Competitive Adsorption of a Multi-functional Amine and Phenol Surfactant with Ethanol on Hematite from Non-Aqueous Solution

Surfactants, which contain phenol and amine groups, are commonly used in industry to protect metallic surfaces and their effciency depends strongly on factors such as pressure and temperature, solvent properties, and the presence of other surfactants in the system. In this work, we present a molecular simulation study of the competitive adsorption between a multi-functional phenol and amine surfactant model and ethanol at the oil/solid interface formed between iso-octane and a model hematite ( - Fe2O3) slab. We show that the surfactant strongly adsorbs at the iso-octane/hematite interface in the absence of ethanol at moderate temperatures. As the concentration of ethanol is increased, the ethanol molecules compete effectively for the adsorption sites on the iron oxide surface. This competition drives the surfactant molecules to remain in the bulk-solution while ethanol forms an ordered and strongly coordinated layers at the oil/solid interface, despite the well-known complete miscibility of ethanol in iso octane in bulk at standard conditions. Potential of mean force calculations show that the free energy of adsorption of the surfactant is approximately two times larger than for a single ethanol molecule, but the simulations also reveal that a single surfactant chain needs to displace up to five ethanol molecules to adsorb onto the surface. The end result is a more favorable ethanol adsorption which agrees with the experimental analysis of similar oil/iron oxide systems also reported in this work.