Density functional theory of gas-liquid phase separation in dilute binary mixtures.
We examine statics and dynamics of phase-separated states of dilute binary mixtures using density functional theory. In our systems, the difference of the solvation chemical potential between liquid and gas [Formula: see text] (the Gibbs energy of transfer) is considerably larger than the thermal energy [Formula: see text] for each solute particle and the attractive interaction among the solute particles is weaker than that among the solvent particles. In these conditions, the saturated vapor pressure increases by [Formula: see text], where [Formula: see text] is the solute density added in liquid. For [Formula: see text], phase separation is induced at low solute densities in liquid and the new phase remains in gaseous states, even when the liquid pressure is outside the coexistence curve of the solvent. This explains the widely observed formation of stable nanobubbles in ambient water with a dissolved gas. We calculate the density and stress profiles across planar and spherical interfaces, where the surface tension decreases with increasing interfacial solute adsorption. We realize stable solute-rich bubbles with radius about 30 nm, which minimize the free energy functional. We then study dynamics around such a bubble after a decompression of the surrounding liquid, where the bubble undergoes a damped oscillation. In addition, we present some exact and approximate expressions for the surface tension and the interfacial stress tensor.
Department of Chemistry, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan.
Ryuichi
R
Okamoto
Akira
A
Onuki