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Preface | |

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Introduction and Definition of Terms | |

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Introduction | |

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The Concept of State | |

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Simple Equilibrium | |

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The Equation of State of an Ideal Gas | |

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The Units of Energy and Work | |

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Extensive and Intensive Properties | |

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Phase Diagrams and Thermodynamic Components | |

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The First Law of Thermodynamics | |

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Introduction | |

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The Relationship between Heat and Work | |

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Internal Energy and the First Law of Thermodynamics | |

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Constant-Volume Processes | |

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Constant-Pressure Processes and the Enthalpy H | |

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Heat Capacity | |

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Reversible Adiabatic Processes | |

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Reversible Isothermal Pressure or Volume Changes of an Ideal Gas | |

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Summary | |

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Numerical Examples | |

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Problems | |

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The Second Law of Thermodynamics | |

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Introduction | |

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Spontaneous or Natural Processes | |

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Entropy and the Quantification of Irreversibility | |

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Reversible Processes | |

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An Illustration of Irreversible and Reversible Processes | |

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Entropy and Reversible Heat | |

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The Reversible Isothermal Compression of an Ideal Gas | |

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The Reversible Adiabatic Expansion of an Ideal Gas | |

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Summary Statements | |

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The Properties of Heat Engines | |

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The Thermodynamic Temperature Scale | |

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The Second Law of Thermodynamics | |

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Maximum Work | |

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Entropy and the Criterion for Equilibrium | |

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The Combined Statement of the First and Second Laws of Thermodynamics | |

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Summary | |

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Numerical Examples | |

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Problems | |

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The Statistical Interpretation of Entropy | |

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Introduction | |

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Entropy and Disorder on an Atomic Scale | |

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The Concept of Microstate | |

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Determination of the Most Probable Microstate | |

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The Influence of Temperature | |

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Thermal Equilibrium and the Boltzmann Equation | |

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Heat Flow and the Production of Entropy | |

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Configurational Entropy and Thermal Entropy | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Auxiliary Functions | |

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Introduction | |

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The Enthalpy H | |

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The Helmholtz Free Energy A | |

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The Gibbs Free Energy G | |

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Summary of the Equations for a Closed System | |

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The Variation of the Composition and Size of the System | |

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The Chemical Potential | |

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Thermodynamic Relations | |

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Maxwell's Equations | |

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The Upstairs-Downstairs-Inside-Out Formula | |

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The Gibbs-Helmholtz Equation | |

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Summary | |

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Example of the Use of the Thermodynamic Relations | |

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Problems | |

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Heat Capacity, Enthalpy, Entropy, and the Third Law of Thermodynamics | |

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Introduction | |

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Theoretical Calculation of the Heat Capacity | |

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The Empirical Representation of Heat Capacities | |

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Enthalpy as a Function of Temperature and Composition | |

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The Dependence of Entropy on Temperature and the Third Law of Thermodynamics | |

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Experimental Verification of the Third Law | |

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The Influence of Pressure on Enthalpy and Entropy | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Phase Equilibrium in a One-Component System | |

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Introduction | |

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The Variation of Gibbs Free Energy with Temperature at Constant Pressure | |

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The Variation of Gibbs Free Energy with Pressure at Constant Temperature | |

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Gibbs Free Energy as a Function of Temperature and Pressure | |

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Equilibrium between the Vapor Phase and a Condensed Phase | |

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Graphical Representation of Phase Equilibria in a One-Component System | |

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Solid-Solid Equilibria | |

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Summary | |

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Numerical Examples | |

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Problems | |

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The Behavior of Gases | |

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Introduction | |

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The P-V-T Relationships of Gases | |

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Deviations from Ideality and Equations of State for Real Gases | |

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The van der Waals Gas | |

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Other Equations of State for Nonideal Gases | |

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The Thermodynamic Properties of Ideal Gases and Mixtures of Ideal Gases | |

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The Thermodynamic Treatment of Nonideal Gases | |

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Summary | |

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Numerical Examples | |

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Problems | |

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The Behavior of Solutions | |

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Introduction | |

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Raoult's Law and Henry's Law | |

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The Thermodynamic Activity of a Component in Solution | |

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The Gibbs-Duhem Equation | |

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The Gibbs Free Energy of Formation of a Solution | |

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The Properties of Raoultian Ideal Solutions | |

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Nonideal Solutions | |

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Application of the Gibbs-Duhem Relation to the Determination of Activity | |

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Regular Solutions | |

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A Statistical Model of Solutions | |

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Subregular Solutions | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Gibbs Free Energy Composition and Phase Diagrams of Binary Systems | |

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Introduction | |

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Gibbs Free Energy and Thermodynamic Activity | |

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The Gibbs Free Energy of Formation of Regular Solutions | |

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Criteria for Phase Stability in Regular Solutions | |

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Liquid and Solid Standard States | |

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Phase Diagrams, Gibbs Free Energy, and Thermodynamic Activity | |

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The Phase Diagrams of Binary Systems That Exhibit Regular Solution Behavior in the Liquid and Solid States | |

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Summary | |

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Numerical Example | |

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Problems | |

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Reactions Involving Gases | |

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Introduction | |

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Reaction Equilibrium in a Gas Mixture and the Equilibrium Constant | |

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The Effect of Temperature on the Equilibrium Constant | |

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The Effect of Pressure on the Equilibrium Constant | |

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Reaction Equilibrium as a Compromise between Enthalpy and Entropy | |

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Reaction Equilibrium in the System SO[subscript 2(g)]-SO[subscript 3(g)]-O[subscript 2(g)] | |

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Equilibrium in H[subscript 2]O-H[subscript 2] and CO[subscript 2]-CO Mixtures | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Reactions Involving Pure Condensed Phases and a Gaseous Phase | |

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Introduction | |

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Reaction Equilibrium in a System Containing Pure Condensed Phases and a Gas Phase | |

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The Variation of the Standard Gibbs Free Energy Change with Temperature | |

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Ellingham Diagrams | |

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The Effect of Phase Transformations | |

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The Oxides of Carbon | |

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Graphical Representation of Equilibria in the System Metal-Carbon-Oxygen | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Reaction Equilibria in Systems Containing Components in Condensed Solution | |

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Introduction | |

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The Criteria for Reaction Equilibrium in Systems Containing Components in Condensed Solution | |

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Alternative Standard States | |

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The Gibbs Phase Rule | |

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Binary Systems Containing Compounds | |

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Graphical Representation of Phase Equilibria | |

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The Formation of Oxide Phases of Variable Composition | |

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The Solubility of Gases in Metals | |

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Solutions Containing Several Dilute Solutes | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Phase Diagrams for Binary Systems in Pressure-Temperature-Composition Space | |

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Introduction | |

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A Binary System Exhibiting Complete Mutual Solubility of the Components in the Solid and Liquid States | |

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A Binary System Exhibiting Complete Mutual Solubility in the Solid and Liquid States and Showing Minima on the Melting, Boiling, and Sublimation Curves | |

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A Binary System Containing a Eutectic Equilibrium and Having Complete Mutual Solubility in the Liquid | |

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A Binary System Containing a Peritectic Equilibrium and Having Complete Mutual Solubility in the Liquid State | |

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Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts, Sublimes, and Boils Congruently | |

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Phase Equilibrium in a Binary System Containing an Intermediate [gamma] Phase That Melts and Sublimes Congruently and Boils Incongruently | |

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Phase Equilibrium in a Binary System with a Eutectic and One Component That Exhibits Allotropy | |

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A Binary Eutectic System in Which Both Components Exhibit Allotropy | |

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Phase Equilibrium at Low Pressure: The Cadmium-Zinc System | |

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Phase Equilibrium at High Pressure: The Na[subscript 2]O[middle dot]Al[subscript 2]O[subscript 3 middle dot]2SiO[subscript 2]-SiO[subscript 2] System | |

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Summary | |

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Electrochemistry | |

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Introduction | |

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The Relationship between Chemical and Electrical Driving Forces | |

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The Effect of Concentration on EMF | |

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Formation Cells | |

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Concentration Cells | |

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The Temperature Coefficient of the EMF | |

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Heat Effects | |

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The Thermodynamics of Aqueous Solutions | |

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The Gibbs Free Energy of Formation of Ions and Standard Reduction Potentials | |

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Pourbaix Diagrams | |

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Summary | |

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Numerical Examples | |

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Problems | |

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Appendices | |

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Selected Thermodynamic and Thermochemical Data | |

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Exact Differential Equations | |

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The Generation of Auxiliary Functions as Legendre Transformations | |

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Nomenclature | |

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Answers | |

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Index | |