Adsorption of the cationic surfactant benzyldimethylhexadecylammonium chloride at the silica-water interface and metal salt effects on the adsorption kinetics.

The adsorption of the cationic surfactant benzyldimethylhexadecylammonium (BDMHA(+)) chloride has been studied at the hydrophilic silica-water interface by Raman spectroscopy in total internal reflection geometry (TIR Raman). This Raman spectroscopic technique takes advantage of an evanescent electric field that is generated at the silica-water interface in TIR mode with specific probing depth. The present study demonstrates the capabilities of the TIR Raman sampling configuration to provide structural information and simultaneously serve as an experimental platform for studying thermodynamic and kinetic properties of BDMHA(+)Cl(-) at the silica-water interface at neutral pH and compare its adsorption behavior with the modified adsorption properties in the presence of four different concentrations of a divalent metal salt. Spectral analysis of the Raman scattering intensities as a function of time and concentration provided the input data for evaluating adsorption properties of the surfactant in the absence and presence of the metal salt additive. Addition of the magnesium metal salt lowered the cmc, altered the surface excess of the surfactant, and increased the Langmuir adsorption constants, as well as the magnitude of the free energy of adsorption, and adsorption kinetics, proportional to the concentrations of the metal salt. Adsorption isotherms based on a modified Langmuir adsorption model were established for five systems: the pure surfactant in aqueous solution, and the surfactant in the presence of 5, 10, 50, and 100 mM of magnesium chloride. The metal salt did not enhance surfactant adsorption at very low surfactant concentrations below 5 μM, where adsorption occurs by electrostatic attraction; the divalent metal salt, however, favorably influenced the adsorption behavior in the aggregate formation region by reducing the electrostatic repulsion between the polar surfactant head groups, and enhancing the hydrophobic effect between the hydrophobic surfactant alkyl chains and the polar water molecules.