Light scattering from mixtures of interacting, nonionic micelles with hydrophobic solutes

Abstract

Model equations for the Rayleigh ratio and the electric field autocorrelation function are derived using thermodynamic fluctuation theory applied to crowded solute-containing micellar solutions and microemulsions with negligible molecular species and polydispersity. This theory invokes non-equilibrium thermodynamics and enforces local equilibrium between molecular solute, surfactant, and the various micellar species, in order to elucidate the influence of self-assembly on light scattering correlation functions. We find that self-assembly driven variations in the average micelle radius and aggregation number along gradients in concentration, which were previously shown to drive strong multicomponent diffusion effects expressed via the ternary diffusivity matrix [D], do not affect the scattering functions in the limit of zero local polydispersity. Hence, theoretical predictions for the Rayleigh ratio and the field autocorrelation function for ternary mixtures of solute-containing, locally monodisperse micellar solutions are identical to those developed for binary mixtures of monodisperse, colloidal hard spheres. However, self-assembly driven multicomponent diffusion phenomena are predicted to influence the thermodynamic driving forces for diffusion in these mixtures. In support of our theoretical results, measurements for the Rayleigh ratio and the field autocorrelation function for ternary aqueous solutions of decaethylene glycol monododecyl ether (C₁₂E₁₀) with either decane or limonene solute were performed for several molar ratios and volume fractions up to ϕ ≈ 0.25, and for binary mixtures of C₁₂E₁₀/water up to ϕ ≈ 0.5. Excellent agreement between our light scattering theory and experimental data is achieved for low to moderate volume fractions (ϕ < 0.3), and at higher concentrations when our theoretical results are corrected to account for micelle dehydration.