Instrumental Analytical Chemistry



Instrumental Analytical Chemistry
An Introduction

James W. Robinson, Eileen M. Skelly Frame, and George M. Frame II


First edition published 2021
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Library of Congress Cataloging‑in‑Publication Data

Names: Robinson, James W., 1923-2018, author. | Frame, Eileen M. Skelly, 1953- author. | Frame, George M., II, author.
Title: Instrumental analytical chemistry : an introduction / James W. Robinson, Eileen M. Skelly Frame, George M. Frame II.
Description: First edition. | Boca Raton : CRC Press, 2021. | Includes bibliographical references and index.
Identifiers: LCCN 2020055162 (print) | LCCN 2020055163 (ebook) | ISBN 9781138196476 (hardback) | ISBN 9781315301150 (ebook)
Subjects: LCSH: Instrumental analysis. | Analytical chemistry.
Classification: LCC QD79.I5 .R59 2021 (print) | LCC QD79.I5 (ebook) | DDC 543/.19--dc23
LC record available at />LC ebook record available at />ISBN: 978-1-138-19647-6 (hbk)
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Contents
Abbreviations and Acronyms Index................................................................................................................................................................................................ xvii
Preface.............................................................................................................................................................................................................................................................. xxiii
Authors.............................................................................................................................................................................................................................................................xxv
Acknowledgments .................................................................................................................................................................................................................................xxvii
Chapter 1 Concepts of Instrumental Analytical Chemistry............................................................................................................................................1
1.1
Introduction: What is Instrumental Analytical Chemistry?......................................................................................................1
1.2 Analytical Approach........................................................................................................................................................................................2
1.2.1 Defining the Problem..................................................................................................................................................................3
1.2.1.1 Qualitative Analysis.................................................................................................................................................4
1.2.1.2 Quantitative Analysis.............................................................................................................................................6
1.2.2 Designing the Analytical Method .......................................................................................................................................9

1.2.3 Sampling...........................................................................................................................................................................................10
1.2.3.1 Gas Samples..............................................................................................................................................................13
1.2.3.2 Liquid Samples........................................................................................................................................................13
1.2.3.3 Solid Samples...........................................................................................................................................................14
1.2.4 Storage of Samples.....................................................................................................................................................................14
1.3 Sample Preparation.......................................................................................................................................................................................15
1.3.1 Acid Dissolution and Digestion...........................................................................................................................................15
1.3.2 Fusions................................................................................................................................................................................................18
1.3.3 Dry Ashing and Combustion............................................................................................................................................... 20
1.3.4 Extraction......................................................................................................................................................................................... 20
1.3.4.1 Solvent Extraction.................................................................................................................................................21
1.3.4.2 Solid Phase Extraction (SPE)............................................................................................................................24
1.3.4.3 QuEChERS.................................................................................................................................................................. 25
1.3.4.4 Solid Phase Microextraction (SPME).......................................................................................................... 26
1.4 Basic Statistics and Data Handling....................................................................................................................................................... 29
1.4.1 Accuracy and Precision........................................................................................................................................................... 29
1.4.2 Types of Errors............................................................................................................................................................................... 30
1.4.2.1 Determinate Error................................................................................................................................................. 30
1.4.2.2 Indeterminate Error............................................................................................................................................. 33
1.4.3 Definitions for Statistics........................................................................................................................................................... 34
1.4.4 Quantifying Random Error.................................................................................................................................................... 35
1.4.4.1 Confidence Limits................................................................................................................................................ 39
1.4.4.2 Variance...................................................................................................................................................................... 40
1.4.5 Rejection of Results....................................................................................................................................................................41
1.5 Performing the Measurement................................................................................................................................................................ 42
1.5.1 Signals and Noise........................................................................................................................................................................ 42
1.6 Methods of Calibration............................................................................................................................................................................... 45
1.6.1 Plotting Calibration Curves................................................................................................................................................... 45
1.6.2 Calibration with External Standards.................................................................................................................................47
1.6.3 Method of Standard Additions........................................................................................................................................... 49

1.6.4 Internal Standard Calibration................................................................................................................................................51
1.7 Assessing the Data........................................................................................................................................................................................ 54
1.7.1 Limit of Detection....................................................................................................................................................................... 55
1.7.2 Limit of Quantitation................................................................................................................................................................. 56
Problems............................................................................................................................................................................................................................. 56
Bibliography...................................................................................................................................................................................................................... 58
v


vi    Contents

Chapter 2 Introduction to Spectroscopy.................................................................................................................................................................................61
2.1
The Interaction Between Electromagnetic Radiation and Matter ...................................................................................61
2.1.1 What is Electromagnetic Radiation?.................................................................................................................................61
2.1.2 How Does Electromagnetic Radiation Interact with Matter?........................................................................... 63
2.2 Atoms and Atomic Spectroscopy........................................................................................................................................................ 67
2.3 Molecules and Molecular Spectroscopy......................................................................................................................................... 69
2.3.1 Rotational Transitions in Molecules.................................................................................................................................. 69
2.3.2 Vibrational Transitions in Molecules................................................................................................................................ 70
2.3.3 Electronic Transitions in Molecules.................................................................................................................................. 70
2.4 Absorption Laws............................................................................................................................................................................................. 71
2.4.1 Deviations from Beer’s Law....................................................................................................................................................74
2.4.2 Errors Associated with Beer’s Law Relationships..................................................................................................... 75
2.5 Optical Systems Used in Spectroscopy............................................................................................................................................ 78
2.5.1 Radiation Sources........................................................................................................................................................................ 79
2.5.2 Wavelength Selection Devices........................................................................................................................................... 79
2.5.2.1 Filters............................................................................................................................................................................ 79
2.5.2.2 Monochromator.................................................................................................................................................... 80
2.5.2.3 Resolution Required to Separate Two Lines of Different Wavelength................................. 83

2.5.3 Optical Slits..................................................................................................................................................................................... 88
2.5.4 Detectors.......................................................................................................................................................................................... 89
2.5.5 Single-Beam and Double-Beam Optics........................................................................................................................ 89
2.5.6 Dispersive Optical Layouts.................................................................................................................................................... 92
2.5.7 Fourier Transform Spectrometers..................................................................................................................................... 93
2.6 Spectroscopic Technique and Instrument Nomenclature................................................................................................... 95
Suggested Experiments............................................................................................................................................................................................ 95
Problems............................................................................................................................................................................................................................. 96
Bibliography...................................................................................................................................................................................................................... 99
Chapter 3 Visible and Ultraviolet Molecular Spectroscopy.......................................................................................................................................101
3.1 Introduction....................................................................................................................................................................................................101
3.1.1 Electronic Excitation in Molecules..................................................................................................................................104
3.1.2 Absorption by Molecules.....................................................................................................................................................107
3.1.3 Molar Absorptivity....................................................................................................................................................................108
3.1.4 The Shape of UV Absorption Curves.............................................................................................................................109
3.1.5 Solvents for UV/VIS Spectroscopy...................................................................................................................................111
3.2 Instrumentation.............................................................................................................................................................................................112
3.2.1 Optical System.............................................................................................................................................................................112
3.2.2 Radiation Sources.......................................................................................................................................................................113
3.2.3 Monochromators.......................................................................................................................................................................115
3.2.4 Detectors.........................................................................................................................................................................................115
3.2.4.1 Barrier Layer Cell...................................................................................................................................................115
3.2.4.2 Photomultiplier Tube.........................................................................................................................................117
3.2.4.3 Semiconductor Detectors: Diodes and Diode Array Systems................................................. 118
3.2.4.4 Diodes........................................................................................................................................................................120
3.2.4.5 Diode Arrays.......................................................................................................................................................... 121
3.2.5 Sample Holders..........................................................................................................................................................................122
3.2.5.1 Liquid and Gas Cells..........................................................................................................................................122
3.2.5.2 Matched Cells........................................................................................................................................................ 124
3.2.5.3 Flow-Through Samplers.................................................................................................................................125

3.2.5.4 Solid Sample Holders.......................................................................................................................................126
3.2.5.5 Fiber Optic Probes.............................................................................................................................................126
3.2.6 Microvolume, Nanovolume and Hand-Held UV/VIS Spectrometers........................................................127
3.3 Analytical Applications.............................................................................................................................................................................134
3.3.1 Qualitative Structural Analysis...........................................................................................................................................134
3.3.2 Quantitative Analysis...............................................................................................................................................................134


Contents    vii

3.3.3
3.3.4

Multicomponent Determinations...................................................................................................................................139
Other Applications...................................................................................................................................................................140
3.3.4.1 Reaction Kinetics.................................................................................................................................................140
3.3.4.2 Spectrophotometric Titrations................................................................................................................... 141
3.3.4.3 Spectroelectrochemistry...............................................................................................................................142
3.3.4.4 Analysis of Solids.................................................................................................................................................142
3.3.5 Measurement of Color...........................................................................................................................................................142
3.4 Nephelometry and Turbidimetry.......................................................................................................................................................144
3.5 Molecular Emission Spectrometry....................................................................................................................................................146
3.5.1 Fluorescence and Phosphorescence............................................................................................................................146
3.5.2 Relationship Between Fluorescence Intensity and Concentration.............................................................148
3.6 Instrumentation for Luminescence Measurements................................................................................................................150
3.6.1 Wavelength Selection Devices.........................................................................................................................................150
3.6.2 Radiation Sources...................................................................................................................................................................... 151
3.6.3 Detectors........................................................................................................................................................................................152
3.6.4 Sample Cells.................................................................................................................................................................................153
3.7 Analytical Applications of Luminescence.....................................................................................................................................153

3.7.1 Advantages of Fluorescence and Phosphorescence..........................................................................................155
3.7.2 Disadvantages of Fluorescence and Phosphorescence ...................................................................................155
Suggested Experiments..........................................................................................................................................................................................156
Problems...........................................................................................................................................................................................................................157
Bibliography.................................................................................................................................................................................................................... 161
Chapter 4 Infrared, Near-Infrared, and Raman Spectroscopy..................................................................................................................................163
4.1
Absorption of IR Radiation by Molecules .....................................................................................................................................164
4.1.1 Dipole Moments in Molecules..........................................................................................................................................164
4.1.2 Types of Vibrations in Molecules.....................................................................................................................................166
4.1.3 Vibrational Motion....................................................................................................................................................................168
4.2 IR Instrumentation.......................................................................................................................................................................................169
4.2.1 Radiation Sources......................................................................................................................................................................172
4.2.1.1 Mid-IR Sources......................................................................................................................................................173
4.2.1.2 NIR Sources............................................................................................................................................................. 174
4.2.1.3 Far-IR Sources........................................................................................................................................................ 175
4.2.1.4 IR Laser Sources................................................................................................................................................... 175
4.2.2 Monochromators and Interferometers........................................................................................................................ 175
4.2.2.1 FT Spectrometers............................................................................................................................................... 176
4.2.2.2 Interferometer Components.......................................................................................................................179
4.2.3 Detectors........................................................................................................................................................................................181
4.2.3.1 Bolometer................................................................................................................................................................182
4.2.3.2 Pyroelectric Detectors.....................................................................................................................................182
4.2.3.3 Photon Detectors...............................................................................................................................................182
4.2.4 Detector Response Time......................................................................................................................................................183
4.3 Sampling Techniques................................................................................................................................................................................184
4.3.1 Techniques for Transmission (Absorption) Measurements..............................................................................184
4.3.1.1 Solid Samples........................................................................................................................................................184
4.3.1.2 Liquid Samples.....................................................................................................................................................187
4.3.1.3 Gas Samples...........................................................................................................................................................189

4.3.2 Background Correction in Transmission Measurements..................................................................................190
4.3.2.1 Solvent Absorption............................................................................................................................................190
4.3.2.2 Air Absorption...................................................................................................................................................... 191
4.3.3 Techniques for Reflectance and Emission Measurements.............................................................................. 191
4.3.3.1 Attenuated Total Reflectance (ATR)......................................................................................................... 191
4.3.3.2 Specular Reflectance........................................................................................................................................193
4.3.3.3 Diffuse Reflectance............................................................................................................................................194
4.3.3.4 IR Emission..............................................................................................................................................................195


viii    Contents

4.4
4.5
4.6

FTIR Microscopy............................................................................................................................................................................................196
Nondispersive IR Systems...................................................................................................................................................................... 200
Analytical Applications of IR Spectroscopy..................................................................................................................................201
4.6.1 Qualitative Analyses and Structural Determination by Mid-IR Absorption Spectroscopy...........202
4.6.2 Quantitative Analyses by IR Spectrometry............................................................................................................... 206
4.7 Near-IR Spectroscopy................................................................................................................................................................................209
4.7.1 Instrumentation.........................................................................................................................................................................210
4.7.2 NIR Vibrational Bands..............................................................................................................................................................210
4.7.3 NIR Calibration: Chemometrics........................................................................................................................................ 212
4.7.4 Sampling Techniques for NIR Spectroscopy............................................................................................................ 213
4.7.4.1 Liquids and Solutions.......................................................................................................................................214
4.7.4.2 Solids..........................................................................................................................................................................214
4.7.4.3 Gases..........................................................................................................................................................................214
4.7.5 Applications of NIR Spectroscopy..................................................................................................................................214

4.8 Raman Spectroscopy................................................................................................................................................................................. 217
4.8.1 Principles of Raman Scattering......................................................................................................................................... 217
4.8.2 Raman Instrumentation........................................................................................................................................................ 219
4.8.2.1 Light Sources......................................................................................................................................................... 219
4.8.2.2 Dispersive Spectrometers Systems..........................................................................................................221
4.8.2.3 FT-Raman Spectrometers..............................................................................................................................222
4.8.2.4 Fiber Optic-Based Modular and Handheld Systems.....................................................................223
4.8.2.5 Samples and Sample Holders for Raman Spectroscopy............................................................224
4.8.3 Applications of Raman Spectroscopy..........................................................................................................................226
4.8.4 The Resonance Raman Effect............................................................................................................................................230
4.8.5 Surface-Enhanced Raman Spectroscopy (SERS)....................................................................................................231
4.8.6 Raman Microscopy...................................................................................................................................................................232
4.9 Chemical Imaging Using NIR, IR, and Raman Spectroscopy.............................................................................................233
Suggested Experiments..........................................................................................................................................................................................240
Problems........................................................................................................................................................................................................................... 241
Bibliography....................................................................................................................................................................................................................242
Chapter 5 Magnetic Resonance Spectroscopy.................................................................................................................................................................245
5.1 Nuclear Magnetic Resonance Spectroscopy: Introduction...............................................................................................245
5.1.1 Properties of Nuclei.................................................................................................................................................................246
5.1.2 Quantization of 1H Nuclei in a Magnetic Field........................................................................................................247
5.1.2.1 Saturation and Magnetic Field Strength..............................................................................................250
5.1.3 Width of Absorption Lines..................................................................................................................................................252
5.1.3.1 The Homogeneous Field...............................................................................................................................252
5.1.3.2 Relaxation Time...................................................................................................................................................253
5.1.3.3 The Chemical Shift............................................................................................................................................ 254
5.1.3.4 Magic Angle Spinning.................................................................................................................................... 254
5.1.3.5 Other Sources of Line Broadening.......................................................................................................... 254
5.2 The FTNMR Experiment...........................................................................................................................................................................255
5.3 Chemical Shifts..............................................................................................................................................................................................258
5.4 Spin-Spin Coupling.....................................................................................................................................................................................263

5.5 Instrumentation............................................................................................................................................................................................269
5.5.1 Sample Holder............................................................................................................................................................................269
5.5.2 Sample Probe..............................................................................................................................................................................272
5.5.3 Magnet............................................................................................................................................................................................272
5.5.4 RF Generation and Detection...........................................................................................................................................274
5.5.5 Signal Integrator and Computer......................................................................................................................................274
5.6 Analytical Applications of NMR...........................................................................................................................................................275
5.6.1 Samples and Sample Preparation for NMR ..............................................................................................................275
5.6.2 Qualitative Analyses: Molecular Structure Determination...............................................................................276
5.6.2.1 Relationship Between the Area of a Peak and Molecular Structure ...................................276


Contents    ix

5.6.2.2 Chemical Exchange...........................................................................................................................................277
5.6.2.3 Double Resonance Experiments...............................................................................................................277
5.6.3 13C NMR...........................................................................................................................................................................................280
5.6.3.1 Heteronuclear Decoupling...........................................................................................................................282
5.6.3.2 The Nuclear Overhauser Effect...................................................................................................................282
5.6.3.3 13C NMR Spectra of Solids..............................................................................................................................283
5.6.4 2D NMR.......................................................................................................................................................................................... 284
5.6.5 Qualitative Analyses: Other Applications....................................................................................................................287
5.6.6 Quantitative Analyses.............................................................................................................................................................288
5.7 Hyphenated NMR Techniques.............................................................................................................................................................291
5.8 NMR Imaging and MRI..............................................................................................................................................................................292
5.9 Low-Field, Portable, and Miniature NMR Instruments.......................................................................................................... 294
5.10 Limitations of NMR......................................................................................................................................................................................297
Suggested Experiments..........................................................................................................................................................................................298
Problems...........................................................................................................................................................................................................................298
Bibliography................................................................................................................................................................................................................... 300

Chapter 6 Atomic Absorption Spectrometry....................................................................................................................................................................303
6.1 Absorption of Radiant Energy by Atoms.......................................................................................................................................303
6.1.1 Spectral Linewidth...................................................................................................................................................................305
6.1.2 Degree of Radiant Energy Absorption........................................................................................................................ 306
6.2 Instrumentation........................................................................................................................................................................................... 306
6.2.1 Radiation Sources......................................................................................................................................................................307
6.2.1.1 Hollow Cathode Lamp (HCL)......................................................................................................................307
6.2.1.2 Electrodeless Discharge Lamp (EDL)......................................................................................................309
6.2.2 Atomizers.......................................................................................................................................................................................310
6.2.2.1 Flame Atomizers..................................................................................................................................................310
6.2.2.2 Electrothermal Atomizers.............................................................................................................................. 312
6.2.2.3 Other Atomizers.................................................................................................................................................. 314
6.2.3 Spectrometer Optics............................................................................................................................................................... 315
6.2.3.1 Monochromator.................................................................................................................................................. 315
6.2.3.2 Optics and Spectrometer Configuration............................................................................................. 316
6.2.4 Detectors........................................................................................................................................................................................ 317
6.2.5 Modulation.................................................................................................................................................................................... 317
6.2.6 Commercial AAS Systems.................................................................................................................................................... 318
6.2.6.1 High-Resolution Continuum Source AAS............................................................................................ 319
6.3 The Atomization Process......................................................................................................................................................................... 319
6.3.1 Flame Atomization................................................................................................................................................................... 319
6.3.2 Graphite Furnace Atomization..........................................................................................................................................324
6.4 Interferences in AAS...................................................................................................................................................................................326
6.4.1 Non-Spectral Interferences.................................................................................................................................................326
6.4.1.1 Chemical Interference......................................................................................................................................326
6.4.1.2 Matrix Interference.............................................................................................................................................327
6.4.1.3 Ionization Interference....................................................................................................................................328
6.4.1.4 Non-Spectral Interferences in GFAAS....................................................................................................328
6.4.1.5 Chemical Modification....................................................................................................................................330
6.4.2 Spectral Interferences.............................................................................................................................................................332

6.4.2.1 Atomic Spectral Interference.......................................................................................................................332
6.4.2.2 Background Absorption and its Correction.......................................................................................332
6.4.2.3 Continuum Source Background Correction.......................................................................................333
6.4.2.4 Zeeman Background Correction...............................................................................................................335
6.4.2.5 Smith-Hieftje Background Correction...................................................................................................336
6.4.2.6 Spectral Interferences In GFAAS...............................................................................................................337
6.5 Analytical Applications of AAS.............................................................................................................................................................338
6.5.1 Qualitative Analysis..................................................................................................................................................................338


x    Contents

6.5.2

Quantitative Analysis...............................................................................................................................................................339
6.5.2.1 Quantitative Analytical Range....................................................................................................................339
6.5.2.2 Calibration...............................................................................................................................................................339
6.5.3 Analysis of Samples..................................................................................................................................................................341
6.5.3.1 Liquid Samples.....................................................................................................................................................341
6.5.3.2 Solid Samples........................................................................................................................................................342
6.5.3.3 Gas Samples.......................................................................................................................................................... 344
6.5.3.4 Cold Vapor Mercury Technique.................................................................................................................345
6.5.3.5 Hydride Generation Technique................................................................................................................. 346
6.5.3.6 Flow Injection Analysis................................................................................................................................... 346
6.5.3.7 Flame Microsampling.......................................................................................................................................347
Suggested Experiments..........................................................................................................................................................................................347
Problems...........................................................................................................................................................................................................................349
Bibliography....................................................................................................................................................................................................................350
Chapter 7 Atomic Emission Spectroscopy...........................................................................................................................................................................353
7.1 Flame Atomic Emission Spectroscopy............................................................................................................................................353

7.1.1 Instrumentation for Flame OES........................................................................................................................................354
7.1.1.1 Burner Assembly.................................................................................................................................................355
7.1.1.2 Wavelength Selection Devices...................................................................................................................355
7.1.1.3 Detectors.................................................................................................................................................................356
7.1.1.4 Flame Excitation Source.................................................................................................................................356
7.1.2 Interferences................................................................................................................................................................................358
7.1.2.1 Chemical Interference......................................................................................................................................358
7.1.2.2 Excitation and Ionization Interferences.................................................................................................358
7.1.2.3 Spectral Interferences......................................................................................................................................359
7.1.3 Analytical Applications of Flame OES.......................................................................................................................... 360
7.1.3.1 Qualitative Analysis........................................................................................................................................... 360
7.1.3.2 Quantitative Analysis....................................................................................................................................... 360
7.2 Atomic Optical Emission Spectroscopy.........................................................................................................................................362
7.2.1 Instrumentation for Emission Spectroscopy............................................................................................................363
7.2.1.1 Electrical Excitation Sources........................................................................................................................ 364
7.2.1.2 Sample Holders................................................................................................................................................... 368
7.2.1.3 Spectrometers......................................................................................................................................................369
7.2.1.4 Detectors.................................................................................................................................................................374
7.2.2 Interferences in Arc and Spark Emission Spectroscopy.....................................................................................376
7.2.2.1 Matrix Effects and Sample Preparation.................................................................................................376
7.2.2.2 Spectral Interference........................................................................................................................................377
7.2.2.3 Internal Standard Calibration.......................................................................................................................377
7.2.3 Applications of Arc and Spark Emission Spectroscopy......................................................................................378
7.2.3.1 Qualitative Analysis............................................................................................................................................378
7.2.3.2 Raies Ultimes.........................................................................................................................................................378
7.2.3.3 Quantitative Analysis........................................................................................................................................381
7.3 Plasma Emission Spectroscopy............................................................................................................................................................382
7.3.1 Instrumentation for Plasma Emission Spectrometry...........................................................................................382
7.3.1.1 Excitation Sources..............................................................................................................................................382
7.3.1.2 Spectrometer Systems for Plasma Spectroscopy.......................................................................... 386

7.3.1.3 Sample Introduction Systems.....................................................................................................................389
7.3.2 Calibration and Interferences in Plasma Emission Spectrometry................................................................395
7.3.2.1 Chemical and Ionization Interference....................................................................................................397
7.3.2.2 Spectral Interference and Correction.....................................................................................................398
7.3.3 Applications of Atomic Emission Spectroscopy.....................................................................................................401
7.3.4 Chemical Speciation with Hyphenated Instruments..........................................................................................403
7.4 Glow Discharge Emission Spectrometry...................................................................................................................................... 404
7.4.1 DC And RF GD Sources......................................................................................................................................................... 404


Contents    xi

7.4.2

Applications of GD Atomic Emission Spectrometry........................................................................................... 405
7.4.2.1 Bulk Analysis.......................................................................................................................................................... 405
7.4.2.2 Depth Profile Analysis..................................................................................................................................... 406
7.5 Atomic Fluorescence Spectroscopy................................................................................................................................................ 406
7.5.1 Instrumentation for AFS....................................................................................................................................................... 409
7.5.2 Interferences in AFS................................................................................................................................................................. 410
7.5.2.1 Chemical Interference...................................................................................................................................... 410
7.5.2.2 Spectral Interference.........................................................................................................................................411
7.5.3 Applications of AFS...................................................................................................................................................................411
7.5.3.1 Mercury Determination and Speciation by AFS...............................................................................411
7.5.3.2 Hydride Generation and Speciation by AFS....................................................................................... 412
7.6 Laser-Induced Breakdown Spectroscopy (LIBS)........................................................................................................................ 412
7.6.1 Principle of Operation............................................................................................................................................................ 412
7.6.2 Instrumentation......................................................................................................................................................................... 413
7.6.3 Applications of LIBS................................................................................................................................................................. 414
7.6.3.1 Qualitative Analysis............................................................................................................................................ 415

7.6.3.2 Quantitative Analysis........................................................................................................................................ 416
7.6.3.3 Remote Analysis.................................................................................................................................................. 417
7.7 Atomic Emission Literature and Resources.................................................................................................................................. 419
Suggested Experiments.......................................................................................................................................................................................... 419
Problems...........................................................................................................................................................................................................................421
Bibliography....................................................................................................................................................................................................................423
Chapter 8 X-ray Spectroscopy.....................................................................................................................................................................................................427
8.1 Origin of X-ray Spectra..............................................................................................................................................................................427
8.1.1 Energy Levels in Atoms..........................................................................................................................................................427
8.1.2 Moseley’s Law.............................................................................................................................................................................433
8.1.3 X-ray Methods ............................................................................................................................................................................434
8.1.3.1 X-ray Absorption Process...............................................................................................................................434
8.1.3.2 X-ray Fluorescence Process...........................................................................................................................437
8.1.3.3 X-ray Diffraction Process................................................................................................................................438
8.2 X-ray Fluorescence......................................................................................................................................................................................439
8.2.1 X-ray Source..................................................................................................................................................................................439
8.2.1.1 X-ray Tube............................................................................................................................................................... 440
8.2.1.2 Secondary XRF Sources.................................................................................................................................444
8.2.1.3 Radioisotope Sources......................................................................................................................................444
8.2.2 Instrumentation for Energy Dispersive X-ray Spectrometry.......................................................................... 445
8.2.2.1 Excitation Source............................................................................................................................................... 446
8.2.2.2 Primary Beam Modifiers..................................................................................................................................447
8.2.2.3 Sample Holders....................................................................................................................................................450
8.2.2.4 EDXRF Detectors.................................................................................................................................................454
8.2.2.5 Multichannel Pulse Height Analyzer.......................................................................................................457
8.2.2.6 Detector Artifact Escape Peaks and Sum Peaks..............................................................................458
8.2.3 Instrumentation for Wavelength Dispersive X-ray Spectrometry.............................................................. 460
8.2.3.1 Collimators..............................................................................................................................................................461
8.2.3.2 Analyzing Crystals..............................................................................................................................................462
8.2.3.3 Detectors................................................................................................................................................................ 465

8.2.3.4 Electronic Pulse Processing Units.............................................................................................................470
8.2.3.5 Sample Changers................................................................................................................................................471
8.2.4 Simultaneous WDXRF Spectrometers.........................................................................................................................471
8.2.5 Micro-XRF Instrumentation.................................................................................................................................................473
8.2.5.1 Micro X-ray Beam Optics................................................................................................................................473
8.2.5.2 Micro-XRF System Components................................................................................................................475
8.2.6 Total Reflection XRF.................................................................................................................................................................476
8.2.7 Comparison Between EDXRF and WDXRF ...............................................................................................................476


xii    Contents

8.2.8

XRF Applications........................................................................................................................................................................476
8.2.8.1 The Analyzed Layer...........................................................................................................................................477
8.2.8.2 Sample Preparation Considerations for XRF......................................................................................479
8.2.8.3 Qualitative Analysis by XRF...........................................................................................................................482
8.2.8.4 Quantitative Analysis by XRF.......................................................................................................................487
8.3 X-ray Absorption...........................................................................................................................................................................................490
8.4 X-ray Diffraction............................................................................................................................................................................................496
8.4.1 Single Crystal X-ray Diffractometry................................................................................................................................499
8.4.2 Crystal Growing..........................................................................................................................................................................499
8.4.3 Crystal Structure Determination......................................................................................................................................501
8.4.4 Powder X-ray Diffractometry.............................................................................................................................................503
8.4.5 Hybrid XRD/XRF Systems.................................................................................................................................................... 504
8.4.6 Applications of XRD................................................................................................................................................................ 506
8.5 X-ray Emission................................................................................................................................................................................................509
Suggested Experiments.......................................................................................................................................................................................... 511
Problems........................................................................................................................................................................................................................... 512

Bibliography.................................................................................................................................................................................................................... 517
Chapter 9 Mass Spectrometry.................................................................................................................................................................................................... 519
9.1 Principles of MS.............................................................................................................................................................................................520
9.1.1 Resolving Power and Resolution of a Mass Spectrometer..............................................................................525
9.2 Instrumentation............................................................................................................................................................................................527
A Brief Digression on Units of Measure—Vacuum Systems.............................................................................................................527
9.2.1 Sample Input Systems............................................................................................................................................................528
9.2.1.1 Gas Expansion.......................................................................................................................................................528
9.2.1.2 Direct Insertion and Direct Exposure Probes....................................................................................528
9.2.1.3 Chromatography and Electrophoresis Systems...............................................................................528
9.2.2 Ionization Sources....................................................................................................................................................................529
9.2.2.1 Electron Ionization (EI).....................................................................................................................................529
9.2.2.2 Chemical Ionization (CI)..................................................................................................................................530
9.2.2.3 Atmospheric Pressure Ionization (API) Sources................................................................................531
9.2.2.4 Desorption Ionization......................................................................................................................................535
9.2.2.5 Ionization Sources for Inorganic MS....................................................................................................... 540
9.2.3 Mass Analyzers............................................................................................................................................................................541
9.2.3.1 Magnetic and Electric Sector Instruments..........................................................................................542
9.2.3.2 Time of Flight (TOF) Analyzer..................................................................................................................... 546
9.2.3.3 Quadrupole Mass Analyzer...........................................................................................................................551
9.2.3.4 MS/MS and MSn Instruments.......................................................................................................................554
9.2.3.5 Quadrupole Ion Trap........................................................................................................................................556
9.2.3.6 Fourier Transform Ion-Cyclotron Resonance (FTICR)....................................................................557
9.2.3.7 The OrbitrapTM TMMS.......................................................................................................................................558
9.2.4 Detectors........................................................................................................................................................................................559
9.2.4.1 Electron Multiplier............................................................................................................................................. 560
9.2.4.2 Faraday Cup............................................................................................................................................................562
9.2.4.3 Array Detectors....................................................................................................................................................562
9.3 Ion Mobility Spectrometry.....................................................................................................................................................................563
9.3.1 Handheld DMS Juno® Chemical Trace Vapor Point Detector....................................................................... 564

9.3.2 The Excellims HPIMS-LC System..................................................................................................................................... 564
9.3.3 Photonis Ion Mobility Spectrometer Engine............................................................................................................565
9.3.4 Synapt G2-S Multistage MS System Incorporating the Triwave Ion Mobility Stage........................ 566
9.4 Applications of Molecular MS.............................................................................................................................................................. 566
9.4.1 High-Resolution Mass Spectrometry............................................................................................................................570
9.4.1.1 Achieving Higher Mass Accuracy (but not Resolution) from Low Resolution
MS Instruments ...................................................................................................................................................572


Contents    xiii

9.4.1.2

Improving the Quantitation Accuracy of Isotope Ratios from Low Resolution
MS Instrument Data Files...............................................................................................................................572
9.4.2 Quantitative Analysis of Compounds and Mixtures............................................................................................573
9.4.3 Protein-Sequencing Analysis (Proteomics)................................................................................................................576
9.4.4 Gas Analysis..................................................................................................................................................................................577
9.4.5 Environmental Applications...............................................................................................................................................578
9.4.6 Other Applications of Molecular MS.............................................................................................................................578
9.4.7 Limitations of Molecular MS...............................................................................................................................................580
9.5 Atomic MS........................................................................................................................................................................................................580
9.5.1 Inductively Coupled Plasma Mass Spectrometry (ICP-MS).............................................................................580
9.5.2 Applications of Atomic MS..................................................................................................................................................583
9.5.2.1 Geological and Materials Characterization Applications............................................................586
9.5.2.2 Speciation by Coupled Chromatography-ICP-MS..........................................................................587
9.5.2.3 Applications in Food Chemistry, Environmental Chemistry, Biochemistry,
Clinical Chemistry, and Medicine..............................................................................................................588
9.5.2.4 Coupled Elemental Analysis-MS................................................................................................................590
9.5.3 Interferences in Atomic MS.................................................................................................................................................591

9.5.3.1 Matrix Effects.........................................................................................................................................................591
9.5.3.2 Spectral (Isobaric) Interferences................................................................................................................592
9.5.4 Instrumental Approaches to Eliminating Interferences.....................................................................................594
9.5.4.1 High-Resolution ICP-MS (HR-ICP-MS).....................................................................................................594
9.5.4.2 Collision and Reaction Cells..........................................................................................................................594
9.5.4.3 MS/MS Interference Removal......................................................................................................................595
9.5.5 Limitations of Atomic MS.....................................................................................................................................................597
9.5.5.1 Common Spurious Effects in Mass Spectrometry.........................................................................598
Problems...........................................................................................................................................................................................................................598
Bibliography................................................................................................................................................................................................................... 600
Chapter 10 Principles of Chromatography.............................................................................................................................................................................603
10.1 Introduction to Chromatography......................................................................................................................................................603
10.2 What is the Chromatographic Process?......................................................................................................................................... 604
10.3 Chromatography in More than One Dimension......................................................................................................................607
10.4 Visualization of the Chromatographic Process at the Molecular Level: Analogy to “People on a
Moving Belt Slideway”............................................................................................................................................................................. 608
10.5 The Central Role of Silicon-Oxygen Compounds In Chromatography...................................................................... 613
10.6 Basic Equations Describing Chromatographic Separations............................................................................................... 616
10.7 How do Column Variables Affect Efficiency (Plate Height)?.............................................................................................. 619
10.8 Practical Optimization of Chromatographic Separations....................................................................................................621
10.9 Extra-Column Band Broadening Effects........................................................................................................................................622
10.10 Qualitative Chromatography: Analyte Identification.............................................................................................................623
10.11 Quantitative Measurements in Chromatography....................................................................................................................624
10.11.1 Peak Area or Peak Height: What is Best for Quantitation?................................................................................625
10.11.2 Calibration with an External Standard..........................................................................................................................626
10.11.3 Calibration with an Internal Standard...........................................................................................................................626
10.12 Examples of Chromatographic Calculations...............................................................................................................................627
Problems...........................................................................................................................................................................................................................629
Questions Based on Example in Section 10.13, Tables 10.1 and 10.2.........................................................................................630
Bibliography....................................................................................................................................................................................................................631

Chapter 11 Gas Chromatography................................................................................................................................................................................................633
11.1 Historical Development of GC: The First Chromatographic Instrumentation........................................................633
11.2 Advances in GC Leading to Present-Day Instrumentation.................................................................................................635
11.3 GC Instrument Component Design (Injectors)..........................................................................................................................637
11.3.1 Syringes...........................................................................................................................................................................................637


xiv    Contents

11.3.2 Autosamplers...............................................................................................................................................................................638
11.3.3 Solid Phase Microextraction (SPME)..............................................................................................................................639
11.3.4 Split Injections............................................................................................................................................................................ 640
11.3.5 Splitless Injections.....................................................................................................................................................................641
11.4 GC Instrument Component Design (The Column).................................................................................................................642
11.4.1 Column Stationary Phase.....................................................................................................................................................642
11.4.2 Selecting a Stationary Phase for an Application....................................................................................................645
11.4.3 Effects of Mobile Phase Choice and Flow Parameters...................................................................................... 646
11.5 GC Instrument Operation (Column Dimensions and Elution Values)......................................................................... 648
11.6 GC Instrument Operation (Column Temperature and Elution Values)........................................................................650
11.7 GC Instrument Component Design (Detectors).......................................................................................................................654
11.7.1 Thermal Conductivity Detector (TCD).........................................................................................................................656
11.7.2 Flame Ionization Detector (FID).......................................................................................................................................657
11.7.3 Electron Capture Detector (ECD).....................................................................................................................................658
11.7.4 Electrolytic Conductivity Detector (ELCD)................................................................................................................ 660
11.7.5 Sulfur–Phosphorus Flame Photometric Detector (SP-FPD)............................................................................661
11.7.6 Sulfur Chemiluminescence Detector (SCD)..............................................................................................................661
11.7.7 Nitrogen-Phosphorus Detector (NPD).........................................................................................................................661
11.7.8 Photoionization Detector (PID)........................................................................................................................................662
11.7.9 Helium Ionization Detector (HID)...................................................................................................................................663
11.7.10 Atomic Emission Detector (AED).................................................................................................................................... 664

11.8 Hyphenated GC Techniques (GC-MS; GC-IR; GC-GC; 2D-GC)............................................................................................665
11.8.1 Gas Chromatography-Mass Spectrometry (GC-MS)............................................................................................665
11.8.2 Gas Chromatography-IR Spectrometry (GC-IR)..................................................................................................... 668
11.8.3 Comprehensive 2D-Gas Chromatography (GcxGc or GC2) ............................................................................669
11.9 Retention Indices (a Generalization of Relative Rt Information).......................................................................................673
11.10 The Scope of GC Analyses......................................................................................................................................................................674
11.10.1 Gc Behavior of Organic Compound Classes.............................................................................................................675
11.10.2 Derivatization of Difficult Analytes to Improve GC Elution Behavior........................................................675
11.10.3 Gas Analysis by GC...................................................................................................................................................................676
11.10.4 Limitations of Gas Chromatography.............................................................................................................................679
Problems...........................................................................................................................................................................................................................679
Bibliography....................................................................................................................................................................................................................682
Chapter 12 Chromatography with Liquid Mobile Phases.............................................................................................................................................683
12.1 High-Performance Liquid Chromatography...............................................................................................................................683
12.1.1 HPLC Column and Stationary Phases........................................................................................................................... 684
12.1.1.1 Support Particle Considerations............................................................................................................... 686
12.1.1.2 Stationary Phase Considerations.............................................................................................................. 689
12.1.1.3 Chiral Phases for Separation of Enantiomers.................................................................................... 689
12.1.1.4 New HPLC Phase Combinations for Assays of Very Polar Biomolecules..........................690
12.1.2 Effects on Separation of Composition of the Mobile Phase...........................................................................691
12.1.3 Design and Operation of an HPLC Instrument.......................................................................................................693
12.1.4 HPLC Detector Design and Operation........................................................................................................................697
12.1.4.1 Refractive Index Detector..............................................................................................................................698
12.1.4.2 Aerosol Detectors: Evaporative Light Scattering Detector and Corona Charged
Aerosol Detector.................................................................................................................................................698
12.1.4.3 UV/VIS and IR Absorption Detectors......................................................................................................701
12.1.4.4 Fluorescence Detector....................................................................................................................................703
12.1.4.5 Electrochemical Detectors............................................................................................................................704
12.1.5 Derivatization In HPLC............................................................................................................................................................709
12.1.6 Hyphenated Techniques in HPLC.................................................................................................................................... 711

12.1.6.1 Interfacing HPLC to Mass Spectrometry..............................................................................................712
12.1.7 Applications of HPLC..............................................................................................................................................................716
12.2 Chromatography of Ions Dissolved in Liquids...........................................................................................................................719


Contents    xv

12.2.1 Ion Chromatography..............................................................................................................................................................722
12.2.1.1 Single-Column IC................................................................................................................................................726
12.2.1.2 Indirect Detection in IC...................................................................................................................................726
12.3 Affinity Chromatography........................................................................................................................................................................727
12.4 Size Exclusion Chromatography (SEC)............................................................................................................................................728
12.5 Supercritical Fluid Chromatography................................................................................................................................................730
12.5.1 Operating Conditions.............................................................................................................................................................731
12.5.2 Effect of Pressure.......................................................................................................................................................................731
12.5.3 Stationary and Mobile Phases...........................................................................................................................................731
12.5.4 SFC Versus Other Column Methods..............................................................................................................................732
12.5.5 Applications..................................................................................................................................................................................733
12.5.6 Ultra Performance Convergence Chromatography (UPCC or UPC2) – A New Synthesis.............733
12.6 Electrophoresis..............................................................................................................................................................................................734
12.6.1 Capillary Zone Electrophoresis (CZE)............................................................................................................................734
12.6.2 Sample Injection In CZE........................................................................................................................................................739
12.6.3 Detection In CZE....................................................................................................................................................................... 741
12.6.4 Applications of CZE.................................................................................................................................................................742
12.6.5 Modes of CE.................................................................................................................................................................................742
12.7 Planar Chromatography And Planar Electrophoresis.............................................................................................................742
12.7.1 Thin Layer Chromatography (TLC).................................................................................................................................742
12.7.2 Planar Electrophoresis on Slab Gels...............................................................................................................................745
Problems and Exercises...........................................................................................................................................................................................747
Bibliography....................................................................................................................................................................................................................749

Chapter 13 Electroanalytical Chemistry...................................................................................................................................................................................751
13.1 Fundamentals of Electrochemistry...................................................................................................................................................751
13.2 Electrochemical Cells.................................................................................................................................................................................753
13.2.1 Line Notation for Cells and Half-Cells............................................................................................................................756
13.2.2 Standard Reduction Potentials: The Standard Hydrogen Electrode..........................................................756
13.2.3 Sign Conventions......................................................................................................................................................................759
13.2.4 Nernst Equation.........................................................................................................................................................................759
13.2.5 Activity Series..............................................................................................................................................................................760
13.2.6 Reference Electrodes..............................................................................................................................................................762
13.2.6.1 Saturated Calomel Electrode.......................................................................................................................762
13.2.6.2 Silver/Silver Chloride Electrode..................................................................................................................763
13.2.7 Electrical Double Layer..........................................................................................................................................................763
13.3 Electroanalytical Methods......................................................................................................................................................................764
13.3.1 Potentiometry.............................................................................................................................................................................764
13.3.1.1 Indicator Electrodes..........................................................................................................................................766
13.3.1.2 Instrumentation for Measuring Potential.............................................................................................773
13.3.1.3 Analytical Applications of Potentiometry............................................................................................775
13.3.2 Coulometry...................................................................................................................................................................................786
13.3.2.1 Instrumentation for Electrogravimetry and Coulometry...........................................................788
13.3.2.2 Applied Potential................................................................................................................................................789
13.3.2.3Electrogravimetry...............................................................................................................................................790
13.3.2.4 Analytical Determinations Using Faraday’s Law..............................................................................791
13.3.2.5 Controlled Potential Coulometry..............................................................................................................792
13.3.2.6 Coulometric Titrations.....................................................................................................................................793
13.3.3 Conductometric Analysis.....................................................................................................................................................795
13.3.3.1 Instrumentation for Conductivity Measurements..........................................................................797
13.3.3.2 Analytical Applications of Conductometric Measurements....................................................798
13.3.4 Polarography................................................................................................................................................................................801
13.3.4.1 Classical or DC Polarography.......................................................................................................................802
13.3.4.2 Half-Wave Potential............................................................................................................................................807



xvi    Contents

13.3.4.3 Normal Pulse Polarography..........................................................................................................................807
13.3.4.4 Differential Pulse Polarography................................................................................................................. 809
13.3.5 Voltammetry................................................................................................................................................................................ 812
13.3.5.1 Instrumentation for Voltammetry............................................................................................................ 813
13.3.5.2 Cyclic Voltammetry............................................................................................................................................ 813
13.3.5.3 Stripping Voltammetry....................................................................................................................................814
13.4 Spectroelectrochemistry......................................................................................................................................................................... 817
Suggested Experiments..........................................................................................................................................................................................821
Problems...........................................................................................................................................................................................................................822
Bibliography....................................................................................................................................................................................................................823
Chapter 14 Thermal Analysis..........................................................................................................................................................................................................825
14.1 Thermogravimetry......................................................................................................................................................................................827
14.1.1 TGA Instrumentation..............................................................................................................................................................829
14.1.2 Analytical Applications of Thermogravimetry........................................................................................................832
14.1.3 Derivative Thermogravimetry...........................................................................................................................................837
14.1.4 Sources of Error in Thermogravimetry.........................................................................................................................839
14.2 Differential Thermal Analysis................................................................................................................................................................ 840
14.2.1 DTA Instrumentation...............................................................................................................................................................841
14.2.2 Analytical Applications of DTA..........................................................................................................................................843
14.3 Differential Scanning Calorimetry......................................................................................................................................................845
14.3.1 DSC Instrumentation..............................................................................................................................................................845
14.3.2 Applications of DSC.................................................................................................................................................................851
14.3.2.1 Pressure DSC..........................................................................................................................................................853
14.3.2.2 Modulated DSC...................................................................................................................................................854
14.4 Hyphenated Techniques.........................................................................................................................................................................854
14.4.1 Hyphenated Thermal Methods........................................................................................................................................854

14.4.2 Evolved Gas Analysis...............................................................................................................................................................855
14.5 Thermometric Titrimetry.........................................................................................................................................................................858
14.6 Direct Injection Enthalpimetry........................................................................................................................................................... 860
14.7 Microcalorimetry..........................................................................................................................................................................................861
14.7.1 Micro-DSC Instrumentation...............................................................................................................................................862
14.7.2 Applications of Micro DSC...................................................................................................................................................863
14.7.3 Isothermal Titration Calorimetry..................................................................................................................................... 866
14.7.4 Microliter Flow Calorimetry................................................................................................................................................ 868
A Note About Reference Materials.................................................................................................................................................................. 868
Suggested Experiment............................................................................................................................................................................................869
Problems...........................................................................................................................................................................................................................870
Bibliography....................................................................................................................................................................................................................872
Index.................................................................................................................................................................................................................................................................875


Abbreviations and Acronyms Index
Instrumentation for analytical chemistry gives rise to many abbreviations, some forming “acronyms.” These are often
more encountered than the terms they abbreviate, and they appear extensively in the text. A reader new to the field may
become lost or disoriented in this thicket of initials. To aid the student in reading the text, the abbreviation/acronym
index below translates these and indicates the chapter where they are best defined or characterized. These acronyms
are frequently compounded, as in UV/VIS (ultraviolet/visible) or LC-CI-TOFMS (interfaced liquid chromatograph to
time-of-flight mass spectrometer operating in chemical ionization mode). The components of such compounded abbreviations are listed individually in the index, but not all the possible combinations. All acronyms are abbreviations, but
the reverse is not true. For example, CLIPS, DART, DRIFTS and COSY are acronyms because they form words or are
pronounced as words; GFAAS, APCI, and FTIR are abbreviations.
Acronym

Chapter Abbreviated Term

Acronym


Chapter Abbreviated Term

AAS

6Atomic absorption
spectrometry
12Alternating current (or
voltage)
12Acetonitrile
11
Atomic emission detector
7Atomic emission
spectroscopy
7Atomic fluorescence
spectroscopy
9
Atomic mass unit
1Association of Official
Analytical Chemists
5American Oil Chemists’
Society
9Atmospheric pressure
chemical ionization
6Ammonium pyrrolidine
dithiocarbamate
1American Public Health
Association
5American Petroleum
Institute
5Active pharmaceutical

ingredients
9Atmospheric pressure
photoionization
5
Attached proton test
8Alpha particle X-ray
spectrometer
5American Society of Brewing
Chemists
1Accelerated solvent
extraction
1American Society for Testing
and Materials

ATP
ATR
BCA
BID

5
Adenosine triphosphate
4Attenuated total reflectance
3
Bicinchoninic acid
11(Dielectric) Barrier discharge
detector (GC)
11Benzene, toluene,
ethylbenzene, xylenes
12Corona charged aerosol
detector

8
Computed axial tomography
4Charge coupled device (or
detector)
1
Compact disks
12
Capillary electrophoresis
13Counter electrode (in
electrochemistry)
13Capillary
electrochromatography
9
Channel electron multiplier
9
Continuous flow-FAB
12
Capillary gel electrophoresis
9
Chemical ionization
7Charge injection device (or
detector)
12Collision-induced
dissociation
3Commission Internationale
de l’Eclairage
13
Capillary isoelectric focusing
14Controlled intensity
modulated photocurrent

spectroscopy
1
Confidence level
7Collection of Line Intensity
Profiles

AC
ACN
AED
AES
AFS
amu
AOAC
AOCS
APCI
APDC
APHA
API
APIs
APPI
APT
APXS
ASBC
ASE
ASTM

BTEX
CAD
CAT
CCD

CDs
CE
CE
CEC
CEM
CFFAB
CGE
CI
CID
CID
CIE
CIEF
CIMPS
CL
CLIP

xvii


xviii    Abbreviations and Acronyms Index

CLIPS
CNES
cm
CMC
COSY
CPC
CPSIA

CP-MAS

CRM
CT
CTD
CTE
CV
CVAAS
CW
CZE
DAD
DART
DC
DCP
DDT
DEPT
DESI
DI
DI
DID
DIE
DIN
DL
DMD
DME
DMS
DMSO
DNA
DR
DRIFTS
dsDNA
DSC

DTA
DTG

9Calculated line intensity
profiles
7Centre national d’études
spatiales
2
Centimeter (length)
12
Critical micelle concentration
5
Correlated spectroscopy
4Compound parabolic
concentrator
8Active pharmaceutical
ingredient (API) Consumer
Protection and Safety
Improvement Act
5
Cross-polarization-MAS
9
Certified reference material
8
Computed tomography
7
Charge transfer device
14Coefficient of thermal
expansion
13

Cyclic voltammetry
6
Cold vapor-AAS
5
Continuous wave
12Capillary zone
electrophoresis
12
Diode array detector
9
Direct analysis in real time
6
Direct current
7
Direct current plasma
1
Dichlorodiphenyltrichloroethane
5Distortionless enhancement
by polarization transfer
9Desorption electrospray
ionization
1
Deionized
9
Desorption ionization
12Discharge ionization
detector
14Direct injection
enthalpimetry
7

Direct insertion nebulizer
6
Detection limit
12Dispersive monochromator
detector
13
Dropping mercury electrode
9Differential (ion) mobility
spectrometry
4
Dimethylsulfoxide
9
Deoxyribonucleic acid
4
Diffuse reflectance
4Diffuse-reflectance-IR-FTspectroscopy
5
Double-stranded DNA
14Differential scanning
calorimetry
14
Differential thermal analysis
14
Derivative thermogravimetry

DTGS
EC
EC
ECD
ECD

ED
EDL
EDS
EDTA
EE+
EGA
EGD
EI
EIE
ELCD
ELSD
EM
EMA
EMEA
emf
ENDOR
EOF
EPA
ESA
ESI
ETA
ETD
ETV
EU
EXAFS
FAAS
FAB
FAME
FC
FET

FFT
FIA
FIAS
FID
FID
FMC

4
Deuterated triglycine sulfate
8Electron capture (radioactive
decay mode)
9
Electron capture (in MS)
11Electron capture detector (in
GC)
12Electrochemical detector (in
HPLC)
8
Energy dispersive (with XRF)
6
Electrodeless discharge lamp
8Energy-dispersive
spectroscopy
14Ethylenediaminetetraacetic
acid
9
Even electron (ion in MS)
14
Evolved gas analysis
14

Evolved gas detection
9
Electron ionization
7
Easily ionized element
11Electrolytic conductivity
detector
12Evaporative light scattering
detector
9
Electron multiplier
8Electron microprobe
analyzer
9
European Medicines Agency
13
Electromotive force (voltage)
5Electron nuclear double
resonance
12
Electroosmotic flow
1Environmental Protection
Agency
9
Electrostatic analyzer
9
Electrospray ionization
6
Electrothermal atomizer
9

Electron transfer dissociation
9
Electrothermal vaporization
3
European Union
8Extended X-ray absorption
fine structure
6
Flame-AAS
9
Fast atom bombardment
11
Fatty acid methyl ester
8
Flow proportional counter
8
Field effect transistor
1Fast Fourier transform
(algorithm)
6
Flow injection analysis
6Flow injection atomic
spectroscopy
5Free induction decay (in
NMR)
11Flame ionization detector (in
GC)
14
Flow microliter calorimeter



Abbreviations and Acronyms Index    xix

FPA
FPC
FPD
FRPs
FT
FT-MS
FTIR
FT-ICR-MS
FT-NMR
FW
FWHM
GC
GC × GC
GD
GDMS
GFAAS
GFC
GFs
GF-LEAFS
GPC
HCD
HCL
HD
HEPS
HETCOR
HETP
HF

HG
HGAAS
HH XRF
HHPLC
HID
HILIC
HMDE
HMF
HMI
HPAE
HPIMS™
HPLC

4
Focal plane array
9
Focal plane camera
11
Flame photometric detector
5
Fiber-reinforced plastics
1
Fourier transform
9FT-ion cyclotron resonance
(MS)
4
Fourier transform IR
9Fourier transform mass
spectrometry
5

Fourier transform-NMR
4
Formula weight
8
Full width at half maximum
11
Gas chromatography
112-D orthogonal GC–GC
coupling
7
Glow discharge
9
Glow discharge MS
6
Graphite furnace-AAS
12Gel filtration
chromatography
7
Graphite furnaces
7Graphite furnace laserexcited AFS
12Gel permeation
chromatography
9High-energy collisional
dissociation
6
Hollow cathode lamp
8
High density
7
High energy prespark

5Heteronuclear chemical shift
correlation
10Height equivalent to a
theoretical plate
1
Hydrofluoric acid
7
Hydride generation
6
Hydride generation-AAS
8
Handheld XRF
12Hyper-HPLC
11
Helium ionization detector
12Hydrophilic interaction liquid
chromatography
13Hanging mercury drop
electrode
3
Hydroxymethylfurfural
9High matrix introduction
(ICP-MS)
12High performance anion
exchange
9high-performance ion
mobility spectrometry
12High performance
(or pressure) liquid
chromatography


HR-CS
HR-ICP-MS
HRT
Hz
IC
ICDD
ICP
ICP-SFMS
ICR
IDL
IDMS
IE
IEC
IEF
IMS
INADEQUATE
IPC
IPCE
IR
IRE
IR-SEC
IS
ISC
ISE
ISFET
ISO
ITC
ITO
IUPAC

JEOL
KED
LAESI
LANL
LASS
LC
LD
LED
LIBS
LIMS

6High resolution continuum
source (AAS)
9
High-resolution ICP-MS
9High-resolution TOF
2
Hertz (frequency)
12
Ion chromatography
8International Centre for
Diffraction Data
7
Inductively coupled plasma
9
ICP-sector field MS
9
Ion cyclotron resonance
1
Instrument detection limit

11Isotope dilution mass
spectrometry
12
Ion exchange
7
Interelement correction
12
Isoelectric focusing
9
Ion mobility spectrometry
5Incredible naturalabundance doublequantum transfer
12
Ion-pairing chromatography
13Incident photon conversion
efficiency
4
Infrared
4
Internal reflection element
13Infrared-SEC
10
Internal standard
3
Intersystem crossing
13
Ion-selective electrode
13Ion-selective field-effect
transistor
5International Standards
Organization

14Isothermal titration
calorimetry
13
Indium tin oxide
3International Union of Pure
and Applied Chemistry
9Japan Electron Optics
Laboratory
9Kinetic energy discrimination
(ICP-MS)
9Laser ablation electrospray
ionization
7Los Alamos National
Laboratory
7
Laser spark spectroscopy
10
Liquid chromatography
8
Low density
3
Light emitting diode
7Laser-induced breakdown
spectroscopy
1Laboratory information
management system


xx    Abbreviations and Acronyms Index


LIPS
LOD
LOQ
L-PAD
LPDA
LVDT
LVP
LVR
m
MALDI
MAS
MC
MCA
MCT
MDL
MDSC
MEK
MEKC
MIBK
MIP
MIT
MOS
MP
MRI
MS
MSA
MSD
MW
NASA
NCE

NICI
NIEHS
NIR
NIRIM
NIST
nm
NMR
NMRFAM
NOE
NOESY

7Laser-induced plasma
spectroscopy
1
Limit of detection
1
Limit of quantitation
7Large format programmable
array detector
3
Linear photodiode array
14Linear variable displacement
transducer
9
Large volume parenteral
14
Linear viscoelastic range
2
Meter (length)
9Matrix-assisted laserdesorption ionization

5
Magic angle spinning
9
Multiple collector
8
Multichannel analyzer
4
Mercury cadmium telluride
1
Method detection limit
14
Modulated DSC®
6
Methyl ethyl ketone
12Micellar electrokinetic
chromatography
1
Methyl isobutyl ketone
7
Microwave-induced plasma
7Massachusetts Institute of
Technology
7
Metal–oxide–semiconductor
7
Microwave plasma (source)
5Magnetic resonance
imaging
9
Mass spectrometry

2Method of standard
additions
11
Mass selective detector
9
Molecular weight
7National Aeronautics and
Space Administration
13
Normal calomel electrode
9Negative ion chemical
ionization
5National Institute of
Environmental Health and
Safety
4
Near infrared
4NIR-Raman imaging
microscope
1National Institute of
Standards and Technology
2
Nanometer (length)
5
Nuclear magnetic resonance
5National Magnetic
Resonance Facility at
Madison
5
Nuclear Overhauser effect

5
NOE-spectroscopy

NP
NPD
NRC
NRCC
NTP
ODS
OE+•
OES
OEM
OTE
PAD
PAGE
PAHs
PBDE
PCA
PCB
PCDE
PCr
PDA
PDE
PDMS
PEEK
PEG
PET
PFTBA
PID
PIN

PIXE
PLOT
PLS
PMI
PMT
POP
ppb, ppt, ppq
PTFE
PVC
Q
QC
QD

12
Normal phase (LC)
11Nitrogen–phosphorous
detector
11Nuclear Regulatory
Commission
1National Research Council of
Canada
12Normal temperature and
pressure
12Octadecylsilyl
9
Odd electron (ion in MS)
7Optical emission
spectroscopy
9Original equipment
manufacturer

13Optically transparent
electrode
12Pulsed amperometric
detection (LC)
12Polyacrylamide gel
electrophoresis
1Polynuclear aromatic
hydrocarbons
9Polybrominated diphenyl
ether
4Principal component
analysis
1
Polychlorinated biphenyl
9Polychlorinated diphenyl
ether
5
Phosphocreatine
3
Photodiode array
9
Permissible daily exposure
11Polydimethylsiloxane
12
Polyether ether ketone
5
Polyethylene glycol
14
Polyethylene terephthalate
9

Perfluorotributylamine
11
Photoionization detector
8(Silicon junction) p-i-n
(diode)
8Particle-induced X-ray
emission
11Porous layer open tubular
4Partial least squares
8Positive material
identification
3Photomultiplier tube
11
Persistent organic pollutant
1Parts per billion (109), trillion
(1012), quadrillion (1015)
4
Polytetrafluoroethylene
14
Polyvinyl chloride
9
Quadrupole mass analyzer
3
Quality control
12
Charge detector (IE-LC)


Abbreviations and Acronyms Index    xxi


QID
QIT
QqQ
QQQ
QTH
QuEChERS
RE
REE
REF
RF
RGA
RI
RI
RNA
RoHS
RP
RRF
RRT
RSD
RT
RU
SBSE
SBW
SC
SCD
SCD
SCE
SCF
SDD
SDS

SEC
SEC
SEM
SEM
SERS
SFC
SFE
SHE
SI
SIM
S/N

9
Quadrupole ion deflector
9
Quadrupole ion trap
9Triple quadrupole mass
analyzer
9Triple quadrupole mass
analyzer
4Quartz tungsten halogen
(lamp)
1Quick, easy, cheap, effective,
safe
2
Relative error
9
Rare earth elements
13
Reference electrode

5
Radiofrequency
9
Residual gas analyzer
11
Retention index (in GC)
12Refractive index (as in LC
detector)
9
Ribonucleic acid
7Restriction of the use of
hazardous substances
12
Reverse phase
10
Relative response factor
10
Relative retention time
1(%) Relative standard
deviation
13Room temperature
7
Raies ultimes
1
Stirbar sorptive extraction
2
Spectral bandwidth
8
Scintillation counter
7

Segmented charge detector
11Sulfur chemiluminescence
detector
13Saturated calomel electrode
12
Supercritical fluid
8
Silicon drift detector
12
Sodium dodecyl sulfate
12Size exclusion
chromatography
13Spectroelectrochemistry
8Scanning electron
microscope
9Secondary electron
multiplier
 4Surface-enhanced Raman
spectroscopy
12Supercritical fluid
chromatography
1
Supercritical fluid extraction
13Standard hydrogen
electrode
1Système International
d’Unités
11
Selected ion monitoring
1

Signal to noise (ratio)

SOPs
SPADNS
SPE
SP-FPD
SPME
SRM
STA
STP
STPF
SWIFT
TA
TBAH
TCD
TDS
TEAP
TEEM
TFME
TG
TGA
THF
TIC
TISAB
TLC
TMAH
TMS
TNT
TOF
TT

TXRF
UHPLC
µm
UPC2
URL
USN
USP
UV
VIS
WD

1Standard operating
procedures
5
See end of Table 3.7
1
Solid phase extraction
11Sulfur–phosphorous flame
photometric detector
1
Solid phase microextraction
9
Standard reference material
14Simultaneous thermal
analysis
9Standard temperature and
pressure
6Stabilized temperature
platform furnace
5Sweep imaging with Fourier

transform
1
Thermal analysis
13Tetrabutylammonium
hydroxide
11Thermal conductivity
detector
13
Total dissolved solids
13Tetraethylammonium
perchlorate
9Tunable-energy electron
monochromator (beam)
13
Thin film mercury electrode
14Thermogravimetry
14
Thermogravimetric analysis
1
Tetrahydrofuran
11
Total ion chromatogram
13Total ionic strength adjusting
buffer
12
Thin layer chromatography
15Tetramethylammonium
hydroxide
5
Tetramethylsilane

9
Trinitrotoluene
9Time of flight (in mass
spectrometry)
14
Thermometric titration
8
Total reflection XRF
10Ultra-high-performance
liquid chromatography
2
Micrometer (length)
12Ultra performance
convergence
chromatography
12
Uniform resource locator
7
Ultrasonic nebulizer
9
United States Pharmacopeia
3
Ultraviolet
3Visible (light wavelength
range)
8Wavelength dispersive (with
XRF)


xxii    Abbreviations and Acronyms Index


WDXRF
WE
WEEE
XIC

8Energy-dispersive XRF
(EDXRF) wavelengthdispersive XRF
13
Working electrode
7Waste electrical and
electronic equipment
11
Extracted ion chromatogram

XRA
XRD
XRF
XRT
YAG
ZPD
% RE

8
8
8
8
3
4
2


X-ray absorption
X-ray diffraction
X-ray fluorescence
X-ray transmission
yttrium aluminum garnet
Zero path difference
Percent relative error


Preface
Analytical chemistry today is almost entirely instrumental analytical chemistry and it is performed by many scientists and engineers who are not chemists. Analytical
instrumentation is crucial to research in molecular biology, medicine, geology, food science, materials science,
and many other fields. While it is true that it is no longer
necessary to have almost artistic skills to obtain accurate
and precise analytical results using instrumentation, the
instruments should not be considered “black boxes” by
those using them. The well-known phrase “garbage in,
garbage out” holds true for analytical instrumentation as
well as computers. We hope this book serves to provide
users of analytical instrumentation with an understanding of their instruments.
This textbook is a concise and updated version of
our Undergraduate Instrumental Analysis Textbook,
designed for teaching undergraduates and those working in chemical fields outside analytical chemistry how
modern analytical instrumentation works and what the
uses and limitations of analytical instrumentation are.

Mathematics is kept to a minimum. No background in
calculus, physics, or physical chemistry is required. The
major fields of modern instrumentation are covered,

including applications of each type of instrumental technique. Each chapter includes a discussion of the fundamental principles underlying each technique, detailed
descriptions of the instrumentation, and a large number
of applications. Each chapter includes an updated bibliography and problems, and most chapters have suggested
experiments appropriate to the technique.
While the authors are extremely grateful to the many
experts listed in the acknowledgments, who have provided graphics, technical advice, rewrites, and reviews of
various sections, any errors that are present are entirely
the responsibility of the authors.
James W. Robinson
Eileen M. Skelly Frame
George M. Frame II

xxiii