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(E + Eref)F 2.303*7
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It would appear from Eq. (3.2.8) that the pH, i.e. the activity of a single type of ion, can be measured exactly. This is not, in reality, true; even if the liquid junction potential is eliminated the value of Eref must be known. This value is always determined by assuming that the activity coefficients depend only on the overall ionic strength and not on the ionic species. Thus the mean activities and mean activity coefficients of the electrolyte must be employed. The use of this assumption in the determination of the value of Eref will, of course, also affect the pH value found from Eq. (3.2.8). Thus, the potentiometric determination of the pH is more difficult than would appear at first glance and will be considered in the special Section 3.3.2. The hydrogen electrode can be used to measure pH values over the whole pH region. However, it is not applicable to reducing or oxidizing media or
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Fig. 3.7 A simple immersion hydrogen electrode
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in the presence of substances that act as catalytic poisons for platinum black. Poisoning of the electrode (p. 173) is indicated by fluctuation of the electrode potential which differs from the value predicted by the Nernst equation. Hydrogen electrodes can be constructed in variously shaped cells according to the purpose. An example is given in Fig. 3.7. The measurement is described in detail in practical manuals. However, for practical measurements, the glass electrode (Section 6.3) is employed. The potential of an anionic electrode of the first kind is given by the relationship \na. Z-F (3.2.9)
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where z_ is the charge number of the corresponding anion (z_ < 0). The equation also often contains a term including the effect of the gas pressure on a gas anionic electrode of the first kind. The chlorine electrode contains gaseous chlorine in equilibrium with atomic chlorine adsorbed on the platinum black and a solution of chloride ions. Its potential is given by the equation RT rl t
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The chlorine electrode behaves reversibly, i.e. electrode equilibrium is
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Table 3.3 Standard electrode potentials in eutectic melts referred to a chlorine reference electrode. (According to R. W. Laity) -E ; (V) System Mn /Mn Cd 2+ /Cd T1+/T1 Co 2+ /Co Pb 2+ /Pb Cu + /Cu Ag + /Au
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KCl-NaCl, 450 C 2.135 1.535 1.277 1.352 1.145 0.905
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KCl-LiCl, 450 C 2.065 1.532 1.586 1.207 1.317 1.067 0.853
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established rapidly; however, side reactions also occur to a small degree: the attack on the platinum electrode by chlorine and the reaction of chlorine with water (C12 + H2O* HOC1 4- H + + Cl"), which can be suppressed in sufficiently acidic medium. In chloride melts, the chlorine electrode (with graphite instead of platinum) is used as a reference electrode (see Table 3.3). Anionic electrodes of the first kind are rarely used in practice; other, more important, sorts of electrode exhibiting a reversible response to anions are the electrodes of the second kind. 3.2.2 Electrodes of the second kind The expression for the potential of electrodes of the second kind on the hydrogen scale can be derived from the affinity of the reaction occurring in a cell with a standard hydrogen electrode. For example, for the silver chloride electrode with the half-cell reaction AgCl(s) + e = Ag + C r
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^Agci/Ag = ^Agci/Ag l n 0 c r
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The same expression is obtained if electrodes of the second kind are considered as electrodes of the first kind, where the activity of the metal cations depends on the solubility product of the given insoluble salt (cf. Eq. 3.1.26): RT
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EAg+/Ag + ~TT In ^Agci
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It can be seen from this equation that the solubility product of silver chloride can be calculated from the known standard potentials of the silver
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176 and silver chloride electrodes. Besides the silver chloride electrode the following electrodes belong to this group: The calomel electrode: KCl(m) | Hg2Cl2(s) | Hg RT
EHg2ci2/Hg = ^H g2 ci 2 /H g - In acr (3.2.14)