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 Ch'telier and Le Ch'telier''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.