This paper explores the association of a nonionic surfactant, Igepal (polyoxyethylene nonylphenol), in aqueous media by means of absorption and fluorescence spectroscopy. The critical micellar concentration (CMC) of the aggregate formed in the aqueous medium has been determined, using three different methods: UV-visible spectroscopy, fluorescence spectroscopy, and Stokes shift. The correlation of CMC with hydrophile-lipophile balance (HLB) indicates that the CMC decreases with decreased HLB. The obtained CMC values from different methods are close to each other and have allowed the determination of DeltaG values associated with the micellization. The association constant of the dye molecule Safranine T (ST) with the nonionic micelle of Igepal, aggregation number of the surfactant monomer, and location of the fluorophore in the micellar environment have been determined. The vertical ionization potential of Igepal, electron affinity of the dye, and degree of charge transfer from the micellar aggregate to the dye molecule have been determined by AM1 calculation. The experimental charge transfer transition energies are well correlated with the determined ionization potential values (ID) of Igepal. The degree of charge transfer (ground state complexes) has been found to be low. The polarity of the micelle solubilization sites has been estimated from the solvatochromic shift, Kosowar Z value, and ET30, and ETN values.
Copyright 2004 Elsevier Inc.