Representation of Phase Behavior of Ionic Liquids Using the Equation of State for Square-well Chain Fluids with Variable Range

Abstract

Abstract: An equation of state(EOS) for square-well chain fluids with variable range(SWCF-VR) developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature(pVT) and phase equilibrium of pure ionic liquids(ILs) and their mixtures.The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges.The molecular parameters of ILs composed of homologous organic cation and an identical anion such as [C_xmim][NTf₂] are good linear with respect to their molecular weight,indicating that the molecular parameters of homologous substances,subsequently pVT and vapor-liquid equilibria vapor-liquid equilibria(VLE) can be predicted using the generalized parameter when no experimental data were available.The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one temperature-independent binary interaction parameter.

Key words: equation of state, ionic liquids, square-well chain, phase behavior

摘要： An equation of state(EOS) for square-well chain fluids with variable range(SWCF-VR) developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature(pVT) and phase equilibrium of pure ionic liquids(ILs) and their mixtures.The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges.The molecular parameters of ILs composed of homologous organic cation and an identical anion such as [C_xmim][NTf₂] are good linear with respect to their molecular weight,indicating that the molecular parameters of homologous substances,subsequently pVT and vapor-liquid equilibria vapor-liquid equilibria(VLE) can be predicted using the generalized parameter when no experimental data were available.The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one temperature-independent binary interaction parameter.

关键词: equation of state, ionic liquids, square-well chain, phase behavior

LI Jinlong, HE Qing, HE Changchun, PENG Changjun, LIU Honglai. Representation of Phase Behavior of Ionic Liquids Using the Equation of State for Square-well Chain Fluids with Variable Range[J]. , 2009, 17(6): 983-989.

李进龙, 何清, 何昌春, 彭昌军, 刘洪来. Representation of Phase Behavior of Ionic Liquids Using the Equation of State for Square-well Chain Fluids with Variable Range[J]. , 2009, 17(6): 983-989.

References

1 Cole-Hamilton, D.J., “Homogeneous catalysis—new approaches to catalyst separation, recovery and recycling”, Science, 299, 1702-1706(2003).
2 Chu, X., Hu, Y., Li, J., Liang, Q., Liu, Y., Zhang, X., Peng, X., Yue, W., “Desulfurization of diesel fuel by extraction with [BF₄]-based ionic lquids”, Chin. J. Chem. Eng., 16, 881-884(2008).
3 Heintz, A., “Recent developments in thermodynamics and thermophysics of non-aqueous mixtures containing ionic liquids. A review”, J. Chem. Thermodyn., 37, 525-535(2005).
4 Scovazzo, P., Camper, D., Kieft, J., Poshusta, J., Koval, C., Noble, R., “Regular solution theory and CO₂ gas solubility in room temperature ionic liquids”, Ind. Eng. Chem. Res., 43, 6855-6860(2004).
5 Wang, J., Sun, W., Li, C., Wang, Z., “Correlation of infinite dilution activity coefficient of solute in ionic liquid using UNIFAC model”, Fluid Phase Equilib., 264, 235-241(2008).
6 Huo, Y., Xia, S., Yi, S., Ma, P., “Measurement and correlation of vapor pressure of benzene and thiophene with [Bmim][PF₆] and [Bmim][BF₄] ionic liquids”, Fluid Phase Equilib., 276, 46-52(2009).
7 Jiang, X., Zhao, S., Sun, X., Fu, D., “Phase equilibrium of ionic liquids and high boiling point aromatic compounds”, J. Chem. Ind. Eng., 58(4), 818-821(2007).(in Chinese)
8 Carvalho, P.J., álvarez, V.H., Machado, J.J.B., Pauly, J., Daridon, J.L., Marrucho, I.M., Aznar, M., Coutinho, J.A.P., “High pressure phase behavior of carbon dioxide in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids”, J. Supercrit. Fluids, 48, 99-107(2009).
9 Kroon, M.C., Karakatsani, E.K., Economou, I.G., Witkamp, G.J., Peters, C.J., “Modeling of the carbon dioxide solubility in imidazolium-based ionic liquids with the tPC-PSAFT equation of state”, J. Phys. Chem. B, 110, 9262-9269(2006).
10 Karakatsani, E.K., Economou, I.G., “Pertured chain statistical associating fluid theory extended to dipolar and quardrupolar molecular fluids”, J. Phys. Chem. B, 110, 9252-9261(2006).
11 Karakatsani, E.K., Economou, I.G., Kroon, M.C., Peters, C.J., Witkamp, G.J., “tPC-PSAFT modeling of gas solubility in imidazolium-based ionic liquids”, J. Phys. Chem. C, 111, 15487-15492(2007).
12 Andreu, J.S., Vega, L.F., “Capturing the solubility behavior of CO₂in ionic liquids by a simple model”, J. Phys. Chem. C, 111, 16028-16034(2007).
13 Wang, T.F., Peng, C.J., Liu, H.L., Hu, Y., “Description of the pVT behavior of ionic liquids and the solubility of gases in ionic liquids using an equation of state”, Fluid Phase Equilib., 250, 150-157(2006).
14 Wang, T.F., Peng, C.J., Liu, H.L., Hu, Y., Jiang, J.W., “Equation of state for the vapor-liquid equilibria of binary systems containing imidazolium-based ionic liquids”, Ind. Eng. Chem. Res., 46, 4323-4329(2007).
15 Geng, Y.F., Wang, T.F., Yu, D.H., Peng, C.J., Liu, H.L., Hu, Y., “Densities and viscosities of the ionic liquid [C₄mim][PF₆] + N,N-dimethylformamide binary mixtures at 293.15 K to 318.15 K”, Chin. J. Chem. Eng., 16, 256-262(2008).
16 Del Popolo, M.G., Voth, G.A., “On the structure and dynamics study of ionic liquids”, J. Phys. Chem. B, 108, 1744-1752(2004).
17 Wang, J., Li, C., Shen, C., Wang, Z., “Towards understanding the effect of electrostatic interactions on the density of ionic liquids”, Fluid Phase Equilib., 279, 87-91(2009).
18 Li, J.L., He, H.H., Peng, C.J., Liu, H.L., Hu, Y., “A new development of equation of state for square-well chain-like molecules with variable width 1.1≤λ≤3”, Fluid Phase Equilib., 276, 57-68(2009).
19 Li, J.L., Peng, C.J., Liu, H.L., “Modeling vapor-liquid equilibrium of refrigerants using an equation of state for square well chain fluid with variable range”, Chem. Ind. Eng. Soc. Chin. J., 60, 545-552(2009).(in Chinese)
20 Li, J.L., He, H.H., Peng, C.J., Liu, H.L., Hu, Y., “Equation of state for square-well chain-like molecules with variable range(I) Application for pure substances”, Fluid Phase Equilib., 286, 8-16(2009).
21 Li, J.L., Tong, M., Peng, C.J., Liu, H.L., Hu, Y., “Equation of state for square-well chain-like molecules with variable range(II) Extension to mixtures”, Fluid Phase Equilib., 287, 50-61(2009).
22 Esperanca, J.M.S.S., Guedes, H.J.R., Blesic, M., Rebelo, L.P.N., “Densities and derived thermodynamic properties of ionic liquids(3) Phosphonium-based ionic liquids over and extended pressure range”, J. Chem. Eng. Data, 51, 237-242(2006).
23 Machida, H., Sato, Y., Smith, Jr. R.L., “Pressure-volume-temperature(PVT) measurements of ionic liquids([bmim⁺][PF₆^-], [bmim⁺][BF₄^-], [bmim⁺][OcSO₄^-]) and analysis with the Sanchez-Lacombe equation of state”, Fluid Phase Equilib., 264, 147-155(2008).
24 Gardas, R.L., Freire, M.G., Carvalho, P.J., Marrucho, I.M., Fonseca, I.M.A., Ferreira, A.G.M., Coutinho, J.A.P., “High pressure densities and derived thermodynamic properties of imidazolium-based ionic liquids”, J. Chem. Eng. Data, 52, 80-88(2007).
25 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).
26 Hofman, T., Goldon, A., Nevines, A., Letcher, T.M., “Densities, excess volumes, isobaric expansivity, and isothermal compressibility of the(1-ethyl-3-methylimidazolium ethylsulfate + methanol) system at temperatures(283.15 to 333.15) K and pressure from(0.1 to 35) MPa”, J. Chem. Thermodyn., 40, 580-591(2008).
27 Fredlake, C.P., Crosthwaite, J.M., Hert, D.G., Aki, S.N.V.K., Brennecke, J.F., “Thermophysical properties of imidazolium-based ionic liquids”, J. Chem. Eng. Data, 49, 954-964(2004).
28 Esperanca, J.M.S.S., Visak, Z.P., Plechkova, N.V., Seddon, K.R., Guedes, H.J.R., Rebelo, P.N., “Density, speed of sound, and derived thermodynamic properties of ionic liquids over and extender pressure range(4) [C₃min][NTf₂] and [C₅min][NTf₂]”, J. Chem. Eng. Data, 51, 2009-2015(2006).
29 Azevedo, R.G., Esperanca, J.M.S.S., Szydlowski, J., Visak, Z.P., Pires, P.F., Guedes, H.J.R., Rebelo, L.P.N., “Thermophysical and thermodynamic properties of ionic liquids over an extended pressure range:[bmim][NTf₂] and [hmim][NTf₂]”, J. Chem. Thermodyn., 37, 888-899(2005).
30 Kato, R., Gmehling, J., “Systems with ionic liquids:Measurement of VLE and data and prediction of their thermodynamic behavior using original UNIFAC, mod. UNIFAC(Do) and COSMO-RS(Ol)”, J. Chem. Thermodyn., 37, 603-619(2005).
31 Gardas, R.L., Freire, M.G., Carvalho, P.J., Marrucho, I.M., Fonseca, I.M.A., Ferreira, A.G.M., Coutinho, J.A.P., “PρT measurements of imidazolium-based ionic liquids”, J. Chem. Eng. Data, 52, 1881-1888(2007).
32 Navia, P., Troncoso, J., Romani, L., “Excess magnitudes for ionic liquid binary mixtures with a common ion”, J. Chem. Eng. Data, 52, 1369-1374(2007).
33 Lopes, J.N.C., Cordeiro, T.C., Esperanca, J.M.S.S., Guedes, H.J.R., Huq, S., Rebelo, L.P., Seddon, K.R., “Deviations from ideality in mixtures of two ionic liquids containing a common ion”, J. Phys. Chem. B, 109, 3519-3525(2005).
34 Kato, R., Gmehling, J., “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”, Fluid Phase Equilib., 231, 38-43(2005).
35 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).
36 Verevkin, S.P., Safarov, J., Bich, E., Hassel, E., Heintz, A., “Thermodynamic properties of mixtures containing ionic liquids vapor pressures and activity coefficients of n-alcohols and benzene in binary mixtures with 1-methyl-3-butyl-imidazolium bis(trifluoromethyl-sulfonyl) imide”, Fluid Phase Equilib., 236, 222-228(2005).
37 Safarov, J., Verevkin, S.P., Bich, E., Heintz, A., “Vapor pressures and activity coefficients of n-alcohols and benzene in binary mixtures with 1-methyl-3-butyl-imidazolium octyl sulfact and 1-methyl-3-butylimidazolium tetrafluoroborate”, J. Chem. Eng. Data, 51, 518-525(2006).
38 Nebig, S., Bolts, R., Gmehling, J., “Measurement of vapor-liquid equilibria(VLE) and excess enthalpies(HE) of binary systems with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and prodiction of these properties and γ^∞ using modified UNIFAC(Dortmund)”, Fluid Phase Equilib., 258, 168-178(2007).
39 Kim, Y.S., Choi, W.Y., Jang, J.H., Yoo, K.P., Lee, C.S., “Solubility measurement and prediction of carbon dioxide in ionic liquids”, Fluid Phase Equilib., 228/229, 439-445(2005).
40 Kroon, M.C., Shariati, A., Costantini, M., Spronsen, J., Witkamp, G.J., Sheldon, R.A., Peters, C.J., “High pressure phase behavior of systems with ionic liquids(V) The binary system carbon dioxide + 1-butyl-3-methylimidazolium tetrafluoroborate”, J. Chem. Eng. Data, 50, 173-176(2005).
41 Lee, B.C., Outcalt, S.L., “Solubilities of gases in the ionic liquid 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide”, J. Chem. Eng. Data, 51, 892-897(2006).
42 Kamps, A.P.S., Tuma, D., Xia, J., Maurer, G., “Solubility of CO₂ in the ionic liquid [bmim][PF₆]”, J. Chem. Eng. Data, 48, 746-749(2003).
43 Shariati, A., Gutkowski, K., Peters, C.J., “Comparison of the phase behavior of some selected binary systems with ionic liquids”, AIChE J., 51, 1532-1540(2005).
44 Zhang, S., Yuan, X., Chen, Y., Zhang, X., “Solubility of CO₂in 1-butyl-3-methylimidazolium hexafluorophosphate and 1,1,3,3-tetramethylguanidium lactate at elevated pressures”, J. Chem. Eng. Data, 50, 1582-1585(2005).
45 Shariati, A., Peters, C.J., “High pressure phase behavior of systems with ionic liquids(III) The binary system carbon dioxide + 1-hexyl-3-methylimidazolium hexafluorophosphate”, J. Supercritical Fluids, 30, 139-144(2004).
46 Aki, S.N.V.K., Mellein, B.R., Saurer, E.M., Brennecke, J.F., “High pressure phase behavior of carbon dioxide with imidazolium-based ionic liquids”, J. Phys. Chem. B, 108, 20355-20365(2004).
47 Shiflett, M.B., Yokozeki, A., “Solubilities and diffusivities of carbon dioxide in ionic liquids:[bmim][PF₆] and [bmim][BF₄]”, Ind. Eng. Chem. Res., 44, 4453-4464(2005).

[1]	Eileen Katherine Coronado-Aldana, Cindy Lizeth Ferreira-Salazar, Nubia Yineth Piñeros-Castro, Rubén Vázquez-Medina, Felipe A. Perdomo. Thermodynamic analysis, synthesis, characterization, and evaluation of 1-ethyl-3-methylimidazolium chloride: Study of its effect on pretreated rice husk [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 143-154.
[2]	Zhonghao Li, Yuanyuan Yang, Huanong Cheng, Yun Teng, Chao Li, Kangkang Li, Zhou Feng, Hongwei Jin, Xinshun Tan, Shiqing Zheng. Measurement and model of density, viscosity, and hydrogen sulfide solubility in ferric chloride/trioctylmethylammonium chloride ionic liquid [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 210-221.
[3]	Chen Chen, Qiong Tang, Hong Xu, Mingxing Tang, Xuekuan Li, Lei Liu, Jinxiang Dong. Alkyl-tetralin base oils synthesized from coal-based chemicals and evaluation of their lubricating properties [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 20-28.
[4]	Yutong Jiang, Yifeng Chen, Fuliu Yang, Jixue Fan, Jun Li, Zhuhong Yang, Xiaoyan Ji. Efficient SO₂ removal using aqueous ionic liquid at low partial pressure [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 355-363.
[5]	Jialei Sha, Chenyi Liu, Zhihong Ma, Weizhong Zheng, Weizhen Sun, Ling Zhao. Understanding the interfacial behaviors of benzene alkylation with butene using chloroaluminate ionic liquid catalyst: A molecular dynamics simulation [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 44-52.
[6]	Yifeng Chen, Hang Yu, Jingjing Chen, Xiaohua Lu, Xiaoyan Ji. Viscous behavior of 1-hexyl-methylimidazolium bis(trifluoromethylsulfonyl)imide/titanium dioxide/polyethylene glycol [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 280-287.
[7]	Mi Feng, Bin He, Xinyan Chen, Junli Xu, Xingmei Lu, Cai Jia, Jian Sun. Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 133-141.
[8]	Xinqiang You, Kai Zhao, Ling Li, Ting Qiu. Ionic liquids as entrainer in extractive distillation for effectively separating 1-propanol–water azeotropic mixture [J]. Chinese Journal of Chemical Engineering, 2022, 49(9): 224-233.
[9]	Minjie Shi, Hangtian Zhu, Cheng Yang, Jing Xu, Chao Yan. Chemical reduction-induced fabrication of graphene hybrid fibers for energy-dense wire-shaped supercapacitors [J]. Chinese Journal of Chemical Engineering, 2022, 47(7): 1-10.
[10]	Song Hu, Jinlong Li, Qihua Wang, Weisheng Yang. Design and optimization of an integrated process for the purification of propylene oxide and the separation of propylene glycol by-product [J]. Chinese Journal of Chemical Engineering, 2022, 45(5): 111-120.
[11]	Alireza Afsharpour. A new approach for correlating of H₂S solubility in [emim][Lac], [bmim][ac] and [emim][pro] ionic liquids using two-parts combined models [J]. Chinese Journal of Chemical Engineering, 2022, 44(4): 521-527.
[12]	Haiyan Jiang, Lu Bai, Bingbing Yang, Shaojuan Zeng, Haifeng Dong, Xiangping Zhang. The effect of protic ionic liquids incorporation on CO₂ separation performance of Pebax-based membranes [J]. Chinese Journal of Chemical Engineering, 2022, 43(3): 169-176.
[13]	Wenjie Xiong, Mingzhen Shi, Yan Lu, Xiaomin Zhang, Xingbang Hu, Zhuoheng Tu, Youting Wu. Efficient conversion of H₂S into mercaptan alcohol by tertiary-amine functionalized ionic liquids [J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 197-204.
[14]	Yuxin Wu, Zhuo Chen, Xiaohui Zhang, Jian Chen, Yundong Wang, Jianhong Xu. Kinetic study of CO₂ fixation into propylene carbonate with water as efficient medium using microreaction system [J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 247-253.
[15]	Lianzheng Zhang, Jie Wang, Lin Yang, Dongmei Xu, Yixin Ma, Jun Gao, Yinglong Wang. Separation of isopropyl alcohol + isopropyl acetate azeotropic mixture: Selection of ionic liquids as entrainers and vapor-liquid equilibrium validation [J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 326-334.