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Accurate and reliable phase equilibrium calculations of microemulsion systems are of great importance. This study deals with the thermodynamic modeling of Liquid–Liquid Equilibrium (LLE) of a system including oil ( n -decane), brine (containing CaCl 2  salt), and ionic surfactant (sodium dodecyl sulfonate). Two models of UNIQUAC and UNIQUAC + Debye–Hückel were used for thermodynamic calculations. The LLE experimental data were utilized to estimate the binary interaction parameters of UNIQUAC model and the adjustable parameter,  b , of the Debye–Hückel model. The thermodynamic model calculates the microemulsion phase’s compositions by minimizing the Gibbs free energy of the LLE system using a combination of genetic algorithm and fmincon function in order to prevent local minima. The thermodynamic modeling results show an appropriate agreement with the experimental data. Accordingly, the presented model of this study can be used as a suitable method to investigate the liquid–liquid equilibrium of systems containing oil, water, and surfactant.

A Gibbs free energy minimization based model for liquid–liquid equilibrium calculation of a system containing oil, brine, and surfactant