Electrolyte-induced structural evolution of Triton X-100 micelles

The long-time self-diffusion coefficients of Triton X-100 micelles have been determined as a function of surfactant and electrolyte concentrations using rotating disk electrode voltammetry in conjunction with ferrocene acting as an electroactive probe. Micellar diffusion conforms to the linear interaction theory and yields micellar hydrodynamic radii values and interaction parameters as a function of electrolyte concentration. The interaction parameters varied from 3.4 to 3.6 over the electrolyte concentration range 0.01-0.8 mol dm(-3) KCl, which is consistent with excluded volume interactions and indicated the absence of significant micellar shape changes with the addition of electrolyte. Micellar hydrodynamic radii varied linearly with respect to [KCI] from 4.22 to 6.21 nm, indicating the progressive evolutionary growth of the oblate micelles due to increasing aggregation number and "hydration". The semimajor to semiminor axial ratio (a/b) increased from 2.0 to 3.5, indicating evolution to a more asymmetric structure. Micellar molecular weights increased from 77 700 to 326 000 over the electrolyte concentration range studied, which is predominantly due to water entrapment at the periphery of the self-assembled structures. Intrinsic viscosities were found to decrease from 6.09 to 4.61 cm(3) g(-1), indicating a decrease in specific micellar volume, which may be attributed to ethylene oxide chain collapse due to dehydration. The decrease in micellar specific volume was found to correlate precisely with the electrolyte induced decrease of the cloud point.