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PROLOGUE Energy，temperature，and chemistry 1

FOCUS 1 The properties of gases 3

TOPIC 1A The perfect gas 4

1A.1 Variables of state 4

（a） Pressure 4

（b） Temperature 5

1A.2 Equations of state 6

（a） The empirical basis 7

（b） Mixtures of gases 9

Checklist of concepts 10

Checklist of equations 10

TOPIC 1B The kinetic model 11

1B.1 The model 11

（a） Pressure and molecular speeds 12

（b） The Maxwell-Boltzmann distribution of speeds 13

（c） Mean values 15

1B.2 Collisions 17

（a） The collision frequency 17

（b） The mean free path 18

Checklist of concepts 18

Checklist of equations 18

TOPIC 1C Real gases 19

1C.1 Deviations from perfect behaviour 19

（a） The compression factor 20

（b） Virial coefficients 20

（c） Critical constants 22

1C.2 The van der Waals equation 23

（a） Formulation of the equation 23

（b） The features of the equation 24

（c） The principle of corresponding states 26

Checklist of concepts 27

Checklist of equations 27

FOCUS 2 The First Law 33

TOPIC 2A Internal energy 34

2A.1 Work，heat，and energy 34

（a） Operational definitions 34

（b） The molecular interpretation of heat and work 36

2A.2 The definition of internal energy 37

（a） Molecular interpretation of internal energy 37

（b） The formulation of the First Law 38

2A.3 Expansion work 38

（a） The general expression for work 39

（b） Expansion against constant pressure 39

（c） Reversible expansion 40

（d） Isothermal reversible expansion of a perfect gas 41

2A.4 Heat transactions 42

（a） Calorimetry 42

（b） Heat capacity 43

Checklist of concepts 45

Checklist of equations 45

TOPIC 2B Enthalpy 46

2B.1 The definition of enthalpy 46

（a） Enthalpy change and heat transfer 46

（b） Calorimetry 47

2B.2 The variation of enthalpy with temperature 48

（a） Heat capacity at constant pressure 48

（b） The relation between heat capacities 49

Checklist of concepts 50

Checklist of equations 50

TOPIC 2C Thermochemistry 51

2C.1 Standard enthalpy changes 51

（a） Enthalpies of physical change 51

（b） Enthalpies of chemical change 52

（c） Hess’s law 53

2C.2 Standard enthalpies of formation 54

2C.3 The temperature dependence of reaction enthalpies 55

2C.4 Experimental techniques 56

（a） Differential scanning calorimetry 56

（b） Isothermal titration calorimetry 57

Checklist of concepts 57

Checklist of equations 58

TOPIC 2D State functions and exact differentials 59

2D.1 Exact and inexact differentials 59

2D.2 Changes in internal energy 60

（a） General considerations 60

（b） Changes in internal energy at constant pressure 62

2D.3 Changes in enthalpy 63

2D.4 The Joule-Thomson effect 64

（a） The observation of the Joule-Thomson effect 64

（b） The molecular interpretation of the Joule-Thomson effect 65

Checklist of concepts 66

Checklist of equations 66

TOPIC 2E Adiabatic changes 67

2B.1 The change in temperature 67

2B.2 The change in pressure 68

Checklist of concepts 69

Checklist of equations 69

FOCUS 3 The Second and Third Laws 77

TOPIC 3A Entropy 78

3A.1 The Second Law 78

3A.2 The definition of entropy 80

（a） The thermodynamic definition of entropy 80

（b） The statistical definition of entropy 81

3A.3 The entropy as a state function 82

（a） The Carnot cycle 82

（b） The thermodynamic temperature 85

（c） The Clausius inequality 85

Checklist of concepts 86

Checklist of equations 87

TOPIC 3B Entropy changes accompanying specific processes 88

3B.1 Expansion 88

3B.2 Phase transitions 89

3B.3 Heating 90

3B.4 Composite processes 90

Checklist of concepts 91

Checklist of equations 91

TOPIC 3C The measurement of entropy 92

3C.1 The calorimetric measurement of entropy 92

3C.2 The Third Law 93

（a） The Nernst heat theorem 93

（b） Third-Law entropies 94

（c） The temperature dependence of reaction entropy 95

Checklist of concepts 96

Checklist of equations 96

TOPIC 3D Concentrating on the system 97

3D.1 The Helmholtz and Gibbs energies 97

（a） Criteria of spontaneity 97

（b） Some remarks on the Helmholtz energy 98

（c） Maximum work 98

（d） Some remarks on the Gibbs energy 99

（e） Maximum non-expansion work 100

3D.2 Standard molar Gibbs energies 100

（a） Gibbs energies of formation 101

（b） The Born equation 102

Checklist of concepts 103

Checklist of equations 103

TOPIC 3E Combining the First and Second Laws 104

3B.1 Properties of the internal energy 104

（a） The Maxwell relations 104

（b） The variation of internal energy with volume 106

3B.2 Properties of the Gibbs energy 106

（a） General considerations 106

（b） The variation of the Gibbs energy with temperature 108

（c） The variation of the Gibbs energy with pressure 108

Checklist of concepts 110

Checklist of equations 110

FOCUS 4 Physical transformations of pure substances 119

TOPIC 4A Phase diagrams of pure substances 120

4A.1 The stabilities of phases 120

（a） The number of phases 120

（b） Phase transitions 120

（c） Thermodynamic criteria of phase stability 121

4A.2 Phase boundaries 122

（a） Characteristic properties related to phase transitions 122

（b） The phase rule 123

4A.3 Three representative phase diagrams 125

（a） Carbon dioxide 125

（b） Water 125

（c） Helium 126

Checklist of concepts 127

Checklist of equations 127

TOPIC 4B Thermodynamic aspects of phase transitions 128

4B.1 The dependence of stability on the conditions 128

（a） The temperature dependence of phase stability 128

（b） The response of melting to applied pressure 129

（c） The vapour pressure of a liquid subjected to pressure 130

4B.2 The location of phase boundaries 131

（a） The slopes of the phase boundaries 131

（b） The solid-liquid boundary 132

（c） The liquid-vapour boundary 132

（d） The solid-vapour boundary 134

Checklist of concepts 134

Checklist of equations 134

FOCUS 5 Simple mixtures 141

TOPIC 5A The thermodynamic description of mixtures 143

5A.1 Partial molar quantities 143

（a） Partial molar volume 143

（b） Partial molar Gibbs energies 145

（c） The wider significance of the chemical potential 146

（d） The Gibbs-Duhem equation 146

5A.2 The thermodynamics of mixing 147

（a） The Gibbs energy of mixing of perfect gases 147

（b） Other thermodynamic mixing functions 149

5A.3 The chemical potentials of liquids 150

（a） Ideal solutions 150

（b） Ideal-dilute solutions 152

Checklist of concepts 153

Checklist of equations 154

TOPIC 5B The properties of solutions 155

5B.1 Liquid mixtures 155

（a） Ideal solutions 155

（b） Excess functions and regular solutions 156

5B.2 Colligative properties 158

（a） The common features of colligative properties 158

（b） The elevation of boiling point 159

（c） The depression of freezing point 161

（d） Solubility 161

（e） Osmosis 162

Checklist of concepts 164

Checklist of equations 165

TOPIC 5C Phase diagrams of binary systems：liquids 166

5C.1 Vapour pressure diagrams 166

5C.2 Temperature-composition diagrams 168

（a） The construction of the diagrams 168

（b） The interpretation of the diagrams 169

5C.3 Distillation 170

（a） Simple and fractional distillation 170

（b） Azeotropes 171

（c） Immiscible liquids 172

5C.4 Liquid-liquid phase diagrams 172

（a） Phase separation 172

（b） Critical solution temperatures 173

（c） The distillation of partially miscible liquids 175

Checklist of concepts 176

Checklist of equations 176

TOPIC 5D Phase diagrams of binary systems：solids 177

5D.1 Eutectics 177

5D.2 Reacting systems 178

5D.3 Incongruent melting 179

Checklist of concepts 179

TOPIC 5E Phase diagrams of ternary systems 180

5E.1 Triangular phase diagrams 180

5E.2 Ternary systems 181

（a） Partially miscible liquids 181

（b） Ternary solids 182

Checklist of concepts 182

TOPIC 5F Activities 183

5F.1 The solvent activity 183

5F.2 The solute activity 183

（a） Ideal-dilute solutions 184

（b） Real solutes 184

（c） Activities in terms of molalities 185

5F.3 The activities of regular solutions 185

5F.4 The activities of ions 187

（a） Mean activity coefficients 187

（b） The Debye-Huckel limiting law 187

（c） Extensions of the limiting law 188

Checklist of concepts 189

Checklist of equations 190

FOCUS 6 Chemical equilibrium 203

TOPIC 6A The equilibrium constant 204

6A.1 The Gibbs energy minimum 204

（a） The reaction Gibbs energy 204

（b） Exergonic and endergonic reactions 205

6A.2 The description of equilibrium 205

（a） Perfect gas equilibria 205

（b） The general case of a reaction 206

（c） The relation between equilibrium constants 209

（d） Molecular interpretation of the equilibrium constant 210

Checklist of concepts 211

Checklist of equations 211

TOPIC 6B The response of equilibria to the conditions 212

6B.1 The response to pressure 212

6B.2 The response to temperature 213

（a） Thevan’tHoffequation 213

（b） The value of Kat different temperatures 215

Checklist of concepts 216

Checklist of equations 216

TOPIC 6C Electrochemical cells 217

6C.1 Half-reactions and electrodes 217

6C.2 Varieties of cells 218

（a） Liquid junction potentials 218

（b） Notation 219

6C.3 The cell potential 219

（a） The Nernst equation 219

（b） Cells at equilibrium 221

6C.4 The determination of thermodynamic functions 221

Checklist of concepts 223

Checklist of equations 223

TOPIC 6D Electrode potentials 224

6D.1 Standard potentials 224

（a） The measurement procedure 225

（b） Combining measured values 226

6D.2 Applications of standard potentials 226

（a） The electrochemical series 226

（b） The determination of activity coefficients 226

（c） The determination of equilibrium constants 227

Checklist of concepts 227

Checklist of equations 228

FOCUS 7 Quantum theory 235

TOPIC 7A The origins of quantum mechanics 237

7A.1 Energy quantization 237

（a） Black-body radiation 237

（b） Heat capacity 240

（c） Atomic and molecular spectra 241

7A.2 Wave-particle duality 242

（a） The particle character of electromagnetic radiation 242

（b） The wave character of particles 244

Checklist of concepts 245

Checklist of equations 245

TOPIC 7B Wavefunctions 246

7B.1 The Schrodinger equation 246

7B.2 The Born interpretation 247

（a） Normalization 248

（b） Constraints on the wavefunction 249

（c） Quantization 250

Checklist of concepts 250

Checklist of equations 250

TOPIC 7C Operators and observables 251

7C.1 Operators 251

（a） Eigenvalue equations 251

（b） The construction of operators 252

（c） Hermitian operators 253

（d） Orthogonality 254

7C.2 Superpositions and expectation values 255

7C.3 The uncertainty principle 257

7C.4 The postulates of quantum mechanics 259

Checklist of concepts 260

Checklist of equations 260

TOPIC 7D Translational motion 261

7D.1 Free motion in one dimension 261

7D.2 Confined motion in one dimension 262

（a） The acceptable solutions 263

（b） The properties of the wavefunctions 264

（c） The properties of the energy 265

7D.3 Confined motion in two and more dimensions 266

（a） Energy levels and wavefunctions 266

（b） Degeneracy 267

7D.4 Tunnelling 268

Checklist of concepts 271

Checklist of equations 272

TOPIC 7E Vibrational motion 273

7E.1 The harmonic oscillator 273

（a） The energy levels 274

（b） The wavefunctions 275

7E.2 Properties of the harmonic oscillator 277

（a） Mean values 277

（b） Tunnelling 278

Checklist of concepts 279

Checklist of equations 280

TOPIC 7F Rotational motion 281

7F.1 Rotation in two dimensions 281

（a） The solutions of the Schrodinger equation 283

（b） Quantization of angular momentum 284

7F.2 Rotation in three dimensions 285

（a） The wavefunctions and energy levels 285

（b） Angular momentum 288

（c） The vector model 288

Checklist of concepts 290

Checklist of equations 290

FOCUS 8 Atomic structure and spectra 303

TOPIC 8A Hydrogenic atoms 304

8A.1 The structure of hydrogenic atoms 304

（a） The separation of variables 304

（b） The radial solutions 305

8A.2 Atomic orbitals and their energies 308

（a） The specification of orbitals 308

（b） The energy levels 308

（c） Ionization energies 309

（d） Shells and subshells 309

（e） s Orbitals 310

（f） Radial distribution functions 311

（g） p Orbitals 313

（h） d Orbitals 314

Checklist of concepts 314

Checklist of equations 315

TOPIC 8B Many-electron atoms 316

8B.1 The orbital approximation 316

8B.2 The Pauli exclusion principle 317

（a） Spin 317

（b） The Pauli principle 318

8B.3 The building-up principle 319

（a） Penetration and shielding 319

（b） Hund’s rules 321

（c） Atomic and ionic radii 323

（d） Ionization energies and electron affinities 324

8B.4 Self-consistent field orbitals 325

Checklist of concepts 325

Checklist of equations 326

TOPIC 8C Atomic spectra 327

8C.1 The spectra of hydrogenic atoms 327

8C.2 The spectra of many-electron atoms 328

（a） Singlet and triplet terms 328

（b） Spin-orbit coupling 329

（c） Term symbols 332

（d） Hund’s rules 335

（e） Selection rules 335

Checklist of concepts 336

Checklist of equations 336

FOCUS 9 Molecular structure 341

PROLOGUE The Born-Oppenheimer approximation 343

TOPIC 9A Valence-bond theory 344

9A.1 Diatomic molecules 344

9A.2 Resonance 346

9A.3 Polyatomic molecules 346

（a） Promotion 347

（b） Hybridization 347

Checklist of concepts 350

Checklist of equations 350

TOPIC 9B Molecular orbital theory：the hydrogen molecule-ion 351

9B.1 Linear combinations of atomic orbitals 351

（a） The construction of linear combinations 351

（b） Bonding orbitals 353

（c） Antibonding orbitals 354

9B.2 Orbital notation 356

Checklist of concepts 356

Checklist of equations 356

TOPIC 9C Molecular orbital theory：homonuclear diatomic molecules 357

9C.1 Electron configurations 357

（a） σ Orbitals and π orbitals 357

（b） The overlap integral 359

（c） Period 2 diatomic molecules 360

9C.2 Photoelectron spectroscopy 362

Checklist of concepts 363

Checklist of equations 364

TOPIC 9D Molecular orbital theory：heteronuclear diatomic molecules 365

9D.1 Polar bonds and electronegativity 365

9D.2 The variation principle 366

（a） The procedure 367

（b） The features of the solutions 369

Checklist of concepts 370

Checklist of equations 370

TOPIC 9E Molecular orbital theory：polyatomic molecules 371

9E.1 The Huckel approximation 371

（a） An introduction to the method 371

（b） The matrix formulation of the method 372

9E.2 Applications 375

（a） π-Electron binding energy 375

（b） Aromatic stability 376

9E.3 Computational chemistry 377

（a） Semi-empirical and ab initio methods 378

（b） Density functional theory 379

（c） Graphical representations 379

Checklist of concepts 380

Checklist of equations 380

FOCUS 10 Molecular symmetry 387

TOPIC 10A Shape and symmetry 388

10A.1 Symmetry operations and symmetry elements 388

10A.2 The symmetry classification of molecules 390

（a） The groups C 1' C i’ and Cs 392

（b） The groups C n' C nv’ and Cnh 392

（c） The groups D n' D nh' and D nd 393

（d） The groups 5n 393

（e） The cubic groups Sn 393

（f） The full rotation group 394

10A.3 Some immediate consequences of symmetry 394

（a） Polarity 394

（b） Chirality 395

Checklist of concepts 395

Checklist of operations and elements 396

TOPIC 10B Group theory 397

10B.1 The elements of group theory 397

10B.2 Matrix representations 398

（a） Representatives of operations 398

（b） The representation of a group 399

（c） Irreducible representations 400

（d） Characters 401

10B.3 Character tables 401

（a） The symmetry species of atomic orbitals 402

（b） The symmetry species of linear combinations of orbitals 403

（c） Character tables and degeneracy 404

Checklist of concepts 405

Checklist of equations 405

TOPIC 10C Applications of symmetry 406

10C.1 Vanishing integrals 406

（a） Integrals of the product of functions 407

（b） Decomposition of a representation 408

10C.2 Applications to molecular orbital theory 409

（a） Orbital overlap 409

（b） Symmetry-adapted linear combinations 409

10C.3 Selection rules 411

Checklist of concepts 411

Checklist of equations 411

FOCUS 11 Molecular spectroscopy 417

TOPIC 11A General features of molecular spectroscopy 419

11A.1 The absorption and emission of radiation 420

（a） Stimulated and spontaneous radiative processes 420

（b） Selection rules and transition moments 421

（c） The Beer-Lambert law 421

11A.2 Spectral linewidths 423

（a） Doppler broadening 423

（b） Lifetime broadening 425

11A.3 Experimental techniques 425

（a） Sources of radiation 426

（b） Spectral analysis 426

（c） Detectors 428

（d） Examples of spectrometers 428

Checklist of concepts 429

Checklist of equations 429

TOPIC 11B Rotational spectroscopy 430

11B.1 Rotational energy levels 430

（a） Spherical rotors 432

（b） Symmetric rotors 432

（c） Linear rotors 434

（d） Centrifugal distortion 434

11B.2 Microwave spectroscopy 435

（a） Selection rules 435

（b） The appearance of microwave spectra 436

11B.3 Rotational Raman spectroscopy 437

11B.4 Nuclear statistics and rotational states 439

Checklist of concepts 441

Checklist of equations 441

TOPIC 11C Vibrational spectroscopy of diatomic molecules 442

11C.1 Vibrational motion 442

11C.2 Infrared spectroscopy 443

11C.3 Anharmonicity 444

（a） The convergence of energy levels 444

（b） The Birge-Sponer plot 445

11C.4 Vibration-rotation spectra 446

（a） Spectral branches 447

（b） Combination differences 448

11C.5 Vibrational Raman spectra 448

Checklist of concepts 449

Checklist of equations 450

TOPIC 11D Vibrational spectroscopy of polyatomic molecules 451

11D.1 Normal modes 451

11D.2 Infrared absorption spectra 452

11D.3 Vibrational Raman spectra 453

Checklist of concepts 454

Checklist of equations 454

TOPIC 11E Symmetry analysis of vibrational spectra 455

11E.1 Classification of normal modes according to symmetry 455

11E.2 Symmetry of vibrational wavefunctions 457

（a） Infrared activity of normal modes 457

（b） Raman activity of normal modes 458

（c） The symmetry basis of the exclusion rule 458

Checklist of concepts 458

TOPIC 11F Electronic spectra 459

11F.1 Diatomic molecules 459

（a） Term symbols 459

（b） Selection rules 461

（c） Vibrational fine structure 462

（d） Rotational fine structure 465

11F.2 Polyatomic molecules 466

（a） d-Metal complexes 467

（b） π*←πandπ*←ntransitions 468

Checklist of concepts 469

Checklist of equations 469

TOPIC 11G Decay of excited states 470

11G.1 Fluorescence and phosphorescence 470

11G.2 Dissociation and predissociation 472

11G.3 Lasers 473

Checklist of concepts 474

FOCUS 12 Magnetic resonance 487

TOPIC 12A General principles 488

12A.1 Nuclear magnetic resonance 488

（a） The energies of nuclei in magnetic fields 488

（b） The NMR spectrometer 490

12A.2 Electron paramagnetic resonance 491

（a） The energies of electrons in magnetic fields 491

（b） The EPR spectrometer 492

Checklist of concepts 493

Checklist of equations 493

TOPIC 12B Features of NMR spectra 494

12B.1 The chemical shift 494

12B.2 The origin of shielding constants 496

（a） The local contribution 496

（b） Neighbouring group contributions 497

（c） The solvent contribution 498

12B.3 The fine structure 499

（a） The appearance of the spectrum 499

（b） The magnitudes of coupling constants 501

（c） The origin of spin-spin coupling 502

（d） Equivalent nuclei 503

（e） Strongly coupled nuclei 504

12B.4 Exchange processes 505

12B.5 Solid-state NMR 506

Checklist of concepts 507

Checklist of equations 508

TOPIC 12C Pulse techniques in NMR 509

12C.1 The magnetization vector 509

（a） The effect of the radiofrequency field 510

（b） Time-and frequency-domain signals 511

12C.2 Spin relaxation 513

（a） The mechanism of relaxation 513

（b） The measurement of T 1 and T 2 514

12C.3 Spin decoupling 515

12C.4 The nuclear Overhauser effect 516

Checklist of concepts 518

Checklist of equations 518

TOPIC 12D Electron paramagnetic resonance 519

12D.1 The g-value 519

12D.2 Hyperfine structure 520

（a） The effects of nuclear spin 520

（b） The McConnell equation 521

（c） The origin of the hyperfine interaction 522

Checklist of concepts 523

Checklist of equations 523

FOCUS 13 Statistical thermodynamics 531

TOPIC 13A The Boltzmann distribution 532

13A.1 Configurations and weights 532

（a） Instantaneous configurations 532

（b） The most probable distribution 533

（c） The values of the constants 535

13A.2 The relative population of states 536

Checklist of concepts 536

Checklist of equations 537

TOPIC 13B Molecular partition functions 538

13B.1 The significance of the partition function 538

13B.2 Contributions to the partition function 540

（a） The translational contribution 540

（b） The rotational contribution 542

（c） The vibrational contribution 546

（d） The electronic contribution 547

Checklist of concepts 548

Checklist of equations 548

TOPIC 13C Molecular energies 549

13C.1 The basic equations 549

13C.2 Contributions of the fundamental modes of motion 550

（a） The translational contribution 550

（b） The rotational contribution 550

（c） The vibrational contribution 551

（d） The electronic contribution 552

（e） The spin contribution 552

Checklist of concepts 553

Checklist of equations 553

TOPIC 13D The canonical ensemble 554

13D.1 The concept of ensemble 554

（a） Dominating configurations 555

（b） Fluctuations from the most probable distribution 555

13D.2 The mean energy of a system 556

13D.3 Independent molecules revisited 556

13D.4 The variation of the energy with volume 557

Checklist of concepts 558

Checklist of equations 558

TOPIC 13E The internal energy and the entropy 559

13E.1 The internal energy 559

（a） The calculation of internal energy 559

（b） Heat capacity 560

13E.2 The entropy 561

（a） Entropy and the partition function 561

（b） The translational contribution 563

（c） The rotational contribution 563

（d） The vibrational contribution 564

（e） Residual entropies 565

Checklist of concepts 566

Checklist of equations 566

TOPIC 13F Derived functions 567

13F.1 The derivations 567

13F.2 Equilibrium constants 570

（a） The relation between K and the partition function 570

（b） A dissociation equilibrium 570

（c） Contributions to the equilibrium constant 571

Checklist of concepts 573

Checklist of equations 573

FOCUS 14 Molecular interactions 583

TOPIC 14A The electric properties of molecules 585

14A.1 Electric dipole moments 585

14A.2 Polarizabilities 587

14A.3 Polarization 588

（a） The frequency dependence of the polarization 588

（b） Molar polarization 590

Checklist of concepts 592

Checklist of equations 592

TOPIC 14B Interactions between molecules 593

14B.1 The interactions of dipoles 593

（a） Charge-dipole interactions 593

（b） Dipole-dipole interactions 594

（c） Dipole-induced dipole interactions 597

（d） Induced dipole-induced dipole interactions 597

14B.2 Hydrogen bonding 598

14B.3 The total interaction 599

Checklist of concepts 601

Checklist of equations 601

TOPIC 14C Liquids 602

14C.1 Molecular interactions in liquids 602

（a） The radial distribution function 602

（b） The calculation of g（r） 603

（c） The thermodynamic properties of liquids 604

14C.2 The liquid-vapour interface 605

（a） Surfacetension 605

（b） Curved surfaces 606

（c） Capillaryaction 606

14C.3 Surface films 608

（a） Surface pressure 608

（b） The thermodynamics of surface layers 609

14C.4 Condensation 611

Checklist of concepts 612

Checklist of equations 612

TOPIC 14D Macromolecules 613

14D.1 Average molar masses 613

14D.2 The different levels of structure 614

14D.3 Random coils 615

（a） Measures of size 615

（b） Constrained chains 618

（c） Partly rigid coils 618

14D.4 Mechanical properties 619

（a） Conformational entropy 619

（b） Elastomers 620

14D.5 Thermal properties 621

Checklist of concepts 622

Checklist of equations 622

TOPIC 14E Self-assembly 623

14E.1 Colloids 623

（a） Classification and preparation 623

（b） Structure and stability 624

（c） The electrical double layer 624

14E.2 Micelles and biological membranes 626

（a） The hydrophobic interaction 626

（b） Micelle formation 627

（c） Bilayers，vesicles，andmembranes 628

Checklist of concepts 630

Checklist of equations 630

FOCUS 15 Solids 639

TOPIC 15A Crystal structure 641

15A.1 Periodic crystal lattices 641

15A.2 The identification of lattice planes 643

（a） The Miller indices 643

（b） The separation of neighbouring planes 644

Checklist of concepts 645

Checklist of equations 645

TOPIC 15B Diffraction techniques 646

15B.1 X-ray crystallography 646

（a） X-ray diffraction 646

（b） Bragg’s law 648

（c） Scattering factors 649

（d） The electron density 649

（e） The determination of structure 652

15B.2 Neutron and electron diffraction 654

Checklist of concepts 655

Checklist of equations 655

TOPIC 15C Bonding in solids 656

15C.1 Metals 656

（a） Close packing 656

（b） Electronic structure of metals 658

15C.2 Ionic solids 660

（a） Structure 660

（b） Energetics 661

15C.3 Covalent and molecular solids 663

Checklist of concepts 664

Checklist of equations 665

TOPIC 15D The mechanical properties of solids 666

Checklist of concepts 667

Checklist of equations 668

TOPIC 15E The electrical properties of solids 669

15E.1 Metallic conductors 669

15E.2 Insulators and semiconductors 670

15E.3 Superconductors 672

Checklist of concepts 673

Checklist of equations 673

TOPIC 15F The magnetic properties of solids 674

15F.1 Magnetic susceptibility 674

15F.2 Permanent and induced magnetic moments 675

15F.3 Magnetic properties of superconductors 676

Checklist of concepts 676

Checklist of equations 677

TOPIC 15G The optical properties of solids 678

15G.1 Excitons 678

15G.2 Metals and semiconductors 679

（a） Light absorption 679

（b） Light-emitting diodes and diode lasers 680

15G.3 Nonlinear optical phenomena 680

Checklist of concepts 681

FOCUS 16 Molecules in motion 689

TOPIC 16A Transport properties of a perfect gas 690

16A.1 The phenomenological equations 690

16A.2 The transport parameters 692

（a） The diffusion coefficient 693

（b） Thermal conductivity 694

（c） Viscosity 696

（d） Effusion 697

Checklist of concepts 697

Checklist of equations 698

TOPIC 16B Motion in liquids 699

16B.1 Experimental results 699

（a） Liquid viscosity 699

（b） Electrolyte solutions 700

16B.2 The mobilities of ions 701

（a） The drift speed 701

（b） Mobility and conductivity 703

（c） The Einstein relations 704

Checklist of concepts 705

Checklist of equations 705

FOCUS 16C Diffusion 706

16C.1 The thermodynamic view 706

16C.2 The diffusion equation 708

（a） Simple diffusion 708

（b） Diffusion with convection 710

（c） Solutions of the diffusion equation 710

16C.3 The statistical view 712

Checklist of concepts 713

Checklist of equations 714

FOCUS 17 Chemical kinetics 721

TOPIC 17A The rates of chemical reactions 723

17A.1 Monitoring the progress of a reaction 723

（a） General considerations 723

（b） Special techniques 724

17A.2 The rates of reactions 725

（a） The definition of rate 725

（b） Rate laws and rate constants 726

（c） Reaction order 727

（d） The determination of the rate law 728

Checklist of concepts 729

Checklist of equations 730

TOPIC 17B Integrated rate laws 731

17B.1 Zeroth-order reactions 731

17B.2 First-order reactions 731

17B.3 Second-order reactions 733

Checklist of concepts 736

Checklist of equations 736

TOPIC 17C Reactions approaching equilibrium 737

17C.1 First-order reactions approaching equilibrium 737

17C.2 Relaxation methods 738

Checklist of concepts 740

Checklist of equations 740

TOPIC 17D The Arrhenius equation 741

17D.1 The temperature dependence of reaction rates 741

17D.2 The interpretation of the Arrhenius parameters 742

（a） A first look at the energy requirements of reactions 743

（b） The effect of a catalyst on the activation energy 744

Checklist of concepts 745

Checklist of equations 745

TOPIC 17E Reaction mechanisms 746

17E.1 Elementary reactions 746

17E.2 Consecutive elementary reactions 747

17E.3 The steady-state approximation 748

17E.4 The rate-determining step 749

17E.5 Pre-equilibria 750

17E.6 Kinetic and thermodynamic control of reactions 752

Checklist of concepts 752

Checklist of equations 752

TOPIC 17F Examples of reaction mechanisms 753

17F.1 Unimolecular reactions 753

17F.2 Polymerization kinetics 754

（a） Stepwise polymerization 755

（b） Chain polymerization 756

17F.3 Enzyme-catalysed reactions 758

Checklist of concepts 761

Checklist of equations 761

TOPIC 17G Photochemistry 762

17G.1 Photochemical processes 762

17G.2 The primary quantum yield 763

17G.3 Mechanism of decay of excited singlet states 764

17G.4 Quenching 765

17G.5 Resonance energy transfer 767

Checklist of concepts 768

Checklist of equations 768

FOCUS 18 Reaction dynamics 779

TOPIC 18A Collision theory 780

18A.1 Reactive encounters 780

（a） Collision rates in gases 781

（b） The energy requirement 781

（c） The steric requirement 784

18A.2 The RRK model 785

Checklist of concepts 786

Checklist of equations 786

TOPIC 18B Diffusion-controlled reactions 787

18B.1 Reactions in solution 787

（a） Classes of reaction 787

（b） Diffusion and reaction 788

18B.2 The material-balance equation 789

（a） The formulation of the equation 789

（b） Solutions of the equation 790

Checklist of concepts 790

Checklist of equations 791

TOPIC 18C Transition-state theory 792

18C.1 The Eyring equation 792

（a） The formulation of the equation 792

（b） The rate of decay of the activated complex 793

（c） The concentration of the activated complex 793

（d） The rate constant 794

18C.2 Thermodynamic aspects 795

（a） Activation parameters 795

（b） Reactions between ions 797

18C.3 The kinetic isotope effect 798

Checklist of concepts 800

Checklist of equations 800

TOPIC 18D The dynamics of molecular collisions 801

18D.1 Molecular beams 801

（a） Techniques 801

（b） Experimental results 802

18D.2 Reactive collisions 804

（a） Probes of reactive collisions 804

（b） State-to-state reaction dynamics 804

18D.3 Potential energy surfaces 805

18D.4 Some results from experiments and calculations 806

（a） The direction of attack and separation 807

（b） Attractive and repulsive surfaces 808

（c） Quantum mechanical scattering theory 808

Checklist of concepts 809

Checklist of equations 809

TOPIC 18E Electron transfer in homogeneous systems 810

18E.1 The rate law 810

18E.2 The role of electron tunnelling 811

18E.3 The rate constant 812

18E.4 Experimental tests of the theory 813

Checklist of concepts 815

Checklist of equations 815

FOCUS 19 Processes at solid surfaces 823

TOPIC 19A An introduction to solid surfaces 824

19A.1 Surface growth 824

19A.2 Physisorption and chemisorption 825

19A.3 Experimental techniques 826

（a） Microscopy 827

（b） Ionization techniques 828

（c） Diffraction techniques 829

（d） Determination of the extent and rates of adsorption and desorption 830

Checklist of concepts 831

Checklist of equations 831

TOPIC 19B Adsorption and desorption 832

19B.1 Adsorption isotherms 832

（a） The Langmuir isotherm 832

（b） The isosteric enthalpy of adsorption 834

（c） The BET isotherm 835

（d） The Temkin and Freundlich isotherms 837

19B.2 The rates of adsorption and desorption 837

（a） The precursor state 837

（b） Adsorption and desorption at the molecular level 838

（c） Mobility on surfaces 839

Checklist of concepts 840

Checklist of equations 840

TOPIC 19C Heterogeneous catalysis 841

19C.1 Mechanisms of heterogeneous catalysis 841

（a） Unimolecular reactions 841

（b） The Langmuir-Hinshelwood mechanism 842

（c） The Eley-Rideal mechanism 843

19C.2 Catalytic activity at surfaces 843

Checklist of concepts 844

Checklist of equations 844

TOPIC 19D Processes at electrodes 845

19D.1 The electrode-solution interface 845

19D.2 The current density at an electrode 846

（a） The Butler-Volmer equation 846

（b） Tafel plots 850

19D.3 Voltammetry 850

19D.4 Electrolysis 852

19D.5 Working galvanic cells 853

Checklist of concepts 854

Checklist of equations 854

Resource section 861

1 Common integrals 862

2 Units 864

3 Data 865

4 Character tables 895

Index 899