RESUMO
Micelle formation enthalpies (Δmic H values) have been calorimetrically determined at 298 K for three sets of mixed zwitterionic/cationic gemini systems consisting of N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-12) and a series of structurally related gemini surfactants, the N,N'-bis(dimethyldodecyl)-α,ω-alkanediammonium dibromide (12-s-12) systems. From the experimental and the estimated ideal micelle formation enthalpies, the excess enthalpies were obtained. The degrees of nonideality of the interaction in the mixed micelle (ß m) from our previous work was used along with the excess enthalpy values to determine excess thermodynamic quantities of the surfactants in the mixed system according to Regular Solution Theory (RST) and Motomura's theory. The excess enthalpies for the ZW3-12/12-4-12 were positive in magnitude and rose sharply when small amounts of the zwittergent were distributed into the gemini micelles. The excess enthalpies for the ZW3-12/12-5-12 and the ZW3-12/12-6-12 systems were also >0 kJ mol-1, and as a function of zwittergent composition, were quite different to those of the ZW3-12/12-4-12 mixed micelles. These results indicate that the heat of mixed micelle formation is strongly dependent on electrostatic interactions and the structure of the surfactants involved, specifically, the length of the tether group for the 12-s-12 gemini surfactants. From the calorimetric data and the application of RST and Motomura's theory, we have obtained estimates of the excess Gibbs energy and entropy of mixing. An analysis of the three thermodynamic properties suggests that the relative contributions of enthalpic and entropic effects to nonideal behavior for mixed micelles involving gemini surfactants are strongly dependent on the gemini structure.
RESUMO
Critical micelle concentration (cmc) values were determined for the mixed zwitterionic/cationic gemini systems of N-dodecyl- N, N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-12)/ N, N'-bis(dimethyldodecyl)-α,ω-alkanediammonium dibromide (12-s-12) systems. The cmc values for the mixed systems were determined through conductivity measurements. The degree of nonideality of the interaction in the mixed micelle (ßm), for each system, was determined according to Rubingh's nonideal solution theory. In most cases, the systems exhibited negative deviations (-ßm values) at high surfactant mole fractions of zwittergent (αZW3-12). Specifically, the ZW3-12/12-4-12 system displayed -ßm values at αZW3-12 ≥ 0.5, while both the ZW3-12/12-5-12 and the ZW3-12/12-6-12 systems displayed -ßm values over the entire mole fraction range. Except for the low mole fraction range in the 12-4-12 system, these mixed surfactant systems demonstrated almost identical behavior to the n-dodecyltrimethylammonium bromide/12-2-12 system studied by Bakshi et al. providing further evidence that ZW3-12 tends to behave as a cationic surfactant in mixed surfactant systems. The manner in which the cosurfactants aggregate in the micelles was determined via two-dimensional (2D) NOESY spectroscopy. In the case of both the ZW3-12/12-5-12 and the ZW3-12/12-6-12 systems, the 2D NOESY spectra exhibited strong cross peaks between the gemini and zwitterionic surfactants over the entire micellar composition range. In the case of the ZW3-12/12-4-12 system, little cross peak intensity was observed between the gemini and the zwitterionic surfactant at low micellar compositions of the zwittergent. The results suggest some micelle demixing is occurring between the gemini and the zwittergent certain micellar composition ranges, a phenomenon rarely associated with hydrocarbon surfactants.
