UNIQUAC correlation of liquid–liquid equilibrium in systems involving ionic liquids: The DFT–PCM approach

In this work, the liquid–liquid equilibrium (LLE) of fifty ternary systems involving twelve different ionic liquids, comprising 408 experimental tie-lines, was correlated by the UNIQUAC model for the activity coefficient. New UNIQUAC structural parameters r and q for the ionic liquids were determined by quantum chemistry calculations performed with the Gaussian 03 and GAMESS 7.1 packages, including the Density Functional Theory (DFT) for the optimization of the structures and the Polarizable Continuum Method (PCM) for the calculation of molecular areas and volumes. The results, expressed by deviations between experimental and calculated compositions, are very satisfactory, with deviation values about 1.75%.

[1]  A. Arce,et al.  Purification of ethyl tert-butyl ether from its mixtures with ethanol by using an ionic liquid , 2006 .

[2]  A. Arce,et al.  Thiophene separation from aliphatic hydrocarbons using the 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid , 2008 .

[3]  J. Prausnitz,et al.  Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems , 1975 .

[4]  A. Arce,et al.  Experimental Determination of Liquid-Liquid Equilibrium Using Ionic Liquids: tert-Amyl Ethyl Ether + Ethanol + 1-Octyl-3-Methylimidazolium Chloride System at 298.15 K , 2004 .

[5]  John A. Nelder,et al.  A Simplex Method for Function Minimization , 1965, Comput. J..

[6]  J. S. Rowlinson,et al.  Molecular Thermodynamics of Fluid-Phase Equilibria , 1969 .

[7]  Ryo Kato,et al.  Systems with ionic liquids: Measurement of VLE and γ ∞ data and prediction of their thermodynamic behavior using original UNIFAC, mod. UNIFAC(Do) and COSMO-RS(Ol) , 2005 .

[8]  Aage Fredenslund,et al.  Liquid—liquid equilibrium data: Their retrieval, correlation and prediction Part II: Correlation , 1979 .

[9]  J. Brennecke,et al.  Ionic liquids: Innovative fluids for chemical processing , 2001 .

[10]  T. Letcher,et al.  Ternary Liquid−Liquid Equilibria for Mixtures of 1-Methyl-3-octylimidazolium Chloride + an Alkanol + an Alkane at 298.2 K and 1 bar , 2003 .

[11]  U. Domańska.  Solubility of n-alkanols (C16, C18, C20) in binary solvent mixtures , 1989 .

[12]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[13]  O Nilsson,et al.  Molecular volumes and surfaces of biomacromolecules via GEPOL: a fast and efficient algorithm. , 1990, Journal of molecular graphics.

[14]  Jacopo Tomasi,et al.  Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method: Theoretical Bases, Computational Implementation, and Numerical Applications , 1997 .

[15]  A. Bondi.  van der Waals Volumes and Radii , 1964 .

[16]  Ana Rodríguez,et al.  Ternary (liquid + liquid) equilibria of the azeotrope (ethyl acetate + 2-propanol) with different ionic liquids at T = 298.15 K , 2007 .

[17]  Youdong Lin,et al.  Modeling Liquid−Liquid Equilibrium of Ionic Liquid Systems with NRTL, Electrolyte-NRTL, and UNIQUAC , 2008 .

[18]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[19]  K. R. Seddon,et al.  Separation of aromatic hydrocarbons from alkanes using the ionic liquid 1-ethyl-3-methylimidazoliumbis{(trifluoromethyl) sulfonyl}amide , 2007 .

[20]  A. Arce,et al.  Solvent extraction of thiophene from n-alkanes (C7, C12, and C16) using the ionic liquid [C8mim][BF4] , 2008 .

[21]  Wolfgang Arlt,et al.  Influence of Ionic Liquids on the Phase Behavior of Aqueous Azeotropic Systems , 2004 .

[22]  J. Canosa,et al.  Liquid-liquid equilibria of 1,3-dimethylimidazolium methyl sulfate with ketones, dialkyl carbonates and acetates , 2007 .

[23]  Jacopo Tomasi,et al.  Remarks on the use of the apparent surface charges (ASC) methods in solvation problems: Iterative versus matrix‐inversion procedures and the renormalization of the apparent charges , 1995, J. Comput. Chem..

[24]  T. Letcher,et al.  Ternary liquid–liquid equilibria for mixtures of 1-methyl-3-octyl-imidazolium chloride + benzene + an alkane at T=298.2 K and 1 atm , 2003 .

[25]  T. Letcher,et al.  Liquid−Liquid Equilibria for Ternary Mixtures (an Ionic Liquid + Benzene + Heptane or Hexadecane) at T = 298.2 K and Atmospheric Pressure , 2006 .

[26]  A. B. Pereiro,et al.  Measurement and correlation of (liquid + liquid) equilibrium of the azeotrope (cyclohexane + 2-butanone) with different ionic liquids at T = 298.15 K , 2008 .

[27]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[28]  F. Hernández‐Fernández,et al.  Ternary liquid-liquid equilibria for mixtures of an ionic liquid + n-hexane + an organic compound involved in the kinetic resolution of rac-1-phenyl ethanol (rac-1-phenyl ethanol, vinyl propionate, rac-1-phenylethyl propionate or propionic acid) at 298.2 K and atmospheric pressure , 2008 .

[29]  H. Bart,et al.  Ternary Liquid−Liquid Equilibria for Six Systems Containing Ethylacetate + Ethanol or Acetic Acid + an Imidazolium-Based Ionic Liquid with a Hydrogen Sulfate Anion at 313.2 K , 2007 .

[30]  Kazuo Kojima,et al.  Prediction of vapor-liquid equilibria by the ASOG method , 1979 .

[31]  tert-Amyl Ethyl Ether Separation from Its Mixtures with Ethanol Using the 1-Butyl-3-methylimidazolium Trifluoromethanesulfonate Ionic Liquid: Liquid−Liquid Equilibrium , 2004 .

[32]  Aage Fredenslund,et al.  UNIFAC parameter table for prediction of liquid-liquid equilibriums , 1981 .

[33]  A. Arce,et al.  Liquid−Liquid Equilibria for [C8mim][NTf2] + Thiophene + 2,2,4-Trimethylpentane or + Toluene , 2008 .

[34]  J. Tomasi,et al.  Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects , 1981 .

[35]  Ternary liquid–liquid equilibria for mixtures of 1-hexyl-3-methylimidozolium (tetrafluoroborate or hexafluorophosphate) + ethanol + an alkene at T=298.2 K , 2004 .

[36]  A. Arce,et al.  Phase behaviour of 1-methyl-3-octylimidazolium bis[trifluoromethylsulfonyl]imide with thiophene and aliphatic hydrocarbons: The influence of n-alkane chain length , 2008 .

[37]  J. Gmehling,et al.  Measurement and correlation of vapor–liquid equilibria and excess enthalpies of binary systems containing ionic liquids and hydrocarbons , 2004 .

[38]  M. Aznar,et al.  Liquid–liquid equilibrium of ternary systems 1-butyl-3-methylimidazolium hexafluorophosphate + aromatic + aliphatic , 2008 .

[39]  Ana Rodríguez,et al.  Phase Equilibria of the Azeotropic Mixture Hexane + Ethyl Acetate with Ionic Liquids at 298.15 K , 2008 .

[40]  G. M. Wilson,et al.  Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing , 1964 .

[41]  G. W. Meindersma,et al.  Ternary liquid-liquid equilibria for mixtures of an aromatic + an aliphatic hydrocarbon + 4-methyl-N-butylpyridinium tetrafluoroborate , 2006 .

[42]  A. Arce,et al.  (Liquid + liquid) equilibria of [C8mim][NTf2] ionic liquid with a sulfur-component and hydrocarbons , 2008 .

[43]  M. Aznar.  Correlation of (liquid + liquid) equilibrium of systems including ionic liquids , 2007 .

[44]  Ryo Kato,et al.  Measurement and correlation of vapor–liquid equilibria of binary systems containing the ionic liquids [EMIM][(CF3SO2)2N], [BMIM][(CF3SO2)2N], [MMIM][(CH3)2PO4] and oxygenated organic compounds respectively water , 2005 .

[45]  R. Sahoo,et al.  Volume, surface and UNIQUAC interaction parameters for imidazolium based ionic liquids via Polarizable Continuum Model , 2005 .

[46]  Hong Meng,et al.  Liquid−Liquid Equilibria for Benzene + Cyclohexane + 1-Methyl-3-methylimidazolium Dimethylphosphate or + 1-Ethyl-3-methylimidazolium Diethylphosphate , 2008 .

[47]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[48]  Trevor M. Letcher,et al.  Determination of Activity Coefficients at Infinite Dilution of Solutes in the Ionic Liquid 1-Hexyl-3-methylimidazolium Tetrafluoroborate Using Gas−Liquid Chromatography at the Temperatures 298.15 K and 323.15 K , 2003 .

[49]  Tamal Banerjee,et al.  UNIQUAC Interaction Parameters with Closure for Imidazolium Based Ionic Liquid Systems Using Genetic Algorithm , 2008 .

[50]  A. Arce,et al.  A comparative study on solvents for separation of tert-amyl ethyl ether and ethanol mixtures. New experimental data for 1-ethyl-3-methyl imidazolium ethyl sulfate ionic liquid , 2006 .

[51]  G. Maurer,et al.  Liquid−Liquid Equilibrium in Mixtures of the Ionic Liquid 1-n-Butyl-3-methylimidazolium Hexafluorophosphate and an Alkanol† , 2006 .

[52]  J. Prausnitz,et al.  LOCAL COMPOSITIONS IN THERMODYNAMIC EXCESS FUNCTIONS FOR LIQUID MIXTURES , 1968 .

[53]  J. Canosa,et al.  HMImPF6 ionic liquid that separates the azeotropic mixture ethanol + heptane , 2006 .

[54]  T. Letcher,et al.  Ternary (liquid + liquid) equilibria for mixtures of 1-hexyl-3-methylimidazolium (tetrafluoroborate or hexafluorophosphate) + benzene + an alkane at T = 298.2 k and p = 0.1 MPa , 2005 .

[55]  APPLICATION OF A GENERALIZED MAXIMUM LIKELIHOOD METHOD IN THE REDUCTION OF MULTICOMPONENT LIQUID-LIQUID EQUILIBRIUM DATA , 1997 .

[56]  A. Arce,et al.  Effect of anion fluorination in 1-ethyl-3-methylimidazolium as solvent for the liquid extraction of ethanol from ethyl tert-butyl ether , 2006 .

[57]  J. Yu,et al.  Liquid-Liquid Equilibria of the System 1-(2-Hydroxyethyl)-3-methylimidozolium Tetrafluoroborate or 1-(2-Hydroxyethyl)-2,3-dimethylimidozolium Tetrafluoroborate + Water + 1-Butanol at 293.15 K , 2006 .

[58]  G. W. Meindersma,et al.  Ternary liquid-liquid equilibria for mixtures of toluene + n-heptane + an ionic liquid , 2006 .

[59]  A. Arce,et al.  Gasoline desulfurization using extraction with [C8mim][BF4] ionic liquid , 2007 .