Flow voltammetry

Hepler, B. R., Weber, S. G., and Purdy, W. G., 1978, The behavior of an electrochemical detector used in liquid chromatography and continuous flow voltammetry. 2. Evaluation of low-temperature isotropic carbon for use as an electrode material, Anal. Chim. Acta 102 41-59. 

The largest division of interfacial electrochemical methods is the group of dynamic methods, in which current flows and concentrations change as the result of a redox reaction. Dynamic methods are further subdivided by whether we choose to control the current or the potential. In controlled-current coulometry, which is covered in Section IIC, we completely oxidize or reduce the analyte by passing a fixed current through the analytical solution. Controlled-potential methods are subdivided further into controlled-potential coulometry and amperometry, in which a constant potential is applied during the analysis, and voltammetry, in which the potential is systematically varied. Controlled-potential coulometry is discussed in Section IIC, and amperometry and voltammetry are discussed in Section IID. 

In voltammetry a time-dependent potential is applied to an electrochemical cell, and the current flowing through the cell is measured as a function of that potential. A plot of current as a function of applied potential is called a voltammogram and is the electrochemical equivalent of a spectrum in spectroscopy, providing quantitative and qualitative information about the species involved in the oxidation or reduction reaction.The earliest voltammetric technique to be introduced was polarography, which was developed by Jaroslav Heyrovsky... 

Electrochemical methods covered in this chapter include poten-tiometry, coulometry, and voltammetry. Potentiometric methods are based on the measurement of an electrochemical cell s potential when only a negligible current is allowed to flow, fn principle the Nernst equation can be used to calculate the concentration of species in the electrochemical cell by measuring its potential and solving the Nernst equation the presence of liquid junction potentials, however, necessitates the use of an external standardization or the use of standard additions. 

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. 

The term polarography basically refers to a method, where the current flowing across the electrochemical interface is recorded as a function of the applied electrode potential, historically in most cases a mercury electrode is involved. Thus polarography might be called also voltammetry. This sometimes results in confusing terms like e.g. AC voltammetry, which is obviously equivalent to AC polarography (see following entry). (Data obtained with this method are labelled DCP.)... 

In conclusion, synthetic dyes can be determined in solid foods and in nonalcoholic beverages and from their concentrated formulas by spectrometric methods or by several separation techniques such as TEC, HPLC, HPLC coupled with diode array or UV-Vis spectrometry, MECK, MEECK, voltammetry, and CE. ° Many analytical approaches have been used for simultaneous determinations of synthetic food additives thin layer chromatography, " " derivative spectrophotometry, adsorptive voltammetry, differential pulse polarography, and flow-through sensors for the specific determination of Sunset Yellow and its Sudan 1 subsidiary in food, " but they are generally suitable only for analyzing few-component mixtures. 

LCEC is a special case of hydrodynamic chronoamperometry (measuring current as a function of time at a fixed electrode potential in a flowing or stirred solution). In order to fully understand the operation of electrochemical detectors, it is necessary to also appreciate hydrodynamic voltammetry. Hydrodynamic voltammetry, from which amperometry is derived, is a steady-state technique in which the electrode potential is scanned while the solution is stirred and the current is plotted as a function of the potential. Idealized hydrodynamic voltammograms (HDVs) for the case of electrolyte solution (mobile phase) alone and with an oxidizable species added are shown in Fig. 9. The HDV of a compound begins at a potential where the compound is not electroactive and therefore no faradaic current occurs, goes through a region... 

Gunasingham, H. and Fleet, B., Hydrodynamic voltammetry in continuous-flow analysis, in Electroanalytical Chemistry A Series of Advances, Vol. 16, Bard, A. J., Ed., Marcel Dekker, New York, 1989, 89. 

In the application of tubular electrodes and electrodes in flow cells, there may often be hydrodynamic complications, especially in voltammetry. 

Voltammetry at other hydrodynamic electrodes The particular features of this technique are (a) plate, conical and tubular electrodes in contact with the flowing solutions and (b) vibrating dme and streaming mercury electrodes. 

In the laboratory, electroanalysis is used for two main purposes, either for direct measurement of a physico-chemical property that is informative with respect to the identity and/or amount of the analyte, or for detecting the course of conversion of the analyte or indicating the separate appearance of analyte components, which is informative with respect to their identity and amount. In the former instance we are dealing with conductometry, voltammetry and coulometry and in the latter with various titrations and mostly separational flow techniques such as chromatography and flow injection analysis. 

Stripping analysis with inherent pre-concentration seems attractive to CFA, but until recently such a procedure appeared rather exceptional. It has been used in the automatic determination of heavy metals in water by anodic stripping voltammetry (ASV12S) in a continuous flow cell with a mercury-covered graphite electrode, having the advantage that one can distinguish... 

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. 

Wangfuengkanagul and Chailapakul [9] described the electroanalysis of ( -penicillamine at a boron-doped diamond thin film (BDD) electrode using cyclic voltammetry. The BDD electrode exhibited a well-resolved and irreversible oxidation voltammogram, and provided a linear dynamic range from 0.5 to 10 mM with a detection limit of 25 pM in voltammetric measurement. In addition, penicillamine has been studied by hydrodynamic voltammetry and flow injection analysis with amperometric detection using the BDD electrode. 

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