A Problem-Solving Approach to Aquatic Chemistry

by Jensen, James N.

• ISBN13: 9781119884347
• ISBN10: 1119884349
• eBook ISBN(s): 9781119884361
• Edition: 2nd
• Format: Hardcover
• Copyright: 2023-01-05
• Publisher: Wiley
• More Book Details

Summary

A Problem-Solving Approach to Aquatic Chemistry

Enables civil and environmental engineers to understand the theory and application of aquatic equilibrium chemistry

The second edition of A Problem-Solving Approach to Aquatic Chemistry provides a detailed introduction to aquatic equilibrium chemistry, calculation methods for systems at equilibrium, applications of aquatic chemistry, and chemical kinetics. The text directly addresses two required ABET program outcomes in environmental engineering: “… chemistry (including stoichiometry, equilibrium, and kinetics)” and “material and energy balances, fate and transport of substances in and between air, water, and soil phases.”

The book is very student-centered, with each chapter beginning with an introduction and ending with a summary that reviews the chapter’s main points. To aid in reader comprehension, important terms are defined in context and key ideas are summarized. Many thought-provoking discussion questions, worked examples, and end of chapter problems are also included. Each part of the text begins with a case study, a portion of which is addressed in each subsequent chapter, illustrating the principles of that chapter. In addition, each chapter has an Historical Note exploring connections with the people and cultures connected to topics in the text.

A Problem-Solving Approach to Aquatic Chemistry includes:

• Fundamental concepts, such as concentration units, thermodynamic basis of equilibrium, and manipulating equilibria
• Solutions of chemical equilibrium problems, including setting up the problems and algebraic, graphical, and computer solution techniques
• Acid–base equilibria, including the concepts of acids and bases, titrations, and alkalinity and acidity
• Complexation, including metals, ligands, equilibrium calculations with complexes, and applications of complexation chemistry
• Oxidation-reduction equilibria, including equilibrium calculations, graphical approaches, and applications
• Gas–liquid and solid–liquid equilibrium, with expanded coverage of the effects of global climate change
• Other topics, including chemical kinetics of aquatic systems, surface chemistry, and integrative case studies

For advanced/senior undergraduates and first-year graduate students in environmental engineering courses, A Problem-Solving Approach to Aquatic Chemistry serves as an invaluable learning resource on the topic, with a variety of helpful learning elements included throughout to ensure information retention and the ability to apply covered concepts in practical settings.

Author Biography

James N. Jensen is Professor in the Department of Civil, Structural and Environmental Engineering at the State University of New York at Buffalo.

Table of Contents

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. Sørensen 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 Châtelier and Le Châtelier’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