ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Experimental Study of Thermodynamic Properties of Mixtures Containing Ionic Liquid 1-Ethyl-3-methylimidazolium Ethyl Sulfate Using Gas−Liquid Chromatography and Transpiration Method

View Author Information
Department of Physical Chemistry, University of Rostock, Hermannstrasse 14, D-18055 Rostock, Germany
Chemical Faculty, Research Institute for Physical Chemical Problems, Belorussian State University, Minsk, Belarus
Cite this: J. Chem. Eng. Data 2006, 51, 6, 2138–2144
Publication Date (Web):October 3, 2006
Copyright © 2006 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Activity coefficients at infinite dilution of 46 solutes such as alkanes, alkenes, alkylbenzenes, linear and branched C1−C6 alcohols, esters, aldehydes, cyclohexanone oxime, and ε-caprolactam in the ionic liquid (IL) 1-ethyl-3-methylimidazolium ethyl sulfate or [EMIM][EtSO4] have been determined by gas chromatography using the IL as the stationary phase. The measurements were carried out at different temperatures between (302 and 396) K. From the temperature dependence of the limiting activity coefficients, partial molar excess enthalpies at infinite dilution of the solutes in the ILs have been derived. Vapor−liquid equilibria (VLE) of binary mixtures containing water with [EMIM][EtSO4] were studied using the transpiration method. VLE measurements were carried out over the broad concentration range at temperatures between (302.9 and 322.9) K. Activity coefficients γi of water in the [EMIM][EtSO4] have been determined from the VLE data and are described formally by using the NRTL equation. Furthermore, activity coefficients in infinity dilution of water in the IL [EMIM][EtSO4] have been derived by extrapolation to the infinite dilution of water.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

     On the leave from the Samara State Technical University, Samara, Russia.


     Corresponding author. Telephone:  +49-381-498-6500. Fax:  +49-381-498-6502. E-mail: [email protected].

    Supporting Information Available

    Jump To

    Two tables showing the critical constants and acentric factors of solutes and carrier gas used in calculation of virial coefficients and the experimental activity coefficients at infinity dilution. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 66 publications.

    1. Kamil Paduszyński . In Silico Calculation of Infinite Dilution Activity Coefficients of Molecular Solutes in Ionic Liquids: Critical Review of Current Methods and New Models Based on Three Machine Learning Algorithms. Journal of Chemical Information and Modeling 2016, 56 (8) , 1420-1437.
    2. Michel Krannich, Florian Heym, and Andreas Jess . Characterization of Six Hygroscopic Ionic Liquids with Regard to Their Suitability for Gas Dehydration: Density, Viscosity, Thermal and Oxidative Stability, Vapor Pressure, Diffusion Coefficient, and Activity Coefficient of Water. Journal of Chemical & Engineering Data 2016, 61 (3) , 1162-1176.
    3. Chengna Dai, Zhigang Lei, and Biaohua Chen . Predictive Thermodynamic Models for Ionic Liquid–SO2 Systems. Industrial & Engineering Chemistry Research 2015, 54 (43) , 10910-10917.
    4. Sayeed Ashique Ahmed, Aninda Chatterjee, Banibrata Maity, and Debabrata Seth . Thermodynamic Behavior of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Iodide and Alcohols. Journal of Chemical & Engineering Data 2015, 60 (8) , 2301-2307.
    5. Sergey P. Verevkin, Aleksandra Yu. Sazonova, Alla K. Frolkova, Dzmitry H. Zaitsau, Igor V. Prikhodko, and Christoph Held . Separation Performance of BioRenewable Deep Eutectic Solvents. Industrial & Engineering Chemistry Research 2015, 54 (13) , 3498-3504.
    6. Matthias Seiler, Annett Kühn, Felix Ziegler, and Xinming Wang . Sustainable Cooling Strategies Using New Chemical System Solutions. Industrial & Engineering Chemistry Research 2013, 52 (47) , 16519-16546.
    7. Aristides P. Carneiro, Christoph Held, Oscar Rodríguez, Gabriele Sadowski, and Eugénia A. Macedo . Solubility of Sugars and Sugar Alcohols in Ionic Liquids: Measurement and PC-SAFT Modeling. The Journal of Physical Chemistry B 2013, 117 (34) , 9980-9995.
    8. Qiao-Li Chen, Ke-Jun Wu, and Chao-Hong He . Thermal Conductivities of [EMIM][EtSO4], [EMIM][EtSO4] + C2H5OH, [EMIM][EtSO4] + H2O, and [EMIM][EtSO4] + C2H5OH + H2O at T = (283.15 to 343.15) K. Journal of Chemical & Engineering Data 2013, 58 (7) , 2058-2064.
    9. Danxing Zheng, Li Dong, and Xianghong Wu . New Approach for Absorbent Species Selection with Excess Gibbs Function. Industrial & Engineering Chemistry Research 2013, 52 (27) , 9480-9489.
    10. Zhigang Lei, Chengna Dai, Xing Liu, Li Xiao, and Biaohua Chen . Extension of the UNIFAC Model for Ionic Liquids. Industrial & Engineering Chemistry Research 2012, 51 (37) , 12135-12144.
    11. Marta L. S. Batista, Catarina M. S. S. Neves, Pedro J. Carvalho, Rafiqul Gani, and João A. P. Coutinho . Chameleonic Behavior of Ionic Liquids and Its Impact on the Estimation of Solubility Parameters. The Journal of Physical Chemistry B 2011, 115 (44) , 12879-12888.
    12. Nilesh R. Dhumal, Hyung J. Kim, and Johannes Kiefer . Electronic Structure and Normal Vibrations of the 1-Ethyl-3-methylimidazolium Ethyl Sulfate Ion Pair. The Journal of Physical Chemistry A 2011, 115 (15) , 3551-3558.
    13. Andrzej Marciniak . Influence of Anion Structure on the Liquid−Liquid Equilibria of 1-Ethyl-3-methyl-imidazolium Cation Based Ionic Liquid-Hydrocarbon Binary Systems. Journal of Chemical & Engineering Data 2011, 56 (3) , 368-374.
    14. A. Yokozeki and Mark B. Shiflett . Water Solubility in Ionic Liquids and Application to Absorption Cycles. Industrial & Engineering Chemistry Research 2010, 49 (19) , 9496-9503.
    15. Andrzej Marciniak and Michał Wlazło. Activity Coefficients at Infinite Dilution Measurements for Organic Solutes and Water in the Ionic Liquid 1-(3-Hydroxypropyl)pyridinium Trifluorotris(perfluoroethyl)phosphate. The Journal of Physical Chemistry B 2010, 114 (20) , 6990-6994.
    16. Luke D. Simoni, Lindsay E. Ficke, Caitlin A. Lambert, Mark A. Stadtherr and Joan F. Brennecke. Measurement and Prediction of Vapor−Liquid Equilibrium of Aqueous 1-Ethyl-3-methylimidazolium-Based Ionic Liquid Systems. Industrial & Engineering Chemistry Research 2010, 49 (8) , 3893-3901.
    17. Hemayat Shekaari and Sedighehnaz S. Mousavi. Osmotic Coefficients and Refractive Indices of Aqueous Solutions of Ionic Liquids Containing 1-Butyl-3-methylimidazolium Halide at T = (298.15 to 328.15) K. Journal of Chemical & Engineering Data 2009, 54 (3) , 823-829.
    18. Tharanga Payagala, Ying Zhang, Eranda Wanigasekara, Ke Huang, Zachary S. Breitbach, Pritesh S. Sharma, Leonard M. Sidisky and Daniel W. Armstrong . Trigonal Tricationic Ionic Liquids: A Generation of Gas Chromatographic Stationary Phases. Analytical Chemistry 2009, 81 (1) , 160-173.
    19. Manish S. Kelkar, Wei Shi and Edward J. Maginn . Determining the Accuracy of Classical Force Fields for Ionic Liquids: Atomistic Simulation of the Thermodynamic and Transport Properties of 1-Ethyl-3-methylimidazolium Ethylsulfate ([emim][EtSO4]) and Its Mixtures with Water. Industrial & Engineering Chemistry Research 2008, 47 (23) , 9115-9126.
    20. Pritesh S. Sharma, Tharanga Payagala, Eranda Wanigasekara, Aruna B. Wijeratne, Junmin Huang and Daniel W. Armstrong. Trigonal Tricationic Ionic Liquids: Molecular Engineering of Trications to Control Physicochemical Properties. Chemistry of Materials 2008, 20 (13) , 4182-4184.
    21. Zhigang Lei,, Biaohua Chen,, Chengyue Li, and, Hui Liu. Predictive Molecular Thermodynamic Models for Liquid Solvents, Solid Salts, Polymers, and Ionic Liquids. Chemical Reviews 2008, 108 (4) , 1419-1455.
    22. Marco Haumann and, Anders Riisager. Hydroformylation in Room Temperature Ionic Liquids (RTILs):  Catalyst and Process Developments. Chemical Reviews 2008, 108 (4) , 1474-1497.
    23. Dong L. Zhang,, Yue F. Deng,, Chuan B. Li, and, Ji Chen. Separation of Ethyl Acetate−Ethanol Azeotropic Mixture Using Hydrophilic Ionic Liquids. Industrial & Engineering Chemistry Research 2008, 47 (6) , 1995-2001.
    24. Noelia Calvar, Begoña González, Elena Gómez and Ángeles Domínguez. Vapor–Liquid Equilibria for the Ternary System Ethanol + Water + 1-Ethyl-3-methylimidazolium Ethylsulfate and the Corresponding Binary Systems Containing the Ionic Liquid at 101.3 kPa. Journal of Chemical & Engineering Data 2008, 53 (3) , 820-825.
    25. Laura Sprunger,, Michael Clark,, William E. AcreeJr., and, Michael H. Abraham. Characterization of Room-Temperature Ionic Liquids by the Abraham Model with Cation-Specific and Anion-Specific Equation Coefficients. Journal of Chemical Information and Modeling 2007, 47 (3) , 1123-1129.
    26. A. Vicent Orchillés,, Pablo J. Miguel,, Ernesto Vercher, and, Antoni Martínez-Andreu. Isobaric Vapor−Liquid Equilibria for Methyl Acetate + Methanol + 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate at 100 kPa. Journal of Chemical & Engineering Data 2007, 52 (3) , 915-920.
    27. Konstantinos Kallitsis, Vassilis Koulocheris, Georgia Pappa, Epaminondas Voutsas. Evaluation of water + imidazolium ionic liquids as working pairs in absorption refrigeration cycles. Applied Thermal Engineering 2023, 233 , 121201.
    28. Amel Ayad, Fabrice Mutelet, Amina Negadi. Temperature-Dependent Linear Solvation Energy Relationship for the Determination of Gas-Liquid Partition Coefficients of Organic Compounds in Ionic Liquids. 2022
    29. Thomas Brouwer, Sascha R.A. Kersten, Gerrald Bargeman, Boelo Schuur. trends in solvent impact on infinite dilution activity coefficients of solutes reviewed and visualized using an algorithm to support selection of solvents for greener fluid separations. Separation and Purification Technology 2021, 272 , 118727.
    30. J.T. Gao, Z.Y. Xu, R.Z. Wang. An air-source hybrid absorption-compression heat pump with large temperature lift. Applied Energy 2021, 291 , 116810.
    31. Hemayat Shekaari, Mohammed Taghi Zafarani-Moattar, Saeid Faraji, Masumeh Mokhtarpour. Prediction of vapor pressure and density for nonaqueous solutions of the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate using PC-SAFT equation of state. Fluid Phase Equilibria 2020, 506 , 112320.
    32. Preeti Jain, Anil Kumar. Probing the solute-solvent interactions in the binary mixtures of ionic liquids with water and alcohols by conductance, viscosity and IR spectroscopy. Journal of Molecular Liquids 2017, 238 , 270-280.
    33. Monika Karpińska, Michał Wlazło, Urszula Domańska. Separation of binary mixtures based on gamma infinity data using [EMIM][TCM] ionic liquid and modelling of thermodynamic functions. Journal of Molecular Liquids 2017, 225 , 382-390.
    34. I.A. Sedov, B.N. Solomonov. Thermodynamic description of the solvophobic effect in ionic liquids. Fluid Phase Equilibria 2016, 425 , 9-14.
    35. Suojiang Zhang, Qing Zhou, Xingmei Lu, Yuting Song, Xinxin Wang. Properties of 1-ethyl-3-methylimidazolium ethylsulfate mixtures. 2016, 235-304.
    36. Suojiang Zhang, Qing Zhou, Xingmei Lu, Yuting Song, Xinxin Wang. Properties of 1-butyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide mixtures. 2016, 485-524.
    37. Johannes Kiefer, Mahesh Namboodiri, Mehdi M. Kazemi, Arnulf Materny. Time‐resolved femtosecond CARS of the ionic liquid 1‐ethyl‐3‐methylimidazolium ethylsulfate. Journal of Raman Spectroscopy 2015, 46 (8) , 722-726.
    38. Elena Lukoshko, Fabrice Mutelet, Kamil Paduszyński, Urszula Domańska. Phase diagrams of binary systems containing tricyanomethanide-based ionic liquids and thiophene or pyridine—New experimental data and PC-SAFT modelling. Fluid Phase Equilibria 2015, 399 , 105-114.
    39. Michał Wlazło, Andrzej Marciniak, Trevor M. Letcher. Activity Coefficients at Infinite Dilution and Physicochemical Properties for Organic Solutes and Water in the Ionic Liquid 1-Ethyl-3-methylimidazolium trifluorotris(perfluoroethyl)phosphate. Journal of Solution Chemistry 2015, 44 (3-4) , 413-430.
    40. Sayeed Ashique Ahmed, Aninda Chatterjee, Banibrata Maity, Debabrata Seth. Osmotic properties of binary mixtures 1-butyl-1-methylpyrrolidinium dicyanamide and 1-methyl-3-octylimidazolium chloride with water: Effect of aggregation of ions. The Journal of Chemical Thermodynamics 2015, 81 , 227-236.
    41. Sayeed Ashique Ahmed, Aninda Chatterjee, Banibrata Maity, Debabrata Seth. Osmotic properties of binary mixtures of 1-butyl-1-methylpyrrolidinium iodide and water. Journal of Molecular Liquids 2014, 200 , 349-353.
    42. Danxing Zheng, Li Dong, Weijia Huang, Xianghong Wu, Nan Nie. A review of imidazolium ionic liquids research and development towards working pair of absorption cycle. Renewable and Sustainable Energy Reviews 2014, 37 , 47-68.
    43. Torben Hector, Jürgen Gmehling. Present status of the modified UNIFAC model for the prediction of phase equilibria and excess enthalpies for systems with ionic liquids. Fluid Phase Equilibria 2014, 371 , 82-92.
    44. Marta Królikowska, Paweł Lipiński, Daria Maik. Density, viscosity and phase equilibria study of {ethylsulfate-based ionic liquid+water} binary systems as a function of temperature and composition. Thermochimica Acta 2014, 582 , 1-9.
    45. Wolfgang Arlt, Alexander Buchele. A Priori Selection of the Type of Ionic Liquid. 2014, 191-208.
    46. Li Dong, Danxing Zheng, Jing Li, Nan Nie, Xianghong Wu. Suitability prediction and affinity regularity assessment of H2O+imidazolium ionic liquid working pairs of absorption cycle by excess property criteria and UNIFAC model. Fluid Phase Equilibria 2013, 348 , 1-8.
    47. Debasmita Dash, Shekhar Kumar, C. Mallika, U. Kamachi Mudali. Thermophysical, Volumetric, and Excess Properties of Aqueous Solutions of 1-Hexyl-3-methyl Imidazolium Bromide at 298.15 K and 0.1 MPa. ISRN Physical Chemistry 2013, 2013 , 1-7.
    48. Torben Hector, Lisa Uhlig, Jürgen Gmehling. Prediction of different thermodynamic properties for systems of alcohols and sulfate-based anion Ionic Liquids using modified UNIFAC. Fluid Phase Equilibria 2013, 338 , 135-140.
    49. Zhigang Lei, Li Xiao, Chengna Dai, Biaohua Chen. Group contribution lattice fluid equation of state (GCLF EOS) for ionic liquids. Chemical Engineering Science 2012, 75 , 1-13.
    50. Hiroyuki Matsuda, Katsumi Tochigi, Vincent Liebert, Jürgen Gmehling. Vapor–liquid equilibria of ternary systems with 1-ethyl-3-methylimidazolium ethyl sulfate using headspace gas chromatography. Fluid Phase Equilibria 2011, 307 (2) , 197-201.
    51. Laura M. Grubbs, Shulin Ye, Mariam Saifullah, McCoy Cornelius McMillan-Wiggins, William E. Acree, Michael H. Abraham, Pamela Twu, Jared L. Anderson. Correlations for describing gas-to-ionic liquid partitioning at 323K based on ion-specific equation coefficient and group contribution versions of the Abraham model. Fluid Phase Equilibria 2011, 301 (2) , 257-266.
    52. Sergey P. Verevkin, Dzmitry H. Zaitsau, Bo Tong, Urs Welz-Biermann. New for old. Password to the thermodynamics of the protic ionic liquids. Physical Chemistry Chemical Physics 2011, 13 (28) , 12708.
    53. F. Heym, J. Haber, W. Korth, B. J. M. Etzold, A. Jess. Vapor Pressure of Water in Mixtures with Hydrophilic Ionic Liquids – A Contribution to the Design of Processes for Drying of Gases by Absorption in Ionic Liquids. Chemical Engineering & Technology 2010, 33 (10) , 1625-1634.
    54. Andrzej Marciniak. Influence of cation and anion structure of the ionic liquid on extraction processes based on activity coefficients at infinite dilution. A review. Fluid Phase Equilibria 2010, 294 (1-2) , 213-233.
    55. Hemayat Shekaari, Sedighehnaz S. Mousavi. Volumetric properties of ionic liquid 1,3-dimethylimidazolium methyl sulfate+molecular solvents at T=(298.15–328.15)K. Fluid Phase Equilibria 2010, 291 (2) , 201-207.
    56. Magdalena Bendová, Zdeněk Wagner. Thermodynamic description of liquid–liquid equilibria in systems 1-ethyl-3-methylimidazolium ethylsulfate+C7-hydrocarbons by polymer-solution models. Fluid Phase Equilibria 2009, 284 (2) , 80-85.
    57. Hemayat Shekaari, Sedighehnaz S. Mousavi. Measurement and modeling of osmotic coefficients of aqueous solution of ionic liquids using vapor pressure osmometry method. Fluid Phase Equilibria 2009, 279 (1) , 73-79.
    58. Hemayat Shekaari, Sedighehnaz S. Mousavi, Yagoub Mansoori. Thermophysical Properties of Ionic Liquid, 1-Pentyl-3-methylimidazolium Chloride in Water at Different Temperatures. International Journal of Thermophysics 2009, 30 (2) , 499-514.
    59. Svetlana A. Kozlova, Sergey P. Verevkin, Andreas Heintz, Tim Peppel, Martin Köckerling. Activity coefficients at infinite dilution of hydrocarbons, alkylbenzenes, and alcohols in the paramagnetic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III) using gas–liquid chromatography. The Journal of Chemical Thermodynamics 2009, 41 (3) , 330-333.
    60. Hemayat Shekaari, Sedighehnaz S. Mousavi. Influence of alkyl chain on the thermodynamic properties of aqueous solutions of ionic liquids 1-alkyl-3-methylimidazolium bromide at different temperatures. The Journal of Chemical Thermodynamics 2009, 41 (1) , 90-96.
    61. U. Domańska, M. Laskowska. Phase Equilibria and Volumetric Properties of (1-Ethyl-3-Methylimidazolium Ethylsulfate + Alcohol or Water) Binary Systems. Journal of Solution Chemistry 2008, 37 (9) , 1271-1287.
    62. Mara G. Freire, Sónia P.M. Ventura, Luís M.N.B.F. Santos, Isabel M. Marrucho, João A.P. Coutinho. Evaluation of COSMO-RS for the prediction of LLE and VLE of water and ionic liquids binary systems. Fluid Phase Equilibria 2008, 268 (1-2) , 74-84.
    63. Ke Huang, Xinxin Han, Xiaotong Zhang, Daniel W. Armstrong. PEG-linked geminal dicationic ionic liquids as selective, high-stability gas chromatographic stationary phases. Analytical and Bioanalytical Chemistry 2007, 389 (7-8) , 2265-2275.
    64. Shahab A. Shamsi, Neil D. Danielson. Utility of ionic liquids in analytical separations. Journal of Separation Science 2007, 30 (11) , 1729-1750.
    65. Hemayat Shekaari, Mohammed Taghi Zafarani-Moattar. Osmotic coefficients of some imidazolium based ionic liquids in water and acetonitrile at temperature 318.15K. Fluid Phase Equilibria 2007, 254 (1-2) , 198-203.
    66. Christina Mintz, William E. Acree. Partition coefficient correlations for transfer of solutes from gas phase and water to room temperature ionic liquids. Physics and Chemistry of Liquids 2007, 45 (3) , 241-249.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect