Physical Chemistry of Natural Waters
by Frank J. Millero

An in-depth discussion of the thermodynamics and kinetics of natural waters.

Physical Chemistry of Natural Waters explores how the basic concepts of physical chemistry can be used to understand the chemistry of natural waters, with most of the text confined to chemical thermodynamics and kinetics.

The extensive material in this book is the result of a course in marine physical chemistry that the author has taught over the past decade. Dr. Millero incorporates his own personal interest in solution physical chemistry and his approach to understanding the physical chemistry of seawater with the text’s vast coverage of the physical chemistry of liquid phases. In addition, detailed reviews of the basics of thermodynamics and kinetics provide a comprehensive overview for a clearer understanding of the topics covered.

Environmental and physical chemists conducting research on water, seawater, rivers, lakes, and groundwater as well as graduate students studying environmental chemistry will find Physical Chemistry of Natural Waters a solid foundation on the subject of the physical chemistry of natural waters.

Contents

1. Basic Thermodynamic Concepts
   
   • The First Law of Thermodynamics
   • The Second Law of Thermodynamics-Entropy
   • The Relationship Between Entropy and Other State Functions
   • Free Energy Functions and Equilibrium Calculations
   • The Thermodynamics of Solutions
   • Activity and Activity Coefficients
   • Nonelectrolyte Solutions
   • Strong Electrolytes
   • Thermodynamics of Electrolyte Solutions

2. Basic Kinetic Concepts
   
   • Transport Properties
   • Rate Processes in Solutions

3. Ionic Interactions
   
   • Water, the Unique Solvent
   • Ion-Water Interactions
   • Ion-Ion Interactions
   • Excess Properties of Mixing Electrolyte Solutions
   • Non-Coulombic Treatments
   • Activity Coefficients of Nonelectrolytes in Salt Solution

4. Physical Chemical Properties of Natural Waters
   
   • The Composition and Stoichiometry of Seawater
   • The Equations of State of Seawater
   • Effect of Changes in the Composition of Seawater on the Density-Salinity Relationship
   • The PVT Properties of Lakes, Rivers, and Estuaries
   • The Thermochemical Properties of Seawater
   • Other Physical Properties of Seawater

5. Chemical Equilibria in Natural Waters
   
   • Solubility of Gases
   • Dissociation of Acids
   • Solid-Liquid Equilibria
   • Formation of Metal Ion Pairs in Water
   • Effects of Pressure and Temperature on Ionic Equilibria
   • Helgeson Equations for Partial Molal Properties

6. Estimation of the Thermodynamic Properties of Natural Waters
   
   • Estimation of the Physical Properties of Natural Waters
   • Estimation of the Activity Coefficients in Natural Waters
   • Estimation of the Partial Molal Properties in Mixed Electrolytes

7. The Kinetics of Oxidation and Reduction of Metals in Natural Waters
   
   • Oxidation of Cu(I) with O₂
   • Oxidation of Cu(I) with H₂O₂
   • Comparisons of the Rates of Oxidation of Cu(I) with O₂ and H₂O₂
   • Rates of Reduction of Cu(II) with H₂O₂
   • Oxidation of Fe(II) with O₂
   • Oxidation of Fe(II) with H₂O₂
   • Comparisons of the Rates of Oxidation of Fe(II) with O₂ and H₂O₂
   • Reduction of Fe(III) with Sulfite
   • Oxidation of Cr(III) with H₂O₂
   • Reduction of Cr(VI) with Fe(II)
   • Reactions of Metals with Superoxide

8. The Oxidation of Hydrogen Sulfide in Natural Waters
   
   • Oxidation of H₂S with O₂
   • Effect of Metals on the Oxidation of H₂S
   • Products from the Oxidation of H₂S
   • Oxidation of H₂SO₃ with O₂
   • Kinetic Model for the Oxidation of H₂S with O₂
   • Oxidation of H₂S in Anoxic Environments
   • Oxidation of H₂S by H₂SO₂
   • Oxidation of H₂S with Fe and Mn Oxides

Index

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