Working electrodes, amperometric

Because the electrode process takes place solely at the surface of the working electrode, amperometric flow cells can determine only local (interfacial) concentrations. Conductometric and potentiometric measuring cells, on the other hand, can track the average volumetric concentrations in the eluate. The same holds for UV detection, which is preferred for routine HPLC studies (see Section 12.2.6.3). 

One important application of amperometry is in the construction of chemical sensors. One of the first amperometric sensors to be developed was for dissolved O2 in blood, which was developed in 1956 by L. C. Clark. The design of the amperometric sensor is shown in Figure 11.38 and is similar to potentiometric membrane electrodes. A gas-permeable membrane is stretched across the end of the sensor and is separated from the working and counter electrodes by a thin solution of KCl. The working electrode is a Pt disk cathode, and an Ag ring anode is the... 

Electrochemical Detectors Another common group of HPLC detectors are those based on electrochemical measurements such as amperometry, voltammetry, coulometry, and conductivity. Figure 12.29b, for example, shows an amperometric flow cell. Effluent from the column passes over the working electrode, which is held at a potential favorable for oxidizing or reducing the analytes. The potential is held constant relative to a downstream reference electrode, and the current flowing between the working and auxiliary electrodes is measured. Detection limits for amperometric electrochemical detection are 10 pg-1 ng of injected analyte. 

Two distinctly different coulometric techniques are available (1) coulometric analysis with controlled potential of the working electrode, and (2) coulometric analysis with constant current. In the former method the substance being determined reacts with 100 per cent current efficiency at a working electrode, the potential of which is controlled. The completion of the reaction is indicated by the current decreasing to practically zero, and the quantity of the substance reacted is obtained from the reading of a coulometer in series with the cell or by means of a current-time integrating device. In method (2) a solution of the substance to be determined is electrolysed with constant current until the reaction is completed (as detected by a visual indicator in the solution or by amperometric, potentiometric, or spectrophotometric methods) and the circuit is then opened. The total quantity of electricity passed is derived from the product current (amperes) x time (seconds) the present practice is to include an electronic integrator in the circuit. 

FIGURE 3-23 Schematic of a carbon-fiber amperometric detector for capillary electrophoresis A, fused silica capillary B, eluent drop C, stainless steel plate RE, reference electrode WE, working electrode, AE, auxiliary electrode. (Reproduced with permission from reference 58.)... 

Polarisation titrations are often referred to as amper-ometric or biamperometric titrations. It is necessary that one of the substances involved in the titration reaction be oxidisable or reducible at the working electrode surface. In general, the polarisation titration method is applicable to oxidation-reduction, precipitation and complex-ation titrations. Relatively few applications involving acid/base titration are found. Amperometric titrations can be applied in the determination of analyte solutions as low as ICE5 M to 10-6 M in concentration. 

Coulometry and amperometry can be distinguished by the extent to which the analyte undergoes a Faradaic reaction at the working electrode, namely complete and partial, respectively. Coulometry is essentially high-efficiency amperometry with working electrodes of large surface area. Successful coulometric or amperometric detection can result only if the applied potential is chosen correctly. 

Figure 3.8 Amperometric detectors (a) measure the current that flows between the working electrode, usually a glassy carbon electrode, and a reference electrode, at a fixed voltage, usually close to the discharge potential for the compound. Coulometric detectors (b) are less common and are designed with a porous carbon flow cell so that all the analyte reacts in the cell, the amount of current consumed during the process being proportional to the amount of the substance.

Hilmi and Luong [25] employed a gold working electrode, formed by electroless deposition onto the chip capillary outlet, for highly sensitive amperometric detection of nitroaromatic explosives [with a detection limit of 24 ppb trinitrotoluene (TNT)]. Analysis of a mixture of four explosives (TNT, 2,4-DNT,... 

A cell with a small Pt disk working electrode coated with a polyelectrolyte multilayer made of poly(allylamine)-poly(vinyl sulfate), a Pt wire counterelectrode and a reference SCSE may be used for selective amperometric determination of H2O2, in the presence of ascorbic acid (22), uric acid (29) and acetaminophen (148). The latter three compounds show a significant response with the bare working electrode at +0.6 V while a practically nil one with the coated electrode. The reason for this selectivity may be an exclusion effect by the coating. ... 

A microsensor system for simultaneous amperometric determination of H2O2 and 02 consists of two working electrodes, one Pt counterelectrode and one WO3 reference electrode. The working electrodes are GCE covered with HRP immobilized in an elec-trodeposited membrane of polypyrrole the working electrode for 02 has in addition a layer of immobilized superoxide dismutase. Operation with this system is at pH 5.1, setting both working electrodes at —60 mV. Other operating modes are also possible. ... 

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