Micellization thermodynamic behavior of gemini cationic surfactants. Modeling its adsorption at air/water interface

Self-assembly structures of gemini surfactants are characterized, among others, for their low CMC. This characteristic could be due to great hydrophobic parts in their molecular structures. That availability could imply great stability of self-assembly structures or monolayers absorbed in an interface. The micellization behavior of two cationic gemini surfactants, α,ω-bis(S-alkyl dimethylammonium) alkane bromides, was studied by a modelization of dynamic surface tension (DST) experimental data and isothermal titration calorimetry (ITC) measurements. The adsorption data at the air/water interface was taken through the analysis of the profile changes of a pendant drop. The thermodynamic characterization of the micellization process of the gemini surfactants was carried out using ITC. A model based on the Frumkin adsorption isotherm and the Ward-Tordai diffusion equation was developed to obtain the characteristic parameters of the adsorption without the need of using the Gibbs adsorption equation. Positive values of lateral interaction show good stability of the adsorbed monolayer. The ITC data were analyzed following a novel protocol based on the identification of the different energetic contributions and regimens observed in the titration enthalpograms from demicellization processes. The presence of exothermic peaks would explain the low values of CMC. [Display omitted] •Ward-Tordai diffusion was used to study dynamic surface tension of gemini surfactant.•The modelization is carried out without the use of the Gibbs adsorption isotherm.•Great stability of the gemini adsorbed monolayers at the air/water interface.•A new intuitive method was developed to analyze the demicellization from ITC data.