Critical micelle concentrations of nonionic surfactants in organic solvents: Approximate prediction with UNIFAC

Flores, M.V. and Voutsas, E.C. and Spiliotis, N. and Eccleston, G.M. and Bell, G. and Tassios, D.P. and Halling, P.J. (2001) Critical micelle concentrations of nonionic surfactants in organic solvents: Approximate prediction with UNIFAC. Journal of Colloid and Interface Science, 240 (1). pp. 277-283. ISSN 0021-9797 (http://dx.doi.org/10.1006/jcis.2001.7627)

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Abstract

The objective of this study was to model the critical micelle concentration (cmc) of nonionic surfactants in nonaqueous systems using the UNIFAC group contribution method. For the prediction of the cmc the phase separation approach was used, where the micellar phase is approximated as a second liquid phase resulting from the liquid-liquid equilibrium between the solvent and the surfactant, with the necessary activity coefficients predicted by UNIFAC. The limited amount of literature data for reverse micelle formation in nonaqueous systems was used to test the predictions, varying surfactant type, solvent, and temperature. The most promising model was the modified UNIFAC of B, L. Larsen, P. Rasmussen, and A. Fredenslund (Ind. Eng. Chem. Res. 26, 2274 (1987)). Since most nonionic surfactants contain oxyethylene chains, a new set of parameters was evaluated for this group, leading to satisfactory predictions. The average deviation between the predicted and the experimental cmc's was about 0.1 log units.

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