Chapter 1 An Overview of Analytical Chemistry 1
1.1 Introduction:The Case of the Mysterious Chemist 1
1.2 The History of Chemical Analysis 2
1.2A Origins of Chemical Analysis 2
1.2B Chemical Analysis in the Modern World 3
1.3 General Terms Used in Chemical Analysis 4
1.3A Sample-Related Terms 4
1.3B Method-Related Terms 5
1.4 Information Provided by Chemical Analysis 7
1.5 Overview of Text 9
Key Words 9
Other Terms 9
Questions 9
References 11
Chapter 2 Good Laboratory Practices 12
2.1 Introduction:A Question of Quality 12
2.1A What Are Good Laboratory Practices? 12
2.1B Establishing Good Laboratory Practices 13
BOX 2.1:The Polymerase Chain Reaction 14
2.2 Laboratory Safety 16
2.2A Common Components of Laboratory Safety 16
2.2B Identifying Chemical Hazards 16
BOX 2.2:Determining the Safety of Chemicals 18
2.2C Sources of Information on Chemicals 19
2.2D Proper Handling of Chemicals 21
2.3 The Laboratory Notebook 22
2.3A Recommended Notebook Practices 22
2.3B Electronic Notebooks and Spreadsheets 23
2.4 Reporting Experimental Data 25
2.4A The SI System of Measurements 25
2.4B Significant Figures 29
Key Words 31
Other Terms 31
Questions 31
References 34
Chapter 3 Mass and Volume Measurements 36
3.1 Introduction:J.J.Berzelius 36
3.2 Mass Measurements 37
3.2A The Determination of Mass 37
3.2B Types of Laboratory Balances 38
BOX 3.1:Atomic Force Microscopy 39
3.2C Recommended Procedures for Mass Measurements 41
3.3 Volume Measurements 43
3.3A The Determination of Volume 44
3.3B Types of Volumetric Equipment 45
3.3C Recommended Procedures for Volume Measurements 48
3.4 Samples,Reagents,and Solutions 50
3.4A Describing Sample and Reagent Composition 50
3.4B Solution Preparation 54
Key Words 58
Other Terms 58
Questions 58
References 63
Chapter 4 Making Decisions with Data 64
4.1 Introduction:Take Me Out to the Ball Game? 64
4.1A Types of Laboratory Errors 65
4.1B Accuracy and Precision 65
4.2 Describing Experimental Results 66
4.2A Determining the Most Representative Value 66
4.2B Reporting the Variation in a Group of Results 67
4.3 The Propagation of Errors 68
4.3A Addition and Subtraction 68
4.3B Multiplication and Division 69
4.3C Logarithms,Antilogarithms,and Exponents 70
4.3D Mixed Calculations 71
4.4 Sample Distributions and Confidence Intervals 71
4.4A Describing the Variation in Large Data Sets 72
4.4B Describing the Variation in Small Data Sets 73
BOX 4.1:Who Was"Student"? 75
4.5 Comparing Experimental Results 76
4.5A General Requirements for the Comparison of Data 76
4.5B Comparing an Experimental Result with a Reference Value 76
4.5C Comparing Two or More Experimental Results 77
BOX 4.2:Selecting a Confidence Level 78
4.5D Comparing the Variation in Results 80
4.6 Detecting Outliers 81
4.6A General Strategy in Handling Outliers 81
4.6B Statistical Tests for Outliers 81
4.7 Fitting Experimental Results 83
4.7A Linear Regression 83
4.7B Testing the Goodness of a Fit 84
Key Words 87
Other Terms 88
Questions 88
References 94
Chapter 5 Characterization and Selection of Analytical Methods 95
5.1 Introduction:The Vinland Map 95
5.2 Method Characterization and Validation 96
5.2A Accuracy and Precision 96
BOX 5.1:A Closer Look at Small Samples 97
5.2B Assay Response 99
5.2C Other Properties of Analytical Methods 103
5.3 Quality Control 103
5.3A General Requirements for Quality Control 103
5.3B Preparing and Using Control Charts 103
5.4 Sample Collection and Preparation 104
5.4A Sample Collection 105
5.4B Sample Preparation 106
Key Words 109
Other Terms 109
Questions 109
References 113
Chapter 6 Chemical Activity and Chemical Equilibrium 115
6.1 Introduction:"And the Long-Range Forecast Is..." 115
6.1A Types of Chemical Reactions and Transitions 115
6.1B Describing Chemical Reactions 116
6.2 Chemical Activity 117
6.2A What Is Chemical Activity? 117
BOX 6.1:Carbon-14 Dating 118
6.2B Chemical Activity in Analytical Methods 121
6.3 Chemical Equilibrium 125
6.3A What Is a Chemical Equilibrium? 125
6.3B Solving Chemical Equilibrium Problems 130
Key Words 136
Other Terms 136
Questions 136
References 139
Chapter 7 Chemical Solubility and Precipitation 141
7.1 Introduction:Fighting Stomach Cancer 141
7.1A What Is Solubility? 141
7.1B What Is Precipitation? 142
7.1C Why Are Solubility and Precipitation Important in Chemical Analysis? 143
7.2 Chemical Solubility 144
7.2A What Determines Chemical Solubility? 144
BOX 7.1:X-Ray Crystallography 145
7.2B How Can We Describe Chemical Solubility? 147
7.2C How Can We Determine the Solubility of a Chemical? 153
7.3 Chemical Precipitation 154
7.3A The Process of Precipitation 154
7.3B Using Solubility Products to Examine Precipitation 155
7.3C Effects of Other Chemicals and Reactions on Precipitation 157
Key Words 159
Other Terms 159
Questions 159
References 164
Chapter 8 Acid-Base Reactions 165
8.1 Introduction:Rain,Rain Go Away 165
8.1A What Is an Acid or a Base? 166
8.1B Why Are Acids and Bases Important in Chemical Analysis? 168
8.2 Describing Acids and Bases 169
8.2A Strong and Weak Acids 169
8.2B Strong and Weak Bases 170
8.2C The Acid and Base Properties of Water 171
8.3 The Acid or Base Properties of a Solution 173
8.3A What Is pH? 173
8.3B Factors that Affect pH 175
8.4 Estimating the pH of Simple Acid-Base Solutions 176
8.4A Monoprotic Strong Acids and Bases 176
8.4B Monoprotic Weak Acids and Bases 178
8.5 Buffers and Polyprotic ACid-Base Systems 181
8.5A Buffer Solutions 181
BOX 8.1:Preparing Buffers 182
8.5B Polyprotic Acid-Base Systems 185
8.5C Zwitterions 190
Key Words 195
Other Terms 195
Questions 195
References 201
Chapter 9 Complex Formation 203
9.1 Introduction:What's in My Mayo? 203
9.1A What Is Complex Formation? 203
9.1B What Are Some Analytical.Applications of Complex Formation? 204
9.2 Simple Metal-Ligand Complexes 204
9.2A What Is a Metal-Ligand Complex? 205
9.2B Formation Constants for Metal-Ligand Complexes 207
9.2C Predicting the Distribution of Metal-Ligand Complexes 208
BOX 9.1:A Closer Look at Metal-Ligand Complex Formation 209
9.3 Complexes of Chelating Agents with Metal Ions 213
9.3A What Is a Chelating Agent? 213
9.3B The Chelate Effect 214
9.3C Ethylenediaminetetraacetic Acid 214
9.3D Dealing with Side Reactions 217
9.4 Other Types of Complexes 220
9.4A A General Description of Complex Formation 220
9.4B Examples of Alternative Complexes 221
BOX 9.2:Immunoassays 222
Key Words 223
Other Terms 223
Questions 223
References 228
Chapter 10 Oxidation-Reduction Reactions 230
10.1 Introduction:Saving the Arizona 230
10.1A What Are Oxidation-Reduction Reactions? 230
10.1B How Are Oxidation-Reduction Reactions Used in Analytical Chemistry? 232
10.2 General Principles of Oxidation-Reduction Reactions 232
10.2A Describing Oxidation-Reduction Reactions 232
10.2B Identifying Oxidation-Reduction Reactions 233
10.2C Predicting the Extent of Oxidation-Reduction Reactions 235
10.3 Electrochemical Cells 238
10.3A Describing Electrochemical Cells 238
BOX 10.1:A Shorthand Description of Electrochemical Cells 240
10.3B Predicting the Behavior of Electrochemical Cells 241
10.4 The Nernst Equation 243
10.4A Working with the Nernst Equation 243
BOX 10.2:A Closer Look at the Nernst Equation 244
10.4B Calculating Potentials for Oxidation-Reduction Reactions 245
10.4C Effects of the Sample Matrix and Side Reactions 247
Key Words 251
Other Terms 251
Questions 252
References 258
Chapter 11 Gravimetric Analysis 259
11.1 Introduction:Fixing the Periodic Table 259
11.1A What Is Gravimetric Analysis? 259
11.1B How Is Gravimetric Analysis Used in Analytical Chemistry? 260
11.2 Performing a Traditional Gravimetric Analysis 261
11.2A General Strategies and Methods 261
11.2B Filtering Precipitates 262
11.2C Drying and Weighing Precipitates 266
11.2D Methods for Obtaining High-Quality Precipitates 266
11.3 Examples of Gravimetric Methods 269
11.3A Precipitation of Silver with Chloride 269
11.3B Precipitation of Iron with Hydroxide 271
11.3C Precipitation of Nickel with Dimethylglyoxime 272
11.3D Combustion Analysis 273
11.3E Thermogravimetric Analysis 275
BOX 11.1:Combustion Analysis,Then and Now 276
Key Words 277
Other Terms 278
Questions 278
References 282
Chapter 12 Acid-Base Titrations 283
12.1 Introduction:Rise of the Titrations 283
12.1A What ls an Acid-Base Titration? 283
12.1B How Are Acid-Base Titrations Used in Analytical Chemistry? 284
BOX 12.1:The Kjeldahl Method 288
12.2 Performing an Acid-Base Titration 289
12.2A Preparing Titrant and Sample Solutions 289
12.2B Performing a Titration 292
12.2C Determining the End Point 293
12.3 Predicting and Optimizing Acid-Base Titrations 296
12.3A Describing Acid-Base Titrations 296
12.3B Titration Curves for Strong Acids and Bases 298
12.3C Titration Curves for Weak Acids and Bases 302
12.3D A Closer Look at Acid-Base Titrations 306
Key Words 312
Other Terms 312
Questions 312
References 318
Chapter 13 Complexometric and Precipitation Titrations 319
13.1 Introduction:How Hard Is the Water? 319
13.1A What Is a Complexometric or Precipitation Titration? 319
13.1B How Are Complexometric and Precipitation Titrations Used in Analytical Chemistry? 322
13.2 Performing a Complexometric Titration 322
13.2A Titrants and Standard Solutions 322
13.2B Using Auxiliary Ligands and Masking Agents 326
13.2C Determining the End Point 327
13.2D Predicting and Optimizing Complexometric Titrations 329
13.3 Performing a Precipitation Titratio n 333
13.3A Titrants and Standard Solutions 333
13.3B Determining the End Point 334
BOX 13.1:A King with a Problem 335
13.3C Predicting and Optimizing Precipitation Titrations 337
Key Words 341
Other Terms 341
Questions 341
References 347
Chapter 14 An Introduction to Electrochemical Analysis 348
14.1 Introduction:Getting a Brighter Smile 348
14.1A Units of Electrical Measurements 348
14.1B Methods for Electrochemical Analysis 351
14.2 General Principles of Potentiometry 351
14.2A Cell Potentials and the Nernst Equation 351
14.2B Cell Components in Potentiometry 352
14.2C Applications of Potentiometry 356
14.3 Ion-Selective Electrodes and Related Devices 356
14.3A Glass Membrane Electrodes 357
BOX 14.1:Creation of the pH Meter 357
14.3B Solid-State Ion-Selective Electrodes 359
14.3C Compound Electrodes 360
Key Words 361
Other Terms 361
Questions 361
References 364
Chapter 15 Redox Titrations 365
15.1 Introduction:Chemical Oxygen Demand 365
15.1A What Is a Redox Titration? 365
15.1B How Are Redox Titrations Used in Analytical Chemistry? 367
15.2 Performing a Redox Titration 368
15.2A Preparing Titrants and Samples 368
15.2B Finding the End Point 370
15.3 Predicting and Optimizing Redox Titrations 373
15.3A General Approach to Calculations for Redox Titrations 373
15.3B Estimating the Shape of a Redox Titration Curve 374
15.3C Using the Fraction of Titration 377
15.4 Examples of Redox Titrations 378
15.4A Titrations Involving Cerate 378
15.4B Titrations Involving Permanganate 378
15.4C Titrations Involving Dichromate 382
15.4D Titrations Involving Iodine 383
BOX 15.1:The Karl Fischer Method 385
Key Words 386
Other Terms 386
Questions 386
References 390
Chapter 16 Coulometry,Voltammetry,and Related Methods 392
16.1 Introduction:The Dead Zone 392
16.2 Electrogravimetry 392
16.3 Coulometry 394
16.3A Direct Coulometry 395
16.3B Coulometric Titrations 395
16.3C Constant Potential Coulometry 397
16.4 Voltammetry and Amperometry 397
16.4A Direct Current Voltammetry 397
16.4B Amperometry 399
BOX 16.1:Cyclic Voltammetry 400
16.4C Anodic Stripping Voltammetry 401
Key Words 402
Other Terms 402
Questions 402
References 404
Chapter 17 An Introduction to Spectroscopy 405
17.1 Introduction:The View from Above 405
17.1A What Is Spectroscopy? 405
17.1B How Is Spectroscopy Used in Analytical Chemistry? 407
17.2 The Properties of Light 407
17.2A What Is Light? 408
BOX 17.1:NMR:Tuning into Chemical Structure 412
17.2B Uptake and Release of Light by Matter 413
17.2C Physical Interactions of Light with Matter 416
17.3 Quantitative Analysis Based on Spectroscopy 421
17.3A Analysis Based on Emission 421
17.3B Analysis Based on Absorption 421
BOX 17.2:A Closer Look at Beer's Law 423
Key Words 427
Other Terms 427
Questions 427
References 433
Chapter 18 Molecular Spectroscopy 434
18.1 Introduction:The Good,the Bad,and the Ugly 434
18.1A What Is Molecular Spectroscopy? 434
18.1B How Is Molecular Spectroscopy Used in Chemical Analysis? 435
18.2 Ultraviolet-Visible Spectroscopy 435
18.2A General Principles of Ultraviolet-Visible Spectroscopy 435
18.2B Instrumentation for Ultraviolet-Visible Spectroscopy 437
18.2C Applications of Ultraviolet-Visible Spectroscopy 440
18.3 Infrared Spectroscopy 445
18.3A General Principles of Infrared Spectroscopy 445
18.3B Instrumentation for Infrared Spectroscopy 446
BOX 18.1:Raman Spectroscopy 447
18.3C Applications of Infrared Spectroscopy 448
18.4 Molecular Luminescence 450
18.4A General Principles of Luminescence 450
18.4B Instrumentation for Luminescence Measurements 452
18.4C Applications of Molecular Luminescence 452
Key Words 453
Other Terms 453
Questions 453
References 457
Chapter 19 Atomic Spectroscopy 459
19.1 Introduction:Star Light,Star Bright 459
19.1A What Is Atomic Spectroscopy? 459
19.1B How Is Atomic Spectroscopy Used in Chemical Analysis? 460
19.2 Principles of Atomic Spectroscopy 461
19.2A Sample Atomization 461
19.2B Sample Excitation 461
19.2C Properties of Flames 461
19.2D Analyte Measurement 463
19.3 Atomic Absorption Spectrometry 464
BOX 19.1:Tuning into Lasers 464
19.3A Laminar Flow Instruments 465
19.3B Graphite-Furnace Instruments 466
19.3C Optimizing Atomic Absorption Spectroscopy 467
19.4 Atomic Emission Spectroscopy 470
19.4A Flame Instruments 470
19.4B Plasma Instruments 470
Key Words 472
Other Terms 472
Questions 472
References 475
Chapter 20 An Introduction to Chemical Separations 476
20.1 Introduction:The Green Revolution 476
20.1A What Is a Chemical Separation? 476
20.1B How Are Chemical Separations Used in Analytical Chemistry? 477
20.2 Chemical Separations Based on Extractions 478
20.2A What Is an Extraction? 478
20.2B Using and Describing Extractions 480
BOX 20.1:Supercritical Fluid Extractions 480
20.2C A Closer Look at Extractions 482
20.3 Chemical Separations Based on Chromatography 485
20.3A What Is Chromatography? 485
20.3B Using and Describing Chromatography 487
20.4A Closer Look at Chromatography 488
20.4A Analyte Retention in Chromatography 488
20.4B Chromatographic Band-Broadening 490
BOX 20.2:A Closer Look at the van Deemter Equation 495
20.4C Controlling Chromatographic Separations 496
Key Words 498
Other Terms 498
Questions 499
References 505
Chapter 21 Gas Chromatography 507
21.1 Introduction:Theree's Something in the Air 507
21.1A What Is Gas Chromatography? 507
21.1B How Is Gas Chromatography Performed? 508
21.2 Factors that Affect Gas Chromatography 510
21.2A Requirements for the Analyte 510
21.2B Factors that Determine Retention in Gas Chromatography 512
21.2C Column Efficiency in Gas Chromatography 515
BOX 21.1:Comparing Gas Chromatography Stationary Phases 515
21.3 Gas Chromatography,Mobile Phases,and Elution Methods 515
21.3A Common Mobile Phases in Gas Chromatography 515
21.3B Elution Methods in Gas Chromatography 516
21.4 Gas Chromatography Supports and Stationary Phases 517
21.4A Gas Chromatography Support Materials 517
BOX 21.2:Analytical Chemistry in Space 518
21.4B Gas Chromatography Stationary Phases 519
21.5 Gas Chromatography Detectors and Sample Handling 522
21.5A Types of Gas Chromatography Detectors 522
21.5B Sample Injection and Pretreatment 527
Key Words 530
Other Terms 530
Questions 531
References 535
Chapter 22 Liquid Chromatography 537
22.1 Introduction:Battling a Modern Epidemic 537
22.1A What Is Liquid Chromatography? 537
22.1B How Is Liquid Chromatography Performed? 538
22.2 Factors that Aftect Liquid Chromatography 539
22.2A Requirements for the Analyte 539
22.2B Column Efficiency in Liquid Chromatography 540
22.2C Role of the Mobile Phase in Liquid Chromatography 540
BOX 22.1:Paper Chromatography and TLC 542
22.3 Types of Liquid Chromatography 543
22.3A Adsorption Chromatography 543
22.3B Partition Chromatography 545
22.3C Ion-Exchange Chromatography 548
22.3D Size-Exclusion Chromatography 552
22.3E Affinity Chromatography 553
22.4 Liquid Chromatography Detectors and Sample Pretreatment 556
22.4A Types of Liquid Chromatography Detectors 556
BOX 2.2:Chiral Separations 557
22.4B Liquid Chromatography Equipment and Sample Pretreatment 561
Key Words 564
Other Terms 564
Questions 564
References 569
Chapter 23 Electrophoresis 571
23.1 Introduction:The Human Genome Project 571
23.1A What Is Electrophoresis? 571
23.1B How Is Electrophoresis Performed? 573
23.2 General Principles of Electrophoresis 574
23.2A Factors Affecting Analyte Migration 574
23.2B Factors Affecting Band-Broadening 576
23.3 Gel Electrophoresis 577
23.3A What Is Gel Electrophoresis? 577
23.3B How Is Gel Electrophoresis Performed? 578
23.3C What Are Some Special Types of Gel Electrophoresis? 579
BOX 23.1:Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry 580
23.4 Capillary Electrophoresis 582
23.4A What Is Capillary Electrophoresis? 582
23.4B How Is Capillary Electrophoresis Performed? 583
23.4C What Are Some Special Types of Capillary Electrophoresis? 587
BOX 23.2:Analytical Chemistry on a Chip 587
Key Words 590
Other Terms 590
Questions 590
References 595
Appendices 597
Answers to Selected Questions 635
Glossary 645
Index 673