Modern Analytical Chemistry by David Harvey

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Modern Analytical Chemistry by David Harvey

Modern Analytical Chemistry by David Harvey

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Modern Analytical Chemistry by David Harvey

David Harvey
DePauw University

Table of Contents

Chapter 1

Introduction 1

1A What is Analytical Chemistry? 2

1B The Analytical Perspective 5

1C Common Analytical Problems 8

1D Key Terms 9

1E Summary 9

1F Problems 9

1G Suggested Readings 10

1H References 10

Chapter 2

Basic Tools of Analytical Chemistry 11

2A Numbers in Analytical Chemistry 12

2A.1 Fundamental Units of Measure 12

2A.2 Significant Figures 13

2B Units for Expressing Concentration 15

2B.1 Molarity and Formality 15

2B.2 Normality 16
(Modern Analytical Chemistry)

2B.3 Molality 18

2B.4 Weight, Volume, and Weight-to-Volume Ratios 18

2B.5 Converting Between Concentration Units 18

2B.6 p-Functions 19

2C Stoichiometric Calculations 20

2C.1 Conservation of Mass 22

2C.2 Conservation of Charge 22

2C.3 Conservation of Protons 22
2C.4 Conservation of Electron Pairs 23

2C.5 Conservation of Electrons 23

2C.6 Using Conservation Principles in

Stoichiometry Problems 23

2D Basic Equipment and Instrumentation 25

2D.1 Instrumentation for Measuring Mass 25

2D.2 Equipment for Measuring Volume 26

2D.3 Equipment for Drying Samples 29

2E Preparing Solutions 30

2E.1 Preparing Stock Solutions 30

2E.2 Preparing Solutions by Dilution 31

2F The Laboratory Notebook 32

2G Key Terms 32

2H Summary 33

2I Problems 33

2J Suggested Readings 34

2K References 34

Chapter 3

The Language of Analytical Chemistry 35

3A Analysis, Determination, and Measurement 36

3B Techniques, Methods, Procedures, and Protocols 36

3C Classifying Analytical Techniques 37

3D Selecting an Analytical Method 38

3D.1 Accuracy 38

3D.2 Precision 39

3D.3 Sensitivity 39

3D.4 Selectivity 40

3D.5 Robustness and Ruggedness 42

3D.6 Scale of Operation 42

3D.7 Equipment, Time, and Cost 44
3D.8 Making the Final Choice 44

3E Developing the Procedure 45

3E.1 Compensating for Interferences 45

3E.2 Calibration and Standardization 47

3E.3 Sampling 47

3E.4 Validation 47

3F Protocols 48

3G The Importance of Analytical Methodology 48

3H Key Terms 50

3I Summary 50

3J Problems 51

3K Suggested Readings 52

3L References 52

Chapter 4

Evaluating Analytical Data 53

4A Characterizing Measurements and Results 54

4A.1 Measures of Central Tendency 54

4A.2 Measures of Spread 55

4B Characterizing Experimental Errors 57

4B.1 Accuracy 57

4B.2 Precision 62

4B.3 Error and Uncertainty 64

4C Propagation of Uncertainty 64

4C.1 A Few Symbols 65

4C.2 Uncertainty When Adding or Subtracting 65

4C.3 Uncertainty When Multiplying or Dividing 66

4C.4 Uncertainty for Mixed Operations 66

4C.5 Uncertainty for Other Mathematical Functions 67

4C.6 Is Calculating Uncertainty Actually Useful? 68

4D The Distribution of Measurements and Results 70

4D.1 Populations and Samples 71

4D.2 Probability Distributions for Populations 71

4D.3 Confidence Intervals for Populations 75

4D.4 Probability Distributions for Samples 77

4D.5 Confidence Intervals for Samples 80

4D.6 A Cautionary Statement 81

4E Statistical Analysis of Data 82

4E.1 Significance Testing 82

4E.2 Constructing a Significance Test 83

4E.3 One-Tailed and Two-Tailed Significance Tests 84

4E.4 Errors in Significance Testing 84

4F Statistical Methods for Normal Distributions 85

4F.1 Comparing

X to m 85

4F.2 Comparing s2 to s2 87

4F.3 Comparing Two Sample Variances 88

4F.4 Comparing Two Sample Means 88

4F.5 Outliers 93

4G Detection Limits 95

4H Key Terms 96

4I Summary 96

4J Suggested Experiments 97

4K Problems 98

4L Suggested Readings 102

4M References 102

Chapter 5

Calibrations, Standardizations and Blank Corrections 104

5A Calibrating Signals 105

5B Standardizing Methods 106

5B.1 Reagents Used as Standards 106

5B.2 Single-Point versus Multiple-Point Standardizations 108

5B.3 External Standards 109

5B.4 Standard Additions 110

5B.5 Internal Standards 115

5C Linear Regression and Calibration Curves 117
(Modern Analytical Chemistry)

5C.1 Linear Regression of Straight-Line Calibration Curves 118

5C.2 Unweighted Linear Regression with Errors in y 119

5C.3 Weighted Linear Regression with Errors in y 124

5C.4 Weighted Linear Regression with Errors in Both x and y 127

5C.5 Curvilinear and Multivariate Regression 127

5D Blank Corrections 128

5E Key Terms 130

5F Summary 130

5G Suggested Experiments 130

5H Problems 131

5I Suggested Readings 133
5J References 134

Chapter 6

Equilibrium Chemistry 135

6A Reversible Reactions and Chemical Equilibria 136

6B Thermodynamics and Equilibrium Chemistry 136

6C Manipulating Equilibrium Constants 138

6D Equilibrium Constants for Chemical Reactions 139

6D.1 Precipitation Reactions 139

6D.2 Acid–Base Reactions 140

6D.3 Complexation Reactions 144

6D.4 Oxidation–Reduction Reactions 145

6E Le Châtelier’s Principle 148

6F Ladder Diagrams 150

6F.1 Ladder Diagrams for Acid–Base Equilibria 150

6F.2 Ladder Diagrams for Complexation Equilibria 153

6F.3 Ladder Diagrams for Oxidation–Reduction Equilibria 155

6G Solving Equilibrium Problems 156

6G.1 A Simple Problem: Solubility of Pb(IO3)2 in Water 156

6G.2 A More Complex Problem: The Common Ion Effect 157

6G.3 Systematic Approach to Solving Equilibrium Problems 159

6G.4 pH of a Monoprotic Weak Acid 160

6G.5 pH of a Polyprotic Acid or Base 163

6G.6 Effect of Complexation on Solubility 165
(Modern Analytical Chemistry)

6H Buffer Solutions 167

6H.1 Systematic Solution to Buffer Problems 168

6H.2 Representing Buffer Solutions with Ladder Diagrams 170

6I Activity Effects 171

6J Two Final Thoughts About Equilibrium

Chemistry 175

6K Key Terms 175

6L Summary 175

6M Suggested Experiments 176

6N Problems 176

6O Suggested Readings 178

6P References 178

Chapter 7

Obtaining and Preparing Samples for Analysis 179

7A The Importance of Sampling 180

7B Designing a Sampling Plan 182

7B.1 Where to Sample the Target

Population 182

7B.2 What Type of Sample to Collect 185

7B.3 How Much Sample to Collect 187
(Modern Analytical Chemistry)

7B.4 How Many Samples to Collect 191

7B.5 Minimizing the Overall Variance 192

7C Implementing the Sampling Plan 193

7C.1 Solutions 193

7C.2 Gases 195

7C.3 Solids 196

7D Separating the Analyte from Interferents 201

7E General Theory of Separation Efficiency 202

7F Classifying Separation Techniques 205

7F.1 Separations Based on Size 205

7F.2 Separations Based on Mass or Density 206
(Modern Analytical Chemistry)

7F.3 Separations Based on Complexation Reactions (Masking) 207

7F.4 Separations Based on a Change of State 209

7F.5 Separations Based on a Partitioning Between Phases 211

7G Liquid–Liquid Extractions 215

7G.1 Partition Coefficients and Distribution Ratios 216

7G.2 Liquid–Liquid Extraction with No Secondary Reactions 216

7G.3 Liquid–Liquid Extractions Involving Acid–Base Equilibria 219

7G.4 Liquid–Liquid Extractions Involving Metal Chelators 221

7H Separation versus Preconcentration 223

7I Key Terms 224

7J Summary 224

7K Suggested Experiments 225

7L Problems 226

7M Suggested Readings 230
7N References 231

Chapter 8

Gravimetric Methods of Analysis 232

8A Overview of Gravimetry 233

8A.1 Using Mass as a Signal 233

8A.2 Types of Gravimetric Methods 234

8A.3 Conservation of Mass 234

8A.4 Why Gravimetry Is Important 235

8B Precipitation Gravimetry 235

8B.1 Theory and Practice 235

8B.2 Quantitative Applications 247

8B.3 Qualitative Applications 254

8B.4 Evaluating Precipitation Gravimetry 254

8C Volatilization Gravimetry 255

8C.1 Theory and Practice 255

8C.2 Quantitative Applications 259

8C.3 Evaluating Volatilization Gravimetry 262

8D Particulate Gravimetry 262

8D.1 Theory and Practice 263

8D.2 Quantitative Applications 264

8D.3 Evaluating Precipitation Gravimetry 265

8E Key Terms 265

8F Summary 266

8G Suggested Experiments 266

8H Problems 267

8I Suggested Readings 271

8J References 272

Chapter 9

Titrimetric Methods of Analysis 273

9A Overview of Titrimetry 274

9A.1 Equivalence Points and End Points 274

9A.2 Volume as a Signal 274

9A.3 Titration Curves 275
(Modern Analytical Chemistry)

9A.4 The Buret 277

9B Titrations Based on Acid–Base Reactions 278

9B.1 Acid–Base Titration Curves 279

9B.2 Selecting and Evaluating the End Point 287

9B.3 Titrations in Nonaqueous Solvents 295

9B.4 Representative Method 296

9B.5 Quantitative Applications 298

9B.6 Qualitative Applications 308

9B.7 Characterization Applications 309

9B.8 Evaluation of Acid–Base Titrimetry 311

9C Titrations Based on Complexation Reactions 314

9C.1 Chemistry and Properties of EDTA 315

9C.2 Complexometric EDTA Titration Curves 317

9C.3 Selecting and Evaluating the End Point 322

9C.4 Representative Method 324

9C.5 Quantitative Applications 327

9C.6 Evaluation of Complexation Titrimetry 331

9D Titrations Based on Redox Reactions 331

9D.1 Redox Titration Curves 332

9D.2 Selecting and Evaluating the End Point 337

9D.3 Representative Method 340

9D.4 Quantitative Applications 341

9D.5 Evaluation of Redox Titrimetry 350

9E Precipitation Titrations 350

9E.1 Titration Curves 350

9E.2 Selecting and Evaluating the End Point 354

9E.3 Quantitative Applications 354

9E.4 Evaluation of Precipitation Titrimetry 357

9F Key Terms 357

9G Summary 357

9H Suggested Experiments 358

9I Problems 360

9J Suggested Readings 366

9K References 367

Modern Analytical Chemistry by David Harvey

Chapter 10

Spectroscopic Methods of Analysis 368

10A Overview of Spectroscopy 369

10A.1 What Is Electromagnetic Radiation 369

10A.2 Measuring Photons as a Signal 372

10B Basic Components of Spectroscopic Instrumentation 374

10B.1 Sources of Energy 375

10B.2 Wavelength Selection 376

10B.3 Detectors 379

10B.4 Signal Processors 380

10C Spectroscopy Based on Absorption 380

10C.1 Absorbance of Electromagnetic Radiation 380

10C.2 Transmittance and Absorbance 384

10C.3 Absorbance and Concentration: Beer’s Law 385

10C.4 Beer’s Law and Multicomponent Samples 386

10C.5 Limitations to Beer’s Law 386

10D Ultraviolet-Visible and Infrared

Spectrophotometry 388

10D.1 Instrumentation 388

10D.2 Quantitative Applications 394

10D.3 Qualitative Applications 402

10D.4 Characterization Applications 403

10D.5 Evaluation 409

10E Atomic Absorption Spectroscopy 412

10E.1 Instrumentation 412

10E.2 Quantitative Applications 415

10E.3 Evaluation 422

10F Spectroscopy Based on Emission 423

10G Molecular Photoluminescence Spectroscopy 423

10G.1 Molecular Fluorescence and

Phosphorescence Spectra 424

10G.2 Instrumentation 427

10G.3 Quantitative Applications Using Molecular

Luminescence 429

10G.4 Evaluation 432

10H Atomic Emission Spectroscopy 434

10H.1 Atomic Emission Spectra 434

10H.2 Equipment 435

10H.3 Quantitative Applications 437

10H.4 Evaluation 440

10I Spectroscopy Based on Scattering 441

10I.1 Origin of Scattering 441

10I.2 Turbidimetry and Nephelometry 441

10J Key Terms 446

10K Summary 446

10L Suggested Experiments 447

10M Problems 450

10N Suggested Readings 458

10O References 459

Modern Analytical Chemistry by David Harvey

Chapter 11

Electrochemical Methods of Analysis 461

11A Classification of Electrochemical Methods 462

11A.1 Interfacial Electrochemical Methods 462

11A.2 Controlling and Measuring Current and Potential 462

11B Potentiometric Methods of Analysis 465

11B.1 Potentiometric Measurements 466

11B.2 Reference Electrodes 471

11B.3 Metallic Indicator Electrodes 473

11B.4 Membrane Electrodes 475

11B.5 Quantitative Applications 485

11B.6 Evaluation 494

11C Coulometric Methods of Analysis 496

11C.1 Controlled-Potential Coulometry 497

11C.2 Controlled-Current Coulometry 499

11C.3 Quantitative Applications 501

11C.4 Characterization Applications 506

11C.5 Evaluation 507

11D Voltammetric Methods of Analysis 508

11D.1 Voltammetric Measurements 509

11D.2 Current in Voltammetry 510

11D.3 Shape of Voltammograms 513

11D.4 Quantitative and Qualitative Aspects of Voltammetry 514

11D.5 Voltammetric Techniques 515

11D.6 Quantitative Applications 520

11D.7 Characterization Applications 527

11D.8 Evaluation 531

11E Key Terms 532

11F Summary 532

11G Suggested Experiments 533

11H Problems 535

11I Suggested Readings 540

11J References 541

Modern Analytical Chemistry by David Harvey

Chapter 12

Chromatographic and Electrophoretic Methods 543

12A Overview of Analytical Separations 544

12A.1 The Problem with Simple Separations 544

12A.2 A Better Way to Separate Mixtures 544

12A.3 Classifying Analytical Separations 546

12B General Theory of Column

Chromatography 547

12B.1 Chromatographic Resolution 549

12B.2 Capacity Factor 550

12B.3 Column Selectivity 552
12B.4 Column Efficiency 552

12B.5 Peak Capacity 554

12B.6 Nonideal Behavior 555

12C Optimizing Chromatographic Separations 556

12C.1 Using the Capacity Factor to Optimize Resolution 556

12C.2 Using Column Selectivity to Optimize Resolution 558

12C.3 Using Column Efficiency to Optimize Resolution 559

12D Gas Chromatography 563

12D.1 Mobile Phase 563

12D.2 Chromatographic Columns 564

12D.3 Stationary Phases 565

12D.4 Sample Introduction 567

12D.5 Temperature Control 568

12D.6 Detectors for Gas Chromatography 569

12D.7 Quantitative Applications 571

12D.8 Qualitative Applications 575

12D.9 Representative Method 576

12D.10 Evaluation 577

12E High-Performance Liquid

Chromatography 578

12E.1 HPLC Columns 578

12E.2 Stationary Phases 579

12E.3 Mobile Phases 580

12E.4 HPLC Plumbing 583

12E.5 Sample Introduction 584

12E.6 Detectors for HPLC 584

12E.7 Quantitative Applications 586

12E.8 Representative Method 588

12E.9 Evaluation 589

12F Liquid–Solid Adsorption Chromatography 590

12G Ion-Exchange Chromatography 590

12H Size-Exclusion Chromatography 593

12I Supercritical Fluid Chromatography 596

12J Electrophoresis 597

12J.1 Theory of Capillary Electrophoresis 598

12J.2 Instrumentation 601

12J.3 Capillary Electrophoresis Methods 604

12J.4 Representative Method 607

12J.5 Evaluation 609

12K Key Terms 609

12L Summary 610

12M Suggested Experiments 610
12N Problems 615

12O Suggested Readings 620

12P References 620

Modern Analytical Chemistry by David Harvey

Chapter 13

Kinetic Methods of Analysis 622

13A Methods Based on Chemical Kinetics 623

13A.1 Theory and Practice 624

13A.2 Instrumentation 634

13A.3 Quantitative Applications 636

13A.4 Characterization Applications 638

13A.5 Evaluation of Chemical Kinetic Methods 639

13B Radiochemical Methods of Analysis 642

13B.1 Theory and Practice 643

13B.2 Instrumentation 643

13B.3 Quantitative Applications 644

13B.4 Characterization Applications 647

13B.5 Evaluation 648

13C Flow Injection Analysis 649

13C.1 Theory and Practice 649

13C.2 Instrumentation 651

13C.3 Quantitative Applications 655

13C.4 Evaluation 658

13D Key Terms 658

13E Summary 659

13F Suggested Experiments 659

13G Problems 661

13H Suggested Readings 664

13I References 665

Modern Analytical Chemistry by David Harvey

Chapter 14

Developing a Standard Method 666

14A Optimizing the Experimental Procedure 667

14A.1 Response Surfaces 667

14A.2 Searching Algorithms for Response Surfaces 668

14A.3 Mathematical Models of Response Surfaces 674

14B Verifying the Method 683

14B.1 Single-Operator Characteristics 683

14B.2 Blind Analysis of Standard Samples 683

14B.3 Ruggedness Testing 684
14B.4 Equivalency Testing 687

14C Validating the Method as a Standard

Method 687

14C.1 Two-Sample Collaborative Testing 688

14C.2 Collaborative Testing and Analysis of Variance 693

14C.3 What Is a Reasonable Result for a Collaborative Study? 698

14D Key Terms 699

14E Summary 699

14F Suggested Experiments 699

14G Problems 700

14H Suggested Readings 704

14I References 704

Modern Analytical Chemistry by David Harvey

Chapter 15

Quality Assurance 705

15A Quality Control 706

15B Quality Assessment 708

15B.1 Internal Methods of Quality Assessment 708

15B.2 External Methods of Quality Assessment 711

15C Evaluating Quality Assurance Data 712

15C.1 Prescriptive Approach 712
15C.2 Performance-Based Approach 714

15D Key Terms 721

15E Summary 722

15F Suggested Experiments 722

15G Problems 722

15H Suggested Readings 724

15I References 724


Appendix 1A Single-Sided Normal Distribution 725

Appendix 1B t-Table 726

Appendix 1C F-Table 727

Appendix 1D Critical Values for Q-Test 728

Appendix 1E Random Number Table 728

Appendix 2 Recommended Reagents for Preparing Primary Standards 729

Appendix 3A Solubility Products 731

Appendix 3B Acid Dissociation Constants 732

Appendix 3C Metal–Ligand Formation Constants 739

Appendix 3D Standard Reduction Potentials 743

Appendix 3E Selected Polarographic Half-Wave Potentials 747

Appendix 4 Balancing Redox Reactions 748

Appendix 5 Review of Chemical Kinetics 750

Appendix 6 Countercurrent Separations 755

Appendix 7 Answers to Selected Problems 762

Glossary 769
Index 781

Modern Analytical Chemistry by David Harvey

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