物理化学 原书第6版 英文【2025|PDF|Epub|mobi|kindle电子书版本百度云盘下载】

物理化学 原书第6版 英文PDF格式电子书版下载

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Chapter 1 THERMODYNAMICS1

1.1 Physical Chemistry1

1.2 Thermodynamics3

1.3 Temperature6

1.4 The Mole9

1.5 Ideal Gases10

1.6 Differential Calculus17

1.7 Equations of State22

1.8 Integral Calculus25

1.9 Study Suggestions30

1.10 Summary32

Chapter 2 THE FIRST LAW OF THERMODYNAMICS37

2.1 Classical Mechanics37

2.2 P-V Work42

2.3 Heat46

2.4 The First Law of Thermodynamics47

2.5 Enthalpy52

2.6 Heat Capacities53

2.7 The Joule and Joule-Thomson Experiments55

2.8 Perfect Gases and the First Law58

2.9 Calculation of First-Law Quantities62

2.10 State Functions and Line Integrals65

2.11 The Molecular Nature of Internal Energy67

2.12 Problem Solving70

2.13 Summary73

Chapter 3 THE SECOND LAW OF THERMODYNAMICS78

3.1 The Second Law of Thermodynamics78

3.2 Heat Engines80

3.3 Entropy85

3.4 Calculation of Entropy Changes87

3.5 Entropy,Reversibility,and Irreversibility93

3.6 The Thermodynamic Temperature Scale96

3.7 What Is Entropy?97

3.8 Entropy,Time,and Cosmology103

3.9 Summary104

Chapter 4 MATERIAL EQUILIBRIUM109

4.1 Material Equilibrium109

4.2 Entropy and Equilibrium110

4.3 The Gibbs and Helmholtz Energies112

4.4 Thermodynamic Relations for a System in Equilibrium115

4.5 Calculation of Changes in State Functions123

4.6 Chemical Potentials and Material Equilibrium125

4.7 Phase Equilibrium129

4.8 Reaction Equilibrium132

4.9 Entropy and Life134

4.10 Summary135

Chapter 5 STANDARD THERMODYNAMIC FUNCTIONS OF REACTION140

5.1 Standard States of Pure Substances140

5.2 Standard Enthalpy of Reaction141

5.3 Standard Enthalpy of Formation142

5.4 Determination of Standard Enthalpies of Formation and Reaction143

5.5 Temperature Dependence of Reaction Heats151

5.6 Use of a Spreadsheet to Obtain a Polynomial Fit153

5.7 Conventional Entropies and the Third Law155

5.8 Standard Gibbs Energy of Reaction161

5.9 Thermodynamics Tables163

5.10 Estimation of Thermodynamic Properties165

5.11 The Unattainability of Absolute Zero168

5.12 Summary169

Chapter 6 REACTION EQUILIBRIUM IN IDEAL GAS MIXTURES174

6.1 Chemical Potentials in an Ideal Gas Mixture175

6.2 Ideal-Gas Reaction Equilibrium177

6.3 Temperature Dependence of the Equilibrium Constant182

6.4 Ideal-Gas Equilibrium Calculations186

6.5 Simultaneous Equilibria191

6.6 Shifts in Ideal-Gas Reaction Equilibria194

6.7 Summary198

Chapter 7 ONE-COMPONENT PHASE EQUILIBRIUM AND SURFACES205

7.1 The Phase Rule205

7.2 One-Component Phase Equilibrium210

7.3 The Clapeyron Equation214

7.4 Solid-Solid Phase Transitions221

7.5 Higher-Order Phase Transitions225

7.6 Surfaces and Nanoparticles227

7.7 The Interphase Region227

7.8 Curved Interfaces231

7.9 Colloids234

7.10 Summary237

Chapter 8 REAL GASES244

8.1 Compression Factors244

8.2 Real-Gas Equations of State245

8.3 Condensation247

8.4 Critical Data and Equations of State249

8.5 Calculation of Liquid-Vapor Equilibria252

8.6 The Critical State254

8.7 The Law of Corresponding States255

8.8 Differences Between Real-Gas and Ideal-Gas Thermodynamic Properties256

8.9 Taylor Series257

8.10 Summary259

Chapter 9 SOLUTIONS263

9.1 Solution Composition263

9.2 Partial Molar Quantities264

9.3 Mixing Quantities270

9.4 Determination of Partial Molar Quantities272

9.5 Ideal Solutions275

9.6 Thermodynamic Properties of Ideal Solutions278

9.7 Ideally Dilute Solutions282

9.8 Thermodynamic Properties of Ideally Dilute Solutions283

9.9 Summary287

Chapter 10 NONIDEAL SOLUTIONS294

10.1 Activities and Activity Coefficients294

10.2 Excess Functions297

10.3 Determination of Activities and Activity Coefficients298

10.4 Activity Coefficients on the Molality and Molar Concentration Scales305

10.5 Solutions of Electrolytes306

10.6 Determination of Electrolyte Activity Coefficients310

10.7 The Debye-Hückel Theory of Electrolyte Solutions311

10.8 Ionic Association315

10.9 Standard-State Thermodynamic Properties of Solution Components318

10.10 Nonideal Gas Mixtures321

10.11 Summary324

Chapter 11 REACTION EQUILIBRIUM IN NONIDEAL SYSTEMS330

11.1 The Equilibrium Constant330

11.2 Reaction Equilibrium in Nonelectrolyte Solutions331

11.3 Reaction Equilibrium in Electrolyte Solutions332

11.4 Reaction Equilibria Involving Pure Solids or Pure Liquids337

11.5 Reaction Equilibrium in Nonideal Gas Mixtures340

11.6 Computer Programs for Equilibrium Calculations340

11.7 Temperature and Pressure Dependences of the Equilibrium Constant341

11.8 Summary of Standard States343

11.9 Gibbs Energy Change for a Reaction343

11.10 Coupled Reactions345

11.11 Summary347

Chapter 12 MULTICOMPONENT PHASE EQUILIBRIUM351

12.1 Colligative Properties351

12.2 Vapor-Pressure Lowering351

12.3 Freezing-Point Depression and Boiling-Point Elevation352

12.4 Osmotic Pressure356

12.5 Two-Component Phase Diagrams361

12.6 Two-Component Liquid-Vapor Equilibrium362

12.7 Two-Component Liquid-Liquid Equilibrium370

12.8 Two-Component Solid-Liquid Equilibrium373

12.9 Structure of Phase Diagrams381

12.10 Solubility381

12.11 Computer Calculation of Phase Diagrams383

12.12 Three-Component Systems385

12.13 Summary387

Chapter 13 ELECTROCHEMICAL SYSTEMS395

13.1 Electrostatics395

13.2 Electrochemical Systems398

13.3 Thermodynamics of Electrochemical Systems401

13.4 Galvanic Cells403

13.5 Types of Reversible Electrodes409

13.6 Thermodynamics of Galvanic Cells412

13.7 Standard Electrode Potentials417

13.8 Liquid-Junction Potentials421

13.9 Applications of EMF Measurements422

13.10 Batteries426

13.11 Ion-Selective Membrane Electrodes427

13.12 Membrane Equilibrium429

13.13 The Electrical Double Layer430

13.14 Dipole Moments and Polarization431

13.15 Bioelectrochemistry435

13.16 Summary436

Chapter 14 KINETIC THEORY OF GASES442

14.1 Kinetic-Molecular Theory of Gases442

14.2 Pressure of an Ideal Gas443

14.3 Temperature446

14.4 Distribution of Molecular Speeds in an Ideal Gas448

14.5 Applications of the Maxwell Distribution457

14.6 Collisions with a Wall and Effusion460

14.7 Molecular Collisions and Mean Free Path462

14.8 The Barometric Formula465

14.9 The Boltzmann Distribution Law467

14.10 Heat Capacities of Ideal Polyatomic Gases467

14.11 Summary469

Chapter 15 TRANSPORT PROCESSES474

15.1 Kinetics474

15.2 Thermal Conductivity475

15.3 Viscosity479

15.4 Diffusion and Sedimentation487

15.5 Electrical Conductivity493

15.6 Electrical Conductivity of Electrolyte Solutions496

15.7 Summary509

Chapter 16 REACTION KINETICS515

16.1 Reaction Kinetics515

16.2 Measurement of Reaction Rates519

16.3 Integration of Rate Laws520

16.4 Finding the Rate Law526

16.5 Rate Laws and Equilibrium Constants for Elementary Reactions530

16.6 Reaction Mechanisms532

16.7 Computer Integration of Rate Equations539

16.8 Temperature Dependence of Rate Constants541

16.9 Relation Between Rate Constants and Equilibrium Constants for Composite Reactions546

16.10 The Rate Law in Nonideal Systems547

16.11 Unimolecular Reactions548

16.12 Trimolecular Reactions550

16.13 Chain Reactions and Free-Radical Polymerizations551

16.14 Fast Reactions556

16.15 Reactions in Liquid Solutions560

16.16 Catalysis564

16.17 Enzyme Catalysis568

16.18 Adsorption of Gases on Solids570

16.19 Heterogeneous Catalysis575

16.20 Summary579

Chapter 17 QUANTUM MECHANICS590

17.1 Blackbody Radiation and Energy Quantization591

17.2 The Photoelectric Effect and Photons593

17.3 The Bohr Theory of the Hydrogen Atom594

17.4 The de Broglie Hypothesis595

17.5 The Uncertainty Principle597

17.6 Quantum Mechanics599

17.7 The Time-Independent Schr？dinger Equation604

17.8 The Particle in a One-Dimensional Box606

17.9 The Particle in a Three-Dimensional Box610

17.10 Degeneracy612

17.11 Operators613

17.12 The One-Dimensional Harmonic Oscillator619

17.13 Two-Particle Problems621

17.14 The Two-Particle Rigid Rotor622

17.15 Approximation Methods623

17.16 Hermitian Operators627

17.17 Summary630

Chapter 18 ATOMIC STRUCTURE637

18.1 Units637

18.2 Historical Background637

18.3 The Hydrogen Atom638

18.4 Angular Momentum647

18.5 Electron Spin649

18.6 The Helium Atom and the Spin-Statistics Theorem650

18.7 Total Orbital and Spin Angular Momenta656

18.8 Many-Electron Atoms and the Periodic Table658

18.9 Hartree-Fock and Configuration-Interaction Wave Functions663

18.10 Summary666

Chapter 19 MOLECULAR ELECTRONIC STRUCTURE672

19.1 Chemical Bonds672

19.2 The Born-Oppenheimer Approximation676

19.3 The Hydrogen Molecule Ion681

19.4 The Simple MO Method for Diatomic Molecules686

19.5 SCF and Hartree-Fock Wave Functions692

19.6 The MO Treatment of Polyatomic Molecules693

19.7 The Valence-Bond Method702

19.8 Calculation of Molecular Properties704

19.9 Accurate Calculation of Molecular Electronic Wave Functions and Properties708

19.10 Density-Functional Theory(DFT)711

19.11 Semiempirical Methods717

19.12 Performing Quantum Chemistry Calculations720

19.13 The Molecular-Mechanics(MM)Method723

19.14 Future Prospects727

19.15 Summary727

Chapter 20 SPECTROSCOPY AND PHOTOCHEMISTRY734

20.1 Electromagnetic Radiation734

20.2 Spectroscopy737

20.3 Rotation and Vibration of Diatomic Molecules743

20.4 Rotational and Vibrational Spectra of Diatomic Molecules750

20.5 Molecular Symmetry756

20.6 Rotation of Polyatomic Molecules758

20.7 Microwave Spectroscopy761

20.8 Vibration of Polyatomic Molecules763

20.9 Infrared Spectroscopy766

20.10 Raman Spectroscopy771

20.11 Electronic Spectroscopy774

20.12 Nuclear-Magnetic-Resonance Spectroscopy779

20.13 Electron-Spin-Resonance Spectroscopy793

20.14 Optical Rotatory Dispersion and Circular Dichroism794

20.15 Photochemistry796

20.16 Group Theory800

20.17 Summary811

Chapter 21 STATISTICAL MECHANICS820

21.1 Statistical Mechanics820

21.2 The Canonical Ensemble821

21.3 Canonical Partition Function for a System of Noninteracting Particles830

21.4 Canonical Partition Function of a Pure Ideal Gas834

21.5 The Boltzmann Distribution Law for Noninteracting Molecules836

21.6 Statistical Thermodynamics of Ideal Diatomic and Monatomic Gases840

21.7 Statistical Thermodynamics of Ideal Polyatomic Gases851

21.8 Ideal-Gas Thermodynamic Properties and Equilibrium Constants854

21.9 Entropy and the Third Law of Thermodynamics858

21.10 Intermolecular Forces861

21.11 Statistical Mechanics of Fluids866

21.12 Summary870

Chapter 22 THEORIES OF REACTION RATES877

22.1 Hard-Sphere Collision Theory of Gas-Phase Reactions877

22.2 Potential-Energy Surfaces880

22.3 Molecular Reaction Dynamics887

22.4 Transition-State Theory for Ideal-Gas Reactions892

22.5 Thermodynamic Formulation of TST for Gas-Phase Reactions902

22.6 Unimolecular Reactions904

22.7 Trimolecular Reactions906

22.8 Reactions in Solution906

22.9 Summary911

Chapter 23 SOLIDS AND LIQUIDS913

23.1 Solids and Liquids913

23.2 Polymers914

23.3 Chemical Bonding in Solids914

23.4 Cohesive Energies of Solids916

23.5 Theoretical Calculation of Cohesive Energies918

23.6 Interatomic Distances in Crystals921

23.7 Crystal Structures922

23.8 Examples of Crystal Structures928

23.9 Determination of Crystal Structures931

23.10 Determination of Surface Structures937

23.11 Band Theory of Solids939

23.12 Statistical Mechanics of Crystals941

23.13 Defects in Solids946

23.14 Liquids947

23.15 Summary951

Bibliography955

Appendix959

Answers to Selected Problems961

Index967