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Study of Ligand Substitution Reactions at Pentacyanoferrates(II) in Aqueous Salt and Micellar Solutions

✍ Scribed by Gaspar Fernández; Marı&#x0301;a del Mar Graciani; Amalia Rodrı&#x0301;guez; Marı&#x0301;a Múñoz; Marı&#x0301;a Luisa Moyá

Book ID: 102582013
Publisher: Elsevier Science
Year: 2000
Tongue: English
Weight: 97 KB
Volume: 225
Category: Article
ISSN: 0021-9797
DOI: 10.1006/jcis.2000.6730

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✦ Synopsis

The ligand substitution reactions Fe(CN)(5)(4-(t)bupy)(3-) + 4-CNpy and Fe(CN)(5)(4-(t)bupy)(3-) + pzCO(2)(-) (4-(t)Bupy = 4-tert-butylpyridine; 4-CNpy = 4-cyanopyridine; pzCO(2)(-) = 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. Copyright 2000 Academic Press.

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