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  The second edition of Gas Chromatography and Mass Spectrometry: A Practical Guide follows thehighly successfulfirstedition by F.G. Kitson, B.S. Larsen, and C.N. McEwen (1996), which was designed as an indispensible resource for GC/MS practitioners regardless of whether they are a novice or well experienced. The Fundamentals section has been extensively reworked from the original edition to give more depth of an understanding of the techniques and science involved with GC/MS. Even with this expansion, the original brevity and simple didactic style has been retained. Information on chromatographic peak deconvolution has been added along with a more in-depth understanding of the use of mass spectral databases in the identification of unknowns. Since the last edition, a number of advances in GC inlet systems and sample introduction techniques have occurred, and they are included in the new edition. Other updates include a discussion on fast GC and options for combining GC detectors with mass spectrometry. The section regarding GC Conditions, Derivatization, and Mass Spectral Interpretation of Specific Compound Types has the same number of compound types as the original edition, but the information in each section has been expanded to not only explain some of the spectra but to also explain why certain fragmentations take place. The number of Appendices has been increased from 12 to 17. The Appendix on Atomic Masses and Isotope Abundances has been expanded to provide tools to aid in determination of elemental composition from isotope peak intensity ratios. An appendix with examples on "Steps to follow in the determination of elemental compositions based on isotope peak intensities" has been added. Appendices on whether to use GC/MS or LC/MS, third-party software for use in data analysis, list of information required in reporting GC/MS data, X+1 and X+2 peak relative intensities based on the number of atoms of carbon in an ion, and list of available EI mass spectral databases have been added. Others such as the ones on derivatization, isotope peak patterns for ions with Cl and/or Br, terms used in GC and in mass spectrometry, and tips on setting up, maintaining and troubleshooting a GC/MS system have all been expanded and updated.          Covers the practical instruction necessary for successful operation of GC/MS equipment    Reviews the latest advances in instrumentation, ionization methods, and quantitation    Includes troubleshooting techniques and a variety of additional information useful for the GC/MS practitioner    Atrue benchtop reference    A guide to a basic understanding of the components of a Gas Chromatograph-Mass Spectrometer (GC-MS)    Quick References to data interpretation    Ready source for information on new analyses  

目录

Table Of Contents:
Preface xv
Acknowledgments xix
Section 1 The Fundamentals Of GC/MS 1(218)

1 Introduction and History 3(12)

1.1 Instrumental Variables 8(1)

1.2 Operational Variables 9(3)

References 12(3)

2 Gas Chromatography 15(70)

2.1 Overview of a Gas Chromatograph 15(1)

2.2 Sample Introduction 16(33)

2.2.1 Inlets for Liquid Samples 16(18)

2.2.2 Analysis of Gas Samples 34(2)

2.2.3 Solvent-Free Determination of Volatile Compounds in Liquids and Solids 36(7)

2.2.4 Probes and Other Direct Sample Introduction Techniques for GC 43(4)

2.2.5 Summary of GC Sample Introduction Methods 47(2)

2.3 Separation of Components in the GC System 49(17)

2.3.1 Columns for GC/MS 49(9)

2.3.2 Selecting Column Temperatures in a GC Separation 58(3)

2.3.3 Carrier Gas Considerations 61(3)

2.3.4 Fast GC 64(2)

2.4 Overview of GC Detectors 66(7)

2.4.1 Thermal Conductivity Detector 66(2)

2.4.2 Flame Ionization Detector 68(1)

2.4.3 Nitrogen鈥揚hosphorus Detector 68(1)

2.4.4 Electron Capture Detector 69(1)

2.4.5 Flame Photometric Detector and Pulsed-Flame Photometric Detector 70(3)

2.5 Adding Versatility to the GC/MS System with Valves, Splitters, and Thermal Modulators 73(6)

2.5.1 Dual-Detector Analysis 74(2)

2.5.2 Multicolumn Systems 76(3)

References 79(6)

3 The GC/MS Interface 85(4)

3.1 Open-Split Interface 85(2)

3.2 Jet Separator 87(1)

References 88(1)

4 Mass Spectrometry Instrumentation 89(60)

4.1 Overview of Mass Spectrometers 89(3)

4.2 Resolution, Resolving Power, and Mass Accuracy 92(7)

4.3 Vacuum System 99(5)

4.3.1 Low-Vacuum Component 99(2)

4.3.2 High-Vacuum Component 101(3)

4.4 Ionization Types 104(9)

4.4.1 Electron Ionization 105(2)

4.4.2 Chemical Ionization 107(3)

4.4.3 Electron Capture Negative Ionization 110(2)

4.4.4 Field Ionization 112(1)

4.4.5 Atmospheric Pressure Chemical Ionization 112(1)

4.5 m/z Analyzer Types 113(15)

4.5.1 Transmission Quadrupole GC-MS (a.k.a. Quadrupole Mass Filter GC-MS) 113(3)

4.5.2 Quadrupole Ion Trap GC-MS 116(7)

4.5.3 Time-of-Flight GC-MS 123(3)

4.5.4 Double-Focusing GC-MS 126(2)

4.6 Ion Detection 128(4)

4.7 m/z Scale Calibration 132(2)

4.8 Tuning the Mass Spectrometer 134(3)

4.9 Data Acquisition 137(5)

4.9.1 Continuous Measurement of Spectra (Full-Spectrum Acquisition) 138(2)

4.9.2 Selected Ion Monitoring 140(2)

4.9.3 Alternate Full-Spectrum Acquisition 142(1)

4.10 Tandem Mass Spectrometry (MS/MS) 142(4)

4.10.1 Tandem-in-Space 145(1)

4.10.2 Tandem-in-Time 146(1)

4.11 Conclusion 146(1)

References 146(3)

5 Mass Spectral Data Interpretation 149(58)

5.1 Using the Database Search 154(11)

5.2 Identification of a Molecular Ion Peak in an El Mass Spectrum 165(13)

5.2.1 Elemental Composition Based on the Relative Intensity of Isotope Peaks 168(6)

5.2.2 Elemental Composition Based on the Accurate Mass Assignment of an Ion 174(2)

5.2.3 After the Molecular Ion's Elemental Composition Has Been Determined 176(2)

5.3 What to Do If There Is No Molecular Ion Peak 178(13)

5.3.1 Soft Ionization 182(3)

5.3.2 Derivatization 185(6)

5.4 Selecting the Spectrum to Be Interpreted 191(7)

5.4.1 Use of Mass Chromatograms 193(1)

5.4.2 Background Subtraction 194(2)

5.4.3 AMDIS 196(2)

5.5 Reading an El Mass Spectrum 198(3)

5.5.1 Odd-Electron and Even-Electron Ions 200(1)

5.5.2 Logical Losses 200(1)

5.6 Final Remarks 201(4)

References 205(2)

6 Quantitation with GC/MS 207(12)

6.1 Introduction 207(2)

6.2 Selection of the Quantitation Ion 209(3)

6.3 Quantitation Methods 212(1)

6.4 Making Standard Solutions 212(1)

6.5 External Standard Method 213(1)

6.6 Internal Standard Method 214(2)

6.7 Standard Additions 216(2)

6.8 Concluding Remarks 218(1)

References 218(1)
Section 2 GC Conditions, Derivatization, And Mass Spectral Interpretation Of Specific Compound Types 219(196)

7 Acids 221(10)

7.1 GC Separations of Underivatized Carboxylic Acids 221(1)

7.2 General Derivatization Procedure for C8鈥揅24 Carboxylic Acids 221(1)

7.3 GC Separation of Derivatized Carboxylic Acids 222(5)

7.4 Mass Spectral Interpretation 227(4)

8 Alcohols 231(8)

8.1 GC Conditions for Underivatized Alcohols 231(1)

8.2 TMS Derivative of > C10 Alcohols 232(1)

8.3 Mass Spectral Interpretation 232(5)

8.4 Aminoalcohols 237(2)

9 Aldehydes 239(4)

9.1 GC Separation of Underivatized Aldehydes 239(1)

9.2 Derivatization of Formaldehyde 239(1)

9.3 Mass Spectra of Aldehydes 240(3)

10 Amides 243(6)

10.1 GC Separation of Underivatized Amides 243(1)

10.2 Derivatization of Amides 243(1)

10.3 GC Separation of Derivatized Amides (TMS or Methyl-8掳) 244(1)

10.4 Mass Spectra of Amides 244(4)

10.5 Mass Spectra of Derivatized Amides 248(1)

11 Amines 249(16)

11.1 GC Separations of Underivatized Amines 249(1)

11.2 Derivatization of Amines and Diamines 250(1)

11.3 GC Separation of Derivatized Amines 250(1)

11.4 Mass Spectral Interpretation of Amines 251(9)

11.5 Amino Alcohols (Aliphatic) 260(2)

11.6 Aminophenols 262(1)

11.7 Solvent Consideration 263(1)

References 263(2)

12 Amino Acids 265(8)

12.1 GC Separation 265(1)

12.2 Derivatization of Amino Acids and PTH鈥揂mino Acids 266(2)

12.3 Mass Spectral Interpretation 268(3)

References 271(2)

13 Common Contaminants 273(4)

13.1 Contaminants Occasionally Observed after Derivatization with TMS Reagents 273(1)

13.2 Contaminants Occasionally Observed in Underivatized Samples 274(1)

13.3 Column Bleed 274(3)

14 Drugs and Their Metabolites 277(8)

14.1 GC Separations 277(1)

14.2 Sample Preparation 278(1)

14.3 Derivatization of Drugs and Metabolites 279(1)

14.4 Mass Spectral Interpretation 280(4)

References 284(1)

15 Esters 285(8)

15.1 GC Separation of Esters of Carboxylic Acids 285(1)

15.2 Mass Spectra of Esters 286(6)

References 292(1)

16 Ethers 293(8)

16.1 GC Separation of Ethers 293(1)

16.2 Mass Spectra of Ethers 293(8)

17 Fluorinated Compounds 301(16)

17.1 GC Separations 301(4)

17.2 Mass Spectra of Fluorinated Compounds 305(12)

18 Gases 317(2)

18.1 GC Separations 317(1)

18.2 General Information 317(2)

19 Glycols 319(4)

19.1 GC Separations 319(1)

19.2 Derivatization of Dry Glycols and Glycol Ethers 319(1)

19.3 Mass Spectral Interpretation 320(2)

References 322(1)

20 Halogenated Compounds (Other Than Fluorinated Compounds) 323(8)

20.1 GC Separations 323(1)

20.2 Mass Spectra of Halogenated Compounds (Other Than Fluorinated Compounds) 324(7)

21 Hydrocarbons 331(10)

21.1 GC Separation of Hydrocarbons 331(1)

21.2 Mass Spectra of Hydrocarbon Compounds 332(7)

References 339(2)

22 Isocyanates 341(4)

22.1 GC Separations 341(1)

22.2 Mass Spectral Interpretation r 341(4)

23 Ketones 345(6)

23.1 GC Separation of Ketones 345(1)

23.2 Derivatives of Ketones 345(1)

23.3 Mass Spectra of Ketones 346(3)

References 349(2)

24 Nitrites 351(4)

24.1 GC Separation of Nitrites 351(1)

24.2 Mass Spectra 351(4)

25 Nitroaromatics 355(8)

25.1 GC Separation of Nitroaromatics 355(1)

25.2 Mass Spectra of Nitroaromatics 355(8)

26 Nitrogen-Containing Heterocyclic Compounds 363(6)

26.1 GC Separations of Nitrogen-Containing Heterocyclic Compounds 363(1)

26.2 Mass Spectra of Nitrogen-Containing Heterocyclics 363(6)

27 Nucleosides (TMS Derivatives) 369(4)

27.1 Derivatization 369(1)

27.2 GC Separation of Derivatized Nucleosides 369(1)

27.3 Mass Spectra of TMS Nucleosides 370(1)

References 371(2)

28 Pesticides 373(10)

28.1 Chlorinated Pesticides 373(3)

28.2 Organophosphorus Pesticides 376(3)

28.3 Mass Spectra of Pesticides 379(2)

References 381(2)

29 Phenols 383(6)

29.1 GC Separations of Underivatized Phenols and Dihydroxybenzenes 383(1)

29.2 Derivatization of Phenols and Dihydroxybenzenes 383(1)

29.3 GC Separations of Derivatized Phenols and Dihydroxybenzenes 384(1)

29.4 Mass Spectra of Phenols 384(3)

29.5 Aminophenols 387(1)

29.6 Antioxidants 387(2)

30 Phosphorus Compounds 389(4)

30.1 GC Separations 389(1)

30.2 Mass Spectra of Phosphorus Compounds 390(3)

31 Plasticizers and Other Polymer Additives (Including Phthalates) 393(4)

31.1 GC Separations 393(1)

31.2 Mass Spectra 394(1)

References 395(2)

32 Prostaglandins (MO鈥擳MS Derivatives) 397(4)

32.1 Derivatization (MO鈥擳MS) 398(1)

32.2 GC Separation of Derivatized Prostaglandins 398(1)

32.3 Mass Spectra of MO鈥擳MS Derivatives of Prostaglandins 399(1)

References 400(1)

33 Solvents and Their Impurities 401(2)

33.1 GC Separations of Industrial Solvent Mixtures 401(1)

33.2 GC Separations of Impurities in Industrial Solvents 401(1)

33.3 Mass Spectra of Solvents and Their Impurities 402(1)

34 Steroids 403(4)

34.1 GC Separation of Underivatized Steroids 403(1)

34.2 Derivatization of Steroids 403(1)

34.3 GC Separation of Derivatized Steroids 403(1)

34.4 Mass Spectra of Underivatized Steroids 404(1)

34.5 Mass Spectra of TMS Derivatives of Steroids 405(1)

34.6 Mass Spectra of MO鈥擳MS Derivatives 405(2)

35 Sugars (Monosaccharides) 407(4)

35.1 GC Separation of Derivatized Sugars 407(1)

35.2 Mass Spectral Interpretation 408(2)

References 410(1)

36 Sulfur Compounds 411(4)

36.1 GC Separations 411(1)

36.2 Mass Spectra of Sulfur Compounds 412(3)
Section 3 Appendices 415(174)

Appendix A Definitions of Terms Related to Gas Chromatography 417(4)

Appendix B Definitions of Terms Related to Mass Spectrometry 421(10)

Appendix C Atomic Masses and Isotope Abundances and Other Information for the Determination of an Elemental Composition from Isotope Peak Intensity Ratios 431(2)

Appendix D X+1 and X+2 Values for Ions Containing Atoms of C and H Based on Isotope Contributions 433(2)

Appendix E Isotope Peak Patterns for Ions Containing Atoms of CI and/or Br 435(2)

Appendix F Steps to Follow in the Determination of an Elemental Composition Based on Isotope Peak Intensity Ratios 437(8)

Appendix G Derivatization in GC/MS 445(14)

Appendix H Points of Comparison of LC/MS vs GC/MS 459(4)

Appendix I List of Available El Mass Spectral Databases 463(6)

Appendix J Information Required for Reporting a GC/MS Analysis 469(4)

Appendix K Third-Party Software for Use with GC/MS 473(20)

Appendix L GC Installation and Maintenance 493(4)

Appendix M Troubleshooting Common GC Problems 497(4)

Appendix N Maintenance, Operating Tips, and Troubleshooting for Mass Spectrometers 501(14)

Appendix O Mixtures for Determining Mass Spectral Resolution 515(2)

Appendix P Cross-Index Chart for GC Stationary Phases 517(2)

Appendix Q Ions for Determining Unknown Structures 519(70)
Index 589

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