbed state of Cytc. This electrochemical aspect of the behaviour of Cytc has very recently incited Cotton et al. and Tanigushi et al. to modify the silver and gold electrode surface in order to accelerate the electron transfer. The authors show that in the presence of 4,4-bipyridine bis (4-pyridyl)disulfide and purine an enhancement of the quasi-reversible redox process is possible. The SERRS spectroscopy has also permitted the characterization of the surface of the modified silver electrode. It has teen thus shown, that in presence of both pyridine derivates the direct adsorption of the heme chromophore is not detected while in presence of purine a coadsorption of Cytc and purine occurs In the case of the Ag-bipyridyl modified electrode the cyclicvoltammetric and SERRS data indicate that the bipyridyl forms an Ag(I) complex on Ag electrodes with the appropriate redox potential to mediate electron transfer between the electrode and cytochrome c. 

A complete analysis of the effects of adsorption on the voltammetry is difficult given the number of different situations that can be found, mainly determined by the adsorption strength of the electroactive species, the time scale of the experiment and the electron transfer kinetics. The schematic in Figure 6.5 summarises some of the main features of cyclic voltammograms in the presence of adsorption of the electroactive species. For the sake of simplicity, the electron transfer processes are assumed to be fully reversible. 

In cyclic voltammetry a redox-active molecule is placed in an electroanalytical cell and the electrode potential is raised from a starting value at which there is no electroactivity. When electron transfer occurs a current is measured, and the shape of the trace depends upon, among other factors, the size and shape of the electrode. Thus, at a disk or wire of millimeter-sized dimensions (millielectrode) under conditions of linear diffusion, an initial current increase imder the control of electron-transfer kinetics meets a current decrease under diffusion control towards an effectively planar surface, and a characteristic peak shape is observed [Fig. 4(a)]. If the electron-transfer reaction produces a relatively stable species, then on reversing the scan direction a current is observed in the opposite direction. 

Andrienx, C.P., Garrean, D., Hapiot, R, Pinson, J. and Saveant, J.M. (1988) Fast sweep cyclic voltammetry at nltra-microelectrodes. Evaluation of the method for fast electron-transfer kinetic measnrements. Journal of Electroanalytical Chemistry, 243, 321-335. 

Cyclic voltammetry (CV) has been in the forefront of the study of electron transfer and its consequences. With the cyclic voltammetric method one can simultaneously activate molecules by electron transfer and probe subsequent chemical reactions. The cyclic voltammetric response curve thus provides information about electron transfer kinetics and thermodynamics as well as the consequences of electron transfer. 

Taylor, A. W., Qiu, F. L., Hu, J. R, Licence, P., Walsh, D. A. Heterogeneous electron transfer kinetics at the ionic liquid/metal interface studied using cyclic voltammetry and scanning electrochemical microscopy. J. Phys. Chem. B 2008, 112, 13292-13299. 

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