ATKINS' PHYSICAL CHEMISTRY 11TH EDITIONPDF|Epub|txt|kindle电子书版本网盘下载

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PROLOGUE Energy，temperature，and chemistry1

FOCUS 1 The properties of gases3

TOPIC 1A The perfect gas4

1A.1 Variables of state4

（a） Pressure4

（b） Temperature5

1A.2 Equations of state6

（a） The empirical basis7

（b） Mixtures of gases9

Checklist of concepts10

Checklist of equations10

TOPIC 1B The kinetic model11

1B.1 The model11

（a） Pressure and molecular speeds12

（b） The Maxwell-Boltzmann distribution of speeds13

（c） Mean values15

1B.2 Collisions17

（a） The collision frequency17

（b） The mean free path18

Checklist of concepts18

Checklist of equations18

TOPIC 1C Real gases19

1C.1 Deviations from perfect behaviour19

（a） The compression factor20

（b） Virial coefficients20

（c） Critical constants22

1C.2 The van der Waals equation23

（a） Formulation of the equation23

（b） The features of the equation24

（c） The principle of corresponding states26

Checklist of concepts27

Checklist of equations27

FOCUS 2 The First Law33

TOPIC 2A Internal energy34

2A.1 Work，heat，and energy34

（a） Operational definitions34

（b） The molecular interpretation of heat and work36

2A.2 The definition of internal energy37

（a） Molecular interpretation of internal energy37

（b） The formulation of the First Law38

2A.3 Expansion work38

（a） The general expression for work39

（b） Expansion against constant pressure39

（c） Reversible expansion40

（d） Isothermal reversible expansion of a perfect gas41

2A.4 Heat transactions42

（a） Calorimetry42

（b） Heat capacity43

Checklist of concepts45

Checklist of equations45

TOPIC 2B Enthalpy46

2B.1 The definition of enthalpy46

（a） Enthalpy change and heat transfer46

（b） Calorimetry47

2B.2 The variation of enthalpy with temperature48

（a） Heat capacity at constant pressure48

（b） The relation between heat capacities49

Checklist of concepts50

Checklist of equations50

TOPIC 2C Thermochemistry51

2C.1 Standard enthalpy changes51

（a） Enthalpies of physical change51

（b） Enthalpies of chemical change52

（c） Hess’s law53

2C.2 Standard enthalpies of formation54

2C.3 The temperature dependence of reaction enthalpies55

2C.4 Experimental techniques56

（a） Differential scanning calorimetry56

（b） Isothermal titration calorimetry57

Checklist of concepts57

Checklist of equations58

TOPIC 2D State functions and exact differentials59

2D.1 Exact and inexact differentials59

2D.2 Changes in internal energy60

（a） General considerations60

（b） Changes in internal energy at constant pressure62

2D.3 Changes in enthalpy63

2D.4 The Joule-Thomson effect64

（a） The observation of the Joule-Thomson effect64

（b） The molecular interpretation of the Joule-Thomson effect65

Checklist of concepts66

Checklist of equations66

TOPIC 2E Adiabatic changes67

2B.1 The change in temperature67

2B.2 The change in pressure68

Checklist of concepts69

Checklist of equations69

FOCUS 3 The Second and Third Laws77

TOPIC 3A Entropy78

3A.1 The Second Law78

3A.2 The definition of entropy80

（a） The thermodynamic definition of entropy80

（b） The statistical definition of entropy81

3A.3 The entropy as a state function82

（a） The Carnot cycle82

（b） The thermodynamic temperature85

（c） The Clausius inequality85

Checklist of concepts86

Checklist of equations87

TOPIC 3B Entropy changes accompanying specific processes88

3B.1 Expansion88

3B.2 Phase transitions89

3B.3 Heating90

3B.4 Composite processes90

Checklist of concepts91

Checklist of equations91

TOPIC 3C The measurement of entropy92

3C.1 The calorimetric measurement of entropy92

3C.2 The Third Law93

（a） The Nernst heat theorem93

（b） Third-Law entropies94

（c） The temperature dependence of reaction entropy95

Checklist of concepts96

Checklist of equations96

TOPIC 3D Concentrating on the system97

3D.1 The Helmholtz and Gibbs energies97

（a） Criteria of spontaneity97

（b） Some remarks on the Helmholtz energy98

（c） Maximum work98

（d） Some remarks on the Gibbs energy99

（e） Maximum non-expansion work100

3D.2 Standard molar Gibbs energies100

（a） Gibbs energies of formation101

（b） The Born equation102

Checklist of concepts103

Checklist of equations103

TOPIC 3E Combining the First and Second Laws104

3B.1 Properties of the internal energy104

（a） The Maxwell relations104

（b） The variation of internal energy with volume106

3B.2 Properties of the Gibbs energy106

（a） General considerations106

（b） The variation of the Gibbs energy with temperature108

（c） The variation of the Gibbs energy with pressure108

Checklist of concepts110

Checklist of equations110

FOCUS 4 Physical transformations of pure substances119

TOPIC 4A Phase diagrams of pure substances120

4A.1 The stabilities of phases120

（a） The number of phases120

（b） Phase transitions120

（c） Thermodynamic criteria of phase stability121

4A.2 Phase boundaries122

（a） Characteristic properties related to phase transitions122

（b） The phase rule123

4A.3 Three representative phase diagrams125

（a） Carbon dioxide125

（b） Water125

（c） Helium126

Checklist of concepts127

Checklist of equations127

TOPIC 4B Thermodynamic aspects of phase transitions128

4B.1 The dependence of stability on the conditions128

（a） The temperature dependence of phase stability128

（b） The response of melting to applied pressure129

（c） The vapour pressure of a liquid subjected to pressure130

4B.2 The location of phase boundaries131

（a） The slopes of the phase boundaries131

（b） The solid-liquid boundary132

（c） The liquid-vapour boundary132

（d） The solid-vapour boundary134

Checklist of concepts134

Checklist of equations134

FOCUS 5 Simple mixtures141

TOPIC 5A The thermodynamic description of mixtures143

5A.1 Partial molar quantities143

（a） Partial molar volume143

（b） Partial molar Gibbs energies145

（c） The wider significance of the chemical potential146

（d） The Gibbs-Duhem equation146

5A.2 The thermodynamics of mixing147

（a） The Gibbs energy of mixing of perfect gases147

（b） Other thermodynamic mixing functions149

5A.3 The chemical potentials of liquids150

（a） Ideal solutions150

（b） Ideal-dilute solutions152

Checklist of concepts153

Checklist of equations154

TOPIC 5B The properties of solutions155

5B.1 Liquid mixtures155

（a） Ideal solutions155

（b） Excess functions and regular solutions156

5B.2 Colligative properties158

（a） The common features of colligative properties158

（b） The elevation of boiling point159

（c） The depression of freezing point161

（d） Solubility161

（e） Osmosis162

Checklist of concepts164

Checklist of equations165

TOPIC 5C Phase diagrams of binary systems：liquids166

5C.1 Vapour pressure diagrams166

5C.2 Temperature-composition diagrams168

（a） The construction of the diagrams168

（b） The interpretation of the diagrams169

5C.3 Distillation170

（a） Simple and fractional distillation170

（b） Azeotropes171

（c） Immiscible liquids172

5C.4 Liquid-liquid phase diagrams172

（a） Phase separation172

（b） Critical solution temperatures173

（c） The distillation of partially miscible liquids175

Checklist of concepts176

Checklist of equations176

TOPIC 5D Phase diagrams of binary systems：solids177

5D.1 Eutectics177

5D.2 Reacting systems178

5D.3 Incongruent melting179

Checklist of concepts179

TOPIC 5E Phase diagrams of ternary systems180

5E.1 Triangular phase diagrams180

5E.2 Ternary systems181

（a） Partially miscible liquids181

（b） Ternary solids182

Checklist of concepts182

TOPIC 5F Activities183

5F.1 The solvent activity183

5F.2 The solute activity183

（a） Ideal-dilute solutions184

（b） Real solutes184

（c） Activities in terms of molalities185

5F.3 The activities of regular solutions185

5F.4 The activities of ions187

（a） Mean activity coefficients187

（b） The Debye-Huckel limiting law187

（c） Extensions of the limiting law188

Checklist of concepts189

Checklist of equations190

FOCUS 6 Chemical equilibrium203

TOPIC 6A The equilibrium constant204

6A.1 The Gibbs energy minimum204

（a） The reaction Gibbs energy204

（b） Exergonic and endergonic reactions205

6A.2 The description of equilibrium205

（a） Perfect gas equilibria205

（b） The general case of a reaction206

（c） The relation between equilibrium constants209

（d） Molecular interpretation of the equilibrium constant210

Checklist of concepts211

Checklist of equations211

TOPIC 6B The response of equilibria to the conditions212

6B.1 The response to pressure212

6B.2 The response to temperature213

（a） Thevan’tHoffequation213

（b） The value of Kat different temperatures215

Checklist of concepts216

Checklist of equations216

TOPIC 6C Electrochemical cells217

6C.1 Half-reactions and electrodes217

6C.2 Varieties of cells218

（a） Liquid junction potentials218

（b） Notation219

6C.3 The cell potential219

（a） The Nernst equation219

（b） Cells at equilibrium221

6C.4 The determination of thermodynamic functions221

Checklist of concepts223

Checklist of equations223

TOPIC 6D Electrode potentials224

6D.1 Standard potentials224

（a） The measurement procedure225

（b） Combining measured values226

6D.2 Applications of standard potentials226

（a） The electrochemical series226

（b） The determination of activity coefficients226

（c） The determination of equilibrium constants227

Checklist of concepts227

Checklist of equations228

FOCUS 7 Quantum theory235

TOPIC 7A The origins of quantum mechanics237

7A.1 Energy quantization237

（a） Black-body radiation237

（b） Heat capacity240

（c） Atomic and molecular spectra241

7A.2 Wave-particle duality242

（a） The particle character of electromagnetic radiation242

（b） The wave character of particles244

Checklist of concepts245

Checklist of equations245

TOPIC 7B Wavefunctions246

7B.1 The Schrodinger equation246

7B.2 The Born interpretation247

（a） Normalization248

（b） Constraints on the wavefunction249

（c） Quantization250

Checklist of concepts250

Checklist of equations250

TOPIC 7C Operators and observables251

7C.1 Operators251

（a） Eigenvalue equations251

（b） The construction of operators252

（c） Hermitian operators253

（d） Orthogonality254

7C.2 Superpositions and expectation values255

7C.3 The uncertainty principle257

7C.4 The postulates of quantum mechanics259

Checklist of concepts260

Checklist of equations260

TOPIC 7D Translational motion261

7D.1 Free motion in one dimension261

7D.2 Confined motion in one dimension262

（a） The acceptable solutions263

（b） The properties of the wavefunctions264

（c） The properties of the energy265

7D.3 Confined motion in two and more dimensions266

（a） Energy levels and wavefunctions266

（b） Degeneracy267

7D.4 Tunnelling268

Checklist of concepts271

Checklist of equations272

TOPIC 7E Vibrational motion273

7E.1 The harmonic oscillator273

（a） The energy levels274

（b） The wavefunctions275

7E.2 Properties of the harmonic oscillator277

（a） Mean values277

（b） Tunnelling278

Checklist of concepts279

Checklist of equations280

TOPIC 7F Rotational motion281

7F.1 Rotation in two dimensions281

（a） The solutions of the Schrodinger equation283

（b） Quantization of angular momentum284

7F.2 Rotation in three dimensions285

（a） The wavefunctions and energy levels285

（b） Angular momentum288

（c） The vector model288

Checklist of concepts290

Checklist of equations290

FOCUS 8 Atomic structure and spectra303

TOPIC 8A Hydrogenic atoms304

8A.1 The structure of hydrogenic atoms304

（a） The separation of variables304

（b） The radial solutions305

8A.2 Atomic orbitals and their energies308

（a） The specification of orbitals308

（b） The energy levels308

（c） Ionization energies309

（d） Shells and subshells309

（e） s Orbitals310

（f） Radial distribution functions311

（g） p Orbitals313

（h） d Orbitals314

Checklist of concepts314

Checklist of equations315

TOPIC 8B Many-electron atoms316

8B.1 The orbital approximation316

8B.2 The Pauli exclusion principle317

（a） Spin317

（b） The Pauli principle318

8B.3 The building-up principle319

（a） Penetration and shielding319

（b） Hund’s rules321

（c） Atomic and ionic radii323

（d） Ionization energies and electron affinities324

8B.4 Self-consistent field orbitals325

Checklist of concepts325

Checklist of equations326

TOPIC 8C Atomic spectra327

8C.1 The spectra of hydrogenic atoms327

8C.2 The spectra of many-electron atoms328

（a） Singlet and triplet terms328

（b） Spin-orbit coupling329

（c） Term symbols332

（d） Hund’s rules335

（e） Selection rules335

Checklist of concepts336

Checklist of equations336

FOCUS 9 Molecular structure341

PROLOGUE The Born-Oppenheimer approximation343

TOPIC 9A Valence-bond theory344

9A.1 Diatomic molecules344

9A.2 Resonance346

9A.3 Polyatomic molecules346

（a） Promotion347

（b） Hybridization347

Checklist of concepts350

Checklist of equations350

TOPIC 9B Molecular orbital theory：the hydrogen molecule-ion351

9B.1 Linear combinations of atomic orbitals351

（a） The construction of linear combinations351

（b） Bonding orbitals353

（c） Antibonding orbitals354

9B.2 Orbital notation356

Checklist of concepts356

Checklist of equations356

TOPIC 9C Molecular orbital theory：homonuclear diatomic molecules357

9C.1 Electron configurations357

（a） σ Orbitals and π orbitals357

（b） The overlap integral359

（c） Period 2 diatomic molecules360

9C.2 Photoelectron spectroscopy362

Checklist of concepts363

Checklist of equations364

TOPIC 9D Molecular orbital theory：heteronuclear diatomic molecules365

9D.1 Polar bonds and electronegativity365

9D.2 The variation principle366

（a） The procedure367

（b） The features of the solutions369

Checklist of concepts370

Checklist of equations370

TOPIC 9E Molecular orbital theory：polyatomic molecules371

9E.1 The Huckel approximation371

（a） An introduction to the method371

（b） The matrix formulation of the method372

9E.2 Applications375

（a） π-Electron binding energy375

（b） Aromatic stability376

9E.3 Computational chemistry377

（a） Semi-empirical and ab initio methods378

（b） Density functional theory379

（c） Graphical representations379

Checklist of concepts380

Checklist of equations380

FOCUS 10 Molecular symmetry387

TOPIC 10A Shape and symmetry388

10A.1 Symmetry operations and symmetry elements388

10A.2 The symmetry classification of molecules390

（a） The groups C 1' C i’ and Cs392

（b） The groups C n' C nv’ and Cnh392

（c） The groups D n' D nh' and D nd393

（d） The groups 5n393

（e） The cubic groups Sn393

（f） The full rotation group394

10A.3 Some immediate consequences of symmetry394

（a） Polarity394

（b） Chirality395

Checklist of concepts395

Checklist of operations and elements396

TOPIC 10B Group theory397

10B.1 The elements of group theory397

10B.2 Matrix representations398

（a） Representatives of operations398

（b） The representation of a group399

（c） Irreducible representations400

（d） Characters401

10B.3 Character tables401

（a） The symmetry species of atomic orbitals402

（b） The symmetry species of linear combinations of orbitals403

（c） Character tables and degeneracy404

Checklist of concepts405

Checklist of equations405

TOPIC 10C Applications of symmetry406

10C.1 Vanishing integrals406

（a） Integrals of the product of functions407

（b） Decomposition of a representation408

10C.2 Applications to molecular orbital theory409

（a） Orbital overlap409

（b） Symmetry-adapted linear combinations409

10C.3 Selection rules411

Checklist of concepts411

Checklist of equations411

FOCUS 11 Molecular spectroscopy417

TOPIC 11A General features of molecular spectroscopy419

11A.1 The absorption and emission of radiation420

（a） Stimulated and spontaneous radiative processes420

（b） Selection rules and transition moments421

（c） The Beer-Lambert law421

11A.2 Spectral linewidths423

（a） Doppler broadening423

（b） Lifetime broadening425

11A.3 Experimental techniques425

（a） Sources of radiation426

（b） Spectral analysis426

（c） Detectors428

（d） Examples of spectrometers428

Checklist of concepts429

Checklist of equations429

TOPIC 11B Rotational spectroscopy430

11B.1 Rotational energy levels430

（a） Spherical rotors432

（b） Symmetric rotors432

（c） Linear rotors434

（d） Centrifugal distortion434

11B.2 Microwave spectroscopy435

（a） Selection rules435

（b） The appearance of microwave spectra436

11B.3 Rotational Raman spectroscopy437

11B.4 Nuclear statistics and rotational states439

Checklist of concepts441

Checklist of equations441

TOPIC 11C Vibrational spectroscopy of diatomic molecules442

11C.1 Vibrational motion442

11C.2 Infrared spectroscopy443

11C.3 Anharmonicity444

（a） The convergence of energy levels444

（b） The Birge-Sponer plot445

11C.4 Vibration-rotation spectra446

（a） Spectral branches447

（b） Combination differences448

11C.5 Vibrational Raman spectra448

Checklist of concepts449

Checklist of equations450

TOPIC 11D Vibrational spectroscopy of polyatomic molecules451

11D.1 Normal modes451

11D.2 Infrared absorption spectra452

11D.3 Vibrational Raman spectra453

Checklist of concepts454

Checklist of equations454

TOPIC 11E Symmetry analysis of vibrational spectra455

11E.1 Classification of normal modes according to symmetry455

11E.2 Symmetry of vibrational wavefunctions457

（a） Infrared activity of normal modes457

（b） Raman activity of normal modes458

（c） The symmetry basis of the exclusion rule458

Checklist of concepts458

TOPIC 11F Electronic spectra459

11F.1 Diatomic molecules459

（a） Term symbols459

（b） Selection rules461

（c） Vibrational fine structure462

（d） Rotational fine structure465

11F.2 Polyatomic molecules466

（a） d-Metal complexes467

（b） π*←πandπ*←ntransitions468

Checklist of concepts469

Checklist of equations469

TOPIC 11G Decay of excited states470

11G.1 Fluorescence and phosphorescence470

11G.2 Dissociation and predissociation472

11G.3 Lasers473

Checklist of concepts474

FOCUS 12 Magnetic resonance487

TOPIC 12A General principles488

12A.1 Nuclear magnetic resonance488

（a） The energies of nuclei in magnetic fields488

（b） The NMR spectrometer490

12A.2 Electron paramagnetic resonance491

（a） The energies of electrons in magnetic fields491

（b） The EPR spectrometer492

Checklist of concepts493

Checklist of equations493

TOPIC 12B Features of NMR spectra494

12B.1 The chemical shift494

12B.2 The origin of shielding constants496

（a） The local contribution496

（b） Neighbouring group contributions497

（c） The solvent contribution498

12B.3 The fine structure499

（a） The appearance of the spectrum499

（b） The magnitudes of coupling constants501

（c） The origin of spin-spin coupling502

（d） Equivalent nuclei503

（e） Strongly coupled nuclei504

12B.4 Exchange processes505

12B.5 Solid-state NMR506

Checklist of concepts507

Checklist of equations508

TOPIC 12C Pulse techniques in NMR509

12C.1 The magnetization vector509

（a） The effect of the radiofrequency field510

（b） Time-and frequency-domain signals511

12C.2 Spin relaxation513

（a） The mechanism of relaxation513

（b） The measurement of T 1 and T 2514

12C.3 Spin decoupling515

12C.4 The nuclear Overhauser effect516

Checklist of concepts518

Checklist of equations518

TOPIC 12D Electron paramagnetic resonance519

12D.1 The g-value519

12D.2 Hyperfine structure520

（a） The effects of nuclear spin520

（b） The McConnell equation521

（c） The origin of the hyperfine interaction522

Checklist of concepts523

Checklist of equations523

FOCUS 13 Statistical thermodynamics531

TOPIC 13A The Boltzmann distribution532

13A.1 Configurations and weights532

（a） Instantaneous configurations532

（b） The most probable distribution533

（c） The values of the constants535

13A.2 The relative population of states536

Checklist of concepts536

Checklist of equations537

TOPIC 13B Molecular partition functions538

13B.1 The significance of the partition function538

13B.2 Contributions to the partition function540

（a） The translational contribution540

（b） The rotational contribution542

（c） The vibrational contribution546

（d） The electronic contribution547

Checklist of concepts548

Checklist of equations548

TOPIC 13C Molecular energies549

13C.1 The basic equations549

13C.2 Contributions of the fundamental modes of motion550

（a） The translational contribution550

（b） The rotational contribution550

（c） The vibrational contribution551

（d） The electronic contribution552

（e） The spin contribution552

Checklist of concepts553

Checklist of equations553

TOPIC 13D The canonical ensemble554

13D.1 The concept of ensemble554

（a） Dominating configurations555

（b） Fluctuations from the most probable distribution555

13D.2 The mean energy of a system556

13D.3 Independent molecules revisited556

13D.4 The variation of the energy with volume557

Checklist of concepts558

Checklist of equations558

TOPIC 13E The internal energy and the entropy559

13E.1 The internal energy559

（a） The calculation of internal energy559

（b） Heat capacity560

13E.2 The entropy561

（a） Entropy and the partition function561

（b） The translational contribution563

（c） The rotational contribution563

（d） The vibrational contribution564

（e） Residual entropies565

Checklist of concepts566

Checklist of equations566

TOPIC 13F Derived functions567

13F.1 The derivations567

13F.2 Equilibrium constants570

（a） The relation between K and the partition function570

（b） A dissociation equilibrium570

（c） Contributions to the equilibrium constant571

Checklist of concepts573

Checklist of equations573

FOCUS 14 Molecular interactions583

TOPIC 14A The electric properties of molecules585

14A.1 Electric dipole moments585

14A.2 Polarizabilities587

14A.3 Polarization588

（a） The frequency dependence of the polarization588

（b） Molar polarization590

Checklist of concepts592

Checklist of equations592

TOPIC 14B Interactions between molecules593

14B.1 The interactions of dipoles593

（a） Charge-dipole interactions593

（b） Dipole-dipole interactions594

（c） Dipole-induced dipole interactions597

（d） Induced dipole-induced dipole interactions597

14B.2 Hydrogen bonding598

14B.3 The total interaction599

Checklist of concepts601

Checklist of equations601

TOPIC 14C Liquids602

14C.1 Molecular interactions in liquids602

（a） The radial distribution function602

（b） The calculation of g（r）603

（c） The thermodynamic properties of liquids604

14C.2 The liquid-vapour interface605

（a） Surfacetension605

（b） Curved surfaces606

（c） Capillaryaction606

14C.3 Surface films608

（a） Surface pressure608

（b） The thermodynamics of surface layers609

14C.4 Condensation611

Checklist of concepts612

Checklist of equations612

TOPIC 14D Macromolecules613

14D.1 Average molar masses613

14D.2 The different levels of structure614

14D.3 Random coils615

（a） Measures of size615

（b） Constrained chains618

（c） Partly rigid coils618

14D.4 Mechanical properties619

（a） Conformational entropy619

（b） Elastomers620

14D.5 Thermal properties621

Checklist of concepts622

Checklist of equations622

TOPIC 14E Self-assembly623

14E.1 Colloids623

（a） Classification and preparation623

（b） Structure and stability624

（c） The electrical double layer624

14E.2 Micelles and biological membranes626

（a） The hydrophobic interaction626

（b） Micelle formation627

（c） Bilayers，vesicles，andmembranes628

Checklist of concepts630

Checklist of equations630

FOCUS 15 Solids639

TOPIC 15A Crystal structure641

15A.1 Periodic crystal lattices641

15A.2 The identification of lattice planes643

（a） The Miller indices643

（b） The separation of neighbouring planes644

Checklist of concepts645

Checklist of equations645

TOPIC 15B Diffraction techniques646

15B.1 X-ray crystallography646

（a） X-ray diffraction646

（b） Bragg’s law648

（c） Scattering factors649

（d） The electron density649

（e） The determination of structure652

15B.2 Neutron and electron diffraction654

Checklist of concepts655

Checklist of equations655

TOPIC 15C Bonding in solids656

15C.1 Metals656

（a） Close packing656

（b） Electronic structure of metals658

15C.2 Ionic solids660

（a） Structure660

（b） Energetics661

15C.3 Covalent and molecular solids663

Checklist of concepts664

Checklist of equations665

TOPIC 15D The mechanical properties of solids666

Checklist of concepts667

Checklist of equations668

TOPIC 15E The electrical properties of solids669

15E.1 Metallic conductors669

15E.2 Insulators and semiconductors670

15E.3 Superconductors672

Checklist of concepts673

Checklist of equations673

TOPIC 15F The magnetic properties of solids674

15F.1 Magnetic susceptibility674

15F.2 Permanent and induced magnetic moments675

15F.3 Magnetic properties of superconductors676

Checklist of concepts676

Checklist of equations677

TOPIC 15G The optical properties of solids678

15G.1 Excitons678

15G.2 Metals and semiconductors679

（a） Light absorption679

（b） Light-emitting diodes and diode lasers680

15G.3 Nonlinear optical phenomena680

Checklist of concepts681

FOCUS 16 Molecules in motion689

TOPIC 16A Transport properties of a perfect gas690

16A.1 The phenomenological equations690

16A.2 The transport parameters692

（a） The diffusion coefficient693

（b） Thermal conductivity694

（c） Viscosity696

（d） Effusion697

Checklist of concepts697

Checklist of equations698

TOPIC 16B Motion in liquids699

16B.1 Experimental results699

（a） Liquid viscosity699

（b） Electrolyte solutions700

16B.2 The mobilities of ions701

（a） The drift speed701

（b） Mobility and conductivity703

（c） The Einstein relations704

Checklist of concepts705

Checklist of equations705

FOCUS 16C Diffusion706

16C.1 The thermodynamic view706

16C.2 The diffusion equation708

（a） Simple diffusion708

（b） Diffusion with convection710

（c） Solutions of the diffusion equation710

16C.3 The statistical view712

Checklist of concepts713

Checklist of equations714

FOCUS 17 Chemical kinetics721

TOPIC 17A The rates of chemical reactions723

17A.1 Monitoring the progress of a reaction723

（a） General considerations723

（b） Special techniques724

17A.2 The rates of reactions725

（a） The definition of rate725

（b） Rate laws and rate constants726

（c） Reaction order727

（d） The determination of the rate law728

Checklist of concepts729

Checklist of equations730

TOPIC 17B Integrated rate laws731

17B.1 Zeroth-order reactions731

17B.2 First-order reactions731

17B.3 Second-order reactions733

Checklist of concepts736

Checklist of equations736

TOPIC 17C Reactions approaching equilibrium737

17C.1 First-order reactions approaching equilibrium737

17C.2 Relaxation methods738

Checklist of concepts740

Checklist of equations740

TOPIC 17D The Arrhenius equation741

17D.1 The temperature dependence of reaction rates741

17D.2 The interpretation of the Arrhenius parameters742

（a） A first look at the energy requirements of reactions743

（b） The effect of a catalyst on the activation energy744

Checklist of concepts745

Checklist of equations745

TOPIC 17E Reaction mechanisms746

17E.1 Elementary reactions746

17E.2 Consecutive elementary reactions747

17E.3 The steady-state approximation748

17E.4 The rate-determining step749

17E.5 Pre-equilibria750

17E.6 Kinetic and thermodynamic control of reactions752

Checklist of concepts752

Checklist of equations752

TOPIC 17F Examples of reaction mechanisms753

17F.1 Unimolecular reactions753

17F.2 Polymerization kinetics754

（a） Stepwise polymerization755

（b） Chain polymerization756

17F.3 Enzyme-catalysed reactions758

Checklist of concepts761

Checklist of equations761

TOPIC 17G Photochemistry762

17G.1 Photochemical processes762

17G.2 The primary quantum yield763

17G.3 Mechanism of decay of excited singlet states764

17G.4 Quenching765

17G.5 Resonance energy transfer767

Checklist of concepts768

Checklist of equations768

FOCUS 18 Reaction dynamics779

TOPIC 18A Collision theory780

18A.1 Reactive encounters780

（a） Collision rates in gases781

（b） The energy requirement781

（c） The steric requirement784

18A.2 The RRK model785

Checklist of concepts786

Checklist of equations786

TOPIC 18B Diffusion-controlled reactions787

18B.1 Reactions in solution787

（a） Classes of reaction787

（b） Diffusion and reaction788

18B.2 The material-balance equation789

（a） The formulation of the equation789

（b） Solutions of the equation790

Checklist of concepts790

Checklist of equations791

TOPIC 18C Transition-state theory792

18C.1 The Eyring equation792

（a） The formulation of the equation792

（b） The rate of decay of the activated complex793

（c） The concentration of the activated complex793

（d） The rate constant794

18C.2 Thermodynamic aspects795

（a） Activation parameters795

（b） Reactions between ions797

18C.3 The kinetic isotope effect798

Checklist of concepts800

Checklist of equations800

TOPIC 18D The dynamics of molecular collisions801

18D.1 Molecular beams801

（a） Techniques801

（b） Experimental results802

18D.2 Reactive collisions804

（a） Probes of reactive collisions804

（b） State-to-state reaction dynamics804

18D.3 Potential energy surfaces805

18D.4 Some results from experiments and calculations806

（a） The direction of attack and separation807

（b） Attractive and repulsive surfaces808

（c） Quantum mechanical scattering theory808

Checklist of concepts809

Checklist of equations809

TOPIC 18E Electron transfer in homogeneous systems810

18E.1 The rate law810

18E.2 The role of electron tunnelling811

18E.3 The rate constant812

18E.4 Experimental tests of the theory813

Checklist of concepts815

Checklist of equations815

FOCUS 19 Processes at solid surfaces823

TOPIC 19A An introduction to solid surfaces824

19A.1 Surface growth824

19A.2 Physisorption and chemisorption825

19A.3 Experimental techniques826

（a） Microscopy827

（b） Ionization techniques828

（c） Diffraction techniques829

（d） Determination of the extent and rates of adsorption and desorption830

Checklist of concepts831

Checklist of equations831

TOPIC 19B Adsorption and desorption832

19B.1 Adsorption isotherms832

（a） The Langmuir isotherm832

（b） The isosteric enthalpy of adsorption834

（c） The BET isotherm835

（d） The Temkin and Freundlich isotherms837

19B.2 The rates of adsorption and desorption837

（a） The precursor state837

（b） Adsorption and desorption at the molecular level838

（c） Mobility on surfaces839

Checklist of concepts840

Checklist of equations840

TOPIC 19C Heterogeneous catalysis841

19C.1 Mechanisms of heterogeneous catalysis841

（a） Unimolecular reactions841

（b） The Langmuir-Hinshelwood mechanism842

（c） The Eley-Rideal mechanism843

19C.2 Catalytic activity at surfaces843

Checklist of concepts844

Checklist of equations844

TOPIC 19D Processes at electrodes845

19D.1 The electrode-solution interface845

19D.2 The current density at an electrode846

（a） The Butler-Volmer equation846

（b） Tafel plots850

19D.3 Voltammetry850

19D.4 Electrolysis852

19D.5 Working galvanic cells853

Checklist of concepts854

Checklist of equations854

Resource section861

1 Common integrals862

2 Units864

3 Data865

4 Character tables895

Index899