Peak voltammetry

A more important practical problem is interpreting the apparently confusing responses obtained with linear potential sweep (peak voltammetry) methods. Although the linear potential sweep method has not been used much in vivo, it is often applied to pretest electrodes in solution, determine oxidation potentials (for example, see Table 3), etc. Depending... 

Cyclic voltammetry provides a simple method for investigating the reversibility of an electrode reaction (table Bl.28.1). The reversibility of a reaction closely depends upon the rate of electron transfer being sufficiently high to maintain the surface concentrations close to those demanded by the electrode potential through the Nemst equation. Therefore, when the scan rate is increased, a reversible reaction may be transfomied to an irreversible one if the rate of electron transfer is slow. For a reversible reaction at a planar electrode, the peak current density, fp, is given by... 

Stripping voltammetry involves the pre-concentration of the analyte species at the electrode surface prior to the voltannnetric scan. The pre-concentration step is carried out under fixed potential control for a predetennined time, where the species of interest is accumulated at the surface of the working electrode at a rate dependent on the applied potential. The detemiination step leads to a current peak, the height and area of which is proportional to the concentration of the accumulated species and hence to the concentration in the bulk solution. The stripping step can involve a variety of potential wavefomis, from linear-potential scan to differential pulse or square-wave scan. Different types of stripping voltaimnetries exist, all of which coimnonly use mercury electrodes (dropping mercury electrodes (DMEs) or mercury film electrodes) [7, 17]. 

Thus, the limiting current, is a linear function of the concentration of O in bulk solution, and a quantitative analysis is possible using any of the standardization methods discussed in Chapter 5. Equations similar to equation 11.35 can be developed for other forms of voltammetry, in which peak currents are related to the analyte s concentration in bulk solution. 

The concentration of copper in a sample of sea water is determined by anodic stripping voltammetry using the method of standard additions. When a 50.0-mL sample is analyzed, the peak current is 0.886 )J,A. A 5.00-)J,L spike of 10.0-ppm Cu + is added, giving a peak current of 2.52 )J,A. Calculate the parts per million of copper in the sample of sea water. 

Peak currents in anodic stripping voltammetry are a linear function of concentration... 

Precision Precision is generally limited by the uncertainty in measuring the limiting or peak current. Under most experimental conditions, precisions of+1-3% can be reasonably expected. One exception is the analysis of ultratrace analytes in complex matrices by stripping voltammetry, for which precisions as poor as +25% are possible. 

Selectivity Selectivity in voltammetry is determined by the difference between half-wave potentials or peak potentials, with minimum differences of+0.2-0.3 V required for a linear potential scan, and +0.04-0.05 V for differential pulse voltammetry. Selectivity can be improved by adjusting solution conditions. As we have seen, the presence of a complexing ligand can substantially shift the potential at which an analyte is oxidized or reduced. Other solution parameters, such as pH, also can be used to improve selectivity. 

X f0 ppb Sb was added, anodic stripping voltammetry is repeated, giving a peak current of f.i4 pA. How many nanograms of Sb is collected from the individual s hand ... 

A novel sensitive and seleetive adsorptive stripping proeedure for simultaneous determination of eopper, bismuth and lead is presented. The method is based on the adsorptive aeeumulation of thymolphetalexone (TPN) eomplexes of these elements onto a hanging mereury drop eleetrode, followed by reduetion of adsorbed speeies by voltammetrie sean using differential pulse modulation. The optimum analytieal eonditions were found to be TPN eoneentration of 4.0 p.M, pH of 9.0, and aeeumulation potential at -800 mV vs. Ag/AgCl with an aeeumulation time of 80 seeonds. The peak eurrents ai e proportional to the eoneentration of eopper, bismuth and lead over the 0.4-300, 1-200 and 1-100 ng mL ranges with deteetion limits of 0.4, 0.8 and 0.7 ng mL respeetively. The proeedure was applied to the simultaneous determination of eopper, bismuth and lead in real and synthetie samples with satisfaetory results. 

A study of the electrochemical oxidation and reduction of certain isoindoles (and isobenzofurans) has been made, using cyclic voltammetry. The reduction wave was found to be twice the height of the oxidation wave, and conventional polarography confirmed that reduction involved a two-electron transfer. Peak potential measurements and electrochemiluminescence intensities (see Section IV, E) are consistent vidth cation radicals as intermediates. The relatively long lifetime of these intermediates is attributed to steric shielding by the phenyl groups rather than electron delocalization (Table VIII). 

Emission spectra have been recorded for four aryl-substituted isoindoles rmder conditions of electrochemical stimulation. Electrochemiluminescence, which was easily visible in daylight, was measured at a concentration of 2-10 mM of emitter in V jV-dimethylformamide with platinum electrodes. Emission spectra due to electrochemi-luminescence and to fluorescence were found to be identical, and quantum yields for fluorescence were obtained by irradiation with a calibrated Hght source. Values are given in Table X. As with peak potentials determined by cyclic voltammetry, the results of luminescence studies are interpreted in terms of radical ion intermediates. ... 

Tire deprotonation of thiazolium salts (see Section II) under argon at room temperature allowed the characterization of nonfused DTDAF of types 52 and 53 by cyclic voltammetry. Their very good donor properties were confirmed by two quasi-reversible peaks of equal intensity (93CC601). It is noteworthy that upon a second scan the first oxidation peak was shifted from -0.03 to -0.04 V. Upon further scans the voltam-mogram remains unchanged. Tliis interesting feature has been observed previously with TTF analogs. It was demonstrated that the neutral form... 

In view of the limitations referred to above, and particularly the influence of electrode characteristics upon the peaks in the voltammogram, some care must be exercised in setting up an apparatus for stripping voltammetry. The optimum conditions require ... 

Voltaic cells 64. 504 Voltammetry 7, 591 anodic stripping, 621 concentration step, 621 mercury drop electrode, 623 mercury film electrode, 623 peak breadth, 622 peak current, 622 peak potential, 622 purity of reagents, 624 voltammogram, 622 D. of lead in tap water, 625 Volume distribution coefficient 196 Volume of 1 g of water at various temperatures, (T) 87... 

A mixture of LiOH and EMD is heated at 420 °C for 2-3 h in order to allow molten LiOH to penetrate into the pores of the EMD. The mixture is then heated from 650 to 800 °C to produce LiMn204. The amount of LiOH and EMD in the mixture must be stoichiometric (LiOH Mn02 = 1 2). The product, LiMn204, is usually tested by cyclic voltammetry (Fig. 22) a good LiMn204does not have peaks at a and b.(peak a (3.3 V) would be due to the oxygen deficiency and peak b (4.5 V) to replacement of the Li ion sites by Mn4+... 

Cyclic voltammetry can also be useful for quantitative purposes, based on measurements of the peak current (equation 2-1). Such quantitative applications require the establishment of the proper baseline. For neighboring peaks (of a mixture), the baseline for the second peak is obtained by extrapolating the current decay of the... 

Cyclic voltammetry is most commonly used to investigate the polymerization of a new monomer. Polymerization and film deposition are characterized by increasing peak currents for oxidation of the monomer on successive cycles, and the development of redox waves for the polymer at potentials below the onset of monomer oxidation. A nucleation loop, in which the current on the reverse scan is higher than on the corresponding forward scan, is commonly observed during the first cycle.56,57 These features are all illustrated in Fig. 3 for the polymerization of a substituted pyrrole.58... 

If the film is nonconductive, the ion must diffuse to the electrode surface before it can be oxidized or reduced, or electrons must diffuse (hop) through the film by self-exchange, as in regular ionomer-modified electrodes.9 Cyclic voltammograms have the characteristic shape for diffusion control, and peak currents are proportional to the square root of the scan speed, as seen for species in solution. This is illustrated in Fig. 21 (A) for [Fe(CN)6]3 /4 in polypyrrole with a pyridinium substituent at the 1-position.243 This N-substituted polypyrrole does not become conductive until potentials significantly above the formal potential of the [Fe(CN)6]3"/4 couple. In contrast, a similar polymer with a pyridinium substituent at the 3-position is conductive at this potential. The polymer can therefore mediate electron transport to and from the immobilized ions, and their voltammetry becomes characteristic of thin-layer electrochemistry [Fig. 21(B)], with sharp symmetrical peaks that increase linearly with increasing scan speed. 

The second approach, followed by Vayenas et al39 is direct measurement of Ntpb and N n using cyclic voltammetry, as in aqueous electrochemistry,49 and measuring the height, Ip, or the area fldt of the cathodic oxygen reduction peak (Fig. 5.28a). Then Ntpb can be estimated from ... 

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