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It could be expected for less dilute solutions that an expression for the effective diffusion coefficient could be derived theoretically from Eq. (2.5.42) by using correction terms for U+ and U_ taken from the Debye-Huckel-Onsager theory of electrolyte conductivities. However, it has been demonstrated experimentally that this approach does not lead to a correct description of the dependence of the diffusion coefficient on the concentration. The mobility of ions in the diffusion process varies far less with changes in the concentration than when charge is transported in an external electric field, and the effect of the concentration on the mobility can be either retarding, zero or accelerating, depending on the type of salt (increasing concentration always reduces ion mobility in an external electric field). This difference between the two transport phenomena is a result of the fact that diffusion is connected with the movement of cations and anions in the same direction, so that faster species are retarded by slower species, and vice versa, whereas during electric current flow, oppositely charged ions move in opposite directions and the two types of ions retard one another. The electrophoretic effect caused by the retardation of the movement of the central ion by the moving ionic atmosphere is thus of a different magnitude in diffusion. The time-of-relaxation effect is completely absent, as the symmetry of the ionic atmosphere is not disturbed during diffusion. As mentioned, the gradient of the diffusion electric potential is suppressed in the case of diffusion of ions present in a low concentration in an excess of indifferent electrolyte ('base electrolyte'). Under these conditions, the simple form of Fick's law (2.3.18) holds for the diffusion of the given ion. The

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You can get even more information on a particular LSA using the show router command. In Listing 9.8, we used LSA for router 172.16.254.1. note the sequence number information.

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Table 2.4 Diffusion coefficients D x 106 (cm2 s l) determined by means of polarography or chronopotentiometry at various indifferent electrolyte concentrations c (mol dm"3) at 25 C. The composition of the indifferent electrolyte is indicated for each ion. (According to J. Heyrovsky and J. Kuta) Ag + c 0.01 0.1 1.0 3.0 KNO3 15.85 15.32 15.46 KNO3 18.2 16.5 Tl + KC1 17.4 15.7 13.5 NaCl 17.7 15.0 9.2 IO 3 NaOH 6.54 5.13 4.18 KC1 10.15 9.89 9.36 NaCl 10.01 8.92 7.24 Pb 2+ KNO3 8.76 8.28 8.02 KC1 8.99 8.67 9.20 8.14 Cd2+ KNO3 6.90 6.81 KC1 8.15 7.15 7.90 7.90 Fe(CN) 6 3 KC1 7.84 7.62 7.63 7.36

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Table 2.5 Diffusion coefficients (cm2 s l x 10 5) of electrolytes in aqueous solutions at various concentrations c (mol dm~ 3 ). (According to H. A. Robinson and R. H. Stokes) Temperature Electrolyte LiCl NaCl KC1 KC1 KC1 RbCl CsCl LiNO, NaNO 3 KC1O4 KNO, AgNO 3 MgCl2 CaCl2 SrCl2 BaCl2 Li2SO4 Na 2 SO 4 Cs2SO4 MgSO4 ZnSO 4 LaCl3 K 4 Fe(CN) 6 ( C) 25 25 20 25 30 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 0 1.366 1.610 1.763 1.993 2.230 2.051 2.004 1.336 1.568 1.871 1.928 1.765 1.249 1.335 1.334 1.385 1.041 1.230 1.569 0.849 0.846 1.293 1.468 0.001 1.345 1.585 1.739 1.964 2.013 1.845 1.899 1.187 1.263 1.269 1.320 0.990 1.175 1.489 0.768 0.748 1.175 0.002 1.337 1.576 1.729 1.954 2.011 2.000 1.535 1.841 1.884 1.169 1.243 1.248 1.298 0.974 1.160 1.454 0.740 0.733 1.145 c 0.003 1.331 1.570 1.722 1.945 2.174 2.007 1.992 1.296 1.835 1.879 1.719 1.158 1.230 1.236 1.283 0.965 1.147 1.437 0.727 0.724 1.126 1.213 0.005 1.323 1.560 1.708 1.934 2.161 1.995 1.978 1.289 1.516 1.829 1.866 1.708 1.213 1.219 1.265 0.950 1.123 1.420 0.710 0.705 1.105 1.184 0.007 1.318 1.555 1.925 2.152 1.984 1.969 1.283 1.513 1.821 1.857 1.698 1.201 1.209 1.084 0.010 1.312 1.545 1.692 1.917 2.144 1.973 1.958 1.276 1.503 1.790 1.846 1.188

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