Analytical voltammetry

In the previous section we saw how voltammetry can be used to determine the concentration of an analyte. Voltammetry also can be used to obtain additional information, including verifying electrochemical reversibility, determining the number of electrons transferred in a redox reaction, and determining equilibrium constants for coupled chemical reactions. Our discussion of these applications is limited to the use of voltammetric techniques that give limiting currents, although other voltammetric techniques also can be used to obtain the same information. 

Zoski, C. G. Charging Current Discrimination in Analytical Voltammetry, /. Chem. Educ. 1986, 63, 910—914. 

The dropping-mercury electrode. The usefulness of the dropping-mercury electrode (DME) for analytical voltammetry was discovered by Heyrovsky, and the history of this discovery has been recounted.102 The DME usually is prepared from a 10-20-cm length of glass-capillary tubing with an approxi-... 

Analytical Voltammetry, a recent volume in the Comprehensive Analytical Chemistry series). 

Baeisci JN, Riley PJ and Wallace GG (1992) Instrumentation. In Smyth MR and Vos JG, volume editors. Analytical voltammetry. In Svehla G, ed. Wilson and WUsoris Comprehensive analytical chemistry, Vol 27, pp. 74—114. Elsevier, Amsterdam. 

Fernandez JM, Hayes PJ and Smyth MR (1992) Analytical voltammetry in environmental science. 

I. Inorganic species. In Smyth MR and Vos JG, volume editors, Analytical voltammetry. In ... 

Analytical voltammetry. In Svehla G, ed. Wilson and Wilson s Comprehensive analytical chemistry, Vol 27. Elsevier, Amsterdam. 

Forster, R.J. and Vos, J.G. (1992) in Smyth, M.R. and Vos, J.G. (eds) Analytical Voltammetry, Comprehensive Analytical Chemistry Vol XXVII, series Editor, Svehhla, Elsevier, Amsterdam, pp465-531. 

Electrochemical methods continue to be important as well, including inverse voltammetry, coulometry. amperometry, and potentiometry (- Analytical Voltammetry and Polarography) indeed, their overall role has actually been expanded with the development of such chemical techniques as ion chromatography and chelate HPLC. 

The signal current is the result of an electrochemical conversion of the analyte by oxidation or reduction at the working electrode (Fig. 17). The currents are in the pA-pA range and are measured by the three-electrode technique (- Analytical Voltammetry and Polarography). As a result extremely low detection limits at the O.l-pmol level can be achieved. 

For the fast-scan technique in HPLC, in which the potential is varied rapidly across its full range, the method of square-wave voltammetry (- Analytical Voltammetry and Polarography) has provided the basis for the development of a rapid-scan square-wave voltammetric detector ... 

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