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Ionic Liquid Materials As Gas Chromatography Stationary Phases and Sorbent Coatings

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Ionic Liquid Materials As Gas Chromatography Stationary Phases and Sorbent Coatings A Dissertation entitled Ionic Liquid Materials as Gas Chromatography Stationary Phases and Sorbent Coatings in Solid-Phase Microextraction by Qichao Zhao Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Chemistry Dr. Jared L. Anderson, Committee Chair Dr. Jon R. Kirchhoff, Committee Member Dr. Xiche Hu, Committee Member Dr. Maria R. Coleman, Committee Member Dr. Patricia R. Komuniecki, Dean College of Graduate Studies The University of Toledo December 2011 Copyright 2011, Qichao Zhao This document is copyrighted material. Under copyright law, no parts of this document may be reproduced without the expressed permission of the author ii An Abstract of Ionic Liquid Materials as Gas Chromatography Stationary Phases and Sorbent Coatings in Solid-Phase Microextraction by Qichao Zhao Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Chemistry The University of Toledo December 2011 Ionic liquids (ILs) are a class of molten salts with melting points below 100 °C. Their unique properties including high thermal stability, wide viscosity range, negligible vapor pressure under room temperature, and the capability of undergoing multiple solvation interactions make them ideal candidates as gas chromatography (GC) stationary phases and sorbent coatings in solid-phase microextraction (SPME). The first part of this dissertation includes an introduction of ionic liquids and their applications as GC stationary phases. The following chapters in this part introduce various example of utilizing ILs as GC stationary phases. Functionalized ILs containing different functional groups and tris(pentafluoroethyl)trifluorophosphate (FAP) anion have been characterized using the solvation parameter model and applied as selective GC stationary phases. A total of fifteen ILs are examined on the basis of multiple solvation interactions. The effect of cation functional group, cation type, and counter anion has been thoroughly evaluated. The binary mixtures iii consisting of two PILs have been employed as highly selective GC stationary phases. The effects of PIL composition on the bleed temperature, system constants, and separation selectivity are examined. PILs have been proven to be an ideal class of SPME sorbent coatings with promising thermal stability, extraction efficiency, and selectivity. The second part of this dissertation begins with an introduction of the application of ILs and PILs as sorbent coatings in SPME. Two chapters are then presented describing the design, synthesis, and application of two different types of PILs as sorbent coatings in SPME for the selective extraction of CO2. The presence of functional groups within the PILs results in different mechanism of CO2 capture. The analytical performances of the PIL fibers are evaluated and compared to that of the commercial fibers. The PIL-fibers and a selected commercial fiber are applied for the selective extraction of CO2 from simulated flue gas. The effects of humidity and temperature on the performance of different SPME fibers are discussed. The PIL-fiber exhibits superior CO2/CH4 and CO2/N2 selectivity to that of the commercial fiber. The final chapter introduces the development of a rapid and convenient analytical method for monitoring the enantiomeric purity of chiral molecules in IL-solvents, using headspace SPME coupled to chiral GC. Two commercial fibers as well as a PIL-based fiber are examined, and the analytical performance of the developed method is thoroughly evaluated. The developed method is successfully applied to the enantiomeric excess determination from selected mixtures of chiral molecules. iv This dissertation is dedicated to my parents: Quansheng Zhao and Minmin Wang for their love, endless support and encouragement Acknowledgments First and foremost, I would like to express my sincere gratitude to my advisor, Dr. Jared L. Anderson, for his guidance, understanding, and patience. He has taught me how good experimental chemistry is done, as well as enlightened how to think logically and execute efficiently. It is my great fortune to be one of his students. For everything you have done for me, Dr. Anderson, thank you. I would like to acknowledge my committee members, Dr. Kirchhoff, Dr. Hu, and Dr. Coleman for all the helps and suggestions. I would like to also thank all my previous and current labmates, Dr. Yao, Fei, Quinner, Dr. Meng, William, Christa, Leah, Pamela, Manish, Tianhao, Tien, Honglian, as well as Dr. Li from Dr. Coleman’s lab. I am grateful to the University of Toledo, Department of Chemistry for giving me the opportunity to pursue my graduate studies here. Finally, and most importantly, I would like to thank my parents and other family members, as well as all my friends, including that little kitty who stayed with me for a short but memorable time. I am heavily indebted to them for everything they did for me, the time they spent with me and their faith in me. This dissertation would not have been possible without their support, encourage, and love. vi Contents Abstract iii Acknowledgments vi Contents vii List of Tables \ xv List of Figures xix 1 Overview: Application of Ionic Liquids as Gas Chromatography Stationary Phases 1 1.1 Introduction 1 1.2 Description of Ionic Liquids and Their Advantages When Used as Gas Chromatography Stationary Phases 2 1.3 General Chemometric and Solvation Models for Gas Chromatography 4 1.3.1 Kovats retention index system 4 1.3.2 Rohrschneider–McReynolds system 5 1.3.3 Abraham’s solvation parameter model 6 vii 1.4 Application of Ionic Liquids as GC Stationary Phases 8 1.4.1 Application of monomeric ionic liquids as GC stationary phases 8 1.4.2 Application of dicationic and tricationic ionic liquids as GC stationary phases 9 1.4.3 Application of polymeric ionic liquids as GC stationary phases \ 11 1.4.4 Application of ionic liquid mixtures as GC stationary phases 12 1.4.5 Application of functionalized ionic liquids as GC stationary phases 13 1.4.6 Application of ionic liquids as chiral GC stationary phases 15 1.5 Summary 16 2 Using the Solvation Parameter Model to Characterize Functionalized Ionic Liquids Containing the Tris(pentafluoroethyl)trifluorophosphate (FAP) Anion 18 Abstract 18 2.1 Introduction 19 2.2 Experimental 22 2.2.1 Materials 22 2.2.2 Methods 24 2.3 Results and Discussion 25 2.3.1 Effects of cation functional group on system constants 31 2.3.2 Effects of cation type on system constants 32 viii 2.3.3 Anion effect on system constants 33 2.3.4 Effect of IL stationary-phase composition on retention behavior for selected solute molecules 36 2.3.5 Effect of IL stationary-phase composition on separation selectivity for selected solutes 39 2.4 Conclusions 41 Acknowledgements 44 References 44 3 Evaluating the Solvation Properties of Functionalized Ionic Liquids with Varied Cation/Anion Composition Using the Solvation Parameter Model 47 Abstract 47 3.1 Introduction 48 3.2 Experimental 51 3.2.1 Materials 51 3.2.2 Methods 53 3.3 Results and Discussion 54 3.3.1 Effects of cation functional group on system constants 63 3.3.2 Effects of cation type on system constants 64 3.3.3 Effects of anion on system constants 65 ix 3.3.4 Effect of IL stationary phase composition on solute molecule retention behavior 66 3.3.5 Effect of IL stationary-phase composition on solute pair separation selectivity 71 3.4 Conclusions 77 Acknowledgements 79 References 80 4 Highly Selective GC Stationary Phases Consisting of Binary Mixtures of Polymeric Ionic Liquids 82 Abstract 82 4.1 Introduction 83 4.2 Experimental 86 4.2.1 Materials 86 4.2.2 Methods 87 4.3 Results and Discussion 90 4.3.1 Measurement of column bleed temperature 90 4.3.2 System constants of neat and mixed PIL stationary phases 94 4.3.3 Effects of PIL stationary phase composition on retention behavior of selected solute molecules 99 4.3.4 Effect of PIL stationary-phase composition on separation selectivity for x selected solute pairs 103 4.4 Concluding Remarks 107 Acknowledgements 108 References 109 5 Overview: Application of Ionic Liquids as Sorbent Coatings in Solid-Phase Microextraction 113 5.1 Introduction 113 5.2 Application of Ionic Liquids as Sorbent Coatings in SPME 114 5.2.1 Physically coated IL-based SPME sorbent coatings 114 5.2.2 Chemically bonded IL-based SPME sorbent coatings 119 5.2.3 PIL-based SPME sorbent coatings 121 5.2.4 Task-specific IL- and PIL-based SPME sorbent coatings 123 5.2.5 IL-mediated SPME sorbent coatings 125 5.3 Summary 126 6 Polymeric Ionic Liquids as CO2 Selective Sorbent Coatings for Solid-Phase Microextraction 128 Abstract 128 6.1 Introduction 129 6.2 Experimental 132 xi 6.2.1 Materials 132 6.2.2 Methods 133 6.3 Results and Discussion 140 6.3.1 Design of PIL-based sorbent coatings 140 6.3.2 Sorption-time profiles 142 6.3.3 Analytical performance 146 6.3.4 Sorbate storage capacity 150 6.4 Concluding Remarks 152 Acknowledgements 153 7 Selective Extraction of CO2 from Simulated Flue Gas Using Polymeric Ionic Liquid Sorbent Coatings in Solid-Phase Microextraction 157 Abstract 157 7.1 Introduction 158 7.2 Experimental 162 7.2.1 Materials 162 7.2.2 Methods 163 7.3 Results and Discussion 167 7.3.1 Effects of water on the extraction of CO2 167 7.3.2 Effects of temperature on the extraction of CO2 169 7.3.3 Selectivity of the PIL-based and Carboxen fibers for CH4 and N2 171 xii 7.4 Conclusions 178 Acknowledgements 179 References 179 8 A Rapid Analytical Method for Monitoring the Enantiomeric Purity of Chiral Molecules Synthesized in Ionic Liquid Solvents 181 Abstract 181 8.1 Introduction 182 8.2 Experimental 186 8.2.1 Chemicals and materials 186 8.2.2 Synthesis of BMIM-NTf2 and poly(VHIM-NTf2) 188 8.2.3 Preparation of PIL-based SPME fiber 189 8.2.4 Extraction of chiral molecules 189 8.2.5 “On-fiber” SPME derivatization 190 8.2.6 Chiral GC separation 191 8.3 Results and Discussion 192 8.3.1 Description of the SPME-GC method 192 8.3.2 Generation of Sorption-Time Profiles 192 8.3.3 Evaluation of Method Performance 194 8.3.4 Determination of enantiomeric excess 201 8.3.5 “On-fiber” SPME derivatization 203 xiii 8.4 Conclusions 206 Acknowledgements 207 References 208 9 Summary 212 References 216 Appendix A.
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