Micellar properties of p-tert-octyl-phenoxy (9.5) polyethylene ether (Triton X-100) in aqueous mixtures of ethylene glycol (EG) were determined using such techniques as surface tension, static and dynamic light scattering, and fluorescence spectroscopy. Thermodynamics of micellization was obtained from the temperature dependence of critical micelle concentration values. The differences in the Gibbs energies of micellization of Triton X-100 between water and binary solvent systems were calculated to evaluate the influence of cosolvent on the micellization process. From this study, it can be concluded that the structure-breaking ability of EG and its interaction with the oxyethylene groups of the surfactant are dominating factors in the micellization process. Thermodynamics of adsorption of the solution−air interface was also evaluated. It was found that the surface activity of the surfactant decreases slightly with increasing concentration of EG at a given temperature. By a combination of static and dynamic light scattering measurements, a reduction of the micelle size was observed, mainly due to a decrease of the micellar aggregation number, whereas the micellar solvation was not substantially modified in magnitude with EG addition. However, the change of the surface area per headgroup of the surfactant suggested an alteration in the nature of its solvation layer, produced probably by a certain participation of cosolvent in the micellar solvation layer. This point was corroborated from the fluorescence polarization studies of several luminescent probes, including coumarin 6, merocyanine 540, and rhodamine B. These experiments revealed a slight increase of the micellar microviscosity. Finally, the proposed mechanism was also supported by the increase observed in the cloud point of Triton X-100, induced by the EG addition.

The course of the differential heats of dilution of a surfactant measured in an isothermal titration microcalorimeter is normally of sigmoidal type. The course of percolation of conductance of a water in oil microemulsion induced by either temperature or the water content of the system is also of sigmoidal nature. Derivation of the critical micellar concentration and the enthalpy of micellization (∆Hm) in the former has been demonstrated to be conveniently obtained by employing the Sigmoidal-Boltzmann equation (SBE). The SBE has been shown also to be conveniently applicable for accurate determination of the threshold temperature (θp) and volume fraction (φp) of percolation in the latter.

changes in the hemimicellar environment.To summarize, this work reports the excited-state Raman spectrum of Ru(bpy)32+ in the adsorbed layers of a surfactant on a solid at a solid-liquid interface under in situ equilibrium conditions. This opens the general possibility of observing the adsorption phenomenon by yet another sensitive technique to provide basic information on adsorbed layers at solid-liquid interfaces.Acknowledgment. P.S. and J.T.K. thank the NSF and DOE for financial support. N.J.T. and J.K.B. thank the NSF, AFOSR, and NIH for financial support.

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