Ionic Liquids IV. Not Just Solvents Anymore

Cover Page......Page 1
Title Page......Page 4
ISBN 978-0841274457......Page 5
Table of Contents......Page 6
Foreword......Page 15
Preface......Page 16
Analysis and Environment......Page 21
1 How to Analyze Imidazolium Ionic Liquids in Environmental Samples?......Page 22
Analysis of Ionic Liquids By Liquid Chromatography......Page 23
Analysis of Ionic Liquids By Capillary Electrophoresis......Page 26
Solid Phase Extraction of Ionic Liquids From Environmental Samples......Page 27
Conclusions......Page 28
References......Page 29
2 Potential Environmental Impact of Imidazolium Ionic Liquids......Page 30
Introduction......Page 31
Molecular Interaction Potential of Ionic Liquid Cations in Environmental Systems......Page 32
Sorption and Stability of Ionic Liquids In the Environment......Page 33
Lipophilicity and Ecotoxicology of Ionic Liquids......Page 36
Conclusions......Page 38
References......Page 39
3 13C NMR Relaxation Studies of Ionic Liquids......Page 41
13C NMR relaxation studies......Page 42
Chemical shift anisotropy (CSA)......Page 43
Solution of the Combined Dipolar and NOE equations......Page 44
Chemical shift anisotropy (CSA)......Page 45
Common sources of error in NMR relaxation analysis......Page 46
Sample analysis......Page 47
13C correlation times for [EMIM] cation and butanesulfonate anion......Page 48
Evidence of CSA in Both Cation and Anion of [EMIM|BSO3......Page 49
Evidence of phase changes from viscosity and NMR data......Page 51
Acknowledgments......Page 52
References......Page 53
Introduction......Page 55
Apparatus......Page 57
Capillary coating procedure......Page 58
Surface characterization......Page 60
Effect of IL concentration in buffer......Page 61
References......Page 65
Introduction......Page 67
Phosphonium Ionic Liquids......Page 68
TGA......Page 69
Objectives......Page 72
Cluster Ions......Page 75
Mobile Phase for HPLC......Page 78
Identification of IL Anions from MS Cluster Ion......Page 81
Conclusion......Page 83
Chromatographic conditions......Page 86
References......Page 87
Theory......Page 89
1. Introduction......Page 90
2.1 All-atom (AA) force field......Page 91
2.2 United-atom (UA) force field......Page 93
3. Molecular Dynamics Simulations......Page 95
3.1.2 Inter-molecular Energies......Page 96
3.2.2 Viscosities......Page 99
Acknowledgements......Page 102
References......Page 105
7 Intra- and Intermodular Structure of Ionic Liquids: From Conformers to Nanostructures......Page 106
Conformational distributions of imidazolium cations in the liquid phase......Page 107
Nanometer-scale structures in ionic liquids......Page 113
Solvation structure of nonpolar, polar and associating solutes......Page 117
Conclusion......Page 119
References......Page 121
8 Molecular Simulation of Mixtures Containing Imidazolium- and Pyridinium-Based Ionic Liquids and 1-Butanol......Page 122
Methodology......Page 123
Fluid Structure and Local Composition......Page 126
Mixtures with the [BF4] anion......Page 127
Mixtures with the [Tf2N] anion......Page 135
Diffusion......Page 141
Conclusions......Page 143
References......Page 144
Applications......Page 146
9 Carbonylation in Ionic Liquids Using Vapor-Takeoff Reactors......Page 148
Development of Vapor Take-off Reactors with Ionic Liquids......Page 149
Conclusions......Page 155
Carbonylation reactions......Page 156
References......Page 157
10 Ionic Liquids for Space Propulsion......Page 158
Introduction......Page 159
Space Propulsion Missions......Page 160
Space Propulsion Performance Parameters......Page 161
Electric Propulsion......Page 162
Discharge-Free Electric Thrusters: Electrospray Thrusters......Page 164
Electrohydrodynamics of Taylor Cones......Page 167
Mass Spectrometric Experiment......Page 170
[Emim][BF4]......Page 171
[Emim][lm]......Page 172
[Emim][NO3]......Page 177
Conclusions......Page 178
References......Page 179
11 Columnar Liquid Crystalline Imidazolium Salts: Self-Organized One-Dimensional Ion Conductors......Page 181
Introduction......Page 182
Synthesis and Liquid Crystalline Properties......Page 183
Anisotropic Ionic Conductivities of Columnar Ionic Liquids (31)......Page 186
Conclusion......Page 188
References......Page 189
12 Ionic Liquids as Versatile Media in Lanthanide Chemistry......Page 192
Trivalent lanthanides in ionic liquids - structural characterizations......Page 193
Optical Properties of Lanthanides in Ionic Liquids......Page 196
Low Valent Lanthanides in Ionic Liquids......Page 199
Acknowledgements......Page 202
References......Page 203
13 Electropolishing and Electroplating of Metals Using Ionic Liquids Based on Choline Chloride......Page 206
Experimental......Page 207
Electropolishing......Page 208
Electroplating of Alloys......Page 212
References......Page 216
14 Ionic Liquids as Vehicles for Reactions and Separations......Page 218
Nucleophilic Substitution Reactions......Page 219
Physical Property Measurements......Page 220
Nucleophilic Substitution Reactions......Page 221
Physical Property Measurements......Page 223
Microviscosity using a fluorescent molecular rotor......Page 224
Local dielectric using a fluorescent molecular rotor......Page 226
Reversible ionic liquids......Page 228
Conclusions......Page 229
References......Page 230
15 Mesoscopic Dye Sensitized Solar Cells Using Hydrophobic Ionic Liquid Electrolyte......Page 232
Experimental......Page 233
Results and Discussion......Page 234
References......Page 238
16 The Application of Trialkyl-Imidazolium Ionic Liquids and Salts for the Preparation of Polymer-Clay Nanocomposites......Page 240
Introduction......Page 241
Instrumentation......Page 245
Imidazolium treated layered silicates.......Page 246
Polymer Layered Silicate Nanocomposites......Page 248
References......Page 251
17 Ionic Liquids as Modifiers for Cationic and Anionic Nanoclays......Page 254
Introduction......Page 255
Materials......Page 256
Characterization......Page 257
Cationic clays......Page 259
Anionic clays......Page 263
Conclusions......Page 264
References......Page 266
18 Solution Chemistry of Cm(III) and Eu(III)in Ionic Liquids......Page 267
Measurements in BumimTf2N......Page 269
Eu(III) and Cm(III) Fluorescence Quenching by Cu(II) in H2O......Page 270
Eu(III) and Cm(III) solvation in BumimTf2N......Page 271
Eu(III) and Cm(III) Fluorescence Quenching by Cu(II) in BumimTf2N......Page 274
References......Page 276
Synthesis and Properties......Page 277
Introduction......Page 278
Quaternization step......Page 279
Transesterification step......Page 280
Kinetics of the transesterification reaction and concepts for scale-up......Page 281
Viscosity......Page 283
Density......Page 284
Synthesis of vinylsulfonate ionic liquids and further functionalization......Page 285
Ion exchange in dry acetone......Page 286
Thermal properties......Page 287
Transformations of Vinylsulfonate Ionic Liquids......Page 288
Hydrogenation of vinylsulfonate......Page 289
References......Page 290
20 Spatial Heterogeneity in Ionic Liquids......Page 292
Introduction......Page 293
Models and Methods......Page 294
Polarizable atomistic models......Page 295
Heterogeneity Order Parameter......Page 297
Molecular Dynamics Procedure......Page 299
Results......Page 300
Finite Size Effects......Page 301
Structural, Dynamical, and Thermodynamical Properties......Page 305
Spatial Heterogeneity......Page 306
Mechanism......Page 314
Discussion and Conclusions......Page 318
Acknowledgments......Page 319
A2.1. C2 and Nitrate......Page 320
A2.4. C8......Page 321
A2.6. C12......Page 322
A3. Force Field Parameters......Page 323
References......Page 326
21 Taylor Cones of Ionic Liquids as Ion Sources: The Role of Electrical Conductivity and Surface Tension......Page 328
Introduction......Page 329
Taylor cones of ionic liquids as sources of ions in vacuum......Page 330
Surface tension measurement......Page 333
Performance of the ionic liquids as ion sources......Page 335
References......Page 337
22 How to Make Ionic Liquids More Liquid......Page 340
Results and Discussion......Page 341
Acknowledgement......Page 352
References......Page 353
23 Molecular Dynamics Study of the Mechanism of Cellulose Dissolution in the Ionic Liquid 1-n-Butyl-3-methylimidazolium Chloride......Page 355
2. Simulation Details......Page 356
3.1. Optimization of Non-bonded Parameters......Page 358
3.2. Structural Features of Neat [C4mim]Cl......Page 359
3.3. Dynamic Properties of Neat [C4mim]Cl......Page 362
4.1 Solute-Solvent Interactions......Page 363
4.2. Solvent Structuring in Cellobiose/[C4mim]Cl Solutions......Page 366
5. Conclusions......Page 367
Acknowledgment......Page 368
References......Page 369
24 New Class of Ionic Liquids Synthesized from Amino Acid and Other Bioderived Materials......Page 371
Room temperature ionic liquids composed of amino acid anions......Page 372
Binary mixtures of amino acid ionic liquids......Page 374
Zwitterions derived from amino acid......Page 375
Fully natural ionie liquids containing amino acids......Page 378
Conclusions......Page 379
References......Page 380
25 Hydrophobic n-Alkyl-N-isoquinolinium Salts: Ionic Liquids and Low Melting Solids......Page 382
Synthesis of [Cnisoq]Cl Salts......Page 383
Physical Property Measurements......Page 384
X-ray Diffraction Studies......Page 385
Physical Properties......Page 386
Single Crystal X-ray Diffraction Studies......Page 388
Solvent Properties......Page 393
Acknowledgements......Page 398
References......Page 399
Author Index......Page 403
A......Page 405
B......Page 406
C......Page 407
D......Page 408
E......Page 409
F......Page 410
H......Page 411
I......Page 413
L......Page 414
M......Page 415
N......Page 418
P......Page 419
S......Page 421
V......Page 426
Z......Page 428
Color Figure Insert (Figure 3 from Chapter 10)......Page 429