Table Of ContentMass
Spectrometry
Pan Stanford Series on Renewable Energy — Volume 2
Mass
Spectrometry
James M. Thompson
editors
Preben Maegaard
Anna Krenz
Wolfgang Palz
The Rise of Modern Wind Energy
Wind Power
for the World
November14,2017 9:24 PSPBook-9inx6in 00-Mass-Spectrometry-Prelims
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MassSpectrometry
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ISBN978-981-4774-77-2(Hardback)
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November14,2017 9:24 PSPBook-9inx6in 00-Mass-Spectrometry-Prelims
Tomydaughter,Christine
November14,2017 9:24 PSPBook-9inx6in 00-Mass-Spectrometry-Prelims
November14,2017 9:24 PSPBook-9inx6in 00-Mass-Spectrometry-Prelims
Contents
Preface xi
Acknowledgments xiii
1 SomeFundamentalsofMassSpectrometry 1
1.1 Introduction 1
1.2 TheMassSpectrometer 2
1.2.1 TheMagneticSectorMassSpectrometer 3
1.2.2 TheQuadrupoleMassSpectrometer 6
1.2.3 TheTime-of-FlightMassSpectrometer 7
1.3 TheMassSpectrum 7
1.3.1 IonFragments 8
1.3.2 TheBasePeak 8
1.3.3 TheMolecularorParentIon(M+) 9
1.3.4 The(M+1)+Ion 9
1.3.5 IsotopicFragments 9
1.3.6 High-ResolutionMassSpectrometry 10
1.4 DepictingMassSpectralData 12
1.5 TheMolecularorParentIon 13
1.6 PredictingtheFormationofM+ 13
1.7 TheNitrogenRule 15
1.8 MetastableIons 15
1.9 DoublyChargedIons 17
1.10 TheGeneralFragmentationProcess 17
1.11 TheFragmentationofaHypotheticalMolecule 18
1.12 IdentifyingtheMolecularIon 20
1.13 ChemicalIonization 21
1.14 High-Molecular-WeightImpurities 23
1.15 TheFragmentationofM+ 23
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viii Contents
1.16 DeterminingtheMolecularIonfromtheFragments 24
1.17 DeterminingtheMolecularIonbyDerivatization 26
1.18 DeterminingM+FromRatesofEffusion 26
1.19 GeneralRearrangement 26
1.20 SkeletalRearrangement 27
1.21 TheMcLaffertyRearrangement 27
1.22 TheLossofNeutralFragments 28
1.23 AtomicWeightDeterminations 30
1.24 TheIsotopesofCarbon 31
1.25 CalculatingRelativeIntensities 33
1.26 TheExperimentalDeterminationofthe
CarbonNumber 34
1.27 CompoundsContainingBromineand/or
Chlorine 37
1.28 CompoundsContainingSulfur 42
1.29 Beynon’sTable 43
1.30 SomeTechniques,Innovations,andApplicationsin
MassSpectrometry 46
1.30.1 ThermogravimetricAnalysis–Mass
Spectrometry(TG/MS)and
ThermogravimetricAnalysis–Fourier
TransformInfrared(TG/FTIR) 46
1.30.2 TG/MSSystems 49
1.30.3 TheTG/MSInterface 51
1.30.4 TG/MSDataCollectingandProcessing
Software 52
1.30.5 GC/MS,GC/FTIRandGC/MS/FTIR 54
1.30.6 TheGC/MSandGC/FTIRandGC/MS/FTIR
Interfaces 56
2 TheAnalysisofMassSpectra 61
2.1 TheFragmentationPatternsofStraight-Chain
Alkanes 61
2.2 BranchedAlkanes 62
2.3 Cycloalkanes 62
2.4 UnsaturatedHydrocarbons 64
2.5 AlkylHalides 67
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Contents ix
2.6 PhenylHalides 69
2.7 BenzylHalides 69
2.8 AliphaticEthers 69
2.9 Alcohols 71
2.10 Phenols 75
2.11 AliphaticKetones 75
2.12 AromaticKetones 76
2.13 AliphaticAldehydes 76
2.14 AromaticAldehydes 77
2.15 Anhydrides 79
2.16 AcetalsandKetals 79
2.17 AliphaticAcids 80
2.18 AromaticAcids 81
2.19 AliphaticAmines 81
2.20 AromaticAmines 84
2.21 Amides 85
2.22 AliphaticNitroCompounds 86
2.23 AromaticNitroCompounds 86
3 ProblemsinMassSpectrometry 89
3.1 Introduction 89
3.2 SomeGeneralSuggestionsforInterpreting
MassSpectra 90
3.3 CriteriaforFindingtheMolecularIon 91
3.4 InterpretationofaMassSpectrumUsingthe
NationalInstituteofStandardsandTechnology
(NIST)MassSpectralSearchProgram 92
3.5 Problems 94
3.6 OntheStabilityofMolecules 147
3.6.1 ComplexMoleculesRevisited 149
3.7 OnDetectingIodineintheMolecule 155
3.8 MoreonNon-BranchedHydrocarbons 157
3.9 OntheLossofFragmentsfromtheMolecularIon 159
3.9.1 LossofH 159
3.10 Lossofamethylgroup 162
3.11 LossofHFfromtheMolecularIon 164
3.12 OntheLossofWaterfromAlcohols 166
Description:It is estimated that there are about 10 million organic chemicals known, and about 100,000 new organic compounds are produced each year. Some of these new chemicals are made in the laboratory and some are isolated from natural products. The structural determination of these compounds is the job of t
