Mesophase formation and thermal behavior of catanionic mixtures of gemini surfactants with sodium alkylsulfates

The thermal behavior for three homologous series of cationic geminis surfactants of the type n-2-n, alkanediyl-α,ω-bis(alkyldimethylammonium bromide), with n = 12, 14, 16, and 18, and sodium alkyl sulfates, SC _m S, with m = 12, 14, and 16, is reported here. The cationic/anionic molar ratio is kept at 1:2 (equicharged mixtures), and salt is also present. Polarizing light microscopy and differential scanning calorimetry show a stepwise fusion for the mixtures with appearance of several mesophases between the crystalline structures and the isotropic liquid. A main endothermic transition is observed, associated with partial chain melting and consequent loss of crystalline order, followed by a transition to a smectic liquid crystal. The phase transition thermodynamics is interpreted in terms of an interplay between van der Waals chain–chain interactions and ionic head group interactions.