Chromatography: Concepts and Contrasts

CHROMATOGRAPHY......Page 3
CONTENTS......Page 7
Preface to Second Edition......Page 15
Acknowledgments......Page 17
Preface to the First Edition......Page 19
Symbols, Abbreviations, and Acronyms......Page 21
1 Impact of Industrial and Government Regulatory Practices on Analytical Chromatography......Page 29
1.1 Locus of Chromatography in Chemical Industry......Page 31
1.2 Governmental Organizations......Page 32
National Institute of Standards and Technology (NIST)......Page 33
Food and Drug Administration (FDA)......Page 34
Environmental Protection Agency (EPA)......Page 39
1.3 Nongovernmental Agencies......Page 40
ASTM International......Page 42
International Organization for Standardization (ISO)......Page 44
1.4 Standards, Calibration, and NIST......Page 45
1.5 USP and Other Pharmacopoeias......Page 47
International Conference on Harmonization Guidlines......Page 49
1.6 International Guidelines for Analytical Laboratories......Page 50
Sources of Guidelines......Page 51
Method of Development, Validation, and Transfer......Page 52
Instrument Qualification......Page 57
1.7 Final Comments......Page 58
References......Page 59
2 Introduction to Chromatography......Page 63
2.1 Brief History......Page 65
Separation......Page 67
Chromatography......Page 69
Chromatographic Symbols......Page 73
Normal Distribution......Page 79
Other Terms......Page 81
References......Page 92
3.1 Configurations of the Stationary Phase......Page 95
Characteristics of Column Packings......Page 96
Column Volume Characteristics......Page 101
Original Van Deemter Theory......Page 103
Other Rate Equations......Page 107
Van Deemter Plots......Page 111
Practical Consequences of the Rate Theory......Page 112
Reduced Rate Equation for HPLC (and GC)......Page 116
Redefinition of H......Page 118
References......Page 119
4.1 Intermolecular and Interionic Forces......Page 121
Sorption Isotherms......Page 122
Types of Forces......Page 124
4.2 Size Exclusion—Molecular Sieving......Page 128
4.3 Some Models......Page 130
Snyder\'s Solvent Parameter......Page 132
References......Page 135
5.1 Kinetics and Zone Broadening......Page 137
5.3 Achievement of Separation......Page 139
5.4 Optimization of Separations......Page 140
References......Page 143
6.1 Gas Chromatography Compared to Liquid Chromatography......Page 145
Gases Compared to Liquids......Page 146
Gas Compressibility in GC......Page 147
Permeability......Page 149
Efficiency and Speed......Page 150
6.2 Supercritical Fluids and Supercritical Fluid Chromatography......Page 152
Mobile-Phase Properties......Page 155
Density Programming......Page 158
Applications......Page 159
6.3 Reduced Parameters......Page 162
Peaks Compared to Bands......Page 163
Retardation Factors......Page 164
References......Page 167
7.1 Early History, Theories, and Classifications......Page 169
Kovats Index......Page 172
Rohrschneider/McReynolds Constants......Page 174
Methods for Selecting Stationary Phases......Page 175
Mobile Phase......Page 176
Injection Ports and Valves......Page 178
Open Tubular Columns......Page 181
Detectors......Page 185
Packed-Column Injection Ports......Page 193
Packed Columns and Stationary Phases......Page 194
7.4 Stationary Phase......Page 196
Typical Liquids......Page 197
7.5 Temperature Effects......Page 198
Programmed Temperature GC......Page 200
Programmed Temperature Vaporizers and Large-Volume Injections......Page 205
Inorganic GC......Page 206
7.7 Summary and Evaluation......Page 207
References......Page 208
8 Liquid Chromatography in Columns......Page 211
Phase Polarities: Normal Versus Reversed......Page 212
Liquid-Solid (LSC) Versus Liquid-Liquid (LLC) Chromatography......Page 213
Low-Pressure Versus High-Pressure Liquid Chromatography......Page 214
Isocratic Versus Gradient Elution......Page 216
Stationary Phase......Page 218
Mobile Phase......Page 219
Liquid-Solid Chromatography......Page 222
Bonded-Phase Chromatography......Page 226
Ion Exchange Chromatography......Page 242
Size Exclusion Chromatography......Page 254
Pumping Systems and the Mobile Phase......Page 262
Sampling......Page 266
Columns......Page 268
Detectors......Page 272
Overlapping Resolution Mapping......Page 277
Phase Selection Diagrams......Page 282
Gradient Elution......Page 284
Computer Methods......Page 286
Troubleshooting and Tips......Page 287
8.5 RP-HPLC Alternatives for the Pharmaceutical Industry......Page 289
8.6 Preparative LC......Page 290
Low-Pressure Preparative LC......Page 291
High-Pressure Preparative LC......Page 294
Pseudophase or Micellar LC......Page 295
8.8 Summary and Evaluation......Page 296
References......Page 298
9 Quantitation: Detectors and Methods......Page 305
Classification of Detectors......Page 306
Detector Characteristics......Page 313
Summary of Detector Terms......Page 323
Peak Height versus Peak Area......Page 324
Measurement of Areas......Page 325
Standards and Calibration......Page 327
Classification of Methods......Page 328
Concluding Comments......Page 333
References......Page 334
10 Chromatography with Mass Spectral Detection (GC/MS and LC/MS)......Page 337
10.1 Basics of Mass Spectrometry......Page 338
Ion Sources......Page 339
Analyzers......Page 346
Other MS Topics......Page 350
10.2 Gas Chromatography / Mass Spectrometry......Page 351
10.3 Liquid Chromatography / Mass Spectrometry......Page 352
10.4 Other Hyphenated Methods......Page 354
Liquid Chromatography/Nuclear Magnetic Resonance......Page 355
References......Page 356
11.1 Paper Chromatography......Page 359
Manual TLC......Page 361
Instrumental TLC......Page 369
Multidimensional TLC......Page 375
11.4 Literature Summary and Applications......Page 376
References......Page 378
12.1 Retention Parameters......Page 381
Two-Column Plots......Page 383
12.2 Other Methods of Qualitative Analysis......Page 385
Instrumental Methods......Page 386
References......Page 390
13 Capillary Electrophoresis and Capillary Electrochromatography......Page 393
Fundamental Equations......Page 394
Weak Acids and Bases......Page 395
Electrolyte Concentration......Page 397
Diffusion......Page 398
13.2 Zone Electrophoresis......Page 399
13.3 Capillary Electrophoresis......Page 400
Capillary Zone Electrophoresis......Page 404
Micellar Electrokinetic Chromatography......Page 407
13.4 Capillary Electrochromatography......Page 408
References......Page 411
14 Sample Preparation......Page 415
14.1 Extraction......Page 418
Simple Liquid-Liquid Extraction......Page 419
Assisted Liquid-Solid Extraction......Page 430
Supercritical Fluid Extraction......Page 432
Solid-Phase Extraction......Page 433
Solid-Phase Microextraction......Page 435
Headspace Methods......Page 438
14.2 Dialysis......Page 439
14.3 Derivatization......Page 440
Methods......Page 441
Examples......Page 443
References......Page 446
15.1 Multidimensional Chromatography......Page 451
Gas Chromatography/Gas Chromatography......Page 453
Liquid Chromatography/Gas Chromatography......Page 455
Liquid Chromatography/Liquid Chromatography......Page 459
Other Combinations......Page 460
15.2 Biological Applications......Page 461
Affinity Chromatography......Page 462
Proteins, Peptides, and Proteomics......Page 466
Other Large Biomolecules......Page 468
Hydrophobic Interaction Chromatography......Page 470
Stereochemical Nomenclature and Conventions......Page 471
Disastereoismeric Separations......Page 473
Chiral Stationary Phases......Page 474
Additional Chiral Methods......Page 481
Other Chromatographic Methods......Page 482
Microfludic Devices for Chromatography and Electrophoresis (Lab-on-a-Chip)......Page 483
References......Page 484
16.1 Methods of Attack......Page 491
Literature Searching......Page 492
Other Sources of Information on the Internet......Page 493
16.3 Experimental Approach......Page 494
Nonvolatile Samples......Page 496
References......Page 499
Some Internet Web Sites of Interest to Chromatographers......Page 500
Appendix A ICH Glossary......Page 503
Appendix B......Page 507
Index......Page 513