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Influence of Micellar Microenvironments on Redox and Kinetic Properties of Radical Ions

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Solution Behavior of Surfactants

Abstract

The effects of micellar microenvironments on the redox properties of solubilized substrates and on the kinetic properties of their corresponding radical ions have been examined in anionic, cationic, and nonionic surfactant systems. Relative to the value observed in the absence of surfactants, the differential pulse voltammetric peak potential for the monoelectronic oxidation of 10-methylphenothiazine (MPTH) to the cation radical (MPTH+·) is not significantly altered by the presence of either cationic CTAB or nonionic Brij-35 micellar systems. In anionic SDS media, however, the formal potential for the oxidation of MPTH is shifted to less anodic values with increasing SDS concentration up to the CMC of this surfactant. This behavior is indicative of preferential stabilization of the cation radical by the anionic dodecylsulfate (DS−) monomer. Analysis of the voltammetric data provides definitive evidence for the formation of an associated species involving one MPTH+· and one DS−. The formation constant for this associate is found to be 2.0 × 103 M −1. Electron spin resonance (ESR) spectra of MPTH+· in SDS media show that above the CMC, the MPTH+·/DS− associate is an integral part of the micelle assembly. UV spectral data indicate that the site of residence of the cation radical is in the Stern region of the micellar phase. While cationic and non-ionic micelles are found to catalyze the hydrolysis of MPTH+·, SDS micelles retard this process due to the strong associative interaction between the cation radical and the anionic surfactant.

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Authors and Affiliations

  1. Brown Chemical Laboratory, The University of Delaware, Newark, Delaware, 19711, USA

    Gregory L. McIntire & Henry N. Blount

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  1. Gregory L. McIntire
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  2. Henry N. Blount
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Editors and Affiliations

  1. IBM Corporation, Hopewell Junction, New York, USA

    K. L. Mittal

  2. The Standard Oil Company (Ohio), Cleveland, Ohio, USA

    E. J. Fendler

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© 1982 Plenum Press, New York

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McIntire, G.L., Blount, H.N. (1982). Influence of Micellar Microenvironments on Redox and Kinetic Properties of Radical Ions. In: Mittal, K.L., Fendler, E.J. (eds) Solution Behavior of Surfactants. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3494-1_24

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  • DOI: https://doi.org/10.1007/978-1-4613-3494-1_24

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-3496-5

  • Online ISBN: 978-1-4613-3494-1

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