Gas Chromatography

Gas Chromatography: Principles, Techniques, and Applications, Second Edition, is a general textbook on gas chromatography suitable for users of the technique and for research workers. It does not presuppose any knowledge of the subject. Starting with an introduction to gas chromatography, the first half of the book is primarily concerned with the ability of gas chromatography to perform separations. The theory of the operation and design of gas chromatographic columns—both packed and open-tube—is described in detail, and it is shown how columns may be designed so as to secure any desired separation. Separate chapters discuss the thermodynamics of solution and the kinetics of chromatography. The third quarter of the book deals with detectors, which are the means of obtaining quantitative analyses by gas chromatography. It also contains a description of the union of gas chromatography with other techniques, and some indication of the use of the more sophisticated methods of handling gas-chromatographic data. The last quarter of the book is a single chapter in a series of sections, each dealing with the chromatography of a particular class of chemical compound

Preface

Acknowledgments

Chapter 1 Definitions and Technical Terms

1.1. Gas Chromatography

1.2. Basic Apparatus of Gas Chromatography

1.3. The Chromatogram

1.4. Peak Shape

1.5. Applications of Gas Chromatography

1.6. History

References

Chapter 2 Retention Volume and Column Variables

2.1. Introduction

2.2. The First Order Conservation Equation

2.3. The Conservation Equation for Linear Isotherms

2.4. Effect of Pressure Gradient

2.5. The Calculation and Use of Retention Volumes

2.6. The Presentation of Relative Retentions

2.7. Effect of Input Distribution on Retention Volume

2.8. Effect of Sample Size on Retention Volume

2.9. Retention Volumes in Non-Linear Chromatography

References

Chapter 3 Retention Volume and Thermodynamic Variables

3.1. Introduction

3.2. Thermodynamic Equations for Partition Coefficient and Vapor Pressure

3.3. Effect of the Vapor Pressure of Solutes on Their Partition Coefficient

3.4. General Thermodynamic Equations for Mixtures

3.5. Activity Coefficients for Alkane Solutions

3.6. Retentions in Polar Solvents

3.7. General Relations between Partition Coefficient and Solute Structure

3.8. Choice of Stationary Phase for a Given Mixture

3.9. Qualitative Analysis

3.10. Effect of Temperature on Partition Coefficients

References

Chapter 4 Adsorbent Stationary Phases

4.1. Theory of Adsorbents in Gas Chromatography

4.2. Adsorbents Used in Gas Chromatography

4.3. Modification of Adsorbents

4.4. Use of Gas Chromatography to Study Adsorbents

4.5. Comparison of GSC and GLC

References

Chapter 5 Column Performance—Fundamentals

5.1. Introduction

5.2. Plate Theory

5.3. Peak Shape from Plate Theory

5.4. Comparison of Theoretical Plates in Chromatography and Distillation

5.5. Methods of Determining Plate-Numbers

5.6. Purity of Separation of Pairs of Solutes

5.7. The Influence of Gas Hold-Up on Resolution

References

Chapter 6 Column Performance—Mechanisms

6.1. Broadening Factors and Column Variables

6.2. Broadening Due to Longitudinal Diffusion in the Gas Phase

6.3. Broadening Due to Non-Instantaneous Equilibration of Vapor

6.4. The General Non-Equilibrium Theory

6.5. Broadening Factors Dependent on the Geometry of Packing

6.6. Effect of the Linearity of Isotherms on Broadening

6.7. Broadening Due to the Input Distribution of the Vapor

6.8. Broadening Due to the Time Constant of the Detecting System

6.9. Equations for Plate-Height

6.10. Effect of Column Length on Performance

6.11. Effect of Flow Rate on Performance

6.12. Effect of Partition Coefficient on Performance

6.13. Effect of the Proportion of Stationary Phase on Performance

6.14. Effect of k on Resolution and Analysis Time

6.15. Effect of Temperature on Performance

6.16. Effect of Carrier Gas on Performance and Speed

6.17. Effect of Column Diameter on Performance

6.18. Effect of Pressure Drop across the Column on Performance and Analysis Time

6.19. Effect of Mass of Sample on Performance

References

Chapter 7 The Preparation and Use of Columns

7.1. Preparation of Packed Columns

7.2. Reactivity of Supports in Packed Columns

7.3. Open-Tube Columns; Capillary Columns

7.4. Use of Two Stationary Liquids

7.5. Programmed Temperature Operation

7.6. Preparative Columns

7.7. Frontal and Displacement Analysis

References

Chapter 8 The Use of Detectors for Quantitative Analysis

8.1. Principles of Quantitative Analysis by Gas Chromatography

8.2. Technique of Quantitative Analysis

8.3. Properties of Detectors

References

Chapter 9 Ionization Detectors

9.1. Introduction

9.2. Conduction of Electricity in Ionized Gases

9.3. Flame Ionization Detector

9.4. Ionization by Radiation

9.5. The ß-Ray Ionization Cross-Section Detector

9.6. The Electron Capture Detector

9.7. The Electron Mobility Detector

9.8. The Argon Detector

9.9. Other Ionization Detectors

References

Chapter 10 Thermal Conductivity Detectors

10.1. Introduction

10.2. Theory of Catharometry

10.3. Sensitivity

10.4. Noise

10.5. Drift

10.6. Linearity

10.7. Independence of Extraneous Variables

10.8. Calibration of Catharometers

10.9. Other Criteria

10.10. Design of Catharometers

References

Chapter 11 Ancillary Apparatus and Techniques

11.1. Introduction

11.2. Sample Injectors

11.3. Other Detectors

11.4. Gas Chromatography and Mass Spectrometry

11.5. Gas Chromatography and Infrared Spectrophotometry

11.6. Chemical Methods Used with Gas Chromatography

11.7. Data Handling Equipment

References

Chapter 12 Applications of Gas Chromatography

12.1. Bibliography of Applications of GC

12.2. Permanent Gases and Methane

12.3. Light Hydrocarbons, C1-C5

12.4. Petroleum Alkanes, Alkenes, and Naphthenes

12.5. Aromatic Hydrocarbons

12.6. Fatty Acids and Esters

12.7. Oxygenated Compounds

12.8. Nitrogen Compounds

12.9. Halogenated Compounds

12.10. Sulphur Compounds

12.11. Polymers and Other Non-Volatiles

12.12. Inorganic Substances

References

List of Symbols

Author Index

Subject Index