Structural organization of cetyltrimethylammonium sulfate in aqueous solution: The effect of Na2SO4

We used dynamic light scattering (DLS), steady-state fluorescence, time resolved fluorescence quenching (TRFQ), tensiometry, conductimetry, and isothermal titration calorimetry (ITC) to investigate the self-assembly of the cationic surfactant cetyltrimethylammonium sulfate (CTAS) in aqueous solution, which has SO2−4 as divalent counterion. We obtained the critical micelle concentration (cmc), aggregation number (Nagg)(Nagg), area per monomer (a0)(a0), hydrodynamic radius (RH)(RH), and degree of counterion dissociation (α)(α) of CTAS micelles in the absence and presence of up to 1 M Na2SO4 and at temperatures of 25 and 40 °C. Between 0.01 and 0.3 M salt the hydrodynamic radius of CTAS micelle RH≈16 ÅRH≈16 Å is roughly independent on Na2SO4 concentration; below and above this concentration range RHRH increases steeply with the salt concentration, indicating micelle structure transition, from spherical to rod-like structures. RHRH increases only slightly as temperature increases from 25 to 40 °C, and the cmc decreases initially very steeply with Na2SO4 concentration up to about 10 mM, and thereafter it is constant. The area per surfactant at the water/air interface, a0a0, initially increases steeply with Na2SO4 concentration, and then decreases above ca. 10 mM. Conductimetry gives α=0.18α=0.18 for the degree of counterion dissociation, and NaggNagg obtained by fluorescence methods increases with surfactant concentration but it is roughly independent of up to 80 mM salt. The ITC data yield cmc of 0.22 mM in water, and the calculated enthalpy change of micelle formation, ΔHmic=3.8 kJmol−1, Gibbs free energy of micellization of surfactant molecules, ΔGmic=−38.0 kJmol−1 and entropy TΔSmic=41.7 kJmol−1 indicate that the formation of CTAS micelles is entropy-driven.

Graphical abstractThe effect of Na2SO4 on the cmc and area per monomer at the water/air interface for CTAS micelles.Figure optionsDownload full-size imageDownload as PowerPoint slide