Citation: FU Su-Zhen, CHEN Qing-De, SHEN Xing-Hai. Aggregation Behavior of 1-Alkyl-3-methylimidazolium Tetrafluoroborate Ionic Liquids in Aqueous Solutions[J]. Acta Physico-Chimica Sinica, ;2011, 27(08): 1913-1918. doi: 10.3866/PKU.WHXB20110713 shu

Aggregation Behavior of 1-Alkyl-3-methylimidazolium Tetrafluoroborate Ionic Liquids in Aqueous Solutions

1.
Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Received Date: 12 April 2011
Available Online: 20 May 2011
Fund Project: 国家自然科学基金(20871009) (20871009)

The aggregation behavior of 1-alkyl-3-methylimidazolium tetrafluoroborate ([Cnmim][BF₄]) ionic liquids in aqueous solutions was investigated by isothermal titration calorimetry (ITC), fluorescence quenching, and conductivity methods. The critical micelle concentration (cmc), the changes of the enthalpy (ΔH_mic), the Gibbs free energy (ΔG_mic), and the entropy (ΔS_mic) for the micelle formation and the mean aggregation number of the micelles at different concentrations were obtained. We found that entropy was the principle driving force leading to the micellization of these types of ionic liquids. The increase in alkyl chain length led to a decrease in ΔG_mic, favoring the formation of micelles. Furthermore, by combining with the aqueous solution data for [C_nmim]X (X=Cl^-, Br^-), the effect of anions on the aggregation behavior of the ionic liquids was investigated. The increase in the hydrophobicity and the volume of the anions favored the formation of micelles when the ionic liquids contained identical cations. This is believed to result from the decrease in electrostatic repulsion between the head groups in the micelles because of the relatively strong binding between the anions and the cations. With respect to [C₁₂mim][BF₄], the addition of β-cyclodextrin (β-CD) caused an increase in its cmc and a decrease in ΔH_mic and ΔS_mic; while the presence of KBF₄ caused a decrease in cmc and ΔH_mic, and an increase in ΔS_mic.
- Ionic liquids,
- 1-Alkyl-3-methylimidazolium tetrafluoroborate,
- Isothermal titration calorimetry,
- Fluorescence,
- Conductivity
1. [1]
  
  (1) Welton, T. Chem. Rev. 1999, 99, 2071.
2. [2]
  (2) Endo, T.; Kato, T.; Nishikawa, K. J. Phys. Chem. B 2010, 114, 9201.
3. [3]
  (3) Yang, Y. K.; Qiu, S. Q.; He, C. G.; He,W. J.; Yu, L. J.; Xie, X. L. Appl. Surf. Sci. 2010, 257, 1010.
4. [4]
  (4) Shokouhi, M.; Adibi, M.; Jalili, A. H.; Hosseini-Jenab, M.; Mehdizadeh, A. J. Chem. Eng. Data 2010, 55, 1663.
5. [5]
  (5) Wang, Y.; Han, J. A.; Xie, X. Q.; Li, C. X. Cent. Eur. J. Chem. 2010, 8, 1185.
6. [6]
  (6) Du, P.; Liu, S. N.;Wu, P.; Cai, C. X. Electrochim. Acta 2007, 52, 6534.
7. [7]
  (7) Qiu, Z. M.; Texter, J. Curr. Opin. Colloid Interface Sci. 2008, 13, 252.
8. [8]
  (8) Shangguan, X. D.; Tang, H. S.; Liu, R. X.; Zheng, J. B. J. Anal. Chem. 2010, 38, 1510.
9. [9]
  (9) Trombetta, F.; de Souza, M. O.; de Souza, R. F.; Martini, E. M. A. J. Appl. Electrochem. 2009, 39, 2315.
10. [10]
  (10) Dorbritz, S.; Ruth,W.; Kragl, U. Adv. Synth. Catal. 2005, 347, 1273.
11. [11]
  (11) Katayanagi, H.; Nishikorbritz, K.; Shimozaki, H.; Miki, K.; Westh, P.; Koga, Y. J. Phys. Chem. B 2004, 108, 19451.
12. [12]
  (12) Malham, I. B.; Letellier, P.; Turmine, M. J. Phys. Chem. B 2006, 110, 14212.
13. [13]
  (13) Archer, D. G.;Widegren, J. A.; Kirklin, D. R.; Magee, J.W. J. Chem. Eng. Data 2005, 50, 1484.
14. [14]
  (14) Bowers, J.; Butts, C. P.; Martin, P. J.; Vergara-Gutierrez, M. C.; Heenan, R. K. Langmuir 2004, 20, 2191.
15. [15]
  (15) Dong, B.; Li, N.; Zheng, L. Q.; Yu, L.; Inoue, T. Langmuir 2007, 23, 4178.
16. [16]
  (16) Bouchemal, K.; Agnely, F.; Koffi, A.; Djabourov, M.; Ponchel, G. J. Mol. Recognit. 2010, 23, 335.
17. [17]
  (17) Bai, G. Y.; Lopes, A.; Bastos, M. J. Chem. Thermodyn. 2008, 40, 1509.
18. [18]
  (18) Guan,W.;Wang, H.; Li, L.; Zhang, Q. G.; Yang, J. Z. Thermo. Acta 2005, 437, 196.
19. [19]
  (19) Luczak, J.; Jungnickel, C.; Joskowska, M.; Thoming, J.; Hupka, J. J. Colloid Interface Sci. 2009, 336, 111.
20. [20]
  (20) Stodghill, S. P.; Smith, A. E.; O'Haver, J. H. Langmuir 2004, 20, 11387.
21. [21]
  (21) Fang, Y.; Liu, X. F.; Xia, Y. M.; Yang, Y.; Cai, K.; Suh, J. M.; Cho, H. Y. Acta Phys. -Chim. Sin. 2001, 17, 828. [方云, 刘雪峰, 夏咏梅, 杨扬, 蔡琨, 徐廷穆, 赵宪英. 物理化学学报, 2001, 17, 828.]
22. [22]
  (22) Molina-Bolivar, J. A.; Hierrezuelo, J. M.; Ruiz, C. C. J. Colloid Interface Sci. 2007, 313, 656.
23. [23]
  (23) Vanyur, R.; Biczok, L.; Miskolczy, Z. Colloid Surf. APhysicochem. Eng. Asp. 2007, 299, 256.
24. [24]
  (24) Klevens, H. B. J. Am. Oil Chem. Soc. 1953, 30, 74.
25. [25]
  (25) Zhao, G. X. Physcal Chemistry of Surfacatants; Peking Universtity Press: Beiijing, 1991; pp 137-143. [赵国玺. 表面活性剂物理化学. 北京: 北京大学出版社, 1991: 137-143.]
26. [26]
  (26) Bouchemal, K.; Agnely, F.; Koffi, A.; Djabourov, M.; Ponchel, G. Drug Discov. Today 2008, 13, 960.
27. [27]
  (27) Tokuda, H.; Hayamizu, K.; Ishii, K.; Susan, M.;Watanabe, M. J. Phys. Chem. B 2005, 109, 6103.
28. [28]
  (28) Sehgal, P.; Sharma, M.; Larsen, K. L.;Wimmer, R.; Otzen, D. E.; Doe, H. J. Dispersion Sci. Technol. 2008, 29, 128.
29. [29]
  (29) Kresheck, G. C. J. Phys. Chem. B 2009, 113, 6732.
30. [30]
  (30) Fernandes, R. M. F.; Marques, E. F.; Silva, B. F. B.;Wang, Y. J. J. Mol. Liq. 2010, 157, 113.
31. [31]
  (31) Du, J.; Jiang, B. Y.; Xie, J. Q.; Zeng, X. C. J. Dispersion Sci. Technol. 2001, 22, 529.
32. [32]
  (32) Chandra, A. K.; Turro, N. J.; Lyons, A. L.; Stone, P. J. Am. Chem. Soc. 1978, 100, 4964.
33. [33]
  (33) Russell, J. C.;Wild, U. P.; Whitten, D. G. J. Phys. Chem. 1986, 90, 1319.
34. [34]
  (34) Wang, J. J.;Wang, H. Y.; Zhang, S. L.; Zhang, H. H.; Zhao, Y. J. Phys. Chem. B 2007, 111, 6181.
35. [35]
  (35) Hadgiivanova, R.; Diamant, H. J. Phys. Chem. B 2007, 111, 8854.
36. [36]
  (36) odchild, I.; Collier, L.; Millar, S. L.; Prokes, I.; Lord, J. C. D.; Butts, C. P.; Bowers, J.;Webster, J. R. P.; Heenan, R. K. J. Colloid Interface Sci. 2007, 307, 455.
1. [1]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
2. [2]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
3. [3]
  YanYuan Jia , Rong Rong , Jie Liu , Jing Guo , GuoYu Jiang , Shuo Guo . Unity is Strength, and Independence Shines: A Science Popularization Experiment on AIE and ACQ Effects. University Chemistry, 2024, 39(9): 349-358. doi: 10.12461/PKU.DXHX202402035
4. [4]
  Qin Li , Kexin Yang , Qinglin Yang , Xiangjin Zhu , Xiaole Han , Tao Huang . Illuminating Chlorophyll: Innovative Chemistry Popularization Experiment. University Chemistry, 2024, 39(9): 359-368. doi: 10.3866/PKU.DXHX202309059
5. [5]
  Zehua Zhang , Haitao Yu , Yanyu Qi . 多重共振TADF分子的设计策略. Acta Physico-Chimica Sinica, 2025, 41(1): 2309042-. doi: 10.3866/PKU.WHXB202309042
6. [6]
  Wenjun Zheng . Application in Inorganic Synthesis of Ionic Liquids. University Chemistry, 2024, 39(8): 163-168. doi: 10.3866/PKU.DXHX202401020
7. [7]
  Yan ZHAO , Xiaokang JIANG , Zhonghui LI , Jiaxu WANG , Hengwei ZHOU , Hai GUO . Preparation and fluorescence properties of Eu³⁺-doped CaLaGaO₄ red-emitting phosphors. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1861-1868. doi: 10.11862/CJIC.20240242
8. [8]
  Shuwen SUN , Gaofeng WANG . Two cadmium coordination polymers constructed by varying Ⅴ-shaped co-ligands: Syntheses, structures, and fluorescence properties. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 613-620. doi: 10.11862/CJIC.20230368
9. [9]
  Dongdong YANG , Jianhua XUE , Yuanyu YANG , Meixia WU , Yujia BAI , Zongxuan WANG , Qi MA . Design and synthesis of two coordination polymers for the rapid detection of ciprofloxacin based on triphenylpolycarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2466-2474. doi: 10.11862/CJIC.20240266
10. [10]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
11. [11]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
12. [12]
  Lin Song , Dourong Wang , Biao Zhang . Innovative Experimental Design and Research on Preparing Flexible Perovskite Fluorescent Gels Using 3D Printing. University Chemistry, 2024, 39(7): 337-344. doi: 10.3866/PKU.DXHX202310107
13. [13]
  Han ZHANG , Jianfeng SUN , Jinsheng LIANG . Hydrothermal synthesis and luminescent properties of broadband near-infrared Na₃CrF₆ phosphor. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 349-356. doi: 10.11862/CJIC.20240098
14. [14]
  Xuewei BA , Cheng CHENG , Huaikang ZHANG , Deqing ZHANG , Shuhua LI . Preparation and luminescent performance of Sr_1-xZrSi₂O₇∶xDy³⁺ phosphor with high thermal stability. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 357-364. doi: 10.11862/CJIC.20240096
15. [15]
  Qin Hou , Jiayi Hou , Aiju Shi , Xingliang Xu , Yuanhong Zhang , Yijing Li , Juying Hou , Yanfang Wang . Preparation of Cuprous Iodide Coordination Polymer and Fluorescent Detection of Nitrite: A Comprehensive Chemical Design Experiment. University Chemistry, 2024, 39(8): 221-229. doi: 10.3866/PKU.DXHX202312056
16. [16]
  Xinyu Liu , Weiran Hu , Zhengkai Li , Wei Ji , Xiao Ni . Algin Lab: Surging Luminescent Sea. University Chemistry, 2024, 39(5): 396-404. doi: 10.3866/PKU.DXHX202312021
17. [17]
  Yingran Liang , Fei Wang , Jiabao Sun , Hongtao Zheng , Zhenli Zhu . Construction and Application of a New Experimental Device for Determination of Alkaline Metal Elements by Plasma Atomic Emission Spectrometry Based on Solution Cathode Glow Discharge: An Alternative Approach for Fundamental Teaching Experiments in Emission Spectroscopy. University Chemistry, 2024, 39(5): 380-387. doi: 10.3866/PKU.DXHX202312024
18. [18]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
19. [19]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
20. [20]
  Siyi ZHONG , Xiaowen LIN , Jiaxin LIU , Ruyi WANG , Tao LIANG , Zhengfeng DENG , Ao ZHONG , Cuiping HAN . Targeting imaging and detection of ovarian cancer cells based on fluorescent magnetic carbon dots. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1483-1490. doi: 10.11862/CJIC.20240093

Get Citation

PDF

XML

Metrics

PDF Downloads(1164)
Abstract views(3331)
HTML views(42)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142