Role of water structure on the high pressure micellization and phase transformations of sodium dodecanoate aqueous...

The aim of this work is to study the micelle formation and possible subsequent transformations of sodium dodecanoate aggregates in aqueous solutions at pressures up to 700 MPa. This pressure range is much larger than in most available studies on surfactant solutions and allows for evaluating the possible effect of the low-density to high-density water transformation on the aggregative behavior of the surfactant. The speed-of-sound and attenuation coefficient were determined at 298.15 K as a function of pressure at concentrations up to 0.13 mol kg(-1) in water. The speed-of-sound behavior with concentration is maintained up to pressures around 350 MPa. The attenuation coefficient, initially insensitive to pressure, exhibits a sudden increase around 250 MPa, reaching a maximum around 350 MPa and a plateau above 500 MPa in the case of the highest studied surfactant concentrations. From the analysis of the changes observed in these properties, it was possible to extend the concentration-pressure phase diagram of sodium dodecanoate at constant temperature. Some peculiarities found were: (1) the critical micellar concentration reaches a maximum around 170 MPa, (2) the micellar phase disappears above 400 MPa, (3) a phase transformation starts around 250 MPa, setting the solubility limit of the surfactant at concentrations around 0.06 mol kg(-1) in this pressure region, and (4) further transformations occur between 350 and 500 MPa. We discuss in length the possibility that such transformations might be driven by structural changes linked to the so-called low-density-water to high-density-water transition.