Ewing's analytical instrumentation handbook

1043 Pages·2005·23.984 MB·English

by  Jack Cazes, Galen Wood Ewing

E ’
WING S
A
NALYTICAL
I
NSTRUMENTATION
H
ANDBOOK
T E
HIRD DITION
Copyright © 2005 by Marcel Dekker
E ’
WING S
A
NALYTICAL
I
NSTRUMENTATION
H
ANDBOOK
T E
HIRD DITION
Jack Cazes
Edited by
Florida Atlantic University
Boca Raton, Florida, U.S.A.
MARCEL DEKKER NEW YORK
Copyright © 2005 by Marcel Dekker
Althoughgreatcarehasbeentakentoprovideaccurateandcurrentinformation,neithertheauthor(s)northepublisher,noranyoneelseassociated
withthispublication,shallbeliableforanyloss,damage,orliabilitydirectlyorindirectlycausedorallegedtobecausedbythisbook.The
materialcontainedhereinisnotintendedtoprovidespecificadviceorrecommendationsforanyspecificsituation.
Trademarknotice:Productorcorporatenamesmaybetrademarksorregisteredtrademarksandareusedonlyforidentificationandexplanation
withoutintenttoinfringe.
LibraryofCongressCataloging-in-PublicationData
AcatalogrecordforthisbookisavailablefromtheLibraryofCongress.
ISBN:0-8247-5348-8
Thisbookisprintedonacid-freepaper.
Headquarters
MarcelDekker,270MadisonAvenue,NewYork,NY10016,U.S.A.
tel:[phone];fax:[phone]
DistributionandCustomerService
MarcelDekker,Inc.,CimarronRoad,Monticello,NewYork12701,U.S.A.
tel:[phone];fax:[phone]
WorldWideWeb
http://www.dekker.com
Copyright(cid:1)c 2005byMarcelDekker.AllRightsReserved.
Neitherthisbooknoranypartmaybereproducedortransmittedinanyformorbyanymeans,electronicormechanical,includingphotocopying,
microfilming,andrecording,orbyanyinformationstorageandretrievalsystem,withoutpermissioninwritingfromthepublisher.
Currentprinting(lastdigit):
10 9 8 7 6 5 4 3 2 1
PRINTEDINTHEUNITEDSTATESOFAMERICA
Copyright © 2005 by Marcel Dekker
Preface to the Third Edition
TheAnalyticalInstrumentationHandbookservesasaguideforworkersinanalyticalchemistry,whoneedastartingplace
forinformationaboutaspecificinstrumentaltechnique,eitherasabasicintroductiontoitorasameansoffindingleading
references dealing with theory andmethodology for an instrumentaltechnique.
Thechapterswhichappearedinthesecondeditionhavebeenthoroughlyexpandedandupdated,withconcepts,appli-
cations,andkeyreferencestotherecentliterature.Onlyonechapter(LaboratoryBalances)hasbeeneliminated;eightnew
chaptershave been added tothe Handbook, dealing with
. Microchip technology
. Biosensor technology
. Validation ofchromatographic methods
. Gelpermeation and sizeexclusion chromatography
. Field-flowfractionation
. Countercurrent chromatography
. Hyphenatedtechniquesin chromatography, including LC-MS, LC-NMR, and soon
. Thin-layer chromatography
The chapters have been written from the standpoint of the instrumentation as it is in use today, with an introductory
description of the technique(s), and a theoretical treatment of the science and technology, wherever it is applicable or
where it will facilitate an understanding of the instrumentation. However, the major emphasis is on the instrumentation.
Thechaptersarenot,simply,a“catalog”ofcommerciallyavailableinstruments.Nevertheless,insomecases,commercially
available instruments have been used as examplesto illustrate design featuresdiscussed inthe text.
It is sincerely intended and anticipated that this third revised and expanded edition of the Analytical Instrumentation
Handbookwill serveas aready-referenceonthe desks ofall practitioners ofinstrumental analyticalchemistry.
iii
Copyright © 2005 by Marcel Dekker
Contents
Preface tothe Third Edition . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . iii
Contributors . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. xxi
1. The Laboratory Use of Computers . . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . 1
WesSchafer,ZhihaoLin
I. Introduction . . .. 1
II. Computer Components andDesignConsiderations .. . . 1
A. Motherboard/CentralProcessingUnit .... 2
B. Memory/Cache .... 3
C. DiskStorage .... 3
D. Video(GraphicsCardandMonitor) .... 4
E. OtherPeripherals .... 5
III. Computer Maintenance . . . . 5
A. PerformanceMonitoring .... 5
B. VirusProtection .... 6
C. BackupandRecovery .... 6
IV. Data Transfer/Instrument Interfaces . . .. 7
A. Transducers .... 7
B. AnalogSignalTransmission .... 7
C. AnalogSignalFiltering .... 7
D. Analog-to-DigitalConversion .... 8
E. DigitalSignalTransmission .... 10
F. DigitalDataFiltering .... 11
V. Data Analysis/Chemometrics .. . . 12
A. MultivariateCalibration .... 12
B. PatternRecognition .... 16
VI. Data Organization and Storage . .. . 18
A. AutomatedDataStorage .... 19
B. LaboratoryInformationManagementSystems .... 19
Bibliography . . . . 20
2. Flow Injection/Sequential Injection Analysis . . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . 21
EloHaraldHansen,JianhuaWang
I. Introduction . . .. 21
II. Flow Injection Analysis . . .. 23
v
Copyright © 2005 by Marcel Dekker
vi Contents
A. BasicPrinciples .... 23
B. BasicFIAInstrumentation .... 23
C. DispersioninFIA .... 24
D. SelectedExamplestoIllustratetheUniqueFeaturesofFIA .... 25
E. FIAGradientTechniques—ExploitingthePhysicalDispersionProcess .... 30
F. FIAforProcessAnalysis/Monitoring .... 32
III. Further Developments of FIA .. . . 32
A. SequentialInjectionAnalysis .... 33
B. Lab-on-Valve .... 33
IV. SelectedApplications ofFIA/SIA andtheir Hyphenations inOn-Line Sample Pretreatments . .. . 34
A. SeparationandPreconcentrationProceduresBasedonColumnReactorsorKRs .... 36
B. FIA/SIAOn-LineSolventExtractionandBackExtractionPreconcentration .... 39
C. On-LineHydride/VaporGenerationPreconcentrationSchemes .... 44
V. Applications of SI-LOV for On-Line Sample Pretreatments . . .. 45
A. TheThirdGenerationofFlowInjectionandMicroTotalAnalysisSystems .... 45
B. ApplicationsofmSI-LOVSystemsforOn-LineSamplePretreatmentswithOpticalMonitoring .... 46
C. SI-BI-LOV:SolvingtheDilemmaofOn-LineColumnSeparation/ProcencentrationSchemes .... 47
References . .. . 52
3. Inductively CoupledPlasmaOptical Emission Spectrometry . . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. 57
TiebangWang
I. Introduction . . . . 57
II. AnOverview . .. . 59
A. PrincipleofAtomicEmissionSpectrometry .... 59
B. AtomicSpectroscopicSources .... 60
C. AtomicSpectroscopicTechniquesandInstruments .... 60
III. Inductively CoupledPlasma . .. . 61
A. TheDischarge .... 61
B. EmissionDetectionandProcessing .... 62
C. AnalyticalPerformanceandGeneralCharacteristics .... 62
IV. ICP-OES Instrumentation . .. . 63
A. Nebulizers .... 63
B. SprayChambers .... 65
C. AlternativeSampleIntroductionSystems .... 65
D. OpticsandtheSpectrometer .... 66
E. EmissionDetectors .... 69
F. RadiallyViewedICP .... 71
V. Applications of ICP-OES . .. . 71
A. Geoanalysis .... 71
B. MetallurgicalSamples .... 72
C. AgriculturalandFoodSamples .... 72
D. BiologicalandClinicalSamples .... 72
E. EnvironmentalSamples .... 73
F. Organics .... 73
G. NuclearMaterials .... 73
VI. Summary andFuturePrognosis . . .. 74
References . .. . 74
4. AtomicAbsorption Spectrometry and Related Techniques . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. 75
BernhardWelz,MariaGoretiR.Vale
I. Introduction . . . . 75
II. The History ofAtomic Spectroscopy . . . . 76
A. TheEarlyHistory .... 76
B. SirAlanWalshandtheRebirthofAAS .... 77
C. BorisL’vovandtheGraphiteFurnace .... 77
Copyright © 2005 by Marcel Dekker
Contents vii
III. Atomic Spectra inAbsorption, Emission, and Fluorescence .. . . 79
A. OriginandCharacteristicsofAtomicSpectra .... 79
B. LineWidthandLineProfile .... 80
C. MeasuringtheAbsorption—theBeer–LambertLaw .... 81
D. TheZeemanEffect .... 82
IV. Spectrometers for AAS . .. . 82
A. Medium-ResolutionLSAAS .... 83
B. High-ResolutionCSAAS .... 92
V. The Techniques ofAtomic Spectrometry . . .. 95
A. TheFAASTechnique .... 95
B. TheGFAASTechnique .... 101
C. ChemicalVaporGeneration .... 112
D. SpectrometersforAFS .... 117
E. SpectrometersforFlameOES .... 118
VI. Measurement, Calibration, and EvaluationinAAS, AFS,and OES . . .. 118
A. SamplesandMeasurementSolutions .... 118
B. Calibration .... 119
C. Evaluation .... 121
References .. . . 123
5. Ultraviolet, Visible, Near-Infrared Spectrophotometers . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. 127
ChrisW.Brown
I. Introduction . . .. 127
A. Beer’sLaw .... 127
B. DeviationsfromBeer’sLaw .... 128
II. SpectrophotometerCharacteristics . . .. 129
A. TheArchitectureofaSpectrophotometer .... 131
III. Present and FutureUV–VIS–NIR Spectrometers . . . . 137
References .. . . 139
6. Molecular Fluorescence and Phosphorescence . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. 141
FernandoM.Lanc¸as,EmanuelCarrilho
I. Introduction . . .. 141
II. Theory . .. . 141
A. Excited-StateProcesses .... 142
B. Excited-StateLifetimes .... 142
C. QuantumYield .... 143
D. Quenching .... 143
E. IntensityandConcentration .... 143
F. LuminescenceSpectra .... 144
G. Polarization .... 144
III. Instrumentation . .. . 145
A. InstrumentComponents .... 145
B. InstrumentConfigurationsforConventionalFluorescenceMeasurements .... 147
C. Phosphorimeters .... 148
D. InstrumentswithSpecialCapabilities .... 150
IV. Practical Considerationsand Applications .. . . 153
A. EnvironmentalEffects .... 155
B. WavelengthCalibrationandSpectralCorrection .... 156
C. BackgroundandInterferingSignals .... 156
D. DirectQuantitativeandQualitativeAnalyses .... 156
E. LowTemperatureTechniques .... 156
F. Room-TemperaturePhosphorescence .... 157
G. TechniquesandApplications .... 157
H. FutureOutlook .... 158
References .. . . 159
Copyright © 2005 by Marcel Dekker
viii Contents
7. Vibrational Spectroscopy: Instrumentation for Infraredand Raman Spectroscopy . .. . . .. . . .. . . .. . . 163
Peter Fredericks, Llewellyn Rintoul,JohnCoates
I. Introduction . . . . 163
A. BackgroundforVibrationalSpectroscopicMeasurements .... 164
B. TheBasicPrinciplesofVibrationalSpectroscopy .... 166
C. ComparisonofTechniquesandRelativeRoles .... 168
II. IR Instrumentation . .. . 170
A. TypesofInstrumentsandRecentTrends .... 170
B. Instrumentation:DesignandPerformanceCriteria .... 172
C. NIRInstrumentation .... 206
D. FIR(Terahertz)Instrumentation .... 209
III. RamanInstrumentation .. . . 211
A. TypesofInstrumentationandRecentTrends .... 211
B. Instrumentation:DesignandPerformanceCriteria .... 213
IV. Practical Issues ofImplementationof IR andRaman Instruments .. . . 230
A. InstrumentArchitectureandPackaging .... 230
B. DataHandlingandComputerApplications .... 232
V. InstrumentationStandards . . .. 233
VI. Recommended Reference Sources .. . . 234
Suggested Reference Texts . . . . 234
General Texts andReviews . .. . 235
Historical Reviews .. . . 235
References . .. . 235
8. X-Ray Methods .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . . 239
NarayanVariankaval
I. Introduction . . . . 239
A. ContinuousandCharacteristicSpectra .... 239
B. DiffractionfromCrystals .... 240
C. AugerEffect .... 241
D. WavelengthDispersiveX-RaySpectrometry .... 241
E. EnergyDispersiveX-RaySpectrometry .... 241
F. X-RayReflectivity .... 241
G. X-RayAbsorption .... 241
II. Instrumentationand Methods . .. . 242
A. OverviewofOpticalComponentsofanX-RayDiffractometer .... 242
B. X-RayMethods .... 247
III. Concluding Remarks . .. . 255
AdditionalReading . . .. 255
General .... 255
X-RayPropertiesofElements .... 255
X-RayDiffraction .... 255
X-RayDetectors .... 255
ParticleInducedX-RayEmission .... 255
X-RayFluorescence .... 255
X-RayPhotoelectronSpectroscopy .... 255
X-RayReflection .... 255
X-RayMicroanalysis .... 255
References . .. . 255
9. PhotoacousticSpectroscopy . . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . . 257
A.K.Rai,S.N.Thakur,J.P.Singh
I. Introduction . . . . 257
II. Photoacoustics and PASpectroscopy .. . . 258
A. History .... 258
B. Principle .... 259
Copyright © 2005 by Marcel Dekker
Contents ix
III. Relevance ofPA toPlant Science . . . . 261
IV. Review ofPA Applications inPlant Sciences . . .. 262
V. PAinDetection ofPlant Disease . . .. 263
A. ExperimentalSetup .... 263
B. DiseasesinWheatPlants .... 263
C. WheatGenotypeEKBSN-1ANDFBPFM-2 .... 267
D. VirusDiseaseinMungBeanPlant .... 267
E. FungalDiseaseinSugarcane .... 268
F. VirusDiseaseinOkraPlants .... 268
G. Seed-BorneDiseasesinWheatandRice .... 268
VI. Conclusion . . . . 268
VII. Future Developments . .. . 268
References .. . . 269
10. Techniques ofChiroptical Spectroscopy . . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. 271
HarryG.Brittain,NeluGrinberg
I. Introductionto Chiroptical Phenomena . . . . 271
II. PolarizationProperties of Light . . . . 272
III. Optical Rotationand ORD . . . . 272
A. ApplicationsofOpticalRotationandORD .... 275
IV. CircularDichroism . . .. 276
A. ApplicationsofCD .... 277
V. CPL Spectroscopy .. . . 278
A. ApplicationsofCPLSpectroscopy .... 280
VI. Vibrational Optical Activity . . .. 283
A. VibrationalCircularDichroism .... 283
B. RamanOpticalActivity .... 285
VII. Fluorescence Detected CircularDichroism . . .. 288
A. ApplicationsofFDCD .... 289
VIII. Concluding Remarks .. . . 290
References .. . . 290
11. Nuclear Magnetic Resonance .. . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. 295
FrederickG.Vogt
I. Introduction . . .. 295
II. InstrumentDesign .. . . 296
A. MagnetSystems .... 296
B. NMRProbes .... 300
C. RFGenerationandSignalDetection .... 303
D. MagneticFieldGradients .... 306
E. ComputerSystems .... 306
F. Accessories .... 307
III. Theoretical Background . .. . 307
A. NuclearSpinDynamics .... 307
B. ExternalManipulationsofSpinCoherence .... 310
C. InternalSpinInteractions .... 311
D. RelaxationPhenomenaandChemicalDynamics .... 314
IV. Experimental Methods . .. . 317
A. BasicPulseMethods .... 317
B. MultidimensionalNMRSpectroscopy .... 322
C. MultipleResonanceandHeteronuclearTechniques .... 325
D. Diffusion,Dynamics,andRelaxationMeasurements .... 332
V. Data Analysis and Interpretation . . .. 334
A. SpectralProcessing .... 335
B. ManualDataInterpretation .... 337
Copyright © 2005 by Marcel Dekker
x Contents
C. PredictiveMethods .... 342
D. Computer-AssistedStructureElucidation .... 343
VI. Conclusion .. . . 343
References . .. . 344
12. Electron Paramagnetic Resonance .. . . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . .. . . .. . . .. . . .. . . .. . . 349
SandraS.Eaton,GarethR.Eaton
I. Introduction . . . . 349
A. EPRExperiment .... 350
B. CWSpectroscopy .... 352
C. PulseSpectroscopy .... 355
D. MultipleResonanceMethods .... 355
II. What One Can Learn From anEPR Measurement . . . . 357
A. IsThereanEPRSignal?UnderWhatConditions? .... 357
B. Lineshape .... 358
C. g-Value .... 358
D. Spin–SpinCoupling .... 360
E. RelaxationTimes .... 360
F. SaturationBehavior .... 361
G. SignalIntensity .... 362
III. EPR Spectrometer .. . . 363
A. MicrowaveSystem .... 363
B. EPRResonators .... 366
C. MagnetSystem .... 370
D. SignalDetectionandAmplification .... 372
E. DataSystem .... 373
F. CommercialEPRSpectrometers .... 373
IV. The Sample . . . . 374
A. SpinSystem .... 374
B. Temperature .... 374
C. AmountofSample .... 375
D. PhaseofSample .... 376
E. Impurities,OverlappingSpectra .... 377
F. Intermolecularvs.IntramolecularInteractions .... 377
G. OtherEnvironmentalEffects .... 377
V. Quantitative Measurements of SpinDensity . .. . 378
A. SpectrometerCalibration .... 378
B. CalibrationofSampleTubes .... 379
C. ConsiderationofCavityQ .... 379
D. ReferenceSamplesforQuantitativeEPR .... 380
E. ScalingResultsforQuantitativeComparisons .... 380
VI. GuidanceonExperimental Technique .. . . 381
A. WordsofCaution .... 381
B. SelectionofOperatingConditions .... 382
C. SecondDerivativeOperation .... 384
D. CWSaturation .... 384
E. MethodsofMeasuringRelaxationTimes .... 384
F. MeasurementofB .... 385
1
G. Linevs.PointSamples .... 386
H. OvercoupledResonators .... 386
I. TheESEFlipAngleforHigh-SpinSystems .... 387
VII. Less Common Measurements withEPR Spectrometers . . . . 387
A. Saturation-TransferSpectroscopy .... 387
B. ElectricalConductivity .... 388
C. StaticMagnetization .... 388
D. EPRImaging .... 388
E. PulsedMagneticFieldGradients .... 388
Copyright © 2005 by Marcel Dekker