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Ionic Liquids IV. Not Just Solvents Anymore PDF

429 Pages·2007·41.729 MB·English
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Ionic Liquids IV In Ionic Liquids IV; Brennecke, J., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. In Ionic Liquids IV; Brennecke, J., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. ACS SYMPOSIUM SERIES 975 Ionic Liquids IV Not Just Solvents Anymore Joan F. Brennecke, Editor University of Notre Dame Robin D. Rogers, Editor The University of Alabama Kenneth R. Seddon, Editor The Queen's University of Belfast Sponsored by the Division of Industrial and Engineering Chemistry, Inc. American Chemical Society, Washington, DC In Ionic Liquids IV; Brennecke, J., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. Library of Congress Cataloging-in-Publication Data Ionic liquids IV : not just solvents anymore / Robin D. Rogers, editor, Joan F. Brennecke, editor, Kenneth R. Seddon, editor ; sponsored by the Division of Industrial and Engineering Chemistry, Inc. p. cm.—(ACS symposium series ; 975) Includes bibliographical references and index. ISBN 978-0-8412-7445-7 (alk. paper) 1. Ionic solutions—Congresses. 2. Ionic structure—Congresses. III. Solution (Chemistry)—Congresses. I. Rogers, Robin D. II. Brennecke, Joan F., 1962- III. Seddon, Kenneth R., 1959- IV. American Chemical Society. Division of Industrial and Engineering Chemistry. V. Title: Ionic liquids 4. QD540.I582 2005 546'.34—dc22 2007060813 The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48-1984. Copyright © 2007 American Chemical Society Distributed by Oxford University Press All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $36.50 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Ionic Liquids IV; Brennecke, J., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. Table of Contents Table of Contents................................................................... i Foreword................................................................................. x Preface.................................................................................... xi Analysis and Environment.................................................... 1 1 How to Analyze Imidazolium Ionic Liquids in Environmental Samples?...................................................... 2 Introduction........................................................................ 3 Analysis of Ionic Liquids By Liquid Chromatography......... 3 Analysis of Ionic Liquids By Capillary Electrophoresis...... 6 Solid Phase Extraction of Ionic Liquids From Environmental Samples..................................................... 7 Conclusions....................................................................... 8 Acknowledgement............................................................. 9 References........................................................................ 9 2 Potential Environmental Impact of Imidazolium Ionic Liquids.................................................................................... 10 Introduction........................................................................ 11 Molecular Interaction Potential of Ionic Liquid Cations in Environmental Systems..................................................... 12 Sorption and Stability of Ionic Liquids In the Environment...................................................................... 13 Lipophilicity and Ecotoxicology of Ionic Liquids................. 16 Conclusions....................................................................... 18 Acknowledgement............................................................. 19 References........................................................................ 19 3 13C NMR Relaxation Studies of Ionic Liquids.................. 21 NMR measurements.......................................................... 22 Methodology...................................................................... 22 13C NMR relaxation studies....................................... 22 Nuclear Overhauser effect.......................................... 23 Spectral densities........................................................ 23 Chemical shift anisotropy (CSA) ............................... 23 CSA in aliphatic carbons............................................. 24 Solution of the Combined Dipolar and NOE equations..................................................................... 24 Chemical shift anisotropy (CSA) ............................... 25 Basic Assumptions...................................................... 26 Sources of Error.......................................................... 26 Common sources of error in NMR relaxation analysis....................................................................... 26 Analysis of the [EMIM]BSO3 ionic liquid........................... 27 NMR relaxation measurements................................... 27 Sample analysis................................................................ 27 13C total relaxation rates for [EMIM] cation and butanesulfonate anion................................................. 28 13C correlation times for [EMIM] cation and butanesulfonate anion................................................. 28 Evidence of CSA in Both Cation and Anion of [EMIM|BSO3............................................................... 29 Evidence of phase changes from viscosity and NMR data............................................................................. 31 NMR correlation time relationship with viscosity......... 32 Acknowledgments............................................................. 32 References........................................................................ 33 4 Ionic Liquids for Silica Modification: Assessment by Capillary Zone Electrophoresis............................................ 35 Introduction........................................................................ 35 Experimental...................................................................... 37 Apparatus.................................................................... 37 Experimental conditions.............................................. 38 Reagents..................................................................... 38 Capillary coating procedure........................................ 38 Results and Discussion..................................................... 40 Surface characterization............................................. 40 Effect of IL concentration in buffer.............................. 41 Conclusion......................................................................... 45 Acknowledgements........................................................... 45 References........................................................................ 45 5 Characterization of Phosphonium Ionic Liquids with Emphasis on Mass Spectrometry and Chromatography... 47 Introduction........................................................................ 47 Phosphonium Ionic Liquids................................................ 48 General Characterization Techniques............................... 49 TGA............................................................................. 49 31P NMR spectroscopy.............................................. 52 Other Traditional Characterization Techniques........... 52 Mass Spectrometry and Chromatographic Techniques.... 52 Objectives................................................................... 52 Mass Spectrometry of Phosphonium ILs.................... 55 Cluster Ions................................................................. 55 Chromatography of Phosphonium ILs......................... 58 Mobile Phase for HPLC............................................... 58 Sensitivity and Linearity of LC/MS.............................. 61 Identification of IL Anions from MS Cluster Ion........... 61 Residual Chloride Analysis......................................... 63 Conclusion......................................................................... 63 Experimental...................................................................... 66 Instruments................................................................. 66 Chromatographic conditions....................................... 66 References........................................................................ 67 Theory..................................................................................... 69 6 Force Field Refinement and Molecular Simulations of Imidazolium-Based Ionic Liquids......................................... 70 1. Introduction.................................................................... 70 2. Force Field Development.............................................. 71 2.1 All-atom (AA) force field ...................................... 71 2.2 United-atom (UA) force field ................................ 73 3. Molecular Dynamics Simulations................................... 75 3.1 Pure ionic liquids................................................... 76 3.1.1 Densities...................................................... 76 3.1.2 Inter-molecular Energies............................. 76 3.2 Mixtures of [bmim][BF4] and acetonitrile (CH3CN) ................................................................... 79 3.2.1 Excess volumetric and energetic properties.............................................................. 79 3.2.2 Viscosities.................................................... 79 3.2.3 Microscopic structures................................. 82 4. Conclusions................................................................... 82 Acknowledgements........................................................... 82 References........................................................................ 85 7 Intra- and Intermodular Structure of Ionic Liquids: From Conformers to Nanostructures................................... 86 Introduction........................................................................ 87 Conformational distributions of imidazolium cations in the liquid phase................................................................. 87 Nanometer-scale structures in ionic liquids....................... 93 Solvation structure of nonpolar, polar and associating solutes............................................................................... 97 Conclusion......................................................................... 99 References........................................................................101 8 Molecular Simulation of Mixtures Containing Imidazolium- and Pyridinium-Based Ionic Liquids and 1-Butanol.................................................................................102 Introduction........................................................................103 Methodology......................................................................103 Results and Discussion.....................................................106 Densities.....................................................................106 Fluid Structure and Local Composition.......................106 Mixtures with the [BF4] anion......................................107 Mixtures with the [Tf2N] anion.....................................115 Diffusion......................................................................121 Conclusions.......................................................................123 Acknowledgements...........................................................124 References........................................................................124 Applications............................................................................126 9 Carbonylation in Ionic Liquids Using Vapor-Takeoff Reactors..................................................................................128 Development of Vapor Take-off Reactors with Ionic Liquids...............................................................................129 Conclusions.......................................................................135 Experimental......................................................................136 Materials......................................................................136 Carbonylation reactions..............................................136 References........................................................................137 10 Ionic Liquids for Space Propulsion.................................138 Introduction........................................................................139 Space Propulsion..............................................................140 Space Propulsion Missions.........................................140 Space Propulsion Performance Parameters...............141 Electric Propulsion......................................................142 Discharge-Free Electric Thrusters: Electrospray Thrusters.....................................................................144 Electrohydrodynamics of Taylor Cones.............................147 Mass Spectrometry Measurements of Ions Field Evaporated from Ionic Liquids...........................................150 Mass Spectrometric Experiment.................................150 [Emim][BF4]................................................................151 [Emim][lm]...................................................................152 [Emim][NO3]................................................................157 Conclusions.......................................................................158 Acknowledgments.............................................................159 References........................................................................159 11 Columnar Liquid Crystalline Imidazolium Salts: Self-Organized One-Dimensional Ion Conductors..............161 Introduction........................................................................162 Results and Discussion.....................................................163 Synthesis and Liquid Crystalline Properties................163 Macroscopic Alignment of the Columns......................166 Anisotropic Ionic Conductivities of Columnar Ionic Liquids (31) ...............................................................166 Conclusion.........................................................................168 Acknowledgements...........................................................169 References........................................................................169 12 Ionic Liquids as Versatile Media in Lanthanide Chemistry................................................................................172 Trivalent lanthanides in ionic liquids - structural Trivalent lanthanides in ionic liquids - structural characterizations...............................................................173 Optical Properties of Lanthanides in Ionic Liquids.............176 Low Valent Lanthanides in Ionic Liquids...........................179 Acknowledgements...........................................................182 References........................................................................183 13 Electropolishing and Electroplating of Metals Using Ionic Liquids Based on Choline Chloride............................186 Introduction........................................................................187 Experimental......................................................................187 Results and Discussion.....................................................188 Electropolishing...........................................................188 Electroplating of Alloys......................................................192 Conclusions.......................................................................196 Acknowledgements...........................................................196 References........................................................................196 14 Ionic Liquids as Vehicles for Reactions and Separations.............................................................................198 Experimental......................................................................199 Nucleophilic Substitution Reactions............................199 Physical Property Measurements...............................200 Results and Discussion.....................................................201 Nucleophilic Substitution Reactions............................201 Physical Property Measurements...............................203 Microviscosity using a fluorescent molecular rotor......204 Local dielectric using a fluorescent molecular rotor....206 Reversible ionic liquids................................................208 Conclusions.......................................................................209 References........................................................................210 15 Mesoscopic Dye Sensitized Solar Cells Using Hydrophobic Ionic Liquid Electrolyte..................................212 Introduction........................................................................213 Experimental......................................................................213 Results and Discussion.....................................................214 Conclusions.......................................................................218 Acknowledgement.............................................................218 References........................................................................218 16 The Application of Trialkyl-Imidazolium Ionic Liquids and Salts for the Preparation of Polymer-Clay Nanocomposites....................................................................220 Introduction........................................................................221 Experimental*....................................................................225 Materials......................................................................225 Instrumentation...........................................................225 Results and Discussion.....................................................226 Imidazolium treated layered silicates..........................226

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