Micellization of dodecyltrimethylammonium bromide in water–dimethylsulfoxide mixtures: A multi-length scale approach in a model system

The micellization in mixed solvent was studied using conductimetry, density measurements (molar volumes), and small angle neutron scattering (SANS) to explore dodecyltrimethylammonium bromide (DTABr) micelle formation throughout the entire composition range of water–dimethylsulfoxide (DMSO) mixtures. As the concentration of DMSO was increased in the mixture, the critical micelle concentration (CMC) increased, the aggregation number decreased and the ionization degree increased, until no aggregates could be detected any more for DMSO molar fraction higher than 0.51. The results were consistent with the presence of globular micelles interacting via a coulombic potential. The experimental CMC values and aggregation numbers were successfully reconciled with a molecular thermodynamic model describing the micellization process in solvent mixtures (R. Nagarajan and C.-C. Wang, Langmuir 16 (2000) 5242). The structural and thermodynamic characterization of the micelles agreed with the prediction of a dissymmetric solvation of the surfactant entity: the hydrocarbon chain was surrounded only by DMSO while the polar head was surrounded only by water. The decrease in the ionization degree was due to the condensation of the counterions and was definitely linked to the geometrical characteristics of the aggregates and by no means to the CMC or salinity. This multi-technique study provides new insight into the role of solvation in micellization and the reason for the decrease in ionization degree, emphasizing the dissymmetric solvation of the chain by DMSO and the head by water. This is the first time that, for a given surfactant in solvent mixtures, micellization is described using combined analysis from molecular to macroscopic scale.

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► Micellization was characterized in the entire DMSO-water composition range.
► Micelles decrease in size, then vanish when the DMSO content is increased.
► Solvation by DMSO around the chains and water around the polar head is observed.
► A DMSO composition threshold in observed for micellization.
► Thermodynamics and statistical physics are combined to describe the micelles.