SOLVENT EFFECTS ON SUBSTITUTION-REACTIONS AT COMPLEXES OF THE [FE(CN)5L]3- TYPE IN BINARY AQUEOUS MIXTURES

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Author list: MOYA ML, BARRIOS A, GRACIANI MD, JIMENEZ R, MUNOZ E, SANCHEZ F, BURGESS J
Publisher: Springer Verlag (Germany)
Publication year: 1991
Volume number: 16
Issue number: 2
Start page: 165
End page: 168
Number of pages: 4
ISSN: 0340-4285
Languages: English-Great Britain (EN-GB)


Abstract

The kinetics of replacement of 4,4'-bipyridine, (4,4'-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)5-(4,4'-bipy)]3- and [Fe(CN)5(4-CNpy)]3- at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constants versus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (k(L)S-1) versus X(H20) is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of delta-DELTA-G(exp)# with A (acidity vector), B (basicity vector) and G(E) is used for both reactions; plots of delta-DELTA-G(calc)# versus delta-DELTA-G(exp)# are linear with slopes of near unity.


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Last updated on 2019-23-08 at 11:15