Applications amperometry

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... 

Other important alternate electrochemical methods under study for pCO rely on measuring current associated with the direct reduction of CO. The electrochemistry of COj in both aqueous and non-aqueous media has been documented for some time 27-29) interferences from more easily reduced species such as O2 as well as many commonly used inhalation anesthetics have made the direct amperometric approach difficult to implement. One recently described attempt to circumvent some of these interference problems employs a two cathode configuration in which one electrode is used to scrub the sample of O by exhaustive reduction prior to COj amperometry at the second electrode. The response time and sensitivity of the approach may prove to be adequate for blood ps applications, but the issue of interfering anesthetics must be addressed more thorou ly in order to make the technique a truly viable alternative to the presently used indirect potentiometric electrode. 

SECM-induced transfer [SECMIT Fig. 2(b)] can be used to characterize reversible phase transfer processes at a wide variety of interfaces. The basic idea is to perturb the process, initially at equilibrium, through local amperometry at the UME. Hitherto, diffusion-limited electrolysis has mainly been used in conjunction with metal tips, but ion transfer voltammetric probes (discussed briefly in Section III, and in detail in Chapter 15) can also be used. The application of a potential to the tip, sufficient to deplete the... 

SECM employs a mobile UME tip (Fig. 3) to probe the properties of a target interface. Although both amperometric and potentiometric electrodes have found application in SECM, amperometry - in which a target species is consumed or generated at the probe UME - has found the most widespread use in kinetic studies at liquid interfaces, as... 

Membranes. Apart from the role of membranes180 in ISEs, there are at least three important applications of membranes as measurement aids in flow analysis. viz., as diffusion membranes in (1) (partial) dialysis and in (2a) membrane amperometry (MEAM) and (2b) membrane voltammetry (MEVA), and as Donnan membranes in (3) differential ionic chromatography. 

The participation of cations in redox reactions of metal hexacyanoferrates provides a unique opportunity for the development of chemical sensors for non-electroactive ions. The development of sensors for thallium (Tl+) [15], cesium (Cs+) [34], and potassium (K+) [35, 36] pioneered analytical applications of metal hexacyanoferrates (Table 13.1). Later, a number of cationic analytes were enlarged, including ammonium (NH4+) [37], rubidium (Rb+) [38], and even other mono- and divalent cations [39], In most cases the electrochemical techniques used were potentiometry and amperometry either under constant potential or in cyclic voltammetric regime. More recently, sensors for silver [29] and arsenite [40] on the basis of transition metal hexacyanoferrates were proposed. An apparent list of sensors for non-electroactive ions is presented in Table 13.1. 

We have already briefly described a popular application of amperometry in Chapter 13. This was the electrochemical detector used in HPLC methods. In this application, the eluting mobile phase flows across the working electrode embedded in the wall of the detector flow cell. With a constant potential applied to the electrode (one sufficient to cause oxidation or reduction of mixture components), a current is detected when a mixture component elutes. This current translates into the chromatography peak... 

In 1C, the election-detection mode is the one based on conductivity measurements of solutions in which the ionic load of the eluent is low, either due to the use of eluents of low specific conductivity, or due to the chemical suppression of the eluent conductivity achieved by proper devices (see further). Nevertheless, there are applications in which this kind of detection is not applicable, e.g., for species with low specific conductivity or for species (metals) that can precipitate during the classical detection with suppression. Among the techniques that can be used as an alternative to conductometric detection, spectrophotometry, amperometry, and spectroscopy (atomic absorption, AA, atomic emission, AE) or spectrometry (inductively coupled plasma-mass spectrometry, ICP-MS, and MS) are those most widely used. Hence, the wide number of techniques available, together with the improvement of stationary phase technology, makes it possible to widen the spectrum of substances analyzable by 1C and to achieve extremely low detection limits. 

Direct-current amperometry (the measurement of electrochemical current in response to a fixed electrode potential) continues to be the most widely used finite-current electrochemical technique. Popular applications include endpoint... 

Another recent development is the advent of pulse amperometry in which the potential is repeatedly pulsed between two (or more) values. The current at each potential or the difference between these two currents ( differential pulse amperometry ) can be used to advantage for a number of applications. Similar advantages can result from the simultaneous monitoring of two (or more) electrodes poised at different potentials. In the remainder of this chapter it will be shown how the basic concepts of amperometry can be applied to various liquid chromatography detectors. There is not one universal electrochemical detector for liquid chromatography, but, rather, a family of different devices that have advantages for particular applications. Electrochemical detection has also been employed with flow injection analysis (where there is no chromatographic separation), in capillary electrophoresis, and in continuous-flow sensors. 

Detection launch the detection in Immusoft in order to follow the enzymatic reaction by chrono-amperometry at 250 mV versus Ag/AgCl (sequential detections of 2 s of potential application performed in each channel one after the other). 

A sensitivity increase and lower detection limit can be achieved in various ways with the use of voltammetric detectors rather than amperometry at fixed potential or with slow sweep. The principle of some of these methods was already mentioned application of a pulse waveform (Chapter 10) and a.c. voltammetry (Chapter 11). There is, nevertheless, another possibility—the utilization of a pre-concentration step that accumulates the electroactive species on the electrode surface before its quantitative determination, a determination that can be carried out by control of applied current, of applied potential or at open circuit. These pre-concentration (or stripping) techniques24"26 have been used for cations and some anions and complexing neutral species, the detection limit being of the order of 10-10m. They are thus excellent techniques for the determination of chemical species at trace levels, and also for speciation studies. At these levels the purity of the water and of the... 

Amperometry — a current (mostly a - faradaic current) is measured as a function of another experimental variable, e.g., concentration, volume of added reagent in analytical applications, or time. When faradaic current is measured as a function of electrode potential the method is called -> voltammetry (derived from - volt and -> ampere), measurement as a function of time is called -> chronoamperometry. See also - amperometric sensor. 

The field of electrochemical detection in CE have been extensively reviewed in Refs. 1-3. Instructive applications can be found for amperometry in Ref. 4, for potentiometry in Ref. 5, and for conductometry in Ref. 6. 

Detectors that have produced the lowest detection Emits to date are based on fluorescence with precolumn derivatization, mass spectrometry, radiometry, and amperometry. Applications are described below for these detection systems employed with conventional CE instrumentation. For applications of these detection methods to CE analysis using microfabricated devices, the reader is referred to a review article.3... 

The accepted reference method for determining chloride in blood serum, plasma, urine, sweat, and other body fluids is the coulometric titration procedure. In this technique, silver ions are generated coulometrically. The silver ions then react with chloride ions to form insoluble silver chloride. The end point is usually detected by amperometry (see Section 23B-4) when a sudden increase in current occurs on the generation of a slight excess of Ag. In principle, the absolute amount of Ag" needed to react quantitatively with Cl can be obtained from application of Faraday s law. In practice, calibration is used. First, the time required to titrate a chloride standard solution with a known number of moles of chloride (nci )s using a constant current I is measured. The same constant current is next used in the titration of the unknown solution, and the time r is measured. The number of moles of chloride in the unknown (ncr)u is then obtained as follows ... 

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