Fundamentals of Analytical Chemistry, Tenth Edition
By Douglas A. Skoog, Donald M. West, F. James Holler and Stanley R. Crouch
Contents:
Chapter 1 The Nature of Analytical Chemistry 1
1A The Role of Analytical Chemistry 2
1B Quantitative Analytical Methods 4
1C A Typical Quantitative Analysis 4
1D An Integral Role for Chemical Analysis: Feedback Control Systems 8
Feature 1-1 Deer Kill: A Case Study Illustrating the Use
of Analytical Chemistry to Solve a Problem in Toxicology 9
PART I QUALITY OF ANALYTICAL MEASUREMENTS 14
Chapter 2 Calculations Used
in Analytical Chemistry 15
2A Some Important Units of Measurement 15
Feature 2-1 Unified Atomic Mass Units and the Mole 18
Feature 2-2 The Factor-Label Approach to Example 2-2 20
2B Solutions and Their Concentrations 20
2C Chemical Stoichiometry 28
Chapter 3 Precision and Accuracy of Chemical Analyses 38
3A Some Important Terms 39
3B Systematic Errors 43
Chapter 4 Random Errors in Chemical Analysis 51
4A The Nature of Random Errors 51
Feature 4-1 Flipping Coins: A Student Activity to Illustrate a Normal Distribution 55
4B Statistical Treatment of Random Errors 56
Feature 4-2 Areas under the Gaussian Curve 59
Feature 4-3 The Significance of the Number of Degrees of Freedom 60
Feature 4-4 Equation for Calculating the Pooled Standard Deviation 64
4C Standard Deviation of Calculated Results 66
4D Reporting Computed Data 71
Chapter 5 Statistical Data Treatment and Evaluation 80
5A Confidence Intervals 81
Feature 5-1 W. S. Gossett (Student) 85
5B Statistical Aids to Hypothesis Testing 86
5C Analysis of Variance 98
5D Detection of Gross Errors 105
Chapter 6 Sampling, Standardization, and Calibration 113
6A Analytical Samples and Methods 114
6B Sampling 116
6C Automated Sample Handling 126
6D Standardization and Calibration 128
Feature 6-1 Lab-on-a-Chip 129
Feature 6-2 A Comparison Method for Aflatoxins 130
Feature 6-3 Multivariate Calibration 141
6E Figures of Merit for Analytical Methods 146
PART II CHEMICAL EQUILIBRIA 159
Chapter 7 Aqueous Solutions and Chemical Equilibria 160
7A The Chemical Composition of Aqueous Solutions 160
7B Chemical Equilibrium 165
Feature 7-1 Stepwise and Overall Formation Constants for Complex Ions 169
Feature 7-2 Why [H2O] Does Not Appear in Equilibrium-
Constant Expressions for Aqueous Solutions 170
Feature 7-3 Relative Strengths of Conjugate Acid-Base Pairs 176
Feature 7-4 The Method of Successive Approximations 181
7C Buffer Solutions 183
Feature 7-5 The Henderson-Hasselbalch Equation 185
Feature 7-6 Acid Rain and the Buffer Capacity of Lakes 191
Chapter 8 Effect of Electrolytes on Chemical Equilibria 199
8A The Effect of Electrolytes on Chemical Equilibria 200
8B Activity Coefficients 203
Feature 8-1 Mean Activity Coefficients 206
Chapter 9 Solving Equilibrium Problems for Complex Systems 214
9A Solving Multiple-Equilibrium Problems Using a Systematic Method 215
9B Calculating Solubilities by the Systematic Method 221
Feature 9-1 Algebraic Expressions Needed to Calculate the Solubility of CaC2O4 in Water 226
9C Separation of Ions by Control of the Concentration of the Precipitating Agent 231
Feature 9-2 Immunoassay: Equilibria in the Specific Determination of Drugs 235
PART III CLASSICAL METHODS OF ANALYSIS 243
Chapter 10 Gravimetric Methods of Analysis 244
10A Precipitation Gravimetry 244
Feature 10-1 Specific Surface Area of Colloids 252
10B Calculation of Results from Gravimetric Data 256
10C Applications of Gravimetric Methods 258
Chapter 11 Titrations in Analytical Chemistry 267
11A Some Terms Used in Volumetric Titrations 268
11B Standard Solutions 270
11C Volumetric Calculations 271
Feature 11-1 Another Approach to Example 11-6(a) 276
Feature 11-2 Rounding the Answer to Example 11-7 277
11D Gravimetric Titrations 279
11E Titration Curves 280
Feature 11-3 Calculating the NaOH Volumes Shown in the
First Column of Table 11-1 282
Chapter 12 Principles of Neutralization Titrations 288
12A Solutions and Indicators for Acid-Base Titrations 288
12B Titration of Strong Acids and Bases 293
Feature 12-1 Using the Charge-Balance Equation to Construct Titration Curves 295
Feature 12-2 Significant Figures in Titration Curve Calculations 297
12C Titration Curves for Weak Acids 298
Feature 12-3 Determining Dissociation Constants of Weak Acids and Bases 301
Feature 12-4 A Master Equation Approach to Weak Acid/ Strong Base Titrations 302
12D Titration Curves for Weak Bases 303
Feature 12-5 Determining the pK Values for Amino Acids 305
12E The Composition of Solutions During Acid-Base Titrations 306
Feature 12-6 Locating Titration End Points from pH Measurements 307
Chapter 13 Complex Acid-Base Systems 314
13A Mixtures of Strong and Weak Acids or Strong and Weak Bases 314
13B Polyfunctional Acids and Bases 317
13C Buffer Solutions Involving Polyprotic Acids 320
13D Calculation of the pH of Solutions of NaHA 321
13E Titration Curves for Polyfunctional Acids 325
Feature 13-1 The Dissociation of Sulfuric Acid 333
13F Titration Curves for Polyfunctional Bases 334
13G Titration Curves for Amphiprotic Species 335
Feature 13-2 Acid-Base Behavior of Amino Acids 335
13H Composition of Polyprotic Acid Solutions as a Function of pH 336
Feature 13-3 A General Expression for Alpha Values 337
Feature 13-4 Logarithmic Concentration Diagrams 339
Chapter 14 Applications of Neutralization Titrations 345
14A Reagents for Neutralization Titrations 345
14B Typical Applications of Neutralization Titrations 351
Feature 14-1 Determining Total Serum Protein 352
Feature 14-2 Other Methods for Determining Organic Nitrogen 352
Feature 14-3 Equivalent Masses of Acids and Bases 358
Chapter 15 Complexation and Precipitation Reactions and Titrations 365
15A The Formation of Complexes 365
Feature 15-1 Calculation of Alpha Values for Metal Complexes 368
15B Titrations with Inorganic Complexing Agents 371
Feature 15-2 Determination of Hydrogen Cyanide in Acrylonitrile Plant Streams 372
15C Organic Complexing Agents 378
15D Aminocarboxylic Acid Titrations 379
Feature 15-3 Species Present in a Solution of EDTA 381
Feature 15-4 EDTA as a Preservative 383
Feature 15-5 EDTA Titration Curves When a Complexing Agent Is Present 393
Feature 15-6 Enhancing the Selectivity of EDTA Titrations
with Masking and Demasking Agents 399
Feature 15-7 Test Kits for Water Hardness 401
PART IV ELECTROCHEMICAL METHODS 406
Chapter 16 Introduction to Electrochemistry 407
16A Characterizing Oxidation/Reduction Reactions 407
Feature 16-1 Balancing Redox Equations 408
16B Electrochemical Cells 412
Feature 16-2 The Daniell Gravity Cell 414
16C Electrode Potentials 417
Feature 16-3 Why We Cannot Measure Absolute Electrode Potentials 420
Feature 16-4 Sign Conventions in the Older Literature 427
Feature 16-5 Why Are There Two Electrode Potentials for Br2 in Table 16-1? 430
Chapter 17 Applications of Standard Electrode Potentials 437
17A Calculating Potentials of Electrochemical Cells 437
17B Determining Standard Potentials Experimentally 444
Feature 17-1 Biological Redox Systems 446
17C Calculating Redox Equilibrium Constants 446
Feature 17-2 A General Expression for Calculating Equilibrium
Constants from Standard Potentials 450
17D Constructing Redox Titration Curves 452
Feature 17-3 The Inverse Master Equation Approach for Redox Titration Curves 460
Feature 17-4 Reaction Rates and Electrode Potentials 465
17E Oxidation/Reduction Indicators 465
17F Potentiometric End Points 468
Chapter 18 Applications of Oxidation/Reduction Titrations 473
18A Auxiliary Oxidizing and Reducing Reagents 473
18B Applying Standard Reducing Agents 475
18C Applying Standard Oxidizing Agents 479
Feature 18-1 Determination of Chromium Species in Water Samples 481
Feature 18-2 Antioxidants 486
Chapter 19 Potentiometry 500
19A General Principles 501
19B Reference Electrodes 502
19C Liquid Junction Potentials 505
19D Indicator Electrodes 505
Feature 19-1 An Easily Constructed Liquid-Membrane Ion- Selective Electrode 517
Feature 19-2 The Structure and Performance of Ion-Sensitive Field Effect Transistors 519
Feature 19-3 Point-of-Care Testing: Blood Gases and Blood
Electrolytes with Portable Instrumentation 523
19E Instruments for Measuring Cell Potential 525
Feature 19-4 The Loading Error in Potential Measurements 525
Feature 19-5 Operational Amplifier Voltage Measurements 527
19F Direct Potentiometry 528
19G Potentiometric Titrations 534
19H Potentiometric Determination of Equilibrium Constants 538
Chapter 20 Bulk Electrolysis: Electrogravimetry and Coulometry 544
20A The Effect of Current on Cell Potential 545
Feature 20-1 Overvoltage and the Lead-Acid Battery 551
20B The Selectivity of Electrolytic Methods 552
20C Electrogravimetric Methods 553
20D Coulometric Methods 559
Feature 20-2 Coulometric Titration of Chloride in Biological Fluids 568
Chapter 21 Voltammetry 575
21A Excitation Signals in Voltammetry 576
21B Voltammetric Instrumentation 577
Feature 21-1 Voltammetric Instruments Based on Operational Amplifiers 578
21C Hydrodynamic Voltammetry 583
21D Polarography 598
21E Cyclic Voltammetry 601
21F Pulse Voltammetry 604
21G Applications of Voltammetry 607
21H Stripping Methods 608
21I Voltammetry with Microelectrodes 610
PART V SPECTROCHEMICAL ANALYSIS 616
Chapter 22 Introduction to Spectrochemical Methods 617
22A Properties of Electromagnetic Radiation 618
22B Interaction of Radiation and Matter 621
Feature 22-1 Spectroscopy and the Discovery of Elements 623
22C Absorption of Radiation 624
Feature 22-2 Deriving Beer’s Law 627
Feature 22-3 Why Is a Red Solution Red? 631
22D Emission of Electromagnetic Radiation 639
Chapter 23 Instruments for Optical Spectrometry 649
23A Instrument Components 649
Feature 23-1 Laser Sources: The Light Fantastic 653
Feature 23-2 Origin of Equation 23-1 659
Feature 23-3 Producing Ruled and Holographic Gratings 661
Feature 23-4 Basis of Equation 23-2 664
Feature 23-5 Signals, Noise, and the Signal-to-Noise Ratio 666
Feature 23-6 Measuring Photocurrents with Operational Amplifiers 674
23B Ultraviolet/Visible Photometers and Spectrophotometers 676
23C Infrared Spectrophotometers 679
Feature 23-7 How Does a Fourier Transform Infrared Spectrometer Work? 681
Chapter 24 Molecular Absorption Spectrometry 689
24A Ultraviolet and Visible Molecular Absorption Spectroscopy 689
24B Automated Photometric and Spectrophotometric Methods 711
24C Infrared Absorption Spectroscopy 714
Feature 24-1 Producing Spectra with an FTIR Spectrometer 718
Chapter 25 Molecular Fluorescence Spectroscopy 728
25A Theory of Molecular Fluorescence 728
25B Effect of Concentration on Fluorescence Intensity 732
25C Fluorescence Instrumentation 733
25D Applications of Fluorescence Methods 734
Feature 25-1 Use of Fluorescence Probes in Neurobiology: Probing the Enlightened 735
25E Molecular Phosphorescence Spectroscopy 737
25F Chemiluminescence Methods 738
Chapter 26 Atomic Spectroscopy 742
26A Origins of Atomic Spectra 743
26B Production of Atoms and Ions 746
26C Atomic Emission Spectrometry 756
26D Atomic Absorption Spectrometry 760
Feature 26-1 Determining Mercury by Cold-Vapor Atomic Absorption Spectroscopy 767
26E Atomic Fluorescence Spectrometry 770
Chapter 27 Mass Spectrometry 774
27A Principles of Mass Spectrometry 774
27B Mass Spectrometers 776
27C Atomic Mass Spectrometry 780
27D Molecular Mass Spectrometry 783
PART VI KINETICS AND SEPARATIONS 791
Chapter 28 Kinetic Methods of Analysis 792
28A Rates of Chemical Reactions 793
Feature 28-1 Enzymes 800
28B Determining Reaction Rates 806
Feature 28-2 Fast Reactions and Stopped-Flow Mixing 806
28C Applications of Kinetic Methods 813
Feature 28-3 The Enzymatic Determination of Urea 815
Chapter 29 Introduction to Analytical Separations 821
29A Separation by Precipitation 822
29B Separation of Species by Distillation 826
29C Separation by Extraction 826
Feature 29-1 Derivation of Equation 29-3 828
29D Separating Ions by Ion Exchange 831
Feature 29-2 Home Water Softeners 833
29E Chromatographic Separations 835
Feature 29-3 What Is the Source of the Terms Plate and Plate Height? 843
Feature 29-4 Derivation of Equation 29-24 845
Chapter 30 Gas Chromatography 860
30A Instruments for Gas-Liquid Chromatography 861
30B Gas Chromatographic Columns and Stationary Phases 870
30C Applications of Gas-Liquid Chromatography 874
Feature 30-1 Use of GC/MS to Identify a Drug Metabolite in Blood 876
30D Gas-Solid Chromatography 882
Chapter 31 High-Performance Liquid Chromatography 886
31A Instrumentation 887
Feature 31-1 LC/MS and LC/MS/MS 894
31B Partition Chromatography 895
31C Adsorption Chromatography 898
31D Ion Chromatography 899
31E Size-Exclusion Chromatography 901
Feature 31-2 Buckyballs: The Chromatographic Separation of Fullerenes 903
31F Affinity Chromatography 905
31G Chiral Chromatography 905
31H Comparison of High-Performance Liquid Chromatography
and Gas Chromatography 906
Chapter 32 Miscellaneous Separation Methods 910
32A Supercritical Fluid Separations 910
32B Planar Chromatography 915
32C Capillary Electrophoresis 917
Feature 32-1 Capillary Array Electrophoresis in DNA Sequencing 924
32D Capillary Electrochromatography 924
32E Field-Flow Fractionation 927
PART VII PRACTICAL ASPECTS
OF CHEMICAL ANALYSIS 934
The following chapters are available as Adobe
Acrobat® PDF files on the companion site for the book.
Chapter 33 The Analysis of Real Samples 935
33A Real Samples 935
33B Choice of Analytical Method 937
33C Accuracy in the Analysis of Complex Materials 942
Chapter 34 Preparing Samples for Analysis 945
34A Preparing Laboratory Samples 945
34B Moisture in Samples 947
34C Determining Water in Samples 950
Chapter 35 Decomposing and Dissolving the Sample 951
35A Sources of Error in Decomposition and Dissolution 952
35B Decomposing Samples with Inorganic Acids in Open Vessels 952
35C Microwave Decompositions 954
35D Combustion Methods for Decomposing Organic Samples 957
35E Decomposing Inorganic Materials with Fluxes 959
Chapter 36 Chemicals, Apparatus, and Unit
Operations of Analytical Chemistry 961
36A Selecting and Handling Reagents
and Other Chemicals 962
36B Cleaning and Marking
of Laboratory Ware 963
36C Evaporating Liquids 964
36D Measuring Mass 964
36E Equipment and Manipulations
Associated with Weighing 971
36F Filtration and Ignition of Solids 974
36G Measuring Volume 980
36H Calibrating Volumetric Glassware 989
36I The Laboratory Notebook 991
36J Safety in the Laboratory 992
Chapter 37 Selected Methods of Analysis 994
37A An Introductory Experiment 995
37B Gravimetric Methods of Analysis 1004
37C Neutralization Titrations 1008
37D Precipitation Titrations 1017
37E Complex-Formation Titrations with EDTA 1020
37F Titrations with Potassium Permanganate 1023
37G Titrations with Iodine 1029
37H Titrations with Sodium Thiosulfate 1031
37I Titrations with Potassium Bromate 1034
37J Potentiometric Methods 1036
37K Electrogravimetric Methods 1040
37L Coulometric Titrations 1042
37M Voltammetry 1044
37N Methods Based on the Absorption of Radiation 1046
37O Molecular Fluorescence 1050
37P Atomic Spectroscopy 1051
37Q Application of Ion-Exchange Resins 1054
37R Gas-Liquid Chromatography 1056
Glossary G-1
APPENDIX 1 The Literature of Analytical Chemistry A-1
APPENDIX 2 Solubility Product Constants at 25°C A-6
APPENDIX 3 Acid Dissociation Constants at 25°C A-8
APPENDIX 4 Formation Constants at 25°C A-10
APPENDIX 5 Standard and Formal Electrode Potentials A-12
APPENDIX 6 Use of Exponential Numbers and Logarithms A-15
APPENDIX 7 Volumetric Calculations Using Normality and Equivalent Weight A-19
APPENDIX 8 Compounds Recommended for the
Preparation of Standard Solutions of Some Common Elements A-26
APPENDIX 9 Derivation of Error Propagation Equations A-28
Answers to Selected Questions and Problems A-33
Index I-1