TY - JOUR
T1 - Density functional theory of gas-liquid phase separation in dilute binary mixtures
AU - Okamoto, Ryuichi
AU - Onuki, Akira
N1 - Publisher Copyright:
© 2016 IOP Publishing Ltd.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2016/4/26
Y1 - 2016/4/26
N2 - 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 Δμs (the Gibbs energy of transfer) is considerably larger than the thermal energy κBT 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 κBT n2 ℓ exp(Δμs/kappa;BT), where n2 ℓ is the solute density added in liquid. For exp(Δμs/κBT)≫1, 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.
AB - 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 Δμs (the Gibbs energy of transfer) is considerably larger than the thermal energy κBT 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 κBT n2 ℓ exp(Δμs/kappa;BT), where n2 ℓ is the solute density added in liquid. For exp(Δμs/κBT)≫1, 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.
KW - Phase separation in dilute binary mixtures
KW - nanobubble
KW - solvation effect
UR - http://www.scopus.com/inward/record.url?scp=84969754340&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84969754340&partnerID=8YFLogxK
U2 - 10.1088/0953-8984/28/24/244012
DO - 10.1088/0953-8984/28/24/244012
M3 - Article
AN - SCOPUS:84969754340
VL - 28
JO - Journal of Physics Condensed Matter
JF - Journal of Physics Condensed Matter
SN - 0953-8984
IS - 24
M1 - 244012
ER -