Charge voltammetry

In adsorptive stripping voltammetry the deposition step occurs without electrolysis. Instead, the analyte adsorbs to the electrode s surface. During deposition the electrode is maintained at a potential that enhances adsorption. For example, adsorption of a neutral molecule on a Hg drop is enhanced if the electrode is held at -0.4 V versus the SCE, a potential at which the surface charge of mercury is approximately zero. When deposition is complete the potential is scanned in an anodic or cathodic direction depending on whether we wish to oxidize or reduce the analyte. Examples of compounds that have been analyzed by absorptive stripping voltammetry also are listed in Table 11.11. 

Zoski, C. G. Charging Current Discrimination in Analytical Voltammetry, /. Chem. Educ. 1986, 63, 910—914. 

The difference between the various pulse voltammetric techniques is the excitation waveform and the current sampling regime. With both normal-pulse and differential-pulse voltammetry, one potential pulse is applied for each drop of mercury when the DME is used. (Both techniques can also be used at solid electrodes.) By controlling the drop time (with a mechanical knocker), the pulse is synchronized with the maximum growth of the mercury drop. At this point, near the end of the drop lifetime, the faradaic current reaches its maximum value, while the contribution of the charging current is minimal (based on the time dependence of the components). 

Normal-pulse voltammetry consists of a series of pulses of increasing amplitude applied to successive drops at a preselected time near the end of each drop lifetime (4). Such a normal-pulse train is shown in Figure 3-4. Between the pidses, the electrode is kept at a constant (base) potential at which no reaction of the analyte occurs. The amplitude of the pulse increases linearly with each drop. The current is measured about 40 ms after the pulse is applied, at which time the contribution of the charging current is nearly zero. In addition, because of the short pulse duration, the diffusion layer is thinner than that in DC polarography (i.e., there is larger flux of... 

Potential of zero charge, 20, 23, 25, 66 Potential scanning detector, 92 Potential step, 7, 42, 60 Potential window, 107, 108 Potentiometry, 2, 140 Potentiometric stripping analysis, 79 Potentiostat, 104, 105 Preconcentrating surfaces, 121 Preconcentration step, 121 Pretreatment, 110, 116 Pulsed amperometric detection, 92 Pulse voltammetry, 67... 

The electrochemistry of a polymer-modified electrode is determined by a combination of thermodynamics and the kinetics of charge-transfer and transport processes. Thermodynamic aspects are highlighted by cyclic voltammetry, while kinetic aspects are best studied by other methods. These methods will be introduced here, with the emphasis on how they are used to measure the rates of electron and ion transport in conducting polymer films. Charge transport in electroactive films in general has recently been reviewed elsewhere.9,11... 

The kinetics of charge transfer between metallic electrodes and conducting polymer films have proved to be difficult to investigate, and little reliable data exist. Charge-transfer limitations have been claimed in cyclic voltammetry, and Butler-Volmer kinetics have been used in a number of... 

One of the most problematic issues, still to be fully resolved, is the dependence of the degree of oxidation on potential, as measured most commonly by cyclic voltammetry at low scan rates. There is currently no accepted model to describe the shape of the curve and the hysteresis between anodic and cathodic scans. The debate over whether the charge has a significant component due to a polymer/solution double layer is still not fully resolved. 

Fig. 11. Cyclic voltammetry of first discharging/charging of galvanostatically prepared PPy films (PC, 0.5 M LiC104) the first three cycles between +0.5 V and —0.3 V, the following between +0.5 V and —1.1 V...

The cis/trans isomerization of cw-polyacetylene, previously only disclosed from spectroscopic data, has recently been detected by cyclic voltammetry The analysis of the redox data reveals that the trans-form is thermodynamically more favorable in the charged than in neutral state. 

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