Macromolecular Structure of Dodecyltrimethylammonium Chloride at the Silica/Water Interface Studied by Sum Frequency Generation Spectroscopy

Adsorption of the cationic surfactant dodecyltrimethylammonium chloride at the silica/water interface was studied using sum frequency generation (SFG) spectroscopy under high ionic strength (100 mM NaCl) and at pH values ranging from 3 to 11, which are conditions relevant to hydraulic fracturing in enhanced oil recovery operations. At surfactant concentrations above the critical micelle concentration, SFG spectra of the CH stretching region indicate a more noncentrosymmetric structure for the surfactant aggregate is formed at the interface under acidic or basic conditions compared to neutral conditions. The SFG spectra also indicate a change in the packing/ordering of the surfactant hydrophobic tails with pH as well. In addition, the observed changes in the SFG spectra of water upon the addition of surfactant vary depending on the pH. At pH 7 and 11, the SFG intensity decreases in the OH stretching region, indicating a decrease in the magnitude of the electrostatic potential at the interface when the cati...