English

Basic Properties of [C₃mim][NTf₂]/DEC/[Li][NTf₂] Systems

• Hui Shurong ^1, ,
• Zhao Liwei ^1, ,
• Liu Qingshan ^{2, ,} ,
• Song Dayong ^{2, ,}

• 1.

  College of Science, Shenyang Agricultural University, Shenyang 110866, P. R. China

• 2.

  School of Life Sciences, Huzhou University, Huzhou 313000, Zhejiang Province, P. R. China

Corresponding author: Liu Qingshan, 02726@zjhu.edu.cn Song Dayong, chsdyq@163.com

• Received Date: 03 October 2019
  Accepted Date: 25 November 2019
  Revised Date: 25 November 2019
  Available Online: 15 November 2020
• Fund Project:

  the China Scholarship Council with Reference 201608210093

  The project was supported by the China Scholarship Council with Reference No. 201608210093

Abstract: The hydrophobic ionic liquid (IL) 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C₃mim][NTf₂]) was synthesized according to traditional methods. By adding different amounts of diethyl carbonate (DEC) solvent and lithium bis[(trifluoromethyl)sulfonyl]imide ([Li][NTf₂]) salt to [C₃mim][NTf₂] IL, eight solution systems were prepared. First, the thermodynamic properties of the eight solution systems were characterized by differential scanning calorimetry (DSC). The semi-stable temperature of the system gradually disappeared with increasing lithium salt content, but the melting point temperature was not apparent in the experiment. These results indicate that DEC and lithium salts can dissolve in ILs within the tested temperature range. The basic properties of the eight systems, including thermodynamic and dynamic properties, were systematically studied at different temperatures. The variation in the self-diffusion coefficient of lithium ion ([Li]⁺) as a function of DEC concentration, density changes, viscosity, conductivity, and the viscosity/conductivity activation energy of the eight systems was calculated by the Vogel Fulcher Taman (VFT), Final Vogel Fulcher Taman (FVFT), and Arrhenius equations. The effect of temperature on the properties of the system was studied in detail. Within the temperature range measured herein, the deviation between the fitting equation and experimental value was small. Consequently, these equations were successfully used to calculate the properties of the system at various temperatures. All fitting parameters of the corresponding equations are provided herein. The viscosity for all systems decreased rapidly with increasing temperature, which increased the conductivity. Based on these experiments, the influence of DEC on the system microstructure was discussed in the context of the molecular dynamics simulation results. In particular, the interaction between [Li]⁺ and [NTf₂]^-/DEC was examined. In all solution systems, [NTf₂]^- coordinates to [Li]⁺ through only the O atom and not the N atom. Radial distribution function (RDF) analysis showed that the interaction between [Li]⁺ and [NTf₂]^- weakened with increasing DEC concentration. DEC molecules were observed in the first solvation layer of [Li]⁺ coordinating to [Li]⁺ through the carbonyl O atom. Although the interaction between [Li]⁺ and DEC was weakened, competition between [NTf₂]^- and DEC in the first solvation layer of [Li]⁺ was observed by the coordination number analysis of the O atom around [Li]⁺. Therefore, the introduction of DEC is beneficial for Li⁺ diffusion, which is consistent with the experimental results.

Key words:
• Ionic liquids
•  /  Diethyl carbonate
•  /  Lithium bis[(trifluoromethyl)sulfonyl]imide
•  /  Basic property

• 1. [1]

     Welton, T. Chem. Rev. 1999, 99, 2071. doi: 10.1021/cr980032t doi: 10.1021/cr980032t
     

  2. [2]

     Rantwijk, F. V.; Sheldon, R. A. Chem. Rev. 2007, 107, 2757. doi: 10.1021/cr050946x doi: 10.1021/cr050946x
     

  3. [3]

     Greaves, T. L.; Drummond, C. J. Chem. Rev. 2008, 108, 206. doi: 10.1021/cr068040u doi: 10.1021/cr068040u
     

  4. [4]

     龚燕燕, 刘海春, 张朵, 佟静.物理化学学报, 2019, 35, (11), 1224. doi: 10.3866/PKU.WHXB201901072Gong, Y.; Liu, C.; Zhang, D.; Tong, J. Acta Phys. -Chim. Sin. 2019, 35, (11), 1224. doi: 10.3866/PKU.WHXB201901072
     

  5. [5]

     胡之楠, 左剑涛, 夏美晨, 房大维, 臧树良.物理化学学报, 2018, 34, (8), 933. doi: 10.3866/PKU.WHXB201801221Hu, Z. N.; Zuo, J. T.; Xia, M. C.; Fang, D. W.; Zang, S. L. Acta Phys. -Chim. Sin. 2018, 34, (8), 933. doi: 10.3866/PKU.WHXB201801221
     

  6. [6]

     Dagade, D.; Pawar, R.; Patil, K. J. Chem. Eng. Data 2004, 49, 341. doi: 10.1021/je034188o doi: 10.1021/je034188o
     

  7. [7]

     Chorążewski, M.; Dzida, M.; Zorębski, E.; Zorębski, M. J. Chem. Thermodyn. 2013, 58, 389. doi: 10.1016/j.jct.2012.09.027 doi: 10.1016/j.jct.2012.09.027
     

  8. [8]

     Comesaña, J. F.; Otero, J. J.; García, E.; Correa, A. J. Chem. Eng. Data 2003, 48, 362. doi: 10.1021/je020153x doi: 10.1021/je020153x
     

  9. [9]

     Corderí, S.; González, B.; Calvar, N.; Gómez, E. Fluid Phase Equilib. 2013, 337, 11. doi: 10.1016/j.fluid.2012.10.004 doi: 10.1016/j.fluid.2012.10.004
     

  10. [10]

      Seoane, R. G.; González, E. J.; González, B. J. Chem. Thermodyn. 2012, 53, 152. doi: 10.1016/j.jct.2012.04.026 doi: 10.1016/j.jct.2012.04.026
      

  11. [11]

      Murulana, L. C.; Singh, A. K.; Shukla, S. K.; Kabanda, M. M.; Ebenso, E. E. Ind. Eng. Chem. Res. 2012, 51, 13282. doi: 10.1021/ie300977d doi: 10.1021/ie300977d
      

  12. [12]

      Domínguez, I.; González, E. J.; González, R.; Domínguez, Á. Sep. Sci. Technol. 2012, 47, 331. doi: 10.1080/01496395.2011.621161 doi: 10.1080/01496395.2011.621161
      

  13. [13]

      Tariq, M.; Serro, A. P.; Mata, J. L.; Saramago, B.; Esperança, J. M. S. S.; Lopes, J. N. C.; Rebelo, L. P. N. Fluid Phase Equilib. 2010, 294, 131. doi: 10.1016/j.fluid.2010.02.020 doi: 10.1016/j.fluid.2010.02.020
      

  14. [14]

      Gómez, E.; Calvar, N.; Macedo, E. A.; Domínguez, Á. J. Chem. Thermodyn. 2012, 45, 9. doi: 10.1016/j.jct.2011.08.028 doi: 10.1016/j.jct.2011.08.028
      

  15. [15]

      Papović, S.; Vraneš, M.; Gadžurić, S. J. Chem. Thermodyn. 2015, 91, 360. doi: 10.1016/j.jct.2015.07.048 doi: 10.1016/j.jct.2015.07.048
      

  16. [16]

      Esperança, J. M. S. S.; Visak, Z. P.; Plechkova, N. V.; Seddon, K. R.; Guedes, H. J. R.; Rebelo, L.P.N. J. Chem. Eng. Data 2006, 51, 2009. doi: 10.1021/je060203o doi: 10.1021/je060203o
      

  17. [17]

      Shukla, K.; Srivastava, V. C. RSC Adv. 2016, 39, 32624. doi: 10.1039/C6RA02518H doi: 10.1039/C6RA02518H
      

  18. [18]

      Tobiszewski, M.; Zabrocka, W.; Bystrzanowska, M. Anal. Methods 2019, 11, 844. doi: 10.1039/C8AY02683A doi: 10.1039/C8AY02683A
      

  19. [19]

      Tong, J.; Xiao, X.; Liang, X.; Solms, N.; Huo, F.; He, H.; Zhang, S. Phys. Chem. Chem. Phys. 2019, 21, 19216. doi: 10.1039/C9CP01848D doi: 10.1039/C9CP01848D
      

  20. [20]

      Pingali, S. R. K.; Upadhyay, S. K.; Jursic, B. S. Green Chem. 2011, 13, 928. doi: 10.1039/C0GC00794C doi: 10.1039/C0GC00794C
      

  21. [21]

      Hassoun, J.; Fernicola, A.; Navarra, M. A.; Panero, S.; Scrosati, B. J. Power Sources 2010, 195, 574. doi: 10.1016/j.jpowsour.2009.07.046 doi: 10.1016/j.jpowsour.2009.07.046
      

  22. [22]

      Reale, P.; Fernicola, A.; Scrosati, B. J. Power Sources 2009, 194, 182. doi: 10.1016/j.jpowsour.2009.05.016 doi: 10.1016/j.jpowsour.2009.05.016
      

  23. [23]

      Liu, Q. S.; Zhao, L. W.; Zheng, Q. G.; Mou, L.; Zhang, P. F. J. Chem. Eng. Data 2018, 63, 4484. doi: 10.1021/acs.jced.8b00591 doi: 10.1021/acs.jced.8b00591
      

  24. [24]

      Mou, L.; Chai, Y. Y.; Yang, G. Z.; Xia, Q.; Liu, Q. S.; Zheng, Q. G.; Zhang, Q. G. J. Chem. Thermodyn. 2019, 130, 183. doi: 10.1016/j.jct.2018.10.015 doi: 10.1016/j.jct.2018.10.015
      

  25. [25]

      郑其格, 刘惠, 夏泉, 刘青山, 牟林.物理化学学报, 2017, 33, (4), 736. doi: 10.3866/PKU.WHXB201612293Zheng, Q. G.; Liu, H.; Xia, Q.; Liu, Q. S.; Mou, L. Acta Phys. -Chim. Sin. 2017, 33 (4), 736. doi: 10.3866/PKU.WHXB201612293
      

  26. [26]

      刘青山, 刘惠, 牟林.物理化学学报, 2016, 32 (3), 617. doi: 10.3866/PKU.WHXB201512171Liu, Q. S.; Liu, H.; Mou, L. Acta Phys. -Chim. Sin. 2016, 32 (3), 617. doi: 10.3866/PKU.WHXB201512171
      

  27. [27]

      Wu, D.; Chen, A.; Johnson, C. S., Jr. J. Magn. Reson. Series A 1995, 115, 260. doi: 10.1006/jmra.1995.1176 doi: 10.1006/jmra.1995.1176
      

  28. [28]

      Chirico, R. D.; Frenkel, M.; Magee, J. W.; Diky, V.; Muzny, C. D.; Kazakov, A. F. J. Chem. Eng. Data 2013, 58, 2699. doi: 10.1021/je400569s. doi: 10.1021/je400569s
      

  29. [29]

      Abraham, M. J.; Murtola, T.; Schulz, R.; Páll, S.; Smith, J. C.; Hess, B.; Lindahl, E. SoftwareX 2015, 1-2, 19. doi: 10.1016/j.softx.2015.06.001 doi: 10.1016/j.softx.2015.06.001
      

  30. [30]

      Jorgensen, W. L.; Tirado-Rives, J. J. Am. Chem. Soc. 1988, 110, 1657. doi: 10.1021/ja00214a001 doi: 10.1021/ja00214a001
      

  31. [31]

      Martínez, L.; Andrade, R.; Birgin, E. G.; Martínez, J. M. J. Comput. Chem. 2009, 30, 2157. doi: 10.1002/jcc.21224 doi: 10.1002/jcc.21224
      

  32. [32]

      Liu, Q. S.; Li, P. P.; Welz-Biermann, U.; Chen, J.; Liu, X. X. J. Chem. Thermodyn. 2013, 66, 88. doi: 10.1016/j.jct.2013.06.008 doi: 10.1016/j.jct.2013.06.008
      

  33. [33]

      Liu, Q. S.; Liu, J.; Liu, X. X.; Zhang, S. T. J. Chem. Thermodyn. 2015, 90, 39. doi: 10.1016/j.jct.2015.06.010 doi: 10.1016/j.jct.2015.06.010
      

  34. [34]

      Liu, Q. S.; Li, P. P.; Welz-Biermann, U.; Liu, X. X.; Chen, J. J. Chem. Eng. Data 2012, 57, 2999. doi: 10.1021/je3004645 doi: 10.1021/je3004645
      

  35. [35]

      Vila, J.; Ginés, P.; Pico, J. M.; Franjo, C.; Jiménez, E.; Varela, L. M.; Cabeza, O. Fluid Phase Equilib. 2006, 242, 141. doi: 10.1016/j.uid.2006.01.022 doi: 10.1016/j.uid.2006.01.022
      

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