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Clusters in a mixture of an “amphiphilic” ionic liquid and a nonionic liquid: Theoretical study
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10.1063/1.3670016
/content/aip/journal/jcp/136/1/10.1063/1.3670016
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/1/10.1063/1.3670016
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Schematic diagram representing the values of the Flory-Huggins parameters characterizing the dispersion interactions between the components of the considered system.

Image of FIG. 2.
FIG. 2.

Volume fractions of: (a) cations, ϕ +, (b) anions, ϕ , and (c) normalized potential of electrostatic field, , as functions of the coordinate z perpendicular to the interface between two macro phases of a IL/nIL mixture (I) and as a function of the distance r to the center of a cluster formed in a IL/nIL mixture (II–V) at , Δχ = 6, χ+− = 0, u = 1.

Image of FIG. 3.
FIG. 3.

Volume fractions of: (a) cations, ϕ +, (b) anions, ϕ , and (c) normalized potential of electrostatic field, , as functions of the coordinate z perpendicular to the interface between two macrophases of a IL/nIL mixture (I) and as a function of the distance r to the center of a cluster formed in a IL/nIL mixture (II–V) at , Δχ = 7.3, χ+− = 0, u = 1.

Image of FIG. 4.
FIG. 4.

Dependencies of surface tension σ s of the phase boundary between the IL and the nIL phases on the amphiphilicityΔχ of the IL at χ+− = 0, u = 1, and different affinities of the IL to the nIL: (a), (b), (c), (d).

Image of FIG. 5.
FIG. 5.

Phase diagram of the IL/nIL mixture in coordinates (, Δχ) (i.e., affinity of the IL to the nIL, and amphiphilicity of the IL) at the average volume fraction of IL in the mixture equal to 0.5, andχ+− = 0, u = 1. (a) The upper boundary of the domain corresponding to the stability of a mixture consisting of two macrophases. The domain over this boundary corresponds also to stability of separate nIL clusters. (b) The upper boundary of the domain corresponding to a homogeneous IL/nIL mixture, in which stable fluctuations of the components concentrations are not possible. (c) The lower boundary of the domain corresponding to the stability of separate IL clusters. (d) The lower boundary of the domain corresponding to the stability of separate nIL clusters having radius smaller than 10 a.

Image of FIG. 6.
FIG. 6.

Schematic drawings of: (I), a cluster of ions surrounded by the nIL phase; (II), a cluster of neutral molecules surrounded by the IL phase; (III), the phase boundary between the IL phase and the nIL phase. The cations and the anions are shown as circles. The neutral molecules are not shown, they are represented by the striped background.

Image of FIG. 7.
FIG. 7.

Dependence of the free energy of the IL/nIL mixture consisting of the nIL phase and IL clusters dispersed over it, as a function of the clusters radius R at , χ+− = 0, u = 1 and (a) Δχ = 5.37, (b) Δχ = 5.38, (c) Δχ = 5.4. The horizontal line represents the free energy the system would have, if it consisted of two macrophases. A cluster is stable if it corresponds to the minimum of a curve, and the minimum is lower than the horizontal line.

Image of FIG. 8.
FIG. 8.

Dependencies of the radius R of a stable cluster formed by ions in the nIL phase on the difference Δχ − Δχ* between the amphiphilicity of the IL and the critical value of the amphiphilicity at which the surface tension of the phase boundary of a macroheterogeneous IL/nIL mixture vanishes. χ+− = 0, u = 1, and (a), (b) , (c) , (d) . The left end of each dependence corresponds to the minimal value Δχ − Δχ*, at which a stable cluster is possible.

Image of FIG. 9.
FIG. 9.

Dependence of the free energy of the IL/nIL mixture consisting of the IL phase and nIL clusters dispersed over it, as a function of the clusters radius R at , χ+− = 0, u = 1 and (a) Δχ = 5.4, (b) Δχ = 5.42, (c) Δχ = 5.43, (d) Δχ = 5.44, (e) Δχ = 5.45, (f) Δχ = 5.46. The horizontal line represents the free energy the system would have, if it consisted of two macrophases. A cluster is stable if it corresponds to the minimum of a curve, and the minimum is lower than the horizontal line.

Image of FIG. 10.
FIG. 10.

Dependencies of the radius R of a stable cluster formed by neutral molecules in the IL phase on the reciprocal 1/(Δχ − Δχ*) of the difference between the amphiphilicity of the IL and the critical value of the amphiphilicity at which the surface tension of the phase boundary of a macroheterogeneous IL/nIL mixture vanishes. χ+− = 0, u = 1, and (a) , (b) , (c) .

Image of FIG. 11.
FIG. 11.

Phase diagram of the IL/nIL mixture in coordinates (T, kTΔχ) at the average volume fraction of IL in the mixture equal to 0.5, andχ+− = 0, , . (a) The upper boundary of the domain corresponding to the stability of a mixture consisting of two macrophases. The domain over this boundary corresponds also to stability of separate nIL clusters. (b) The lower boundary of the domain corresponding to the stability of separate IL clusters. c) The lower boundary of the domain corresponding to the stability of separate nIL clusters having radius smaller than 20 a.

Image of FIG. 12.
FIG. 12.

Dependencies of the surface tension σ s of the phase boundary between the IL and the nIL phases on the absolute temperature T at χ+− = 0, and different amphiphilicities of the IL: (a) , (b) , (c) .

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/content/aip/journal/jcp/136/1/10.1063/1.3670016
2012-01-04
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Clusters in a mixture of an “amphiphilic” ionic liquid and a nonionic liquid: Theoretical study
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/1/10.1063/1.3670016
10.1063/1.3670016
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