Absorption of carbon dioxide, nitrous oxide, ethane and nitrogen by 1-alkyl-3-methylimidazolium (C(n)mim, n = 2,4,6) tris(pentafluoroethyl)trifluorophosphate ionic liquids (eFAP).

We measured the densities of 1-alkyl-3-methylimidazolium (C(n)mim, n = 2,4,6) tris(pentafluoroethyl)trifluorophosphate ionic liquids (eFAP) as a function of temperature and pressure and their viscosities as a function of temperature. These ionic liquids are less viscous than those based in the same cations but with other anions such as bis(trifluoromethylsulfonyl)imide. The ionic liquids studied are only partially miscible with water, their solubility increasing with the size of the alkyl side-chain of the cation and with temperature (from x(H(2)O) = 0.20 ± 0.03 for [C(4)mim][eFAP] at 303.10 K to x(H(2)O) = 0.49 ± 0.07 for [C(6)mim][eFAP] at 315.10 K). The solubility of carbon dioxide, nitrous oxide, ethane, and nitrogen in the three ionic liquids was measured as a function of temperature and at pressures close to atmospheric. Carbon dioxide and nitrous oxide are the more soluble gases with mole fraction solubilities of the order of 3 × 10(-2) at 303 K. The solubility of these gases does not increase linearly with the size of the alkyl-side chain of the cation. The solubilities of ethane and nitrogen are much lower than those of carbon dioxide and nitrous oxide (mole fractions 60% and 90% lower, respectively). The higher solubility of CO(2) and N(2)O can be explained by more favorable interactions between the solutes and the polar region of the ionic liquids as shown by the enthalpies of solvation determined experimentally and by the calculation of the site-site solute-solvent radial distribution functions using molecular simulation.

[1]  A. Pádua,et al.  Nanostructural organization in ionic liquids. , 2006, The journal of physical chemistry. B.

[2]  A. Pádua,et al.  Influence of ester functional groups on the liquid-phase structure and solvation properties of imidazolium-based ionic liquids. , 2011, The journal of physical chemistry. B.

[3]  P. Kollman,et al.  A Second Generation Force Field for the Simulation of Proteins, Nucleic Acids, and Organic Molecules , 1995 .

[4]  Ioanna Ntai,et al.  CO(2) capture by a task-specific ionic liquid. , 2002, Journal of the American Chemical Society.

[5]  M. Gomes,et al.  Low-pressure solubilities and thermodynamics of solvation of eight gases in 1-butyl-3-methylimidazolium hexafluorophosphate , 2006 .

[6]  T. Schiestel,et al.  Gas solubilities in room temperature ionic liquids – Correlation between RTiL-molar mass and Henry's law constant , 2011 .

[7]  Thomas Foo,et al.  Physical and chemical absorptions of carbon dioxide in room-temperature ionic liquids. , 2008, The journal of physical chemistry. B.

[8]  B. Widom,et al.  Some Topics in the Theory of Fluids , 1963 .

[9]  A. Triolo,et al.  MORPHOLOGY OF 1-ALKYL-3-METHYLIMIDAZOLIUM HEXAFLUOROPHOSPHATE ROOM TEMPERATURE IONIC LIQUIDS , 2008 .

[10]  G. Voth,et al.  Unique spatial heterogeneity in ionic liquids. , 2005, Journal of the American Chemical Society.

[11]  A. Pádua,et al.  Using ethane and butane as probes to the molecular structure of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ionic liquids. , 2012, Faraday discussions.

[12]  Johan Jacquemin,et al.  Density and viscosity of several pure and water-saturated ionic liquids , 2006 .

[13]  W. L. Jorgensen,et al.  Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids , 1996 .

[14]  A. Pádua,et al.  Interactions of nitrous oxide with fluorinated liquids. , 2006, The journal of physical chemistry. B.

[15]  J. Brennecke,et al.  Improving carbon dioxide solubility in ionic liquids. , 2007, The journal of physical chemistry. B.

[16]  A. Pádua,et al.  Interactions of fluorinated gases with ionic liquids: solubility of CF4, C2F6, and C3F8 in trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide. , 2008, The journal of physical chemistry. B.

[17]  J. Jacquemin,et al.  High-pressure volumetric properties of imidazolium-based ionic liquids : Effect of the anion , 2007 .

[18]  M. Gomes,et al.  Solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon, and carbon monoxide in 1-butyl-3-methylimidazolium tetrafluoroborate between temperatures 283 K and 343 K and at pressures close to atmospheric , 2006 .

[19]  A. Pádua,et al.  Molecular force field for ionic liquids v: hydroxyethylimidazolium, dimethoxy-2- methylimidazolium, and fluoroalkylimidazolium cations and bis(fluorosulfonyl)amide, perfluoroalkanesulfonylamide, and fluoroalkylfluorophosphate anions. , 2010, The journal of physical chemistry. B.

[20]  A. Yokozeki,et al.  Carbon Dioxide Capture Using Ionic Liquid 1-Butyl-3-methylimidazolium Acetate , 2010 .

[21]  A. Pádua,et al.  Modeling Ionic Liquids Using a Systematic All-Atom Force Field , 2004 .

[22]  M. Gomes,et al.  Influence of water on the carbon dioxide absorption by 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide , 2010 .

[23]  A. Pádua,et al.  Thermophysical properties, low pressure solubilities and thermodynamics of solvation of carbon dioxide and hydrogen in two ionic liquids based on the alkylsulfate anion , 2008 .

[24]  Kwong H. Yung,et al.  Carbon Dioxide's Liquid-Vapor Coexistence Curve And Critical Properties as Predicted by a Simple Molecular Model , 1995 .

[25]  G. Voth,et al.  On the Structure and Dynamics of Ionic Liquids , 2004 .

[26]  M. Mezei The finite difference thermodynamic integration, tested on calculating the hydration free energy difference between acetone and dimethylamine in water , 1987 .

[27]  P. Malfreyt,et al.  Effect of alkyl chain length and hydroxyl group functionalization on the surface properties of imidazolium ionic liquids. , 2011, Physical chemistry chemical physics : PCCP.

[28]  R. Caminiti,et al.  Morphology and intermolecular dynamics of 1-alkyl-3-methylimidazolium bis{(trifluoromethane)sulfonyl}amide ionic liquids: structural and dynamic evidence of nanoscale segregation , 2009 .

[29]  Wenchuan Wang,et al.  Screening of ionic liquids to capture CO2 by COSMO-RS and experiments , 2008 .

[30]  Jared L. Anderson,et al.  Ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate anion: a new class of highly selective and ultra hydrophobic solvents for the extraction of polycyclic aromatic hydrocarbons using single drop microextraction. , 2009, Analytical chemistry.

[31]  W. Shi,et al.  Absorption of CO2 in the ionic liquid 1-n-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([hmim][FEP]): a molecular view by computer simulations. , 2009, The journal of physical chemistry. B.

[32]  N. Ignat’ev,et al.  New ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions , 2005 .

[33]  T. Gefflaut,et al.  Effect of fluorination and size of the alkyl side-chain on the solubility of carbon dioxide in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids. , 2010, The journal of physical chemistry. B.

[34]  E. di Cola,et al.  Nanoscale segregation in room temperature ionic liquids. , 2007, The journal of physical chemistry. B.

[35]  A. Pádua,et al.  Molecular Force Field for Ionic Liquids Composed of Triflate or Bistriflylimide Anions , 2004 .