Part 1 Equilibrium 1
1 The properties of gases 3
The perfect gas 3
1.1 The states of gases 3
1.2 The gas laws 8
Realgases 16
1.3 Molecular interactions 16
1.4 The van der Waals equation 19
1.5 The principle of corresponding states 23
Checklist of key ideas 24
Further reading 25
Exercises 26
Problems 28
2 The First Law：the concepts 30
The basic concepts 30
2.1 Work，heat，and energy 31
2.2 The First Law 33
Work and heat 37
2.3 Expansion work 37
2.4 Heat transactions 41
2.5 Enthalpy 45
2.6 Adiabatic changes 52
Thermochemistry 55
2.7 Standard enthalpy changes 55
2.8 Standard enthalpies of formation 60
2.9 The temperature dependence of reaction enthalpies 62
Checklist of key ideas 64
Further reading 65
Exercises 66
Problems 69
3 The First Law：the machinery 73
State functions and exact differentials 73
3.1 State and path functions 73
3.2 Exact and inexact differentials 74
Thermodynamic consequences 75
3.3 Changes in internal energy 75
3.4 The temperature dependence of the enthalpy 79
3.5 The relation between Cv and Cp 85
Checklist of key ideas 86
Further reading 87
Exercises 87
Problems 88
4 The Second Law：the concepts 90
The direction of spontaneous change 90
4.1 The dispersal of energy 91
4.2 Entropy 92
4.3 Entropy changes accompanying specific processes 100
4.4 The Third Law of thermodynamics 106
Concentrating on the system 108
4.5 The Helmholtz and Gibbs energies 108
4.6 Standard molar Gibbs energies 114
Checklist of key ideas 115
Further reading 116
Exercises 116
Problems 118
5 The Second Law：the machinery 121
Combining the First and Second Laws 121
5.1 The fundamental equation 121
5.2 Properties of the internal energy 122
Properties of the Gibbs energy 124
5.3 General considerations 124
5.4 The variation of the Gibbs energy with temperature 126
5.5 The variation of the Gibbs energy with pressure 127
Checklist of key ideas 130
Further reading 131
Exercises 131
Problems 132
6 Physical transformations of pure substances 135
Phase diagrams 135
6.1 The stabilities of phases 135
6.2 Phase boundaries 136
6.3 Three typical phase diagrams 138
Phase stability and phase transitions 140
6.4 The thermodynamic criterion of equilibrium 141
6.5 The dependence of stability on the conditions 141
6.6 The location of phase boundaries 144
6.7 The Ehrenfest classification of phase transitions 148
The physical liquid surface 150
6.8 Surface tension 150
6.9 Curved surfaces 151
6.10 Capillary action 153
Checklist of key ideas 155
Further reading 156
Exercises 156
Problems 157
7 Simple mixtures 160
The thermodynamic description of mixtures 160
7.1 Partial molar quantities 161
7.2 The thermodynamics of mixing 166
7.3 The chemical potentials of liquids 168
The properties of solutions 172
7.4 Liquid mixtures 173
7.5 Colligative properties 175
Activities 182
7.6 The solvent activity 182
7.7 The solute activity 183
7.8 The activities of regular solutions 186
Checklist of key ideas 187
Further reading 188
Exercises 189
Problems 190
8 Phase diagrams 193
Phases，components，and degrees of freedom 193
8.1 Definitions 193
8.2 The phase rule 195
Two-component systems 198
8.3 Vapour pressure diagrams 198
8.4 Temperature-composition diagrams 202
8.5 Liquid-liquid phase diagrams 204
8.6 Liquid-solid phase diagrams 208
Checklist of key ideas 214
Further reading 214
Exercises 215
Problems 218
9 Chemical equilibrium 222
Spontaneous chemical reactions 222
9.1 The Gibbs energy minimum 222
9.2 The description of equilibrium 226
The response of equilibria to the conditions 233
9.3 How equilibria respond to pressure 234
9.4 The response of equilibria to temperature 235
9.5 The response of equilibria to pH 240
Checklist of key ideas 246
Further reading 246
Exercises 247
Problems 249
10 Equilibrium electrochemistry 252
The thermodynamic properties of ions in solution 252
10.1 Thermodynamic functions of formation 253
10.2 Ion activities 256
Electrochemical cells 262
10.3 Half-reactions and electrodes 263
10.4 Varieties of cells 265
10.5 Standard potentials 270
Applications of standard potentials 274
10.6 The electrochemical series 274
10.7 The measurement of pH and pKa 277
10.8 Thermodynamic functions 280
Checklist of key ideas 282
Further reading 283
Exercises 284
Problems 286
Part 2 Structure 291
11 Quantum theory：introduction and principles 293
The origins of quantum mechanics 293
11.1 The failures of classical physics 294
11.2 Wave-particle duality 299
The dynamics of microscopic systems 304
11.3 The Schrodinger equation 304
11.4 The Born interpretation of the wavefunction 306
Quantum mechanical principles 309
11.5 The information in a wavefunction 310
11.6 The uncertainty principle 317
Checklist of key ideas 320
Further reading 321
Exercises 322
Problems 323
12 Quantum theory：techniques and applications 325
Translational motion 325
12.1 A particle in a box 326
12.2 Motion in two and more dimensions 331
12.3 Tunnelling 334
Vibrational motion 338
12.4 The energy levels 338
12.5 The wavefunctions 339
Rotational motion 345
12.6 Rotation in two dimensions：the particle on a ring 345
12.7 Rotation in three dimensions：the particle on a sphere 349
12.8 Spin 354
Techniques of approximation 355
12.9 Time-independent perturbation theory 355
12.10 Time-dependent perturbation theory 358
Checklist of key ideas 360
Further reading 361
Exercises 361
Problems 363
13 Atomic structure and atomic spectra 365
The structure and spectra of hydrogenic atoms 366
13.1 The structure of hydrogenic atoms 367
13.2 Atomic orbitals and their energies 372
13.3 Spectroscopic transitions and selection rules 381
The structures of many-electron atoms 383
13.4 The orbital approximation 384
13.5 Self-consistent field orbitals 392
The spectra of complex atoms 393
13.6 Quantum defects and ionization limits 395
13.7 Singlet and triplet states 395
13.8 Spin-orbit coupling 396
13.9 Term symbols and selection rules 399
Checklist of key ideas 404
Further reading 405
Exercises 406
Problems 408
14 Molecular structure 410
The Born-Oppenheimer approximation 410
Valence-bond theory 411
14.1 The hydrogen molecule 411
14.2 Homonuclear diatomic molecules 413
14.3 Polyatomic molecules 414
Molecular orbital theory 417
14.4 The hydrogen molecule-ion 418
14.5 The structures of diatomic molecules 422
14.6 Heteronuclear diatomic molecules 427
Molecular orbitals for polyatomic systems 432
14.7 The Huckel approximation 433
14.8 Extended Huckel theory 438
14.9 Self-consistent field calculations 441
Checklist of key ideas 446
Further reading 447
Exercises 448
Problems 450
15 Molecular symmetry 453
The symmetry elements of objects 453
15.1 Operations and symmetry elements 454
15.2 The symmetry classification of molecules 456
15.3 Some immediate consequences of symmetry 459
Character tables 463
15.4 Character tables and symmetry labels 463
15.5 Vanishing integrals and orbital overlap 469
15.6 Vanishing integrals and selection rules 474
Checklist of key ideas 476
Further reading 477
Exercises 477
Problems 478
16 Spectroscopy 1：rotational and vibrational spectra 481
General features of spectroscopy 483
16.1 Experimental techniques 483
16.2 The intensities of spectral lines 491
16.3 Linewidths 495
Pure rotation spectra 497
16.4 Moments of inertia 497
16.5 The rotational energy levels 500
16.6 Rotational transitions 504
16.7 Rotational Raman spectra 507
16.8 Nuclear statistics and rotational states 510
The vibrations of diatomic molecules 511
16.9 Molecular vibrations 512
16.10 Selection rules 513
16.11 Anharmonicity 515
16.12 Vibration-rotation spectra 517
16.13 Vibrational Raman spectra of diatomic molecules 519
The vibrations of polyatomic molecules 520
16.14 Normal modes 520
16.15 Infrared absorption spectra of polyatomic molecules 523
16.16 Vibrational Raman spectra of polyatomic molecules 524
16.17 Symmetry aspects of molecular vibrations 526
Checklist of key ideas 529
Further reading 531
Exercises 532
Problems 534
17 Spectroscopy 2：electronic transitions 538
The characteristics of electronic transitions 539
17.1 The electronic spectra of diatomic molecules 539
17.2 The electronic spectra of polyatomic molecules 545
The fates of electronically excited states 550
17.3 Fluorescence and phosphorescence 550
17.4 Dissociation and predissociation 552
Lasers 553
17.5 General principles of laser action 554
17.6 Practical lasers 558
17.7 Applications of lasers in chemistry 562
Photoelectron spectroscopy 568
17.8 The technique 568
17.9 Ultraviolet photoelectron spectroscopy 569
17.10 X-ray photoelectron spectroscopy 570
Checklist of key ideas 571
Further reading 573
Exercises 574
Problems 575
18 Spectroscopy 3：magnetic resonance 579
The effect of magnetic fields on electrons and nuclei 579
18.1 The energies of electrons in magnetic fields 580
18.2 The energies of nuclei in magnetic fields 581
18.3 Magnetic resonance spectroscopy 583
Nuclear magnetic resonance 583
18.4 The NMR spectrometer 584
18.5 The chemical shift 585
18.6 The fine structure 590
Pulse techniques in NMR 599
18.7 The magnetization vector 599
18.8 Linewidths and rate processes 602
18.9 Spin decoupling 607
18.10 The nuclear Overhauser effect 608
18.11 Two-dimensional NMR 610
18.12 Solid-state NMR 614
Electron spin resonance 615
18.13 The ESR spectrometer 615
18.14 The g-value 617
18.15 Hyperfine structure 618
Checklist of key ideas 621
Further reading 623
Exercises 624
Problems 626
19 Statistical thermodynamics：the concepts 628
The distribution of molecular states 629
19.1 Configurations and weights 629
19.2 The molecular partition function 634
The internal energy and the entropy 639
19.3 The internal energy 640
19.4 The statistical entropy 642
The canonical partition function 647
19.5 The canonical ensemble 647
19.6 The thermodynamic information in the partition function 648
19.7 Independent molecules 649
Checklist of key ideas 652
Further reading 652
Exercises 653
Problems 654
20 Statistical thermodynamics：the machinery 656
Fundamental relations 656
20.1 The thermodynamic functions 656
20.2 The molecular partition function 658
Using statistical thermodynamics 667
20.3 Mean energies 667
20.4 Heat capacities 669
20.5 Equations of state 671
20.6 Residual entropies 672
20.7 Equilibrium constants 674
Checklist of key ideas 681
Further reading 682
Exercises 682
Problems 683
21 Molecular interactions 686
Electric properties of molecules 686
21.1 Electric dipole moments 686
21.2 Polarizabilities 689
21.3 Relative permittivities 692
21.4 Refractive index 694
Interactions between molecules 696
21.5 Interactions between dipoles 698
21.6 Repulsive and total interactions 705
21.7 Molecular interactions in gases 706
21.8 Molecular interactions in liquids 709
Checklist of key ideas 713
Further reading 715
Exercises 715
Problems 716
22 Macromolecules and aggregates 719
Structure and dynamics 720
22.1 The different levels of structure 720
22.2 Random coils 721
22.3 The structure of proteins 725
22.4 The structure of nucleic acids 729
22.5 The stability of biological polymers 731
Determination of size and shape 732
22.6 Mean molar masses 732
22.7 Mass spectrometry 735
22.8 Laser light scattering 736
22.9 Ultracentrifugation 742
22.10 Electrophoresis 745
22.11 Size-exclusion chromatography 747
22.12 Viscosity 748
Self-assembly 750
22.13 Colloids 752
22.14 Micelles and biological membranes 754
22.15 Surface films 757
Checklist of key ideas 760
Further reading 762
Exercises 763
Problems 764
23 The solid state 767
Crystal lattices 767
23.1 Lattices and unit cells 767
23.2 The identification of lattice planes 770
23.3 The investigation of structure 772
23.4 Neutron and electron diffraction 783
Crystal structure 784
23.5 Metallic solids 784
23.6 Ionic solids 786
23.7 Molecular solids and covalent networks 789
The properties of solids 791
23.8 Mechanical properties 791
23.9 Electrical properties 795
23.10 Magnetic properties 801
Checklist of key ideas 805
Further reading 807
Exercises 808
Problems 810
Part 3 Change 813
24 Molecules in motion 815
Molecular motion in gases 815
24.1 The kinetic model of gases 816
24.2 Collisions with walls and surfaces 822
24.3 The rate of effusion 824
24.4 Transport properties of a perfect gas 826
Molecular motion in liquids 832
24.5 Experimental results 832
24.6 The conductivities of electrolyte solutions 833
24.7 The mobilities of ions 835
24.8 Conductivities and ion-ion interactions 841
Diffusion 842
24.9 The thermodynamic view 842
24.10 The diffusion equation 846
24.11 Diffusion probabilities 852
24.12 The statistical view 853
Checklist of key ideas 854
Further reading 856
Exercises 856
Problems 859
25 The rates of chemical reactions 862
Empirical chemical kinetics 862
25.1 Experimental techniques 863
25.2 The rates of reactions 866
25.3 Integrated rate laws 871
25.4 Reactions approaching equilibrium 876
25.5 The temperature dependence of reaction rates 879
Accounting for the rate laws 882
25.6 Elementary reactions 882
25.7 Consecutive elementary reactions 883
25.8 Unimolecular reactions 890
Checklist of key ideas 892
Further reading 893
Exercises 894
Problems 896
26 The kinetics of complex reactions 899
Chain reactions 899
26.1 The rate laws of chain reactions 900
26.2 Explosions 902
Polymerization kinetics 904
26.3 Stepwise polymerization 904
26.4 Chain polymerization 906
Homogeneous catalysis 908
26.5 Features of homogeneous catalysis 909
26.6 Enzymes 909
Oscillating reactions 914
26.7 Autocatalysis 915
26.8 Autocatalytic mechanisms of oscillating reactions 916
26.9 Bistability 917
26.10 Chemical chaos 919
Photochemistry 920
26.11 Kinetics of photophysical and photochemical processes 927
26.12 Complex photochemical processes 934
Checklist of key ideas 936
Further reading 937
Exercises 938
Problems 940
27 Molecular reaction dynamics 944
Reactive encounters 944
27.1 Collision theory 945
27.2 Diffusion-controlled reactions 951
27.3 The material balance equation 954
Activated complex theory 956
27.4 The Eyring equation 956
27.5 Thermodynamic aspects 960
The dynamics of molecular collisions 963
27.6 Reactive collisions 963
27.7 Potential energy surfaces 966
27.8 Some results from experiments and calculations 967
Checklist of key ideas 971
Further reading 972
Exercises 973
Problems 974
28 Processes at solid surfaces 977
The growth and structure of solid surfaces 977
28.1 Surface growth 977
28.2 Surface composition 979
The extent of adsorption 987
28.3 Physisorption and chemisorption 988
28.4 Adsorption isotherms 989
28.5 The rates of surface processes 994
Catalytic activity at surfaces 999
28.6 Adsorption and catalysis 999
28.7 Examples of catalysis 1001
Checklist of key ideas 1006
Further reading 1007
Exercises 1008
Problems 1009
29 Dynamics of electron transfer 1013
Electron transfer in homogeneous systems 1014
29.1 Theory of electron transfer processes 1014
29.2 Experimental results 1018
Electron transfer in heterogeneous systems 1021
29.3 The electrode-solution interface 1021
29.4 The rate of charge transfer 1024
29.5 Voltammetry 1031
29.6 Electrolysis 1036
29.7 Working galvanic cells 1037
29.8 Corrosion 1039
Checklist of key ideas 1041
Further reading 1043
Exercises 1043
Problems 1045
Further information 1 Mathematical techniques 1048
Basic procedures 1048
1.1 Logarithms and exponentials 1048
1.2 Combinatorial functions 1048
1.3 Complex numbers and complex functions 1049
1.4 Vectors 1050
Calculus 1051
1.5 Differentiation and integration 1051
1.6 Power series and Taylor expansions 1052
1.7 Partial derivatives 1053
1.8 Undetermined multipliers 1054
1.9 Differential equations 1055
Matrix algebra 1057
1.10 Matrix addition and multiplication 1058
1.11 Simultaneous equations 1059
1.12 Eigenvalue equations 1060
Further reading 1061
Further information 2 Essential concepts of physics 1062
Energy 1062
2.1 Kinetic and potential energy 1062
2.2 Energy units 1062
Classical mechanics 1063
2.3 The trajectory in terms of the energy 1063
2.4 Newton’s second law 1064
2.5 Rotational motion 1064
2.6 The harmonic oscillator 1065
Waves 1066
2.7 The electromagnetic field 1066
2.8 Features of electromagnetic radiation 1067
Electrostatics 1068
2.9 The Coulomb interaction 1068
2.10 The Coulomb potential 1068
2.11 The strength of the electric field 1069
2.12 The dipole-dipole interaction 1069
2.13 Electric current and power 1070
Further reading 1070
Data section 1071
Answers to exercises 1112
Answers to problems 1124
Index 1137