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研究生: Asalil Mustain
Asalil - Mustain
論文名稱: 由生物相容緩衝劑衍生之新型離子液體的合成與熱物性質研究
New Ionic Liquids Derived from Biological Buffers: Synthesis and Thermophysical Properties
指導教授: 李明哲
Ming-Jer Lee
口試委員: 林河木
Ho-Mu Lin
李夢輝
Meng-Hui Li
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2013
畢業學年度: 101
語文別: 英文
論文頁數: 119
中文關鍵詞: Ionic LiquidsBiological BuffersSynthesisThermophysical Properties
外文關鍵詞: Ionic Liquids, Biological Buffers, Synthesis, Thermophysical Properties
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  • Two new ionic liquids derived from biological buffers, N-(2-hydroxyethyl)piperazine-N′-(3-propanesulfonic acid) (EPPS) or 3-(cyclohexylamino)-1-propanesulfonic acid (CAPS), with tetramethylammonium hydroxide (TMA) have been synthesized by simple acid-base neutralization method. The molecular structures of these two ionic liquids, [TMA][EPPS] and [TMA][CAPS], were confirmed by using nuclear magnetic resonance (NMR) analysis. The thermal stabilities and the melting points of the ionic liquids were determined by using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques, respectively. Water contents in the prepared ionic liquids were measured with Karl Fischer titration.
    The physical properties, including density, thermal expansion, apparent molar volume, solubility, viscosity, conductivity, and molar conductivity, of the binary ionic solutions of [TMA][EPPS] and [TMA][CAPS] with water or organic solvents have been determined over wide temperature and concentration ranges under atmospheric pressure. Several correlated equations as a function of temperature or concentration were used to fit the physical properties data which are a polynomial equation for density, the Vogel-Fulcher-Tammann equation for viscosity, the Casteel-Amis equation for conductivity, and the Debye-Hückel-Onsager equation for molar conductivity. In addition, the Walden plot was used to represent the ionicity of ionic liquids. These two new ionic liquids were found to be soluble in water and in organic solvents, such as methanol and ethanol. As a consequence, these two new ionic liquids could be applied to broad applications in which the systems containing either water or organic solvents.


    Two new ionic liquids derived from biological buffers, N-(2-hydroxyethyl)piperazine-N′-(3-propanesulfonic acid) (EPPS) or 3-(cyclohexylamino)-1-propanesulfonic acid (CAPS), with tetramethylammonium hydroxide (TMA) have been synthesized by simple acid-base neutralization method. The molecular structures of these two ionic liquids, [TMA][EPPS] and [TMA][CAPS], were confirmed by using nuclear magnetic resonance (NMR) analysis. The thermal stabilities and the melting points of the ionic liquids were determined by using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques, respectively. Water contents in the prepared ionic liquids were measured with Karl Fischer titration.
    The physical properties, including density, thermal expansion, apparent molar volume, solubility, viscosity, conductivity, and molar conductivity, of the binary ionic solutions of [TMA][EPPS] and [TMA][CAPS] with water or organic solvents have been determined over wide temperature and concentration ranges under atmospheric pressure. Several correlated equations as a function of temperature or concentration were used to fit the physical properties data which are a polynomial equation for density, the Vogel-Fulcher-Tammann equation for viscosity, the Casteel-Amis equation for conductivity, and the Debye-Hückel-Onsager equation for molar conductivity. In addition, the Walden plot was used to represent the ionicity of ionic liquids. These two new ionic liquids were found to be soluble in water and in organic solvents, such as methanol and ethanol. As a consequence, these two new ionic liquids could be applied to broad applications in which the systems containing either water or organic solvents.

    Abstract i Acknowledgements iii Table of Content v List of Figures vii List of Tables xii Chapter 1. Introduction 1 1.1. Introduction 1 1.2. Previous Studies 2 1.3. Problem Statement 4 1.4. Research Objective 6 1.5. Outline 6 Chapter 2. Literature Study 7 2.1. Biological Buffers 7 2.2. Introduction of Ionic Liquids 8 2.3. Applications of Ionic Liquids 9 Chapter 3. Experimental Section 15 3.1. Materials 15 3.2. Apparatus and Procedure 16 3.2.1. Synthesis of Ionic Liquids 16 3.2.2. Analytical Techniques for Synthesized Ionic Liquids 16 3.2.3. Density 17 3.2.4. Solubility 18 3.2.5. Viscosity 19 3.2.6. Conductivity 20 Chapter 4. Results and Discussion 26 4.1. Synthesis and Characterization of Ionic Liquids 26 4.2. Density Measurement Results 28 4.3. Thermal Expansion 29 4.4. Apparent Molar Volumes 30 4.5. Solubility Measurement Results 30 4.6. Viscosity Measurement Results 32 4.7. Conductivity Measurement Results 33 4.8. Molar Conductivities 34 Chapter 5. Conclusion 103 References 105 Nomenclatures 118

    Álvarez, V.H., Mattedi, S., Martin-Pastor, M., Aznar, M., and Iglesias, M. (2010), "Synthesis and Thermophysical Properties of Two New Protic Long-Chain Ionic Liquids with the Oleate Anion", Fluid Phase Equilib., 299(1), 42-50.

    Andreatta, A.E., Arce, A., Rodil, E., and Soto, A. (2009), "Physical Properties of Binary and Ternary Mixtures of Ethyl Acetate, Ethanol, and 1-Octyl-3-methyl-imidazolium Bis(trifluoromethylsulfonyl)imide at 298.15 K", J. Chem. Eng. Data, 54(3), 1022-1028.

    Anouti, M., Timperman, L., el hilali, M., Boisset, A., and Galiano, H. (2012), "Sulfonium Bis(trifluorosulfonimide) Plastic Crystal Ionic Liquid as an Electrolyte at Elevated Temperature for High-Energy Supercapacitors", J. Phys. Chem. C, 116(17), 9412-9418.

    Arce, A., Arce, A., Rodil, E., and Soto, A. (2000), "Density, Refractive Index, and Speed of Sound for 2-Ethoxy-2-Methylbutane + Ethanol + Water at 298.15 K", J. Chem. Eng. Data, 45(4), 536-539.

    Attri, P., Venkatesu, P., Kumar, A., and Byrne, N. (2011), "A Protic Ionic Liquid Attenuates the Deleterious Actions of Urea on -Chymotrypsin", Phys. Chem. Chem. Phys., 13(38), 17023-17026.

    Bandrés, I., Alcalde, R., Lafuente, C., Atilhan, M., and Aparicio, S. (2011), "On the Viscosity of Pyridinium Based Ionic Liquids: An Experimental and Computational Study", J. Phys. Chem. B, 115(43), 12499-12513.

    Bittner, B., Wrobel, R.J., and Milchert, E. (2012), "Physical Properties of Pyridinium Ionic Liquids", J. Chem. Thermodynamics, 55, 159-165.

    Bouvy, C., Baker, G.A., Yin, H., and Dai, S. (2010), "Growth of Gold Nanosheets and Nanopolyhedra in Pyrrolidinium-Based Ionic Liquids: Investigation of the Cation Effect on the Resulting Morphologies", Cryst. Growth Des., 10(3), 1319-1322.

    Brennecke, J.F. and Gurkan, B.E. (2010), "Ionic Liquids for CO2 Capture and Emission Reduction", J. Phys. Chem. Lett., 1(24), 3459-3464.

    Calvar, N., Gómez, E., González, B., and Domínguez, A. (2010), "Experimental Vapor−Liquid Equilibria for the Ternary System Ethanol + Water + 1-Ethyl-3-methylpyridinium Ethylsulfate and the Corresponding Binary Systems at 101.3 kPa: Study of the Effect of the Cation", J. Chem. Eng. Data, 55(8), 2786-2791.

    Calvar, N., González, B., Gómez, E., and Domínguez, A. (2009), "Vapor-Liquid Equilibria for the Ternary System Ethanol + Water + 1-Butyl-3-methylimidazolium Methylsulfate and the Corresponding Binary Systems at 101.3 kPa", J. Chem. Eng. Data, 54(3), 1004-1008.

    Casteel, J.F. and Amis, E.S. (1972), "Specific Conductance of Concentrated Solutions of Magnesium Salts in Water-Ethanol System", J. Chem. Eng. Data, 17(1), 55-59.

    Clifford, G. and Campbell, J.A. (1951), "Densities in the Methanol-Water System at 25.00°", J. Am. Chem. Soc., 73(11), 5449-5449.

    Ding, M.S. (2004), "Casteel−Amis Equation: Its Extension from Univariate to Multivariate and Its Use as a Two-Parameter Function", J. Chem. Eng. Data, 49(5), 1469-1474.

    Ding, M.S. and Jow, T.R. (2003), "Conductivity and Viscosity of PC-DEC and PC-EC Solutions of LiPF6", J. Electrochem. Soc., 150(5), A620-A628.

    Döbbelin, M., Azcune, I., Bedu, M., Ruiz de Luzuriaga, A., Genua, A., Jovanovski, V., Cabañero, G., and Odriozola, I. (2012), "Synthesis of Pyrrolidinium-Based Poly(ionic liquid) Electrolytes with Poly(ethylene glycol) Side Chains", Chem. Mater., 24(9), 1583-1590.

    Domínguez, I., González, E.J., González, R., and Domínguez, A. (2011), "Extraction of Benzene from Aliphatic Compounds Using Commercial Ionic Liquids as Solvents: Study of the Liquid–Liquid Equilibrium at T = 298.15 K", J. Chem. Eng. Data, 56(8), 3376-3383.

    Dong, K., Zhang, S., Wang, D., and Yao, X. (2006), "Hydrogen Bonds in Imidazolium Ionic Liquids", J. Phys. Chem. A, 110(31), 9775-9782.

    Erdemi, H., Akbey, Ü., and Meyer, W.H. (2010), "Conductivity Behavior and Solid State NMR Investigation of Imidazolium-Based Polymeric Ionic Liquids", Solid State Ionics, 181(35-36), 1586-1595.

    Ferguson, W.J., Braunschweiger, K.I., Braunschweiger, W.R., Smith, J.R., McCormick, J.J., Wasmann, C.C., Jarvis, N.P., Bell, D.H., and Good, N.E. (1980), "Hydrogen Ion Buffers for Biological Research", Anal. Biochem., 104(2), 300-310.

    Ferreira, A.F., Simões, P.N., and Ferreira, A.G.M. (2012), "Quaternary Phosphonium-Based Ionic Liquids: Thermal Stability and Heat Capacity of the Liquid Phase", J. Chem. Thermodynamics, 45(1), 16-27.

    Ferreira, C.E., Talavera-Prieto, N.M.C., Fonseca, I.M.A., Portugal, A.T.G., and Ferreira, A.G.M. (2012), "Measurements of pVT, Viscosity, and Surface Tension of Trihexyltetradecylphosphonium Tris(pentafluoroethyl)-trifluorophosphate Ionic Liquid and Modelling with Equations of State", J. Chem. Thermodynamics, 47, 183-196.

    Forsyth, S.A., MacFarlane, D.R., Thomson, R.J., and von Itzstein, M. (2002), "Rapid, Clean, and Mild O-acetylation of Alcohols and Carbohydrates in an Ionic Liquid", Chem. Commun., 7, 714-715.

    Galiński, M., Lewandowski, A., and Stępniak, I. (2006), "Ionic Liquids as Electrolytes", Electrochim. Acta, 51(26), 5567-5580.

    García, A., Torres-González, L.C., Padmasree, K.P., Benavides-Garcia, M.G., and Sánchez, E.M. (2013), "Conductivity and Viscosity Properties of Associated Ionic Liquids Phosphonium Orthoborates", J. Mol. Liq., 178, 57-62.

    Gardas, R.L. and Coutinho, J.A.P. (2008), "A Group Contribution Method for Viscosity Estimation of Ionic Liquids", Fluid Phase Equilib., 266(1-2), 195-201.

    Ghatee, M.H., Zare, M., Zolghadr, A.R., and Moosavi, F. (2010), "Temperature Dependence of Viscosity and Relation with the Surface Tension of Ionic Liquids", Fluid Phase Equilib., 291(2), 188-194.

    Gómez, E., Calvar, N., Domínguez, Á., and Macedo, E.A. (2010), "Synthesis and Temperature Dependence of Physical Properties of Four Pyridinium-Based Ionic Liquids: Influence of the Size of the Cation", J. Chem. Thermodynamics, 42(11), 1324-1329.

    Gómez, E., Calvar, N., Macedo, E.A., and Domínguez, Á. (2012), "Effect of the Temperature on the Physical Properties of Pure 1-Propyl 3-methylimidazolium Bis(trifluoromethylsulfonyl)imide and Characterization of Its Binary Mixtures with Alcohols", J. Chem. Thermodynamics, 45(1), 9-15.

    Gong, Y.-h., Shen, C., Lu, Y.-z., Meng, H., and Li, C.-x. (2011), "Viscosity and Density Measurements for Six Binary Mixtures of Water (Methanol or Ethanol) with an Ionic Liquid ([BMIM][DMP] or [EMIM][DMP]) at Atmospheric Pressure in the Temperature Range of (293.15 to 333.15) K", J. Chem. Eng. Data, 57(1), 33-39.

    González, E.J., González, B., Calvar, N., and Domínguez, Á. (2011), "Study of [EMim][ESO4] Ionic Liquid as Solvent in the Liquid–Liquid Extraction of Xylenes from Their Mixtures with Hexane", Fluid Phase Equilib., 305(2), 227-232.

    Good, N.E., Winget, G.D., Winter, W., Connolly, T.N., Izawa, S., and Singh, R.M.M. (1966), "Hydrogen Ion Buffers for Biological Research", Biochemistry, 5(2), 467-477.

    Hwang, I.-C., Park, S.-J., and Han, K.-J. (2011), "Vapor–Liquid Equilibria at 333.15 K and Excess Molar Volumes and Deviations in Molar Refractivity at 298.15 K for Mixtures of Diisopropyl Ether, Ethanol and Ionic Liquids", Fluid Phase Equilib., 309(2), 145-150.

    Iken, H., Guillen, F., Chaumat, H., Mazières, M.-R., Plaquevent, J.-C., and Tzedakis, T. (2012), "Scalable Synthesis of Ionic Liquids: Comparison of Performances of Microstructured and Stirred Batch Reactors", Tetrahedron Lett., 53(27), 3474-3477.

    Joshi, S.S., Aminabhavi, T.M., and Shukla, S.S. (1990), "Densities and Viscosities of Binary Liquid Mixtures of Anisole with Methanol and Benzene", J. Chem. Eng. Data, 35(2), 187-189.

    Karadağ, A. and Destegül, A. (2013), "N-(2-hydroxyethyl)-ethylenediamine-Based Ionic Liquids: Synthesis, Structural Characterization, Thermal, Dielectric and Catalytic Properties", J. Mol. Liq., 177, 369-375.

    Kawai, K., Kaneko, K., and Yonezawa, T. (2011), "Hydrophilic Quaternary Ammonium Type Ionic Liquids. Systematic Study of the Relationship among Molecular Structures, Osmotic Pressures, and Water-Solubility", Langmuir, 27(12), 7353-7356.

    Kogelnig, D., Stojanovic, A., Galanski, M., Groessl, M., Jirsa, F., Krachler, R., and Keppler, B.K. (2008), "Greener Synthesis of New Ammonium Ionic Liquids and Their Potential as Extracting Agents", Tetrahedron Lett., 49(17), 2782-2785.

    Kolbeck, C., Lehmann, J., Lovelock, K.R.J., Cremer, T., Paape, N., Wasserscheid, P., Fröba, A.P., Maier, F., and Steinrück, H.P. (2010), "Density and Surface Tension of Ionic Liquids", J. Phys. Chem. B, 114(51), 17025-17036.

    Lee, J.H., Lee, J.S., Lee, J.-W., Hong, S.M., and Koo, C.M. (2013), "Ion Transport Behavior in Polymerized Imidazolium Ionic Liquids Incorporating Flexible Pendant Groups", Eur. Polym. J., 49(5), 1017-1022.

    Lee, J.-M. (2011), "Solvent Properties of Piperidinium Ionic Liquids", Chem. Eng. J., 172(2-3), 1066-1071.

    Li, Q., Sun, X., Cao, L., Wang, B., Chen, Z., and Zhang, Y. (2013), "Effect of Ionic Liquids on the Isobaric Vapor–Liquid Equilibrium Behavior of Methanol–Methyl Ethyl Ketone", J. Chem. Eng. Data, 58(5), 1133-1140.

    Li, W.-J., Han, B.-X., Tao, R.-T., Zhang, Z.-F., and Zhang, J.-L. (2007), "Measurement and Correlation of The Ionic Conductivity of Ionic Liquid-Molecular Solvent Solutions", Chin. J. Chem . 25(9), 1349-1356.

    Liu, W., Cheng, L., Zhang, Y., Wang, H., and Yu, M. (2008), "The Physical Properties of Aqueous Solution of Room-Temperature Ionic Liquids Based on Imidazolium: Database and Evaluation", J. Mol. Liq., 140(1–3), 68-72.

    Machanová, K., Boisset, A., Sedláková, Z., Anouti, M., Bendová, M., and Jacquemin, J. (2012), "Thermophysical Properties of Ammonium-Based Bis{(trifluoromethyl)sulfonyl}imide Ionic Liquids: Volumetric and Transport Properties", J. Chem. Eng. Data, 57(8), 2227-2235.

    Mikhail, S.Z. and Kimel, W.R. (1961), "Densities and Viscosities of Methanol-Water Mixtures", J. Chem. Eng. Data, 6(4), 533-537.

    Millero, F.J. (1970), "The Apparent and Partial Molal Volume of Aqueous Sodium Chloride Solutions at Various Temperatures", J. Phys. Chem., 74(2), 356-362.

    Moosbauer, D., Zugmann, S., Amereller, M., and Gores, H.J. (2010), "Effect of Ionic Liquids as Additives on Lithium Electrolytes: Conductivity, Electrochemical Stability, and Aluminum Corrosion", J. Chem. Eng. Data, 55(5), 1794-1798.

    Moreno, M., Montanino, M., Carewska, M., Appetecchi, G.B., Jeremias, S., and Passerini, S. (2013), "Water-Soluble, Triflate-Based, Pyrrolidinium Ionic Liquids", Electrochim. Acta, 99, 108-116.

    Nozaki, Y. and Tanford, C. (1963), "The Solubility of Amino Acids and Related Compounds in Aqueous Urea Solutions", J. Biol. Chem., 238(12), 4074-4081.

    Perry, R.H. and Green, D.W. (1997), Perry’s Chemical Engineers’ Handbook, 7th edition, McGraw-Hill Companies, Inc., New York.

    Paduszyński, K., Królikowski, M., and Domańska, U. (2013), "Excess Enthalpies of Mixing of Piperidinium Ionic Liquids with Short-Chain Alcohols: Measurements and PC-SAFT Modeling", J. Phys. Chem. B, 117(14), 3884-3891.

    Quijada-Maldonado, E., van der Boogaart, S., Lijbers, J.H., Meindersma, G.W., and de Haan, A.B. (2012), "Experimental Densities, Dynamic Viscosities and Surface Tensions of the Ionic Liquids Series 1-Ethyl-3-methylimidazolium Acetate and Dicyanamide and Their Binary and Ternary Mixtures with Water and Ethanol at T = (298.15 to 343.15 K)", J. Chem. Thermodynamics, 51, 51-58.

    Sakaebe, H. and Matsumoto, H. (2003), "N-Methyl-N-propylpiperidinium Bis(trifluoromethanesulfonyl)imide (PP13–TFSI) – Novel Electrolyte Base for Li Battery", Electrochem. Commun., 5(7), 594-598.

    Seki, S., Kobayashi, Y., Miyashiro, H., Ohno, Y., Mita, Y., Terada, N., Charest, P., Guerfi, A., and Zaghib, K. (2008), "Compatibility of N-Methyl-N-propylpyrrolidinium Cation Room-Temperature Ionic Liquid Electrolytes and Graphite Electrodes", J. Phys. Chem. C, 112(42), 16708-16713.

    Seoane, R.G., Gómez, E., González, E.J., and Domínguez, Á. (2012), "(Liquid +Liquid) Equilibria for the Ternary Mixtures (Alkane + Toluene + Ionic Liquid) at T = 298.15 K: Influence of the Anion on the Phase Equilibria", J. Chem. Thermodynamics, 47, 402-407.

    Shamsipur, M., Beigi, A.A.M., Teymouri, M., Pourmortazavi, S.M., and Irandoust, M. (2010), "Physical and Electrochemical Properties of Ionic Liquids 1-Ethyl-3-methylimidazolium Tetrafluoroborate, 1-Butyl-3-methylimidazolium Trifluoromethanesulfonate and 1-Butyl-1-methylpyrrolidinium bis(Trifluoromethylsulfonyl)imide", J. Mol. Liq., 157(1), 43-50.

    Sun, J., Howlett, P.C., MacFarlane, D.R., Lin, J., and Forsyth, M. (2008), "Synthesis and Physical Property Characterisation of Phosphonium Ionic Liquids Based on P(O)2(OR)2− and P(O)2(R)2− Anions with Potential Application for Corrosion Mitigation of Magnesium Alloys", Electrochim. Acta, 54(2), 254-260.

    Taha, M. and Lee, M.-J. (2010), "Buffer Interactions: Solubilities and Transfer Free Energies of TRIS, TAPS, TAPSO, and TABS from Water to Aqueous Ethanol Solutions", Fluid Phase Equilib., 289(2), 122-128.

    Thiel, T., Liczkowski, L., and Bissen, S.T. (1998), "New Zwitterionic Butanesulfonic Acids that Extend the Alkaline Range of Four Families of Good Buffers: Evaluation for Use in Biological Systems", J. Biochem. Bioph. Methods, 37(3), 117-129.

    Tseng, M.-C., Liang, Y.-M., and Chu, Y.-H. (2005), "Synthesis of Fused Tetrahydro--carbolinequinoxalinones in 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([bdmim][Tf2N]) and 1-n-butyl-2,3-dimethylimidazolium perfluorobutylsulfonate ([bdmim][PFBuSO3]) Ionic Liquids", Tetrahedron Lett., 46(36), 6131-6136.

    Wang, C., Guo, L., Li, H., Wang, Y., Weng, J., and Wu, L. (2006), "Preparation of Simple Ammonium Ionic Liquids and Their Application in the Cracking of Dialkoxypropanes", Green Chem., 8(7), 603-607.

    Wasserscheid, P. and Keim, W. (2000), "Ionic Liquids-New “Solutions” for Transition Metal Catalysis", Angew. Chem. Int. Ed., 39(21), 3772-3789.

    Wu, T.-Y., Wang, H.-C., Su, S.-G., Gung, S.-T., Lin, M.-W., and Lin, C.-B. (2010), "Characterization of Ionic Conductivity, Viscosity, Density, and Self-Diffusion Coefficient for Binary Mixtures of Polyethyleneglycol (or Polyethyleneimine) Organic Solvent with Room Temperature Ionic Liquid BMIBF4 (or BMIPF6)", J. Taiwan Inst. Chem. Eng., 41(3), 315-325.

    Yamaguchi, T., Nakahara, E., Sueda, K., and Koda, S. (2013), "Interpretation of the Variation of the Walden Product of Ionic Liquids with Different Alkyl Chain Lengths in Terms of Relaxation Spectra", J. Phys. Chem. B, 117(15), 4121-4126.

    Yue, C., Fang, D., Liu, L., and Yi, T.-F. (2011), "Synthesis and Application of Task-Specific Ionic Liquids Used as Catalysts and/or Solvents in Organic Unit Reactions", J. Mol. Liq., 163(3), 99-121.

    Zhang, Q., Liu, S., Li, Z., Li, J., Chen, Z., Wang, R., Lu, L., and Deng, Y. (2009), "Novel Cyclic Sulfonium-Based Ionic Liquids: Synthesis, Characterization, and Physicochemical Properties", Chem. Eur. J., 15(3), 765-778.

    Zhu, A., Wang, J., Han, L., and Fan, M. (2009), "Measurements and Correlation of Viscosities and Conductivities for the Mixtures of Imidazolium Ionic Liquids with Molecular Solutes", Chem. Eng. J., 147(1), 27-35.

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