Dilute emulsions of dodecane in water were prepared under constant flow rate conditions with binary surfactant systems. The droplet size distribution was measured as a function of the mixed surfactant composition in solution. The systems studied were (a) the mixture of anionic sodium dodecyl sulfate (SDS) with nonionic hexa(ethyleneglycol) mono n-dodecylether (C 12E 6) and (b) the mixture of cationic dodecyl pyridinium chloride (DPC) with C 12E 6. At a constant concentration of SDS or DPC surfactant in solution (below the CMC) the mean emulsion droplet size decreases with the increase in the amount of C 12E 6 added to the solution. However, a sharp break of this droplet size occurs at a critical concentration and beyond this point the mean droplet size did not significantly change upon further increase of the C 12E 6. This point was found to corresponded to the CMC of the mixed surfactant systems (as previously determined from microcalorimetry measurements) and this result suggested the mixed adsorption layer on the emulsion droplet was similar to the surfactant composition on the mixed micelles. The emulsion droplet size as a function of composition at the interface was also studied. The mean emulsion droplet size in SDS–C 12E 6 solution was found to be lower than that in DPC–C 12E 6 system at the equivalent mole fraction of ionic surfactant at interface. This was explained by the stronger interactions between sulphate and polyoxyethylene head groups at the interface, which facilitate the droplet break-up. Counterion binding parameter ( β) was also determined from zeta-potential of dodecane droplets under the same conditions and it was found that ( β) was independent of the type of the head group and the mole fraction of ionic surfactant at interface.
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