Structural and Thermodynamic Properties of Solutions of Butane in Aqueous Sodium Dodecyl Sulfate: A Study Using Neutron Scattering and Solubility Measurements.

The solubility of n-butane at a pressure of 1.013 bar in aqueous solutions of sodium dodecyl sulfate (SDS) has been measured over a range of concentration from below the critical micelle concentration (CMC) at about 8 mol kg(-1) to about 90 mol kg(-1) at three different temperatures. The free energy, enthalpy, and entropy of transfer of butane from water to the micelle were respectively -19.0 kJ mol(-1), 5.5 kJ mol(-1), and 80 J K(-1) mol(-1). At 68 mol kg(-1) a transition was found with a free energy of about -400 J mol(-1). Small-angle neutron experiments were used to study the effect of butane on the state of aggregation of the SDS. For each butane molecule incorporated into a micelle, the aggregation number of the SDS increased by an average of about 1.4 molecules. Thus, at 1.013 bar of butane and 50 mM SDS, where the solubility is about 1 butane to 10 SDS, the average micelle increases in size by about 20%, most of which comes from the additional SDS molecules. The aggregation behavior is qualitatively similar to that reported for hexane, heptane, and octane, but the effect seems to be larger for butane for a given volume of solute hydrocarbon. Small-angle scattering did not observe any substantial change in structure across the phase transition at 68 mol kg(-1). Copyright 1999 Academic Press.