Chemical Analysis : Modern Instrumentation Methods and Techniques

599 Pages·2007·11.05 MB·English

Chemical Analysis
Modern Instrumentation Methods and Techniques
Second Edition
Francis Rouessac and Annick Rouessac
University of Le Mans, France
Translated by
Francis and Annick Rouessac and Steve Brooks
Chemical Analysis
Second Edition
Chemical Analysis
Modern Instrumentation Methods and Techniques
Second Edition
Francis Rouessac and Annick Rouessac
University of Le Mans, France
Translated by
Francis and Annick Rouessac and Steve Brooks
Englishlanguagetranslationcopyright© 2007byJohnWiley&SonsLtd,
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TranslatedintoEnglishbyFrancisandAnnickRouessacandSteveBrooks
FirstPublishedinFrench© 1992Masson
2ndEdition© 1994Masson
3rdEdition© 1997Masson
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5thEdition© 2000Dunod
6thEdition© 2004Dunod
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Rouessac,Francis.
[Analysechimique.English]
Chemicalanalysis:moderninstrumentationandmethodsandtechniques/FrancisRouessacandAnnick
Rouessac;translatedbySteveBrooksandFrancisandAnnickRouessac.—2nded.
p. cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-85902-5(cloth:alk.paper)—ISBN978-0-470-85903-2(pbk.:alk.paper)
1. Instrumentalanalysis. I. Rouessac,Annick. II.Title.
QD79.I5R68132007
543—dc22 2006036196
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ISBN978-0-470-85902-5(HB)
ISBN978-0-470-85903-2(PB)
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Contents
Foreword to the first English edition xiii
Preface to the first English edition xv
Preface to second edition xvii
Acknowledgments xix
Introduction xxi
PART 1 SEPARATION METHODS 1
1 General aspects of chromatography 3
1.1 Generalconceptsofanalyticalchromatography 3
1.2 Thechromatogram 6
1.3 Gaussian-shapedelutionpeaks 7
1.4 Theplatetheory 9
1.5 Nernstpartitioncoefficient(K) 11
1.6 Columnefficiency 12
1.7 Retentionparameters 14
1.8 Separation(orselectivity)factorbetweentwo
solutes 17
1.9 Resolutionfactorbetweentwopeaks 17
1.10 Theratetheoryofchromatography 19
1.11 Optimizationofachromatographicanalysis 22
1.12 Classificationofchromatographictechniques 24
Problems 27
2 Gas chromatography 31
2.1 ComponentsofaGCinstallation 31
2.2 Carriergasandflowregulation 33
2.3 Sampleintroductionandtheinjection
chamber 34
2.4 Thermostaticallycontrolledoven 39
2.5 Columns 39
2.6 Stationaryphases 41
2.7 Principalgaschromatographicdetectors 46
2.8 Detectorsprovidingstructuraldata 50
2.9 Fastchromatography 52
2.10 Multi-dimensionalchromatography 53
2.11 Retentionindexesandstationaryphaseconstants 54
Problems 58
vi CONTENTS
3 High-performance liquid chromatography 63
3.1 ThebeginningsofHPLC 63
3.2 GeneralconceptofanHPLCsystem 64
3.3 Pumpsandgradientelution 65
3.4 Injectors 68
3.5 Columns 68
3.6 Stationaryphases 70
3.7 Chiralchromatography 75
3.8 Mobilephases 76
3.9 Paired-ionchromatography 78
3.10 Hydrophobicinteractionchromatography 80
3.11 Principaldetectors 80
3.12 EvolutionandapplicationsofHPLC 87
Problems 89
4 Ion chromatography 93
4.1 Basicsofionchromatography 93
4.2 Stationaryphases 96
4.3 Mobilephases 98
4.4 Conductivitydetectors 100
4.5 Ionsuppressors 101
4.6 Principleandbasicrelationship 104
4.7 Areasofthepeaksanddatatreatmentsoftware 105
4.8 Externalstandardmethod 105
4.9 Internalstandardmethod 107
4.10 Internalnormalizationmethod 110
Problems 112
5 Thin layer chromatography 117
5.1 PrincipleofTLC 117
5.2 CharacteristicsofTLC 120
5.3 Stationaryphases 121
5.4 Separationandretentionparameters 122
5.5 QuantitativeTLC 123
Problems 125
6 Supercritical fluid chromatography 127
6.1 Supercriticalfluids:areminder 127
6.2 Supercriticalfluidsasmobilephases 129
6.3 InstrumentationinSFC 130
6.4 ComparisonofSFCwithHPLCandGC 131
6.5 SFCinchromatographictechniques 133
7 Size exclusion chromatography 135
7.1 PrincipleofSEC 135
7.2 Stationaryandmobilephases 137
7.3 Calibrationcurves 138
7.4 Instrumentation 139
7.5 ApplicationsofSEC 140
Problems 143
CONTENTS vii
8 Capillary electrophoresis and electrochromatography 145
8.1 Fromzoneelectrophoresistocapillaryelectrophoresis 145
8.2 Electrophoreticmobilityandelectro-osmoticflow 148
8.3 Instrumentation 152
8.4 Electrophoretictechniques 155
8.5 PerformanceofCE 157
8.6 Capillaryelectrochromatography 159
Problems 161
PART 2 SPECTROSCOPIC METHODS 165
9 Ultraviolet and visible absorption spectroscopy 167
9.1 TheUV/Visspectralregionandtheoriginoftheabsorptions 167
9.2 TheUV/Visspectrum 169
9.3 Electronictransitionsoforganiccompounds 171
9.4 Chromophoregroups 173
9.5 Solventeffects:solvatochromism 174
9.6 Fieser–Woodwardrules 176
9.7 InstrumentationintheUV/Visible 178
9.8 UV/Visspectrophotometers 181
9.9 Quantitativeanalysis:lawsofmolecularabsorption 186
9.10 Methodsinquantitativeanalysis 190
9.11 Analysisofasingleanalyteandpuritycontrol 192
9.12 Multicomponentanalysis(MCA) 193
9.13 Methodsofbaselinecorrection 196
9.14 Relativeerrordistributionduetoinstruments 198
9.15 Derivativespectrometry 200
9.16 Visualcolorimetrybytransmissionorreflection 202
Problems 203
10 Infrared spectroscopy 207
10.1 Theoriginoflightabsorptionintheinfrared 207
10.2 Absorptionsintheinfrared 208
10.3 Rotational–vibrationalbandsinthemid-IR 208
10.4 Simplifiedmodelforvibrationalinteractions 210
10.5 Realcompounds 212
10.6 Characteristicbandsfororganiccompounds 212
10.7 Infraredspectrometersandanalysers 216
10.8 Sourcesanddetectorsusedinthemid-IR 221
10.9 Sampleanalysistechniques 225
10.10 Chemicalimagingspectroscopyinthe
infrared 230
10.11 Archivingspectra 232
10.12 Comparisonofspectra 233
10.13 Quantitativeanalysis 234
Problems 238
viii CONTENTS
11 Fluorimetry and chemiluminescence 241
11.1 Fluorescenceandphosphorescence 241
11.2 Theoriginoffluorescence 243
11.3 Relationshipbetweenfluorescenceandconcentration 245
11.4 RayleighscatteringandRamanbands 247
11.5 Instrumentation 249
11.6 Applications 253
11.7 Time-resolvedfluorimetry 255
11.8 Chemiluminescence 256
Problems 259
12 X-ray fluorescence spectrometry 263
12.1 Basicprinciples 263
12.2 TheX-rayfluorescencespectrum 264
12.3 ExcitationmodesofelementsinX-rayfluorescence 266
12.4 DetectionofX-rays 271
12.5 Differenttypesofinstruments 273
12.6 Samplepreparation 277
12.7 X-rayabsorption–X-raydensimetry 278
12.8 QuantitativeanalysisbyX-rayfluorescence 279
12.9 ApplicationsofX-rayfluorescence 279
Problems 281
13 Atomic absorption and flame emission spectroscopy 285
13.1 Theeffectoftemperatureuponanelement 285
13.2 Applicationstomoderninstruments 288
13.3 Atomicabsorptionversusflameemission 288
13.4 MeasurementsbyAASorbyFES 290
13.5 BasicinstrumentationforAAS 291
13.6 Flamephotometers 297
13.7 Correctionofinterferingabsorptions 298
13.8 Physicalandchemicalinterferences 302
13.9 SensitivityanddetectionlimitsinAAS 304
Problems 305
14 Atomic emission spectroscopy 309
14.1 Opticalemissionspectroscopy(OES) 309
14.2 Principleofatomicemissionanalysis 310
14.3 Dissociationofthesampleintoatomsorions 311
14.4 Dispersivesystemsandspectrallines 315
14.5 Simultaneousandsequentialinstruments 317
14.6 Performances 321
14.7 ApplicationsofOES 323
Problems 324
15 Nuclear magnetic resonance spectroscopy 327
15.1 Generalintroduction 327
15.2 Spin/magneticfieldinteractionforanucleus 328
15.3 NucleithatcanbestudiedbyNMR 331
CONTENTS ix
15.4 BlochtheoryforanucleusofspinnumberI=1/2 331
15.5 Larmorfrequency 333
15.6 PulsedNMR 335
15.7 Theprocessesofnuclearrelaxation 339
15.8 Chemicalshift 340
15.9 Measuringthechemicalshift 341
15.10 Shieldinganddeshieldingofthenuclei 342
15.11 Factorsinfluencingchemicalshifts 342
15.12 Hyperfinestructure–spin–spincoupling 344
15.13 Heteronuclearcoupling 345
15.14 Homonuclearcoupling 347
15.15 Spindecouplingandparticularpulsesequences 352
15.16 HPLC-NMRcoupling 354
15.17 FluorineandphosphorusNMR 355
15.18 QuantitativeNMR 356
15.19 AnalysersusingpulsedNMR 360
Problems 364
PART 3 OTHER METHODS 367
16 Mass spectrometry 369
16.1 Basicprinciples 369
16.2 Themagnetic-sectordesign 372
16.3 ‘EB’or‘BE’geometrymassanalysers 374
16.4 Timeofflightanalysers(TOF) 379
16.5 Quadrupoleanalysers 381
16.6 Quadrupoleiontrapanalysers 385
16.7 Ioncyclotronresonanceanalysers(ICRMS) 387
16.8 Massspectrometerperformances 389
16.9 Sampleintroduction 391
16.10 Majorvacuumionizationtechniques 392
16.11 Atmosphericpressureionization(API) 397
16.12 Tandemmassspectrometry(MS/MS) 401
16.13 Iondetection 402
16.14 Identificationbymeansofaspectrallibrary 404
16.15 Analysisoftheelementarycompositionofions 405
16.16 Determinationofmolecularmassesfrommultichargedions 407
16.17 Determinationofisotoperatiosforanelement 408
16.18 Fragmentationoforganicions 410
Problems 415
17 Labelling methods 419
17.1 Theprincipleoflabellingmethodologies 419
17.2 Directisotopedilutionanalysiswitharadioactive
label 420
17.3 Substoichiometricisotopedilutionanalysis 421
17.4 Radioimmuno-assays(RIA) 422
17.5 Measuringradioisotopeactivity 423
17.6 Antigensandantibodies 425