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Modeling Gas-Liquid Interfaces by Dissipative Particle Dynamics: Adsorption and Surface Tension of Cetyl Trimethyl Ammonium Bromide at the Air-Water Interface
Adsorption of surfactants at gas-liquid interfaces that causes reduction in the surface tension is a classical problem in colloid and interface science with multiple practical applications in oil and gas recovery, separations, cosmetics, personal care, and biomedicine. Here, we develop an original coarse-grained model of the liquid-gas interface within the conventional dissipative particle dynamics (DPD) framework with the goal of quantitatively predicting the surface tension in the presence of surfactants. As a practical case-study example, we explore the adsorption of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) on the air-water interface. The gas phase is modeled as a DPD fluid composed of fictitious hard-core gas beads with exponentially decaying repulsive potentials to prevent penetration of the liquid phase components. A rigorous parametrization scheme is proposed based on matching the bulk and interfacial properties of water and octane taken as the reference compounds. Quantitative agreement between the simulated and experimental surface tension of CTAB solutions is found for a wide range of bulk surfactant concentrations (similar to 10(-3) to similar to 1 mmol/L) with the reduction of the surface tension from , similar to 72 mN/m (pure water) to the limiting value of similar to 37.5 mN/m at the critical micelle concentration. The gas phase DPD model with the proposed parametrization scheme can be extended and applied to modeling various gas-liquid interfaces with surfactant and lipid monolayers, such as bubble suspensions, foams, froths, etc.
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