Liquid-liquid interfacial tension of electrolyte solutions

It is theoretically shown that the excess liquid-liquid interfacial tension between two electrolyte solutions as a function of the ionic strength I behaves asymptotically as O(- I^0.5) for small I and as O(+- I) for large I. The former regime is dominated by the electrostatic potential due to an unequal partitioning of ions between the two liquids whereas the latter regime is related to a finite interfacial thickness. The crossover between the two asymptotic regimes depends sensitively on material parameters suggesting that, depending on the actual system under investigation, the experimentally accessible range of ionic strengths can correspond to either the small or the large ionic strength regime. In the limiting case of a liquid-gas surface where ion partitioning is absent, the image chage interaction can dominate the surface tension for small ionic strength I such that an Onsager-Samaras limiting law O(- I ln(I)) is expected. The proposed picture is consistent with more elaborate models and published measurements.Comment: Accepted for publication in Physical Review Letter

Stability of additive-free water-in-oil emulsions

We calculate ion distributions near a planar oil-water interface within non-linear Poisson-Boltzmann theory, taking into account the Born self-energy of the ions in the two media. For unequal self-energies of cations and anions, a spontaneous charge separation is found such that the water and oil phase become oppositely charged, in slabs with a typical thickness of the Debye screening length in the two media. From the analytical solutions, the corresponding interfacial charge density and the contribution to the interfacial tension is derived, together with an estimate for the Yukawa-potential between two spherical water droplets in oil. The parameter regime is explored where the plasma coupling parameter exceeds the crystallization threshold, i.e. where the droplets are expected to form crystalline structures due to a strong Yukawa repulsion, as recently observed experimentally. Extensions of the theory that we discuss briefly include numerical calculations on spherical water droplets in oil, and analytical calculations of the linear PB-equation for a finite oil-water interfacial width.Comment: 9 pages, 4 figures, accepted by JPCM for proceedings of LMC