Gas Chromatography

Resolving power 81 ... Alkyl boronates as bifunctional derivatizing agents 164 7. ... Chiral separations by gas chromatography 237...

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Gas Chromatography A Practical Approach Edited by P. J. BAUGH Department of Chemistry and Applied Chemistry University of Salford The Crescent, Salford

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OXFORD UNIVERSITY PRESS Oxford New York Tokyo

Contents List of contributors Abbreviations 1. Introduction to the theory of Chromatographie separations with reference to gas chromatography Keith D. Bartle 1. Introduction and history of GC

1

2. The GC chromatogram

4

3. Resolution in GC

5

4. Band broadening in GC

6

5. GC columns

7

6. Speed of GC analysis

8

7. Retention in GC Effect of temperature Temperature programming Dependence of retention on solute properties in GC Retention indices

10 10 10 12 12

References

13

2. Gas chromatography instrumentation, Operation, and experimental considerations

15

Andrew Tipler 1. Introduction

15

2. Instrumental components and funetion Fundamental components The Chromatographie oven Pneumatics Sample introduction Gas Chromatographie detectors

15 15 16 17 20 31

3. Operation and experimental considerations Where to Start

38 39

Contents Installation and preparation of the Chromatograph Chromatographie method development

39 49

4. Data handling Introduction Potential information from chromatography Detector signal processing Approaches to data handling Microprocessor-based data handling Systems

61 61 61 61 63 63

References

70

3. Development, technology, and utilization of capillary columns for gas chromatography

71

Peter A. Dawes 1. Introduction

71

2. Types of capillary column

72

3. Evolution of the modern capillary column Column support material Stationary phase criteria and development Types of stationary phase for partitioning Manufacturing methods

72 73 73 75 78

4. Column Performance evaluation Resolving power Determination of efficiency and Performance parameters Kövats' retention index Speed of analysis Sample capacity Inertness Bleed

80 81 81 84 84 85 86 90

5. Column selection Stationary phase Internal diameter Film thickness Length

93 94 95 97 98

6. Care of a capillary column Protection of fused silica fabric and installation hints Column contamination Column Operation

98 99 99 101

References

102 x

Contents

4. Applications of packed and capillary GC Peter J.

103

Baugh

1. I n t r o d u c t i o n

103

2. E x p e r i m e n t a l c o n s i d e r a t i o n s Column requirements

104 104

3. M u l t i d i m e n s i o n a l gas c h r o m a t o g r a p h y Capillary-capillary column coupling with differing film thickness of SP Capillary-capillary column coupling with consecutive non-polar and polar SPs Capillary column and FID/ECD as dual detectors Packed-capillary coupling

106 107 107 109 109

4. A p p l i c a t i o n s of p a c k e d a n d c a p i l l a r y c o l u m n s Specific applications for packed columns Comparison of applications of packed and capillary columns Applications of wide-bore capillary columns

109 110 111 115

5. H i g h - t e m p e r a t u r e GC (HTGC) a n d a n a l y s i s of h i g h m o l e c u l a r w e i g h t l o w volatile a n a l y t e s Analysis of polyaromatic hydrocarbons Analysis of triglycerides Analysis of porphyrins Other analytes

121 123 124 125 126

6. Gas—solid c h r o m a t o g r a p h y (GSC) a n d gas—liquid c h r o m a t o g r a p h y (GLC) for t h e a n a l y s i s of h i g h l y volatile organics (HVOs) GSC using packed columns GSC using capillary columns GLC using thick film capillary columns

127 127 128 129

7. C o n c l u s i o n s

131

References

131

5. Chemical derivatization in gas chromatography David G.

133

Watson

1. I n t r o d u c t i o n

133

2. A p p a r a t u s Sample Containers and reaction vessels Hearing and evaporation Sample and reagent handling Removal of derivatizing reagents

134 134 135 135 136

3. S t a n d a r d p r o c e d u r e s i n d e r i v a t i z a t i o n

136

xi

Contents 4. Derivatization reactions involving one reagent Silylation reactions Acylation reactions Alkylation reactions Condensation reactions Derivatives of miscellaneous types

137 137 141 145 150 152

5. Mixed derivatives Silyl-acyl and silyl-carbamate derivatives Acyl/acyl derivatives Acyl/alkyl derivatives Acyl/amide derivatives Silyl/alkyl oxime and acyl/oxime derivatives Derivatization procedures for Prostaglandins

154 154 156 157 158 159 161

6. Bifunctional and mixed bifunctional monofunctional derivatives Bifunctional silylating agents Aldehydes and ketones as bifunctional derivatizing agents Alkyl boronates as bifunctional derivatizing agents

162 163 163 164

7. Derivatives used for Separation of enantiomers Acylation with chiral reagents Chiral alkylating reagents Formation of diastereomeric amides

166 166 168 168

References

169

6. Gas chromatography in analytical toxicology: principles and practice

m

Robert J. Flanagan 1. Introduction

171

2. Use of GC in analytical toxicology Sample collection and storage Sample preparation Columns and column packings Detectors General considerations

172 172 173 181 186 188

3. Applications of GC in analytical toxicology Screening for unknowns Drugs Pesticides Gases, solvents, and other poisons

192 193 194 200 202

4. Conclusions

206

Acknowledgements

208

References

208 xii

Contents

Gas chromatography in clinical chemistry

213

Jagadish Chakraborty 1. Introduction

213

2. Applications of GC Organic volatiles Organic acids Cholesterol and related Compounds Amines and related Compounds Polyols and sugars

214 214 219 226 229 232

3. Conclusions

235

References

235

Chiral separations by gas chromatography

237

David R. Taylor 1. Introduction Terminology and definitions

237 238

2. Role of derivatization in chiral separations by GC Typical protocols for diastereoisomeric derivatization

240 243

3. GC on chiral stationary phases (CSP) Phases based on monomeric peptides Phases based on polymeric amides Chiral GC using metal complexation Inclusion phases for chiral GC

245 247 252 260 269

4. Applications of chiral stationary phases in GC

277

5. Conclusions and future prospects

278

References

278

Environmental analysis using gas chromatography

283

Gerry A. Best and J. Paul Dawson 1. Introduction Pathways to the environment Instrumentation

283 283 285

2. The need for GC analysis of environmental samples Pollution problems Statutory regulations

285 285 285

3. Analytical quality control of GC data

286

4. Isolation of target Compounds from the sample matrix

289

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Contents Contamination Procedure for the extraction of organochlorine Compounds and PCBs from water Procedure for the extraction of organochlorine Compounds from samples of effluent Extraction of organochlorine Compounds from Sediment samples Extraction of organochlorine Compounds from tissue samples

290

5. Clean-up procedures Clean-up and Separation of extracts using alumina and silica columns Modified method for clean-up and Separation using alumina/ silica nitrate and silica gel Clean-up and Separation of extracts using solid-phase extraction (SPE) cartridges Extraction of semi-volatile Compounds from water samples using extraction discs

297

6. Analysis of pentachlorophenol

306

7. Determination of non-persistent pesticides present in water samples Extraction and determination of organophosporus and organonitrogen Compounds in water Extraction and clean-up of permethrin from water samples Extraction and determination of phenoxyacetic acid type of herbicides

291 293 295 297

298 300 303 304

307 308 310 311

8. GC Separation and quantification of target Compounds Choice of column Calculation of concentration in samples using the internal Standard method Typical GC chromatograms for target Compound analysis

313 313 315 315

9. Sampling and analysis of gases and vapours Sampling Desorption of components

316 316 322

10. Determination of types of oil in pollution samples Oil fingerprinting Oil fingerprinting—GC operating conditions

323 323 326

References

327

10. The role of gas chromatography in petroleum exploration

331

Gareth E. Harriman 1. Introduction

331

2. Composition of crude oils and source rock extracts

332

XIV

Contents 3. Whole oil GC

333

4. GC analysis of fractions isolated from crude oils and source rock extracts

337

5. GC-MS analysis of fractions isolated from crude oils and source rock extracts

343

6. Conclusions

354

References

356

11. Combined gas chromatography-mass spectrometry

359

Richard P. Evershed 1. General considerations

359

2. GC-MS Instrumentation Use of packed columns Use of capillary columns Ion sources Use of different mass analysers Ion detection Data collection and interpretation

360 360 360 362 364 367 368

3. Applications Mixture analysis Trace analysis

368 368 381

References

390

Appendices AI Combined gas chromatography—Fourier transform infrared spectroscopy 393 Peter Jackson 1. Introduction

393

2. Techniques description Lightpipe GC-FTIR Low-temperature matrix isolation GC-FTIR Low-temperature solid sample deposition GC-FTIR

395 395 395 397

3. GC-FTIR sensitivity

398

4. GC-FTIR resolution

399

5. GC-FTIR spectra

402

6. Quantitative GC-FTIR

404

7. Multiple detector Systems

406 XV

Contents 8. GC-FTIR applications Industrial applications: commercial alcohols Advanced sampling techniques Pesticides analysis

406 407 408 410

9. Summary

411

Acknowledgements

413

References

413

A2 Suppliers of specialist items

415

Index

417

xvi