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In practice, it is very often necessary to determine the potential of a test (indicator) electrode connected in a cell with a well defined second electrode. This reference electrode is usually a suitable electrode of the second kind, as described in Section 3.2.2. The potentials of these electrodes are tabulated, so that Eq. (3.1.66) can be used to determine the potential of the test electrode from the measured EMF. The standard hydrogen electrode is a hydrogen electrode saturated with gaseous hydrogen with a partial pressure equal to the standard pressure and immersed in a solution with unit hydrogen ion activity. Its potential is set equal to zero by convention. Because of the relative difficulty involved in preparing this electrode and various other complications (see Section 3.2.1), it is not used as a reference electrode in practice. The term 'electrode potential' is often used in a broader sense, e.g. for the potential of an ideally polarized electrode ( 4) or for potentials in non-equilibrium systems ( 5). Similar to electrode potentials, standard electrode potentials have so far been referred to the standard hydrogen electrode (SHE). These data are thus designated by 'vs. SHE' after the symbol V, that is Agci/Ag,ci- =

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167 0.2224 V vs. SHE. Sometimes electrode potentials are referred to other reference electrodes, such as the saturated calomel electrode (SCE), etc. So far, a cell containing a single electrolyte solution has been considered (a galvanic cell without transport). When the two electrodes of the cell are immersed into different electrolyte solutions in the same solvent, separated by a liquid junction (see Section 2.5.3), this system is termed a galvanic cell with transport. The relationship for the EMF of this type of a cell is based on a balance of the Galvani potential differences. This approach yields a result similar to that obtained in the calculation of the EMF of a cell without transport, plus the liquid junction potential value A0 L . Thus Eq. (3.1.66) assumes the form cell = rhs - .hs + A0 L (3.1.67)

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However, in contrast to the EMF of a galvanic cell, the resultant expressions contain the activities of the individual ions, which must be calculated by using the extrathermodynamic approach described in Section 1.3. Concentration cells are a useful example demonstrating the difference between galvanic cells with and without transfer. These cells consist of chemically identical electrodes, each in a solution with a different activity of potential-determining ions, and are discussed on page 171. It is very often necessary to characterize the redox properties of a given system with unknown activity coefficients in a state far from standard conditions. For this purpose, formal {conditional) potentials are introduced, defined in terms of concentrations. Definitions are not given unambiguously in the literature; the following would seem most suitable. The formal (conditional) potential is the potential assumed by an electrode immersed in a solution with unit concentrations of all the species appearing in the Nernst equation; its value depends on the overall composition of the solution. If the solution also contains additional species that do not appear in the Nernst equation (indifferent electrolyte, buffer components, etc.), their concentrations must be precisely specified in the formal potential data. The formal potential, denoted as EOf, is best characterized by an expression in parentheses, giving both the half-cell reaction and the composition of the medium, for example '(Zn 2+ 4- 2e = Zn, 10"3M H2SO4). Coming back to equations for Galvani potential differences, (3.1.11) to (3.1.26), we find that equation (3.1.67) can be written in the form cci = A^220 - Agj'0 + A0 L (3.1.68)

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