A Problem-Solving Approach to Aquatic Chemistry

Transcription

1 A Problem-Solving Approach to Aquatic Chemistry James N. Jensen University at Buffalo John Wiley & Sons, Inc.

2 Table of Contents Partfc I^damental^^ 1_ Chapter 1: Getting Started with the Fundamental Concepts Introduction Why Calculate Chemical Species Concentrations? Master Variables: The Importance of ph and pe Properties of Water Part I Road Map Summary Part I Case Study: Can Methylmercury Be Formed in Water? 10 Summary of Key Ideas 12 Chapter 2: Concentration Units Introduction Units Analysis Molar Concentration Units Mass Concentration Units Dimensionless Concentration Units Equivalents Review of Units Interconversion Common Concentration Units in the Gas Phase Common Concentration Units in the Solid Phase Activity Summary Part I Case Study: Can Methylmercury Be Formed in Water? 27 Summary of Key Ideas 28 Historical Note: Amadeo Avogadro and Avogadro's Number 29 Problems 30 Chapter 3: Thermodynamic Basis of Equilibrium Introduction Thermodynamic Properties Why Do We Need Thermodynamics to Calculate Species Concentrations? Thermodynamic Laws Gibbs Free Energy Properties of Thermodynamic Functions Changes in Thermodynamic Properties During Chemical Reactions Relating Gibbs Free Energy to Species Concentrations Chemical Equilibrium and the Equilibrium Constant Summary Part I Case Study: Can Methylmercury Be Formed in Water? 61 Summary of Key Ideas 62 Historical Note: Josiah Willard Gibbs 63 Problems 63 vm

3 IX Chapter 4: Manipulating Equilibria Introduction Chemical and Mathematical Forms of Equilibrium Units of Equilibrium Constants Reversing Equilibria Effects of Stoichiometry Adding Equilibria Creating Equilibria Summary Part I Case Study: Can Methylmercury Be Formed in Water? 82 Summary of Key Ideas 83 Historical Note: Henri-Louis Le Chatelier and Le Chatelier's Principle 84 Problems 85 ;Part II: Solution of Chemical Equilibrium Problems 87 Chapter 5: Getting Started with the Solution of Chemical Equilibrium Problems Introduction A Framework for Solving Equilibrium Problems Introduction to Defining the Chemical System Introduction to Enumerating Chemical Species Introduction to Defining the Constraints on Species Concentrations Road Map to Part II Summary Part II Case Study: Have You Had Your Zinc Today? 95 Summary of Key Ideas 96 Chapter 6: Setting Up Chemical Equilibrium Problems Introduction Defining the Chemical System Enumerating Chemical Species Defining Constraints on Species Concentrations Review of Procedures for Setting Up Equilibrium Systems Concise Mathematical Form for Equilibrium Systems: An Advanced Topic Summary Part II Case Study: Have You Had Your Zinc Today? 113 Summary of Key Ideas 117 Problems 117 Chapter 7: Algebraic Solution Techniques Introduction Background on Algebraic Solutions Method of Substitution Method of Approximation Summary Part II Case Study: Have You Had Your Zinc Today? 134 Summary of Key Ideas 137 Problems 138 x

4 Chapter 8: Graphical Solution Techniques Introduction Introduction to Log Concentration and pc-ph Diagrams Using pc-ph Diagrams with More Complex Systems Special Shortcuts for Monoprotic Acids When Graphical Methods Fail: The Proton Condition Conclusions Part II Case Study: Have You Had Your Zinc Today? 165 Summary of Key Ideas 166 Problems 168 Chapter 9: Computer Solution Techniques Introduction Chapter Problem Spreadsheet Solutions Equilibrium Calculation Software Nanoql The Tableau Method and Other Equilibrium Calculation Programs Summary Part II Case Study: Have You Had Your Zinc Today? 189 Summary of Key Ideas 189 Problems 190 Part III: Acid-Base Equilibria in Homogenous Aqueous Systems 191 Chapter 10: Getting Started with Acid-Base Equilibria in Homogenous Aqueous Systems Introduction Homogeneous Systems Types of Reactions in Homogeneous Systems The Wonderful World of Acids and Bases Part III Road Map Summary Part III Case Study: Acid Rain 200 : Summary of Key Ideas 201 Chapter 11: Acids and Bases Introduction Definitions of Acids and Bases Acid and Base Strength Polyprotic Acids Distribution Functions (Alpha Values) Summary Part III Case Study: Acid Rain 222 Summary of Key Ideas 224 Problems 225 '

5 XI Chapter 12: Titrations Introduction Principles of-acid-base Titrations Equivalence Points Titration of Diprotic Acids Buffers Interpretation of Titration Curves with Complex Mixtures Summary Part III Case Study: Acid Rain 260 Summary of Key Ideas 262 Problems 264 Chapter 13: Alkalinity and Acidity Introduction Alkalinity and the Acid Neutralizing Capacity Alkalinity and the Charge Balance Characteristics of Alkalinity and Acidity Using the Definitions of Alkalinity to Solve Problems Effects of Other Weak Acids and Bases on Alkalinity Summary Part III Case Study: Acid Rain 290 Summary of Key Ideas 291 Problems 292 Part IV: Other Equilibria in Homogenous Aqueous Systems 295 Chapter 14: Getting Started with Other Equilibria in Homogenous Aqueous Systems Introduction Electron-sharing Reactions Electron Transfer Part IV Road Map Summary Part IV Case Study: Which Form of Copper Plating Should You Use? 302 Summary of Key Ideas 303 Chapter 15: Complexation Introduction Metals Ligands Equilibrium Calculations with Complexes Systems with Several Metals and Ligands Applications of Complexation Chemistry Summary Part IV Case Study: Which Form of Copper Plating Should You Use? 330 Summary of Key Ideas 333 Problems 334

6 xu Chapter 16: Oxidation and Reduction Introduction A Few Definitions Balancing Redox Reactions Which Redox Reactions Occur? Redox Thermodynamics and Oxidant and Reductant Strength Algebraic Equilibrium Calculations in Systems Undergoing Electron Transfer Graphical Representations of Systems Undergoing Electron Transfer Applying Redox Equilibrium Calculations to the Real World Summary Part IV Case Study: Which Form of Copper Plating Should You Use? 375 Summary of Key Ideas 377 Historical Note: Walther Hermann Nernst 378 Problems 379 Part V: Heterogeneous Systemsj 383_ Chapter 17: Getting Started with Heterogenous Systems Introduction Equilibrium Exchange Between Gas and Aqueous Phases Equilibrium Exchange Between Solid and Aqueous Phases Part V Road Map Summary Part V Case Study: The Killer Lakes 389 Summary of Key Ideas 389 Chapter 18: Gas-Liquid Equilibria Introduction Raoult's Law and Henry's Law Equilibrium Calculations Involving Gas-Liquid Equilibria Dissolved Carbon Dioxide Summary Part V Case Study: The Killer Lakes 410 ; Summary of Key Ideas 412 Problems 413 Chapter 19: Solid-Liquid Equilibria and the Aquatic Chemistry of Surfaces Introduction Saturation and the Activity of Pure Solids Equilibrium Calculations Involving Solid-Liquid Equilibria Factors Affecting Metal Solubility Solubility of Calcium Carbonate Summary of the Acid-Base Chemistry of Natural Waters Aquatic Chemistry of Surfaces Summary Part V Case Study: The Killer Lakes 451 Summary of Key Ideas 452 Problems 453

7 Xlll Part VI: Beyond DttuteJSyjftejns^^ Chapter 20: Getting Started with Beyond Dilute Systems at Equilibrium Introduction ~ Extensions to Nonideal and Nonstandard Conditions Nonequilibrium Conditions Integrated Case Studies Part VI Road Map Summary 466 Summary of Key Ideas 466 Chapter 21: Thermodynamics Revisited Introduction Effects of Ionic Strength Effects of Temperature on Chemical Equilibria Effects of Pressure on Equilibrium Constants Summary 486 Summary of Key Ideas 487 Historical Note: Jacobus Henricus Van't Hoff 488 Problems 488 Chapter 22: Chemical Kinetics of Aquatic Systems Introduction The Need for Chemical Kinetics Reaction Rates Common Rate Expressions More Complex Kinetic Forms Effects of Temperature and Ionic Strength on Reaction Kinetics Summary 514 Summary of Key Ideas 515 Problems '516 Chapter 23: Putting It All Together: Integrated Chemistry of Aquatic Systems Introduction Integrated Case Study 1: Metal Finishing Integrated Case Study 2: Oxidation of Ferrous Iron by Oxygen Integrated Case Study 3: Inorganic Mercury Chemistry in Natural Waters Summary 535 Appendix A: Background Information 537 A.I Introduction 537 A.2 Chemical Principles 537 A.3 Mathematical Principles 540 A.4 Computer Skills 540 Summary of Key Ideas 542 Appendix B: Equilibrium and Steady State 543 B.I Introduction 543 B.2 Steady-State Analysis 543 : J

8 XIV B.3 Comparison of Steady State and Equilibrium Solutions 544 Summary of Key Ideas 545 Appendix C: Summary of Procedures 547 C.I Oxidation State and Balancing Reactions 547 C.2 Setting Up Chemical Equilibrium Systems (section 6.4) 548 C.3 Algebraic Solution Techniques 549 C.4 Graphical Solutions 549 C.5 Computer Solutions: Tableau Method 552 C.6 Acid-Base Titrations 553 C.7 Complexation (section ) 553 C.8 Ionic Strength Effects (section ) 554 C.9 Chemical Kinetics (section ) 554 Appendix D: Selected Chemical Equilibrium Constants 555 Appendix E: Animations and Example Computer Files 567 E.I Animations 567 E.2 Variation of Equilibrium ph of a Monoprotic Acid Solution with Total Acid Concentration and K a 567 E.3 How to Draw a pc-ph Diagram 569 E.4 Equilibrium ph During the Titration of a Monoprotic Acid with a Strong Base 570 E.5 Other Computer Files 571 Appendix F: Nanoql (also on CD) 573 F.I Installation 573 F.2 Using and Manipulating Files in Nanoql 573 F.3 Tips on Using Nonoql 575 References 577 Index 581