Abstract
The ligand substitution reactions Fe(CN)5(4-tbupy)3− + 4-CNpy and Fe(CN)5(4-tbupy)3− + pzCO2− (4-tBupy = 4-tert-butylpyridine; 4-CNpy = 4-cyanopyridine; pzCO2− = pyrazinecarboxylate) were studied in several aqueous salt and micellar solutions. Kinetic data in aqueous solutions showed that the two processes follow a dissociative mechanism, D, and the dependence of the first-order rate constants on [salt] on electrolyte aqueous solutions allow the estimation of the activation volumes corresponding to both reactions. Under true first-order conditions no kinetic micellar effects were found in anionic (SDS) and nonionic (Triton X-100) aqueous micellar solutions. In cationic micellar solutions (CTAB, CTAC, and TTAB) small kinetic micellar effects were found. These were related to the different ionic concentrations and the different polarity and structure of the Stern layer surrounding the cationic micellar aggregates, where the reactions take place, with respect to pure water.
Published Version
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