TABLE OF CONTENTS
Chapter 1 States of matter and the properties of gases...1
The description of states of matter...3
1.1 Pressure...3
1.2 Temperature...6
1.3 Amount of substance...7
Equations of state...10
1.4 The perfect gas equation of state...10
1.5 Using the perfect gas law...12
Mixtures of gases: partial pressures...15
The kinetic theory of gases...18
1.6 The pressure of a gas...18
1.7 The speed of gas molecules...19
1.8 Molecular collisions...23
Real gases...25
1.9 Intermolecular interactions...25
1.10 The critical temperature...26
1.11 Real equaitons of state...27
1.12 The liquefaction of gases...30

Chapter 2 Thermodynamics: the First Law...35
The conservation of energy...36
2.1 Work and heat...37
2.2 The measurement of work...38
The internal energy...42
2.3 Notation...43
2.4 The First Law...45
The enthalpy...49
2.5 The definition of enthalpy...50
2.6 The enthalpy of physical change...52
2.7 The enthalpy of chemical change...62
2.8 The variation of enthalpy with temperature...69

Chapter 3 Thermodynamics: the Second Law...75
Entropy...76
3.1 The direction of spontaneous change...76
3.2 Entropy and the Second Law...77
The Gibbs energy...88
3.3 Focusing on the system...89
3.4 The relation between and ...99
Reactions at equilibrium...105
3.5 The condition of equilibrium...105
3.6 The response of equilibria to the conditions...107

Chapter 4 Phase equilibria...115
Phase diagrams of single substances...116
4.1 Phase boundaries...117
4.2 Phase diagrams of typical materials...121
The properties of nonelectrolyte solutions...123
4.3 The thermodynamic description of mixtures...123
4.4 Colligative properties...136
Phase diagrams of mixtures...141
4.5 Mixtures of volatile liquids...142
4.6 Liquid-liquid phase diagrams...144
4.7 Liquid-solid phase diagrams...147

Chapter 5 Chemical equilibrium...153
The interpretation of equilibrium constants...154
Acids and bases...158
5.1 The Bronsted-Lowry theory...159
5.2 Acidity constants...162
5.3 Weak and strong bases...172
5.4 Conjugate acids and bases...176
5.5 Salts in water...178
5.6 Acid-base titrations...180
Solubility equilibria...187
5.7 The solubility constant...188
5.8 The common-ion effect...190
Coupled reactions...192
5.9 Biological activity: the thermodynamics of ATP...192
5.10 The extraction of metals from their oxides...194

Chapter 6 Electrochemistry...199
Electrochemical cells...199
6.1 Half-reactions and electrodes...200
6.2 Varieties of cell...208
6.3 Reduction potentials...214
Applications of reduction potentials...223
6.4 The electrochemical series...223
6.5 Thermodynamic functions from cell potential measurements...225

Chapter 7 The rates of reactions...233
Empirical chemical kinetics...233
7.1 Experimental techniques...234
7.2 Reaction rates...237
7.3 Integrated rate laws...243
7.4 Half-lives...248
7.5 The temperature dependence of reaction rates...250
Accounting for the rate laws...259
7.6 Elementary reactions...260
7.7 The formulation of rate laws...261
7.8 Unimolecular reactions...271
Chain reactions...273
7.9 The structure of chain reactions...273
7.10 The rate laws of chain reactions...274
7.11 Explosions...276
7.12 Photochemical reactions...277

Chapter 8 Atomic structure...285
The failure of classical physics...285
8.1 Black-body radiation...286
8.2 Heat capacities...290
8.3 Waves as particles and particles as waves...292
8.4 Atomic and molecular spectra...296
The dynamics of microscopic systems...296
8.5 The Schrodinger equation...297
8.6 Applications of quantum mechanics...302
The structures of atoms...308
8.7 The experimental basis: the spectra of hydrogenic atoms...308
8.8 The interpretation: the structures of hydrogenic atoms...310
8.9 Electron spin...317
8.10 Spectral transitions and selection rules...319
The structures of many-electron atoms...320
8.11 The orbital approximation...321
8.12 Periodic trends in atomic properties...327

Chapter 9 The chemical bond...333
Valence bond theory...335
9.1 Diatomic molecules...335
9.2 Polyatomic molecules...337
Molecular orbitals...342
9.3 Linear combinations of atomic orbitals...342
9.4 Bonding and antibonding orbitals...343
9.5 The structures of diatomic molecules...345
9.6 Heteronuclear diatomic molecules...355
9.7 The structures of polyatomic molecules...358
The band theory of solids...360
9.8 The formation of bands...360
9.9 The occupation of orbitals...362
9.10 Insulators and semiconductors...363

Chapter 10 Cohesion and structure...365
The origin of cohesion...365
10.1 Lattice enthalpy...366
10.2 Permanent and induced electric dipole moments...370
10.3 The total interaction...378
Fluids...380
10.4 Real gases...380
10.5 Liquids...381
10.6 Molecular motion in liquids...382
10.7 Liquid crystals...385
10.8 Disperse systems...385
Crystal structure...390
10.9 Unit cells...391
10.10 The identification of crystal planes...392
10.11 The determination of structure...395
10.12 Information from X-ray analysis...400
10.13 The packing of identical spheres: metal crystals...401
10.14 Ionic crystals...403
Natural bioploymers...404
10.15 The primary and secondary structures...405
10.16 High-order structure...406

Chapter 11 Molecular spectroscopy...411
General features of spectroscopy...411
11.1 Experimental techniques...412
11.2 Intensities and linewidths...418
Rotational spectroscopy...420
11.3 The rotational energies of molecules...420
11.4 Rotational transitions: microwave spectroscopy...422
11.5 Rotational Raman spectra...424
Vibrational spectra...425
11.6 The vibrations of molecules...426
11.7 The vibrations of polyatomic molecules...430
11.8 Vibrational Raman spectra of polyatomic molecules...433
Electronic transitions: ultraviolet and visible spectra...436
11.9 The Franck-Condon principle...437
11.10 Specific types of transition...438
11.11 Radiative decay...439
11.12 Circular dichroism...442
11.13 Photoelectron spectroscopy...443
Nuclear magnetic resonance...445
11.14 Principles of magnetic resonance...446
11.15 The information of NMR spectra...448
11.16 Magnetic resonance imaging...454

Further information...457
1. Mathematical techniques...457
2. Quantities and units...460
3. Energy and force...461
4. The kinetic theory of gases...462
5. Concepts of electrostatics...462
6. Electromagnetic radiation and photons...463
7. Oxidation numbers...464
8. The Lewis theory of covalent bonding...465
9. The VSEPR model...467
10. The Boltzmann distribution...469

APPENDIXES
Appendix 1: Thermodynamic data...471
Appendix 2: Standard potentials...480
Answers to exercises...483
Index...489

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W. H. Freeman & Co. and Sumanas, Inc.
The Elements of Physical Chemistry, January, 1997