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,'T INSPhysical Chemistry
Seventh Edition
Peter Atkins
Julio de Paula
Conventions
xx
Part 1 Equilibrium
1=.n
1 The properties of gases
32 The First Law: the concepts
303 The First Law: the machinery
734 The Second Law: the concepts
905 The Second Law: the machinery
12 16 Physical transformations of pure substances
1357 Simple mixtures
1608 Phase diagrams
1939 Cherrycal equilibrium
22210 Equilibrium electrochemistry
252
Pori 2 Structure
29 1
11 Quantum theory: introduction and principles
29312 Quantum theory: techniques and applications
32513 Atomic structure and atomic spectra
36514 Molecular structure
41 015 Molecular symmetry
.45316 Spectroscopy 1 : rotational and vibrational spectra
48 117 Spectroscopy 2 : electronic transitions
53818 Spectroscopy 3 : magnetic resonance
57919 Statistical thermodynamics : the concepts
62820 Statistical thermodynamics : the machinery
65621 Molecular interactions
68622 Macromolecules and aggregates
71 623 The solid state
767
Part 3 Change
81 3
24 Molecules in motion
81 525 The rates of chemical reactions
86226 The kinetics of complex reactions
89927 Molecular reaction dynamics
94428 Processes at solid surfaces
977
29 Dynamics of electron transfer
101 3
Further information 1 : Mathematical techniques
1048Further information 2 : Essential concepts of physics
1062
Data section
107 1
Answers to exercises
111 2
Answers to problems
1124
Index
1137
Conventions
xx
Part 1 Equilibrium
1 The properties of gases
3
The perfect gas
3
1 .1 The states of gases
3
1 .2 The gas laws
8
Real gases
1 6
1 .3 Molecular interactions
1 6
1 .4 The van der Waals equation
1 9
1 .5 The principle of corresponding states
2 3
Checklist of key ideas
24
Further reading
2 5
Exercises
2 6
Problems
2 8
2 The First Law : the concepts
30
The basic concepts
30
2 .1 Work, heat, and energy
3 1
2 .2 The First Law
3 3
Work and heat
37
2 .3 Expansion work
3 7
2 .4 Heat transactions
4 1
2 .5 Enthalpy
4 5
2 .6 Adiabatic changes
5 2
Thermochemistry
55
2 .7 Standard enthalpy changes
5 5
2 .8 Standard enthalpies of formation
60
2 .9 The temperature dependence of reaction
enthalpies
6 2
Checklist of key ideas
64
Further reading
6 5
Exercises
66Problems
6 9
3 The First Law : the machinery
73
State functions and exactdifferentials
73
3 .1
State and path functions
7 3
3 .2 Exact and inexact differentials
74
Thermodynamic consequences
75
3 .3 Changes in internal energy
7 5
3 .4 The temperature dependence of the enthalpy 7 9
3 .5 The relation between Cv and Cp
8 5
Checklist of key ideas
8 6
Further reading
8 7
Exercises
8 7
Problems
8 8
4 The Second Law: the concepts
90
The direction of spontaneous change
90
4 .1 The dispersal of energy
9 1
4 .2 Entropy
92
4 .3 Entropy changes accompanying specifi c
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
11 5
Further reading
11 6
Exercises
116
Problems
11 8
5 The Second Law: the machinery
121
Combining the First and Second Laws
12 1
5 .1 The fundamental equation
12 15 .2 Properties of the internal energy
12 2
Properties of the Gibbs energy
124
5 .3 General considerations
1245 .4 The variation of the Gibbs energy with
temperature
12 65 .5 The variation of the Gibbs energy with
pressure
127
Checklist of key ideas
13 0
Further reading
13 1
Exercises
13 1
Problems
13 2
6 Physical transformations of pure substances 13 5
Phase diagrams
135
6 .1
The stabilities of phases
13 5
6 .2 Phase boundaries
13 6
6 .3 Three typical phase diagrams
138
Phase stability and phas etransitions
140
6.4 The thermodynamic criterion of
equilibrium
14 1
6 .5 The dependence of stability on
the conditions
141
6 .6 The location of phase boundaries
14 4
6.7 The Ehrenfest classification of phase
transitions
148
The physical liquid surface
150
6 .8 Surface tension
15 0
6 .9 Curved surfaces
15 1
6 .10 Capillary action
15 3
Checklist of key ideas
15 5
Further reading
15 6
Exercises
15 6
Problems
157
7 Simple mixtures
160
The thermodynamic descriptio nof mixtures
160
7 .1
Partial molar quantities
16 1
7 .2 The thermodynamics of mixing
166
7 .3 The chemical potentials of liquids
16 8
The properties of solutions
172
7 .4 Liquid mixtures
17 3
7 .5
Colligative properties
17 5
Activities
182
7 .6 The solvent activity
182
7 .7 The solute activity
18 3
7 .8
The activities of regular solutions
18 6
Checklist of key ideas
187
Further reading
18 8
Exercises
18 9
Problems
19 0
8 Phase diagrams
193
Phases, components, and degree sof freedom
193
8 .1
Definitions
19 3
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
20 4
8 .6 Liquid-solid phase diagrams
208
Checklist of key ideas
214
Further reading
214
Exercises
21 5
Problems
21 8
9 Chemical equilibrium
222
Spontaneous chemical reactions
22 2
9 .1 The Gibbs energy minimum
222
9 .2 The description of equilibrium
226
The response of equilibria t othe conditions
23 3
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 ionsin solution
252
10.1 Thermodynamic functions of
formation
253
10 .2 Ion activities
256
Electrochemical cells
262
10 .3 Half-reactions and electrodes
26 3
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
29 1
11 Quantum theory: introductio nand principles
293
The origins of quantum mechanics
29 3
11 .1 The failures of classical physics
294
11 .2 Wave-particle duality
299
The dynamics of microscopic systems
304
11 .3 The Schrödinger equation
30411 .4 The Born interpretation of th e
wavefunction
306
Quantum mechanical principles
309
11 .5 The information in a wavefunction
31 0
11 .6 The uncertainty principle
317
Checklist of key ideas
32 0
Further reading
32 1
Exercises
32 2Problems
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
33 1
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
36 1
Exercises
36 1
Problems
36 3
13 Atomic structure and atomic spectra
365
The structure and spectra o f
hydrogenic atoms
366
13.1 The structure of hydrogenic atoms
36713 .2 Atomic orbitals and their energies
37 213 .3 Spectroscopic transitions and
selection rules
38 1
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
39 3
13 .6 Quantum defects and ionization limits
39 5
13 .7 Singlet and triplet states
39 5
13 .8 Spin-orbit coupling
396
13 .9 Term symbols and selection rules
399
Checklist of key ideas
404
Further reading
40 5
Exercises
406
Problems
408
14 Molecular structure
410
The Born-Oppenheimer approximation
410
Valence-bond theory
41 1
14 .1 The hydrogen molecule
411
14 .2 Homonuclear diatomic molecules
413
14 .3 Polyatomic molecules
414
Molecular orbital theory
41 7
14.4 The hydrogen molecule-ion
418
14 .5 The structures of diatomic molecules
422
14 .6 Heteronuclear diatomic molecules
427
Molecular orbitals for polyatomi c
systems
432
14.7 The Hückel approximation
433
14 .8 Extended Hückel theory
438
14 .9 Self-consistent field calculations
441
Checklist of key ideas
446Further reading
447
Exercises
448
Problems
450
15 Molecular symmetry
453
The symmetry elements of objects
45 3
15.1 Operations and symmetry elements
454
15 .2 The symmetry classification o f
molecules
456
15 .3 Some immediate consequences o f
symmetry
459
Character tables
46 3
15 .4 Character tables and symmetry labels
463
15 .5 Vanishing integrals and orbita l
overlap
469
15 .6 Vanishing integrals and selection rules
474
Checklist of key ideas
476
Further reading
477
Exercises
47 7Problems
478
16 Spectroscopy 1 : rotational and vibrational
spectra
48 1
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
50 4
16 .7 Rotational Raman spectra
507
16 .8 Nuclear statistics and rotationa l
states
51 0
The vibrations of diatomic molecules
51 1
16.9 Molecular vibrations
51 2
16 .10 Selection rules
51 3
16 .11 Anharmonicity
51 5
16 .12 Vibration-rotation spectra
51 7
16 .13 Vibrational Raman spectra of diatomi c
molecules
51 9
The vibrations of polyatomic molecules
520
16 .14 Normal modes
52 0
16 .15 Infrared absorption spectra of polyatomi c
molecules
52 3
16 .16 Vibrational Raman spectra of polyatomi c
molecules
524
16 .17 Symmetry aspects of molecular vibrations
52 6
Checklist of key ideas
529
Further reading
53 1
Exercises
53 2
Problems
53 4
17 Spectroscopy 2 : electronic transitions
538
The characteristics of electroni ctransitions
539
17.1 The electronic spectra of diatomi c
molecules
53 9
17 .2 The electronic spectra of polyatomic
molecules
545
The fates of electronically excited states
550
17 .3 Fluorescence and phosphorescence
55 0
17.4 Dissociation and predissociation
55 2
Lasers
553
17 .5 General principles of laser action
55417 .6 Practical lasers
55 817 .7 Applications of lasers in chemistry
562
Photoelectron spectroscopy
56 8
17.8 The technique
568
17 .9 Ultraviolet photoelectron spectroscopy
569
17 .10 X-ray photoelectron spectroscopy
570
Checklist of key ideas
57 1
Further reading
57 3
Exercises
574
Problems
575
18 Spectroscopy 3 : magnetic resonance
579
The effect of magnetic fields on electrons
and nuclei
57 9
18.1 The energies of electrons in magnetic fields
580
18 .2 The energies of nuclei in magnetic fields
58 1
18 .3 Magnetic resonance spectroscopy
58 3
Nuclear magnetic resonance
583
18 .4 The NMR spectrometer
58 4
18.5 The chemical shift
58 5
18.6 The fine structure
590
Pulse techniques in NMR
599
18.7 The magnetization vector
599
18 .8 Linewidths and rate processes
60 2
18 .9 Spin decoupling
60 7
18 .10 The nuclear Overhauser effect
60 8
18 .11 Two-dimensional NMR
61 0
18 .12 Solid-state NMR
61 4
Electron spin resonance
61 5
18 .13 The ESR spectrometer
61 518 .14 The g-value
61 718 .15 Hyperfine structure
618
Checklist of key ideas
621
Further reading
62 3
Exercises
62 4Problems
62 6
19 Statistical thermodynamics: the concepts
628
The distribution of molecular states
629
19 .1 Configurations and weights
62919 .2 The molecular partition function
63 4
The internal energy and the entropy
639
19 .3 The internal energy
640
19 .4 The statistical entropy
642
The canonical partition function
64 7
19 .5 The canonical ensemble
647
19 .6 The thermodynamic information in th e
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
67 1
20 .6 Residual entropies
672
20 .7 Equilibrium constants
674
Checklist of key ideas
68 1
Further reading
682
Exercises
68 2
Problems
.
683
21 Molecular interactions
686
Electric properties of molecules
686
21 .1 Electric dipole moments
68 6
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
70 9
Checklist of key ideas
71 3
Further reading
71 5
Exercises
715
Problems
716
22 Macromolecules and aggregates
71 9
Structure and dynamics
720
22 .1 The different levels of structure
72022.2 Random coils
72 122 .3 The structure of proteins
72522 .4 The structure of nucleic acids
72922 .5 The stability of biological polymers
73 1
Determination of size and shape
732
22.6 Mean molar masses
73 2
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
75 2
22 .14 Micelles and biological membranes
754
22 .15 Surface films
75 7
Checklist of key ideas
760
Further reading
76 2Exercises
76 3
Problems
76 4
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
77223 .4 Neutron and electron diffraction
783
Crystal structure
78 4
23.5 Metallic solids
784
23.6 Ionic solids
786
23 .7 Molecular solids and covalent networks
789
The properties of solids
79 1
23.8 Mechanical properties
791
23 .9 Electrical properties
79 5
23 .10 Magnetic properties
80 1
Checklist of key ideas
80 5
Further reading
80 7
Exercises
80 8
Problems
81 0
Part 3 Change
813
24 Molecules in motion
81 5
Molecular motion in gases
81 5
24.1 The kinetic model of gases
81 6
24 .2 Collisions with walls and surfaces
82 2
24.3 The rate of effusion
82 4
24 .4 Transport properties of a perfect gas
82 6
Molecular motion in liquids
832
24.5 Experimental results
83 2
24 .6 The conductivities of electrolyte solutions
83 3
24.7 The mobilities of ions
83 5
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
85 3
Checklist of key ideas
85 4
Further reading
85 6
Exercises
85 6
Problems
85 9
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
87 1
25 .4 Reactions approaching equilibrium
876
25 .5 The temperature dependence o f
reaction rates
87 9
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
90 2
Polymerization kinetics
904
26.3 Stepwise polymerization
90 4
26 .4 Chain polymerization
90 6
Homogeneous catalysis
908
26.5 Features of homogeneous catalysis
90 9
26.6 Enzymes
90 9
Oscillating reactions
914
26.7 Autocatalysis
91 5
26 .8 Autocatalytic mechanisms of
oscillating reactions
91 6
26 .9 Bistability
91 726 .10 Chemical chaos
91 9
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
93 8
Problems
94 0
27 Molecular reaction dynamics
944
Reactive encounters
944
27.1 Collision theory
945
27 .2 Diffusion-controlled reactions
95 1
27 .3 The material balance equation
95 4
Activated complex theory
956
27.4 The Eyring equation
956
27 .5 Thermodynamic aspects
96 0
The dynamics of molecular collisions
963
27.6 Reactive collisions
963
27 .7 Potential energy surfaces
96 6
27 .8 Some results from experiments
and calculations
967
Checklist of key ideas
97 1
Further reading
97 2
Exercises
973
Problems
974
28 Processes at solid surfaces
977
The growth and structure of soli d
surfaces
97 7
28.1 Surface growth
977
28 .2 Surface composition
979
The extent of adsorption
98 7
28.3 Physisorption and chemisorption
98 8
28 .4 Adsorption isotherms
989
28 .5 The rates of surface processes
994
Catalytic activity at surfaces
99 9
28.6 Adsorption and catalysis
999
28 .7 Examples of catalysis
100 1
Checklist of key ideas
100 6
Further reading
100 7
Exercises
100 8
Problems
100 9
29 Dynamics of electron transfer
101 3
Electron transfer in homogeneou s
systems
101 4
29.1 Theory of electron transfer processes
101 4
29.2 Experimental results
1018
Electron transfer in heterogeneoussystems
102 1
29.3 The electrode-solution interface
102 129 .4 The rate of charge transfer
102429.5 Voltammetry
103 129 .6 Electrolysis
103 629 .7 Working galvanic cells
103 729.8 Corrosion
103 9
Checklist of key ideas
104 1Further reading
1043Exercises
1043Problems
1045
Further information 1 Mathematica ltechniques
1048
Basic procedures
1048
1 .1 Logarithms and exponentials
104 81 .2 Combinatorial functions
104 8
1 .3 Complex numbers and complex
functions
104 9
1.4 Vectors
105 0
Calculus
105 1
1 .5 Differentiation and integration
105 1
1 .6 Power series and Taylor expansions
105 2
1 .7
Partial derivatives
105 31 .8 Undetermined multipliers
105 4
1 .9 Differential equations
105 5
Matrix algebra
1057
1 .10 Matrix addition and multiplication
105 81 .11 Simultaneous equations
1060
1 .12 Eigenvalue equations
105 9
Further reading
106 1
Further information 2 Essential conceptsof physics
1062
Energy
1062
2 .1 Kinetic and potential energy
106 2
2 .2 Energy units
106 2
Classical mechanics
106 3
2 .3 The trajectory in terms of the energy
106 3
2 .4 Newton's second law
1064
2.5 Rotational motion
1064
2.6 The harmonic oscillator
1065
Waves
106 6
2 .7 The electromagnetic field
10662 .8 Features of electromagnetic radiation
1067
Electrostatics
1068
2 .9 The Coulomb interaction
106 8
2 .10 The Coulomb potential
106 8
2.11 The strength of the electric field
106 9
2.12 The dipole-dipole interaction
106 9
2.13 Electric current and power
107 0
Further reading
107 0
Data section
107 1
Answers to exercises
1112
Answers to problems
1124
Index
1137
