Phase behavior and microstructure of C12E5 nonionic microemulsions with chlorinated oils

New non-ionic microemulsions consisting of pentaethyleneglycol dodecyl ether, water, and 1-chloroalkanes were prepared, and their phase behavior was studied. A homologous series of five different 1-chloroalkanes from 1-chlorooctane to 1-chlorohexadecane was studied. The phase behavior of the microemulsions was determined by vertical sections through the Gibbs' phase prism ("fish" plots), from which valuable information such as the microemulsion balance temperature (T(0)), efficiency of the surfactant (phi*), temperature extension of the three-body phase (DeltaT), mean temperature (T(m)), and the monomeric solubility in oil (phi(mon,oil)) was obtained. The chlorinated alkanes in the microemulsions shift the balance temperature to about 14 degrees C lower compared with their n-alkane counterparts. This indicates the polar nature of the chlorinated oils and their ability to penetrate the surfactant film. The chlorinated alkanes thus behave as short n-alkane molecules and lower the spontaneous curvature of the microemulsion droplets. The efficiency of the surfactant and the monomeric solubility in oil systematically depend on the alkyl chain length of the oil, with the efficiency and solubility decreasing with increasing alkyl chain length of 1-chloroalkane. The size and shape of the microemulsion droplets in the microemulsion phase were studied by small-angle X-ray scattering (SAXS). For a surfactant-to-oil volume fraction ratio of 0.80, the droplets can be described by ellipsoidal shapes, and the size of the droplets increased with increasing alkyl chain length.