Preface xix
Part I Fundamental Concepts
1 Getting Started with the Fundamental Concepts 3
1.1 Introduction 3
1.2 Why Calculate Chemical Species Concentrations at Equilibrium? 3
1.3 Primary Variables: Importance of pH and pe 6
1.4 Properties of Water 7
1.5 Part I Roadmap 9
1.6 Chapter Summary 9
1.7 Part I Case Study: Can Methylmercury be Formed Chemically in Water? 10
Chapter Key Ideas 11
Chapter Glossary 11
Historical Note: S.P.L. Sorensen and the p in pH 11
Chapter References 12
2 Concentration Units 13
2.1 Introduction 13
2.2 Units Analysis 13
2.3 Molar Concentration Units 14
2.4 Mass Concentration Units 19
2.5 Dimensionless Concentration Units 24
2.6 Equivalents 25
2.7 Review of Units Interconversion 26
2.8 Common Concentration Units in the Gas Phase 27
2.9 Common Concentration Units in the Solid Phase 28
2.10 Activity 28
2.11 Chapter Summary 30
2.12 Part I Case Study: Can Methylmercury Be Formed Chemically in Water? 30
Chapter Key Ideas 31
Chapter Glossary 31
Historical Note: Amadea Avogadro and Avogadro's Number 32
Problems 33
Chapter References 34
3 Thermodynamic Basis of Equilibrium 35
3.1 Introduction 35
3.2 Thermodynamic Properties 36
3.3 Why Do We Need Thermodynamics to Calculate Species Concentrations? 39
3.4 Thermodynamic Laws 42
3.5 Gibbs Free Energy 45
3.6 Properties of Thermodynamic Functions 48
3.7 Changes in Thermodynamic Properties During Chemical Reactions 50
3.8 Relating Gibbs Free Energy to Species Concentrations 55
3.9 Chemical Equilibrium and the Equilibrium Constant 60
3.10 Chapter Summary 62
3.11 Part I Case Study: Can Methylmercury Be Formed Chemically in Water? 63
Chapter Key Ideas 63
Chapter Glossary 64
Historical Note: Josiah Willard Gibbs 66
Problems 67
Chapter References 68
4 Manipulating Equilibrium Expressions 69
4.1 Introduction 69
4.2 Chemical and Mathematical Forms of Equilibria 69
4.3 Units of Equilibrium Constants 73
4.4 Reversing Equilibria 75
4.5 Effects of Stoichiometry 76
4.6 Adding Equilibria 78
4.7 Creating Equilibria 81
4.8 Chapter Summary 87
4.9 Part I Case Study: Can Methylmercury Be Formed Chemically in Water? 87
Chapter Key Ideas 88
Chapter Glossary 89
Historical Note: Henri- Louis Le Chatelier and Le Chatelier's Principle 89
Problems 90
Chapter References 91
Part II Solving Chemical Equilibrium Problems
5 Getting Started withSolving Equilibrium Problems 95
5.1 Introduction 95
5.2 A Framework for Solving Chemical Equilibrium Problems 95
5.3 Introduction to Defining the Chemical System 97
5.4 Introduction to Enumerating Chemical Species 98
5.5 Introduction to Defining the Constraints on Species Concentrations 98
5.6 Part II Roadmap 100
5.7 Chapter Summary 100
5.8 Part II Case Study: Have You Had Your Zinc Today? 101
Chapter Key Ideas 101
Chapter Glossary 101
Historical Note: Active Mass and Familial Relations 102
Chapter References 103
6 Setting Up Chemical Equilibrium Calculations 105
6.1 Introduction 105
6.2 Defining the Chemical System 105
6.3 Enumerating Chemical Species 106
6.4 Defining the Constraints on Species Concentrations 112
6.5 Review of Procedures for Setting up Equilibrium Systems 120
6.6 Concise Mathematical Form for Equilibrium Systems 121
6.7 Chapter Summary 122
6.8 Part II Case Study: Have You Had Your Zinc Today? 123
Chapter Key Ideas 126
Chapter Glossary 126
Historical Note: Salts of the Ocean 127
Problems 129
Chapter References 130
7 Algebraic Solutions to Chemical Equilibrium Problems 131
7.1 Introduction 131
7.2 Background on Algebraic Solutions 131
7.3 Method of Substitution 133
7.4 Method of Approximation 139
7.5 Chapter Summary 148
7.6 Part II Case Study: Have You Had Your Zinc Today? 148
Chapter Key Ideas 152
Historical Note: What's in a Name? 152
Problems 153
8 Graphical Solutions to Chemical Equilibrium Problems 155
8.1 Introduction 155
8.2 Log Concentration and pC- pH Diagrams 156
8.3 Using pC- pH Diagrams with More Complex Systems 162
8.4 Special Shortcuts for Monoprotic Acids 167
8.5 When Graphical Methods Fail: The Proton Condition 171
8.6 Chapter Summary 177
8.7 Part II Case Study: Have You Had Your Zinc Today? 178
Chapter Key Ideas 179
Chapter Glossary 180
Historical Note: Who Was First? 180
Problems 181
Chapter Reference 182
9 Computer Solutions to Chemical Equilibrium Problems 183
9.1 Introduction 183
9.2 Chapter Problem 183
9.3 Spreadsheet Solutions 184
9.4 Equilibrium Calculation Software 188
9.5 Nanoql SE 190
9.6 The Tableau Method and Other Equilibrium Calculation Apps 192
9.7 Visual MINTEQ 201
9.8 Chapter Summary 202
9.9 Part II Case Study: Have You Had Your Zinc Today? 202
Chapter Key Ideas 203
Chapter Glossary 203
Historical Note: ALGOL to VBA 203
Problems 204
Chapter References 205
Part III Acid-Base Equilibria in Homogenous Aqueous Systems
10 Getting Started with Acid-Base Equilibrium in Homogenous Aqueous Systems 209
10.1 Introduction 209
10.2 Homogeneous Systems 209
10.3 Types of Reactions in Homogeneous Systems 211
10.4 The Wonderful World of Acids and Bases 212
10.5 Part III Roadmap 215
10.6 Chapter Summary 215
10.7 Part III Case Study: Acid Rain 215
Chapter Key Ideas 216
Chapter Glossary 216
Historical Note: An Evil of the Highest Magnitude 217
Chapter References 218
11 Acids and Bases 219
11.1 Introduction 219
11.2 Definitions of Acids and Bases 219
11.3 Acid and Base Strength 223
11.4 Polyprotic Acids 228
11.5 Alpha Values (Distribution Functions) 236
11.6 Chapter Summary 239
11.7 Part II Case Study: Acid Rain 239
Chapter Key Ideas 241
Chapter Glossary 242
Historical Note: Why Is a Base a Base? 242
Problems 243
Addendum: A Surprising Exact Solution 245
Chapter References 248
12 Acid-Base Titrations 249
12.1 Introduction 249
12.2 Principles of Acid-Base Titrations 250
12.3 Equivalence Points 255
12.4 Titration of Polyprotic Acids 265
12.5 Buffers 269
12.6 Interpretation of Acid-Base Titration Curves with Complex Mixtures 277
12.7 Chapter Summary 279
12.8 Part III Case Study: Acid Rain 280
Chapter Key Ideas 282
Chapter Glossary 283
Historical Note: Mohr about Titrations 284
Problems 285
Chapter References 286
13 Alkalinity and Acidity 287
13.1 Introduction 287
13.2 Alkalinity and the Acid Neutralizing Capacity 287
13.3 Alkalinity and the Charge Balance 290
13.4 Characteristics of Alkalinity and Acidity 292
13.5 Using the Definitions of Alkalinity to Solve Problems 302
13.6 Effects of Other Weak Acids and Bases on Alkalinity 308
13.7 Chapter Summary 310
13.8 Part III Case Study: Acid Rain 310
Chapter Key Ideas 311
Chapter Glossary 312
Historical Note: Can You Pass the Litmus Test? 313
Problems 314
Chapter References 316
Part IV Other Equilibria in Homogenous Aqueous Systems
14 Getting Started with Other Equilibria in Homogeneous Aqueous Systems 319
14.1 Introduction 319
14.2 Electron- Sharing Reactions 319
14.3 Electron Transfer 321
14.4 Part IV Roadmap 323
14.5 Chapter Summary 323
14.6 Part IV Case Study: Which Form of Copper Plating Should You Use? 323
Chapter Key Ideas 324
Historical Note: Hauptvalenz and Nebenvalenz 324
Chapter References 325
15 Complexation 327
15.1 Introduction 327
15.2 Metals 327
15.3 Ligands 330
15.4 Equilibrium Calculations with Complexes 335
15.5 Systems with Several Metals and Ligands 345
15.6 Applications of Complexation Chemistry 357
15.7 Chapter Summary 361
15.8 Part IV Case Study: Which Form of Copper Plating Should You Use? 362
Chapter Key Ideas 364
Chapter Glossary 365
Historical Note: British Anti- Lewisite - A WMD- Inspired Ligand 366
Problems 368
Chapter References 369
16 Oxidation and Reduction 371
16.1 Introduction 371
16.2 A Few Definitions 371
16.3 Balancing Redox Reactions 374
16.4 Which Redox Reactions Occur? 383
16.5 Redox Thermodynamics and Oxidant and Reductant Strength 386
16.6 Manipulating Half Reactions 393
16.7 Algebraic Equilibrium Calculations in Systems Undergoing Electron Transfer 396
16.8 Graphical Representations of Systems Undergoing Electron Transfer 399
16.9 Applying Redox Equilibrium Calculations to the Real World 413
16.10 Chapter Summary 414
16.11 Part IV Case Study: Which Form of Copper Plating Should You Use? 415
Chapter Key Ideas 417
Chapter Glossary 418
Historical Note: Walther Hermann Nernst 419
Problems 420
Chapter References 422
Part V Heterogeneous Systems
17 Getting Started with Heterogeneous Systems 425
17.1 Introduction 425
17.2 Equilibrium Exchange Between Gas and Aqueous Phases 426
17.3 Equilibrium Exchange Between Solid and Aqueous Phases 427
17.4 Part V Roadmap 428
17.5 Chapter Summary 428
17.6 Part V Case Study: The Killer Lakes 428
Chapter Key Ideas 429
Historical Note: A Spirit Case and a Gasogene 429
Chapter References 430
18 Gas-Liquid Equilibria 431
18.1 Introduction 431
18.2 Raoult's Law and Henry's Law 431
18.3 Equilibrium Calculations Involving Gas-Liquid Equilibria 438
18.4 Dissolved Carbon Dioxide 449
18.5 Chapter Summary 456
18.6 Part V Case Study: The Killer Lakes 456
Chapter Key Ideas 457
Chapter Glossary 458
Historical Note: A Brief History of Carbon Dioxide 459
Problems 460
Chapter References 462
19 Solid-Liquid Equilibria 463
19.1 Introduction 463
19.2 Saturation and the Activity of Pure Solids 463
19.3 Equilibrium Calculations with Solid-Liquid Equilibria 466
19.4 Factors Affecting Metal Solubility 474
19.5 Solubility of Calcium Carbonate 480
19.6 Models for the Acid-Base Chemistry of Natural Waters 484
19.7 Chapter Summary 491
19.8 Part V Case Study: The Killer Lakes 491
Chapter Key Ideas 492
Chapter Glossary 493
Historical Note: Black Smokers and White Smokers 493
Problems 494
Addendum: Information Requirements 497
Chapter References 498
Part VI Beyond Dilute Solutions at Equilibrium
20 Getting Started with Beyond Dilute Solutions at Equilibrium 501
20.1 Introduction 501
20.2 Extensions to Nonideal and Nonstandard Conditions 502
20.3 The Strange World of Surfaces 503
20.4 Nonequilibrium Conditions 504
20.5 Integrated Case Studies 504
20.6 Part VI Roadmap 505
20.7 Chapter Summary 505
Chapter Key Ideas 506
Chapter Glossary 506
Historical Note: Harcourt, Come to Me! 506
Chapter References 507
21 Thermodynamics Revisited: The Effects of Ionic Strength, Temperature, and Pressure 509
21.1 Introduction 509
21.2 Effects of Ionic Strength 510
21.3 Effects of Temperature on Equilibrium Constants 522
21.4 Effects of Pressure on Equilibrium Constants 528
21.5 Chapter Summary 529
Chapter Key Ideas 530
Chapter Glossary 531
Historical Note: Jacobus Henricus van't Hoff 531
Problems 532
Chapter References 534
22 Aquatic Chemistry ofSurfaces 535
22.1 Introduction 535
22.2 Nomenclature 535
22.3 Isotherms and Ion Exchange 538
22.4 Introduction to Surface Complexation Modeling 543
22.5 Surface Complexation Modeling 546
22.6 Chapter Summary 552
Chapter Key Ideas 553
Chapter Glossary 553
Historical Note: From Cat's Cradle to the Swiss Model to Surface Complexation Modeling 554
Problems 555
Addendum: The Freundlich Isotherm and Adsorption Equilibria 556
Chapter References 557
23 Chemical Kinetics of Aquatic Systems 559
23.1 Introduction 559
23.2 The Need for Chemical Kinetics 560
23.3 Reaction Rates 561
23.4 Common Rate Expressions 569
23.5 More Complex Kinetic Forms 577
23.6 Effects of Temperature and Ionic Strength on Kinetics 582
23.7 Chapter Summary 587
Chapter Key Ideas 587
Chapter Glossary 588
Historical Note: Arrhenius, Chick, and Foote 589
Problems 590
Chapter References 592
24 Putting It All Together: Integrated Case Studies in Aquatic Chemistry 593
24.1 Introduction 593
24.2 Integrated Case Study 1: Metal Finishing 594
24.3 Integrated Case Study 2: Oxidation of Fe(+II) by Oxygen 598
24.4 Integrated Case Study 3: Inorganic Mercury Chemistry in Natural Waters 603
24.5 Integrated Case Study 4: Phosphate Buffers 607
24.6 Integrated Case Study 5: Global Climate Change 610
24.7 Chapter Summary 613
Historical Note: Stumm and Morgan 614
Chapter References 614
Appendix A: Background Information 617
A.1 Introduction 617
A.2 Chemical Principles 617
A.3 Mathematical Principles 619
A.4 Spreadsheet Skills 620
Chapter Key Ideas 623
Chapter Glossary 623
Useful Physical Constants and Conversions 623
Appendix B: Equilibrium Revisited 625
B.1 Introduction 625
B.2 Equilibrium and Steady State 625
B.3 Energy Minimization and Algebraic Solutions 628
Chapter Key Ideas 631
Chapter Glossary 631
Appendix C: Summary of Procedures 633
C.1 Oxidation States and Balancing Reactions 633
C.2 Setting Up Chemical Equilibrium Systems (Section 6.5) 634
C.3 Algebraic Solution Techniques 635
C.4 Graphical Solutions 635
C.5 Computer Solutions: Tableau Method (Section 9.6.6) 637
C.6 Acid-Base Titrations 638
C.7 Complexation (Section 15.4.4) 638
C.8 Ionic Strength Effects (Section 21.2.7) 639
C.9 Surface Complexation Modeling Method (Section 22.5.4) 639
C.10 Chemical Kinetics (Section 23.3.4) 639
Appendix D: Selected Equilibrium Constants 641
Chapter References 651
Appendix E: Animations and Example Spreadsheet Files 653
E.1 Introduction to Animations 653
E.2 Variation of the Equilibrium pH of a Monoprotic Acid Solution with the Total Acid Concentration and K a 653
E.3 How to Draw pC- pH Diagrams for Monoprotic Acids 654
E.4 Equilibrium pH During the Titration of a Monoprotic Acid with a Strong Base 656
E.5 Spreadsheet Examples 657
Appendix F: Nanoql SE 661
F.1 Introduction 661
F.2 Entering Your System 661
F.3 How to Solve Systems and Vary System Parameters 663
F.4 Nanoql SE Examples 666
Chapter Reference 668
Index 669
Biographical Index 677
