Phase equilibria of size- and charge-asymmetric primitive models of ionic fluids: the method of collective variables

Patsahan, Oksana

doi:10.5488/cmp.13.23004

Cited by 3 publications

(3 citation statements)

References 27 publications

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“…where ρ i = ρ + + ρ − is the total ionic number density. It should be noted that for the bulk PM our theory predicts a reduction of the coexistence regions as well as a decrease of the critical parameters T * c and ρ * i,c with an increase of size asymmetry [26,27]. This behavior qualitatively agrees with simulation results [14][15][16][17][18][19].…”

Section: Resultssupporting

confidence: 87%

“…However, certain arbitrariness in determining the association constant is implied in these theories. On the other hand, the effect of asymmetry on the vapor-liquid phase diagram has been studied within the framework of the theory based on the method of collective variables (CVs) [24][25][26][27][28]. The theory allows one to take into account the effects of higher-order correlations between ions and, as a result, to obtain, on an analytical basis, the trends of the critical parameters with charge and size asymmetry that qualitatively agree with simulation findings.…”

Section: Introductionmentioning

confidence: 99%

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Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: The collective-variables-based approach

Patsahan

Holovko

2018

Phys. Rev. E

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We develop a theory based on the method of collective variables to study the vapor-liquid equilibrium of asymmetric ionic fluids confined in a disordered porous matrix. The approach allows us to formulate the perturbation theory using an extension of the scaled particle theory for a description of a reference system presented as a two-component hard-sphere fluid confined in a hard-sphere matrix. Treating an ionic fluid as a size-and charge-asymmetric primitive model (PM) we derive an explicit expression for the relevant chemical potential of a confined ionic system which takes into account the third-order correlations between ions. Using this expression, the phase diagrams for a size-asymmetric PM are calculated for different matrix porosities as well as for different sizes of matrix and fluid particles. It is observed that general trends of the coexistence curves with the matrix porosity are similar to those of simple fluids under disordered confinement, i.e., the coexistence region gets narrower with a decrease of porosity, and simultaneously the reduced critical temperature T * c and the critical density ρ * i,c become lower. At the same time, our results suggest that an increase in size asymmetry of oppositely charged ions considerably affects the vapor-liquid diagrams leading to a faster decrease of T * c and ρ * i,c and even to a disappearance of the phase transition, especially for the case of small matrix particles.

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Section: Resultssupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: The collective-variables-based approach

Patsahan

Holovko

2018

Phys. Rev. E

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“…The situation with theoretical estimates is less satisfactory, i.e. while the position of the critical point is predicted with reasonable accuracy the phase diagram is still too narrow in comparison with computer simulation phase diagrams [29,30,31,32,33,34].…”

Section: Introductionmentioning

confidence: 86%

Primitive models of room temperature ionic liquids. Liquid-gas phase coexistence

Kalyuzhnyi

Reščič

Holovko

et al. 2018

Journal of Molecular Liquids

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We propose several versions of primitive models of room temperature ionic liquids (RTILs) and develop a mean spherical approximation (MSA)-type theory for their description. RTIL is modeled as a two-component mixture of hard-sphere anions and flexible linear chain cations, represented by tangentially bonded hard spheres with the charge located on one of the terminal beads. The theoretical description of the model is carried out using the solution of the appropriately modified associative MSA (AMSA). Our solution reduces to solving one nonlinear algebraic equation for the Blum's screening parameter Γ, which in turn is used to express all thermodynamic properties of the models of interest. We calculate liquid-gas phase diagrams using theoretical and computer simulation methods for two versions of the model, represented by the dimer (D) and chain (C) models. Theoretical predictions for the phase diagrams appear to be in reasonably good agreement with computer simulation results. It is demonstrated that the models and theory are able to qualitatively reproduce experimentally observed phase behavior of RTILs, in particular the decrease of the critical temperature and critical density with increasing asymmetry of the model in its shape and position of the charge.

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Gas–liquid coexistence in asymmetric primitive models of ionic fluids

Patsahan

2011

Journal of Molecular Liquids

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Phase equilibria of size- and charge-asymmetric primitive models of ionic fluids: the method of collective variables

Cited by 3 publications

References 27 publications

Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: The collective-variables-based approach

Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: The collective-variables-based approach

Primitive models of room temperature ionic liquids. Liquid-gas phase coexistence

Gas–liquid coexistence in asymmetric primitive models of ionic fluids

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