AbstractA source of waste‐water pollution in machining is the lubricating/cooling fluid used. This study investigates the application of the flotation technique for the removal of emulsifiable oil. Research has been carried out on a process of selective separation of oil using mixtures of anionic/nonionic surfactants as collectors and a cationic surfactant as a de‐emulsifier (coagulant). The behaviour of the mixtures at the aqueous solution‐air interface has been studied, and the critical micelle concentration, efficiency, effectiveness, minimum surface area, and free energy of micellisation determined. The effect of the optimum mole fraction of the mixtures on oil separation has been discussed from the point of view of physical parameters. The selectivity achieved can be explained in terms of surfactant concentration and the structure of the mic