Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF6- in Six Alcohols

doi:10.1016/S1004-9541(14)60056-2

Chinese Journal of Chemical Engineering ›› 2014, Vol. 22 ›› Issue (4): 435-446.DOI: 10.1016/S1004-9541(14)60056-2

• 催化、动力学与反应工程 • 上一篇下一篇

Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF₆- in Six Alcohols

何志坚^1,2, 王小敏², 姚田², 宋航², 姚舜²

1 School of Chemistry and Chemical Engineering, Mianyang Normal University, Mianyang 621000, China;
2 School of Chemical Engineering, Sichuan University, Chengdu 610065, China

收稿日期:2013-08-06 修回日期:2013-12-22 出版日期:2014-04-28 发布日期:2014-04-04
通讯作者: YAO Shun
基金资助:
Supported by the National Natural Science Foundation of China (81102344), the Scientific Research Fund of Sichuan Province Education Department (12ZA080), Mianyang Normal University for Excellent Plan Fund (QD2012A06) and the Project of Mianyang Science and Technology Bureau (10Y003-8).

Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF₆- in Six Alcohols

HE Zhijian^1,2, WANG Xiaomin², YAO Tian², SONG Hang², YAO Shun²

1 School of Chemistry and Chemical Engineering, Mianyang Normal University, Mianyang 621000, China;
2 School of Chemical Engineering, Sichuan University, Chengdu 610065, China

Received:2013-08-06 Revised:2013-12-22 Online:2014-04-28 Published:2014-04-04
Supported by:
Supported by the National Natural Science Foundation of China (81102344), the Scientific Research Fund of Sichuan Province Education Department (12ZA080), Mianyang Normal University for Excellent Plan Fund (QD2012A06) and the Project of Mianyang Science and Technology Bureau (10Y003-8).

摘要/Abstract

摘要： Four novel benzothiazolium ionic liquids with PF₆-([C₁Bth][PF₆], [C₄Bth][PF₆], [C₅Bth][PF₆] and [C₆Bth][PF₆]) were synthesized, and the rang of their melting points were determined between 358.35 K-424.05 K. The relationship of their melting points and the length of the straight alkyl chain on cation reflected ‘S' type tendency. Then, the solubilities of the four ionic liquids in six lower alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-1-propanol) were measured in the temperature rang of 253.15-383.15 K at atmospheric pressure with static analytical method, respectively. It was found that [C₆Bth][PF₆] in all investigated ionic liquids had the largest solubility in six alcohols and the solubility of [C₄Bth][PF₆] in methanol was very sensitive for temperature in 313.15-333.15 K, which was so-called "temperature-sensitivity". This feature is of great significance to their application of catalyzing reaction or extraction process, and makes the recovery and reuse of ionic liquids (ILs) become easier. Moreover, the experimental solubility data were correlated with the modified Apelblat equation and λh equation, respectively. It was found that the result of correlation using two divided temperature ranges was better than that of using the whole temperature range.

关键词: ionic liquids, benzothiazolium, alkanol, solubility, temperature-sensitivity, correlation

Abstract: Four novel benzothiazolium ionic liquids with PF₆-([C₁Bth][PF₆], [C₄Bth][PF₆], [C₅Bth][PF₆] and [C₆Bth][PF₆]) were synthesized, and the rang of their melting points were determined between 358.35 K-424.05 K. The relationship of their melting points and the length of the straight alkyl chain on cation reflected ‘S' type tendency. Then, the solubilities of the four ionic liquids in six lower alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-1-propanol) were measured in the temperature rang of 253.15-383.15 K at atmospheric pressure with static analytical method, respectively. It was found that [C₆Bth][PF₆] in all investigated ionic liquids had the largest solubility in six alcohols and the solubility of [C₄Bth][PF₆] in methanol was very sensitive for temperature in 313.15-333.15 K, which was so-called "temperature-sensitivity". This feature is of great significance to their application of catalyzing reaction or extraction process, and makes the recovery and reuse of ionic liquids (ILs) become easier. Moreover, the experimental solubility data were correlated with the modified Apelblat equation and λh equation, respectively. It was found that the result of correlation using two divided temperature ranges was better than that of using the whole temperature range.

Key words: ionic liquids, benzothiazolium, alkanol, solubility, temperature-sensitivity, correlation

何志坚, 王小敏, 姚田, 宋航, 姚舜. Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF₆- in Six Alcohols[J]. Chinese Journal of Chemical Engineering, 2014, 22(4): 435-446.

HE Zhijian, WANG Xiaomin, YAO Tian, SONG Hang, YAO Shun. Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF₆- in Six Alcohols[J]. Chin.J.Chem.Eng., 2014, 22(4): 435-446.

参考文献

1 Young, G., Nippen, F., Titterbrandt, S., Cooney, M.J., "Lipid extraction from biomass using co-solvent mixtures of ionic liquids and polar covalent molecules", J. Sep. Purif. Technol., 72 (1), 118-121 (2010).

2 Huddleston, J.G., Visse, A.E., Reiehert, W.R., Willauer, H.D., Broker, G.A., Rogers, R.D., "Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation", J. Green Chem., 3 (4), 156-164 (2001).

3 Hu, Y.S., Wang, Z.X., Huang, X.J., Chen, L.Q., "Physical and electrochemical properties of new binary room-temperature molten salt electrolyte based on LiBETI and acetamide", J. Solid State Ionics., 175 (14), 277-280 (2004).

4 Sun, J., Forsyth, M., Macfarlane, D.R., "Room-temperature molten salts based on the quaternary ammonium ion", J. Phys. Chem. B., 102 (44), 8858-8864 (1998).

5 Plechkova, N.V., Seddon, K. R., "Applications of ionic liquids in the chemical industry", J. Chem. Soc. Rev., 2008 (37), 123-150 (2008).

6 Abbott, A.P., Capper, G., Davies, D.L., Rasheed, R.K., Shikotra, P., "Selective extraction of metals from mixed oxide matrixes using choline-based ionic liquids", J. Inorg. Chem., 44 (19), 6497-6499 (2005).

7 De Los Ríos, A.P., Heández-Ferández, F.J., Lozano, L.J., Sánchez, S., Moreno, J.I., Godínez, C., "Removal of metal ions from aqueous solutions by extraction with ionic liquids", J. Chem. Eng. Data., 55 (2), 605-608 (2010).

8 Pârvulescu, V.I., Hardacre, C., "Catalysis in ionic liquids", J. Chem. Rev., 107 (6), 2615-2665 (2007).

9 Abedin, S.Z.E., Endres, F., "Electrodeposition of metals and semiconductors in air and water stable ionic liquids", J. Chem. Phys. Chem., 7 (1), 58-61 (2006).

10 Cole, A.C., Jensen, J.L., Ntai, I., Tran, K.L., Weaver, K.T., Forbes, D.C., Davis, J.H., "Novel brønsted acidic ionic liquids and their use as dual solvent catalysts", J. Am. Chem. Soc., 124 (21), 5962-5963 (2002).

11 Leng, Y., Wang, J., Zhu, D., Ren, X.Q., Ge, H.Q., Shen, L., "Heteropolyanion-based ionic liquids: reaction induced self separation catalysts for esterification", Angew. Chem., 121 (1), 174-177 (2008).

12 Zhang, W.H., Leng, Y., Zhu, D.R., Wu, Y.J., Wang, J., "Phosphotungstic acid salt of triphenyl (3-sulfopropyl)phosphonium: an efficient and reusable solid catalyst for esterification", Catal. Commun., 11 (3), 151-154 (2009).

13 Zhou, X.S., Liu, J.B., Luo, W.F., Zhang, Y.W., Song, H., "Novel brønsted-acidic ionic liquids based on benzothiazolium cations as catalysts for esterification reactions", J. Serb Chem. Soc., 76 (12), 1607-1615 (2011).

14 Li, X., Gu, Y.Q., Yang, Y., Song, H., Yao, S., "Novel brønsted-acidic ionic liquids based on benzothiazolium cations as catalysts for the acetalization reactions", J. Adv. Mater. Res., 396-398, 1969-1974 (2012).

15 Peng, Q., Zhang, Y.W., Wang, X.M., Wang, Z.D., Yao, S., Song, H., "Synthesis of novel ionic liquid with benzothiazolium and research on their physical chemical property", Chin. J. Synth. Chem., 20 (1), 28-31( 2012).

16 Long, B.W., Li, J., Zhang, R.R., Li, W., "Solubility of benzoic acid in acetone, 2-propanol, acetic acid and cyclohexane: Experimental measurement and thermodynamic modeling", Fluid Phase Equilib., 297 (1), 113-120 (2010).

17 Chokradjaroen, C., Li, X.L., Tamura, K., "Mutual solubility measurements and correlations of imidazolium-based ionic liquid mixtures with alcohols", J. Chem. Thermodyn., 46, 72-79 (2012).

18 Jiang, D., Wang, Y.Y., Liu J., Dai, L.L., "Structure-activity relationship and essential rule of the structure and melting point of imidazolium ionic liquids", Chem., 70 (5), 371-375 (2007).

19 Tian, G.C., Li, Y.D., Jiao, Z.L., "On the structure and properties of 1-alkyl-3-methylimidazolium hexafluorophosphates [C_nmim] PF₆ ionic liquids", Nonferr. Met. Sci. Eng., 1 (2), 3-9 (2010).

20 Gao, Y., Zhao, J.Y., "Discuss on the relationship between melting points of symmetric ionic liquids and molecular structure", J. Jiangsu Inst. Edu. (Nat. Sci.), 26 (3), 9-12 (2009).

21 Shi, X.H., Li, M., Zhou, C.R., "Measurement and correlation for solubility of 2-chloro-5-chloromethyl pyridine in different solvents", Chin. J. Chem. Eng., 18 (4), 654-658 (2010).

22 Li, Y., Lu, X.Y., "Solubilities of nizatidine in methanol+water, ethanol+water and #em/em#-propanol+water from 273.15 to 303.15 K*", Chin. J. Chem. Eng., 20 (5), 937-941(2012).

23 Liu, Q.S., Yao, S., Zhu, T.F., Zeng, H., Song, H., "Vapor pressure measurement and Correlation of 2-methyl-butanol acetate containing calcium chloride", Chin. J. Chem. Eng., 19 (1), 97-100 (2011).

24 Cai, S.F., Wang, L.S., Yan, G.Q., Li, Y., "Solubilities of 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate in selected solvents", Chin. J. Chem. Eng., 18 (6), 1008-1012 (2010).

25 Lu, Y.C., Lin, Q., Luo, G.S., Dai, Q.Y., "Solubility of emodin in alcohols", Chin. J. Chem. Eng., 17 (2), 251-253 (2009).

26 Apelblat, A., Manzurola, E., "Solubility of o-acetylsalicylic, 4-aminosalicylic, 3, 5-dinitrosalicylic, and p-toluic acid, and magnesium-DL-aspartate in water from T=(278 to 348) K", J. Chem. Thermodyn., 31 (1), 85-91 (1999).

27 Buchowskl, H., Kslazcak, A., Pletrzyk, S., Pletrzyk, S., "Solvent activity along a saturation line and solubility of hydrogen-bonding Solids", J. Phys. Chem., 84 (9), 975-979 (1980).

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Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF₆- in Six Alcohols

Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF₆- in Six Alcohols

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