Potential and Voltaic Cells

Volta potentials are measured by means of voltaic cells, i.e., systems composed of conducting, condensed phases in series, with a gas, liquid dielectric (e.g., decane) or a vacuum (in the case of solid conductors such as metals) gap situated between two condensed phases. The gap, g, may contain a gas such as pure air or nitrogen, saturated with vapors of the liquids present. Owing to the presence of a dielectric, special methods are necessary for the investigation of voltaic cells (see Section IV). 

In the schemes shown in this chapter a single vertical bar ( ) is used to represent a metal/metal-, metal/gas, metal/solutio/gas phase boundary. 

The basic principle of every measurement of the Volta potential and generally of the investigations of voltaic cells too, in contrast to galvanic cells, may thus be presented for systems containing metal/solution (Fig. 2) and liquid/liquid interfaces (Fig. 3), respectively. This interface is created at the contact of aqueous and organic solutions (w and s, respectively) of electrolyte MX in the partition equilibrium. Of course, electrolyte MX, shown in Fig. 2 and other figures of this chapter, may be different in organic (s) and aqueous (w) phases. 

Thus the Volta potential may be operationally defined as the compensating voltage of the cell. Very often the terms Volta potential and compensation voltage are used interchangeably. It should be stressed that the compensating voltage of a voltaic cell is not always the direct measure of the Volta potential. 

In contradiction to the usual treatment, relation (5) is not general (see below). For this reason, as well as the lack of an exact thermodynamic relation with the changes in Gibbs energy, the term compensation voltage is also recommended instead of emf, which is commonly used for 

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