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Confinement-induced fluid-fluid phase transitions in simple fluid mixtures, under bulk supra-critical conditions

Haddadi, Sara LU ; Woodward, Clifford E. and Forsman, Jan LU (2021) In Fluid Phase Equilibria 540.
Abstract

In a previous publication (Xie et al., Langmuir 29, 2659 (2013)), we demonstrated that polymer solutions, which display a bulk lower critical solution temperature (LCST) may undergo a phase transition in a porous environment below the LCST. Such capillary induced transitions are thus supra-critical, given that the associated bulk solution only contains a single fluid phase. The current work explores this phenomenon for mixtures of simple particles, with ostensibly isotropic interactions, that also display a bulk LCST. We demonstrate that capillary-induced phase transitions may occur at temperatures considerably below the LCST, in these cases as well. The connection to systems with anisotropic interactions, e.g., aqueous solutions... (More)

In a previous publication (Xie et al., Langmuir 29, 2659 (2013)), we demonstrated that polymer solutions, which display a bulk lower critical solution temperature (LCST) may undergo a phase transition in a porous environment below the LCST. Such capillary induced transitions are thus supra-critical, given that the associated bulk solution only contains a single fluid phase. The current work explores this phenomenon for mixtures of simple particles, with ostensibly isotropic interactions, that also display a bulk LCST. We demonstrate that capillary-induced phase transitions may occur at temperatures considerably below the LCST, in these cases as well. The connection to systems with anisotropic interactions, e.g., aqueous solutions containing hydrogen-bonding solutes, is also elucidated. In contrast to the complex analysis carried out in polymeric systems, a simple classical density functional approach is employed here, which serves to illustrate the ubiquitous nature of this phenomenon. This makes the conclusions of the present study more accessible to researchers in a range of fields, which may inspire experimental confirmation of our qualitative theoretical predictions. Possible future applications may include utilisation of this phenomenon in chromatographic methods.

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publication status
published
subject
keywords
Capillary Induced Phase Separation, Classical Density Functional Theory, Lower Critical Solution Temperature, Supercritical
in
Fluid Phase Equilibria
volume
540
article number
112983
publisher
Elsevier
external identifiers
  • scopus:85104317864
ISSN
0378-3812
DOI
10.1016/j.fluid.2021.112983
language
English
LU publication?
yes
id
65f19b89-67ce-4a9e-abe8-ae616921060e
date added to LUP
2021-04-26 08:28:28
date last changed
2021-04-26 08:28:28
@article{65f19b89-67ce-4a9e-abe8-ae616921060e,
  abstract     = {<p>In a previous publication (Xie et al., Langmuir 29, 2659 (2013)), we demonstrated that polymer solutions, which display a bulk lower critical solution temperature (LCST) may undergo a phase transition in a porous environment below the LCST. Such capillary induced transitions are thus supra-critical, given that the associated bulk solution only contains a single fluid phase. The current work explores this phenomenon for mixtures of simple particles, with ostensibly isotropic interactions, that also display a bulk LCST. We demonstrate that capillary-induced phase transitions may occur at temperatures considerably below the LCST, in these cases as well. The connection to systems with anisotropic interactions, e.g., aqueous solutions containing hydrogen-bonding solutes, is also elucidated. In contrast to the complex analysis carried out in polymeric systems, a simple classical density functional approach is employed here, which serves to illustrate the ubiquitous nature of this phenomenon. This makes the conclusions of the present study more accessible to researchers in a range of fields, which may inspire experimental confirmation of our qualitative theoretical predictions. Possible future applications may include utilisation of this phenomenon in chromatographic methods.</p>},
  author       = {Haddadi, Sara and Woodward, Clifford E. and Forsman, Jan},
  issn         = {0378-3812},
  language     = {eng},
  publisher    = {Elsevier},
  series       = {Fluid Phase Equilibria},
  title        = {Confinement-induced fluid-fluid phase transitions in simple fluid mixtures, under bulk supra-critical conditions},
  url          = {http://dx.doi.org/10.1016/j.fluid.2021.112983},
  doi          = {10.1016/j.fluid.2021.112983},
  volume       = {540},
  year         = {2021},
}