Molecular interactions of cationic and anionic surfactants in mixed monolayers and aggregates

The properties of anionic-rich and cationic-rich mixtures of CTAB (cetyltrimethylammonium bromide) and SDS (sodium dodecyl sulfate) were investigated with conductometry and surface tension measurements and by determining the surfactant NMR self-diffusion coefficients. The critical aggregate concentration (CAC), surface tension reduction effectiveness(gamma(CAC)), surface excess(Gamma(max)), and mean molecular surface area (A(min)) were determined from plots of the surface tension (gamma) as a function of the total surfactant concentration. The compositions of the adsorbed films (Z) and aggregates (chi) were estimated by using regular solution theory, and then the interaction parameters in the aggregates (beta) and the adsorbed film phases (beta(sigma)) were calculated. The results showed that the synergism between the surfactants enhances the formation of mixed aggregates and reduces the surface tension. Further, the nature and strength of the interaction between the surfactants in the mixtures were obtained by calculating the values of the following parameters: the interaction parameter, beta, the size parameter, rho, and the nonrandom mixing parameter, P*. These results indicate that in ionic surfactant mixtures the optimized packing parameter has the highest value and that the size parameter can be used to account for deviations from the predictions of regular solution theory. It was concluded that, for planar air/aqueous interfaces and aggregation systems, this nonideality increases as the temperature increases. This trend is attributed to the increased dehydration of the surfactant head groups that results from increases in temperature. Further, our conductometry measurements show that the counterion binding number of mixed micelles formed in mixtures with a high CTAB content is different to those with a high SDS content. This difference is due to either their different aggregation sizes or the different interactions between the head groups and the counterions.