Effects of Surfactant Headgroups on Oil‐in‐Water Emulsion Droplet Formation: An Experimental and Simulation Study

Abstract Nonpolar oils such as kerosene and diesel oil are common collectors in coal flotation. Surfactants are usually added to the pulp to emulsify the oil collectors. The present study used dodecane as the oil collector and anionic sodium dodecyl sulfonate (SDS) and nonionic tetraethylene glycol monododecyl ether (C 12 EO) with different headgroups and identical chain alkyls to investigate the effect of the surfactant headgroups on oil‐in‐water emulsion droplet formation. The morphology and stability of dodecane emulsions were determined experimentally. Density functional theory (DFT) and molecular dynamics (MD) simulations were used to explain the microscopic mechanism. The results of DFT indicated a larger interaction between SDS and the water molecules than that between C 12 EO and water molecules. The results obtained by MD suggested that the SDS headgroup exhibited a loose arrangement and a relatively large gap size, thereby weakening the interaction between SDS and water molecules at the dodecane/water interface. In contrast, the headgroups of C 12 EO were bent and interwoven with others to form a tight reticulation at the interface. According to the simulation results, the ability of the surfactant to form dodecane‐in‐water emulsion droplets depends on the arrangement of the surfactants at the oil–water interface rather than on the interaction strength between the headgroups of the surfactants and water molecules. The presented microscopic mechanism of the surfactant headgroup formation of oil‐in‐water emulsion droplets offers surfactant selection and design references.