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Synchronized Electrodes

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). [Pg.67]

Another technique consists of MC measurements during potential modulation. In this case the MC change is measured synchronously with the potential change at an electrode/electrolyte interface and recorded. To a first approximation this information is equivalent to a first derivative of the just-explained MC-potential curve. However, the signals obtained will depend on the frequency of modulation, since it will influence the charge carrier profiles in the space charge layer of the semiconductor. [Pg.455]

Both methods obtain the necessary sensitivity by modulating the electrode potential between two values which define two distinct states of the electrode surface thus the chemistry to be observed is directly modulated and may be detected with great sensitivity by an appropriate form of synchronous detection. In the case of EMIRS, the modulation frequency is made sufficiently high compared to the wavelength scanning rate to enable a phase sensitive detection system to be used whereas, for SNIFTIRS, the electrode potential is held for a sufficient period at each potential to accumulate data from several interferometric scans and, after an adequate number, the two sets of data are ratioed. [Pg.551]

Since the CL reaction is being produced by an electrochemical stimulus, greater control is gained over the initiation, rate, and course of the CL reaction. Indeed this control can be to the extent that the CL reaction may be switched on and off, allowing for synchronous detection, effective background correction, and ready automation with computer control. By careful selection of the electrode material, surface treatment, and applied potential, an additional degree of electrochemical selectivity can also be introduced. [Pg.213]

Polarography is the classical name for LSV with a DME. With DME as the working electrode, the surface area increases until the drop falls off. This process produces an oscillating current synchronized with the growth of the Hg-drop. A typical polarogram is shown in Fig. 18b. 10a. The plateau current (limiting diffusion current as discussed earlier) is given by the Ilkovic equation... [Pg.681]

The effect of the volume and the surface catalytic reaction is sketched in Figs. 2.80 and 2.81, respectively. Obviously, the voltammetric behavior of the mechanism (2.188) is substantially different compared to the simple catalytic reaction described in Sect. 2.4.4. In the current mechanism, the effect of the volume catalytic reaction is remarkably different to the surface catalytic reaction, revealing that SWV can discriminate between the volume and the surface follow-up chemical reactions. The extremely high maxima shown in Fig. 2.81 correspond to the exhaustive reuse of the electroactive material adsorbed on the electrode surface, as a consequence of the synchronization of the surface catalytic reaction rate, adsorption equilibria, mass transfer rate of the electroactive species, and duration of the SW potential pulses. These results clearly reveal how powerful square-wave voltammetry is for analytical purposes when a moderate adsorption is combined with a catalytic regeneration of the electroactive material. This is also illustrated by a comparative analysis of the mechanism (2.188) with the simple surface catalytic reaction (Sect. 2.5.3) and the simple catalytic reaction of a dissolved redox couple (Sect. 2.4.4), given in Fig. 2.82. [Pg.118]

Urea in kidney dialysate can be determined by immobilizing urease (via silylation or with glutaraldehyde as binder) on commercially available acid-base cellulose pads the process has to be modified slightly in order not to alter the dye contained in the pads [57]. The stopped-flow technique assures the required sensitivity for the enzymatic reaction, which takes 30-60 s. Synchronization of the peristaltic pumps PI and P2 in the valveless impulse-response flow injection manifold depicted in Fig. 5.19.B by means of a timer enables kinetic measurements [62]. Following a comprehensive study of the effect of hydrodynamic and (bio)chemical variables, the sensor was optimized for monitoring urea in real biological samples. A similar system was used for the determination of penicillin by penicillinase-catalysed hydrolysis. The enzyme was immobilized on acid-base cellulose strips via bovine serum albumin similarly as in enzyme electrodes [63], even though the above-described procedure would have been equally effective. [Pg.299]


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See also in sourсe #XX -- [ Pg.46 ]




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