Chemical Analysis: Modern Instrumentation Methods and Techniques

Chemical Analysis......Page 3
Title Page......Page 4
ISBN 0470859024......Page 5
Contents......Page 6
Foreword to the first English edition......Page 14
Preface to the first English edition......Page 16
Preface to second edition......Page 18
Acknowledgments......Page 20
Introduction......Page 22
Part 1 Separation methods......Page 26
1.1 General concepts of analytical chromatography......Page 28
1.2 The chromatogram......Page 31
1.3 Gaussian-shaped elution peaks......Page 32
1.4 The plate theory......Page 34
1.5 Nernst partition coefficient (K)......Page 36
1.6 Column efficiency......Page 37
1.7 Retention parameters......Page 39
1.9 Resolution factor between two peaks......Page 42
1.10 The rate theory of chromatography......Page 44
1.11 Optimization of a chromatographic analysis......Page 47
1.12 Classification of chromatographic techniques......Page 49
Problems......Page 52
2.1 Components of a GC installation......Page 56
2.2 Carrier gas and flow regulation......Page 58
2.3 Sample introduction and the injection chamber......Page 59
2.5 Columns......Page 64
2.6 Stationary phases......Page 66
2.7 Principal gas chromatographic detectors......Page 71
2.8 Detectors providing structural data......Page 75
2.9 Fast chromatography......Page 77
2.10 Multi-dimensional chromatography......Page 78
2.11 Retention indexes and stationary phase constants......Page 79
Problems......Page 83
3.1 The beginnings of HPLC......Page 88
3.2 General concept of an HPLC system......Page 89
3.3 Pumps and gradient elution......Page 90
3.5 Columns......Page 93
3.6 Stationary phases......Page 95
3.7 Chiral chromatography......Page 100
3.8 Mobile phases......Page 101
3.9 Paired-ion chromatography......Page 103
3.11 Principal detectors......Page 105
3.12 Evolution and applications of HPLC......Page 112
Problems......Page 114
4.1 Basics of ion chromatography......Page 118
4.2 Stationary phases......Page 121
4.3 Mobile phases......Page 123
4.4 Conductivity detectors......Page 125
4.5 Ion suppressors......Page 126
4.6 Principle and basic relationship......Page 129
4.8 External standard method......Page 130
4.9 Internal standard method......Page 132
4.10 Internal normalization method......Page 135
Problems......Page 137
5.1 Principle of TLC......Page 142
5.2 Characteristics of TLC......Page 145
5.3 Stationary phases......Page 146
5.4 Separation and retention parameters......Page 147
5.5 Quantitative TLC......Page 148
Problems......Page 150
6.1 Supercritical fluids: a reminder......Page 152
6.2 Supercritical fluids as mobile phases......Page 154
6.3 Instrumentation in SFC......Page 155
6.4 Comparison of SFC with HPLC and GC......Page 156
6.5 SFC in chromatographic techniques......Page 158
7.1 Principle of SEC......Page 160
7.2 Stationary and mobile phases......Page 162
7.3 Calibration curves......Page 163
7.4 Instrumentation......Page 164
7.5 Applications of SEC......Page 165
Problems......Page 168
8.1 From zone electrophoresis to capillary electrophoresis......Page 170
8.2 Electrophoretic mobility and electro-osmotic flow......Page 173
8.3 Instrumentation......Page 177
8.4 Electrophoretic techniques......Page 180
8.5 Performance of CE......Page 182
8.6 Capillary electrochromatography......Page 184
Problems......Page 186
Part 2 Spectroscopic methods......Page 190
9.1 The UV/Vis spectral region and the origin of the absorptions......Page 192
9.2 The UV/Vis spectrum......Page 194
9.3 Electronic transitions of organic compounds......Page 196
9.4 Chromophore groups......Page 198
9.5 Solvent effects: solvatochromism......Page 199
9.6 Fieser–Woodward rules......Page 201
9.7 Instrumentation in the UV/Visible......Page 203
9.8 UV/Vis spectrophotometers......Page 206
9.9 Quantitative analysis: laws of molecular absorption......Page 211
9.10 Methods in quantitative analysis......Page 215
9.11 Analysis of a single analyte and purity control......Page 217
9.12 Multicomponent analysis (MCA)......Page 218
9.13 Methods of baseline correction......Page 221
9.14 Relative error distribution due to instruments......Page 223
9.15 Derivative spectrometry......Page 225
9.16 Visual colorimetry by transmission or reflection......Page 227
Problems......Page 228
10.1 The origin of light absorption in the infrared......Page 232
10.3 Rotational–vibrational bands in the mid-IR......Page 233
10.4 Simplified model for vibrational interactions......Page 235
10.6 Characteristic bands for organic compounds......Page 237
10.7 Infrared spectrometers and analysers......Page 241
10.8 Sources and detectors used in the mid-IR......Page 246
10.9 Sample analysis techniques......Page 250
10.10 Chemical imaging spectroscopy in the infrared......Page 255
10.11 Archiving spectra......Page 257
10.12 Comparison of spectra......Page 258
10.13 Quantitative analysis......Page 259
Problems......Page 263
11.1 Fluorescence and phosphorescence......Page 266
11.2 The origin of fluorescence......Page 268
11.3 Relationship between fluorescence and concentration......Page 270
11.4 Rayleigh scattering and Raman bands......Page 272
11.5 Instrumentation......Page 274
11.6 Applications......Page 278
11.7 Time-resolved fluorimetry......Page 280
11.8 Chemiluminescence......Page 281
Problems......Page 284
12.1 Basic principles......Page 288
12.2 The X-ray fluorescence spectrum......Page 289
12.3 Excitation modes of elements in X-ray fluorescence......Page 291
12.4 Detection of X-rays......Page 296
12.5 Different types of instruments......Page 298
12.6 Sample preparation......Page 302
12.7 X-ray absorption – X-ray densimetry......Page 303
12.9 Applications of X-ray fluorescence......Page 304
Problems......Page 306
13.1 The effect of temperature upon an element......Page 310
13.3 Atomic absorption versus flame emission......Page 313
13.4 Measurements by AAS or by FES......Page 315
13.5 Basic instrumentation for AAS......Page 316
13.6 Flame photometers......Page 322
13.7 Correction of interfering absorptions......Page 323
13.8 Physical and chemical interferences......Page 327
13.9 Sensitivity and detection limits in AAS......Page 329
Problems......Page 330
14.1 Optical emission spectroscopy (OES)......Page 334
14.2 Principle of atomic emission analysis......Page 335
14.3 Dissociation of the sample into atoms or ions......Page 336
14.4 Dispersive systems and spectral lines......Page 340
14.5 Simultaneous and sequential instruments......Page 342
14.6 Performances......Page 346
14.7 Applications of OES......Page 348
Problems......Page 349
15.1 General introduction......Page 352
15.2 Spin/magnetic field interaction for a nucleus......Page 353
15.4 Bloch theory for a nucleus of spin number I = 1/2......Page 356
15.5 Larmor frequency......Page 358
15.6 Pulsed NMR......Page 360
15.7 The processes of nuclear relaxation......Page 364
15.8 Chemical shift......Page 365
15.9 Measuring the chemical shift......Page 366
15.11 Factors influencing chemical shifts......Page 367
15.12 Hyperfine structure – spin–spin coupling......Page 369
15.13 Heteronuclear coupling......Page 370
15.14 Homonuclear coupling......Page 372
15.15 Spin decoupling and particular pulse sequences......Page 377
15.16 HPLC-NMR coupling......Page 379
15.17 Fluorine and phosphorus NMR......Page 380
15.18 Quantitative NMR......Page 381
15.19 Analysers using pulsed NMR......Page 385
Problems......Page 389
Part 3 Other methods......Page 392
16.1 Basic principles......Page 394
16.2 The magnetic-sector design......Page 397
16.3 'EB' or 'BE' geometry mass analysers......Page 399
16.4 Time of flight analysers (TOF)......Page 404
16.5 Quadrupole analysers......Page 406
16.6 Quadrupole ion trap analysers......Page 410
16.7 Ion cyclotron resonance analysers (ICRMS)......Page 412
16.8 Mass spectrometer performances......Page 414
16.9 Sample introduction......Page 416
16.10 Major vacuum ionization techniques......Page 417
16.11 Atmospheric pressure ionization (API)......Page 422
16.12 Tandem mass spectrometry (MS/MS)......Page 426
16.13 Ion detection......Page 427
16.14 Identification by means of a spectral library......Page 429
16.15 Analysis of the elementary composition of ions......Page 430
16.16 Determination of molecular masses from multicharged ions......Page 432
16.17 Determination of isotope ratios for an element......Page 433
16.18 Fragmentation of organic ions......Page 435
Problems......Page 440
17.1 The principle of labelling methodologies......Page 444
17.2 Direct isotope dilution analysis with a radioactive label......Page 445
17.3 Substoichiometric isotope dilution analysis......Page 446
17.4 Radio immuno-assays (RIA)......Page 447
17.5 Measuring radioisotope activity......Page 448
17.6 Antigens and antibodies......Page 450
17.7 Enzymatic-immunoassay (EIA)......Page 451
17.8 Other immunoenzymatic techniques......Page 454
17.9 Advantages and limitations of the ELISA test in chemistry......Page 455
17.11 Stable isotope labelling......Page 456
17.12 Neutron activation analysis (NAA)......Page 457
Problems......Page 462
18.1 Particular analyses......Page 466
18.2 Elemental organic microanalysis......Page 467
18.3 Total nitrogen analysers (TN)......Page 470
18.5 Total carbon analysers (TC, TIC and TOC)......Page 472
18.6 Mercury analysers......Page 475
Problems......Page 476
19.1 General principles......Page 478
19.2 A particular ISE: the pH electrode......Page 480
19.3 Other ion selective electrodes......Page 482
19.4 Slope and calculations......Page 485
Problems......Page 488
20.1 General principles......Page 490
20.3 Direct current polarography (DCP)......Page 492
20.4 Diffusion current......Page 493
20.5 Pulsed polarography......Page 495
20.7 Amperometric sensors......Page 497
20.8 Stripping voltammetry (SV)......Page 503
20.9 Potentiostatic coulometry and amperometric coulometry......Page 505
20.10 Coulometric titration of water by the Karl Fischer reaction......Page 506
Problems......Page 509
21.1 The need for sample pretreatment......Page 512
21.2 Solid phase extraction (SPE)......Page 513
21.3 Immunoaffinity extraction......Page 515
21.4 Microextraction procedures......Page 516
21.5 Gas extraction on a cartridge or a disc......Page 518
21.6 Headspace......Page 519
21.7 Supercritical phase extraction (SPE)......Page 521
21.9 On-line analysers......Page 523
22.1 Mean value, accuracy of a collection of measurements......Page 526
22.3 Random or indeterminate errors......Page 529
22.4 Confidence interval of the mean......Page 531
22.5 Comparison of results – parametric tests......Page 533
22.6 Rejection criteria Q-test (or Dixon test)......Page 535
22.7 Calibration curve and regression analysis......Page 536
22.8 Robust methods or non-parametric tests......Page 538
22.9 Optimization through the one-factor-at-a-time (OFAT) experimentation......Page 540
Problems......Page 541
Solutions......Page 544
Appendix - List of acronyms......Page 586
Bibliography......Page 590
Table of some useful constants......Page 592
Index......Page 594