solutions are not too alkaline, is given by the equation in .NET

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429 solutions are not too alkaline, is given by the equation
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The theory of the function of the glass electrode is based on the concept of exchange reactions at the surface of the glass. The glass consists of a solid silicate matrix in which the alkali metal cations are quite mobile. The glass membrane is hydrated to a depth of about 100 nm at the surface of contact with the solution and the alkali metal cations can be exchanged for other cations in the solution, especially hydrogen ions. For example, the following reaction occurs at the surface of sodium glass: Na+(glass) + H+(solution) + H+(glass) + Na+(solution) (6.3.12)
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characterized by an ion-exchange equilibrium constant (cf. Eq. (6.3.5)). These concepts were developed kinetically by M. Dole and thermodynamically by B. P. Nikolsky. The last-named author deduced a relationship that is analogous to Eq. (6.3.10). It is approximated by Eq. (6.3.11) for pH 1-10 and corresponds well to deviations from this equation in the alkaline region. The potentials measured in the alkaline region are, of course, lower than those corresponding to Eq. (6.3.11). The difference between the measured potential and that calculated from Eq. (6.3.11) is termed the alkaline or 'sodium' error of the glass electrode, and depends on the type of glass and the cation in solution (see Fig. 6.6). This dependence is understandable on the basis of the concepts given above. The cation of the glass can be replaced by hydrogen or by some other cation that is of the same size or smaller than the original cation. The smaller the cation in the glass, the fewer the ionic sorts other than hydrogen ion that can replace it and the greater the concentration of these ions must be in solution for them to enter the surface to a significant degree. The smallest alkaline error is thus exhibited by lithium glass electrodes. For a given type of glass, the error is greatest in LiOH solutions, smaller in NaOH solutions, etc. Glass for glass electrodes must have rather low resistance, small alkaline error (so that the electrodes can be used in as wide a pH range as possible) and low solubility (so that the pH in the solution layer around the electrode is not different from that of the analyte). These requirements are contradictory to a certain degree. For example, lithium glasses have a small alkaline error but are rather soluble. Examples of glasses suitable for glass electrodes are, for example, Corning 015 with a composition of 72% SiO2, 6% CaO and 22% Na2O, and lithium glass with 72% SiO2, 6% CaO and 22% Li2O. Glasses containing aluminium oxide or oxides of other trivalent metals exhibit high selectivity for the alkali metal ions, often well into the acid pH region. A glass electrode with a glass composition of llmol.% Na2O, 18 mol.% A12O3 and 71 mol.% SiO2, which is sensitive for sodium ions and
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Fig. 6.6 pH-dependence of the potential of the Beckman general, purpose glass electrode (Li2O, BaO, SiO2). (According to R. G. Bates)
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431 poorly sensitive for both hydrogen and potassium ions, has found a wide application. At pH 11 its selectivity constant for potassium ions with respect to sodium ions is K^+^K+ = 3.6 x 10~3. The membranes of the other ion-selective electrodes can be either homogeneous (a single crystal, a pressed polycrystalline pellet) or heterogeneous, where the crystalline substance is incorporated in the matrix of a suitable polymer (e.g. silicon rubber or Teflon). The equation controlling the potential is analogous to Eq. (6.3.9). Silver halide electrodes (with properties similar to electrodes of the second kind) are made of AgCl, AgBr and Agl. These electrodes, containing also Ag2S, are used for the determination of Cl~, Br~, I~ and CN~ ions in various inorganic and biological materials. The lanthanum fluoride electrode (discussed in Section 2.6) is used to determine F~ ions in neutral and acid media. After the pH-glass electrode, this is the most important of this group of electrodes. The silver sulphide electrode is the most reliable electrode of this kind and is used to determine S2~, Ag+ and Hg2+ ions. Electrodes containing a mixture of divalent metal sulphides and Ag2S are used to determine Pb 2+ , Cu2+ and Cd2+. 6.3.3 Calibration of ion -selective electrodes It has been emphasized repeatedly that the individual activity coefficients cannot be measured experimentally. However, these values are required for a number of purposes, e.g. for calibration of ion-selective electrodes. Thus, a conventional scale of ionic activities must be defined on the basis of suitably selected standards. In addition, this definition must be consistent with the definition of the conventional activity scale for the oxonium ion, i.e. the definition of the practical pH scale. Similarly, the individual scales for the various ions must be mutually consistent, i.e. they must satisfy the relationship between the experimentally measurable mean activity of the electrolyte and the defined activities of the cation and anion in view of Eq. (1.1.11). Thus, by using galvanic cells without transport, e.g. a sodium-ionselective glass electrode and a Cl~-selective electrode in a NaCl solution, a series of a (NaCl) is obtained from which the individual ion activity aNa+ is determined on the basis of the Bates-Guggenheim convention for a cl (page 37). Table 6.1 lists three such standard solutions, where pNa = -loga Na +, etc. 6.3.4 Biosensors and other composite systems Devices based on the glass electrode can be used to determine certain gases present in gaseous or liquid phase. Such a gas probe consists of a glass electrode covered by a thin film of a plastic material with very small pores,
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432 Table 6.1 Conventional standards of ion ;activities. (According to R. G. Bates and M. Alfenaar) Electrolyte NaCl Molality (mol kg"1) 0.001 0.01
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