《atkins physical chemistry seventh edition P1150》求取 ⇩

Part 1Equilibrium1

1The properties of gases3

The perfect gas3

1.1The states of gases3

1.2 The gas laws8

Realgases16

1.3Molecular interactions16

1.4 The van der Waals equation19

1.5 The principle of corresponding states23

Checklist of key ideas24

Further reading25

Exercises26

Problems28

2The First Law:the concepts30

The basic concepts30

2.1Work,heat,and energy31

2.2 The First Law33

Work and heat37

2.3Expansion work37

2.4 Heat transactions41

2.5 Enthalpy45

2.6 Adiabatic changes52

Thermochemistry55

2.7Standard enthalpy changes55

2.8 Standard enthalpies of formation60

2.9 The temperature dependence of reaction enthalpies62

Checklist of key ideas64

Further reading65

Exercises66

Problems69

3The First Law:the machinery73

State functions and exact differentials73

3.1State and path functions73

3.2 Exact and inexact differentials74

Thermodynamic consequences75

3.3Changes in internal energy75

3.4 The temperature dependence of the enthalpy79

3.5 The relation between Cv and Cp85

Checklist of key ideas86

Further reading87

Exercises87

Problems88

4 The Second Law:the concepts90

The direction of spontaneous change90

4.1The dispersal of energy91

4.2 Entropy92

4.3 Entropy changes accompanying specific processes100

4.4 The Third Law of thermodynamics106

Concentrating on the system108

4.5The Helmholtz and Gibbs energies108

4.6 Standard molar Gibbs energies114

Checklist of key ideas115

Further reading116

Exercises116

Problems118

5The Second Law:the machinery121

Combining the First and Second Laws121

5.1The fundamental equation121

5.2 Properties of the internal energy122

Properties of the Gibbs energy124

5.3General considerations124

5.4 The variation of the Gibbs energy with temperature126

5.5 The variation of the Gibbs energy with pressure127

Checklist of key ideas130

Further reading131

Exercises131

Problems132

6Physical transformations of pure substances135

Phase diagrams135

6.1The stabilities of phases135

6.2 Phase boundaries136

6.3 Three typical phase diagrams138

Phase stability and phase transitions140

6.4The thermodynamic criterion of equilibrium141

6.5 The dependence of stability on the conditions141

6.6 The location of phase boundaries144

6.7 The Ehrenfest classification of phase transitions148

The physical liquid surface150

6.8Surface tension150

6.9 Curved surfaces151

6.10 Capillary action153

Checklist of key ideas155

Further reading156

Exercises156

Problems157

7 Simple mixtures160

The thermodynamic description of mixtures160

7.1Partial molar quantities161

7.2 The thermodynamics of mixing166

7.3 The chemical potentials of liquids168

The properties of solutions172

7.4Liquid mixtures173

7.5 Colligative properties175

Activities182

7.6The solvent activity182

7.7 The solute activity183

7.8 The activities of regular solutions186

Checklist of key ideas187

Further reading188

Exercises189

Problems190

8Phase diagrams193

Phases,components,and degrees of freedom193

8.1Definitions193

8.2 The phase rule195

Two-component systems198

8.3Vapour pressure diagrams198

8.4 Temperature-composition diagrams202

8.5 Liquid-liquid phase diagrams204

8.6 Liquid-solid phase diagrams208

Checklist of key ideas214

Further reading214

Exercises215

Problems218

9Chemical equilibrium222

Spontaneous chemical reactions222

9.1The Gibbs energy minimum222

9.2 The description of equilibrium226

The response of equilibria to the conditions233

9.3How equilibria respond to pressure234

9.4 The response of equilibria to temperature235

9.5 The response of equilibria to pH240

Checklist of key ideas246

Further reading246

Exercises247

Problems249

10 Equilibrium electrochemistry252

The thermodynamic properties of ions in solution252

10.1Thermodynamic functions of formation253

10.2 Ion activities256

Electrochemical cells262

10.3Half-reactions and electrodes263

10.4 Varieties of cells265

10.5 Standard potentials270

Applications of standard potentials274

10.6The electrochemical series274

10.7 The measurement of pH and pKa277

10.8 Thermodynamic functions280

Checklist of key ideas282

Further reading283

Exercises284

Problems286

Part 2Structure291

11Quantum theory:introduction and principles293

The origins of quantum mechanics293

11.1 The failures of classical physics294

11.2Wave-particle duality299

The dynamics of microscopic systems304

11.3The Schrodinger equation304

11.4 The Born interpretation of the wavefunction306

Quantum mechanical principles309

11.5The information in a wavefunction310

11.6 The uncertainty principle317

Checklist of key ideas320

Further reading321

Exercises322

Problems323

12Quantum theory:techniques and applications325

Translational motion325

12.1A particle in a box326

12.2 Motion in two and more dimensions331

12.3 Tunnelling334

Vibrational motion338

12.4 The energy levels338

12.5The wavefunctions339

Rotational motion345

12.6Rotation in two dimensions:the particle on a ring345

12.7 Rotation in three dimensions:the particle on a sphere349

12.8 Spin354

Techniques of approximation355

12.9 Time-independent perturbation theory355

12.10 Time-dependent perturbation theory358

Checklist of key ideas360

Further reading361

Exercises361

Problems363

13Atomic structure and atomic spectra365

The structure and spectra of hydrogenic atoms366

13.1The structure of hydrogenic atoms367

13.2 Atomic orbitals and their energies372

13.3 Spectroscopic transitions and selection rules381

The structures of many-electron atoms383

13.4 The orbital approximation384

13.5 Self-consistent field orbitals392

The spectra of complex atoms393

13.6Quantum defects and ionization limits395

13.7 Singlet and triplet states395

13.8 Spin-orbit coupling396

13.9 Term symbols and selection rules399

Checklist of key ideas404

Further reading405

Exercises406

Problems408

14Molecular structure410

The Born-Oppenheimer approximation410

Valence-bond theory411

14.1 The hydrogen molecule411

14.2Homonuclear diatomic molecules413

14.3 Polyatomic molecules414

Molecular orbital theory417

14.4 The hydrogen molecule-ion418

14.5The structures of diatomic molecules422

14.6 Heteronuclear diatomic molecules427

Molecular orbitals for polyatomic systems432

14.7The Huckel approximation433

14.8 Extended Huckel theory438

14.9 Self-consistent field calculations441

Checklist of key ideas446

Further reading447

Exercises448

Problems450

15Molecular symmetry453

The symmetry elements of objects453

15.1Operations and symmetry elements454

15.2 The symmetry classification of molecules456

15.3 Some immediate consequences of symmetry459

Character tables463

15.4 Character tables and symmetry labels463

15.5 Vanishing integrals and orbital overlap469

15.6 Vanishing integrals and selection rules474

Checklist of key ideas476

Further reading477

Exercises477

Problems478

16 Spectroscopy 1:rotational and vibrational spectra481

General features of spectroscopy483

16.1Experimental techniques483

16.2 The intensities of spectral lines491

16.3 Linewidths495

Pure rotation spectra497

16.4Moments of inertia497

16.5 The rotational energy levels500

16.6 Rotational transitions504

16.7 Rotational Raman spectra507

16.8 Nuclear statistics and rotational states510

The vibrations of diatomic molecules511

16.9Molecular vibrations512

16.10 Selection rules513

16.11 Anharmonicity515

16.12 Vibration-rotation spectra517

16.13 Vibrational Raman spectra of diatomic molecules519

The vibrations of polyatomic molecules520

16.14 Normal modes520

16.15 Infrared absorption spectra of polyatomic molecules523

16.16 Vibrational Raman spectra of polyatomic molecules524

16.17 Symmetry aspects of molecular vibrations526

Checklist of key ideas529

Further reading531

Exercises532

Problems534

17Spectroscopy 2:electronic transitions538

The characteristics of electronic transitions539

17.1 The electronic spectra of diatomic molecules539

17.2 The electronic spectra of polyatomic molecules545

The fates of electronically excited states550

17.3Fluorescence and phosphorescence550

17.4 Dissociation and predissociation552

Lasers553

17.5 General principles of laser action554

17.6Practical lasers558

17.7 Applications of lasers in chemistry562

Photoelectron spectroscopy568

17.8The technique568

17.9 Ultraviolet photoelectron spectroscopy569

17.10 X-ray photoelectron spectroscopy570

Checklist of key ideas571

Further reading573

Exercises574

Problems575

18Spectroscopy 3:magnetic resonance579

The effect of magnetic fields on electrons and nuclei579

18.1 The energies of electrons in magnetic fields580

18.2 The energies of nuclei in magnetic fields581

18.3 Magnetic resonance spectroscopy583

Nuclear magnetic resonance583

18.4The NMR spectrometer584

18.5 The chemical shift585

18.6 The fine structure590

Pulse techniques in NMR599

18.7The magnetization vector599

18.8 Linewidths and rate processes602

18.9 Spin decoupling607

18.10 The nuclear Overhauser effect608

18.11 Two-dimensional NMR610

18.12 Solid-state NMR614

Electron spin resonance615

18.13 The ESR spectrometer615

18.14 The g-value617

18.15 Hyperfine structure618

Checklist of key ideas621

Further reading623

Exercises624

Problems626

19 Statistical thermodynamics:the concepts628

The distribution of molecular states629

19.1 Configurations and weights629

19.2 The molecular partition function634

The internal energy and the entropy639

19.3 The internal energy640

19.4 The statistical entropy642

The canonical partition function647

19.5 The canonical ensemble647

19.6 The thermodynamic information in the partition function648

19.7Independent molecules649

Checklist of key ideas652

Further reading652

Exercises653

Problems654

20 Statistical thermodynamics:the machinery656

Fundamental relations656

20.1The thermodynamic functions656

20.2 The molecular partition function658

Using statistical thermodynamics667

20.3Mean energies667

20.4 Heat capacities669

20.5 Equations of state671

20.6 Residual entropies672

20.7 Equilibrium constants674

Checklist of key ideas681

Further reading682

Exercises682

Problems683

21Molecular interactions686

Electric properties of molecules686

21.1Electric dipole moments686

21.2 Polarizabilities689

21.3 Relative permittivities692

21.4 Refractive index694

Interactions between molecules696

21.5Interactions between dipoles698

21.6 Repulsive and total interactions705

21.7 Molecular interactions in gases706

21.8 Molecular interactions in liquids709

Checklist of key ideas713

Further reading715

Exercises715

Problems716

22 Macromolecules and aggregates719

Structure and dynamics720

22.1The different levels of structure720

22.2 Random coils721

22.3 The structure of proteins725

22.4 The structure of nucleic acids729

22.5 The stability of biological polymers731

Determination of size and shape732

22.6Mean molar masses732

22.7 Mass spectrometry735

22.8 Laser light scattering736

22.9 Ultracentrifugation742

22.10 Electrophoresis745

22.11 Size-exclusion chromatography747

22.12 Viscosity748

Self-assembly750

22.13 Colloids752

22.14 Micelles and biological membranes754

22.15 Surface films757

Checklist of key ideas760

Further reading762

Exercises763

Problems764

23The solid state767

Crystal lattices767

23.1Lattices and unit cells767

23.2 The identification of lattice planes770

23.3 The investigation of structure772

23.4 Neutron and electron diffraction783

Crystal structure784

23.5Metallic solids784

23.6 Ionic solids786

23.7 Molecular solids and covalent networks789

The properties of solids791

23.8 Mechanical properties791

23.9Electrical properties795

23.10 Magnetic properties801

Checklist of key ideas805

Further reading807

Exercises808

Problems810

Part 3Change813

24Molecules in motion815

Molecular motion in gases815

24.1 The kinetic model of gases816

24.2 Collisions with walls and surfaces822

24.3 The rate of effusion824

24.4 Transport properties of a perfect gas826

Molecular motion in liquids832

24.5 Experimental results832

24.6 The conductivities of electrolyte solutions833

24.7 The mobilities of ions835

24.8 Conductivities and ion-ion interactions841

Diffusion842

24.9The thermodynamic view842

24.10 The diffusion equation846

24.11 Diffusion probabilities852

24.12 The statistical view853

Checklist of key ideas854

Further reading856

Exercises856

Problems859

25The rates of chemical reactions862

Empirical chemical kinetics862

25.1Experimental techniques863

25.2 The rates of reactions866

25.3 Integrated rate laws871

25.4 Reactions approaching equilibrium876

25.5 The temperature dependence of reaction rates879

Accounting for the rate laws882

25.6Elementary reactions882

25.7 Consecutive elementary reactions883

25.8 Unimolecular reactions890

Checklist of key ideas892

Further reading893

Exercises894

Problems896

26 The kinetics of complex reactions899

Chain reactions899

26.1The rate laws of chain reactions900

26.2 Explosions902

Polymerization kinetics904

26.3 Stepwise polymerization904

26.4Chain polymerization906

Homogeneous catalysis908

26.5Features of homogeneous catalysis909

26.6 Enzymes909

Oscillating reactions914

26.7 Autocatalysis915

26.8Autocatalytic mechanisms of oscillating reactions916

26.9 Bistability917

26.10 Chemical chaos919

Photochemistry920

26.11 Kinetics of photophysical and photochemical processes927

26.12 Complex photochemical processes934

Checklist of key ideas936

Further reading937

Exercises938

Problems940

27Molecular reaction dynamics944

Reactive encounters944

27.1Collision theory945

27.2 Diffusion-controlled reactions951

27.3 The material balance equation954

Activated complex theory956

27.4The Eyring equation956

27.5 Thermodynamic aspects960

The dynamics of molecular collisions963

27.6Reactive collisions963

27.7 Potential energy surfaces966

27.8 Some results from experiments and calculations967

Checklist of key ideas971

Further reading972

Exercises973

Problems974

28Processes at solid surfaces977

The growth and structure of solid surfaces977

28.1Surface growth977

28.2 Surface composition979

The extent of adsorption987

28.3Physisorption and chemisorption988

28.4 Adsorption isotherms989

28.5 The rates of surface processes994

Catalytic activity at surfaces999

28.6 Adsorption and catalysis999

28.7Examples of catalysis1001

Checklist of key ideas1006

Further reading1007

Exercises1008

Problems1009

29Dynamics of electron transfer1013

Electron transfer in homogeneous systems1014

29.1Theory of electron transfer processes1014

29.2 Experimental results1018

Electron transfer in heterogeneous systems1021

29.3The electrode-solution interface1021

29.4 The rate of charge transfer1024

29.5 Voltammetry1031

29.6 Electrolysis1036

29.7 Working galvanic cells1037

29.8 Corrosion1039

Checklist of key ideas1041

Further reading1043

Exercises1043

Problems1045

Further information 1Mathematical techniques1048

Basic procedures1048

1.1Logarithms and exponentials1048

1.2 Combinatorial functions1048

1.3 Complex numbers and complex functions1049

1.4 Vectors1050

Calculus1051

1.5Differentiation and integration1051

1.6 Power series and Taylor expansions1052

1.7 Partial derivatives1053

1.8 Undetermined multipliers1054

1.9 Differential equations1055

Matrix algebra1057

1.10Matrix addition and multiplication1058

1.11 Simultaneous equations1059

1.12 Eigenvalue equations1060

Further reading1061

Further information 2 Essential concepts of physics1062

Energy1062

2.1Kinetic and potential energy1062

2.2 Energy units1062

Classical mechanics1063

2.3The trajectory in terms of the energy1063

2.4 Newton’s second law1064

2.5 Rotational motion1064

2.6 The harmonic oscillator1065

Waves1066

2.7The electromagnetic field1066

2.8 Features of electromagnetic radiation1067

Electrostatics1068

2.9The Coulomb interaction1068

2.10 The Coulomb potential1068

2.11 The strength of the electric field1069

2.12 The dipole-dipole interaction1069

2.13 Electric current and power1070

Further reading1070

Data section1071

Answers to exercises1112

Answers to problems1124

Index1137

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