分析化学和定量分析 英文版PDF电子书下载

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