Study on Solution Enthalpies of Ionic Liquids [Cnmim][H2PO4] (n= 3, 4, 5, 6) by Using Pitzer's Equation

Citation: HU Zhinan, ZUO Jiantao, XIA Meichen, FANG Dawei, ZANG Shuliang. Study on Solution Enthalpies of Ionic Liquids [C_nmim][H₂PO₄] (n= 3, 4, 5, 6) by Using Pitzer's Equation[J]. Acta Physico-Chimica Sinica, 2018, 34(8): 933-937. doi: 10.3866/PKU.WHXB201801221 shu

Pitzer方程应用于离子液体[C_nmim][H₂PO₄](n= 3, 4, 5, 6)溶解焓研究

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辽宁省稀散元素重点实验室，辽宁大学化学院，沈阳 110036

通讯作者: 房大维, davidfine@163.com
臧树良, slzang@lnu.edu.cn

基金项目:
国家自然科学基金 21673107

国家自然科学基金(21673107, 21703090, 21471073, 21373005)资助项目

国家自然科学基金 21703090

国家自然科学基金 21471073

国家自然科学基金 21373005

摘要: 在298.15 K下，利用等温环境溶解反应热量计，测定了离子液体[C_nmim][H₂PO₄] (n= 3, 4, 5, 6) (1-烷基-3-甲基咪唑磷酸盐)在水中不同浓度的摩尔溶解热(Δ_solH_m)，根据Pitzer电解质溶液理论计算得到了标准摩尔溶解焓(Δ_solH_m⁰)和Pitzer焓参数：β_MX^(0)L, β_MX^(1)L, 和C^ϕL，并计算了表观相对摩尔焓。通过推导讨论，得到了离子液体[C_nmim][H₂PO₄](n= 3, 4, 5, 6)同系物每摩尔亚甲基对标准摩尔溶解焓的贡献。

关键词:

English

Study on Solution Enthalpies of Ionic Liquids [C_nmim][H₂PO₄] (n= 3, 4, 5, 6) by Using Pitzer's Equation

Key Laboratory of Rare and Scattered Elements, College of Chemistry, Liaoning University, Shenyang 110036, P. R. China

Corresponding author: FANG Dawei, davidfine@163.com ZANG Shuliang, slzang@lnu.edu.cn

Received Date: 03 January 2018
Accepted Date: 17 January 2018
Revised Date: 17 January 2018
Available Online: 15 August 2018
Fund Project:

This project was supported by the National Natural Science Foundation of China (21673107, 21703090, 21471073, 21373005)

Abstract: Ionic liquids (ILs) have become one of the most rapidly growing new research areas of ionic liquid and have attracted considerable attention from industry and the academic community since they are derived from natural ions and are heralded a new "natural ILs" or "bio-ILs". ILs can be expected to find application in all of the biological, medical, and pharmaceutical sciences. However, the fundamental physical properties of an IL are extremely important in determining if a particular IL is appropriate for a given application. Recently, there is a developing trend in the literature towards estimation of thermodynamic properties for IL's, which is to be commended because it provides valuable insight into the origins of the behaviour of ILs. Acidic ionic liquids have been applied in desulfuration process widely. Phosphoric acid IL is one kind of acidic ILs, which are also stable and economical efficiency. ILs [C_nmim][H₂PO₄] (n= 3, 4, 5, 6; 1-alkyl-3-methylimidazolium phosphonate) were synthesized and characterized. An on-line solution-reaction isoperibol calorimeter was constructed. It consists of a water thermostat, a 200 mL pyrex-glass plated silver Dewar, a 4 mL glass sample cell, a calibration heater, a glass-sheathed thermistor probe, an amplifier, a circuit used as an A/D converter and a personal computer for data acquisition and processing. The performance and accuracy of the calorimetric system was tested by measuring the molar enthalpy of solution of KCl in water and THAM [tris-(hydroxymethyl) aminomethane] in 0.1 mol∙dm⁻³ HCl(aq) at 298.15 K. The molar enthalpies of solutions of the ILs [C_nmim][H₂PO₄] (n= 3, 4, 5, 6) at various molalities in water were measured by using a solution-reaction isoperibol calorimeter at 298.15 K respectively. According to the Pitzer's electrolyte solution theory, the molar standard enthalpy of the solution of [C_nmim][H₂PO₄] (n = 3, 4, 5, 6), Δ_solH_m⁰, and Pitzer's parameters, β_MX^(0)L, β_MX^(1)L, and C_MX^ϕ, were calculated and deduced. The standard molar enthalpies of solution of [C_nmim][H₂PO₄] (n = 3, 4, 5, 6) decreases with increasing alkyl chain length. When we make a plot with the standard molar enthalpy of solution vs carbon number in alkyl chains of the ionic liquid, a straight line was obtained with a correlation coefficient 0.99 and a slope of 1.54. The mean contribution per methylene (―CH₂―) group to the standard molar enthalpies of the solution of [C_nmim][H₂PO₄] (n = 3, 4, 5, 6) was then obtained, which will give reliable estimation of other IL properties.

Key words:

1. [1]
  Wilkes, J. S. Green Chem. 2002, 4, 73. doi: 10.1039/b110838g
2. [2]
  Dupont, J.; Suarez, P. A. Z. Phys. Chem. Chem. Phys. 2006, 8, 2441. doi: 10.1039/B602046A
3. [3]
  Archer, D. G.; Widegren, J. A.; Kirklin, D. R.; Magee, J. W. J. Chem. Eng. 2005, 50, 1484. doi: 10.1021/je050136i
4. [4]
  Wang, J.; Pei, Y.; Zhao, Y.; Hu, Z. Green Chem. 2005, 7, 196.doi: 10.1039/B415842C
5. [5]
  佟静, 屈晔, 井立强, 刘璐, 刘春辉.物理化学学报, 2018, 34(2), 194. doi: 10.3866/PKU.WHXB201707262Tong, J.; Qu, Y.; Jing, L.; Liu, L.; Liu, C.Acta Phys. -Chim. Sin. 2018, 34(2), 194. doi: 10.3866/PKU.WHXB201707262
6. [6]
  关伟, 李垒, 王恒, 许维国, 杨家振.高等学校化学学报, 2006, 27, 310. doi: 0251-0790(2006)02-0310-04Guan, W.; Li, L.; Wang, H.; Xu, W. G.; Yang, J. Z. Chem. J. Chin. Univ. 2006, 27, 310.
7. [7]
  Yang, J. Z.; Lu, X. M.; Gui, J. S.; Xu, W. G. Green Chem. 2004, 6, 541. doi: 10.1039/B412286K
8. [8]
  Guan, W.; Yang, J. Z.; Li, L.; Wang, H.; Zhang, Q. G. Fluid Phase Equilib. 2006, 239, 161. doi: 10.1016/j.fluid.2005.11.015
9. [9]
  Yang, J. Z.; Zhang, Z. H.; Fang, D. W.; Li, J. G.; Guan, W.; Tong, J. Fluid Phase Equilib. 2006, 247, 80.doi: 10.1016/j.fluid.2006.06.016
10. [10]
  Guan, W.; Wang, H.; Li, L.; Zhang, Q. G.; Yang, J. Z. Thermochim. Acta 2005, 437, 196. doi: 10.1016/j.tca.2005.04.032
11. [11]
  Di, Y. Y.; Qu, S. S.; Liu, Y.; Wen, D. C.; Tang, H. K.; Li, L. W. Thermochim. Acta 2002, 387, 115.doi: 10.1016/S0040-6031(01)00831-0
12. [12]
  Yu, G.; Liu, Y.; Tan, Z. C.; Dong, J. X.; Zou, T. J; Huang, X. M.; Qu, S. S. Thermochim. Acta 2003, 401, 217.doi: 10.1016/S0040-6031(02)00566-X
13. [13]
  Fang, D. W.; Wang, H.; Yue, S.; Xiong, Y.; Yang, J. Z.; Zang, S. L. J. Phys. Chem.. 2012, 116, 2513. doi: 10.1021/jp2111132
14. [14]
  Rychly, R.; Pekarek, V. T. J. Chem. Thermodyn. 1977, 9, 391.doi: 10.1016/0021-9614(77)90060-X
15. [15]
  Montgomery, R. L.; Melaugh, R. A.; Lau, C. C.; Meier, G. H.; Chan, H. H.; Rossini, F. D. J. Chem. Thermodyn. 1977, 9, 915.doi: 10.1016/0021-9614[77]90214-2
16. [16]
  汪存信, 宋昭华, 熊文高, 屈松生.物理化学学报, 1991, 7, 586. doi: 10.3866/PKU.WHXB19910514Wang, C.; Song, S.; Xiong, W.; Qu, S. Acta Phys. -Chim. Sin. 1991, 7, 586. doi: 10.3866/PKU.WHXB19910514
17. [17]
  Pitzer, K. S. Activity Coefficients in Electrolyte Solutions, 2nd ed.; Pitzer, K. S., Ed.; CRC: Boca Raton, FL, USA, 1991; Chapter 3.
18. [18]
  Yang, J. Z.; Guan, W.; Tong, J.; Wang, H.; Li, L. J. Solution Chem. 2006, 3.(6), 845. doi: 10.1007/s10953-006-9028-y
19. [19]
  郑其格, 刘惠, 夏泉, 刘青山, 牟林.物理化学学报, 2017, 33, 736. doi: 10.3866/PKU.WHXB201612293Zheng, Q. G, ; Liu, H.; Xia, Q.; Liu, Q. S.; Mou, L. Acta Phys. -Chim. Sin. 2017, 33, 736. doi: 10.3866/PKU.WHXB201612293
20. [20]
  佟静, 刘璐, 张朵, 郑煦, 陈霞, 杨家振.物理化学学报, 2018, 34, 194. doi: 10.3866/PKU.WHXB201707262Tong, J.; Qu, Y.; Jing, L. Q.; Liu, L.; Liu, C. H. Acta Phys. -Chim. Sin. 2018, 34, 194. doi: 10.3866/PKU.WHXB201707262
21. [21]
  吴阳, 岳丽丽, 刘巧珍, 王霞.物理化学学报, 2016, 32, 1960. doi: 10.3866/PKU.WHXB201605123Wu, Y.; Yue, L. L.; Liu, Q. Z.; Wang, X. Acta Phys. -Chim. Sin. 2016, 32, 1960. doi: 10.3866/PKU.WHXB201605123
22. [22]
  佟静, 陈腾飞, 张朵, 王林富, 佟健, 杨家振.物理化学学报, 2016, 32, 1161.doi: 10.3866/PKU.WHXB201602232Tong, J.; Chen, T. F.; Zhang, D.; Wang, L. F.; Tong, J.; Yang, J. Z. Acta Phys. -Chim. Sin. 2016, 32, 1161. doi: 10.3866/PKU.WHXB201602232
23. [23]
  陈凤凤, 董艳, 桑晓艳, 周言, 陶瑞健.物理化学学报, 2016, 32, 605.doi: 10.3866/PKU.WHXB201512241Chen, F. F.; Dong, Y.; Sang, X. Y.; Zhou, Y.; Tao, D. J. Acta Phys. -Chim. Sin. 2016, 32, 605. doi: 10.3866/PKU.WHXB201512241
24. [24]
  郑玲, 范本汉, 卜晓雪, 潘懿, 董家新, 关伟.物理化学学报, 2015, 31, 2036. doi: 10.3866/PKU.WHXB201509111Zheng, L.; Fan, B. H.; Bu, X. X.; Pan, Y, ; Dong, J. X.; Guan, W. Acta Phys. -Chim. Sin. 2015, 31, 2036. doi: 10.3866/PKU.WHXB201509111
25. [25]
  李长平, 李琢, 邹本雪, 刘青山, 刘晓霞.物理化学学报, 2013, 29, 2157. doi: 10.3866/PKU.WHXB201307293Li, C. P.; Li, Z.; Zou, B. X.; Liu, Q. S.; Liu, X. X. Acta Phys. -Chim. Sin. 2013, 29, 2157. doi: 10.3866/PKU.WHXB201307293

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沈阳化工大学材料科学与工程学院沈阳 110142

Pitzer方程应用于离子液体[C_nmim][H₂PO₄](n= 3, 4, 5, 6)溶解焓研究

通讯作者: 房大维, davidfine@163.com
臧树良, slzang@lnu.edu.cn

English

Study on Solution Enthalpies of Ionic Liquids [C_nmim][H₂PO₄] (n= 3, 4, 5, 6) by Using Pitzer's Equation

Corresponding author: FANG Dawei, davidfine@163.com ZANG Shuliang, slzang@lnu.edu.cn

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Pitzer方程应用于离子液体[Cnmim][H2PO4](n= 3, 4, 5, 6)溶解焓研究

通讯作者: 房大维, davidfine@163.com 臧树良, slzang@lnu.edu.cn

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