Sample preparation in chromatography v. 65.

Table of Contents Part 1. Introduction and General Considerations 1. Preparatory Information 1.1. Overview of a Chemical Analysis 3 1.2. Types of Operations Used in Sample Preparation 10 1.3. Some Theoretical Aspects of Phase Transfers 16 1.4. Introductory Approach to Theory of Distribution Equilibria 24 1.5. Some Aspects of Mass Transfer Processes 33 1.6. Characterization of Chromatographic Separations 43 1.7. General Characteristics of Separations 61 1.8. Elementary Discussion on Thermodynamic and Kinetic Factors in Chemical Reactions 66 1.9. Brief Survey on Molecular Interactions 69 1.10. Empirical and Estimated Parameters for Sample Preparation Problems... 77 1.11. Introductory Discussion on Precision, Accuracy, Sensitivity, and Limit of Detection in Chemical Analysis 94 1.12. Validation of an Analytical Method 107 References 1 108 2. Sampling and Its Connection with Sample Preparation 2.1. Relation of Sampling to Sample Preparation 113 2.2. Representative Samples 114 2.3. Techniques for Sample Collection 118 2.4. Handling, Preservation, and Storage of Samples 130 References 2 132 3. Overview on Sample Preparation for Chromatography 3.1. The Role of Sample Preparation 137 3.2. The Use of Preliminary Information for the Choice of a Sample Preparation Procedure 141 3.3. Sample Homogenization and Dissolution 146 3.4. Sample Cleanup, Fractionation, and Concentration 147 3.5. Chemical Modifications of the Sample 152 3.6. Other Types of Sample Modifications 153 3.7. Differences in Sample Preparation for Different Chromatographic Techniques 154 3.8. Quantitation Techniques in Chromatography and Their Relation to Sample Preparation 156 3.9. Method Development in Sample Preparation 159 References 3 163 viii Table of Contents 4. Chromatography as the Core Step in an Analytical Process 4.1. The Choice of the Core Analytical Technique 165 4.2. Gas Chromatography as a Core Step in the Analytical Process 169 4.3. Conventional High Performance Liquid Chromatography as a Core Analytical Technique 182 4.4. Other Chromatography Types Used as a Core Analytical Technique 201 References 4 209 5. Data Processing in Chromatographic Methods 5.1. Information Gain from Chromatographic Data 213 5.2. Qualitative and Quantitative Data from the Chromatographic Process 214 References 5 218 6. Automation in Sample Preparation 6.1. Automation in the Instrumentation Used in Sample Preparation 219 6.2. Computer Assisted Method Development 221 References 6 221 Part 2. Sample Preparation Techniques Using Physical Processes 7. Mechanical Processing in Sample Preparation 7.1. Grinding, Sieving, and Blending 225 7.2. Filtration, Microfiltration, and Ultrafiltration 7.3. Centrifugation 238 References 7 241 8 Phase Transfer Separations Applied in Sample Preparations 8.1. Distillation, Vaporization, and Drying 243 8.2. Dissolution, Crystallization, and Precipitation 255 References 8 265 9. Headspace Sampling Techniques in Gas Chromatography 9.1. Static Headspace Techniques 267 9.2. Dynamic Headspace 272 9.3. Other Headspace Techniques 283 References 9 285 ix Table of Contents 10. Solvent Extraction 10.1. Liquid-Liquid Extraction 287 10.2. Conventional Liquid-Solid Extraction 304 10.3. Accelerated Solvent Extraction 310 10.4. Microwave-Assisted Solvent Extraction 314 10.5. Simultaneous Distillation and Extraction 317 10.6. Supercritical Solvent Extraction 322 References 10 334 11. Sorbent Extraction 11.1. Solid Phase Extraction Procedures 341 11.2. Solid Phase Microextraction 373 11.3. Matrix Solid Phase Dispersion 394 11.4. Other Solid Phase Sample Preparation Techniques 396 References 11 399 12. Chromatographic Procedures as Preliminary Separation 12.1. Gas Chromatography as a Sample Preparation Technique and Bidimensional GC 403 12.2. Liquid Chromatography as a Sample Preparation Technique 408 12.3. Size Exclusion Used in Sample Preparation 415 References 12 420 13. Membrane Separations 13.1. Gas Diffusion through Membranes and Stripping 423 13.2. Reverse Osmosis and Dialysis 425 References 13 431 14. Electroseparation Techniques in Sample Preparation 14.1. Electrophoretic Techniques 433 14.2. Other Electroseparation Techniques 440 References 14 441 15. Other Separation Techniques in Sample Preparation 15.1. Ion Exchange in Sample Preparation 443 15.2. Other Techniques in Sample Preparation 459 References 15 460 X Table of Contents Part 3. Sample Preparation Techniques Involving Chemical Modifications 16. Chemical Modifications for Dissolution and Fractionation 16.1. Chemical Modifications for Sample Dissolution 463 16.2. Changes in pH and Chemical Modifications for Fractionation Purposes... 466 References 16 470 17. Purpose of Derivatization in Chromatographic Analysis 17.1. General Aspects Regarding Derivatization 473 17.2. Preparation of the Sample for Derivatization and Common Derivatization Labware 476 17.3. Derivatization for Improving Gas Chromatographic Process 478 17.4. Derivatization for Improving Detection in GC 486 17.5. Derivatization for Improving Mass Spectral Identification 493 17.6. Derivatization for Improving Detection in HPLC and TLC 502 17.7. Derivatization for Chiral Separations 514 References 17 523 18. Chemical Reactions Used in Derivatization 18.1. Reactions with Formation of Alkyl or Aryl Derivatives 525 18.2. Silylation Reactions 545 18.3. Acylation Reactions 569 18.4. Reactions of Addition to Carbon-Heteroatom Multiple Bonds Used for Derivatization 581 18.5. Derivatization Reactions with Formation of Cyclic Compounds 591 18.6. Other Derivatization Reactions .613 18.7. Derivatization Reactions Involving Solid Phase Reagents 623 18.8. Derivatization on a Solid Support 629 References 18 631 19. Derivatization Reactions for Analytes with Various Functional Groups 19.1. Derivatization of Compounds with Alcohols, Epoxide, or Ether Groups.... 639 19.2. Derivatization Reactions for Phenols 669 19.3. Derivatization Reactions for Thiols and Sulfides 675 19.4. Derivatization of Compounds with Amino and Other Nitrogen-Containing Groups 683 19.5. Derivatization of Aldehydes and Ketones 724 19.6. Derivatization of Carboxylic Acids 739 19.7. Derivatization of Amides, Esters, and Other Derivatives of Carboxylic Acids, and of Carbonic Acid 761 19.8. Derivatization of Other Types of Organic Groups and of Organometallic and Inorganic Compounds 776 Table of Contents XI 19.9. Derivatization of Carbohydrates 788 19.10. Derivatization of Amino Acids and Related Compounds 798 19.11. Derivatization of Other Multifunctional Compounds 814 References 19 823 20. Chemical Degradation of Polymers and Pyrolysis 20.1. Chemical Degradation of Polymeric Carbohydrates 847 20.2. Chemical Degradation of Proteins for Analytical Purposes 859 20.3. Chemical Degradation of other Macromolecular Compounds 864 20.4. Overview of Analytical Pyrolysis 869 20.5. Pyrolysis as a Chemical Modification Technique 877 20.6. Instrumentation Used in Analytical Pyrolysis 895 20.7. Application of Analytical Pyrolysis 901 References 20 913 Symbols, Units, and Constants 919 Index 923