Water Chemistry:  by Mark M. Benjamin
907 pages, $137.95 list
1-4786-2308-X
978-1-4786-2308-3
Instructor's Manual available
Water Chemistry
Second Edition
Aquatic chemistry students need a solid foundation in fundamental concepts as well as numerical techniques for solving the variety of problems they will encounter as practicing engineers. For over a decade, Mark Benjamin’s Water Chemistry has brought to the classroom a balanced coverage of fundamentals and analytical algorithms in a student-friendly, accessible way. The text distinguishes itself with longer and more detailed explanations of the relevant chemistry and mathematics, allowing students to understand not only which techniques work best for a given application, but also why those techniques should be applied and what their limitations are. The end result is a solid, thorough framework for comprehending equilibrium in complex aquatic systems.

The second edition includes a thorough introductory explanation of chemical reactivity and a new chapter on reaction kinetics, providing much-needed context, as well as full treatments of the tableau method and TOTH equation. The discussion of the thermodynamic perspective on chemical reactivity has been extensively revised. The entire book now integrates Visual Minteq—the most popular software for analyzing chemical equilibria—into the problem-solving approach. Additional exercises range more widely in difficulty, giving instructors more flexibility and diversity in their assignments.

Notable features!

• Seamlessly integrates spreadsheet, graphical, and software approaches to solving for the equilibrium composition of a solution.

• Demonstrates a simple, intuitive approach for identifying dominant species, and uses that approach to clarify frequently misunderstood concepts related to alkalinity and titrations.

• Presents a unique and unified approach to understanding chemical thermodynamics, activity coefficients, redox potential, and electrostatic interactions in adsorption reactions.

Errata


A revised version of problem 3.19 (found on page 128) can be downloaded here.

Users of the first printing (copies with grayish green spines) can access that printing’s errata here and improved problems here. These corrections appear in copies of the second and subsequent printings (with lavender spines).

Errata for later printings (with lavender spines) can be downloaded here. (Note that fourth printings incorporate all the posted errata.)
Reactions
“Dr. Benjamin’s revisions in the second edition are excellent. The thermodynamics discussion is more on target with the audience. This is the best water chemistry text for upper-level undergraduates and graduate students on the market today.” — Paul A. Chadik, University of Florida

“Like the First Edition of Water Chemistry, the Second Edition remains didactic and written for the student, but with improvements throughout. The book will serve well many future generations of students of water chemistry.” — David Dzombak, Carnegie-Mellon University

“Professor Benjamin is one of the best writers in this area. He brings his A-game to this edition. His discussions of how to solve acid/base, precipitation, and redox are exceptionally clear and easy to use. I am particularly appreciative of his lucid yet rigorous discussion of adsorption and the origin of the many isotherms. The connection to Visual Minteq is very helpful to the students, especially those in Environmental Engineering who will one day use the material in their jobs. A hidden jewel, that most will not be aware of, is the answer key with fully worked solutions and clear discussion of how to solve each problem along with in-depth comments about significance, etc.” — Mason Tomson, Rice University
Table of Contents
1. Concepts in Aquatic Chemistry
Introduction / The Structure of Water Molecules and Interactions among Them / The Behavior of Solutes in Water; Dissolution of Salts / Common Approaches for Expressing Concentrations in Environmental Chemistry

2. Chemical Reactivity, Reactions, and Equilibrium
Overview / Characterizing Chemical Reactivity / Predicting Activity Coefficients from Knowledge of the Solution Composition / The Activity as an Intensive Property; The Activity of Solids Dispersed in Water / Models of Chemical Equilibrium / Effect of Temperature on the Equilibrium Constant / Combining Chemical Reactions / Summary

3. Reaction Kinetics and the Kinetics-Based Interpretation of Equilibrium
A Molecular-Level Picture of an Elementary Reaction and the Factors that Affect Its Rate / Effect of Temperature on Reaction Rate Constants / The Kinetics of Some Important Categories of Environmental Chemical Reactions / Kinetics of Elementary Chemical Reactions / Reaction Reversibility and the Definition of the Equilibrium Constant / Effect of Temperature on the Equilibrium Constant / Combining Chemical Reactions: Kinetics and Equilibrium Constants of Nonelementary Reactions / Experimental Evaluation of Reaction Kinetics / Rate-Limiting Steps and Some Classical, Model Reaction Pathways / Heterogeneous (Phase-Transfer) Reactions / Summary

4. Potentials, Energy, and Forces: Interpreting Changes in Physical/Chemical Systems
Introduction / Potential Energy, Potentials, and Forces / Overview of Potential and Potential Energy in Chemical Systems / Entropy and Gibbs Energy / The Chemical Potential and Its Use to Predict Chemical Change / Other Molar Thermodynamic Quantities / Quantifying Gi, Hi, and Si / The Dependence of Gi on System Composition, Temperature, and Pressure / Comparison of Gi of Different Species / The Dependence of Gi on Pressure and Temperature / Comparing the Magnitude of Factors That Affect Gi / Chemical Potential as the Driving Force for Chemical Reactions / Summary

5. Acids and Bases, Part 1: Acid/Base Speciation and Exact Solutions to Acid/Base Problems
Introduction / The Dissociation of Water; Kw / The Structure of Acids and Bases / Strong and Weak Acids, Ka, and Conjugate Acid/Base Pairs / A Brief Diversion: The Structure of Some Important Organic Acids and Bases / Combining Acidity Reactions and the Definition of Basicity / Acid/Base Speciaation as a Function of pH; Diagrams of Log C versus pH / Log C-pH Diagrams for Monoprotic Acids / Effects of Nonideal Solute Behavior on log C-pH Diagrams / Log C-pH Diagrams for Multiprotic Acids / Determining Species and Relevant Equations for Solving Equilibrium Problems / Numerical Approaches for Solving Acid/Base Problems / The pH of Solutions Containing Only Water and Strong Acids or Bases / The pH of Ideal Solutions Containing Weak Acids and Bases / A Simple Spreadsheet Analysis for Determining Acid/Base Speciation / The pH and Speciation of Systems Containing Multiprotic Weak Acids and Bases / Acid/Base Equilibria in Nonideal Solutions / Summary

6. Acids and Bases, Part 2: Use of log C-pH Diagrams and the TOTH Equation
Graphical Solutions for Sets of Simultaneous Equations / Using log C–pH Diagrams to Solve Weak Acid/Base Problems / The Mass Balance on H (the TOTH Equation and Proton Condition) / Defining the Composition of the System: Components, Species, and the System Tableau / Expressing Input and Equilibrium Concentrations in Terms of Components; Component Mass Balances / Identifying Dominant Species / Comparison of Approaches for Solving Acid/Base Problems / Summary / Appendix 6A: Arithmetic Operations and log-log Diagrams

7. Software for Solving Chemical Equilibrium Problems
Introduction / The Computer Algorithm for Solving a Simple Acid/Base Problem / Systems in Which the Equilibrium Activities of One or More Species Are Known / Using Chemical Equilibrium Software to Develop log C-pH Diagrams / Modifying the Component and Species Databases in Visual Minteq / Summary

8. Titrations and Buffers
Introduction / Reactions Occurring during a Titration: Qualitative Considerations / Quantitative Interpretation of Titration Data / Using Visual Minteq to Simulate Titrations / Titrations with Weak Acids or Bases / The Effect of the Acidity of Water on Titration Curves / Titration of Solutions Containing Unknown Acids and Bases / Titration Equivalence Points / Alkalinity and Acidity / Acid/Base Titrations of Natural Organic Matter / Buffers / Summary / Appendix 8A: Determining Alkalinity Factors and Inserting Them into the Visual Minteq Database / Appendix 8B: Derivation of the Buffer Intensity of Multiprotic Acids

9. Gas/Liquid Equilibrium
Introduction / Basic Concepts and Terminology for Gas/Liquid Equilibrium / Effect of Gas/Liquid Equilibration on Gas-Phase Composition / Factors Affecting Volatility and Henry's Constant / Henry's Law and Aqueous-Phase Speciation / The pH of Solutions in Equilibrium with Acidic or Basic Gases / Gas-Liquid Equilibrium in Visual Minteq / Buffering in Solutions Equilibrated with Weak Acid and Weak Base Gases / CO2 Dissolution, Alkalinity, and Acidity / Summary / Appendix 9A: The Liquid-Phase Activity Coefficient in Henry's Law Using the Raoult's Law Standard State Convention

10. Chemistry of Metals in Aqueous Systems 1: Solution-Phase Reactions
Introduction / Metal Oxidation States / Formation and Structure of Metal Complexes / Complexes with Hydroxide Ions / log C-pH Diagrams for Dissolved Metals / Complexes with Ligands Other than Water and Hydroxide / Mixed Ligand Complexes and Chelating Agents / Metal Speciation in Systems Containing Complexing Ligands / Metal Ion Buffers / Predominance Area Diagrams / Summary

11. Chemistry of Metals in Aqueous Systems 2: Precipitation and Dissolution Reactions
Introduction / Formation of Solids Containing Metal Ions / The Chemical Activity of Pure Solids / The Solubility Product / Precipitation of Solids Other than Hydroxides / Formation of Nonhydroxo Complexes in Systems with Solids / Adding New Solids to the Visual Minteq Database / Determining whether a Solid Will Precipitate under Given Conditions / The Gibbs Phase Rule / Predominance Area Diagrams Considering Possible Precipitation of Solids / Summary

12. Redox Chemistry
Introduction / Determining Oxidation Numbers / Balancing Redox Reactions / Redox Half-Reactions / The Activity of Free Electrons; Equilibrium Constants for Redox Half-Reactions / Definition of eo and peo / Computing pe from Species Activities: The Nernst Equation / Combining Redox Reactions / Redox Speciation and log C-pe Diagrams / Summary of Some Key Similarities between Acid/Base and Redox Systems / Redox Reactions Involving Exchange of Both Electrons and Protons / Computing Equilibrium Speciation in Redox Systems / Modeling Redox Reactions with Visual Minteq / Oxidation and Reduction of Water / Energy Changes Accompanying Redox Reactions / Redox Titrations and the Geochemical Redox Sequence / pe-pH Predominance Area Diagrams / Redox Reactions and Electrochemistry / Summary

13. Adsorption Reactions
Introduction / Two Views of the Interface and Adsorption Equilibrium / Quantitative Representations of Adsorption Equilibrium: The Adsorption Isotherm / Modeling Adsorption with Visual Minteq / Adsorption of Ions in the Presence of a Surface Electrical Potential / Modeling Surface-Adsorbate Electrical Interactions in Visual Minteq / Surface Precipitation / Summary

Appendix A: Thermodynamic Data and Equilibrium Constants
Appendix B: List of Important Equations