ISSN:
1572-901X
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary 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-. 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 constantsversus 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 (kL/s−1)versus XH2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of δΔG exp ≠ with A (acidity vector), B (basicity vector) and GE is used for both reactions; plots of δΔG calc ≠ versus ΔΔG exp ≠ are linear with slopes of near unity.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01032825
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