Book contents
- Frontmatter
- Contents
- Preface
- 1 Introduction
- PART ONE FUNDAMENTALS OF STATISTICAL THERMODYNAMICS
- PART TWO QUANTUM MECHANICS AND SPECTROSCOPY
- PART THREE STATISTICAL THERMODYNAMICS IN THE DILUTE LIMIT
- PART FOUR STATISTICAL THERMODYNAMICS BEYOND THE DILUTE LIMIT
- PART FIVE NONEQUILIBRIUM STATISTICAL THERMODYNAMICS
- PART SIX THE ENSEMBLE METHOD OF STATISTICAL THERMODYNAMICS
- PART SEVEN APPENDICES
- A Physical Constants and Conversion Factors
- B Series and Integrals
- C Periodic Table
- D Mathematical Procedures
- E Thermochemical Data for Ideal Gases
- F Summary of Classical Thermodynamics
- G Review of Classical Mechanics
- H Review of Operator Theory
- I The Spherical Coordinate System
- J Electronic Energy Levels
- K Energy-Mode Parameters for Molecules
- L Normal Mode Analysis
- M Tabulation of Debye Function
- N Maxwell–Boltzmann Energy Distribution
- O Force Constants for the Lennard–Jones Potential
- P Collision Integrals for Calculating Transport Properties from the Lennard–Jones Potential
- Q Reduced Second Virial Coefficient from the Lennard–Jones Potential
- R References and Acknowledgments
- Index
F - Summary of Classical Thermodynamics
Published online by Cambridge University Press: 05 June 2012
- Frontmatter
- Contents
- Preface
- 1 Introduction
- PART ONE FUNDAMENTALS OF STATISTICAL THERMODYNAMICS
- PART TWO QUANTUM MECHANICS AND SPECTROSCOPY
- PART THREE STATISTICAL THERMODYNAMICS IN THE DILUTE LIMIT
- PART FOUR STATISTICAL THERMODYNAMICS BEYOND THE DILUTE LIMIT
- PART FIVE NONEQUILIBRIUM STATISTICAL THERMODYNAMICS
- PART SIX THE ENSEMBLE METHOD OF STATISTICAL THERMODYNAMICS
- PART SEVEN APPENDICES
- A Physical Constants and Conversion Factors
- B Series and Integrals
- C Periodic Table
- D Mathematical Procedures
- E Thermochemical Data for Ideal Gases
- F Summary of Classical Thermodynamics
- G Review of Classical Mechanics
- H Review of Operator Theory
- I The Spherical Coordinate System
- J Electronic Energy Levels
- K Energy-Mode Parameters for Molecules
- L Normal Mode Analysis
- M Tabulation of Debye Function
- N Maxwell–Boltzmann Energy Distribution
- O Force Constants for the Lennard–Jones Potential
- P Collision Integrals for Calculating Transport Properties from the Lennard–Jones Potential
- Q Reduced Second Virial Coefficient from the Lennard–Jones Potential
- R References and Acknowledgments
- Index
Summary
The basic concepts of classical thermodynamics can be summarized by invoking the following four postulates (Callen, 1985):
There exist particular states (called equilibrium states) of simple compressible systems that, macroscopically, are characterized completely by the internal energy, U, the volume, V, and the mole or particle numbers, of the chemical components.
There exists a function called the entropy, S, of the extensive parameters of any composite system, defined for all equilibrium states and having the following property: The values assumed by the extensive parameters in the absence of an internal constraint are those which maximize the entropy for the composite isolated system.
The entropy of a composite system is additive over the constituent subsystems. Moreover, the entropy is a continuous, differentiable, and monotonically increasing function of the internal energy.
The entropy of any system vanishes in the state for which (i.e., at the zero of temperature).
Recall that a simple compressible system is defined as one that is macroscopically homogeneous, uncharged, and chemically inert, that is sufficiently large that surface effects can be neglected, and that is not acted on by electric, magnetic, or gravitational fields. Although these four basic postulates are restricted to simple compressible systems, they can readily be extended to more complex systems (Lewis and Randall, 1961).
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- Information
- Statistical ThermodynamicsFundamentals and Applications, pp. 409 - 414Publisher: Cambridge University PressPrint publication year: 2005