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constant tends to increase with increasing ionic radius or with decreasing strength of solvation. In Et4NClO4-DMF, for example, the value of ks is 0.00011 cm s 1 for Li+, 0.09 cm s 1 for Na+, 0.65 cm s 1 for K+, 0.59 cm s 1 for Rb+, and 1.10 cm s 1 for Cs+ [23 b]. The relationship between the kinetic data for metal amalgam formation and solvent properties is discussed in detail in Refs [24] and [25]. Polarographic reductions of metal ions are also influenced by the supporting electrolyte: 1. If the anion of the supporting electrolyte forms a complex with the metal ion, the reduction potential of the metal ion shifts to the negative side by complexation [Eq. (5.9)]. Although it also occurs in water, it is more marked in aprotic solvents in which small anions are reactive because of their weak solvations. 2. A striking effect of the cation of the supporting electrolyte is shown in Fig. 8.6 [26]. Figure 8.6 (a) is for the reductions of alkali metal ions in HMPA + 0.05 M Et4NClO4: the reduction waves for Cs+ and Rb+ are diffusion-controlled, but Na+ and Li+ are not reduced until the negative end of the potential window. The K+-wave is lower in height than expected for the diffusion-controlled process and has some kinetic current characteristic. 3) Figure 8.6 (b) indicates the influence of the cation of the supporting electrolyte on the reduction of Na+. If the cation is Me4N+ or Et4N+, Na+ is not reduced at all. If it is Hep4N+ or Li+, on the other hand, Na+ gives a diffusion-controlled reduction wave. When Bu4N+ is the supporting electrolyte cation, Na+ gives a small reduction current, c# wpf preview pdf Generate a pdf thumbnail (open source/free) - Stack Overflow
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