CYCLIC VOLTAMMETRY

Introduction Cyclic voltammetry is a very versatile electrochemical technique which allows to probe the mechanics of redox and transport properties of a system in solution. This is accomplished with a three electrode arrangement whereby the potential relative to some reference electrode is scanned at a working electrode while the resulting current flowing through a counter (or auxiliary) electrode is monitored in a quiescent solution. The technique is ideally suited for a quick search of redox couples present in a system; once located, a couple may be characterized by more careful analysis of the cyclic voltammogram. More precisely, the controlling electronic is designed such that the potential between the reference and the working electrodes can be adjusted but the big impedance between these two components effectively forces any resulting current to flow through the auxiliary electrode. Usually the potential is scanned back and forth linearly with time between two extreme values the switching potentials using triangular potential waveform (see Fig.1). When the potential of the working electrode is more positive than that of a redox couple present in the solution, the corresponding species may be oxidized ( i.e. electrons going from the solution to the electrode) and produce an anodic current. Similarly, on the return scan, as the working electrode potential becomes more negative than the reduction potential of a redox couple, reduction (i.e. electrons flowing away from the electrode) may occur to cause a cathodic current. By IUPAC convention, anodic currents are positive and cathodic currents negative.

Figure 1. A cyclic voltammetry potential waveform with switching potentials [1]

Fig.2 The expected response of a reversible redox couple during a single potential cycle [1].

The magnitude of the observed faradaic current can provide information on the overall rate of the many processes occurring at the working electrode surface. As is the case for any multistep process, the overall rate is determined by the slowest step. For an redox reaction induced at a working electrode, the rate determining step may be any one of the following individual step depending on the system: rate of mass transport of the electro-active species, rate of adsorption or de-sorption at the electrode surface, rate of the electron transfer between the electro-active

species and the electrode, or rates of the individual chemical reactions which are part of the overall reaction scheme. For the oxidation reaction involving n electrons the Nernst Equation gives the relationship between the potential and the concentrations of the oxidized and reduced form of the redox couple at equilibrium (at 298 K):

where E is the applied potential and E the formal potential; [OX] and [Red] represent surface concentrations at the electrode/solution interface, not bulk solution concentrations. Note that the Nernst equation may or may not be obeyed depending on the system or on the experimental conditions. A typical voltammogram is shown in Fig. 2. The scan shown starts at a slightly negative potential, (A) up to some positive switching value, (D) at which the scan is reversed back to the starting potential. The current is first observed to peak at Epa (with value ipa) indicating that an oxidation is taking place and then drops due to depletion of the reducing species from the diffusion layer. During the return scan the processes are reversed (reduction is now occurring) and a peak current is observed at Epc (corresponding value, ipc). Providing that the chargetransfer reaction is reversible, that there is no surface interaction between the electrode and the reagents, and that the redox products are stable (at least in the time frame of the experiment), the ratio of the reverse and the forward current ipr/ipf = 1.0 (in Fig. 2 ipa = ipf and ipc = ipr). In addition, for such a system it can be shown that: - the corresponding peak potentials Epa and Epc are independent of scan rate and concentration, - the formal potential for a reversible couple E0' is centered between Epa and Epc: E0'= (Epa + Epc)/2 - the separation between peaks is given by Ep = Epa Epc = 59/n mV (for a n electron transfer reaction) at all scan rates (however, the measured value for a reversible process is generally higher due to uncompensated solution resistance and non-linear diffusion. Larger values of Ep, which increase with increasing scan rate, are characteristic of slow electron transfer kinetics).
0'

It is possible to relate the half-peak potential (E p/2 , where the current is half of the peak current) to the polarographic half-wave potential, E1/2: Ep/2 = E1/2 29mV/n (The sign is positive for a reduction process.) For multielectron-transfer (reversible) processes, the cyclic voltammogram consists of several distinct peaks, if the Eo values for the individual steps are successively higher and are well separated. An example of such mechanism is the six-step reduction of the fullerenes C60 and C70 to yield the hexaanion products C606- and C706- where six successive reduction peaks can be observed. To distinguish between reversible ( diffusion-controlled) and irreversible (charge-transfer controlled) kinetics of electrode process potential scan-rate is used as diagnostic tool the rate of reagent transport is proportional to square root of scan-rate. Thus in one experimental set a shift in reversibility might be executed and analysis of Ep vs. v1/2 gives information on reversibility and applicability of further calculations. In simple terms, the working electrode may be regarded as a "reagent" of adjustable oxidizing or reducing strength. However, this is a purely conceptual image. In actual fact, the electrochemical processes are occurring at the interface of two different phases, the electrode and the electro-

active species in solution. In other words, the processes under studies are heterogeneous in nature. For the electron transfer to occur, the molecules in solution have to approach the electrode. In a cyclic voltammetry experiment, the solution is kept unstirred; in this situation, mass transport can occur only by diffusion due to concentration gradients created around the electrode surface. Such concentrationdistance profiles at different steps of a cyclic voltammogram scan are illustrated in Fig. 3. The magnitude of the observed signal will be very much a function of these diffusional properties of the system. Intuitively, the current intensity (i.e. the flow of electrons) is expected to depend on the surface area of the working electrode and the concentration of the electro-active species. Also, one can expect the voltage scanning rate to affect the concentration profile around the electrode which itself directly affects the rate of charge transport, and for this matter the diffusion coefficient appears explicitly. The expression of the peak current (A) for the forward sweep in a reversible system at 298 K is given by the Randles Sevcik equation:

where n is the number of electron equivalent exchanged during the redox process, A (cm2) the active area of the working electrode, D (cm2 s1) and C* (mol cm3) the diffusion coefficient and the bulk concentration of the electroactive species; is the voltage scan rate (V s1). In the present experiment, the dependence of ipf on scan rate and concentration will be examined.

Figure 3. Qualitative diagrams showing concentration--distance profile at various stage of the cyclic voltammogram shown in Fig. 2; the solid lines correspond to the reducing species and the dotted lines to the oxidizing species. [1

Irreversible and Quasi-reversible Systems For irreversible processes (those with sluggish electron exchange), the individual peaks are reduced in size and widely separated. Totally irreversible systems are characterized by a shift of the peak potential with the scan rate: Ep = E - (RT/naF)[0.78 - ln(ko/(D)1/2) + ln (naF/RT)1/2]

where is the transfer coefficient and na is the number of electrons involved in the chargetransfer step. Thus, Ep occurs at potentials higher than E, with the overpotential related to k (standard rate constant) and . Independent of the value k, such peak displacement can be compensated by an appropriate change of the scan rate. The peak potential and the half-peak potential (at 25C) will differ by 48/ n mV. Hence, the voltammogram becomes more drawn-out as n decreases The peak current, given by: ip = (2.99x105)n(na)1/2ACD1/21/2 is still proportional to the bulk concentration, but will be lower in height (depending upon the value of ). Assuming = 0.5, the ratio of the reversible-to-irreversible current peaks is 1.27 (i.e. the peak current for the irreversible process is about 80% of the peak for a reversible one). For quasi-reversible systems (with 10-1 > k > 10-5 cm/s) the current is controlled by both the charge transfer and mass transport. The shape of the cyclic voltammogram is a function of the ratio k/(nFD/RT)1/2. As the ratio increases, the process approaches the reversible case. For small values of it, the system exhibits an irreversible behavior. Overall, the voltammograms of a quasi-reversible system are more drawn out and exhibit a larger separation in peak potentials compared to a reversible system. For quasi-reversible reaction (Ep up to 200 mV) a numerical approach brings values of function : Ep 64 6 68 3 72 2 84 1 92 0,75 105 0,5 121 0,35 141 0,25 212 0,1

to calculate the rate constant, using following equation:

= ks (Dox/Dred)/2 / [ Dox(nF/RT)]1/2
References 1. Wang, J., Analytical Electrochemistry, Chapter 2, John Wiley & Sons (2000) 2. Nicholson, R.S.; Shain, I., Anal. Chem., 36, 706 (1964). 3. David K. Gosser, Jr., Cyclic Voltammetry: Simulation and Analysis of Reaction Mechanisms, VCH Publishers (1993). 4. Allen J. Bard and Larry R. Faulkner, Electrochemical Methods: Fundamentals and Applications, Second Edition, John Wiley and Sons Publishers (2001).