atkins physical chemistry seventh editionPDF电子书下载

Part 1 Equilibrium 1

1 The properties of gases 3

The perfect gas 3

1.1 The states of gases 3

1.2 The gas laws 8

Realgases 16

1.3 Molecular interactions 16

1.4 The van der Waals equation 19

1.5 The principle of corresponding states 23

Checklist of key ideas 24

Further reading 25

Exercises 26

Problems 28

2 The First Law：the concepts 30

The basic concepts 30

2.1 Work，heat，and energy 31

2.2 The First Law 33

Work and heat 37

2.3 Expansion work 37

2.4 Heat transactions 41

2.5 Enthalpy 45

2.6 Adiabatic changes 52

Thermochemistry 55

2.7 Standard enthalpy changes 55

2.8 Standard enthalpies of formation 60

2.9 The temperature dependence of reaction enthalpies 62

Checklist of key ideas 64

Further reading 65

Exercises 66

Problems 69

3 The First Law：the machinery 73

State functions and exact differentials 73

3.1 State and path functions 73

3.2 Exact and inexact differentials 74

Thermodynamic consequences 75

3.3 Changes in internal energy 75

3.4 The temperature dependence of the enthalpy 79

3.5 The relation between Cv and Cp 85

Checklist of key ideas 86

Further reading 87

Exercises 87

Problems 88

4 The Second Law：the concepts 90

The direction of spontaneous change 90

4.1 The dispersal of energy 91

4.2 Entropy 92

4.3 Entropy changes accompanying specific processes 100

4.4 The Third Law of thermodynamics 106

Concentrating on the system 108

4.5 The Helmholtz and Gibbs energies 108

4.6 Standard molar Gibbs energies 114

Checklist of key ideas 115

Further reading 116

Exercises 116

Problems 118

5 The Second Law：the machinery 121

Combining the First and Second Laws 121

5.1 The fundamental equation 121

5.2 Properties of the internal energy 122

Properties of the Gibbs energy 124

5.3 General considerations 124

5.4 The variation of the Gibbs energy with temperature 126

5.5 The variation of the Gibbs energy with pressure 127

Checklist of key ideas 130

Further reading 131

Exercises 131

Problems 132

6 Physical transformations of pure substances 135

Phase diagrams 135

6.1 The stabilities of phases 135

6.2 Phase boundaries 136

6.3 Three typical phase diagrams 138

Phase stability and phase transitions 140

6.4 The thermodynamic criterion of equilibrium 141

6.5 The dependence of stability on the conditions 141

6.6 The location of phase boundaries 144

6.7 The Ehrenfest classification of phase transitions 148

The physical liquid surface 150

6.8 Surface tension 150

6.9 Curved surfaces 151

6.10 Capillary action 153

Checklist of key ideas 155

Further reading 156

Exercises 156

Problems 157

7 Simple mixtures 160

The thermodynamic description of mixtures 160

7.1 Partial molar quantities 161

7.2 The thermodynamics of mixing 166

7.3 The chemical potentials of liquids 168

The properties of solutions 172

7.4 Liquid mixtures 173

7.5 Colligative properties 175

Activities 182

7.6 The solvent activity 182

7.7 The solute activity 183

7.8 The activities of regular solutions 186

Checklist of key ideas 187

Further reading 188

Exercises 189

Problems 190

8 Phase diagrams 193

Phases，components，and degrees of freedom 193

8.1 Definitions 193

8.2 The phase rule 195

Two-component systems 198

8.3 Vapour pressure diagrams 198

8.4 Temperature-composition diagrams 202

8.5 Liquid-liquid phase diagrams 204

8.6 Liquid-solid phase diagrams 208

Checklist of key ideas 214

Further reading 214

Exercises 215

Problems 218

9 Chemical equilibrium 222

Spontaneous chemical reactions 222

9.1 The Gibbs energy minimum 222

9.2 The description of equilibrium 226

The response of equilibria to the conditions 233

9.3 How equilibria respond to pressure 234

9.4 The response of equilibria to temperature 235

9.5 The response of equilibria to pH 240

Checklist of key ideas 246

Further reading 246

Exercises 247

Problems 249

10 Equilibrium electrochemistry 252

The thermodynamic properties of ions in solution 252

10.1 Thermodynamic functions of formation 253

10.2 Ion activities 256

Electrochemical cells 262

10.3 Half-reactions and electrodes 263

10.4 Varieties of cells 265

10.5 Standard potentials 270

Applications of standard potentials 274

10.6 The electrochemical series 274

10.7 The measurement of pH and pKa 277

10.8 Thermodynamic functions 280

Checklist of key ideas 282

Further reading 283

Exercises 284

Problems 286

Part 2 Structure 291

11 Quantum theory：introduction and principles 293

The origins of quantum mechanics 293

11.1 The failures of classical physics 294

11.2 Wave-particle duality 299

The dynamics of microscopic systems 304

11.3 The Schrodinger equation 304

11.4 The Born interpretation of the wavefunction 306

Quantum mechanical principles 309

11.5 The information in a wavefunction 310

11.6 The uncertainty principle 317

Checklist of key ideas 320

Further reading 321

Exercises 322

Problems 323

12 Quantum theory：techniques and applications 325

Translational motion 325

12.1 A particle in a box 326

12.2 Motion in two and more dimensions 331

12.3 Tunnelling 334

Vibrational motion 338

12.4 The energy levels 338

12.5 The wavefunctions 339

Rotational motion 345

12.6 Rotation in two dimensions：the particle on a ring 345

12.7 Rotation in three dimensions：the particle on a sphere 349

12.8 Spin 354

Techniques of approximation 355

12.9 Time-independent perturbation theory 355

12.10 Time-dependent perturbation theory 358

Checklist of key ideas 360

Further reading 361

Exercises 361

Problems 363

13 Atomic structure and atomic spectra 365

The structure and spectra of hydrogenic atoms 366

13.1 The structure of hydrogenic atoms 367

13.2 Atomic orbitals and their energies 372

13.3 Spectroscopic transitions and selection rules 381

The structures of many-electron atoms 383

13.4 The orbital approximation 384

13.5 Self-consistent field orbitals 392

The spectra of complex atoms 393

13.6 Quantum defects and ionization limits 395

13.7 Singlet and triplet states 395

13.8 Spin-orbit coupling 396

13.9 Term symbols and selection rules 399

Checklist of key ideas 404

Further reading 405

Exercises 406

Problems 408

14 Molecular structure 410

The Born-Oppenheimer approximation 410

Valence-bond theory 411

14.1 The hydrogen molecule 411

14.2 Homonuclear diatomic molecules 413

14.3 Polyatomic molecules 414

Molecular orbital theory 417

14.4 The hydrogen molecule-ion 418

14.5 The structures of diatomic molecules 422

14.6 Heteronuclear diatomic molecules 427

Molecular orbitals for polyatomic systems 432

14.7 The Huckel approximation 433

14.8 Extended Huckel theory 438

14.9 Self-consistent field calculations 441

Checklist of key ideas 446

Further reading 447

Exercises 448

Problems 450

15 Molecular symmetry 453

The symmetry elements of objects 453

15.1 Operations and symmetry elements 454

15.2 The symmetry classification of molecules 456

15.3 Some immediate consequences of symmetry 459

Character tables 463

15.4 Character tables and symmetry labels 463

15.5 Vanishing integrals and orbital overlap 469

15.6 Vanishing integrals and selection rules 474

Checklist of key ideas 476

Further reading 477

Exercises 477

Problems 478

16 Spectroscopy 1：rotational and vibrational spectra 481

General features of spectroscopy 483

16.1 Experimental techniques 483

16.2 The intensities of spectral lines 491

16.3 Linewidths 495

Pure rotation spectra 497

16.4 Moments of inertia 497

16.5 The rotational energy levels 500

16.6 Rotational transitions 504

16.7 Rotational Raman spectra 507

16.8 Nuclear statistics and rotational states 510

The vibrations of diatomic molecules 511

16.9 Molecular vibrations 512

16.10 Selection rules 513

16.11 Anharmonicity 515

16.12 Vibration-rotation spectra 517

16.13 Vibrational Raman spectra of diatomic molecules 519

The vibrations of polyatomic molecules 520

16.14 Normal modes 520

16.15 Infrared absorption spectra of polyatomic molecules 523

16.16 Vibrational Raman spectra of polyatomic molecules 524

16.17 Symmetry aspects of molecular vibrations 526

Checklist of key ideas 529

Further reading 531

Exercises 532

Problems 534

17 Spectroscopy 2：electronic transitions 538

The characteristics of electronic transitions 539

17.1 The electronic spectra of diatomic molecules 539

17.2 The electronic spectra of polyatomic molecules 545

The fates of electronically excited states 550

17.3 Fluorescence and phosphorescence 550

17.4 Dissociation and predissociation 552

Lasers 553

17.5 General principles of laser action 554

17.6 Practical lasers 558

17.7 Applications of lasers in chemistry 562

Photoelectron spectroscopy 568

17.8 The technique 568

17.9 Ultraviolet photoelectron spectroscopy 569

17.10 X-ray photoelectron spectroscopy 570

Checklist of key ideas 571

Further reading 573

Exercises 574

Problems 575

18 Spectroscopy 3：magnetic resonance 579

The effect of magnetic fields on electrons and nuclei 579

18.1 The energies of electrons in magnetic fields 580

18.2 The energies of nuclei in magnetic fields 581

18.3 Magnetic resonance spectroscopy 583

Nuclear magnetic resonance 583

18.4 The NMR spectrometer 584

18.5 The chemical shift 585

18.6 The fine structure 590

Pulse techniques in NMR 599

18.7 The magnetization vector 599

18.8 Linewidths and rate processes 602

18.9 Spin decoupling 607

18.10 The nuclear Overhauser effect 608

18.11 Two-dimensional NMR 610

18.12 Solid-state NMR 614

Electron spin resonance 615

18.13 The ESR spectrometer 615

18.14 The g-value 617

18.15 Hyperfine structure 618

Checklist of key ideas 621

Further reading 623

Exercises 624

Problems 626

19 Statistical thermodynamics：the concepts 628

The distribution of molecular states 629

19.1 Configurations and weights 629

19.2 The molecular partition function 634

The internal energy and the entropy 639

19.3 The internal energy 640

19.4 The statistical entropy 642

The canonical partition function 647

19.5 The canonical ensemble 647

19.6 The thermodynamic information in the partition function 648

19.7 Independent molecules 649

Checklist of key ideas 652

Further reading 652

Exercises 653

Problems 654

20 Statistical thermodynamics：the machinery 656

Fundamental relations 656

20.1 The thermodynamic functions 656

20.2 The molecular partition function 658

Using statistical thermodynamics 667

20.3 Mean energies 667

20.4 Heat capacities 669

20.5 Equations of state 671

20.6 Residual entropies 672

20.7 Equilibrium constants 674

Checklist of key ideas 681

Further reading 682

Exercises 682

Problems 683

21 Molecular interactions 686

Electric properties of molecules 686

21.1 Electric dipole moments 686

21.2 Polarizabilities 689

21.3 Relative permittivities 692

21.4 Refractive index 694

Interactions between molecules 696

21.5 Interactions between dipoles 698

21.6 Repulsive and total interactions 705

21.7 Molecular interactions in gases 706

21.8 Molecular interactions in liquids 709

Checklist of key ideas 713

Further reading 715

Exercises 715

Problems 716

22 Macromolecules and aggregates 719

Structure and dynamics 720

22.1 The different levels of structure 720

22.2 Random coils 721

22.3 The structure of proteins 725

22.4 The structure of nucleic acids 729

22.5 The stability of biological polymers 731

Determination of size and shape 732

22.6 Mean molar masses 732

22.7 Mass spectrometry 735

22.8 Laser light scattering 736

22.9 Ultracentrifugation 742

22.10 Electrophoresis 745

22.11 Size-exclusion chromatography 747

22.12 Viscosity 748

Self-assembly 750

22.13 Colloids 752

22.14 Micelles and biological membranes 754

22.15 Surface films 757

Checklist of key ideas 760

Further reading 762

Exercises 763

Problems 764

23 The solid state 767

Crystal lattices 767

23.1 Lattices and unit cells 767

23.2 The identification of lattice planes 770

23.3 The investigation of structure 772

23.4 Neutron and electron diffraction 783

Crystal structure 784

23.5 Metallic solids 784

23.6 Ionic solids 786

23.7 Molecular solids and covalent networks 789

The properties of solids 791

23.8 Mechanical properties 791

23.9 Electrical properties 795

23.10 Magnetic properties 801

Checklist of key ideas 805

Further reading 807

Exercises 808

Problems 810

Part 3 Change 813

24 Molecules in motion 815

Molecular motion in gases 815

24.1 The kinetic model of gases 816

24.2 Collisions with walls and surfaces 822

24.3 The rate of effusion 824

24.4 Transport properties of a perfect gas 826

Molecular motion in liquids 832

24.5 Experimental results 832

24.6 The conductivities of electrolyte solutions 833

24.7 The mobilities of ions 835

24.8 Conductivities and ion-ion interactions 841

Diffusion 842

24.9 The thermodynamic view 842

24.10 The diffusion equation 846

24.11 Diffusion probabilities 852

24.12 The statistical view 853

Checklist of key ideas 854

Further reading 856

Exercises 856

Problems 859

25 The rates of chemical reactions 862

Empirical chemical kinetics 862

25.1 Experimental techniques 863

25.2 The rates of reactions 866

25.3 Integrated rate laws 871

25.4 Reactions approaching equilibrium 876

25.5 The temperature dependence of reaction rates 879

Accounting for the rate laws 882

25.6 Elementary reactions 882

25.7 Consecutive elementary reactions 883

25.8 Unimolecular reactions 890

Checklist of key ideas 892

Further reading 893

Exercises 894

Problems 896

26 The kinetics of complex reactions 899

Chain reactions 899

26.1 The rate laws of chain reactions 900

26.2 Explosions 902

Polymerization kinetics 904

26.3 Stepwise polymerization 904

26.4 Chain polymerization 906

Homogeneous catalysis 908

26.5 Features of homogeneous catalysis 909

26.6 Enzymes 909

Oscillating reactions 914

26.7 Autocatalysis 915

26.8 Autocatalytic mechanisms of oscillating reactions 916

26.9 Bistability 917

26.10 Chemical chaos 919

Photochemistry 920

26.11 Kinetics of photophysical and photochemical processes 927

26.12 Complex photochemical processes 934

Checklist of key ideas 936

Further reading 937

Exercises 938

Problems 940

27 Molecular reaction dynamics 944

Reactive encounters 944

27.1 Collision theory 945

27.2 Diffusion-controlled reactions 951

27.3 The material balance equation 954

Activated complex theory 956

27.4 The Eyring equation 956

27.5 Thermodynamic aspects 960

The dynamics of molecular collisions 963

27.6 Reactive collisions 963

27.7 Potential energy surfaces 966

27.8 Some results from experiments and calculations 967

Checklist of key ideas 971

Further reading 972

Exercises 973

Problems 974

28 Processes at solid surfaces 977

The growth and structure of solid surfaces 977

28.1 Surface growth 977

28.2 Surface composition 979

The extent of adsorption 987

28.3 Physisorption and chemisorption 988

28.4 Adsorption isotherms 989

28.5 The rates of surface processes 994

Catalytic activity at surfaces 999

28.6 Adsorption and catalysis 999

28.7 Examples of catalysis 1001

Checklist of key ideas 1006

Further reading 1007

Exercises 1008

Problems 1009

29 Dynamics of electron transfer 1013

Electron transfer in homogeneous systems 1014

29.1 Theory of electron transfer processes 1014

29.2 Experimental results 1018

Electron transfer in heterogeneous systems 1021

29.3 The electrode-solution interface 1021

29.4 The rate of charge transfer 1024

29.5 Voltammetry 1031

29.6 Electrolysis 1036

29.7 Working galvanic cells 1037

29.8 Corrosion 1039

Checklist of key ideas 1041

Further reading 1043

Exercises 1043

Problems 1045

Further information 1 Mathematical techniques 1048

Basic procedures 1048

1.1 Logarithms and exponentials 1048

1.2 Combinatorial functions 1048

1.3 Complex numbers and complex functions 1049

1.4 Vectors 1050

Calculus 1051

1.5 Differentiation and integration 1051

1.6 Power series and Taylor expansions 1052

1.7 Partial derivatives 1053

1.8 Undetermined multipliers 1054

1.9 Differential equations 1055

Matrix algebra 1057

1.10 Matrix addition and multiplication 1058

1.11 Simultaneous equations 1059

1.12 Eigenvalue equations 1060

Further reading 1061

Further information 2 Essential concepts of physics 1062

Energy 1062

2.1 Kinetic and potential energy 1062

2.2 Energy units 1062

Classical mechanics 1063

2.3 The trajectory in terms of the energy 1063

2.4 Newton’s second law 1064

2.5 Rotational motion 1064

2.6 The harmonic oscillator 1065

Waves 1066

2.7 The electromagnetic field 1066

2.8 Features of electromagnetic radiation 1067

Electrostatics 1068

2.9 The Coulomb interaction 1068

2.10 The Coulomb potential 1068

2.11 The strength of the electric field 1069

2.12 The dipole-dipole interaction 1069

2.13 Electric current and power 1070

Further reading 1070

Data section 1071

Answers to exercises 1112

Answers to problems 1124

Index 1137