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An Introduction to Statistical Thermodynamics

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567

ISBN-13:
9780486130903
Veröffentl:
2012
Seiten:
544
Autor:
Terrell L. Hill
Serie:
Dover Books on Physics
eBook Typ:
EPUB
eBook Format:
EPUB
Kopierschutz:
2 - DRM Adobe
Sprache:
Englisch
Beschreibung:

"A large number of exercises of a broad range of difficulty make this book even more useful...a good addition to the literature on thermodynamics at the undergraduate level." ? Philosophical MagazineAlthough written on an introductory level, this wide-ranging text provides extensive coverage of topics of current interest in equilibrium statistical mechanics. Indeed, certain traditional topics are given somewhat condensed treatment to allow room for a survey of more recent advances.The book is divided into four major sections. Part I deals with the principles of quantum statistical mechanics and includes discussions of energy levels, states and eigenfunctions, degeneracy and other topics. Part II examines systems composed of independent molecules or of other independent subsystems. Topics range from ideal monatomic gas and monatomic crystals to polyatomic gas and configuration of polymer molecules and rubber elasticity. An examination of systems of interacting molecules comprises the nine chapters in Part Ill, reviewing such subjects as lattice statistics, imperfect gases and dilute liquid solutions. Part IV covers quantum statistics and includes sections on Fermi-Dirac and Bose-Einstein statistics, photon gas and free-volume theories of quantum liquids.Each chapter includes problems varying in difficulty ? ranging from simple numerical exercises to small-scale "research" propositions. In addition, supplementary reading lists for each chapter invite students to pursue the subject at a more advanced level. Readers are assumed to have studied thermodynamics, calculus, elementary differential equations and elementary quantum mechanics.Because of the flexibility of the chapter arrangements, this book especially lends itself to use in a one-or two-semester graduate course in chemistry, a one-semester senior or graduate course in physics or an introductory course in statistical mechanics.
PART I. PRINCIPLES OF QUANTUM STATISTICAL MECHANICSCHAPTER 1. STATISTICAL-MECHANICAL ENSEMBLES AND THERMODYNAMICS1-1 Introduction1-2 Ensembles and postulates1-3 Canonical ensemble1-4 Canonical ensemble and thermodynamics1-5 Grand canonical ensemble1-6 Micronomical ensemble1-7 Other ensemblesCHAPTER 2. FURTHER DISCUSSION OF ENSEMBLES AND THERMODYNAMICS2-1 Fluctuations2-2 Thermodynamic equivalence of ensembles2-3 Second law of thermodynamics2-4 Third law of thermodynamicsPART II. SYSTEMS COMPOSED OF INDEPENDENT MOLECULES OR SUBSYSTEMS AND INDISTINGUISHABLE MOLECULES OR SUBSYSTEMSCHAPTER 3. GENERAL RELATIONS FOR INDEPENDENT DISTINGUISHABLE AND INDISTINGUISHABLE MOLECULES OR SUBSYSTEMS3-1 Independent and distinguishable molecules or subsystems3-2 Independent and indistinguishable molecules or subsystems3-3 Energy distribution among independent molecules3-4 "Ensembles" of small, independent "systems"CHAPTER 4. IDEAL MONATOMIC GAS4-1 Energy levels and canonical ensemble partion function4-2 Thermodynamic functions4-3 Grand ensemble and others4-4 Internal degrees of freedomCHAPTER 5. MONATOMIC CRYSTALS5-1 Einstien model of a monatomic crystal5-2 General treatment of molecular vibrations in a monatomic crystal5-3 The Debye approximation5-4 Exact treatments of the frequency distribution problemCHAPTER 6. CLASSICAL STATISTICAL MECHANICS6-1 Introductory examples6-2 More general systems6-3 Phase space and ensembles in classical statistics6-4 Maxwell-Boltzmann velocity distribution"CHAPTER 7. INTRODUCTION TO LATTICE STATISTICS: ADSORPTION, BINDING, AND TITRATION PROBLEMS"7-1 Ideal lattice gas (Langmiur adsorption theory)7-2 Grand partition function for a single independent site or subsystem7-3 Systems composed of independent and indistinguishable subsystems7-4 Elasticity of and adsorption on a linear polymer chainCHAPTER 8. IDEAL DIATOMIC GAS8-1 Independence of degrees of freedom8-2 Vibration8-3 Rotation8-4 Thermodynamic functionsCHAPTER 9. IDEAL POLYATOMIC GAS9-1 Potential energy surface9-2 Vibration9-3 Rotation9-4 Thermodynamic functions9-5 Hindred internal rotation in ethane9-6 Hindred translation on a surfaceCHAPTER 10. CHEMICAL EQUILIBRIUM IN IDEAL GAS MIXTURES10-1 General relations10-2 Statistical derivation in a special case10-3 Fluctuations in a simple chemical equilibrium10-4 Examples of chemical equilibriaCHAPTER 11. THE RATE OF CHEMICAL REACTIONS IN IDEAL GAS MIXTURES11-1 Potential surfaces11-2 Absolute rate theory11-3 A nonchemical application of the Eyring theoryCHAPTER 12. IDEAL GAS IN AN ELECTRIC FIELD12-1 Thermodynamic background12-2 Statistical-mechanical background12-3 Dilute gas in an electric field12-4 Lattice of noninteracting magnetic dipolesCHAPTER 13. CONFIGURATION OF POLYMER MOLECULES AND RUBBER ELASTICITY13-1 Freely jointed chain13-2 Gaussian probability distribution for free polymer molecules13-3 Rubber elasticityPART III. SYSTEMS OF INTERACTING MOLECULES CHAPTER 14. LATTICE STATISTICS14-1 One-dimensional lattice gas (adsorption) 14-2 Elasticity of a linear polymer chain14-3 Two-dimensional square lattice 14-4 Bragg-Williams approximation 14-5 Quasi-chemical approximation14-6 First-order phase transitions CHAPTER 15. IMPERFECT GASES15-1 Virial expansion of a one-component gas15-2 One-component classical monatomic gas15-3 Two-component imperfect gas15-4 Imperfect gas near a surface 15-5 Imperfect gas in an electric field CHAPTER 16. APPROXIMATE CELL AND HOLE THEORIES OF THE LIQUID STATE 16-1 The van der Waals equation of state16-2 Cell theories of liquids16-3 Hole theories of liquids16-4 Law of corresponding states CHAPTER 17. DISTRIBUTION FUNCTIONS IN CLASSICAL MONATOMIC FLUIDS 17-1 Radial distribution function17-2 Relation of thermodynamic functions to g( r )17-3 Integral equation for g(r;x) 17-4 Formal definition of distribution functions17-5 Surface tension CHAPTER 18. DILUTE ELECTROLYTE SOLUTIONS AND PLASMAS18-1 Debye-Hückel theory18-2 Kirkwood theory of solutions 18-3 Electrolyte solutionsCHAPTER 19. DILUTE LIQUID SOLUTIONS 19-1 McMillan-Mayer solution theory 19-2 Applications of the McMillan-Mayer theory 19-3 Constant pressure solution theory CHAPTER 20. THEORY OF CONCENTRATED SOLUTIONS 20-1 Lattice theory of solutions20-2 Cell theories of binary solutions 20-3 "Random-mixing, corresponding-states theory "20-4 Conformal solution theoryCHAPTER 21. POLYMER AND POLYELECTROLYTE SOLUTIONS AND GELS21-1 Wall theory of rubber elasticity21-2 Flory-Hugging polymer solution theory21-3 Swelling of polymer gels21-4 Swelling of polyelectrolyte gels21-5 Isolated polymer or polyelectrolyte molecules in solution21-6 Second Virial coefficient in polymer and polyelectrolyte solutionsCHAPTER 22. QUANTUM STATISTICS22-1 Introduction to Fermi-Dirac and Bose-Einstein statistics22-2 Ideal Fermi-Dirac gas; electrons in metals22-3 Ideal Bose-Einstein gas; helium22-4 Blackbody radiation (photon gas)22-5 Quantum statistics with intermolecular interactions22-6 The factors hn and N! in classical statistics22-7 Free-volume theories of quantum liquids22-8 Gas of symmetrical diatomic modules at low temperaturesAPPENDIX I. Natural ConstantsAPPENDIX II. Maximum-Term MethodAPPENDIX III. Method of Undetermined MultipliersAPPENDIX IV. The Lennard-Jones PotentialAPPENDIX V. Normal Coordinate Analysis in a Special CaseAPPENDIX VI. Vibrational Frequency Distribution in a Solid ContinuumAPPENDIX VII. Generalized CoordinatesINDEX

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