Voltammetry basic theory

Before discussing the voltammogram obtained with the triangular waveform of figure 16.3, which is simply a plot of the observed current intensity versus the applied potential, it is useful to describe some experimental details of a cyclic voltammetry experiment [335-337] and to recall some basic theory of dynamic electrochemistry [180,332], A typical cell (figure 16.4) consists of... 

The summary given by this author rests on the work of several theorists who followed the work of Sevcik. Among the most outstanding of these is Paul Delahay who. with Strassner and others in 1951 1953 contributed much to the basic theory of linear sweep voltammetry with partial interfacial control. Students interested in programs for such simulations should contact Prof. David K. Gosser, Chemistry Department, City College of New York, NY, 10031. 

Several electrochemical techniques may yield the reduction or oxidation potentials displayed in figure 16.1 [332-334], In this chapter, we examine and illustrate the application of two of those techniques cyclic voltammetry and photomodulation voltammetry. Both (particularly the former) have provided significant contributions to the thermochemical database. But before we do that, let us recall some basic ideas that link electrochemistry with thermodynamics. More in-depth views of this relationship are presented in some general physical-chemistry and thermodynamics textbooks [180,316]. A detailed discussion of theory and applications of electrochemistry may be found in more specialized works [332-334],... 

The theory of linear-sweep voltammetry (LSV) applied to heterogeneous redox reactions accompanied by the nondissociative adsorption of the reactant or the product is developed. The basic criterial relationships of LSV in this case are invariant with respect to the type of adsorption isotherm and the number of adsorption sites occupied by one species. The degree of irreversibility of the discharge-ionization step can be evaluated from the effect of the potential scan rate on the peak potential. The nature of the adsorbate can be deduced from the effect of the reactant concentrations on the peak current. 

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