Ionic Interactions: Kinetics and Structure v. 2: From Dilute by Sergio Petrucci

By Sergio Petrucci

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Extra resources for Ionic Interactions: Kinetics and Structure v. 2: From Dilute Solutions to Fused Salts (Physical chemistry, a series of monographs)

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The third contribution describes the deviations from the limiting law 1. ab). In the special case of symmetrical electrolytes, we assume the following relations to be valid: fl-t Tin . Θ-χ Bo % CL ivii 11 * = £12 = — I n = — £22 = IVio Λ90, ( 1 0 0 ^ e^jDJtTa. Substituting this into Eq. (99), we get (see the note on p. 59) F* = -kTV{xsl\2n + 8π«,2α3Α0(δ) + O « 2 In « , ) } , (101) where k0(b) = i[K0(b) + K0(-b)]. (102) The function kQ{b)jbz is represented in Table I I I . As seen from Eq. 3. At b = b0 the first deviations from Debye's limiting law are vanishing.

Z. Physik. Chem. (Leipzig) 168, 147. , and ROZENTHAL, D . K. (1966). In "Chemical Physics of Ionic Solutions" (B. E. Conway and R. G. ). Wiley, New York. , and WRIGLEY, H. E. (1957). Discussions Faraday Soc. 24, 43. M C M I L L A N , W. , and MAYER, J. E. ( 1 9 4 5 ) . / . Chem. Phys. 13, 276. MARCUS, R. A. (1965). / . Chem. Phys. 43, 58. MARTYNOV, G. A. (1968). Zh. Eksperim. i Teor. Fiz. 54, 159. MAYER, J. E. (1950). / . Chem. Phys. 18, 1426. MEERON, E. (1957). J. Chem. Phys. 26, 804. MEERON, E.

138), (139), (155), and (156) is replaced by the full DebyeHückel factor (1 + κ^α)-1 and in Eqs. (136), (153), and (154) the power series with respect to κ*α completely corresponds to Eqs. (47)—(51). The improved theory is in much better agreement with experimental data.

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