Physical Chemistry An Advanced Treatise

Physical Chemistry: An Advanced Treatise, Volume I: Thermodynamics deals with the applications of thermodynamics to mixtures, fluids, and solid systems at high pressures and temperatures, critical phenomena, practical handling of coupled gas equilibriums, and matter in electric, magnetic, and gravitational fields.

This book begins with a survey of basic laws, followed by discussions on questions of stability, irreversible processes, surfaces, the third law, and a short introduction to Caratheodory's axiomatic foundation. The zeroth law of thermodynamics, gaseous mixtures, internal equilibrium in solids, thermodynamic properties of the mixture, and theory of linear differential forms are also elaborated.

This publication presents a comprehensive treatment of physical chemistry for advanced students and researchers.

Contenu

List of Contributors
Foreword
Preface
Contents of Previous and Future Volume
Chapter 1 / Survey of Fundamental Laws
I. Introduction
II. Some Basic Concepts
III. Mass, Amount of Substance, and Composition
IV. Zeroth Law of Thermodynamics (Empirical Temperature)
V. Equation of State
VI. Specific, Molar, and Partial Molar Quantities, and Generalized Densities
VII. Work
VIII. First Law of Thermodynamics (Energy and Heat)
IX. Enthalpy
X. Open Systems
XI. Second Law of Thermodynamics (Entropy and Thermodynamic Temperature)
XII. Caratheodory's Approach
XIII. Generalized Gibbs Equation (Chemical Potential)
XIV. Connection between Entropy and Heat
XV. Helmholtz Function and Gibbs Function
XVI. Fundamental Equations
XVII. Relation of Empirical to Thermodynamic Temperature
XVIII. Heat Capacity
XIX. Generalized Gibbs-Duhe Relation
XX. Chemical Reactions
XXI. Galvanic Cells
XXII. Equilibrium
XXIII. Nernst Heat Theorem
XXIV. Unattainability of Absolute Zero
Nomenclature
References
Chapter 2A / Equilibrium, Stability, and Displacements
Introduction
I. Thermodynamic Potentials
II. Affinity
III. Affinity and Thermodynamic Potentials
IV. The Gibbs Chemical Potential
V. The Phase Rule
VI. The Equilibrium Constant
VII. Standard Functions and Functions of Mixing
VIII. Numerical Examples
IX. Real Gases
X. Stability of Chemical Systems
XI. Equilibrium Displacements in Closed Systems
XII. Equilibrium Displacements in Open Systems
XIII. Thermodynamics of Solutions
XIV. Osmotic Pressure
XV. Equilibrum Curves between Two Phases
References
Chapter 2B / Irreversible Processes
I. Introduction
II. Conservation of Energy in Open Systems
III. Equality of Exchange Flow of Energy
IV. Entropy Production in Open Systems
V. Continuous Systems
VI. Transport and Chemical Equations
VII. Stationary States
VIII. Diffusion in Systems at Uniform Temperature
IX. Diffusion in Systems at Nonuniform Temperature
X. Electrokinetic Effects
XI. Entropy Production due to Viscosity
References
Chapter 2C / Thermodynamics of Surfaces
I. Mechanical Properties of an Interface
II. Pressure Tensor in Surface Layers
III. Gibbs's Surface Model
IV. Phase Rule
V. Influence of Temperature on Surface Tension
VI. Properties of Monolayers
VII. Multilayer Model and Interfacial Orientation
VIII. Capillary Condensation
IX. Surface Tensions of Crystals
References
Chapter 3 / Thermodynamic Properties of Gases, Liquids, and Solids
I. Introduction
II. Chemical Species and Components
III. Pure Gases
IV. Gaseous Mixtures
V. Pure Liquids
VI. Liquid Mixtures
VII. Pure Solids
VIII. Solid Mixtures
Nomenclature
References
Chapter 4 / Gas-Liquid and Gas-Solid Equilibria at High Pressure, Critical Curves, and Miscibility Gaps
I. Introduction
II. General Description
III. Detailed Description-Weak Interaction in the Gas Phase
IV. Detailed Description-Strong Interaction in the Gas Phase
V. Liquid-Gas Critical Phenomena in Binary Systems
References
Chapter 5 / Thermodynamics of Matter in Gravitational, Electric, and Magnetic Fields
I. Thermodynamics of Matter in Gravitational Fields and in Rotational Frames of Reference
II. Static Electric and Magnetic Fields
III. The Thermodynamic Potentials of Dielectric and Magnetic Substances
IV. Applications
V. The Magnetic Properties of Matter
References
Chapter 6 / The Third Law of Thermodynamics
I. Introduction
II. The Third Law and Low-Temperature Physics
III. Liquid Helium
IV. The Third Law and the Determination of Entropy
V. Statistical Mechanics and the Third Law
VI. Chemical Equilibrium
VII. Internal Equilibrium in Solids
VIII. Nuclei and Entropy
IX. The Third Law and the Entropy of Gases
X. Thermal Motion on Solids
XI. The Third Law and Very Low Temperatures
References
Chapter 7 / Practical Treatment of Coupled Gas Equilibrium
I. Introduction
II. Direct Minimization of the Free Energy
III. The Equilibrium-Constant Method
IV. Transformations among Sets of Reference Species
V. Some Problems in the Calculation of Ideal-Gas Functions for the Individual Species
VI. The Thermodynamic Properties of the Mixture
VII. Numerical Methods
Appendix A. Illustrations of the Matrices Associated with the Stoichiometry of Reacting Gaseous Mixtures
Appendix B. The Introduction of Real-Gas Effects
References
Chapter 8 / Equilibria at Very High Temperatures
I. Introduction
II. The Ideal Plasma
III. Internal Partition Function and Internal Energy
IV. Transition Equilibria and Characteristic Temperature
V. Plasma at Higher Densities
References
Chapter 9 / High Pressure Phenomena
I. Introduction
II. Techniques
III. Observations
References
Chapter 10 / Caratheodory's Formulation of the Second Law
I . Introduction
II. Theory of Linear Differential Forms
III. Caratheodory's Principle
IV. Carnot's Theorem
V. Entropy Changes
VI. Law of Increasing Entropy
VII. Nonadiabatic Processes
VIII. Conclusion
Appendix A. Vector Formulation of the Theory of Differential Expressions
Appendix B. Solution Curve for Nonintegrable Pfaff Equation
Appendix C. Proof of Caratheodory's Theorem
Appendix D. Rigorous Proof of Carnot's Theorem
References
Author Index
Subject Index