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165 as the procedure following from Eq. (3.1.39) or from Eqs (3.1.45) to (3.1.49). It should be noted that all terms concerning the electrons in the metals as well as those connected with the metals not directly participating in the cell reaction (Pt) have disappeared from the final Eq. (3.1.49). This result is of general significance, i.e. the EMFs of cell reactions involving oxidationreduction processes do not depend on the nature of the metals where those reactions take place. The situation is, of course, different in the case of a metal directly participating in the cell reaction (for example, silver in the above case). For cell reactions in general, both approaches yield the equation for the EMF: RT ln (3.1.60) nr where E is the standard EMF (standard cell reaction potential), n is the charge number and Q is the quotient of the activities of the reactants in the cell reaction raised to the appropriate stoichiometric coefficients; this quotient has the same form as the equilibrium constant of the cell reaction. For practical reasons it is often useful to separate the EMF of a galvanic cell into two terms and assign each of them to one of the electrodes. The half-cell reactions provide a basis for unambiguous separation. The equation for the overall EMF is converted to the difference between two expressions, in which the expression corresponding to the electrode on the left is subtracted from the expression corresponding to the electrode on the right. Thus, for example, it follows for Eq. (3.1.59), with inclusion of a term containing the relative hydrogen pressure, that ^ - ( w ) - RT In qcl-(w)

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(3.1.61) The terms Agci/Ag,ci- and EH+/H2 are designated as the electrode potentials. These are related to the standard electrode potentials and to the activities of the components of the system by the Nernst equations. By a convention for the standard Gibbs energies of formation, those related to the elements at standard conditions are equal to zero. According to a further convention, cf. Eq. (3.1.56), JI2,+(W) - AG}>(H+, w) = 0 Then ) (3.1.63) (3.1.62)

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Table 3-6: Properties of the ListBox control Property Rows Description Represents the vertical size of the ListBox control and takes value in number of rows. If the control contains more than the specified number of items, the control displays a vertical scroll bar. Represents the number of items that can be selected. To allow users to select only one item, set the SelectionMode property to ListSelectionMode.Singl e. To allow users to select multiple items, set the SelectionMode property to ListSelectionMode. Multiple. ListSelectionMode is the enum that allows you to specify the selection mode. To select more than one item, users can hold the Ctrl or Shift key while clicking multiple items. This is possible only when you set the SelectionMode property to ListSelectionMode.Multi ple.

166 It follows from Eqs (3.1.53) and (3.1.55) that RT EAgcuAg,ci- = ^Agci/Ag,ci- - In cr(w) r RT RT ln H Euvu2 = ~y{naH+~JP ^ 2 (3.1.64) (3.1.65)

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which are the Nernst equations. They will be discussed in detail in Section 3.2. It should be recalled that, in contrast to standard electrode potentials, which are thermodynamic quantities, the electrode potentials must be calculated by using the extrathermodynamic expressions described in Sections 1.3.1 to 1.3.4. The electrode potentials do not have the character of Galvani potential differences, but are simply operational quantities permitting simple calculation or interpretation of the EMF of a galvanic cell and are well suited to the application of electrochemistry in analytical chemistry, technology and biology. In the subsequent text the half-cell reactions will be used to characterize the electrode potentials instead of the cell reactions of the type of Eq. (3.1.42) under the tacit assumption that such a half-cell reaction describes the cell reaction in a cell with the standard hydrogen electrode on the left-hand side. The EMF of a cell is calculated from the electrode potentials (expressed for both electrodes with respect to the same reference electrode) as the difference of the potentials of these electrodes written on the right and left in the scheme:

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^cell = ^rhs ^lhs (3.1.66)

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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