A partially flocculated Fe(OH)3 sol has been used as an emulsifying agent to stabilize toluene/water system. The electrophoretic mobilities of the emulsion thus obtained in the presence of different anionic detergents have been measured microelectrophoretically and from these values the zeta potentials have been calculated. At the charge reversal concentrations the adsorption and free energy constants were calculated. From the surface potential values the repulsion and attraction energies were evaluated which clearly showed that the flocculation occurrs in the secondary minima. The operating van der Waals constant A has been estimated by correlating the results of degree of aggregation obtained haemocytometrically with the theoretical values. It was found to be 1.05×10−12 erg. The values of interfacial tension have been reduced by the addition of these detergents which are directly connected with the chain length of the detergent and adsorption characteristics.