Electrochemistry in Ordered Systems. 2. Electrochemical and Spectroscopic Examination of the Interactions between Nitrobenzene and Anionic, Cationic, and Nonionic Micelles
The reductive electrochemistry of nitrobenzene (NB) to the corresponding anion radical (NB-)and dianion has been examined in anionic, cationic, and nonionioc micelles.The observed voltammetry of NB in these systems has been related to the nature of the interactions of NB and NB- with the respective micelles.These interactions have been interpreted in terms of models of various micelle/substrate interactions which were tested by using values of the diffusion coefficient of NB in each micelle system over a range of NB concentrations.Results indicate that the stability of NB- in anionic micelles arises from a relatively strong surface interaction.The stability of nitrobenzene anion radical in nonionic micelles suggested by voltammetry and supported by ESR also derives from a surface interaction.Cationic micelles, however, provide a pseudophase into which NB partitions such that NB- resulting from reduction of NB is concentrated within the small volume of the micelle and therein undergoes homogeneous chemical reactions to yield phenylhydroxylamine.These results point to the importance of understanding potential interactions between substrates and micelles in describing the behavior of micelle-solubilized substrates.
Intire, Gregory L. Mc,Chiappardi, Donna Marie,Casselberry, Robert L.,Blount, Henry N.
p. 2632 - 2640
(2007/10/02)
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