Classical and Geometrical Theory of Chemical and Phase Thermodynamics

Name: Classical and Geometrical Theory of Chemical and Phase Thermodynamics
Brand: Wiley
Price: 152.99 EUR
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Frank Weinhold(Autor*in)

Wiley (Verlag)

Erschienen am 18. Februar 2009

476 Seiten

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978-0-470-43505-2 (ISBN)

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Inhalt

Intro
CLASSICAL AND GEOMETRICAL THEORY OF CHEMICAL AND PHASE THERMODYNAMICS
CONTENTS
PREFACE
PART I INDUCTIVE FOUNDATIONS OF CLASSICAL THERMODYNAMICS
1. Mathematical Preliminaries: Functions and Differentials
1.1 Physical Conception of Mathematical Functions and Differentials
1.2 Four Useful Identities
1.3 Exact and Inexact Differentials
1.4 Taylor Series
2. Thermodynamic Description of Simple Fluids
2.1 The Logic of Thermodynamics
2.2 Mechanical and Thermal Properties of Gases: Equations of State
2.3 Thermometry and the Temperature Concept
2.4 Real and Ideal Gases
2.4.1 Compressibility Factor and Ideal Gas Deviations
2.4.2 Van der Waals and Other Model Equations of State
2.4.3 The Virial Equation of State
2.5 Condensation and the Gas-Liquid Critical Point
2.6 Van der Waals Model of Condensation and Critical Behavior
2.7 The Principle of Corresponding States
2.8 Newtonian Dynamics in the Absence of Frictional Forces
2.9 Mechanical Energy and the Conservation Principle
2.10 Fundamental Definitions: System, Property, Macroscopic, State
2.10.1 System
2.10.2 Property
2.10.3 Macroscopic
2.10.4 State
2.11 The Nature of the Equilibrium Limit
3. General Energy Concept and the First Law
3.1 Historical Background of the First Law
3.2 Reversible and Irreversible Work
3.3 General Forms of Work
3.3.1 Pressure-Volume Work
3.3.2 Surface Tension Work
3.3.3 Elastic Work
3.3.4 Electrical (emf) Work
3.3.5 Electric Polarization Work
3.3.6 Magnetic Polarization Work
3.3.7 Overview of General Work Forms
3.4 Characterization and Measurement of Heat
3.5 General Statements of the First Law
3.6 Thermochemical Consequences of the First Law
3.6.1 Heat Capacity and the Enthalpy Function
3.6.2 Joule's Experiment
3.6.3 Joule-Thomson Porous Plug Experiment
3.6.4 Ideal Gas Thermodynamics
3.6.5 Thermochemistry: Enthalpies of Chemical Reactions
3.6.6 Temperature Dependence of Reaction Enthalpies
3.6.7 Heats of Solution
3.6.8 Other Aspects of Enthalpy Decompositions
4. Engine Efficiency, Entropy, and the Second Law
4.1 Introduction: Heat Flow, Spontaneity, and Irreversibility
4.2 Heat Engines: Conversion of Heat to Work
4.3 Carnot's Analysis of Optimal Heat-Engine Efficiency
4.4 Theoretical Limits on Perpetual Motion: Kelvin's and Clausius' Principles
4.5 Kelvin's Temperature Scale
4.6 Carnot's Theorem and the Entropy of Clausius
4.7 Clausius' Formulation of the Second Law
4.8 Summary of the Inductive Basis of Thermodynamics
PART II GIBBSIAN THERMODYNAMICS OF CHEMICAL AND PHASE EQUILIBRIA
5. Analytical Criteria for Thermodynamic Equilibrium
5.1 The Gibbs Perspective
5.2 Analytical Formulation of the Gibbs Criterion for a System in Equilibrium
5.3 Alternative Expressions of the Gibbs Criterion
5.4 Duality of Fundamental Equations: Entropy Maximization versus Energy Minimization
5.5 Other Thermodynamic Potentials: Gibbs and Helmholtz Free Energy
5.6 Maxwell Relations
5.7 Gibbs Free Energy Changes in Laboratory Conditions
5.8 Post-Gibbsian Developments
5.8.1 The Fugacity Concept
5.8.2 The "Third Law" of Thermodynamics: A Critical Assessment
6. Thermodynamics of Homogeneous Chemical Mixtures
6.1 Chemical Potential in Multicomponent Systems
6.2 Partial Molar Quantities
6.3 The Gibbs-Duhem Equation
6.4 Physical Nature of Chemical Potential in Ideal and Real Gas Mixtures
7. Thermodynamics of Phase Equilibria
7.1 The Gibbs Phase Rule
7.2 Single-Component Systems
7.2.1 The Phase Diagram of Water
7.2.2 Clapeyron and Clausius-Clapeyron Equations for Phase Boundaries
7.2.3 Illustrative Phase Diagrams for Pure Substances
7.3 Binary Fluid Systems
7.3.1 Vapor-Pressure (P-x) Diagrams: Raoult and Henry Limits
7.3.2 The Lever Rule
7.3.3 Positive and Negative Deviations
7.3.4 Boiling-Point Diagrams: Theory of Distillation
7.3.5 Immiscibility and Consolute Behavior
7.3.6 Colligative Properties and Van't Hoff Osmotic Equation
7.3.7 Activity and Activity Coefficients
7.4 Binary Solid-Liquid Equilibria
7.4.1 Eutectic Behavior
7.4.2 Congruent Melting
7.4.3 Incongruent Melting and Peritectics
7.4.4 Alloys and Partial Miscibility
7.4.5 Phase Boundaries and Gibbs Free Energy of Mixing
7.5 Ternary and Higher Systems
8. Thermodynamics of Chemical Reaction Equilibria
8.1 Analytical Formulation of Chemical Reactions in Terms of the Advancement Coordinate
8.2 Criterion of Chemical Equilibrium: The Equilibrium Constant
8.3 General Free Energy Changes: de Donder's Affinity
8.4 Standard Free Energy of Formation
8.5 Temperature and Pressure Dependence of the Equilibrium Constant
8.5.1 Temperature Dependence: Van't Hoff Equation
8.5.2 Pressure Dependence
8.6 Le Chatelier's Principle
8.7 Thermodynamics of Electrochemical Cells
8.8 Ion Activities in Electrolyte Solutions
8.9 Concluding Synopsis of Gibbs' Theory
PART III METRIC GEOMETRY OF EQUILIBRIUM THERMODYNAMICS
9. Introduction to Vector Geometry and Metric Spaces
9.1 Vector and Matrix Algebra
9.2 Dirac Notation
9.3 Metric Spaces
10. Metric Geometry of Thermodynamic Responses
10.1 The Space of Thermodynamic Response Vectors
10.2 The Metric of Thermodynamic Response Space
10.3 Linear Dependence, Dimensionality, and Gibbs-Duhem Equations
11. Geometrical Representation of Equilibrium Thermodynamics
11.1 Thermodynamic Vectors and Geometry
11.2 Conjugate Variables and Conjugate Vectors
11.3 Metric of a Homogeneous Fluid
11.4 General Transformation Theory in Thermodynamic Metric Space
11.5 Saturation Properties Along the Vapor-Pressure Curve
11.6 Self-Conjugate and Normal Response Modes
11.7 Geometrical Characterization of Common Fluids
11.8 Stability Conditions and the "Third Law" for Homogeneous Phases
11.9 The Critical Instability Limit
11.10 Critical Divergence and Exponents
11.11 Phase Heterogeneity and Criticality
12. Geometrical Evaluation of Thermodynamic Derivatives
12.1 Thermodynamic Vectors and Derivatives
12.2 General Solution for Two Degrees of Freedom and Relationship to Jacobian Methods
12.3 General Partial Derivatives in Higher-Dimensional Systems
12.4 Phase-Boundary Derivatives in Multicomponent Systems
12.5 Stationary Points of Phase Diagrams: Gibbs-Konowalow Laws
12.6 Higher-Order Derivatives and State Changes
13. Further Aspects of Thermodynamic Geometry
13.1 Reversible Changes of State: Riemannian Geometry
13.2 Near-Equilibrium Irreversible Thermodynamics: Diffusional Geometry
13.3 Quantum Statistical Thermodynamic Origins of Chemical and Phase Thermodynamics
13.3.1 Nonequilibrium Displacement Variables of Mayer and Co-workers
13.3.2 Quantum Statistical Thermodynamics and the Statistical Origins of Metric Geometry
13.3.3 Evaluation of Molecular Partition Functions for Reactive Mixtures
13.3.4 Quantum Cluster Equilibrium Theory of Phase Thermodynamics
Appendix: Units and Conversion Factors
AUTHOR INDEX
SUBJECT INDEX

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