Forward current component Frequency

The voltammetric features of a reversible reaction are mainly controlled by the thickness parameter A = The dimensionless net peak current depends sigmoidally on log(A), within the interval —0.2 < log(A) <0.1 the dimensionless net peak current increases linearly with A. For log(A )< —0.5 the diSusion exhibits no effect to the response, and the behavior of the system is similar to the surface electrode reaction (Sect. 2.5.1), whereas for log(A) > 0.2, the thickness of the layer is larger than the diffusion layer and the reaction occurs under semi-infinite diffusion conditions. In Fig. 2.93 is shown the typical voltammetric response of a reversible reaction in a film having a thickness parameter A = 0.632, which corresponds to L = 2 pm, / = 100 Hz, and Z) = 1 x 10 cm s . Both the forward and backward components of the response are bell-shaped curves. On the contrary, for a reversible reaction imder semi-infinite diffusion condition, the current components have the common non-zero hmiting current (see Figs. 2.1 and 2.5). Furthermore, the peak potentials as well as the absolute values of peak currents of both the forward and backward components are virtually identical. The relationship between the real net peak current and the frequency depends on the thickness of the film. For Z, > 10 pm and D= x 10 cm s tlie real net peak current depends linearly on the square-root of the frequency, over the frequency interval from 10 to 1000 Hz, whereas for L <2 pm the dependence deviates from linearity. The peak current ratio of the forward and backward components is sensitive to the frequency. For instance, it varies from 1.19 to 1.45 over the frequency interval 10 < //Hz < 1000, which is valid for Z < 10 pm and Z) = 1 x 10 cm s It is important to emphasize that the frequency has no influence upon the peak potential of all components of the response and their values are virtually identical with the formal potential of the redox system. 

In lasers, luminescent diodes, power diodes and solar cells it was found that in the low injection region the current noise spectral density is a quadratic function of the forward current. Typically, the excess current is a dominant current component in this region. The current noise spectral density vs. frequency for PN junction is shown in Fig. 19. Curve 1 denotes the current noise spectral density for the low injection range, curve 2 is the current noise spectral density for the... 

For the catalytic electrode mechanism, the total surface concentration of R plus O is conserved throughout the voltammetric experiment. As a consequence, the position and width of the net response are constant over entire range of values of the parameter e. Figure 2.35 shows that the net peak current increases without limit with e. This means that the maximal catalytic effect in particular experiment is obtained at lowest frequencies. Figure 2.36 illustrates the effect of the chemical reaction on the shape of the response. For log(e) < -3, the response is identical as for the simple reversible reaction (curves 1 in Fig. 2.36). Due to the effect of the chemical reaction which consumes the O species and produces the R form, the reverse component decreases and the forward component enhances correspondingly (curves 2 in Fig. 2.36). When the response is controlled exclusively by the rate of the chemical reaction, both components of the response are sigmoidal curves separated by 2i sw on the potential axes. As shown by the inset of Fig. 2.36, it is important to note that the net currents are bell-shaped curves for any observed kinetics of the chemical reaction, with readily measurable peak current and potentials, which is of practical importance in electroanalytical methods based on this electrode mecharusm. 

Figure 3.12 shows the forward and backward components of square-wave voltam-mograms of mercury(ll)-ferron complex adsorbed on the surface of static mercuiy drop electrode [208]. The ratio of the current and the corresponding SW frequency is reported. At pH 3.5 the electrode reaction involves the direct transfer of two electrons, whereas at pH 5.8 only one electron is exchanged. The simulated responses are presented by symbols. The best fit was achieved by using the following standard rate constants and the transfer coefficients k. = 1550 50 s and a = 0.5 (at pH 3.5), and = 1900 400s and a = 0.55 (at pH 5.8) [208]. 

Separation of the cathodic and anodic components of the net current (measured at the end of forward and backward pulses) in square-wave voltammetries (SQWVs) provided only anodic components for PTA Y electrodes immersed into BU4NPI ),/ MeCN, as depicted in Figure 8.15. In contrast, SQWVs display well-developed anodic and cathodic components for PTA Y electrodes in contact with LiClO4/ MeCN. This feature, indicative of reversible electron transfer processes, was found to be more pronounced on decreasing square-wave frequency. 

The net current of a totally irreversible electrode reaction (Fq. II.3.1) is smaller than its forward component because the backward component is positive for all potentials (see Fig. II.3.4), regardless of the amplitude [43 5]. The ratio and the half-peak width are both independent of the frequency, but the net... 

In linear or pseudo-linear systems, the current response to a sinusoidal voltage input will be a sinusoid at the same frequency but shifted in phase (either forward or backward depending on the system s characteristics) that is determined by the ratio of capacitive and resistive components of the output current (Fig. 1). In a linear system, the response current signal I(t) is shifted in phase (i ) and has a different amplitude, 1a ... 

The square wave voltammetric waveform consists of a square wave superimposed on a staircase, as shown in Fig. 2.37. The currents at the end of the forward and reverse pulses are both registered as a function of staircase potential. The difference between them, the net current, is larger than either of its two component parts in the region of the peak which is centred on the half-wave potential. Capacitative contributions can be effectively discriminated against before they die away, since, over a small potential range between forward and reverse pulses, the capacitance is constant and is thus annulled by subtraction. In this way the pulses can be shorter than in DPV and the square wave frequency can be higher. Instead of the effective sweep rates of 1-10 mVs of DPV, scan rates of 1 Vs can be employed. 

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