Cyclic voltammetry peak shape

Cyclic voltammetric behaviour of redox polymers including PVF has been studied previously in acetonitrile and in water solutions [18]. In acetonitrile, PVF exhibits stable, symmetrically shaped cyclic voltammetry peaks at potentials characteristic of oxidation and re-reduction of ferrocene sites in the polymer film. In aqueous electrolyte solutions, non-symmetrical peaks are evident in both anodic and cathodic branches. Differences in PVF behaviour in the two solvents have been attributed to solvent uptake in the polymer film (lower for aqueous solutions), changes in site-site interaction parameters for the polymer film (attractive for aqueous electrolytes and repulsive for acetonitrile electrolytes), and differences in deswelling processes in aqueous solution in the reduction half of the cycle as compared with the oxidation half (Figure 2.4). Acetonitrile is a better swelling solvent for PVF than water [18] and break in of the spin-coated films usually requires more cycling in water than in acetonitrile. 

Cyclic voltammetry at spherical electrodes. As discussed in Chapter 1, Section 4.2.3, diffusion laws at a spherical electrode must take into account the curvature r0 of the electrode. The mathematical treatment of diffusion at a spherical electrode becomes somewhat more complicated6 with respect to the preceding one for planar diffusion and we will not dwell on it. On the basis of what we will see in Chapter 11, Section 2, it is important to consider that, under radial diffusion, the cyclic voltammogram loses its peak-shaped profile to assume a sigmoidal profile, see Figure 6. 

In polarography, we obtained the half-wave potential E// by analysing the shapes of the polarographic wave. E1/2 is a useful characteristic of the analyte in the same way as E . In cyclic voltammetry, the position o/both peaks (both forward and back in Figure 6.13 cathodic and anodic, respectively, in this example) gives us thermodynamic information. Provided that the couple is fully reversible, in the thermodynamic sense defined in Table 6.3, the two peaks are positioned on either side of the formal electrode potential E of the analyte redox couple, as follows ... 

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 also very useful for the study of adsorbed species1415,28-30. In the examples discussed above, it was assumed that the electroactive species and its reaction products are soluble in the solution and that surface processes can be neglected. However, if the shape of the peak is unusual (e.g. very sharp), the electrochemical reaction is probably complicated by surface processes, such as adsorption. Usually, adsorption of species favours the electrode reaction taking place at lower potentials in the case of a deposition, one speaks about under potential deposition. Different ways of adsorption can be obtained ... 

DDPV curves is shown for spherical and disc electrodes and different AEf values. As can be seen, independently of the electrode size, a peak-shaped response is obtained with the same peak potential and width (see the superimposed A/pDPV/ A/[, 5 pyk — E curves in the inserted Figures) since these responses are independent of the electrode geometry (see Eqs. (4.173) and (4.176)). This is a notable advantage over Cyclic Voltammetry where sigmoidal curves are obtained when small electrodes are employed which makes data analysis more difficult and less... 

This technique is of special interest in the case of charge transfer processes at surface-bound molecules since it allows a simple and more effective correction of the non-faradaic components of the response than Cyclic Voltammetry. Moreover, this technique presents an intense peak-shaped signal for fast charge transfer, whereas other multipulse techniques give rise to nonmeasurable currents under these conditions and it is necessary to use short potential pulses to transform the response to quasi-reversible, which is much more difficult to analyze [4, 6, 10]. 

The DSCVC response has a peak-shaped feature similar to that obtained in Cyclic Voltammetry. Indeed, the most appropriate way of analyzing the DSCVC response is to divide Qdscvc by the pulse amplitude AE in order to obtain the (Qdscvc/AE) — E response, since the following relationship between the continuous current-potential curve corresponding to CV and the (QdscvcM-E) — curve obtained from a discrete staircase potential sequence can be established for AE < RT/F ... 

When applied to immobilized redox systems at an electrode surface (or to stagnant solutions in -> thin-layer cells), cyclic voltammetry produces distinct peak shape and the peak current characteristics. 

Fig. S Voltammetric shapes commonly encountered (a) asymmetric peak-shaped response (e.g. cyclic voltammetry) and (b) sigmoidal-shaped response (e.g. steady-state...

A reversible one-electron transfer process (19) is initially examined. For all forms of hydrodynamic electrode, material reaches the electrode via diffusion and convection. In the cases of the RDE and ChE under steady-state conditions, solutions to the mass transport equations are combined with the Nernst equation to obtain the reversible response shown in Fig. 26. A sigmoidal-shaped voltammogram is obtained, in contrast to the peak-shaped voltammetric response obtained in cyclic voltammetry. 

Pyryliiim [181-183] and isobenzopyrylium [184] salts have been shown to be polaro-graphically reducible in a one-electron reduction. In cyclic voltammetry in aprotic solvents, 2,4,6-trisubstituted pyrylium salts show two peaks the shape of the peak depends on the rate of dimerization. This process occurs more rapidly at C-4 than at C-2 (C-6) [182, 183], and the dimerization takes place spontaneously for 4-unsubstituted pyrylium salts. The equilibrium between radicals and dimer is displaced in favor of the radicals on introduction of electron-withdrawing substituents such groups enhance the aromatic character of the radical [185]. If the reduction of pyrylium salts is made in the presence of an alkyl iodide a fair yield of the 4-alkylated 4i/-pyrane is isolated with the dimer [182]. 

Similar observations have been reported by Saveant et al. in their studies on the electrochemical reduction of simple aliphatic halides [132g] (/ -.. s-, and t-butyl halides) at a glassy carbon electrode. Cyclic voltammetry of the butyl halides showed one or two irre crsible waves, depending on the relative reducibility of the alkyl halide RX and of the radical R. All transfer coefficients reported were smaller than 0.5 (between 0.2 and 0.32). The fact that the transfer coefficient was small was taken as further evidence that the reduction pathways do not involve the RX anion radical as an intermediate. Our observations from the electrochemical reduction of 18, 158, 19, and 131 at a glassy carbon electrode are in agreement with this. The cyclic voltammetric shape, the peak width tp 2 — p = (180-150) mV, and the value of a =0.25-0.32 at different scan rates [137] showed, without question, that electron transfer and decomposition of the anion radical... 

According to eq. 2 a constant current appears in the cyclic voltammogram (CV) when Q is plotted versus U. In real systems such as porous carbon electrodes, both load resistances due to the spatial distributed capacitance in the pores (circuit model in fig.l) and surface functional groups cause a deviation from the rectangular CV-shape. While the first induces a finite time constant in the charging process, the latter are identified by current peaks in the CV [14,6]. The voltage range used for cyclic voltammetry was -0.2 to 0.8 Volt vs.. g/, gCl at a scanrate of 5 mV/s, respectively. 

In the type of linear-sweep voltammetry discussed thus far, the potential is changed slowly enough and mass transfer is rapid enough that a steady state is reached at the electrode surface. Hence, the mass transport rate of analyte A to the electrode just balances its reduction rate at the electrode. Likewise, the mass transport of P away from the electrode is just equal to its production rate at the electrode surface. There is another type of linear-sweep voltammetry in which fast scan rates (1 V/s or greater) are used with unstirred solutions. In this type of voltammetry, a peak-shaped current-time signal is obtained because of depletion of the analyte in the solution near the electrode. Cyclic voltammetry (see Section 23D) is an example of a process in which forward and reverse linear scans are applied. With cyclic voltammetry, products formed on the forward scan can be detected on the reverse scan if they have not moved away from the electrode or been altered by a chemical reaction. 

Several newer techniques, such as cyclic voltammetry (CV) are now used to identify a proper choice of an antioxidant. CV is an electrolytic method that uses microelectrodes and an unstirred solution, so that the measured current is limited by analyte diffusion at the electrode surface. The electrode potential is ramped linearly to a more negative potential, and then ramped in reverse back to the starting voltage. The forward scan produces a current peak for any analyte that can be reduced through the range of the potential scan. The current will increase as the potential reaches the reduction potential of the analyte, but then falls off as the concentration of the analyte is depleted close to the electrode surface. As the applied potential is reversed, it wiU reach a potential that will reoxidize the product formed in the first reduction reaction, and produce a current of reverse polarity from the forward scan. This oxidation peak will usually have a similar shape to the reduction peak. The peak current, ip, is described by the Randles-Sevcik equation ... 

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