Skip to main content
Log in

Phase Equilibria and Volumetric Properties of (1-Ethyl-3-Methylimidazolium Ethylsulfate + Alcohol or Water) Binary Systems

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Solid–liquid and liquid–liquid phase equilibria in binary mixtures that contain a room-temperature ionic liquid and an alcohol, or water—namely, 1-ethyl-3-methylimidazolium ethylsulfate, [EMIM][EtSO4] with an alcohol (1-octanol, or 1-decanol, or 1-undecanol, or 1-dodecanol) and water have been measured at normal pressure by a dynamic method from 250 to 350 K. By increasing the alkyl chain length of an alcohol, the upper critical solution temperature, UCST, increased (changing from 1-undecanol to 1-dodecanol). Complete miscibility was observed for the systems ([EMIM][EtSO4]+methanol, or ethanol, or 1-propanol, or 1-butanol, 1-pentanol, or 1-hexanol, or 1-heptanol, or 1-octanol, or 1-nonanol, -or 1-decanol and water) at the temperature 298.15 K. Densities and excess molar volumes, V Em , have been determined for [EMIM][EtSO4] with either 1-propanol, or 1-butanol, or 1-pentanol, or 1-hexanol, or 1-heptanol, or 1-octanol, or 1-nonanol, or 1-decanol at 298.15 K and ambient pressure. These systems exhibit negative or positive molar excess volumes. Our experimental V Em data were used for the description of H Em for the chosen systems of [EMIM][EtSO4] with the alcohols under study. The simple Prigogine-Flory-Paterson (PFP) model has given slightly worse results than the Flory-Benson-Treszczanowicz (FBT) model. Negative excess molar volumes observed for 1-propanol and 1-butanol are attributed to hydrogen bonding between the short chain alcohols and ionic liquid, and high packing effects. The FBT model overestimates the self-association of the alcohols in the solutions under study and shifts the calculated curves to higher mole fraction of the alcohol. For each system and for chosen number of the Redlich-Kister parameters, A r, the partial molar volumes, V E1 and V E2 , are presented.

The paper includes a basic thermophysical characterization (enthalpy of fusion and temperature of glass phase transition) of the pure ionic liquid obtained via differential scanning calorimetry (DSC) and temperature of decomposition (TG/DTA).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Rogers, R.D., Seddon, K.R.: Ionic liquids-solvents of the future? Science 302, 792–793 (2003)

    Article  Google Scholar 

  2. Meindersma, G.W., Podt, A.J.G., de Haan, A.B.: Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures. Fuel Process Technol. 87, 59–70 (2005)

    Article  CAS  Google Scholar 

  3. Lei, Z., Arlt, W., Wasserscheid, P.: Selection of entrainers in the 1-hexene/n-hexane system with a limited solubility. Fluid Phase Equilib. 241, 290–299 (2006)

    Article  CAS  Google Scholar 

  4. Meindersma, G.W., Podt, A.J.G., deHaan, A.: A ternary liquid–liquid equilibria for mixtures of toluene+n-heptane + an ionic liquid. Fluid Phase Equil. 247, 158–168 (2006)

    Article  CAS  Google Scholar 

  5. Arce, A., Rodriguez, O., Soto, A.: 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. Chem. Eng. Sci. 61, 6929–6934 (2006)

    Article  CAS  Google Scholar 

  6. Arce, A., Rodriguez, H., Soto, A.: Effect of anion fluorination in 1-ethyl-3-methylimidazolium as solvent for the liquid extraction of ethanol from ethyl tert-butyl ether. Fluid Phase Equilib. 242, 164–168 (2006)

    Article  CAS  Google Scholar 

  7. Arce, A., Rodriguez, H., Soto, A.: Use of green and cheap ionic liquid to purify gasoline octane boosters. Green Chem. 9, 247–253 (2007)

    Article  CAS  Google Scholar 

  8. Arce, A., Rodriguez, H., Soto, A.: Purification of ethyl tert-butyl ether from its mixtures with ethanol by using an ionic liquid. Chem. Eng. J. 115, 219–223 (2006)

    Article  CAS  Google Scholar 

  9. Gómez, E., González, B., Calvar, N., Tojo, E., Domínguez, Á.: Physical properties of pure 1-ethyl-3-methylimidazolium ethylsulfate and its binary mixtures with ethanol and water at several temperatures. J. Chem. Eng. Data 51, 2096–2102 (2006)

    Article  CAS  Google Scholar 

  10. González, E.J., González, B., Calvar, N., Dominguez, Á.: Physical properties of binary mixtures of the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate with several alcohols at T=(298.15,313.15, and 328.15) K and atmospheric pressure. J. Chem. Eng. Data 52, 2138–2144 (2007)

    Article  CAS  Google Scholar 

  11. Sumartschenkowa, I.A., Verevkin, S.P., Vasiltsova, T.V., Bich, E., Heintz, A., Shevelyova, M.P., Kabo, G.J.: J. Chem. Eng. Data 51, 2138–2144 (2006)

    Article  CAS  Google Scholar 

  12. Crosthwaite, J.M., Muldoon, M.J., Akai, S.N.V.K., Maginn, E., Brennecke, J.F.: Liquid phase behavior of ionic liquids with alcohols: Experimental studies and modeling. J. Phys. Chem. B 110, 9354–9361 (2006)

    Article  CAS  Google Scholar 

  13. Domańska, U., Bogel-Łukasik, R.: Solubility of ethyl-(2-hydroxyethyl)-dimethylammonium bromide in alcohols (C2–C12). Fluid Phase Equilib. 233, 220–227 (2005)

    Article  CAS  Google Scholar 

  14. Domańska, U., Casás, L.M.: Solubility of phosphonium ionic liquid in alcohols, benzene and alkylbenzenes. J. Phys. Chem. B 111, 4109–4115 (2007)

    Article  CAS  Google Scholar 

  15. Marsh, K.N., Deev, A.V., Wu, C.-T., Tran, E., Klamt, A.: Room temperature ionic liquids as replacements for conventional solvents – A review. Kor. J. Chem. Eng. 19, 357–362 (2002)

    Article  CAS  Google Scholar 

  16. Wu, C.-T., Marsh, K.N., Deev, A.V., Boxall, J.A.: Liquid–liquid equilibria of room-temperature ionic liquids and butan-1-ol. J. Chem. Eng. Data 48, 486–493 (2003)

    Article  CAS  Google Scholar 

  17. Sahandzhieva, K., Tuma, D., Breyer, S., Kamps, A.P.-S., Maurer, G.: Liquid–liquid equilibrium in mixtures of the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate and an alcohol. J. Chem. Eng. Data 51, 1516–1525 (2006)

    Article  CAS  Google Scholar 

  18. Heintz, A., Klasen, D., Lehmann, J.K., Wertz, Ch.: Excess molar volumes and liquid-liquid equilibria of the ionic liquid 1-methyl-3-octyl-imidazolium tetrafluoroborate mixed with butan-1-ol and pentan-1-ol. J. Solution Chem. 34, 1135–1144 (2005)

    Article  CAS  Google Scholar 

  19. Heintz, A., Lehmann, J.K., Wertz, Ch.: Thermodynamic properties of mixtures containing ionic liquids. 3. Liquid-liquid equilibria of binary mixtures of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide with propan-1-ol, butan-1-ol, and pentan-1-ol. J. Chem. Eng. Data 48, 472–474 (2003)

    Article  CAS  Google Scholar 

  20. Crosthwaite, J.M., Aki, S.N.V.K., Maginn, E.J., Brennecke, J.F.: Liquid phase behavior of imidazolium-based ionic liquids with alcohols. J. Phys. Chem. B 108, 5113–5119 (2004)

    Article  CAS  Google Scholar 

  21. Crosthwaite, J.M., Aki, S.N.V.K., Maginn, E.J., Brennecke, J.F.: Liquid phase behavior of imidazolium-based ionic liquids with alcohols: Effect of hydrogen bonding and non-polar interactions. Fluid Phase Equilib. 228–229, 303–309 (2005)

    Article  CAS  Google Scholar 

  22. Domańska, U., Marciniak, A.: Solubility of ionic liquid [emim][PF6] in alcohols. J. Phys. Chem. B 108, 2376–2382 (2004)

    Article  CAS  Google Scholar 

  23. Domańska, U., Pobudkowska, A., Eckert, F.: (Liquid-liquid) phase equilibria of 1-alkyl-3-methylmidazolium methylsulfate with alcohols, ketones, or ethers. J. Chem. Thermodyn. 38, 685–695 (2006)

    Article  CAS  Google Scholar 

  24. Wang, J.F., Li, Ch.X., Wang, Z.H.: Measurement and prediction of vapor pressure of binary and ternary systems containing 1-ethyl-3-methylimidazolium ethyl sulfate. J. Chem. Eng. Data 52, 1307–1312 (2007)

    Article  CAS  Google Scholar 

  25. Domańska, U., Pobudkowska, A., Wiśniewska, A.: Solubility and excess molar properties of 1,3-dimethylimidazolium methylsulfate, or 1-butyl-3-methylimidazolium methylsulfate, or 1-butyl-3-methylimidazolium octylsulfate ionic liquids with n-alkanes and alcohols: Analysis in terms of the PFP and FBT models. J. Solution Chem. 35, 311–334 (2006)

    Article  CAS  Google Scholar 

  26. Treszczanowicz, A.J., Benson, G.C.: Excess volumes of alkanol + alkane binary systems in terms of an association model with a Flory contribution term. Fluid Phase Equilib. 23, 117–135 (1985)

    Article  CAS  Google Scholar 

  27. Hofman, T., Gołdon, A., Nevines, A., Letcher, T.M.: Densities, excess volumes, isothermal expansivities, and isobaric compressibilities of the (1-ethyl-3-methyl imidazolium ethylsulfate + methanol) system at temperature (283.15 to 333.15) K and pressures from (0.1 to 35) MPa. J. Chem. Thermodyn. 40, 580–591 (2008)

    Article  CAS  Google Scholar 

  28. Rodriguez, H., Brennecke, J.F.: Temperature and composition dependence of the density and viscosity of binary mixtures of water + ionic liquid. J. Chem. Eng. Data 51, 2145–2155 (2006)

    Article  CAS  Google Scholar 

  29. Domańska, U.: The excess molar volumes of (a hydrocarbon + a branched chain ether) at 298.15 K and 308.15 K and the application of the PFP theory. Fluid Phase Equilib. 130, 207–222 (1997)

    Article  Google Scholar 

  30. Wingefors, S.: Development of the correlation between the non-polar solubility parameter. Refractive index and molecular structure. II. Aliphatic ethers and alcohols. J. Chem. Tech. Biotechnol. 31, 530–534 (1981)

    CAS  Google Scholar 

  31. Peña, M.D., Tardajos, G.: Isothermal compressibilities of n-alcohols from methanol to 1-dodecanol at 298.15, 308.15, 318.15 and 333.15 K. J. Chem. Thermodyn. 11, 441–445 (1979)

    Article  Google Scholar 

  32. Liu, A., Pusicha, K., Demiriz, A.M., Kohler, F.: Model for alkanol + alkane mixtures: Extension and experimental verification. J. Solution Chem. 20, 39–56 (1991)

    Article  CAS  Google Scholar 

  33. Meyer, J.D., Reid, E.E.: Isomorphism and alternation in the melting points of the normal alcohols, acetates, bromides, acids and ethyl esters from C10 to C18. J. Am. Chem. Soc. 55, 1574–1584 (1933)

    Article  CAS  Google Scholar 

  34. Letcher, T.M., Łachwa, J., Domańska, U.: The excess molar volumes, and excess molar enthalpies of (N-methyl-2-pyrrolidinone + an alkanol) at the temperature 298.15 K. J. Chem. Thermodyn. 34, 1581–1599 (2002)

    Article  CAS  Google Scholar 

  35. Scharlin, P., Steinby, K., Domańska, U.: Volumetric properties of binary mixtures of N,N-dimethylformamide with water or water-d 2 at temperature from 277.13 K to 318.15 K. J. Chem. Thermodyn. 34, 927–957 (2002)

    Article  CAS  Google Scholar 

  36. Krummen, M., Wasserscheid, P., Gmehling, J.: Measurement of activity coefficients at infinite dilution in ionic liquids using the dilutor technique. J. Chem. Eng. Data 47, 1411–1417 (2002)

    Article  CAS  Google Scholar 

  37. Jacquemin, J., Husson, P., Padua, A.A.H., Majer, V.: Density and viscosity of several pure and water-saturated ionic liquids. Green Chem. 8, 172–180 (2006)

    Article  CAS  Google Scholar 

  38. Yang, J.-Z., Lu, X.-M., Gui, J.-S., Xu, W.-G., Li, L.-W.: Volumetric properties of room temperature ionic liquid 2: The concentrated aqueous solutions of {1-methyl-3-ethylimidazolium ethyl sulfate + water} in a temperature range of 278.2 K to 338.2 K. J. Chem. Thermodyn. 37, 1250–1255 (2005)

    Article  CAS  Google Scholar 

  39. Yang, J.-Z., Lu, X.-M., Gui, J.-S., Xu, W.-G.: A new theory for ionic liquids—the Interstice Model. Part 1. The density and surface tension of ionic liquid EMISE. Green Chem. 6, 541–543 (2004)

    Article  CAS  Google Scholar 

  40. Holbrey, J.D., Reichert, W.M., Swatloski, R.P., Broker, G.A., Pitner, W.R., Seddon, K.R., Rogers, R.D.: Efficient halide free synthesis of near low cost ionic liquids. Allylimidoazolium salts containing methyl- and ethyl-sulfate anions. Green Chem. 4, 407–413 (2002)

    Article  CAS  Google Scholar 

  41. Srehmel, V., Laschewsky, A., Wetzel, H., Görnitz, E.: Free radical polymerization of n-butyl methacrylate in ionic liquids. Macromolecules 39, 923–930 (2006)

    Article  CAS  Google Scholar 

  42. Kato, R., Krummen, M., Gmehling, J.: Measurement and correlation of vapor-liquid equilibria and excess enthalpies of binary systems containing ionic liquids and hydrocarbons. Fluid Phase Equilib. 224, 47–54 (2004)

    Article  CAS  Google Scholar 

  43. Kato, R., Gmehling, J.: 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(01). J. Chem. Thermodyn. 37, 603–619 (2005)

    Article  CAS  Google Scholar 

  44. Flory, P.J.: Statistical thermodynamics of liquid mixtures. J. Am. Chem. Soc. 87, 1833–1835 (1965)

    Article  CAS  Google Scholar 

  45. Abe, A., Flory, P.J.: The thermodynamic properties of mixtures of small, nonpolar molecules. J. Am. Chem. Soc. 87, 1838–1842 (1965)

    Article  CAS  Google Scholar 

  46. Orwoll, R.A., Flory, P.J.: Equation of state parameters for normal alkanes. Correlation with chain length. J. Am. Chem. Soc. 89, 6822–6825 (1967)

    Article  CAS  Google Scholar 

  47. Nagata, I.: Thermodynamics of alcohol solutions. Phase equilibria and excess molar enthalpies of mixtures containing two alcohols. Thermochim. Acta 107, 199–205 (1986)

    Article  CAS  Google Scholar 

  48. Sahli, B., Gager, H., Richard, A.J.: Ultracentrifugal studies of the isothermal compressibilities of organic alcohols and alkanes. Correlation with surface tension. J. Chem. Thermodyn. 8, 179–188 (1976)

    Article  CAS  Google Scholar 

  49. Heintz, A.: A New theoretical approach for predicting excess properties of alkanol/alkane mixtures. Ber. Bunsenges. Phys. Chem. 89, 172–181 (1985)

    CAS  Google Scholar 

  50. Kehiaian, H., Treszczanowicz, A.: Thermodynamics of chemically reacting mixtures. Excess free enthalpy of athermal associated mixtures of the Mecke-Kempter type. Bull. Acad. Polon. Sci., Ser. Sci. Chim. 16, 445–449 (1968)

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to U. Domańska.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Cite this article

Domańska, U., Laskowska, M. Phase Equilibria and Volumetric Properties of (1-Ethyl-3-Methylimidazolium Ethylsulfate + Alcohol or Water) Binary Systems. J Solution Chem 37, 1271–1287 (2008). https://doi.org/10.1007/s10953-008-9306-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-008-9306-y

Keywords

Navigation