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Part 1 Equilibrium
1 The properties of gases
The perfect gas
1.1 The states of gases
1.2 The gas laws
Realgases
1.3 Molecular interactions
1.4 The van der Waals equation
1.5 The principle of corresponding states
Checklist of key ideas
Further reading
Exercises
Problems
2 The First Law：the concepts
The basic concepts
2.1 Work，heat，and energy
2.2 The First Law
Work and heat
2.3 Expansion work
2.4 Heat transactions
2.5 Enthalpy
2.6 Adiabatic changes
Thermochemistry
2.7 Standard enthalpy changes
2.8 Standard enthalpies of formation
2.9 The temperature dependence of reaction enthalpies
Checklist of key ideas
Further reading
Exercises
Problems
3 The First Law：the machinery
State functions and exact differentials
3.1 State and path functions
3.2 Exact and inexact differentials
Thermodynamic consequences
3.3 Changes in internal energy
3.4 The temperature dependence of the enthalpy
3.5 The relation between Cv and Cp
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Further reading
Exercises
Problems
4 The Second Law：the concepts
The direction of spontaneous change
4.1 The dispersal of energy
4.2 Entropy
4.3 Entropy changes accompanying specific processes
4.4 The Third Law of thermodynamics
Concentrating on the system
4.5 The Helmholtz and Gibbs energies
4.6 Standard molar Gibbs energies
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Further reading
Exercises
Problems
5 The Second Law：the machinery
Combining the First and Second Laws
5.1 The fundamental equation
5.2 Properties of the internal energy
Properties of the Gibbs energy
5.3 General considerations
5.4 The variation of the Gibbs energy with temperature
5.5 The variation of the Gibbs energy with pressure
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Further reading
Exercises
Problems
6 Physical transformations of pure substances
Phase diagrams
6.1 The stabilities of phases
6.2 Phase boundaries
6.3 Three typical phase diagrams
Phase stability and phase transitions
6.4 The thermodynamic criterion of equilibrium
6.5 The dependence of stability on the conditions
6.6 The location of phase boundaries
6.7 The Ehrenfest classification of phase transitions
The physical liquid surface
6.8 Surface tension
6.9 Curved surfaces
6.10 Capillary action
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Further reading
Exercises
Problems
7 Simple mixtures
The thermodynamic description of mixtures
7.1 Partial molar quantities
7.2 The thermodynamics of mixing
7.3 The chemical potentials of liquids
The properties of solutions
7.4 Liquid mixtures
7.5 Colligative properties
Activities
7.6 The solvent activity
7.7 The solute activity
7.8 The activities of regular solutions
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Further reading
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Problems
8 Phase diagrams
Phases，components，and degrees of freedom
8.1 Definitions
8.2 The phase rule
Two-component systems
8.3 Vapour pressure diagrams
8.4 Temperature-composition diagrams
8.5 Liquid-liquid phase diagrams
8.6 Liquid-solid phase diagrams
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Further reading
Exercises
Problems
9 Chemical equilibrium
Spontaneous chemical reactions
9.1 The Gibbs energy minimum
9.2 The description of equilibrium
The response of equilibria to the conditions
9.3 How equilibria respond to pressure
9.4 The response of equilibria to temperature
9.5 The response of equilibria to pH
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10 Equilibrium electrochemistry
The thermodynamic properties of ions in solution
10.1 Thermodynamic functions of formation
10.2 Ion activities
Electrochemical cells
10.3 Half-reactions and electrodes
10.4 Varieties of cells
10.5 Standard potentials
Applications of standard potentials
10.6 The electrochemical series
10.7 The measurement of pH and pKa
10.8 Thermodynamic functions
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Further reading
Exercises
Problems
Part 2 Structure
11 Quantum theory：introduction and principles
The origins of quantum mechanics
11.1 The failures of classical physics
11.2 Wave-particle duality
The dynamics of microscopic systems
11.3 The Schrodinger equation
11.4 The Born interpretation of the wavefunction
Quantum mechanical principles
11.5 The information in a wavefunction
11.6 The uncertainty principle
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Further reading
Exercises
Problems
12 Quantum theory：techniques and applications
Translational motion
12.1 A particle in a box
12.2 Motion in two and more dimensions
12.3 Tunnelling
Vibrational motion
12.4 The energy levels
12.5 The wavefunctions
Rotational motion
12.6 Rotation in two dimensions：the particle on a ring
12.7 Rotation in three dimensions：the particle on a sphere
12.8 Spin
Techniques of approximation
12.9 Time-independent perturbation theory
12.10 Time-dependent perturbation theory
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Further reading
Exercises
Problems
13 Atomic structure and atomic spectra
The structure and spectra of hydrogenic atoms
13.1 The structure of hydrogenic atoms
13.2 Atomic orbitals and their energies
13.3 Spectroscopic transitions and selection rules
The structures of many-electron atoms
13.4 The orbital approximation
13.5 Self-consistent field orbitals
The spectra of complex atoms
13.6 Quantum defects and ionization limits
13.7 Singlet and triplet states
13.8 Spin-orbit coupling
13.9 Term symbols and selection rules
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Further reading
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Problems
14 Molecular structure
The Born-Oppenheimer approximation
Valence-bond theory
14.1 The hydrogen molecule
14.2 Homonuclear diatomic molecules
14.3 Polyatomic molecules
Molecular orbital theory
14.4 The hydrogen molecule-ion
14.5 The structures of diatomic molecules
14.6 Heteronuclear diatomic molecules
Molecular orbitals for polyatomic systems
14.7 The Huckel approximation
14.8 Extended Huckel theory
14.9 Self-consistent field calculations
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Problems
15 Molecular symmetry
The symmetry elements of objects
15.1 Operations and symmetry elements
15.2 The symmetry classification of molecules
15.3 Some immediate consequences of symmetry
Character tables
15.4 Character tables and symmetry labels
15.5 Vanishing integrals and orbital overlap
15.6 Vanishing integrals and selection rules
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16 Spectroscopy 1：rotational and vibrational spectra
General features of spectroscopy
16.1 Experimental techniques
16.2 The intensities of spectral lines
16.3 Linewidths
Pure rotation spectra
16.4 Moments of inertia
16.5 The rotational energy levels
16.6 Rotational transitions
16.7 Rotational Raman spectra
16.8 Nuclear statistics and rotational states
The vibrations of diatomic molecules
16.9 Molecular vibrations
16.10 Selection rules
16.11 Anharmonicity
16.12 Vibration-rotation spectra
16.13 Vibrational Raman spectra of diatomic molecules
The vibrations of polyatomic molecules
16.14 Normal modes
16.15 Infrared absorption spectra of polyatomic molecules
16.16 Vibrational Raman spectra of polyatomic molecules
16.17 Symmetry aspects of molecular vibrations
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Problems
17 Spectroscopy 2：electronic transitions
The characteristics of electronic transitions
17.1 The electronic spectra of diatomic molecules
17.2 The electronic spectra of polyatomic molecules
The fates of electronically excited states
17.3 Fluorescence and phosphorescence
17.4 Dissociation and predissociation
Lasers
17.5 General principles of laser action
17.6 Practical lasers
17.7 Applications of lasers in chemistry
Photoelectron spectroscopy
17.8 The technique
17.9 Ultraviolet photoelectron spectroscopy
17.10 X-ray photoelectron spectroscopy
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Further reading
Exercises
Problems
18 Spectroscopy 3：magnetic resonance
The effect of magnetic fields on electrons and nuclei
18.1 The energies of electrons in magnetic fields
18.2 The energies of nuclei in magnetic fields
18.3 Magnetic resonance spectroscopy
Nuclear magnetic resonance
18.4 The NMR spectrometer
18.5 The chemical shift
18.6 The fine structure
Pulse techniques in NMR
18.7 The magnetization vector
18.8 Linewidths and rate processes
18.9 Spin decoupling
18.10 The nuclear Overhauser effect
18.11 Two-dimensional NMR
18.12 Solid-state NMR
Electron spin resonance
18.13 The ESR spectrometer
18.14 The g-value
18.15 Hyperfine structure
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Problems
19 Statistical thermodynamics：the concepts
The distribution of molecular states
19.1 Configurations and weights
19.2 The molecular partition function
The internal energy and the entropy
19.3 The internal energy
19.4 The statistical entropy
The canonical partition function
19.5 The canonical ensemble
19.6 The thermodynamic information in the partition function
19.7 Independent molecules
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20 Statistical thermodynamics：the machinery
Fundamental relations
20.1 The thermodynamic functions
20.2 The molecular partition function
Using statistical thermodynamics
20.3 Mean energies
20.4 Heat capacities
20.5 Equations of state
20.6 Residual entropies
20.7 Equilibrium constants
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21 Molecular interactions
Electric properties of molecules
21.1 Electric dipole moments
21.2 Polarizabilities
21.3 Relative permittivities
21.4 Refractive index
Interactions between molecules
21.5 Interactions between dipoles
21.6 Repulsive and total interactions
21.7 Molecular interactions in gases
21.8 Molecular interactions in liquids
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22 Macromolecules and aggregates
Structure and dynamics
22.1 The different levels of structure
22.2 Random coils
22.3 The structure of proteins
22.4 The structure of nucleic acids
22.5 The stability of biological polymers
Determination of size and shape
22.6 Mean molar masses
22.7 Mass spectrometry
22.8 Laser light scattering
22.9 Ultracentrifugation
22.10 Electrophoresis
22.11 Size-exclusion chromatography
22.12 Viscosity
Self-assembly
22.13 Colloids
22.14 Micelles and biological membranes
22.15 Surface films
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23 The solid state
Crystal lattices
23.1 Lattices and unit cells
23.2 The identification of lattice planes
23.3 The investigation of structure
23.4 Neutron and electron diffraction
Crystal structure
23.5 Metallic solids
23.6 Ionic solids
23.7 Molecular solids and covalent networks
The properties of solids
23.8 Mechanical properties
23.9 Electrical properties
23.10 Magnetic properties
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Further reading
Exercises
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Part 3 Change
24 Molecules in motion
Molecular motion in gases
24.1 The kinetic model of gases
24.2 Collisions with walls and surfaces
24.3 The rate of effusion
24.4 Transport properties of a perfect gas
Molecular motion in liquids
24.5 Experimental results
24.6 The conductivities of electrolyte solutions
24.7 The mobilities of ions
24.8 Conductivities and ion-ion interactions
Diffusion
24.9 The thermodynamic view
24.10 The diffusion equation
24.11 Diffusion probabilities
24.12 The statistical view
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Exercises
Problems
25 The rates of chemical reactions
Empirical chemical kinetics
25.1 Experimental techniques
25.2 The rates of reactions
25.3 Integrated rate laws
25.4 Reactions approaching equilibrium
25.5 The temperature dependence of reaction rates
Accounting for the rate laws
25.6 Elementary reactions
25.7 Consecutive elementary reactions
25.8 Unimolecular reactions
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Exercises
Problems
26 The kinetics of complex reactions
Chain reactions
26.1 The rate laws of chain reactions
26.2 Explosions
Polymerization kinetics
26.3 Stepwise polymerization
26.4 Chain polymerization
Homogeneous catalysis
26.5 Features of homogeneous catalysis
26.6 Enzymes
Oscillating reactions
26.7 Autocatalysis
26.8 Autocatalytic mechanisms of oscillating reactions
26.9 Bistability
26.10 Chemical chaos
Photochemistry
26.11 Kinetics of photophysical and photochemical processes
26.12 Complex photochemical processes
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27 Molecular reaction dynamics
Reactive encounters
27.1 Collision theory
27.2 Diffusion-controlled reactions
27.3 The material balance equation
Activated complex theory
27.4 The Eyring equation
27.5 Thermodynamic aspects
The dynamics of molecular collisions
27.6 Reactive collisions
27.7 Potential energy surfaces
27.8 Some results from experiments and calculations
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28 Processes at solid surfaces
The growth and structure of solid surfaces
28.1 Surface growth
28.2 Surface composition
The extent of adsorption
28.3 Physisorption and chemisorption
28.4 Adsorption isotherms
28.5 The rates of surface processes
Catalytic activity at surfaces
28.6 Adsorption and catalysis
28.7 Examples of catalysis
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29 Dynamics of electron transfer
Electron transfer in homogeneous systems
29.1 Theory of electron transfer processes
29.2 Experimental results
Electron transfer in heterogeneous systems
29.3 The electrode-solution interface
29.4 The rate of charge transfer
29.5 Voltammetry
29.6 Electrolysis
29.7 Working galvanic cells
29.8 Corrosion
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Further reading
Exercises
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Further information 1 Mathematical techniques
Basic procedures
1.1 Logarithms and exponentials
1.2 Combinatorial functions
1.3 Complex numbers and complex functions
1.4 Vectors
Calculus
1.5 Differentiation and integration
1.6 Power series and Taylor expansions
1.7 Partial derivatives
1.8 Undetermined multipliers
1.9 Differential equations
Matrix algebra
1.10 Matrix addition and multiplication
1.11 Simultaneous equations
1.12 Eigenvalue equations
Further reading
Further information 2 Essential concepts of physics
Energy
2.1 Kinetic and potential energy
2.2 Energy units
Classical mechanics
2.3 The trajectory in terms of the energy
2.4 Newton’s second law
2.5 Rotational motion
2.6 The harmonic oscillator
Waves
2.7 The electromagnetic field
2.8 Features of electromagnetic radiation
Electrostatics
2.9 The Coulomb interaction
2.10 The Coulomb potential
2.11 The strength of the electric field
2.12 The dipole-dipole interaction
2.13 Electric current and power
Further reading
Data section
Answers to exercises
Answers to problems
Index
