Student Solutions
Manual to
Accompany Atkins’
Physical Chemistry
INTERNATIONAL EDITION
Peter Bolgar
Haydn Lloyd
Aimee North
Vladimiras Oleinikovas
Stephanie Smith
and
James Keeler
Department of Chemistry
University of Cambridge
UK
, Table of contents
Preface vii
1 The properties of gases 1
1A The perfect gas 1
1B The kinetic model 12
1C Real gases 23
2 Internal energy 39
2A Internal energy 39
2B Enthalpy 45
2C Thermochemistry 48
2D State functions and exact differentials 57
2E Adiabatic changes 63
3 The second and third laws 69
3A Entropy 69
3B Entropy changes accompanying specific processes 75
3C The measurement of entropy 86
3D Concentrating on the system 96
3E Combining the First and Second Laws 102
4 Physical transformations of pure substances 113
4A Phase diagrams of pure substances 113
4B Thermodynamic aspects of phase transitions 115
5 Simple mixtures 131
5A The thermodynamic description of mixtures 131
5B The properties of solutions 142
5C Phase diagrams of binary systems: liquids 159
5D Phase diagrams of binary systems: solids 166
5E Phase diagrams of ternary systems 172
5F Activities 177
6 Chemical equilibrium 193
6A The equilibrium constant 193
,iv TABLE OF CONTENTS
6B The response of equilibria to the conditions 202
6C Electrochemical cells 215
6D Electrode potentials 221
7 Quantum theory 237
7A The origins of quantum mechanics 237
7B Wavefunctions 243
7C Operators and observables 247
7D Translational motion 256
7E Vibrational motion 271
7F Rotational motion 281
8 Atomic structure and spectra 291
8A Hydrogenic Atoms 291
8B Many-electron atoms 300
8C Atomic spectra 303
9 Molecular Structure 311
9A Valence-bond theory 311
9B Molecular orbital theory: the hydrogen molecule-ion 315
9C Molecular orbital theory: homonuclear diatomic molecules 319
9D Molecular orbital theory: heteronuclear diatomic molecules 323
9E Molecular orbital theory: polyatomic molecules 329
10 Molecular symmetry 345
10A Shape and symmetry 345
10B Group theory 355
10C Applications of symmetry 366
11 Molecular Spectroscopy 377
11A General features of molecular spectroscopy 377
11B Rotational spectroscopy 387
11C Vibrational spectroscopy of diatomic molecules 400
11D Vibrational spectroscopy of polyatomic molecules 413
11E Symmetry analysis of vibrational spectroscopy 416
11F Electronic spectra 418
11G Decay of excited states 428
, TABLE OF CONTENTS v
12 Statistical thermodynamics 439
12A The Boltzmann distribution 439
12B Partition functions 443
12C Molecular energies 453
12D The canonical ensemble 461
12E The internal energy and entropy 463
12F Derived functions 476
13 Molecules in motion 487
13A Transport properties of a perfect gas 487
13B Motion in liquids 494
13C Diffusion 499
14 Chemical kinetics 509
14A The rates of chemical reactions 509
14B Integrated rate laws 515
14C Reactions approaching equilibrium 531
14D The Arrhenius equation 535
14E Reaction mechanisms 539
14F Examples of reaction mechanisms 545
14G Photochemistry 551
15 Reaction dynamics 569
15A Collision theory 569
15B Diffusion-controlled reactions 574
15C Transition-state theory 577
15D The dynamics of molecular collisions 589
15E Electron transfer in homogeneous systems 591
16 Magnetic resonance 599
16A General principles 599
16B Features of NMR spectra 602
16C Pulse techniques in NMR 612
16D Electron paramagnetic resonance 620
17 Molecular Interactions 625
17A Electric properties of molecules 625
Manual to
Accompany Atkins’
Physical Chemistry
INTERNATIONAL EDITION
Peter Bolgar
Haydn Lloyd
Aimee North
Vladimiras Oleinikovas
Stephanie Smith
and
James Keeler
Department of Chemistry
University of Cambridge
UK
, Table of contents
Preface vii
1 The properties of gases 1
1A The perfect gas 1
1B The kinetic model 12
1C Real gases 23
2 Internal energy 39
2A Internal energy 39
2B Enthalpy 45
2C Thermochemistry 48
2D State functions and exact differentials 57
2E Adiabatic changes 63
3 The second and third laws 69
3A Entropy 69
3B Entropy changes accompanying specific processes 75
3C The measurement of entropy 86
3D Concentrating on the system 96
3E Combining the First and Second Laws 102
4 Physical transformations of pure substances 113
4A Phase diagrams of pure substances 113
4B Thermodynamic aspects of phase transitions 115
5 Simple mixtures 131
5A The thermodynamic description of mixtures 131
5B The properties of solutions 142
5C Phase diagrams of binary systems: liquids 159
5D Phase diagrams of binary systems: solids 166
5E Phase diagrams of ternary systems 172
5F Activities 177
6 Chemical equilibrium 193
6A The equilibrium constant 193
,iv TABLE OF CONTENTS
6B The response of equilibria to the conditions 202
6C Electrochemical cells 215
6D Electrode potentials 221
7 Quantum theory 237
7A The origins of quantum mechanics 237
7B Wavefunctions 243
7C Operators and observables 247
7D Translational motion 256
7E Vibrational motion 271
7F Rotational motion 281
8 Atomic structure and spectra 291
8A Hydrogenic Atoms 291
8B Many-electron atoms 300
8C Atomic spectra 303
9 Molecular Structure 311
9A Valence-bond theory 311
9B Molecular orbital theory: the hydrogen molecule-ion 315
9C Molecular orbital theory: homonuclear diatomic molecules 319
9D Molecular orbital theory: heteronuclear diatomic molecules 323
9E Molecular orbital theory: polyatomic molecules 329
10 Molecular symmetry 345
10A Shape and symmetry 345
10B Group theory 355
10C Applications of symmetry 366
11 Molecular Spectroscopy 377
11A General features of molecular spectroscopy 377
11B Rotational spectroscopy 387
11C Vibrational spectroscopy of diatomic molecules 400
11D Vibrational spectroscopy of polyatomic molecules 413
11E Symmetry analysis of vibrational spectroscopy 416
11F Electronic spectra 418
11G Decay of excited states 428
, TABLE OF CONTENTS v
12 Statistical thermodynamics 439
12A The Boltzmann distribution 439
12B Partition functions 443
12C Molecular energies 453
12D The canonical ensemble 461
12E The internal energy and entropy 463
12F Derived functions 476
13 Molecules in motion 487
13A Transport properties of a perfect gas 487
13B Motion in liquids 494
13C Diffusion 499
14 Chemical kinetics 509
14A The rates of chemical reactions 509
14B Integrated rate laws 515
14C Reactions approaching equilibrium 531
14D The Arrhenius equation 535
14E Reaction mechanisms 539
14F Examples of reaction mechanisms 545
14G Photochemistry 551
15 Reaction dynamics 569
15A Collision theory 569
15B Diffusion-controlled reactions 574
15C Transition-state theory 577
15D The dynamics of molecular collisions 589
15E Electron transfer in homogeneous systems 591
16 Magnetic resonance 599
16A General principles 599
16B Features of NMR spectra 602
16C Pulse techniques in NMR 612
16D Electron paramagnetic resonance 620
17 Molecular Interactions 625
17A Electric properties of molecules 625
