The self-assembly of amphiphilic molecules into supramolecular aggregates involves a number of complex phenomena and forces. Recent developments of highly sensitive, densimetric and acoustic methods on small volume samples have provided novel sensitive probes to explore the physical properties of these complex fluids. We have investigated, by high precision densimetry and ultrasound velocimetry, reverse micelles of [sodium bis(2-ethylhexyl)sulfosuccinate] in oil (isooctane and decane), at increasing water concentration and at variable micellar volume fractions. The size of these spherical micelles has been determined by small angle x-ray scattering. Using these results, in the framework of the effective medium theory, we have developed a simple model of micellar compressibility, allowing the calculation of physical parameters (aggregation number, volume, and compressibility) of the surfactant monomolecular film as well as that of the micellar waters. In particular, we show that the central aqueous core designated as "free" water, located at a distance from the oil-water interacting interface, is twice as compressible as "bulk" water. One notable feature of this work is the influence of the nature of the oil on the above parameters.
We have used a custom-built ultrasound velocimeter to carry out
high-precision velocity measurements of
reverse micelle solutions, made of ionic (AOT) and nonionic
(C12E4) surfactants in oil, as a function of
water
concentration. We show that the observed velocity variation as a
function of increasing water concentration
differs from the characteristics of the surfactant polar headgroups.
The complex profile of compressibility
curves obtained from velocity and densimetric measurements can be
accounted for by the relation existing
between the surface polar headgroup of each surfactant and the number
of interacting water molecules. At
the highest water concentration, the compressibility parameters
obtained are different from those reported for
“bulk” water and reflect the peculiar properties of confined
water.
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