Densities and viscosities of binary system containing 1,3-dimethylimidazolium dimethylphosphate and dimethyl sulfoxide or acetonitrile

WANG Xinxin1 ZHOU Qing1,2 ZHANG Xiaochun1 ZHANG Zhibo1 LYU Xingmei1,2 ZHANG Suojiang1,2

(1.Beijing Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China 100190)
(2.College of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing, China 100049)
【Knowledge Link】ionic liquid

【Abstract】Due to their special structure and properties, ionic liquids (ILs) have shown good results in the application of cellulose pretreatment. Relevant physical property data are indispensable in promoting the industrialization of ILs. In this study, IL 1,3-dimethylimidazolium dimethylphosphate ([Mmim][DMP]) was synthesized and the densities and viscosities of the binary systems of [Mmim][DMP] with dimethylsulfoxide (DMSO) or acetonitrile were measured in the temperature range from 293.15 K to 323.15 K over the whole concentration. Then volume properties and excess property data were calculated and fitted. Based on the data of apparent molar volume , apparent molar volume at infinite dilution , partial molar volume, excess molar volume VE, and molecular simulation results, the influence of the interaction between IL and solvents and hydrogen bonds formed between IL and DMSO (or acetonitrile) were analyzed.

【Keywords】 ionic liquids; DMSO; acetonitrile; density; viscosity;


【Funds】 National Natural Science Foundation of China (21890760, 21978291, 21776289, 51674234, 21878292)

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(Translated by WANG YX)


    [1] Wang H, Gurau G, Rogers R D. Ionic liquid processing of cellulose [J]. Chem. Soc. Rev., 2012, 41 (4): 1519–1537.

    [2] Zhao Y, Liu X, Wang J, et al. Insight into the cosolvent effect of cellulose dissolution in imidazolium-based ionic liquid systems [J]. J. Phys. Chem. B, 2013, 117 (30): 9042–9049.

    [3] Xu J, Yao X, Zhou Q, et al. Enhanced delignification of cornstalk by employing superbase TBD in ionic liquids [J]. RSC Adv., 2014, 4 (52): 27430–27438.

    [4] Xu J, Yao X, Xin J, et al. An effective two-step ionic liquids method for cornstalk pretreatment [J]. J. Chem. Technol. Biotechnol., 2015, 90: 2057–2065.

    [5] Chen Z, Zeng J, Di J, et al. Facile microwave-assisted ionic liquid synthesis of sphere-like BiOBr hollow and porous nanostructures with enhanced photocatalytic performance [J]. Green Energy Environ., 2017, 2 (2): 124–133.

    [6] Vitz J, Erdmenger T, Haensch C, et al. Extended dissolution studies of cellulose in imidazolium based ionic liquids [J]. Green Chem., 2009, 11 (3): 417–424.

    [7] Abe M, Fukaya Y, Ohno H. Extraction of polysaccharides from bran with phosphonate or phosphinate-derived ionic liquids under short mixing time and low temperature [J]. Green Chem., 2010, 12: 1274–1280.

    [8] Fukaya Y, Hayashi K, Wada M, et al. Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions [J]. Green Chem., 2008, 10 (1): 44–46.

    [9] Xu A, Wang J, Wang H. Effects of anionic structure and lithium salts addition on the dissolution of cellulose in 1-butyl-3-methylimidazolium-based ionic liquid solvent systems [J]. Green Chem., 2010, 12 (2): 268–275.

    [10] Swatloski R P, Spear S K, Holbrey J D, et al. Dissolution of cellose with ionic liquids [J]. J. Am. Chem. Soc., 2002, 124 (18): 4974–4975.

    [11] Zhao Y, Liu X, Wang J, et al. Effects of anionic structure on the dissolution of cellulose in ionic liquids revealed by molecular simulation [J]. Carbohydr Polym., 2013, 94 (2): 723–730.

    [12] Zhao Y, Liu X, Wang J, et al. Effects of cationic structure on cellulose dissolution in ionic liquids: a molecular dynamics study [J]. Chem Phys Chem, 2012, 13 (13): 3126–3133.

    [13] Rooney D, Jacquemin J, Gardas R. Thermophysical properties of ionic liquids [J]. Top Curr. Chem., 2009, 290: 185–212.

    [14] Seddon K R, Stark A, Torres M J. Influence of chloride, water, and organic solvents on the physical properties of ionic liquids [J]. Pure Appl. Chem., 2000, 72 (12): 2275–2287.

    [15] Wahlström R, Rahikainen J, Kruus K, et al. Cellulose hydrolysis and binding with trihoderma reesei Cel5A and Cel7A and their core domains in ionic liquid solutions [J]. Biotechnol. Bioeng., 2014, 111 (4): 726–733.

    [16] Qing Q, Hu R, He Y, et al. Investigation of a novel acid-catalyzed ionic liquid pretreatment method to improve biomass enzymatic hydrolysis conversion [J]. Appl. Microbiol. Biotechnol., 2014, 98 (11): 5275–5286.

    [17] Wahlstrom R, Rovio S, Suurnakki A. Analysis of mono- and oligosaccharides in ionic liquid containing matrices [J]. Carbohydr. Res., 2013, 373: 42–51.

    [18] Engel P, Krull S, Seiferheld B, et al. Rational approach to optimize cellulase mixtures for hydrolysis of regenerated cellulose containing residual ionic liquid [J]. Bioresour. Technology., 2012, 115: 27–34.

    [19] Abels C, Redepenning C, Moll A, et al. Simple purification of ionic liquid solvents by nanofiltration in biorefining of lignocellulosic substrates [J]. J. Membr. Sci., 2012, 405/406: 1–10.

    [20] Engel P, Mladenov R, Wulfhorst H, et al. Point by point analysis: how ionic liquid affects the enzymatic hydrolysis of native and modified cellulose [J]. Green Chem., 2010, 12 (11): 1959–1966.

    [21] Mazza M, Catana D A, Vaca-Garcia C, et al. Influence of water on the dissolution of cellulose in selected ionic liquids [J]. Cellulose, 2008, 16 (2): 207–215.

    [22] Zhu S, Wu Y, Chen Q, et al. Dissolution of cellulose with ionic liquids and its application: a mini-review [J]. Green Chem., 2006, 8 (4): 325–327.

    [23] Cao Y, Zhang R, Cheng T, et al. Imidazolium-based ionic liquids for cellulose pretreatment: recent progresses and future perspectives [J]. Appl. Microbiol. Biotechnol., 2017, 101 (2): 521–532.

    [24] Zhao D, Li H, Zhang J, et al. Dissolution of cellulose in phosphate-based ionic liquids [J]. Carbohydr. Polym., 2012, 87 (2): 1490–1494.

    [25] Cai F, Zhu W, Wang Y, et al. Dialkylphosphate-based ionic liquids as solvents to extract toluene from heptane [J]. J. Chem. Eng. Data, 2015, 60 (6): 1776–1780.

    [26] Cai F, Zhao M, Wang Y, et al. Phosphoric-based ionic liquids as solvents to separate the azeotropic mixture of ethanol and hexane [J]. J. Chem. Thermodyn., 2015, 81: 177–183.

    [27] Cai F, Xiao G. Liquid–liquid equilibria for ternary systems ethanol + heptane + phosphoric-based ionic liquids [J]. Fluid Phase Equilib., 2015, 386: 155–161.

    [28] Cai F, Xiao G. (Liquid + liquid) extraction of methanol from alkanes using dialkylphosphate-based ionic liquids as solvents [J]. J. Chem. Thermodyn., 2015, 87: 110–116.

    [29] Cai F, Ibrahim J J, Niu L, et al. Liquid–liquid equilibrium for ternary system methanol + methyl acetate + 1,3-dimethylimidazolium dimethylphosphate at several temperatures and atmospheric pressure [J]. J. Chem. Eng. Data, 2015, 60 (1): 57–64.

    [30] Sakal S A, Shen C, Li C X. (Liquid + liquid) equilibria of {benzene + cyclohexane + two ionic liquids} at different temperature and atmospheric pressure [J]. J. Chem. Thermodyn., 2012, 49: 81–86.

    [31] Cao J, Yu G, Chen X, et al. Determination of vapor–liquid equilibrium of methyl acetate + methanol + 1-alkyl-3-methylimidazolium dialkylphosphates at 101.3 kPa [J]. J. Chem. Eng. Data, 2017, 62 (2): 816–824.

    [32] Chen X, Yang B, Abdeltawab A A, et al. Isobaric vapor–liquid equilibrium for acetone + methanol + phosphate ionic liquids [J]. J. Chem. Eng. Data, 2015, 60 (3): 612–620.

    [33] Li Q, Cao L, Zhang Y, et al. Isobaric vapor–liquid equilibrium for chloroform + methanol + 1,3-dimethylimidazolium dimethylphosphate at 101.3 kPa [J]. J. Chem. Eng. Data, 2014, 59 (2): 234–239.

    [34] Wang J, Li Z. Measurement and modeling of vapor–liquid equilibria for systems containing alcohols, water, and imidazolium-based phosphate ionic liquids [J]. J. Chem. Eng. Data, 2013, 58 (6): 1641–1649.

    [35] Dong L, Zheng D, Li J, et al. Suitability prediction and affinity regularity assessment of H2O + imidazolium ionic liquid working pairs of absorption cycle by excess property criteria and UNIFAC model [J]. Fluid Phase Equilib., 2013, 348: 1–8.

    [36] Li Q, Zhu W, Wang H, et al. Isobaric vapor–liquid equilibrium for the ethanol + water + 1,3-dimethylimidazolium dimethylphosphate system at 101. 3 k Pa [J]. J. Chem. Eng. Data, 2012, 57 (3): 696–700.

    [37] Jia P, Zhao Z, Gao Q, et al. Isobaric vapor–liquid equilibrium of the acetonitrile + 1-propanol + ionic liquids at an atmospheric pressure [J]. J. Chem. Eng. Data, 2019, 64 (7): 2963–2972.

    [38] Luo C, Wang Y, Li Y, et al. Thermodynamic properties and application of LiNO3-MIM DMP/H2O ternary working pair [J]. Renewable Energy, 2019, 134: 147–160.

    [39] Dong L, Zheng D, Nie N, et al. Performance prediction of absorption refrigeration cycle based on the measurements of vapor pressure and heat capacity of H2O + [DMIM] DMP system [J]. Appl. Energy, 2012, 98: 326–332.

    [40] Ge M L, Lu C Y, Liu X Y, et al. Activity coefficients at infinite dilution of alkanes, alkenes, alkyl benzenes in dimethylphosphate based ionic liquids using gas–liquid chromatography [J]. J. Chem. Thermodyn., 2015, 91: 279–285.

    [41] Gaciño F M, Regueira T, Bolotov A V, et al. Volumetric behaviour of six ionic liquids from T = (278 to 398) K and up to 120 MPa [J]. J. Chem. Thermodyn., 2016, 93: 24–33.

    [42] Ghani N A, Sairi N A, Aroua M K, et al. Density, surface tension, and viscosity of ionic liquids (1-ethyl-3-methylimidazolium diethylphosphate and 1,3-dimethylimidazolium dimethylphosphate) aqueous ternary mixtures with MDEA [J]. J. Chem. Eng. Data, 2014, 59 (6): 1737–1746.

    [43] He Z, Zhao Z, Zhang X, et al. Thermodynamic properties of new heat pump working pairs: 1,3-dimethylimidazolium dimethylphosphate and water, ethanol and methanol [J]. Fluid Phase Equilib., 2010, 298 (1): 83–91.

    [44] Zhang Z, Zhou Q, Lu X, et al. Densities and viscosities of binary mixtures containing 1,3-dimethylimidazolium dimethylphosphate and alcohols [J]. J. Chem. Eng. Data, 2014, 59 (8): 2377–2388.

    [45] Wang J, Zhang Z, Jin S, et al. Efficient conversion of carbohydrates into 5-hydroxylmethylfurfan and 5-ethoxymethylfurfural over sufonic acid-functionalized mesoporous carbon catalyst [J]. Fuel, 2017, 192: 102–107.

    [46] Sampath G, Srinivasan K. Remarkable catalytic synergism of alumina, metal salt and solvent for conversion of biomass sugars to furan compounds [J]. Appl. Catal., A, 2017, 533: 75–80.

    [47] Morais-de-Carvalho D, Martinez-Abad A, Evtuguin D V, et al. Isolation and characterization of acetylated glucuronoarabinoxylan from sugarcane bagasse and straw [J]. Carbohydr Polym., 2017, 156: 223–234.

    [48] Holding A J, Parviainen A, Kilpeläinen I, et al. Efficiency of hydrophobic phosphonium ionic liquids and DMSO as recyclable cellulose dissolution and regeneration media [J]. RSC Adv., 2017, 7 (28): 17451–17461.

    [49] Gajula S, Inthumathi K, Arumugam S R, et al. Strategic designing on selection of solvent systems for conversion of biomass sugars to furan derivatives and their separation [J]. ACS Sustainable Chem. Eng., 2017, 5 (6): 5373–5381.

    [50] Chen T Y, Wang B, Shen X J, et al. Assessment of structural characteristics of regenerated cellulolytic enzyme lignin based on a mild DMSO/[Emim] OAc dissolution system from triploid of populus tomentosa carr [J]. RSC Adv., 2017, 7 (6): 3376–3387.

    [51] Brzonova I, Asina F, Andrianova A A, et al. Fungal biotransformation of insoluble kraft lignin into a water soluble polymer [J]. Ind. Eng. Chem. Res., 2017, 56 (21): 6103–6113.

    [52] Bhanja P, Modak A, Chatterjee S, et al. Bifunctionalized mesoporous SBA-15: a new heterogeneous catalyst for the facile synthesis of 5-hydroxymethylfurfural [J]. ACS Sustainable Chem. Eng., 2017, 5 (3): 2763–2773.

    [53] Xue Z, Zhao X, Sun R C, et al. Biomass-derived γ-valerolactone-based solvent systems for highly efficient dissolution of various lignins: dissolution behavior and mechanism study [J]. ACSSustainable Chem. Eng., 2016, 4 (7): 3864–3870.

    [54] Zuo M, Le K, Li Z, et al. Green process for production of 5-hydroxymethylfurfural from carbohydrates with high purity in deep eutectic solvents [J]. Ind. Crops Prod., 2017, 99: 1–6.

    [55] Hattori K, Arai A. Preparation and hydrolysis of water-stable amorphous cellulose [J]. ACS Sustainable Chem. Eng., 2016, 4 (3): 1180–1186.

    [56] Chen H, Zhou J, Mao J, et al. Enhancement of mass transfer through bubbling effect during extraction and reaction in biphasic systems containing ionic liquid [J]. RSC Adv., 2016, 6 (103): 101485–101491.

    [57] Chidambaram M, Bell A T. A two-step approach for the catalytic conversion of glucose to 2,5-dimethylfuran in ionic liquids [J]. Green Chem., 2010, 12 (7): 1253–1262.

    [58] Tian S, Ren S, Hou Y, et al. Densities, viscosities and excess properties of binary mixtures of 1,1,3,3-tetramethylguanidinium lactate + water at T = (303.15 to 328.15) K [J]. J. Chem. Eng. Data, 2013, 58 (7): 1885–1892.

    [59] Kermanpour F, Niakan H Z, Sharifi T. Density and viscosity measurements of binary alkanol mixtures from (293.15 to 333.15) K at atmospheric pressure [J]. J. Chem. Eng. Data, 2013, 58 (5): 1086–1091.

    [60] Ciocirlan O, Croitoru O, Iulian O. Densities and viscosities for binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid with molecular solvents [J]. J. Chem. Eng. Data, 2011, 56 (4): 1526–1534.

    [61] Roy M N, Sarkar B K, Chanda R. Viscosity, density, and speed of sound for the binary mixtures of formamide with 2-methoxyethanol, acetophenone, acetonitrile, 1,2-dimethoxyethane, and dimethylsulfoxide at different temperatures [J]. J. Chem. Eng. Data, 2007, 52: 1630–1637.

    [62] Yasmeen S, Riyazuddeen, Anwar N. Interaction of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide with methanol/dimethyl sulfoxide at (298.15, 303.15, 308.15, 313.15, 318.15 and 323.15) K: measurements and correlations of thermophysical properties [J]. J. Mol. Liq., 2016, 221: 1207–1217.

    [63] Keshapolla D, Gardas R L. Apparent molar volumes and isentropic compressions of benzylalkylammonium ionic liquids in dimethylsulfoxide from 293.15 K to 328.15 K [J]. Fluid Phase Equilib., 2014, 383: 32–42.

    [64] Redlich O, Meyer D M. The molal volumes of electrolytes [J]. Chem Rev., 1964, 24 (3): 221–227.

    [65] Carmen Grande M D, JuliáJ A, García M, et al. On the density and viscosity of (water + dimethylsulphoxide) binary mixtures [J]. J. Chem. Thermodyn., 2007, 39 (7): 1049–1056.

    [66] Tôrres R B, Marchiore A C M, Volpe P L O. Volumetric properties of binary mixtures of (water + organic solvents) at temperatures between T = 288.15 K and T = 303.15 K at p = 0.1 MPa [J]. J. Chem. Thermodyn., 2006, 38 (5): 526–541.

    [67] González E J, Alonso L, DomínguezÁ. Physical properties of binary mixtures of the ionic liquid 1-methyl-3-octylimidazolium chloride with methanol, ethanol, and 1-propanol at T = (298.15, 313.15, and 328.15) K and at P = 0.1 MPa [J]. J. Chem. Eng. Data, 2006, 51 (4): 1446–1452.

    [68] González E J, González B, Macedo E A. Thermophysical properties of the pure ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide and its binary mixtures with alcohols [J]. J. Chem. Eng. Data, 2013, 58 (6): 1440–1448.

    [69] Zheng Y, Dong K, Wang Q, et al. Density, viscosity, and conductivity of lewis acidic 1-butyl- and 1–hydrogen-3-methylimidazolium chloroaluminate ionic liquids [J]. J. Chem. Eng. Data, 2013, 58 (1): 32–42.

    [70] Ciocirlan O, Iulian O. Properties of pure 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ionic liquid and its binary mixtures with dimethyl sulfoxide and acetonitrile [J]. J. Chem. Eng. Data, 2012, 57 (11): 3142–3148.

    [71] Iulian O, Ciocirlan O. Volumetric properties of binary mixtures of two 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids with molecular solvents [J]. J. Chem. Eng. Data, 2012, 57 (10): 2640–2646.

This Article


CN: 11-1946/TQ

Vol 71, No. 01, Pages 177-191

January 2020


Article Outline



  • Introduction
  • 1 Experimental materials and methods
  • 2 Results and discussion
  • 3 Conclusions
  • Symbols
  • References