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Probing the formation of Wormlike Micelles formed by cationic surfactant with chlorobenzoate derivatives.

The energy released when tetradecyltrimethylammonium bromide (C14TAB) is combined with different derivatives of chlorobenzoates in an isothermal titration calorimeter (ITC) allows a direct evaluation of the spontaneity of the threading of the aromatic anions into the micellar palisade. The comparison between the enthalpimetric curves with the one for viscosity of the solutions, hydrodynamic radii of the aggregates (DLS experiments) and fraction of aromatic anions incorporated (DOSY experiments), allows the establishment of the variations of enthalpy with formation, growing and decreasing of the wormlike micelles (WLM). The formation of WLM with C14TAB is very favored (very exothermic) for titrations of chlorobenzoate derivatives which present the chlorine atom in the positions 3 or 4 of the aromatic ring. However, the aggregation is highly unfavorable if the chlorine is at the position 2 of the chlorobenzoate. According to the results, it was demonstrated the high potential of the ITC to determine critical concentrations and the energies associated with the aggregation of a cationic surfactant and aromatic anions for the formation of WLM.