《INTRODUCTION TO CHEMICAL PHYSICS》

PART ⅠTHERMODYNAMICS,STATISTICAL MECHANICS,AND KINETIC THEORY1

CHAPTER ⅠHEAT AS A MODE OF MOTION3

INTRODUCTION3

1.THE CONSERVATION OF ENERGY3

2.INTERNAL ENERGY,EXTERNAL WORK,AND HEAT FLOW6

3.THE ENTROPY AND IRREVERSIBLE PROCESSES9

4.THE SECOND LAW OF THERMODYNAMICS12

CHAPTER ⅡTHERMODYNAMICS16

INTRODUCTION16

1.THE EQUATION OF STATE16

2.THE ELEMENTARY PARTIAL DERIVATIVES18

3.THE ENTHALPY,AND HELMHOLTZ AND GIBBS FREE ENERGIES20

4.METHODS OF DERIVING THERMODYNAMIC FORMULAS23

5.GENERAL CLASSIFICATION OF THERMODYNAMIC FORMULAS27

6.COMPARISON OF THERMODYNAMIC AND GAS SCALES OF TEMPERATURE30

CHAPTER ⅢSTATISTICAL MECHANICS32

INTRODUCTION32

1.STATISTICAL ASSEMBLIES AND THE ENTROPY32

2.COMPLEXIONS AND THE PHASE SPACE36

3.CELLS IN THE PHASE SPACE AND THE QUANTUM THEORY38

4.IRREVERSIBLE PROCESSES43

5.THE CANONICAL ASSEMBLY46

CHAPTER ⅣTHE MAXWELL-BOLTZMANN DISTRIBUTION LAW52

INTRODUCTION52

1.THE CANONICAL ASSEMBLY AND THE MAXWELL-BOLTZMANN DISTRIBUTION52

2.MAXWELL’S DISTRIBUTION OF VELOCITIES55

3.THE EQUATION OF STATE AND SPECIFIC HEAT OF PERFECT MONATOMIC GASES58

4.THE PERFECT GAS IN A FORCE FIELD62

CHAPTER ⅤTHE FERMI-DIRAC AND EINSTEIN-BOSE STATISTICS65

INTRODUCTION65

1.THE MOLECULAR PHASE SPACE65

2.ASSEMBLIES IN THE MOLECULAR PHASE SPACE68

3.THE FERMI-DIRAC DISTRIBUTION FUNCTION72

4.THERMODYNAMIC FUNCTIONS IN THE FERMI STATISTICS76

5.THE PERFECT GAS IN THE FERMI STATISTICS80

6.THE EINSTEIN-BOSE DISTRIBUTION LAW83

CHAPTER ⅥTHE KINETIC METHOD AND THE APPROACH TO THERMAL EQUILIBRIUM86

INTRODUCTION86

1.THE EFFECT OF MOLECULAR COLLISIONS ON THE DISTRIBUTION FUNCTION IN THE BOLTZMANN STATISTICS86

2.THE EFFECT OF COLLISIONS ON THE ENTROPY89

3.THE CONSTANTS IN THE DISTRIBUTION EUNCTION92

4.THE KINETIC METHOD FOR FERMI-DIRAC AND EINSTEIN-BOSE STATISTICS96

CHAPTER ⅦFLUCTUATIONS101

INTRODUCTION101

1.ENERGY FLUCTUATIONS IN THE CANONICAL ASSEMBLY101

2.DISTRIBUTION FUNCTIONS FOR FLUCTUATIONS104

3.FLUCTUATIONS OF ENERGY AND DENSITY107

PART ⅡGASES,LIQUIDS,AND SOLIDS113

CHAPTER ⅧTHERMODYNAMIC AND STATISTICAL TREATMENT OF THE PERFECT GAS AND MIXTURES OF GASES115

INTRODUCTION115

1.THERMODYNAMICS OF A PERFECT GAS115

2.THERMODYNAMICS OF A MIXTURE OF PERFECT GASES120

3.STATISTICAL MECHANICS OF A PERFECT GAS IN BOLTZMANN STATISTICS124

CHAPTER ⅨTHE MOLECULAR STRUCTURE AND SPECIFIC HEAT OF POLYATOMIC GASES130

INTRODUCTION130

1.THE STRUCTURE OF DIATOMLC MOLECULES130

2.THE ROTATIONS OF DIATOMLC MOLECULES134

3.THE PARTITION FUNCTION FOR ROTATION138

4.THE VIBRATION OF DIATOMIC MOLECULES140

5.THE PARTITION FUNCTION FOR VIBRATION142

6.THE SPECIFIC HEATS OF POLYATOMIC GASES145

CHAPTER ⅩCHEMICAL EQUILIBRIUM IN GASES150

INTRODUCTION150

1.RATES OF REACTION AND THE MASS ACTION LAW151

2.THE EQUILIBRIUM CONSTANT,AND VAN’T HOFF’S EQUATION154

3.ENERGIES OF ACTIVATION AND THE KINETICS OF REACTIONS158

CHAPTER ⅪTHE EQUILIBRIUM OF SOLIDS,LIQUIDS,AND GASES166

INTRODUCTION166

1.THE COEXISTENCE OF PHASES166

2.THE EQUATION OF STATE169

3.ENTROPY AND GIBBS FREE ENERGY170

4.THE LATENT HEATS AND CLAPEYRON’S EQUATION174

5.THE INTEGRATION OF CLAPEYRON’S EQUATION AND THE VAPOR PRESSURE CURVE176

6.STATISTICAL MECHANICS AND THE VAPOR PRESSURE CURVE178

7.POLYMORPHIC PHASES OF SOLIDS180

CHAPTER ⅫVAN DER WAALS’EQUATION182

INTRODUCTION182

1.VAN DER WAALS’EQUATION182

2.ISOTHERMALS OF VAN DER WAALS’ EQUATION184

3.GIBBS FREE ENERGY AND THE EQUILIBRIUM OF PHASES FOR A VAN DER WAALS GAS187

4.STATISTICAL MECHANICS AND THE SECOND VIRIAL COEFFICIENT190

5.THE ASSUMPTIONS OF VAN DER WAALS’EQUATION194

6.THE JOULE-THoMSON EFFECT AND DEVIATIONS FROM THE PERFECT GAS LAW196

CHAPTER ⅩⅢTHE EQUATION OF STATE OF SOLIDS199

INTRODUCTION199

1.THE EQUATION OF STATE AND SPECIFIC HEAT OF SOLIDS199

2.TIERMODYNAMIC FUNCTIONS FOR SOLIDS205

3.THE STATISTICAL MECHANICS OF SOLIDS211

4.STATISTICAL MECHANICS OF A SYSTEM OF OSCILLATORS215

5.POLYMORPHIC TRANSITIONS220

CHAPTER ⅩⅣDEBYE’S THEORY OF SPECIFIC HEATS222

INTRODUCTION222

1.ELASTIC VIBRATIONS OF A CONTINUOUS SOLID222

2.VIBRATIONAL FREQUENCY SPECTRUM OF A CONTINUOUS SOLID225

3.DEBYE’S THEORY OF SPECIFIC HEATS234

4.DEBYE’S THEORY AND THE PARAMETER γ238

CHAPTER ⅩⅤTHE SPECIFIC HEAT OF COMPOUNDS241

INTRODUCTION241

1.WAVE PROPAGATION IN A ONE-DIMENSIONAL CRYSTAL LATTICE241

2.WAVES IN A ONE-DIMENSIONAL DIATOMIC CRYSTAL247

3.VIBRATION SPECTRA AND SPECIFIC HEATS OF POLYATOMIC CRYSTALS252

4.INFRARED OPTICAL SPECTRA OF CRYSTALS254

CHAPTER ⅩⅥTHE LIQUID STATE AND FUSION256

INTRODUCTION256

1.THE LIQUID PHASE256

2.THE LATENT HEAT Of MELTING258

3.THE ENTROPY OF MELTING260

4.STATISTICAL MECHANICS AND MELTING265

CHAPTER ⅩⅦPHASE EQUILIBRIUM IN BINARY SYSTEMS270

INTRODUCTION270

1.TYPES OF PHASES IN BINARY SYSTEMS271

2.ENERGY AND ENTROPY OF PHASES OF VARIABLE COMPOSITION275

3.THE CONDITION FOR EQUILIBRIUM BETWEEN PHASES278

4.PHASE EQUILIBRIUM BETWEEN MUTUALLY INSOLUBLE SOLIDS283

5.LOWERING OF MELTING POINTS OF SOLUTIONS288

CHAPTER ⅩⅧPHASE CHANGES OF THE SECOND ORDER291

INTRODUCTION291

1.ORDER-DISORDER TRANSITIONS IN ALLOYS293

2.EQUILIBRIUM IN TRANSITIONS OF THE CU-ZN TYPE296

3.TRANSITIONS OF THE CU-ZN TYPE WITH ARBITRARY COMPOSITION301

PART ⅢATOMS,MOLECULES,AND THE STRUCTURE OF MATTER305

CHAPTER ⅩⅨRADIATION AND MATTER307

INTRODUCTION307

1.BLACK BODY RADIATION AND THE STEFAN-BOLTZMANN LAW307

2.THE PLANCK RADIATION LAW313

3.EINSTEIN’S HYPOTHESIS AND THE INTERACTION OF RADIATION AND MATTER316

CHAPTER ⅩⅩIONIZATION AND EXCITATION OF ATOMS321

INTRODUCTION321

1.BOHR’S FREQUENCY CONDITION321

2.THE KINETICS OF ABSORPTION AND EMISSION OF RADIATION324

3.THE KINETICS OF COLLISION AND IONIZATION326

4.THE EQUILLBRIUM OF ATOMS AND ELECTRONS333

CHAPTER ⅩⅪATOMS AND THE PERIODIC TABLE336

INTRODUCTION336

1.THE NUCLEAR ATOM336

2.ELECTRONIC ENERGY LEVELS OF AN ATOM338

3.THE PERIODIC TABLE OF THE ELEMENTS344

CHAPTER ⅩⅫINTERATOMIC AND INTERMOLECULAR FORCES352

INTRODUCTION352

1.THE ELECTROSTATIC INTERACTIONS BETWEEN RIGID ATOMS OR MOLECULES AT LARGE DISTANCES353

2.THE ELECTROSTATIC OR COULOMB INTERACTIONS BETWEEN OVERLAPPING RIGID ATOMS361

3.POLARIZATION AND INTERATOMIC FORCES363

4.EXCHANGE INTERACTIONS BETWEEN ATOMS AND MOLECULES367

5.TYPES OF CHEMICAL SUBSTANCES375

CHAPTER ⅩⅫⅠIONIC CRYSTALS377

INTRODUCTION377

1.STRUCTURE OF SIMPLE BINARY IONIC COMPOUNDS377

2.IONIC RADII382

3.ENERGY AND EQUATION OF STATE OF SIMPLE IONIC LATTICES AT THE ABSOLUTE ZERO385

4.THE EQUATION OF STATE OF THE ALKALI HALIDES390

5.OTHER TYPES OF IONIC CRYSTALS396

6.POLARIZABILITY AND UNSYMMETRICAL STRUCTURES398

CHAPTER ⅩⅪⅤTHE HOMOPOLAR BOND AND MOLECULAR COMPOUNDS400

INTRODUCTION400

1.THE HOMOPOLAR BOND400

2.THE STRUCTURE OF TYPICAL HOMOPOLAR MOLECULES402

3.GASEOUS AND LIQUID PHASES OF HOMOPOLAR SUBSTANCES407

4.MOLECULAR CRYSTALS414

CHAPTER ⅩⅩⅤORGANIC MOLECULES AND THEIR CRYSTALS420

INTRODUCTION420

1.CARBON BONDING IN ALIPATEIC MOLECULES420

2.ORGANIC RADICALS425

3.THE DOUBLE BOND,AND THE AROMATIC COMPOUNDS428

4.ORGANIC CRYSTALS432

CHAPTER ⅩⅩⅥHOMOPOLAR BONDS IN THE SILICATES435

INTRODUCTION435

1.THE SILICON-OXYGEN STRUCTURE435

2.SILICON-OXYGEN CHAINS436

3.SILICON-OXYGEN SHEETS439

4.THREE-DIMENSIONAL SILICON-OXYGEN STRUCTURES441

CHAPTER ⅩⅩⅦMETALS444

INTRODUCTION444

1.CRYSTAL STRUCTURES OF METALS444

2.ENERGY RELATIONS IN METALS450

3.GENERAL PROPERTIES OF METALS456

CHAPTER ⅩⅩⅧTHERMIONIC EMISSION AND THE VOLTA EFFECT460

INTRODUCTION460

1.THE COLLISIONS OF ELECTRONS AND METALS460

2.THE EQUILIBRIUM OF A METAL AND AN ELECTRON GAS463

3.KINETIC DETERMINATION OF THERMIONIC EMISSION464

4.CONTACT DIFFERENCE OF POTENTIAL467

CHAPTER ⅩⅩⅨTHE ELECTRONIC STRUCTURE OF METALS472

INTRODUCTION472

1.THE ELECTRIC FIELD WITHIN A METAL472

2.THE FREE ELECTRON MODEL OF A METAL475

3.THE FREE ELECTRON MODEL AND THERMIONIC EMISSION480

4.TEE FREE ELECTRON MODEL AND ELECTRICAL CONDUCTIVITY484

5.ELECTRONS IN A PERIODIC FORCE FIELD489

6.ENERGY BANDS,CONDUCTORS,AND INSULATORS495

PROBABLE VALUES OF THE GENERAL PHYSICAL CONSTANTS503

SUGGESTED REFERENCES505

INDEX507