The micellization behavior of quasi-binary mixture of zwitterionic cocamidopropyl hydroxysultaine (CAPHS) with cationic cetyltrimethylammonium bromide (CTAB) was investigated both in aqueous solution and in glycerol-water. Both the tensiometric and the conductive techniques were adopted to determine the critical micelle concentrations (cmc) of individual and mixed surfactants. In the framework of the regular solution theory and based on the pseudophase separation model, some micellization and thermodynamic parameters were estimated by the Rubingh’s and the Clint’s models. The results indicate that the nonideal mixing of CAPHS with CTAB and the synergistic interaction between them play vital roles on the reduction of mixed cmc, the amplitude of synergistic interaction depends on the composition of mixture and the presence of glycerol induces the increase in the individual and mixed cmc values and the change of the participation of CAPHS in mixed micelle with the composition in bulk solution. The electrostatic repulsion, the diversity of molecular conformation and the steric hindrance can account for the formation of mixed micelle and the difference in micellar composition. Thermodynamic parameters show that the entropy makes overwhelming contributions on the spontaneous process of micellization, the release of mixing heat makes the stable mixed micelle formed and the presence of glycerol makes for reducing the contribution of entropy and forming the more stable mixed micelle. These findings help with understanding the interaction behavior between two species and the effect of glycerol and further providing some information for the design of the related surfactant formulations.
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