Linear potential scan techniques

The widespread use of large-amplitude relaxation techniques in the investigations of anodic organic oxidations, requires further comment on the value of these methods. Reinmuth divided these techniques into three classes based on the types of applications quantitative kinetic studies, qualitative kinetic studies, and analytical studies. We are not concerned here with the analytical applications. For studies in kinetics, controlled-potential techniques, particularly linear-potential scan, in either single sweep or in cycles, and to some extent chronopotentiometry, have been primarily employed. Chronopotentiometry has been successfully utilized in the study of transient reactions, e.g., the reaction of CO with platinum oxide or the reaction of oxalic acid with platinum oxide, and the study of simple charge-transfer reactions with linear diffusion (cf. Refs. 159-161). However, since the general application of chronopotentiometry is severely limited for the study of anodic organic oxidations, as commented previously, this technique will not be further discussed. The quantitative analysis of data obtained by linear potential scan techniques is complicated because the form of theoretical results even for the simplest cases, requires the use of computers and consequently very little quantitative kinetic information has been obtained. This... 

Sensitivity In many voltammetric experiments, sensitivity can be improved by adjusting the experimental conditions. For example, in stripping voltammetry, sensitivity is improved by increasing the deposition time, by increasing the rate of the linear potential scan, or by using a differential-pulse technique. One reason for the popularity of potential pulse techniques is an increase in current relative to that obtained with a linear potential scan. 

For the individual types of transient measuring techniques, special names exist but their terminology lacks uniformity. The potentiostatic techniques where the time-dependent current variation is determined are often called chronoamperometric, and the galvanostatic techniques where the potential variation is determined are called chronopotentiometric. For the potentiodynamic method involving linear potential scans, the term voltammetry is used, but this term is often used for other transient methods as well. 

The first version of a polarographic technique was put forward in 1922 by the Czech scientist Jaroslav Heyrovsky. Classsical polarography is the measurement of quasisteady-state polarization curves with linear potential scans applied to the DME sufficiently slowly (v between 1 and 20mV/s), so that within the lifetime, of an individual drop, the potential would not change by more than 3 to 5 mV. With special instruments (polarographs), one can record the resulting 7 vs. E curves (polaro-grams) automatically. 

In conventional electrochemistry in solution, quantitation of analytes can be obtained by using several techniques. Thus, exhaustive electrolysis provides an absolute quantitation of an electroactive component in the sample. Voltammetric measurements (linear potential scan, cyclic, pulse, and square-wave techniques) can be used for determination of analytes in solution via calibration because peak currents (and peak areas) are usually proportional to the analyte concentration under fixed electrochemical conditions. 

In linear potential scan (LSV) and cyclic (CV) voltammetries, a potential varying linearly with time is applied between an initial potential, usually at a value where no faradaic processes occur, and a final potential (LSV) or cycled between two extreme (or switching) potential values at a given potential scan rate v (usually expressed in mV/sec). In other techniques, such as normal and differential pulse voltammetries (NPV and DPV, respectively), or square-wave voltammetry (SQWV), the excitation signal incorporates potential pulses to a linear or staircase potential/time variation. 

Differential pulse voltammetry (DPV) is essentially an instrumental manipulation of chronoamperometry. It provides very high sensitivity because charging current is almost wholly eliminated. More important for CNS applications, it often helps to resolve oxidations which overlap in potential. The method combines linear potential sweep and square-wave techniques. The applied signal is shown in Fig. 16A and consists of short-duration square-wave pulses (<100 msec) with constant amplitude (typically 20 or 50 mV) and fixed repetition interval, superimposed on a slow linear potential scan. The Fapp waveform can be generated with a laboratory-built potentiostat, but most DPV work is done with a commercial pulse polarograph (see Appendix). The inset of Fig. 16A shows an enlargement of one pulse. The current is measured just before the pulse... 

In ac cyclic voltammetry, a small amplitude sine wave perturbation is superimposed upon the linear potential scan, and a phase sensitive detector is used to extract and display the in-phase current response as a function of potential. This technique [40-42] is discussed in more detail in Chapter 8, but it is worth noting here that it may have some advantage for the study of fast coupled chemical reactions. At the present stage it is, however, a technique for obtaining numerical parameters when the mechanism is known and there is little in the literature concerning its use as a tool to investigate complex mechanisms. 

Similar to EIS, SWV (square-wave voltammetry) is another frequency-dependent electrochemical technique that could also be used in label-free Faradaic immunosensing [167]. In this case, a train of potential pulses is superimposed on a staircase potential signal with the latter centered between a cathodic pulse and an anodic pulse of the same amplitude. During each cathodic pulse, the analyte diffuses to the electrode surface and it is immediately reduced. During the anodic pulse, analyte that was just reduced is reoxidized. The current is sampled just before and at the end of each pulse and the current difference between these two points is then plotted against the staircase potential in a SW voltammogram. A linear potential scan in SWV is faster than EIS record and a familiar peak-shaped signal is more easily interpreted. 

Nowadays, sophisticated instrumentation, such as a potentiostat/galvanostat is commercially available for conducting electrochemical experiments for characterizing the electrochemical behavior a metal or an alloy in a few minutes. Nevertheless, a polarization diagram or curve is a potent control technique. This curve can experimentally be obtained statically or dynamically. The latter approach requires a linear potential scan rate to be applied over a desired potential range in order to measure the current response. 

EPS voltammetry employing a linear potential scan j = vt is a widely applied technique. The theoretical basis of this method was elaborated for different... 

Different transient techniques have also been suggested for the measurement of corrosion rate. Pulse techniques can be used to eliminate from the polarization data the effects of uncompensated solution resistance and mass transport, or to minimize the effect of time-dependent phenomena. However, these techniques must be used with caution because the classical electrode kinetic theory can be used in the data evaluation only if /corrA/<0.9. The square-wave techniqueand ac impedance techniquehave also been used to measure the polarization resistance. The linear potential scan (potentiodynamic) technique has been used to obtain the polarization curve or the polarization resistance (small-amplitude cyclic voltammetry and exponential scan techniques were also proposed to determine the polarization curve. 

As mentioned in the introduction of the amperometry techniques, the voltammetry with periodical renewal of the diffusion layer is particularly effective in monitoring a process differently involving an electroactive species, e.g., in the already mentioned amperometric titrations, in the determination of the stability of a species, etc. In particular cases, also simple chronoamperometry, i.e., at a fixed, suitably chosen potential, may be effective to this purpose. Noteworthy, it will be clear in the following that the much more widely diffused linear potential scan and cyclic voltammetric techniques are not always suitable to substitute for voltammetry with periodical renewal of the diffusion layer to the purpose of monitoring electroactive species during their transformation. Voltammetry with periodical renewal of the diffusion layer, as well as the voltammetry at rotating disk electrode, only allows the estimation of the concentrations of both partners of a redox couple, on the basis of the ratio between the anodic and cathodic limiting currents. 

In linear sweep voltammetric techniques the applied electrode potential is varied from an initial value E to a final value f at a constant scan rate v (single sweep voltammetry). Once the value is reached the direction of the scan can be reversed, maintaining the same scan rate v, and the potential brought back to the initial value (cyclic voltammetry). In the two cases the form of the potential-time impulse can be represented as shown in Figure 1. 

The development of ultramicroelectrodes with characteristic physical dimensions below 25 pm has allowed the implementation of faster transients in recent years, as discussed in Section 2.4. For CA and DPSC this means that a smaller step time x can be employed, while there is no advantage to a larger t. Rather, steady-state currents are attained here, owing to the contribution from spherical diffusion for the small electrodes. However, by combination of the use of ultramicroelectrodes and microelectrodes, the useful time window of the techniques is widened considerably. Compared to scanning techniques such as linear sweep voltammetry and cyclic voltammetry, described in the following, the step techniques have the advantage that the responses are independent of heterogeneous kinetics if the potential is properly adjusted. The result is that fewer parameters need to be adjusted for the determination of rate constants. 

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 ... 

Cydodextrins (CyDs) with their largely hydrophobic cavities of variable size and numerous ways of chemical modification are the subject of intensive electrochemical research induding both their behavior in homogeneous solutions and in thin films attached to the electrode surfaces [1-8]. Electroanalytical methods measuring the current response to the potential applied, linear scan, staircase, and pulse voltammetries, and potential-step techniques such as chronoamperometry and... 

The majority of measurements for electroanalysis with microelectrodes are recorded under steady-state conditions by using either chronoamperometry (CA), linear sweep voltammetry (LSV) or cyclic voltammetry (CV) [1,2, 9,10]. Moreover, to solve problems related to the selectivity between species with similar redox potentials, pulsed techniques such as differential pulse voltammetry (DPV) [1, 7, 43 5] and square-wave voltammetry (SWV) [1, 45-49] have been employed. The use of the latter technique also minimizes the influence of oxygen in aerated natural samples [47]. In order to enhance sensitivity in these measurements, fast-scan voltammetry (FSV) [50] or the accumulation of analytes onto an electrode surface has also been performed, in conjunction with stripping analysis (SA) [51]. 

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