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Handbook of Analytical Techniques edited by Helmut Gunzler and Alex Williams For more information about analytical techniques please visit our website (www.wiley-vch.de) or register for our free e-mail alerting service (www.wiley-vch.de/home/pas) Handbook of Analytical Techniques edited by Helmut G...

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Handbook of Analytical Techniques edited by Helmut Gunzler and Alex Williams

For more information about analytical techniques please visit our website (www.wiley-vch.de) or register for our free e-mail alerting service (www.wiley-vch.de/home/pas)

Handbook of Analytical Techniques edited by Helmut Giinzler and Alex Williams

~WILEY-VCH Weinheim . New York . Chichester . Brisbane . Singapore . Toronto

Prof. Dr. Helmut Gunrler Bismarckstr. 4 D-69469 Weinheim Germany

Alex Williams 19 Hamesmoor Way, Mytchett Camberley, Surrey GU16 6JG United Kingdom

Nevertheless, authors, editors and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

1st Edition 2001 1st Reprint 2001

2snd Reprint 2002

Library of Congress Card No. applied for. British Library Cataloguing-in-Publication Data: A catalogue record for this book is available from the British Library. Deutsche Bibliothek CIP Cataloguing-in-Publication-Data: A catalogue record for this publication is available from Die Deutsche Bibliothek. ~

ISBN 3-527-30165-8

0 WILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany), 2001 Printed on acid-free paper. All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form - by photoprinting, microfilm, or any other means - nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked au such, are not to be considered unprotected by law. Composition: Rombach GmbH, D-79 I 1 5 Freiburg Printing: Strauss Offsetdruck GmbH, D-69509 Miirlenbach Bookbinding: Wilhelm Osswald & Co., D-67433 Neustadt (WeinstraRe) Cover Design: Gunter Schuls, D-67 I36 Ful3gonheim Printed in the Federal Republic of Germany.

Preface

v

The broad spectrum of analytical techniques available today is covered in this handbook. It starts with general articles on purpose and procedures of analytical chemistry, quality assurance, chemometrics, sampling and sample preparation followed by articles on individual techniques, including not only chromatographic and spectrometric techniques but also e. g. immunoassays, activation analysis, chemical and biochemical sensors, and techniques for DNA-analysis. Most of the information presented is a thoroughly updated version of that included in the 5th edition of the 36-volume “Ullmann’s Encyclopedia of Industrial Chemistry”, the last edition that is available in print format. Some chapters were completely rewritten. The wealth of material in that Encyclopedia provides the user with both broad introductory information and in-depth detail of utmost importance in both industrial and academic environments. Due to its sheer size, however, the unabridged Ullmann’s is inaccessible to many potential users, particularly individuals, smaller companies, or independent analytical laboratories. In addition there have been significant developments in analytical techniques since the last printed edition of the Encyclopedia was published, which is currently available in its 6th edition in electronic formats only. This is why all the information on analytical techniques has been revised and published in this convenient two-volume set. Users of the “Handbook of Analytical Techniques” will have the benefit of up-to-date professional information on this topic, written and revised by acknowledged experts. We believe that this new handbook will prove to be very helpful to meet the many challenges that analysts in all fields are facing today. Weinheim, Germany Camberley, United Kingdom January 2001

Helmut Gunzler Alex Williams

Contents

VI I

Contents Volume I 1. Analytical Chemistry: Purpose and Procedures 1.1.

1.2. 1.3. 1.4.

.

The Evolution of Analytical Chemistry . . . . . . . . . . . . . . . . . . . The Functional Organization of Analytical Chemistry . . . . . . . . . . . Analysis Today . . . . . . . . . . . . . . . Computers . . . . . . . . . . . . . . . . . .

1

1.5. 1.6. 1.7.

4 5 7

1.8.

Analytical Tasks and Structures . . . Definitions and Important Concepts . “Legally Binding Analytical Results” . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . .

2

Quality Assurance in Instrumentation

2.1. 2.2. 2.3.

Introduction . . . . . . . . . . . . . . . . . Selecting a Vendor . . . . . . . . . . . . Installation and Operation of Equipment . . . . . . . . . . . . . . . . . . Qualification of Software and Computer Systems . . . . . . . . . . . . .

2.4.

.

3

Chemometrics

3.1. 3.2.

Introduction . . . . . . . . . . . . . . . . . Measurements and Statistical Distributions . . . . . . . . . . . . . . . . . Statistical Tests . . . . . . . . . . . . . . . Comparison of Several Measurement Series . . . . . . . . . . . . . . . . . . . . . Regression and Calibration . . . . . . . Characterization of Analytical Procedures . . . . . . . . . . . . . . . . . .

3.3. 3.4. 3.5. 3.6.

4

.

4.1. 4.2. 4.3. 4.4. 4.5. 4.6.

Weighing

23 24 25

2.5. 2.6. 2.7.

........

..................

Routine Maintenance and Ongoing Performance Control . . . . . . . . . . . Handling of Defective Instruments . References . . . . . . . . . . . . . . . . . .

8 13 20 20

23 30 34 35

29

............ 37 38 40 44 45

...... .......................... 3.7. 3.8. 3.9. 3.10. 3.11. 3.12. 3.13.

Signal Processing . . . . . . . . . . . . . Basic Concepts of Multivariate Methods . . . . . . . . . . . . . . . . . . . . Factorial Methods . . . . . . . . . . . . . Classification Methods . . . . . . . . . . Multivariate Regression . . . . . . . . . Multidimensional Arrays . . . . . . . . References . . . . . . . . . . . . . . . . . .

37 49

51 53 56 58 59 61

47

.................. .... ..............................

Introduction . . . . . . . . . . . . . . . . . The Principle of Magnetic Force Compensation . . . . . . . . . . . . . . . . Automatic and Semiautomatic Calibration . . . . . . . . . . . . . . . . . . Processing and Computing Functions Balance Performance . . . . . . . . . . . Fitness of a Balance for Its Application . . . . . . . . . . . . . . . . . .

1

63 63 65 66 66 67

Gravity and Air Buoyancy . . . . . . . The Distinction Between Mass and Weight . . . . . . . . . . . . . . . . . . . . . 4.9. Qualitative Factors in Weighing . . . 4.10. Governmental Regulations and Standardization . . . . . . . . . . . . . . . 4.11. References . . . . . . . . . . . . . . . . . . 4.7. 4.8.

63 67 68 68 69 69

Vlll

Contents

.

Sampling

5

....................................................

Introduction and Terminology . . . . . Probability Sampling . . . . . . . . . . . Basic Sampling Statistics . . . . . . . .

5.1. 5.2. 5.3.

.

71 72 73

5.4. 5.5. 5.6

Acceptance Sampling . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . .

6

Sample Preparation for Trace Analysis

6.1. 6.2.

Introduction . . . . . . . . . . . . . . . . . Sample Preparation and Digestion in Inorganic Analysis . . . . . . . . . . . . .

7

.

Trace Analysis

.

6.3.

80

6.4

Sample Preparation in Organic Analysis . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . .

.............................................

Subject and Scope . . . . . . . . . . . . . Fields of Work . . . . . . . . . . . . . . . Methods of Modem Trace Analysis .

7.1. 7.2. 7.3.

78

110 1 10 1 11

7.4. 7.5. 7.6

Calibration and Validation . . . . . . . Environmental Analysis . . . . . . . . . References . . . . . . . . . . . . . . . . . .

8

Radionuclides in Analytical Chemistry

8.1. 8.2.

Introduction . . . . . . . . . . . . . . . . . Requirements for Analytical Use of Radionuclides . . . . . . . . . . . . . . . . Radiotracers in Methodological Studies . . . . . . . . . . . . . . . . . . . . .

8.3.

.

.................

127 131

8.4. 8.5. 8.6

..................

Isotope Dilution Analysis . . . . . . . . Radioreagent Methods . . . . . . . . . . References . . . . . . . . . . . . . . . . . .

Enzyme and Immunoassays

..............................

9.1. 9.2.

Enzymatic Analysis Methods . . . . . Immunoassays in Analytical Chemistry . . . . . . . . . . . . . . . . . . .

9.3

147

References . . . . . . . . . . . . . . . . . .

77 96 104

109 113 117 125

127 136 140 145

147 171

158

.

10 Basic Principles of Chromatography Introduction . . . . . . . . . . . . . . . . . Historical Development . . . . . . . . . Chromatographic Systems . . . . . . . Theory of Linear Chromatography . Flow Rate of the Mobile Phase . . . . The Thermodynamics of Phase Equilibria and Retention . . . . . . . .

74 76 76

134

9

10.1. 10.2. 10.3. 10.4. 10.5. 10.6.

71

174 175 176 177 182 183

....................

10.7. Band Broadening . . . . . . . . . . . . . 10.8. Qualitative Analysis . . . . . . . . . . . 10.9. Quantitative Analysis . . . . . . . . . . . 10.10. Theory of Nonlinear Chromatography . . . . . . . . . . . . . . 10.1 1. Reference Material . . . . . . . . . . . . 10.12 References . . . . . . . . . . . . . . . . . .

173 186 189 192 194 196 197

Contents

.

11 Gas Chromatography

.....................................

11.1 Introduction . . . . . . . . . . . . . . . . . 1I .2. Instrumental Modules . . . . . . . . . .

11.3. 1 1.4. 11.5.

I 1.6.

200 20 1 The Separation System . . . . . . . . . 201 Choice of Conditions of Analysis . . 212 Sample Inlet Systems . . . . . . . . . . 2 15 Detectors . . . . . . . . . . . . . . . . . . . 23 I

.

12 Liquid Chromatography 12.1. 12.2. 12.3. 12.4. 12.5. 12.6. 12.7.

General . . . . . . . . . . . . . . . . . . . . Equipment . . . . . . . . . . . . . . . . . . Solvents (Mobile Phase). . . . . . . . . Column Packing (Stationary Phase) . Separation Processes . . . . . . . . . . . Gradient Elution Technique . . . . . . Quantitative Analysis . . . . . . . . . . .

262 266 283 285 288 297 298

.

Introduction . . . . . . . . . . . . . . . . . Choice of the Sorbent Layer . . . . . . Sample Cleanup . . . . . . . . . . . . . . Sample Application . . . . . . . . . . . . The Mobile Phase . . . . . . . . . . . . .

14 Electrophoresis

327 327 330 332 334

Qualitative and Quantitative Analysis 1.8. Coupled Systems. . . . . . . . . . . . . . 1.9. Applicability. . . . . . . . . . . . . . . . . 1.10. Recent and Future Developments . . 1.11. References . . . . . . . . . . . . . . . . . .

.

...................... 12.8. Sample Preparation and Derivatization . . . . . . . . . . . . . . . . 12.9. Coupling Techniques . . . . . . . . . . . 12.10. Supercritical Fluid Chromatography . . . . . . . . . . . . . . 12.1 1. Affinity Chromatography . . . . . . . . 12.12. References . . . . . . . . . . . . . . . . . .

Introduction . . . . . . . . . . . . . . . . . Basic Principles . . . . . . . . . . . . . . Electrophoretic Matrices . . . . . . . . Discontinuous Electrophoresis . . . . Isoelectric Focusing . . . . . . . . . . . . Sodium Dodecyl Sulfate Electrophoresis . . . . . . . . . . . . . . . 14.7. Porosity Gradient Gels . . . . . . . . . . 14.1. 14.2. 14.3. 14.4. 14.5. 14.6.

...........................

13.6. 13.7. 13.8. 13.9.

Development . . . . . . . . . . . . . . . . Visualization . . . . . . . . . . . . . . . . Quantitation . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . .

...............................

...... 345 346 346 350 35 1 355 355

14.8. Two-Dimensional Maps (Proteome Analysis) . . . . . . . . . . . . . . . . . . . 14.9. Isotachophoresis . . . . . . . . . . . . . . 14.10. Immunoelectrophoresis . . . . . . . . . 14.11 . Staining Techniques and Blotting . . 14.12. Immobilized pH Gradients . . . . . . . 14.13. Capillary Zone Electrophoresis . . . . 14.14. Preparative Electrophoresis. . . . . . . 14.15. References . . . . . . . . . . . . . . . . . .

15. Structure Analysis by Diffraction 15.1. 15.2. 15.3. 15.4.

General Principles . . . . . . . . . . . . . Structure Analysis of Solids . . . . . . Synchrotron Radiation . . . . . . . . . . Neutron Diffraction . . . . . . . . . . . .

373 374 41 2 4 12

199

1 1.7. Practical Considerations in

13. Thin Layer Chromatography 13.1. 13.2. 13.3. 13.4. 13.5.

IX

.............

242 244 250 254 258

261 301 305 308 316 323

327 337 339 341 344

345 356 358 360 362 362 363 364 369

373

15.5. Electron Diffraction. . . . . . . . . . . . 413 15.6. Future Developments . . . . . . . . . . . 413 15.7. References . . . . . . . . . . . . . . . . . . 414

X

Contents

.

16 Ultraviolet and Visible Spectroscopy 16.1. Introduction . . . . . . . . . . . . . . . . . 420 16.2. Theoretical Principles . . . . . . . . . . 421 16.3. Optical Components and Spectrometers . . . . . . . . . . . . . . . . 430

419

16.4. Uses of UV - VIS Spectroscopy in Absorption, Fluorescence, and Reflection . . . . . . . . . . . . . . . . . . 443 16.5. Special Methods . . . . . . . . . . . . . . 452 16.6. References . . . . . . . . . . . . . . . . . . 459

.

17 Infrared and Raman Spectroscopy 17.1. Introduction . . . . . . . . . . . . . . . . . 17.2. Techniques . . . . . . . . . . . . . . . . . . 17.3. Basic Principles of Vibrational Spectroscopy . . . . . . . . . . . . . . . . 17.4. Interpretation of Infrared and Raman Spectra of Organic Compounds. . . .

....................

466 466

......................

465

17.5. Applications of Vibrational Spectroscopy . . . . . . . . . . . . . . . . 489 17.6. Near-Infrared Spectroscopy . . . . . . 502 17.7. References . . . . . . . . . . . . . . . . . . 504

470 474

18. Nuclear Magnetic Resonance and Electron Spin Resonance Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18.1. Introduction . . . . . . . . . . . . . . . . . 5 10 18.2. Principles of Magnetic Resonance . . 51 1 18.3. High-Resolution Solution NMR Spectroscopy . . . . . . . . . . . . . . . . 5 14

509

18.4. NMR of Solids and Heterogeneous Systems . . . . . . . . . . . . . . . . . . . 18.5. NMR Imaging . . . . . . . . . . . . . . . 18.6. ESR Spectroscopy. . . . . . . . . . . . . 18.7. References . . . . . . . . . . . . . . . . . .

546 547 548 557

...

561

19.4. Preparation of Mossbauer Source and Absorber . . . . . . . . . . . . . . . . . . . 19.5. Hyperfine Interactions . . . . . . . . . . 19.6. Evaluation of Mossbauer Spectra . . 19.7. Selected Applications . . . . . . . . . . 19.8. References . . . . . . . . . . . . . . . . . .

567 568 573 574 577

... ..........................

579

20.8. MS/MS Instrumentation . . . . . . . . . 20.9. Detectors and Signals . . . . . . . . . . 20.10. Computer and Data Systems. . . . . . 20 . I 1 . Applications . . . . . . . . . . . . . . . . . 20.12. References . . . . . . . . . . . . . . . . . .

604 607 610 613 622

Volume I1

19. Mossbauer Spectroscopy 19.1. Introduction . . . . . . . . . . . . . . . . . 561 19.2. Principle and Experimental Conditions of Recoil-free Nuclear Resonance Fluorescence. . . . . . . . . 561 19.3. Mossbauer Experiment . . . . . . . . . . 564

20. Mass Spectrometry 20.1. 20.2. 20.3. 20.4. 20.6. 20.7.

Introduction . . . . . . . . . . . . . . . . . General Techniques and Definitions Sample Inlets and Interfaces . . . . . . Ion Generation . . . . . . . . . . . . . . . Analyzers . . . . . . . . . . . . . . . . . . . Metastable Ions and Linked Scans. .

580 580 585 590 597 603

.

Contents

21. Atomic Spectroscopy 21.1. 21.2. 21.3. 21.4. 21.5. 21.6.

Introduction . . . . . . . . . . . . . . . . . Basic Principles . . . . . . . . . . . . . . Spectrometric Instrumentation . . . . . Sample Introduction Devices . . . . . Atomic Absorption Spectrometry . . Atomic Emission Spectrometry . . . .

...................................... 628 629 642 660 673 688

21.7. Plasma Mass Spectrometry . . . . . . . 21.8. Atomic Fluorescence Spectrometry . 21.9. Laser-Enhanced Ionization Spectrometry . . . . . . . . . . . . . . . . 21.10. Comparison With Other Methods . . 21 .1 1. References . . . . . . . . . . . . . . . . . .

.

22 Laser Analytical Spectroscopy 22.1. Introduction . . . . . . . . . . . . . . . . . 727 22.2. Tunable Lasers . . . . . . . . . . . . . . . 730 22.3. Laser Techniques for Elemental Analysis . . . . . . . . . . . . . . . . . . . . 732

...........................

.

24 Activation Analysis 24.1. 24.2. 24.3. 24.4.

.......................

Accuracy . . . . . . . . . . . . . . . . . . . Quantitative Analysis . . . . . . . . . . . Trace Analysis . . . . . . . . . . . . . . . New developments in Instrumentation and Techniques . . . 23.9. References . . . . . . . . . . . . . . . . . .

23.5. 23.6. 23.7. 23.8.

........................................

Introduction . . . . . . . . . . . . . . . . . Neutron Activation Analysis . . . . . . Photon Activation Analysis . . . . . . Charged-Particle Activation Analysis

767 768 779 780

.

Introduction . . . . . . . . . . . . . . . . . 785 Techniques . . . . . . . . . . . . . . . . . . 788 Instrumentation . . . . . . . . . . . . . . . 803 Evaluation and Calculation . . . . . . . 808 Sample Preparation . . . . . . . . . . . . 8 10

.

827 836

716 718 721

727

753 760 761 762 763 765

767

.............

785

25.6. Supporting Electrolyte Solution . . . 812 25.7. Application to Inorganic and Organic Trace Analysis . . . . . . . . . . . . . . . 814 25.8. References . . . . . . . . . . . . . . . . . . 823

26 Thermal Analysis and Calorimetry 26.1. Thermal Analysis . . . . . . . . . . . . . 26.2. Calorimetry . . . . . . . . . . . . . . . . .

704 713

24.5. Applications . . . . . . . . . . . . . . . . . 781 24.6. Evaluation of Activ...