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P R I N C I P L E S OF INSTRUMENTAL
ANALYSIS
FOURTH EDITION
Douglas A. Skoog Stanford University
James J. Leary James Madison University
Saunders College Publishing Harcourt Brace College Publishers Fort Worth Philadelphia San Diego
New York Orlando Austin San Antonio Toronto Montreal London Sydney Tokyo
Contents
1 Introduction 1 1A Classification of Analytical Methods 1 1B Types of Instrumental Methods 2 IC Instruments for Analysis 3 1D Selecting an Analytical Method 5 IE Questions and Problems 9
2 Operational Amplifiers in Chemical Instrumentation 10
2A Properties of Operational Amplifiers 10 2B Circuits Employing Operational
Amplifiers 12 2C Amplification and Measurement of
Transducer Signals 15 2D Application of Operational Amplifiers to
Voltage and Current Control 19 2E Application of Operational Amplifiers to
Mathematical Operations 20 2F Application of Operational Amplifiers to
Switching 24 2G Questions and Problems 24
3 Digital Electronics, Microprocessors, and Computers 29
3A Analog and Digital Signals 29 3B Counting and Arithmetic with Binary
Numbers 30 3C Basic Digital Circuit Components 32 3D Microprocessors and Microcomputers 36 3E Components of a Computer 39 3F Computer Programming 41 3G Applications of Computers 41 3H Computer Networks 43
4 Signals and Noise 46 4A Signal-to-Noise 46 4B Sources of Noise in Instrumental
Analyses 47 4C Signal-to-Noise Enhancement 49 4D Questions and Problems 56
5 Properties of Electromagnetic Radiation 58 5A An Overview 58 5B Electromagnetic Radiation 60 5C Quantum-Mechanical Properties of
Radiation 70 5D Questions and Problems 77
IX
Instruments for Optical Spectroscopy 6A Components of Optical Instruments 6B Radiation Sources 81 6C Wavelength Selectors 87 6D Sample Containers 97 6E Radiation Detectors 98 6F Signal Processors and Readouts 107 6G Fiber Optics 108 6H Instrument Designs 109 61 Questions and Problems 120
1 0 Atomic Spectroscopy Based Upon 79 Flame and Electrothermal
79 Atomizat ion 196 10A Sample Atomization 196 10B Types and Sources of Atomic
Spectra 198 IOC Flame Atomization 205 10D Atomic Absorption Spectroscopy 211 10E Flame Emission Spectroscopy 223 10F Atomic Fluorescence Spectroscopy 228 10G Questions and Problems 230
An Introduction to Molecular Ultraviolet/Visible and Near-Infrared Absorption Spectroscopy 123
7A Terms Employed in Absorption Spectroscopy 123
7B Quantitative Aspects of Absorption Measurements 126
7C Instruments for Absorption Measurements in the Ultraviolet, Visible, and Near-Infrared Regions 136
7D Question and Problems 147
Application of Molecular Ultraviolet/ Visible Absorption Spectroscopy 150
8A The Magnitude of Molar Absorptivities 150
8B Absorbing Species 150 8C Application of Absorption Measurement to
Qualitative Analysis 160 8D Quantitative Analysis by Absorption
Measurements 161 8E Photometrie Titrations 166 8F Photoacoustic Spectroscopy 168 8G Questions and Problems 170
Molecular Fluorescence, Phosphorescence, and Chemiluminescence 174 9A Theory of Fluorescence and
Phosphorescence 175 9B Instruments for Measuring Fluorescence and
Phosphorescence 18 3 9C Applications and Photoluminescence
Methods 188 9D Chemiluminescence 191 9E Questions and Problems 193
1 1 Emission Spectroscopy Based Upon Plasma, Are, and Spark Atomization 233 IIA Spectra from Higher-Energy Sources 234 IIB Emission Spectroscopy Based on Plasma
Sources 234 HC Emission Spectroscopy Based on Are and
Spark Sources 244 HD Questions and Problems 251
1 2 Infrared Absorption Spectroscopy 252 12A Theory of Infrared Absorption 253 12B Infrared Sources and Detectors 260 12C Infrared Instruments 263 12D Sample Handling Techniques 272 12E Qualitative Applications of Mid-Infrared
Absorption 275 12F Quantitative Applications 280 12G Internal-Reflection Infrared
Spectroscopy 283 12H Photoacoustic Infrared Spectroscopy 285 121 Near-Infrared Spectroscopy 285 12J Far-Infrared Spectroscopy 288 12K Infrared Emission Spectroscopy 288 12L Questions and Problems 288
1 3 Raman Spectroscopy 13A Theory of Raman Spectroscopy 297 13B Instrumentation 302 13C Applications of Raman Spectroscopy 13D Application of Other Types of Raman
Spectroscopy 306 13E Questions and Problems 308
296
304
CONTENTS Xi
1 4 Nuclear Magnetic Resonance Spectroscopy 310 14A Theory of Nuclear Magnetic
Resonance 311 14B Environmental Effects on NMR
Spectra 322 14C NMR Spectrometers 334 14D Applications of Proton NMR 340 14E Carbon-13 NMR 344 14F Application of NMR to Other Nuclei 348 14G Two-Dimensional Fourier Transform
NMR 350 14H Questions and Problems 351
1 5 X-Ray Spectroscopy 357 15A Fundamental Principles 357 15B Instrument Components 364 15C X-Ray Fluorescence Methods 373 15D X-Ray Absorption Methods 378 15E X-Ray Diffraction Methods 378 15F The Electron Microprobe 380 15G Questions and Problems 381
1 6 Analysis of Surfaces with Electron Beams 383 16A Electron Spectroscopy 383 16B The Scanning Electron Microscope and
Microprobe 394 16C Questions and Problems 399
1 7 Radiochemical Methods 401 17A Radioactive Isotopes 401 17B Instrumentation 408 17C Neutron Activation Methods 410 17D Isotope Dilution Methods 414 17E Questions and Problems 416
1 8 Mass Spectrometry 420 18A The Mass Spectrometer 422 18B Molecular Spectra from Various Ion
Sources 439 18C Identification of Pure Compounds by Mass
Spectrometry 448 18D Analysis of Mixtures by Hyphenated Mass
Spectral Methods 451 18E Quantitative Applications of Mass
Spectrometry 454 18F Surface Analysis by Mass
Spectrometry 458 18G Questions and Problems 459
1 9 An Introduction to Electroanalytical Chemistry 462 19A Electrochemical Cells 462 19B Cell Potentials 466 19C Electrode Potentials 466 19D Calculation of Cell Potentials from Electrode
Potentials 475 19E Currents in Electrochemical Cells 478 19F Types of Electroanalytical Methods 485 19G Questions and Problems 486
2 0 Potentiometrie Methods 489 20A Reference Electrodes 489 20B Metallic Indicator Electrodes 492 20C Membrane Indicator Electrodes 494 20D Molecular-Selective Electrode
Systems 503 20E Instruments for Measuring Cell
Potentials 506 20F Direct Potentiometrie Measurements 508 20G Potentiometrie Titrations 514 20H Questions and Problems 514
2 1 Coulometric Methods 517 21A Current-Voltage Relationships During
Electrolysis 517 21B An Introduction to Coulometric Methods of
Analysis 522 21C Potentiostatic Coulometry 523 21D Coulometric Titrations (Amperostatic
Coulometry) 527 21E Questions and Problems 531
2 2 Voltammetry 535 22A Excitation Signals in Voltammetry 536 22B Linear-Scan Voltammetry 536 22C Pulse Polarographic and Voltammetric
Methods 554 22D Stripping Methods 559 22E Voltammetry with Microscopic
Electrodes 562 22F Cyclic Voltammetry 563 22G Questions and Problems 565
2 3 Thermal Methods 568 23A Thermogravimetric Methods (TG) 568 23B Differential Thermal Analysis (DTA) 571
23C Differential Scanning Calorimetry (DSC) 575
23D Questions and Problems 577
An Introduction to Chromatographie Separations 24A A General Description of
Chromatography 579 24B Migration Rates of Species 581 24C Band Broadening and Column
Efficiency 585 24D Optimization of Column
Performance 592 24E Summary of Important Relationships for
Chromatography 598 24F Applications of Chromatography 598 24G Questions and Problems 601
2 8 Automated Methods of Analysis 681
579
28A An Overview of Automatic Instruments and Automation 681
28B Flow-Injection Analysis 683 28C Discrete Automatic Systems 690 28D Automatic Analyses Based Upon Multilayer
Films 696 28E Questions and Problems 700
A p p e n d i x 1 Evaluation of Analytical Data A-l a1A Precision and Accuracy A-l a1B Statistical Treatment of Random
Errors A-6 a1C Method of Least Squares
A-17 a1D Questions and Problems
A-19
Gas Chromatography 25A Principles of Gas-Liquid
Chromatography 606 25B Instruments for Gas-Liquid
Chromatography 607 25C Gas-Chromatographie Columns and Station
ary Phase 613 25D Applications of Gas-Liquid
Chromatography 619 25E Gas-Solid Chromatography 623 25F Questions and Problems 625
High-Performance Liquid Chromatography 628 26A ScopeofHPLC 629 26B Column Efficiency in Liquid
Chromatography 629 26C Instruments for Liquid
Chromatography 631 26D Partition Chromatography 642 26E Adsorption Chromatography 651 26F Ion Chromatography 654 26G Size-Exclusion Chromatography 659 26H Thin-Layer Chromatography 663 261 Questions and Problems 667
605 Appendix 2
Appendix 3
Some Electrical Circuit Components A-24 a2A Direct Current Circuits and
Measurements A-24 a2B Alternating Current Circuits
A-29 a2C Questions and Problems
A-39
Some Electronic Circuit Components and Devices A-43 a3A Semiconductors and Semiconduc-
tor Devices A-43 a3B Power Supplies and Regulators
A-49 a3C Readout Devices A-50
A p p e n d i x 4 Activity Coefficients A-54 a4A Properties of Activity
Coefficients A-54 a4B Experimental Evaluation of Ac
tivity Coefficients A-55 a4C The Debye-Huckel Equation
A-56
A p p e n d i x 5 Some Standard and Formal Electrode Potentials A-58
Other Separation Methods 27A Supercritical Fluid Chromatography 27B Capillary Electrophoresis 675 27C Questions and Problems 680
A p p e n d i x 6 Compounds Recommended for the Prep-670 aration of Standard Solutions of Some 670 Common Elements A-62
Answers to Selected Problems A-64