Ionic Liquids IV. Not Just Solvents Anymore

429 Pages·2007·41.729 MB·English

by  Joan F. Brennecke, Robin D. Rogers, and Kenneth R. Seddon (Eds.)

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
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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