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