Kirkwood-Buff Analysis of Binary and Ternary Systems Consisting of Alcohols (Methanol, Ethanol, 1-Propanol, and 2-Propanol), Water, and n-Hexane to Understand the Formation of Surfactant-Free Microemulsions.

Surfactant-free microemulsion (SFME) represents a class of fluid mixtures that can form microheterogeneous structures without detergents, offering an environmentally benign alternative to traditional microemulsions. However, the formation mechanism is still elusive. This work applies the Kirkwood-Buff theory to mixtures of alcohols, water, and n-hexane to elucidate the SFME formation mechanism. To ensure robust calculation of the Kirkwood-Buff integrals (KBIs), we construct a data set of densities and excess free energies of binary and ternary systems. Multiple excess Gibbs free energy models are assessed against this data set to select the most suitable model reproducing the experimental results. In addition, we introduce statistical methods to determine the optimal polynomial order of the Redlich-Kister correlation for the excess volume data. We first validate our methodology in binary systems. Then, we extend the calculation method to ternary mixtures. The KBI calculation results reveal that the alcohol-hexane and water-hexane interactions do not significantly affect SFME formation. In contrast, the interplay among water-water, water-alcohol, and alcohol-alcohol interactions critically influences the ability of a liquid mixture to form SFME structures. SFME systems exhibit the facile formation of water aggregates enveloped by alcohols, whereas non-SFME systems demonstrate homogeneous alcohol/water droplets dispersed in an oil continuous medium.