Thermotropic behavior of a cationic surfactant in the adsorbed and micellar state: an NMR study.

Knowledge about how temperature affects the internal structure and dynamics of surfactant aggregates can lead to a better understanding of their behavior in complex environments and processes. (13)C chemical shifts of the cationic surfactant tetradecytrimethylammonium bromide (TTAB) in micellar solution and when adsorbed on silica particles are recorded in the temperature range 8-78 °C, and give information on the conformation of the alkyl chain carbons. Adsorbed TTAB has conformational disorder similar to free TTAB at about 70 °C, with an increase in the rate of conformational changes occurring above 50 °C. Furthermore, no significant change in TTAB adsorption density was observed in the temperature range studied, and the results indicate a bilayer arrangement of the adsorbed surfactants. The number of gauche conformers increases linearly with temperature for the alkyl chain carbons in TTAB micelles. However, the total increase in gauche conformers is significantly smaller for micellar than for adsorbed TTAB within the temperature range studied. The fraction of micellized TTAB molecules in solution is found to increase with temperature.