ACKNOWLEDGEMENTS xix Richard Wells,University of Aberdeen We also thank Fabienne Meyers (of the IUPAC Secretariat)for help- Ben Whitaker,U 00n of Manchester Mark Wilson,University College London Oxford University Press and W.H. Kazushige Yokoyama,State University of New York at Geneseo encouragement,advice,and assistance,and in particular our editors hing environment
ACKNOWLEDGEMENTS xix Richard Wells, University of Aberdeen Ben Whitaker, University of Leeds Christopher Whitehead, University of Manchester Mark Wilson, University College London Kazushige Yokoyama, State University of New York at Geneseo Nigel Young, University of Hull Sidney H. Young, University of South Alabama We also thank Fabienne Meyers (of the IUPAC Secretariat) for helping us to bring colour to most of the illustrations and doing so on a very short timescale. We would also like to thank our two publishers, Oxford University Press and W.H. Freeman & Co., for their constant encouragement, advice, and assistance, and in particular our editors Jonathan Crowe, Jessica Fiorillo, and Ruth Hughes. Authors could not wish for a more congenial publishing environment
Summary of contents PART 1 Equilibrium 1 The properties of gases 2 The First Law 3 The Secondl aw 4 Physical transformations of pure substances 5 Simple mixtures 6 Phase diagrams 3261101100 7 Chemical equilibrium PART 2 Structure 241 112 Molecular structure cop 1:rotational and vibrational spectra ics 1:the 2477004领0饮配所 Materials 1 Materials2:the solid state and aggregate PART 3 Change 745 23245 Appendix 1:Quantities,units and notational conventions to'a' ax ed problems Index
Summary of contents PART 1 Equilibrium 1 1 The properties of gases 3 2 The First Law 28 3 The Second Law 76 4 Physical transformations of pure substances 117 5 Simple mixtures 136 6 Phase diagrams 174 7 Chemical equilibrium 200 PART 2 Structure 241 8 Quantum theory: introduction and principles 243 9 Quantum theory: techniques and applications 277 10 Atomic structure and atomic spectra 320 11 Molecular structure 362 12 Molecular symmetry 404 13 Molecular spectroscopy 1: rotational and vibrational spectra 430 14 Molecular spectroscopy 2: electronic transitions 481 15 Molecular spectroscopy 3: magnetic resonance 513 16 Statistical thermodynamics 1: the concepts 560 17 Statistical thermodynamics 2: applications 589 18 Molecular interactions 620 19 Materials 1: macromolecules and aggregates 652 20 Materials 2: the solid state 697 PART 3 Change 745 21 Molecules in motion 747 22 The rates of chemical reactions 791 23 The kinetics of complex reactions 830 24 Molecular reaction dynamics 869 25 Processes at solid surfaces 909 Appendix 1: Quantities, units and notational conventions 959 Appendix 2: Mathematical techniques 963 Appendix 3: Essential concepts of physics 979 Data section 988 Answers to ‘a’ exercises 1028 Answers to selected problems 1034 Index 1040
Contents PART 1 Equilibrium Discussion questions Exercises 70 Problems 73 1 The properties of gases The perfect gas 3 3 The Second Law 1.1 The states of gases 1.2 The gas laws > The direction of spontaneous change 1.1 persal of energy 11 32 3.1 Impact on engineering Refrigeration 14 3.3 ular inte Entropy changes accompanying specific processes 3.4 The Third Law of thermodynamics centrating on the systen 94 Checklist of key ideas Futher reading TmcHetnholonceibscmegs Discussion questions 23 Combining the First a d Second Laws 25 The fundar Problems 1 3.9 2 The First Law Checkist of key ideas The basic 28 Further information 3.1:The Bom equation 110 Further intommation 3.2:Real gases:the fugacity The internal en cussion questions 2.3 Exnansion work 2.4 Heat transactions Enthalpy 12.1 4 Physical transformations of pure substances 117 2.6 Adiabatic changes Phase diagrams 117 Thermochemistry 4.1 The stabilities of phases 17 2.7 Standard enthalpy changes 4.2 Phase boundaries 12.2 Impact on biology:Food and energy reserves 14.1 Standard enthalpies of formation Impact on engn ering and technology: 2.8 2.9 The temperature-dependence of reaction enthalpies 4.3 diagrams State functions and exact diferen e hase tra sition Exact and i ium 212 4.6 The location of phase boundaries 4.7 The Ehrenfest classification of phase transitions Checklist of key ideas 67 Further reading Checkist of key ideas Further information 2.1:Adiabatic processes Further reading Further intommation 2.2:The relation between heat capacities 69 Discussion questions 12
Contents 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 7 I1.1 Impact on environmental science: The gas laws and the weather 11 Real gases 14 1.3 Molecular interactions 14 1.4 The van der Waals equation 17 1.5 The principle of corresponding states 21 Checklist of key ideas 23 Further reading 23 Discussion questions 23 Exercises 24 Problems 25 2 The First Law 28 The basic concepts 28 2.1 Work, heat, and energy 29 2.2 The internal energy 30 2.3 Expansion work 33 2.4 Heat transactions 37 2.5 Enthalpy 40 I2.1 Impact on biochemistry and materials science: Differential scanning calorimetry 46 2.6 Adiabatic changes 47 Thermochemistry 49 2.7 Standard enthalpy changes 49 I2.2 Impact on biology: Food and energy reserves 52 2.8 Standard enthalpies of formation 54 2.9 The temperature-dependence of reaction enthalpies 56 State functions and exact differentials 57 2.10 Exact and inexact differentials 57 2.11 Changes in internal energy 59 2.12 The Joule–Thomson effect 63 Checklist of key ideas 67 Further reading 68 Further information 2.1: Adiabatic processes 69 Further information 2.2: The relation between heat capacities 69 Discussion questions 70 Exercises 70 Problems 73 3 The Second Law 76 The direction of spontaneous change 77 3.1 The dispersal of energy 77 3.2 Entropy 78 I3.1 Impact on engineering: Refrigeration 85 3.3 Entropy changes accompanying specific processes 87 3.4 The Third Law of thermodynamics 92 Concentrating on the system 94 3.5 The Helmholtz and Gibbs energies 95 3.6 Standard reaction Gibbs energies 100 Combining the First and Second Laws 102 3.7 The fundamental equation 102 3.8 Properties of the internal energy 103 3.9 Properties of the Gibbs energy 105 Checklist of key ideas 109 Further reading 110 Further information 3.1: The Born equation 110 Further information 3.2: Real gases: the fugacity 111 Discussion questions 112 Exercises 113 Problems 114 4 Physical transformations of pure substances 117 Phase diagrams 117 4.1 The stabilities of phases 117 4.2 Phase boundaries 118 I4.1 Impact on engineering and technology: Supercritical fluids 119 4.3 Three typical phase diagrams 120 Phase stability and phase transitions 122 4.4 The thermodynamic criterion of equilibrium 122 4.5 The dependence of stability on the conditions 122 4.6 The location of phase boundaries 126 4.7 The Ehrenfest classification of phase transitions 129 Checklist of key ideas 131 Further reading 132 Discussion questions 132
CONTENTS Exercises 132 7 Chemical equilibrium 200 Problems 133 Spontaneous chemical reactions 0 5 Simple mixtures 136 72 The Gibbs e 20 The thermodynamic desc ription of mixtures 136 The response of equilibria to the conditions 210 5.1 Partial molar o antitie 136 141 7.3 How equilibria respond to pressure 210 7.4 Thechemical potentials ofliquids 143 The response of equilibria to temperature 211 5.1 Impact on biology:Gas solubility and 7.1 147 215 thing The properties of solutions 148 Equilibrium electrochemistry 216 7.5 Half-reactions and electrodes 130 7.6 varieties ofcells mosis in physiology 7.7 The electromotive force 156 Standard potential Activities standard 158 72 nergy conversion The solvent a 225 The activities of regula solutions 162 Checklist of key ideas 59 The activities ofions in solution 163 estions 品 Checklist of kev idea 1 Exercises Further reading 167 Problems 236 Further information 5.1:The Debye-Hockel theory ofionicsolutions 167 169 PART 2 Structure 241 Problems 171 8 Quantum theory:introduction and principles 243 6 Phase diagrams 174 The origins of quantum mechanics 243 ts,and degrees of freedom 174 8.1 The failures of classical physics 244 6.1 Definitions 174 8.2 Wave-particle duality 6.2 The phase rule 176 8.1 Impact on biology:Electron microscopy component systems The dynamics of microscopic systems 254 tion 64 apour p osition diagrams 6.5 liguid-ingeile diag 185 6.6 Liquid-solid phase diagrams 189 mm 260 6.1 Impact on materials science:Liquid crystals 19 The information efunction 16.2 ence:Ultrapurity 192 The pet yprincipl echanic 193 19 195 Problems 197 Problems 275
xxiv CONTENTS Exercises 132 Problems 133 5 Simple mixtures 136 The thermodynamic description of mixtures 136 5.1 Partial molar quantities 136 5.2 The thermodynamics of mixing 141 5.3 The chemical potentials of liquids 143 I5.1 Impact on biology: Gas solubility and breathing 147 The properties of solutions 148 5.4 Liquid mixtures 148 5.5 Colligative properties 150 I5.2 Impact on biology: Osmosis in physiology and biochemistry 156 Activities 158 5.6 The solvent activity 158 5.7 The solute activity 159 5.8 The activities of regular solutions 162 5.9 The activities of ions in solution 163 Checklist of key ideas 166 Further reading 167 Further information 5.1: The Debye–Hückel theory of ionic solutions 167 Discussion questions 169 Exercises 169 Problems 171 6 Phase diagrams 174 Phases, components, and degrees of freedom 174 6.1 Definitions 174 6.2 The phase rule 176 Two-component systems 179 6.3 Vapour pressure diagrams 179 6.4 Temperature–composition diagrams 182 6.5 Liquid–liquid phase diagrams 185 6.6 Liquid–solid phase diagrams 189 I6.1 Impact on materials science: Liquid crystals 191 I6.2 Impact on materials science: Ultrapurity and controlled impurity 192 Checklist of key ideas 193 Further reading 194 Discussion questions 194 Exercises 195 Problems 197 7 Chemical equilibrium 200 Spontaneous chemical reactions 200 7.1 The Gibbs energy minimum 200 7.2 The description of equilibrium 202 The response of equilibria to the conditions 210 7.3 How equilibria respond to pressure 210 7.4 The response of equilibria to temperature 211 I7.1 Impact on engineering: The extraction of metals from their oxides 215 Equilibrium electrochemistry 216 7.5 Half-reactions and electrodes 216 7.6 Varieties of cells 217 7.7 The electromotive force 218 7.8 Standard potentials 222 7.9 Applications of standard potentials 224 I7.2 Impact on biochemistry: Energy conversion in biological cells 225 Checklist of key ideas 233 Further reading 234 Discussion questions 234 Exercises 235 Problems 236 PART 2 Structure 241 8 Quantum theory: introduction and principles 243 The origins of quantum mechanics 243 8.1 The failures of classical physics 244 8.2 Wave–particle duality 249 I8.1 Impact on biology: Electron microscopy 253 The dynamics of microscopic systems 254 8.3 The Schrödinger equation 254 8.4 The Born interpretation of the wavefunction 256 Quantum mechanical principles 260 8.5 The information in a wavefunction 260 8.6 The uncertainty principle 269 8.7 The postulates of quantum mechanics 272 Checklist of key ideas 273 Further reading 273 Discussion questions 274 Exercises 274 Problems 275
CONTENTS XXV 9 Quantum theory:techniques and applications 277 11 Molecular structure 362 Translational motion 277 The Born-Oppenheimer approximation 362 Aparticle inabox Valence-bond theory 363 。2 Motion in two and more dimensions 11.1 Homonuclear diatomic molecules 11.2 Polyatomic molecules 365 19.1 nanoscience:Scanning probe 288 ularorbita theory Vibrational motion 290 113 The hydrogen m 95 291 11.5 Hete ac m on 292 Rotational motion 297 biochemical reactivity ofN and NO 385 9.6 Rotation in two dimensions:a particle ona ring 297 Molecular orbitals for polyatomic systems 9.7 Rotation in three dimensions:the particle ona 386 spher 301 11.6 The Huckelapproximation 19.2 cience:Quantum dots 9.8 30s Techniques of approximation 310 Checklist of key ideas 38 9.9 Time-independent perturbation theory 310 Further reading 9.10 Time-dependent perturbation theory 311 Discussion questions Exercises 399 313 Problems 400 Further information 9.1:Dirac notation 313 Further information 92:Perturbation theory 313 12 Molecular symmetry 404 Discussion questions 316 319 esymmetry element ts of objects 122 etry e 10 Atomic structure and atomic spectra 320 12.3 Some immediate cons nces of symn Applications to molecular orbital theory and structure and spectra of hydrogenic atoms 320 spectroscopy 10.1 The structt ogenic atom 32 03 12 copic tra 35 12.Vanishing integrals and seection rules The structures of many-electron atoms 336 cklist of key ideas 425 10.4 The orbital approximation 336 Further reading 426 10.5 Self-consistent field orbitals 344 Discussion questions 426 The spectra of complex atoms 345 Exercises 426 6 Problems 427 10.6 Quantum defects and ion 346 10.7 Singlet and triplet states 347 13 Molecula spectros copy 1:rotational and 108 Spin-orbit coupling 348 vibrational spectra 430 10.9 Term symbols and selection rules 352 356 General features of pectroscopy Further infommation 10.1:The separation of motion 257 2 al line Discussion questions 358 13.3 Linewidths 436 Exercises 358 113.1 Impact on astrophysics:Rotational and Problems 36g vibrational spectroscopy of interstellar space
CONTENTS xxv 9 Quantum theory: techniques and applications 277 Translational motion 277 9.1 A particle in a box 278 9.2 Motion in two and more dimensions 283 9.3 Tunnelling 286 I9.1 Impact on nanoscience: Scanning probe microscopy 288 Vibrational motion 290 9.4 The energy levels 291 9.5 The wavefunctions 292 Rotational motion 297 9.6 Rotation in two dimensions: a particle on a ring 297 9.7 Rotation in three dimensions: the particle on a sphere 301 I9.2 Impact on nanoscience: Quantum dots 306 9.8 Spin 308 Techniques of approximation 310 9.9 Time-independent perturbation theory 310 9.10 Time-dependent perturbation theory 311 Checklist of key ideas 312 Further reading 313 Further information 9.1: Dirac notation 313 Further information 9.2: Perturbation theory 313 Discussion questions 316 Exercises 316 Problems 317 10 Atomic structure and atomic spectra 320 The structure and spectra of hydrogenic atoms 320 10.1 The structure of hydrogenic atoms 321 10.2 Atomic orbitals and their energies 326 10.3 Spectroscopic transitions and selection rules 335 The structures of many-electron atoms 336 10.4 The orbital approximation 336 10.5 Self-consistent field orbitals 344 The spectra of complex atoms 345 I10.1 Impact on astrophysics: Spectroscopy of stars 346 10.6 Quantum defects and ionization limits 346 10.7 Singlet and triplet states 347 10.8 Spin–orbit coupling 348 10.9 Term symbols and selection rules 352 Checklist of key ideas 356 Further reading 357 Further information 10.1: The separation of motion 357 Discussion questions 358 Exercises 358 Problems 359 11 Molecular structure 362 The Born–Oppenheimer approximation 362 Valence-bond theory 363 11.1 Homonuclear diatomic molecules 363 11.2 Polyatomic molecules 365 Molecular orbital theory 368 11.3 The hydrogen molecule-ion 368 11.4 Homonuclear diatomic molecules 373 11.5 Heteronuclear diatomic molecules 379 I11.1 Impact on biochemistry: The biochemical reactivity of O2, N2, and NO 385 Molecular orbitals for polyatomic systems 386 11.6 The Hückel approximation 387 11.7 Computational chemistry 392 11.8 The prediction of molecular properties 396 Checklist of key ideas 398 Further reading 399 Discussion questions 399 Exercises 399 Problems 400 12 Molecular symmetry 404 The symmetry elements of objects 404 12.1 Operations and symmetry elements 405 12.2 The symmetry classification of molecules 406 12.3 Some immediate consequences of symmetry 411 Applications to molecular orbital theory and spectroscopy 413 12.4 Character tables and symmetry labels 413 12.5 Vanishing integrals and orbital overlap 419 12.6 Vanishing integrals and selection rules 423 Checklist of key ideas 425 Further reading 426 Discussion questions 426 Exercises 426 Problems 427 13 Molecular spectroscopy 1: rotational and vibrational spectra 430 General features of spectroscopy 431 13.1 Experimental techniques 431 13.2 The intensities of spectral lines 432 13.3 Linewidths 436 I13.1 Impact on astrophysics: Rotational and vibrational spectroscopy of interstellar space 438