A theoretical analysis of synergistic effects in mixed surfactant systems
2000 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 16, no 18, 7173-7181 p.Article in journal (Refereed) Published
Synergistic effects in mixed binary surfactant systems have been investigated by analyzing the main contributions to the free energy of forming a mixed surfactant aggregate. We show that a nonlinear behavior of the critical micelle concentration (cmc) with respect to the surfactant composition of the aggregates is determined by a nonlinear behavior of the free energy per aggregated surfactant. It appears that synergistic effects are due mainly to entropic free energy contributions related with the surfactant headgroups. For a mixture of a monovalent ionic and a nonionic surfactant in the absence of added salt we obtain, entirely because of electrostatic reasons, a negative deviation from ideal behavior of the cmc vs the aggregate composition corresponding to an interaction parameter beta approximate to -1, whereas beta values on the order of -5 or even less can arise for mixtures of two ionic surfactants with the same charge number but with different hydrocarbon moieties. Moreover, we introduce a novel expression for the free energy of mixing aggregated surfactant headgroups with surrounding solvent molecules. Accordingly, synergistic effects arise as a result of different headgroup cross-section areas in mixtures of two nonionic surfactants with rigid headgroups. These effects are found to be rather small, with 0 > beta > -1, when the difference in headgroup size is modest but can become more significant when the size difference is larger. In mixtures of an ionic and a nonionic surfactant with different headgroup cross-section areas the two contributions to synergistic effects always enhance one another and, hence, beta values below -1 are obtained. Generally, the synergistic effects tend to increase with increasing asymmetry between the two surfactants.
Place, publisher, year, edition, pages
2000. Vol. 16, no 18, 7173-7181 p.
critical micelle concentrations, curvature elasticity, shaped micelles, binary-mixtures, prediction, thermodynamics, mechanics, vesicles
IdentifiersURN: urn:nbn:se:kth:diva-20011DOI: 10.1021/la000397kISI: 000089118500013OAI: oai:DiVA.org:kth-20011DiVA: diva2:338704
QC 201005252010-08-102010-08-10Bibliographically approved