Criticality of Ionic Liquids in Solution

Schröer, Wolffram

doi:10.1007/1-4020-3659-0_6

Cited by 10 publications

(10 citation statements)

References 101 publications

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“…The results obtained for the Ginzburg temperature were similar to those found for simple fluids in comparable fashion that is in variance to what is expected from the experiments [5,6]. Nearly at the same time in [36] the crossover behavior of the lattice version of a fluid exhibiting the Ising behavior was studied as additional symmetrical electrostatic interactions were turned on.…”

Section: Introductionsupporting

confidence: 87%

“…The analysis of experimental data for various ionic solutions confirmed that such systems generally exhibit crossover or, at least a tendency to crossover from the Ising behavior asymptotically close to the critical point, to the mean-field behavior upon increasing distance from the critical point [34]. Moreover, the systematic experimental investigations of the ionic systems such as tetran-butylammonium picrate, Bu 4 NPic, (for tetra-n-butylammonium picrate we will follow the notations from [5,6]) in long chain n-alkanols with dielectric constant ranging from 3.6 for 1-tetradecanol to 16.8 for 2-propanol suggest an increasing tendency for crossover to the mean-field behavior when the Coulomb contribution becomes essential [5,6,35]. They also indicate that the "Coulomb limit" reduced temperature of the RPM T c ≃ 0.05 is valid for the almost non-polar long chain alkanols [6,35].…”

Section: Introductionmentioning

confidence: 72%

“…These studies were stimulated by controversial experimental results, demonstrating the three types of the critical behavior in electrolytes solutions: (i) classical (or mean-field) and (ii) Ising-like behavior as well as (iii) crossover between the two [1,2,3,4,5,6]. In accordance with these peculiarities, ionic solutions were conventionally divided into two classes, namely: "solvophobic" systems with Ising-like critical behavior in which Coulomb forces are not supposed to play a major role (the solvent is generally characterized by high dielectric constant) and "Coulombic" systems in which the phase separation is primarily driven by Coulomb interactions (the solvent is characterized by low dielectric constant).…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, the systematic experimental investigations of the ionic systems such as tetran-butylammonium picrate, Bu 4 NPic, (for tetra-n-butylammonium picrate we will follow the notations from [5,6]) in long chain n-alkanols with dielectric constant ranging from 3.6 for 1-tetradecanol to 16.8 for 2-propanol suggest an increasing tendency for crossover to the mean-field behavior when the Coulomb contribution becomes essential [5,6,35]. They also indicate that the "Coulomb limit" reduced temperature of the RPM T c ≃ 0.05 is valid for the almost non-polar long chain alkanols [6,35]. It has been stressed [35] that for solutions of Bu 4 NPic in 1-alkanols, the upper critical solution points are found to increase linearly with the chain length of the alcohols (that corresponds to the decrease of dielectric constant of the solvent).…”

Section: Introductionmentioning

confidence: 99%

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Crossover behavior in fluids with Coulomb interactions

2007

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According to extensive experimental findings, the Ginzburg temperature t G for ionic fluids differs substantially from that of nonionic fluids [Schröer W., Weigärtner H. 2004 Pure Appl. Chem. 76 19]. A theoretical investigation of this outcome is proposed here by a mean field analysis of the interplay of short and long range interactions on the value of t G . We consider a quite general continuous charge-asymmetric model made of charged hard spheres with additional short-range interactions (without electrostatic interactions the model belongs to the same universality class as the 3D Ising model). The effective Landau-Ginzburg Hamiltonian of the full system near its gas-liquid critical point is derived from which the Ginzburg temperature is calculated as a function of the ionicity. The results obtained in this way for t G are in good qualitative and sufficient quantitative agreement with available experimental data.

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Section: Introductionsupporting

confidence: 87%

Section: Introductionmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Crossover behavior in fluids with Coulomb interactions

2007

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“…For reviews of experimental and theoretical situation see Refs. [1, 2,3,4,5,6,7] and the references cited therein. Basic properties of ionic systems can be described by the primitive model (PM) consisting of a mixture of m species of charged hard spheres.…”

Section: Introductionmentioning

confidence: 99%

Gas–liquid critical point in ionic fluids

Patsahan¹,

Mryglod²,

Patsahan³

2006

J. Phys.: Condens. Matter

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Based on the method of collective variables we develop the statistical field theory for the study of a simple charge-asymmetric 1 : z primitive model (SPM). It is shown that the well-known approximations for the free energy, in particular DHLL and ORPA, can be obtained within the framework of this theory. In order to study the gas-liquid critical point of SPM we propose the method for the calculation of chemical potential conjugate to the total number density which allows us to take into account the higher order fluctuation effects. As a result, the gas-liquid phase diagrams are calculated for z = 2 − 4. The results demonstrate the qualitative agreement with MC simulation data: critical temperature decreases when z increases and critical density increases rapidly with z.

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The General Phase Behavior of Mixtures of 1‐Alkyl‐3‐Methylimidazolium Bis[(trifluoromethyl)sulfonyl]amide Ionic Liquids with n‐Alkyl Alcohols

et al. 2012

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The liquid–liquid equilibrium (LLE) phase behavior of mixtures of 1‐ethyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]amide (C2mimNTf2) with the n‐alkyl alcohols (CnOH; 3≤n≤8) is described. By applying the cloud‐point method, the LLEs were determined over a temperature range of 275–423 K at ambient pressure. Partial miscibility with upper critical solution temperatures (UCST) was observed. The UCST increase with increasing chain length of the alcohols. The phase diagrams were analyzed numerically by presuming Ising criticality. Concepts for the description of the asymmetry of the phase diagram by presuming the validity of the rectilinear diameter rule or a nonlinear diameter requested by the theory of complete scaling were applied. The results (UCST, critical composition, width and diameter of the phase diagrams) are compared with similar systems and discussed in terms of the corresponding state behavior; they map on a single curve. From at least 45 individual phase diagrams, general aspects of the behavior of this ionic liquid–alcohol mixture type were extracted. A simple empirical relationship was formulated to allow the description of the UCST with an accuracy of about 10 K when taking the ratio of the molar volumes of the alcohol and the 1‐alkyl‐3‐methylimidazolium cation of the ionic liquid into account.

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Criticality of Ionic Liquids in Solution

Cited by 10 publications

References 101 publications

Crossover behavior in fluids with Coulomb interactions

Crossover behavior in fluids with Coulomb interactions

Gas–liquid critical point in ionic fluids

The General Phase Behavior of Mixtures of 1‐Alkyl‐3‐Methylimidazolium Bis[(trifluoromethyl)sulfonyl]amide Ionic Liquids with n‐Alkyl Alcohols

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