0000000000470944
AUTHOR
M. Liria Turco Liveri
Transfer of Some Alkyl Substituted Ferrocenes from Water to Cationic Surfactant Micelles Studied by Kinetic Method
Abstract Binding of ferrocene and its 1,1′-dimethyl and n -butyl derivatives to dodecyl and tetradecyltrimethylammonium nitrate micellar aggregates has been studied at 20.0°C and ionic strength 0.02 tool dm -3 by examining the micellar retarding effects on the rates of iron(III) oxidation of these substrates. Solubilization of the ferrocenes in the cationic micellar phase increases as the substrate hydrophobic character increases and, to a lesser extent, as the surfactant hydrocarbon chain length becomes longer. The critical micelle concentrations of the surfactants used and the incremental free energy of transfer of methylene groups of both the substrate and the surfactant from the aqueous…
Rate Effects of AOT-Stabilized Microemulsions on Reactions of Ligand Substitution in Cationic Palladium(II) Complexes
Rate data for the substitution reactions of the coordinated ligand X (=2,2‘-bipyridine or 4,4‘-dimethyl-2,2‘-bipyridine) of the palladium(II) complex [Pd(en)X]2+, where en = ethylenediamine, by en or N,N-dimethylethylenediamine in heptane−AOT−water microemulsions have been obtained at 25.0 °C as a function of the AOT concentration at the constant R (=[H2O]/[AOT]) values of 3, 8, and 20 or 30. The overall second-order rate constants are higher in microemulsions than in bulk water and decrease significantly as both the AOT concentration (at constant R) and the molar ratio R (at a given [AOT]) increase. The quantitative analysis of the kinetic data, made by applying the pseudophase model, lead…
Chemical Reactivity in AOT Microemulsions: Kinetics of Water Replacement in a Square-Planar Palladium(II) Aquo Complex by Monoalkylthioureas
The kinetics of water replacement in the cationic palladium(II) aquo complex [Pd(Et4dien)(H2O)]2+, where Et4dien = Et2N(CH2)2NH(CH2)2NEt2, by thiourea, methylthiourea, and ethylthiourea have been studied at 25.0 °C in heptane−AOT−water microemulsion over a wide range of the molar ratio R (=[H2O]/[AOT]) at the constant surfactant concentration of 0.13 mol dm-3. The reaction rates are significantly higher in microemulsions than in bulk water and decrease rapidly as the parameter R increases. The kinetic data, interpreted quantitatively by applying the pseudophase model to the microemulsion, indicate that there is a weak partitioning of the nucleophiles between the water core and the AOT inter…
A kinetic study of the basic hydrolysis of 2-phenylethyl nitrite in the presence of borate buffer and β-cyclodextrin
The kinetics of the hydrolysis of 2-phenylethyl nitrite have been studied in basic aqueous solutions (borate buffer) in the absence and presence of β-cyclodextrin. The observed kinetic trends show that the hydrolysis reaction consists of at least three subsequent processes. The first is a fast acid-base reaction between the boron atom of boric acid and oxygen atom of the alkyl nitrite. The second one should be the nucleophilic attack of hydroxyl ion on the alkyl nitrite. The last process could be referred to as a combination of transfer of hydrogen acid to a water molecule followed by ruptures of nitrogen-oxygen and boron-oxygen bonds. The effect of β- cyclodextrin on each process is also d…