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PRINCIPLES OF.:. . . .InstrumentalAnalysis. Ш ШFifth EditionDouglas A. SkoogStanford UniversityF. James HollerUniversity of KentuckyTimothy A. NiemanUniversity of Illinoisat Urbana-ChatnpaignSAUNDERS GOLDEN SUNBURST SERIES SAUNDERS COLLEGE PUBLISHINGHARCOURT BRACE COLLEGE PUBLISHERSPHILADELPHIAAUSTIN FORT WORTHMONTREAL CHICAGOTORONTO SAN FRANCISCOLONDON SYDNEY TOKYO

ContentsOverviewCHAPTER 1 Introduction1Section IMeasurementBasics21CHAPTER 2 Electrical Components andCircuits 22CHAPTER 3Operational Amplifiers in ChemicalInstrumentation 53CHAPTER 4 Digital Electronics andMicrocomputers 73CHAPTER 5 Signals and Noise 99Section IIAtomic SpectroscopyUSCHAPTER 6An Introduction to SpectrometricMethods 116CHAPTER 7Components of OpticalInstruments 143CHAPTER 8An Introduction to Optical AtomicSpectrometry 792CHAPTER 9Atomic Absorption and AtomicFluorescence Spectrometry 206CHAPTER 10 Atomic EmissionSpectrometry 230CHAPTER 11 Atomic Mass Spectrometry 253CHAPTER 12 Atomic X-Ray Spectrometry 272Section IIIMolecular Spectroscopy299CHAPTER 13 An Introduction toUltraviolet/Visible MolecularAbsorption Spectrometry 300CHAPTER 14 Applications of Ultraviolet/VisibleMolecular AbsorptionSpectrometry 329CHAPTER 15 Molecular LuminescenceSpectrometry 355CHAPTER 16 An Introduction to InfraredSpectrometry 380ix

xContents OverviewCHAPTER 29CHAPTER 17 Applications of InfraredSpectrometry 404CHAPTER 18 Raman Spectroscopy 429CHAPTER 19 Nuclear Magnetic ResonanceSpectroscopy 445CHAPTER 30CHAPTER 20 Molecular Mass SpectrometryCHAPTER 21 Surface Characterization bySpectroscopy and Microscopy498Section VI535Section IVElectroanalyticalChemistry563CHAPTER 22 Introduction to ElectroanalyticalChemistry 564CHAPTER 23 Potentiometry 597CHAPTER 24 Coulometry 622CHAPTER 25 Voltammetry 639Methods673CHAPTER 26 An Introduction to ChromatographicSeparations 673CHAPTER 27 Gas Chromatography 707CHAPTER 28MiscellaneousHigh-Performance LiquidChromatography 725Methods797CHAPTER 31 Thermal Methods 798CHAPTER 32 Radiochemical MethodsCHAPTER 33Appendices810Automated Methods of Analysis829A-lAPPENDIX 1 Evaluation of Analytical DataAPPENDIX 2 Activity Coefficients A-25APPENDIX 3Section VSeparationSupercritical Fluid Chromatographyand Extraction 768Capillary Electrophoresis andCapillary Electrochromatography778APPENDIX 4APPENDIX 5A-lSome Standard and Formal ElectrodePotentials A-28Compounds for Preparing StandardSolutions of Some CommonElements A—32Common Acronyms Encountered inChemical Instrumentation A-34Answers to Selected ProblemsIndex 7-7ANS-1

ContentsL lL L l Ll lll L L L L l , , , l , Li-'-'- - -'- - - - -'- - -'- -'- - - - - - - - - - - -c" ' .1A Classification of Analytical MethodsIB Types of Instrumental Methods.,1С Instruments for AnalysisID Selecting an Analytical Method.IE Calibration of Instrumental MethodsIF Questions and Problems1231115.18Section IMeasurementBasics21CHAPTER 2 Electrical Components andCircuits 222A Direct Current Circuits and Measurements . 222B Alternating Current Circuits.282C2D2E2FSemiconductors and SemiconductorDevicesPower Supplies and Regulators.Readout DevicesQuestions and Problems38444649CHAPTER 3ЗАOperational Amplifiers in ChemicalInstrumentation 53Properties of Operational Amplifiers533BOperational Amplifier Circuits3CAmplification and Measurement ofTransducer SignalsApplication of Operational Amplifiers toVoltage and Current Control3D.56.58633EApplication of Operational Amplifiers toMathematical Operations643FApplication of Operational Amplifiers toSwitching68Questions and Problems693GCHAPTER 44A4B4C4DDigital Electronics andMicrocomputers 73Analog and Digital SignalsCounting and Arithmetic with BinaryNumbersBasic Digital Circuit ComponentsMicroprocessors and Microcomputers.74747683XI

xii4E4F4G4H41ContentsComponents of a Computer.Computer SoftwareApplications of ComputersComputer Networks.Questions and Problems.85,89.919496CHAPTER 5 Signals and Noise 995A The Signal-to-Noise Ratio995B Sources of Noise in Instrumental Analysis. 1005C Signal-to-Noise Enhancement1025D Questions and Problems.113Section IIAtomic SpectroscopyCHAPTER 6 An Introduction to SpectrometricMethods 1166A6C1179A Sample Atomization Techniques.9B Atomic Absorption Instrumentation2062139CInterferences in Atomic AbsorptionSpectroscopy9DAtomic Absorption Analytical Techniques. .2239EAtomic Fluorescence Spectroscopy2259FQuestions and Problems227217231Emission Spectroscopy Based on Arcand Spark Sources24410C Miscellaneous Sources for Optical EmissionSpectroscopy25010D Questions and ProblemsQuantitative Aspects of SpectrochemicalMeasurements.1386EQuestions and Problems139CHAPTER 7 Components of OpticalInstruments 143CHAPTER 11 Atomic Mass Spectrometry11AIIB11C7AGeneral Designs of Optical Instruments1437BSources of Radiation145154166.167178Fiber Optics.25111DHE11F11GSome General Features of Atomic MassSpectrometry.Mass SpectrometersInductively Coupled Plasma MassSpectrometrySpark Source Mass SpectrometryGlow-Discharge Mass SpectrometryElemental Surface Analysis by MassSpectrometry.Questions and Problems253253.255.262269270271.2711797H Types of Optical Instruments71 Principles of Fourier Transform OpticalMeasurements.7J Questions and Problems.181CHAPTER 12 Atomic X-Ray Spectrometry12A182189CHAPTER 8 An Introduction to Optical AtomicSpectrometry 7928A Optical Atomic Spectra.8B Atomization MethodsCHAPTER 9 Atomic Absorption and AtomicFluorescence Spectrometry 2061286D7G201.20410B116Quantum-Mechanical Properties ofRadiation7C Wavelength Selectors7D Sample Containers7E Radiation Transducers7F Signal Processors and ReadoutsSample Introduction MethodsQuestions and ProblemsCHAPTER 10 Atomic EmissionSpectrometry 23010A Emission Spectroscopy Based on PlasmaSources115General Properties of ElectromagneticRadiation.6B Wave Properties of ElectromagneticRadiation8C8D.192200Fundamental Principles27227212B Instrument Components12C X-Ray Fluorescence Methods12D X-Ray Absorption Methods279.288.29312E X-Ray Diffraction Methods.29412F The Electron Microprobe12G Questions and Problems296296

ContentsCHAPTER 17Section IIIMolecular Spectroscopy299CHAPTER 13 An Introduction toUltraviolet/Visible MolecularAbsorption Spectrometry 30013A13BхшApplications of InfraredSpectrometry 40417A Mid-Infrared Absorption Spectrometry17B Mid-Infrared Reflection Spectrometry17C Photoacoustic Infrared Spectroscopy40441842117D Near-Infrared Spectroscopy17E Far-Infrared Spectroscopy422424Measurement of Transmittance andAbsorbance30017F Infrared Emission Spectroscopy425Beer's Law30217GInfrared Microspectrometry42517HQuestions and Problems42613C The Effects of Instrumental Noise onSpectrophotometric Analyses13D Instrumentation13E Questions and Problems306312325CHAPTER 14 Applications of Ultraviolet/VisibleMolecular AbsorptionSpectrometry 32914A The Magnitude of Molar Absorptivities32914B Absorbing Species33014C Application of Absorption Measurement toQualitative Analysis34014D Quantitative Analysis by AbsorptionMeasurements.34214E Photometric Titrations34714F Photoacoustic Spectroscopy34914G Questions and Problems351CHAPTER 15 Molecular LuminescenceSpectrometry 35515A Theory of Fluorescence andPhosphorescence.35615B Instruments for Measuring Fluorescence andPhosphorescence36515C Applications and PhotoluminescenceMethods37115D Chemiluminescence.37415E Questions and Problems377CHAPTER 16 An Introduction to InfraredSpectrometry 38016A Theory of Infrared AbsorptionSpectrometry16B Infrared Sources and Transducers16C Infrared Instruments16D Questions and Problems381389392401CHAPTER 18 Raman Spectroscopy18A Theory of Raman Spectroscopy42943018B Instrumentation18C Applications of Raman Spectroscopy43543818D Other Types of Raman Spectroscopy18E Questions and Problems441443CHAPTER 19 Nuclear Magnetic ResonanceSpectroscopy 44519A Theory of Nuclear Magnetic Resonance19B Environmental Effects on NMR Spectra44645719C NMR Spectrometers19D Applications of Proton NMR47047619E19F19G47948419HCarbon-13 NMRApplication of NMR to Other NucleiTwo-Dimensional Fourier TransformNMR.485Magnetic Resonance Imaging486191 Questions and ProblemsCHAPTER 20 Molecular MassSpectrometry 49820A Molecular Mass Spectra20B Ion Sources20C Mass Spectrometers20D Applications of Molecular MassSpectrometry20E Quantitative Applications of MassSpectrometry20F Questions and Problems491499499511524.531533

xivContentsCHAPTER 2121A21B21C21D21ESurface Characterization bySpectroscopy and MicroscopyIntroduction to the Study of SurfacesSpectroscopic Surface MethodsScanning Electron Microscopy.Scanning Probe MicroscopesQuestions and Problems535535536549553561Section IVElectroanalyticalCHAPTER 22Chemistry563An Introduction to ElectroanalyticalChemistry 56422A Electrochemical Cells22B Potentials in Electroanalytical Cells22C Electrode Potentials565569571CHAPTER 25 Voltammetry 63925A Excitation Signals in Voltammetry25B Voltammetric Instrumentation25C Hydrodynamic Voltammetry25D Cyclic HStripping MethodsVoltammetry with UltramicroelectrodesQuestions and Problems666669670Section VSeparationMethods673CHAPTER 26An Introduction to ChromatographicSeparations 67426AA General Description of Chromatography. .67522D Calculation of Cell Potentials from ElectrodePotentials58022E Currents in Electrochemical Cells58222F Types of Electroanalytical Methods58722G Questions and Problems58926B26C26D26EMigration Rates of Solutes.678Zone Broadening and Column Efficiency. 680Optimization of Column Performance687Summary of Important Relationships forChromatography693CHAPTER 23 Potentiometry59726FApplications of Chromatography23AReference Electrodes59126GQuestions and Problems23BMetallic Indicator Electrodes594CHAPTER 2723C Membrane Indicator Electrodes59623D Ion-Selective Field-Effect Transistors(ISFETs)60623E Molecular-Selective Electrode Systems60723F Instruments for Measuring Cell Potentials .61023G Direct Potentiometrie Measurements61223H Potentiometrie Titrations618231 Questions and Problems618CHAPTER 24Coulometry6221AK Current-Voltage Relationships During anElectrolysis.62224B An Introduction to Coulometric Methods ofAnalysis62724C Potentiostatic Coulometry.62824D Coulometric Titrations (AmperostaticCoulometry)63224E Questions and Problems63627AGas Chromatography.695697707Principles of Gas-Liquid Chromatography .70227BInstruments for Gas-LiquidChromatography.70327C Gas Chromatographic Columns andStationary Phases71127D Applications of Gas-Liquid Chromatography(GLC).71627E Gas-Solid Chromatography72127F Questions and Problems722CHAPTER 28High-Performance LiquidChromatography 72528A28BScope of HPLCColumn Efficiency in LiquidChromatography.72672628CInstruments for Liquid Chromatography72828D Partition Chromatography73928E Adsorption Chromatography748