Thermodynamics and statistical mechanics of the perfect gas

This course text provides an accessible introduction to thermodynamics and statistical mechanics, at a level that is suitable for both physics and engineering majors. Concepts are approached in a pedagogical way, using precise language, clear explanations and discussions of how the ideas developed over time. All of the material required for a one-semester (14-week) course in thermodynamics and statistical mechanics is provided, alongside worked examples, concept questions, worksheets, and independent-study exercises. The material has been thoroughly class-tested and acts as a core text for undergraduate courses, particularly for students who find the topics challenging. It also acts as valuable supplementary reading for postgraduates who would benefit from the supplementary material and clear explanations of the concepts.

Key features

• Provides an accessible introduction to thermodynamics and statistical mechanics.

• Suitable for mixed classes of physics and engineering majors.

• Acts as a core text for undergraduate courses, particularly for students who find the topics challenging.

• Introduces concepts with stories by key physicists, providing a historical perspective on how the concepts were developed.

• Includes worked examples, concept questions, worksheets and independent-study exercises.

Copyright © IOP Publishing Ltd 2021
Online ISBN: 978-0-7503-3083-1Print ISBN: 978-0-7503-3081-7


  • Author's Preface

    Editor's Preface

    Translator's Preface

    Chapter I. Thermodynamics. General Considerations

    1. Temperature as a Property of a System

    2. Work and Heat

    3. The Perfect Gas

    A. Boyle's Law (The Law of Boyle and Mariotte)

    B. Charles' Law (The Law of Gay-Lussac)

    C. Avogadro's Law and the Universal Gas Constant

    4. The First Law. Energy and Enthalpy as Properties

    A. Equivalence of Heat and Work

    B. The Enthalpy as a Property

    C. Digression on the Ratio of Specific Heats cp and cv

    5. The Reversible and the Irreversible Adiabatic Process

    A. The Reversible Adiabatic Process

    B. The Irreversible Adiabatic Process

    C. The Joule-Kelvin Porous Plug Experiment

    D. A Conclusion of Great Consequence

    6. The Second Law

    A. The Carnot Cycle and Its Efficiency

    B. The First Part of the Second Law

    C. The Second Part of the Second Law

    D. Simplest Numerical Examples

    E. Remarks on the Literature of the Second Law

    F. On the Relative Rank of Energy and Entropy

    7. The Thermodynamic Potentials and the Reciprocity Relations

    8. Thermodynamic Equilibria

    A. Unconstrained Thermodynamic Equilibrium and Maximum of Entropy

    B. An Isothermal and Isobaric System in Unconstrained Thermodynamic Equilibrium

    C. Additional Degrees of Freedom in Retarded Equilibrium

    D. Extremum Properties of the Thermodynamic Potentials

    E. The Theorem on Maximum Work

    9. The van der Waals Equation

    A. Course of Isotherms

    B. Entropy and the Caloric Behavior of the van der Waals Gas

    10. Remarks on the Liquefaction of Gases According to van der Waals

    A. The Integral and the Differential Joule-Thomson Effect

    B. The Inversion Curve and Its Practical Utilization

    C. The Boundary of the Region of Co-existing Liquid-Vapor Phases in the p, v Plane

    11. The Kelvin Temperature Scale

    12. Nernst's Third Law of Thermodynamics

    Chapter II. The Application of Thermodynamics To Special Systems

    13. Gaseous Mixtures. Gibbs' Paradox. The Law Due to Guldberg and Waage

    A. Reversible Separation of Gases

    B. The Increase in Entropy During Diffusion and Gibbs' Paradox

    C. The Law of Mass Action Due to Guldberg and Waage

    14. Chemical Potentials and Chemical Constants

    A. The Chemical Potentials μi

    B. Relation Between the μi's and the gi's for Ideal Mixtures

    C. The Chemical Constant of a Perfect Gas

    15. Dilute Solutions

    A. General and Historical Remarks

    B. Van 't Hoff's Equation of State for Dilute Solutions

    16. The Different Phases of Water. Remarks on the Theory of the Steam Engine

    A. The Vapor-Pressure Curve and Clapeyron's Equation

    B. Phase Equilibrium Between Ice and Water

    C. The Specific Heat of Saturated Steam

    17. General Remarks on the Theory of Phase Equilibria

    A. The Triple Point of Water

    B. Gibbs' Phase Rule

    C. Raoult's Laws for Dilute Solutions

    D. Henry's Law of Absorption (1803)

    18. The Electromotive Force of Galvanic Cells

    A. Electrochemical Potentials

    B. The Daniell Cell, 1836

    C. Contraction of Individual Reactions into a Simplified Overall Reaction

    D. The Gibbs-Helmholtz Fundamental Equation

    E. Numerical Example

    F. Remarks on the Integration of the Fundamental Equation

    19. Ferro- and Paramagnetism

    A. Work of Magnetization and Magnetic Equation of State

    B. Langevin's Equation for Paramagnetic Substances

    C. The Theory of Ferromagnetic Phenomena Due to Weiss

    D. The Specific Heats cH and cM

    E. The Magneto-Caloric Effect

    20. Black Body Radiation

    A. Kirchhoff 's Law

    B. The Stefan-Boltzmann Law

    C. Wien's Law

    D. Planck's Law of Radiation

    21. Irreversible Processes. Thermodynamics of Near-Equilibrium Processes

    A. Conduction of Heat and Local Entropy Generation

    B. The Conduction of Heat in an Anisotropie Body and Onsager's Reciprocal Relations

    C. Thermoelectric Phenomena

    D. Internal Transformations

    E. General Relations

    F. Limitations of the Thermodynamic Theory of Irreversible Processes

    Chapter III. The Elementary Kinetic Theory of Gases

    22. The Equation of State of a Perfect Gas

    23. The Maxwellian Velocity Distribution

    A. The Maxwellian Distribution for a Monatomic Gas. Proof of 1860

    B. Numerical Values and Experimental Results

    C. General Remarks on the Energy Distribution. The Boltzmann Factor

    24. Brownian Motion

    25. Statistical Considerations on Paramagnetic Substances

    A. The Classical Langevin Function

    B. Modification of Langevin's Function with the Aid of Quantum Mechanics

    26. The Statistical Significance of the Constants in van der Waals' Equation

    A. The Volume of a Molecule and the Constant b

    B. The van der Waals Cohesion Forces and the Constant a

    27. The Problem of the Mean Free Path

    A. Calculation of the Mean Free Path in One Special Case

    B. Viscosity

    C. Thermal Conductivity

    D. Some General Remarks on the Problems Associated with the Concept of the Mean Free Path

    Chapter IV. General Statistical Mechanics: Combinatorial Method

    28. Liouville's Theorem, Γ-space and μ-space

    A. The Multidimensional Γ-space (Phase Space)

    B. Liouville's Theorem

    C. Equality of Probability for the Perfect Gas

    29. Boltzmann's Principle

    A. Permutability as a Measure of the Probability of a State

    B. The Maximum of Probability as a Measure of Entropy

    C. The Combining of Elementary Cells

    30. Comparison with Thermodynamics

    A. Constant Volume Process

    B. General Process Performed by a Gas in the Absence of External Forces

    C. A Gas in a Field of Forces; the Boltzmann Factor

    D. The Maxwell-Boltzmann Velocity Distribution Law

    E. Gaseous Mixtures

    31. Specific Heat and Energy of Rigid Molecules

    A. The Monatomic Gas

    B. Gas Composed of Diatomic Molecules

    C. The Polyatomic Gas and Kelvin's Clouds

    32. The Specific Heat of Vibrating Molecules and of Solid Bodies

    A. The Diatomic Molecule

    B. Polyatomic Gases

    C. The Solid Body and the Dulong-Petit Rule

    33. The Quantization of Vibrational Energy

    A. The Linear Oscillator

    B. The Solid Body

    C. Generalization to Arbitrary Quantum States

    34. The Quantization of Rotational Energy

    35. Supplement to the Theory of Radiation and to that of Solid Bodies

    A. Method of Natural Vibrations

    B. Debye's Theory of the Specific Heat of a Solid

    36. Partition Function in the Γ-space

    A. The Gibbs Condition

    B. Connection with Boltzmann's Method

    C. Correction for Quantum Effects

    D. Analysis of Gibbs' Hypothesis

    37. Fundamentals of Quantum Statistics

    A. Quantum Statistics of Identical Particles

    B. The Method Due to Darwin and Fowler

    C. Bose-Einstein and Fermi-Dirac Statistics

    D. The Saddle-Point Method

    38. Degenerate Gases

    A. Bose-Einstein and Fermi-Dirac Distribution

    B. Degree of Gas Degeneration

    C. Highly Degenerate Bose-Einstein Gas

    39. Electron Gas in Metals

    A. Introductory Remark to Drude's Method

    B. The Completely Degenerate Fermi-Dirac Gas

    C. Almost Complete Degeneracy

    D. Special Problems

    40. The Mean Square of Fluctuations

    Chapter V. Outline of an Exact Kinetic Theory of Gases

    41. The Maxwell-Boltzmann Collision Equation

    A. Description of a State in the Kinetic Theory of Gases

    B. The Variation of / with Time

    C. The Laws of Elastic Collision

    D. Boltzmann's Collision Integral

    E. Boltzmann's Hypothesis About Molecular Chaos

    42. The H-theorem and Maxwellian Distribution

    A. The H-theorem

    B. Maxwellian Distribution

    C. Equilibrium Distributions

    43. Fundamental Equations of Fluid Dynamics

    A. Series Expansion for the Distribution Function

    B. Maxwell's Transport Equation

    C. Conservation of Mass

    D. Conservation of Momentum

    E. Conservation of Energy

    F. Entropy Theorem

    44. On the Integration of the Collision Equation

    A. Integration with the Aid of Moment Equations

    B. Transformation of the Equations for Moments

    C. Evaluation of Collision Moments

    D. Viscosity and Thermal Conductivity

    45. Conductivity and the Wiedemann-Franz Law

    A. The Collision and Transfer Equations for Electrons in Metals

    B. Approximate Solution of the Collision Equation

    C. Flux of Current and Energy

    D. Ohm's Law

    E. Thermal Conductivity and Absolute Thermal Electromotive Force

    F. The Wiedemann-Franz Law

    Problems for Chapter I

    Problems for Chapter II

    Problems for Chapter III

    Problems for Chapter IV

    Problems for Chapter V

    Hints for the Solution of Problems

    Index

What is statistical mechanics and thermodynamics?

Statistical thermodynamics. The primary goal of statistical thermodynamics (also known as equilibrium statistical mechanics) is to derive the classical thermodynamics of materials in terms of the properties of their constituent particles and the interactions between them.

What is ideal gas in statistical mechanics?

An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics.

What is statistical thermodynamics in chemistry?

Statistical thermodynamics is a theory that uses molecular properties to predict the behavior of macroscopic quantities of compounds.

Who spent much of his life studying statistical mechanics?

Ludwig Boltzmann, who spent much of his life studying statistical mechanics, died in 1906, by his own hand. Paul Ehrenfest, carrying on the work, died similarly in 1933.