Atkins' Physical Chemistry

Cover
Fundamental Constants
Atkins' Physcial Chemistry
Copyright
Preface
Using the Book
About the Authors
Acknowledgements
Brief Contents
Full Contents
Conventions
Physical chemistry: people and perspectives
List of Tables
List of the Chemist's Toolkits
List of material provided as A deeper look
List of Impacts
Energy: A First Look
1 Force
(a) Linear momentum
(b) Angular momentum
(c) Newton’s second law of motion
2 Energy
(a) Work
(b) The definition of energy
3 Temperature
(a) The Boltzmann distribution
(b) The equipartition theorem
Checklist of concepts
Checklist of equations
Focus 1: The properties of gases
Topic 1A: The perfect gas
1A.1 Variables of state
1A.1(a) Pressure and volume
1A.1(b) Temperature
1A.1(c) Amount
1(d) Intensive and extensive properties
1A.2 Equations of state
1A.2(a) The empirical basis of the perfect gas law
1A.2(b) The value of the gas constant
1A.2(c) Mixtures of gases
Checklist of concepts
Checklist of equations
Topic 1B: The kinetic model
1B.1 The model
1B.1(a) Pressure and molecular speeds
1B.1(b) The Maxwell–Boltzmann distribution of speeds
1B.1(c) Mean values
1B.2 Collisions
1B.2(a) The collision frequency
1B.2(b) The mean free path
Checklist of concepts
Checklist of equations
Topic 1C: Real gases
1C.1 Deviations from perfect behaviour
1C.1(a) The compression factor
1C.1(b) Virial coefficients
1C.1(c) Critical constants
1C.2 The van der Waals equation
1C.2(a) Formulation of the equation
1C.2(b) The features of the equation
1C.2(c) The principle of corresponding states
Checklist of concepts
Checklist of equations
Focus 2: The First Law
Topic 2A: Internal energy
2A.1 Work, heat, and energy
2A.1(a) Definitions
2A.1(b) The molecular interpretation of heat and work
2A.2 The definition of internal energy
2A.2(a) Molecular interpretation of internal energy
2A.2(b) The formulation of the First Law
2A.3 Expansion work
2A.3(a) The general expression for work
2A.3(b) Expansion against constant pressure
2A.3(c) Reversible expansion
2A.3(d) Isothermal reversible expansion of a perfect gas
2A.4 Heat transactions
2A.4(a) Calorimetry
2A.4(b) Heat capacity
Checklist of concepts
Checklist of equations
Topic 2B: Enthalpy
2B.1 The definition of enthalpy
2B.1(a) Enthalpy change and heat transfer
2B.1(b) Calorimetry
2B.2 The variation of enthalpy with temperature
2B.2(a) Heat capacity at constant pressure
2B.2(b) The relation between heat capacities
Checklist of concepts
Checklist of equations
Topic 2C: Thermochemistry
2C.1 Standard enthalpy changes
2C.1(a) Enthalpies of physical change
2C.1(b) Enthalpies of chemical change
2C.1(c) Hess’s law
2C.2 Standard enthalpies of formation
2C.3 The temperature dependence of reaction enthalpies
2C.4 Experimental techniques
2C.4(a) Differential scanning calorimetry
2C.4(b) Isothermal titration calorimetry
Checklist of concepts
Checklist of equations
Topic 2D: State functions and exact differentials
2D.1 Exact and inexact differentials
2D.2 Changes in internal energy
2D.2(a) General considerations
2D.2(b) Changes in internal energy at constant pressure
2D.3 Changes in enthalpy
2D.4 The Joule–Thomson effect
Checklist of concepts
Checklist of equations
Topic 2E: Adiabatic changes
2E.1 The change in temperature
2E.2 The change in pressure
Checklist of concepts
Checklist of equations
Focus 3: The Second and Third Laws
Topic 3A: Entropy
3A.1 The Second Law
3A.2 The definition of entropy
3A.2(a) The thermodynamic definition of entropy
3A.2(b) The statistical definition of entropy
3A.3 The entropy as a state function
3A.3(a) The Carnot cycle
3A.3(b) The thermodynamic temperature
3A.3(c) The Clausius inequality
Checklist of concepts
Checklist of equations
Topic 3B Entropy changes accompanying specific processes
3B.1 Expansion
3B.2 Phase transitions
3B.3 Heating
3B.4 Composite processes
Checklist of concepts
Checklist of equations
Topic 3C The measurement of entropy
3C.1 The calorimetric measurement of entropy
3C.2 The Third Law
3C.2(a) The Nernst heat theorem
3C.2(b) Third-Law entropies
3C.2(c) The temperature dependence of reaction entropy
Checklist of concepts
Checklist of equations
Topic 3D Concentrating on the system
3D.1 The Helmholtz and Gibbs energies
3D.1(a) Criteria of spontaneity
3D.1(b) Some remarks on the Helmholtz energy
3D.1(c) Maximum work
3D.1(d) Some remarks on the Gibbs energy
3D.1(e) Maximum non-expansion work
3D.2 Standard molar Gibbs energies
3D.2(a) Gibbs energies of formation
3D.2(b) The Born equation
Checklist of concepts
Checklist of equations
Topic 3E Combining the First and Second Laws
3E.1 Properties of the internal energy
3E.1(a) The Maxwell relations
3E.1(b) The variation of internal energy with volume
3E.2 Properties of the Gibbs energy
3E.2(a) General considerations
3E.2(b) The variation of the Gibbs energy with temperature
3E.2(c) The variation of the Gibbs energy of condensed phases with pressure
3E.2(d) The variation of the Gibbs energy of gases with pressure
Checklist of concepts
Checklist of equations
Focus 4: Physical transformations of pure substances
Topic 4A Phase diagrams of pure substances
4A.1 The stabilities of phases
4A.1(a) The number of phases
4A.1(b) Phase transitions
4A.1(c) Thermodynamic criteria of phase stability
4A.2 Coexistence curves
4A.2(a) Characteristic properties related to phase transitions
4A.2(b) The phase rule
4A.3 Three representative phase diagrams
4A.3(a) Carbon dioxide
4A.3(b) Water
4A.3(c) Helium
Checklist of concepts
Checklist of equations
Topic 4B Thermodynamic aspects of phase transitions
4B.1 The dependence of stability on the conditions
4B.1(a) The temperature dependence of phase stability
4B.1(b) The response of melting to applied pressure
4B.1(c) The vapour pressure of a liquid subjected to pressure
4B.2 The location of coexistence curves
4B.2(a) The slopes of the coexistence curves
4B.2(b) The solid–liquid coexistence curve
4B.2(c) The liquid–vapour coexistence curve
4B.2(d) The solid–vapour coexistence curve
Checklist of concepts
Checklist of equations
Focus 5: Simple mixtures
Topic 5A The thermodynamic description of mixtures
5A.1 Partial molar quantities
5A.1(a) Partial molar volume
5A.1(b) Partial molar Gibbs energies
5A.1(c) The Gibbs–Duhem equation
5A.2 The thermodynamics of mixing
5A.2(a) The Gibbs energy of mixing of perfect gases
5A.2(b) Other thermodynamic mixing functions
5A.3 The chemical potentials of liquids
5A.3(a) Ideal solutions
5A.3(b) Ideal–dilute solutions
Checklist of concepts
Checklist of equations
Topic 5B: The properties of solutions
5B.1 Liquid mixtures
5B.1(a) Ideal solutions
5B.1(b) Excess functions and regular solutions
5B.2 Colligative properties
5B.2(a) The common features of colligative properties
5B.2(b) The elevation of boiling point
5B.2(c) The depression of freezing point
5B.2(d) Solubility
5B.2(e) Osmosis
Checklist of concepts
Checklist of equations
Topic 5C Phase diagrams of binary systems: liquids
5C.1 Vapour pressure diagrams
5C.2 Temperature–composition diagrams
5C.2(a) The construction of the diagrams
5C.2(b) The interpretation of the diagrams
5C.3 Distillation
5C.3(a) Fractional distillation
5C.3(b) Azeotropes
5C.3(c) Immiscible liquids
5C.4 Liquid–liquid phase diagrams
5C.4(a) Phase separation
5C.4(b) Critical solution temperatures
5C.4(c) The distillation of partially miscible liquids
Checklist of concepts
Checklist of equations
Topic 5D Phase diagrams of binary systems: solids
5D.1 Eutectics
5D.2 Reacting systems
5D.3 Incongruent melting
Checklist of concepts
Topic 5E Phase diagrams of ternary systems
5E.1 Triangular phase diagrams
5E.2 Ternary systems
5E.2(a) Partially miscible liquids
5E.2(b) Ternary solids
Checklist of concepts
Topic 5F Activities
5F.1 The solvent activity
5F.2 The solute activity
5F.2(a) Ideal–dilute solutions
5F.2(b) Real solutes
5F.2(c) Activities in terms of molalities
5F.3 The activities of regular solutions
5F.4 The activities of ions
5F.4(a) Mean activity coefficients
5F.4(b) The Debye–Hückel limiting law
5F.4(c) Extensions of the limiting law
Checklist of concepts
Checklist of equations
Focus 6: Chemical equilibrium
Topic 6A The equilibrium constant
6A.1 The Gibbs energy minimum
6A.1(a) The reaction Gibbs energy
6A.1(b) Exergonic and endergonic reactions
6A.2 The description of equilibrium
6A.2(a) Perfect gas equilibria
6A.2(b) The general case of a reaction
6A.2(c) The relation between equilibrium constants
6A.2(d) Molecular interpretation of the equilibrium constant
Checklist of concepts
Checklist of equations
Topic 6B The response of equilibria to the conditions
6B.1 The response to pressure
6B.2 The response to temperature
6B.2(a) The van ’t Hoff equation
6B.2(b) The value of K at different temperatures
Checklist of concepts
Checklist of equations
Topic 6C Electrochemical cells
6C.1 Half-reactions and electrodes
6C.2 Varieties of cell
6C.2(a) Liquid junction potentials
6C.2(b) Notation
6C.3 The cell potential
6C.3(a) The Nernst equation
6C.3(b) Cells at equilibrium
6C.4 The determination of thermodynamic functions
Checklist of concepts
Checklist of equations
Topic 6D Electrode potentials
6D.1 Standard potentials
6D.1(a) The measurement procedure
6D.1(b) Combining measured values
6D.2 Applications of standard electrode potentials
6D.2(a) The electrochemical series
6D.2(b) The determination of activity coefficients
6D.2(c) The determination of equilibrium constants
Checklist of concepts
Checklist of equations
Focus 7: Quantum theory
Topic 7A The origins of quantummechanics
7A.1 Energy quantization
7A.1(a) Black-body radiation
7A.1(b) Heat capacity
7A.1(c) Atomic and molecular spectra
7A.2 Wave–particle duality
7A.2(a) The particle character of electromagnetic radiation
7A.2(b) The wave character of particles
Checklist of concepts
Checklist of equations
Topic 7B Wavefunctions
7B.1 The Schrödinger equation
7B.2 The Born interpretation
7B.2(a) Normalization
7B.2(b) Constraints on the wavefunction
7B.2(c) Quantization
Checklist of concepts
Checklist of equations
Topic 7C Operators and observables
7C.1 Operators
7C.1(a) Eigenvalue equations
7C.1(b) The construction of operators
7C.1(c) Hermitian operators
7C.1(d) Orthogonality
7C.2 Superpositions and expectation values
7C.3 The uncertainty principle
7C.4 The postulates of quantum mechanics
Checklist of concepts
Checklist of equations
Topic 7D Translational motion
7D.1 Free motion in one dimension
7D.2 Confined motion in one dimension
7D.2(a) The acceptable solutions
7D.2(b) The properties of the wavefunctions
7D.2(c) The properties of the energy
7D.3 Confined motion in two and more dimensions
7D.3(a) Energy levels and wavefunctions
7D.3(b) Degeneracy
7D.4 Tunnelling
Checklist of concepts
Checklist of equations
Topic 7E Vibrational motion
7E.1 The harmonic oscillator
7E.1(a) The energy levels
7E.1(b) The wavefunctions
7E.2 Properties of the harmonic oscillator
7E.2(a) Mean values
7E.2(b) Tunnelling
Checklist of concepts
Checklist of equations
Topic 7F Rotational motion
7F.1 Rotation in two dimensions
7F.1(a) The solutions of the Schrödinger equation
7F.1(b) Quantization of angular momentum
7F.2 Rotation in three dimensions
7F.2(a) The wavefunctions and energy levels
7F.2(b) Angular momentum
7F.2(c) The vector model
Checklist of concepts
Checklist of equations
Focus 8: Atomic structure and spectra
Topic 8A Hydrogenic atoms
8A.1 The structure of hydrogenic atoms
8A.1(a) The separation of variables
8A.1(b) The radial solutions
8A.2 Atomic orbitals and their energies
8A.2(a) The specification of orbitals
8A.2(b) The energy levels
8A.2(c) Ionization energies
8A.2(d) Shells and subshells
8A.2(e) s Orbitals
8A.2(f ) Radial distribution functions
8A.2(g) p Orbitals
8A.2(h) d Orbitals
Checklist of concepts
Checklist of equations
Topic 8B Many-electron atoms
8B.1 The orbital approximation
8B.2 The Pauli exclusion principle
8B.2(a) Spin
8B.2(b) The Pauli principle
8B.3 The building-up principle
8B.3(a) Penetration and shielding
8B.3(b) Hund’s rules
8B.3(c) Atomic and ionic radii
8B.3(d) Ionization energies and electron affinities
8B.4 Self-consistent field orbitals
Checklist of concepts
Checklist of equations
Topic 8C Atomic spectra
8C.1 The spectra of hydrogenic atoms
8C.2 The spectra of many-electron atoms
8C.2(a) Singlet and triplet terms
8C.2(b) Spin–orbit coupling
8C.2(c) Term symbols
8C.2(d) Hund’s rules and term symbols
8C.2(e) Selection rules
Checklist of concepts
Checklist of equations
Focus 9: Molecular structure
Prologue: The Born–Oppenheimer approximation
Topic 9A Valence-bond theory
9A.1 Diatomic molecules
9A.2 Resonance
9A.3 Polyatomic molecules
9A.3(a) Promotion
9A.3(b) Hybridization
Checklist of concepts
Checklist of equations
Topic 9B Molecular orbital theory: the hydrogen molecule-ion
9B.1 Linear combinations of atomic orbitals
9B.1(a) The construction of linear combinations
9B.1(b) Bonding orbitals
9B.1(c) Antibonding orbitals
9B.2 Orbital notation
Checklist of concepts
Checklist of equations
Topic 9C Molecular orbital theory: homonuclear diatomic molecules
9C.1 Electron configurations
9C.1(a) MO energy level diagrams
9C.1(b) σ Orbitals and π orbitals
9C.1(c) The overlap integral
9C.1(d) Period 2 diatomic molecules
9C.2 Photoelectron spectroscopy
Checklist of concepts
Checklist of equations
Topic 9D Molecular orbital theory: heteronuclear diatomic molecules
9D.1 Polar bonds and electronegativity
9D.2 The variation principle
9D.2(a) The procedure
9D.2(b) The features of the solutions
Checklist of concepts
Checklist of equations
Topic 9E Molecular orbital theory: polyatomic molecules
9E.1 The Hückel approximation
9E.1(a) An introduction to the method
9E.1(b) The matrix formulation of the method
9E.2 Applications
9E.2(a) π-Electron binding energy
9E.2(b) Aromatic stability
9E.3 Computational chemistry
9E.3(a) Basis functions and basis sets
9E.3(b) Electron correlation
9E.3(c) Density functional theory
9E.3(d) Practical calculations
9E.3(e) Graphical representations
Checklist of concepts
Checklist of equations
Topic 9F Computational chemistry
9F.1 The central challenge
9F.2 The Hartree−Fock formalism
9F.3 The Roothaan equations
9F.4 Evaluation and approximation of the integrals
9F.5 Density functional theory
Checklist of concepts
Checklist of equations
Focus 10: Molecular symmetry
Topic 10A Shape and symmetry
10A.1 Symmetry operations and symmetry elements
10A.2 The symmetry classification of molecules
10A.2(a) The groups C1, Ci, and Cs
10A.2(b) The groups Cn, Cnv, and Cnh
10A.2(c) The groups Dn, Dnh, and Dnd
10A.2(d) The groups Sn
10A.2(e) The cubic groups
10A.2(f) The full rotation group
10A.3 Some immediate consequences of symmetry
10A.3(a) Polarity
10A.3(b) Chirality
Checklist of concepts
Checklist of symmetry operations and elements
Topic 10B Group theory
10B.1 The elements of group theory
10B.2 Matrix representations
10B.2(a) Representatives of operations
10B.2(b) The representation of a group
10B.2(c) Irreducible representations
10B.2(d) Characters
10B.3 Character tables
10B.3(a) The symmetry species of atomic orbitals
10B.3(b) The symmetry species of linear combinations of orbitals
10B.3(c) Character tables and degeneracy
Checklist of concepts
Checklist of equations
Topic 10C Applications of symmetry
10C.1 Vanishing integrals
10C.1(a) Integrals of the product of functions
10C.1(b) Decomposition of a representation
10C.2 Applications to molecular orbital theory
10C.2(a) Orbital overlap
10C.2(b) Symmetry-adapted linear combinations
10C.3 Selection rules
Checklist of concepts
Checklist of equations
Focus 11: Molecular spectroscopy
Topic 11A General features ofmolecularspectroscopy
11A.1 The absorption and emission of radiation
11A.1(a) Stimulated and spontaneous radiative processes
11A.1(b) Selection rules and transition moments
11A.1(c) The Beer–Lambert law
11A.2 Spectral linewidths
11A.2(a) Doppler broadening
11A.2(b) Lifetime broadening
11A.3 Experimental techniques
11A.3(a) Sources of radiation
11A.3(b) Spectral analysis
11A.3(c) Detectors
11A.3(d) Examples of spectrometers
Checklist of concepts
Checklist of equations
Topic 11B Rotational spectroscopy
11B.1 Rotational energy levels
11B.1(a) Spherical rotors
11B.1(b) Symmetric rotors
11B.1(c) Linear rotors
11B.1(d) Centrifugal distortion
11B.2 Microwave spectroscopy
11B.2(a) Selection rules
11B.2(b) The appearance of microwave spectra
11B.3 Rotational Raman spectroscopy
11B.4 Nuclear statistics and rotational states
Checklist of concepts
Checklist of equations
Topic 11C Vibrational spectroscopy of diatomic molecules
11C.1 Vibrational motion
11C.2 Infrared spectroscopy
11C.3 Anharmonicity
11C.3(a) The convergence of energy levels
11C.3(b) The Birge–Sponer plot
11C.4 Vibration–rotation spectra
11C.4(a) Spectral branches
11C.4(b) Combination differences
11C.5 Vibrational Raman spectra
Checklist of concepts
Checklist of equations
Topic 11D Vibrational spectroscopy ofpolyatomic molecules
11D.1 Normal modes
11D.2 Infrared absorption spectra
11D.3 Vibrational Raman spectra
Checklist of concepts
Checklist of equations
Topic 11E Symmetry analysis of vibrationalspectra
11E.1 Classification of normal modes according to symmetry
11E.2 Symmetry of vibration alwavefunctions
11E.2(a) Infrared activity of normal modes
11E.2(b) Raman activity of normal modes
11E.2(c) The symmetry basis of the exclusion rule
Checklist of concepts
Topic 11F Electronic spectra
11F.1 Diatomic molecules
11F.1(a) Term symbols
11F.1(b) Selection rules
11F.1(c) Vibrational fine structure
11F.1(d) Rotational fine structure
11F.2 Polyatomic molecules
11F.2(a) d-Metal complexes
11F.2(b) π⋆ ← π and π⋆ ← n transitions
Checklist of concepts
Checklist of equations
Topic 11G Decay of excited states
11G.1 Fluorescence and phosphorescence
11G.2 Dissociation and predissociation
11G.3 Lasers
Checklist of concepts
Focus 12: Magnetic resonance
Topic 12A General principles
12A.1 Nuclear magnetic resonance
12A.1(a) The energies of nuclei in magnetic fields
12A.1(b) The NMR spectrometer
12A.2 Electron paramagnetic resonance
12A.2(a) The energies of electrons in magnetic fields
12A.2(b) The EPR spectrometer
Checklist of concepts
Checklist of equations
Topic 12B Features of NMR spectra
12B.1 The chemical shift
12B.2 The origin of shielding constants
12B.2(a) The local contribution
12B.2(b) Neighbouring group contributions
12B.2(c) The solvent contribution
12B.3 The fine structure
12B.3(a) The appearance of the spectrum
12B.3(b) The magnitudes of coupling constants
12B.4 The origin of spin–spin coupling
12B.4(a) Equivalent nuclei
12B.4(b) Strongly coupled nuclei
12B.5 Exchange processes
12B.6 Solid-state NMR
Checklist of concepts
Checklist of equations
Topic 12C Pulse techniques in NMR
12C.1 The magnetization vector
12C.1(a) The effect of the radiofrequency field
12C.1(b) Time- and frequency-domain signals
12C.2 Spin relaxation
12C.2(a) The mechanism of relaxation
12C.2(b) The measurement of T1 and T2
12C.3 Spin decoupling
12C.4 The nuclear Overhauser effect
Checklist of concepts
Checklist of equations
Topic 12D Electron paramagnetic resonance
12D.1 The g-value
12D.2 Hyperfine structure
12D.2(a) The effects of nuclear spin
12D.3 The McConnell equation
12D.3(a) The origin of the hyperfine interaction
Checklist of concepts
Checklist of equations
Focus 13: Statistical thermodynamics
Topic 13A The Boltzmann distribution
13A.1 Configurations and weights
13A.1(a) Instantaneous configurations
13A.1(b) The most probable distribution
13A.2 The relative populations of states
Checklist of concepts
Checklist of equations
Topic 13B Molecular partition functions
13B.1 The significance of the partition function
13B.2 Contributions to the partition function
13B.2(a) The translational contribution
13B.2(b) The rotational contribution
13B.2(c) The vibrational contribution
13B.2(d) The electronic contribution
Checklist of concepts
Checklist of equations
Topic 13C Molecular energies
13C.1 The basic equations
13C.2 Contributions of the fundamental modes of motion
13C.2(a) The translational contribution
13C.2(b) The rotational contribution
13C.2(c) The vibrational contribution
13C.2(d) The electronic contribution
13C.2(e) The spin contribution
Checklist of concepts
Checklist of equations⋆
Topic 13D The canonical ensemble
13D.1 The concept of ensemble
13D.1(a) Dominating configurations
13D.1(b) Fluctuations from the most probable distribution
13D.2 The mean energy of a system
13D.3 Independent molecules revisited
13D.4 The variation of the energy with volume
Checklist of concepts
Checklist of equations⋆
Topic 13E The internal energy and the entropy
13E.1 The internal energy
13E.1(a) The calculation of internal energy
13E.1(b) Heat capacity
13E.2 The entropy
13E.2(a) Entropy and the partition function
13E.2(b) The translational contribution
13E.2(c) The rotational contribution
13E.2(d) The vibrational contribution
13E.2(e) Residual entropies
Checklist of concepts
Checklist of equations⋆
Topic 13 F Derived functions
13F.1 The derivations
13F.2 Equilibrium constants
13F.2(a) The relation between K and the partition function
13F.2(b) A dissociation equilibrium
13F.2(c) Contributions to the equilibrium constant
Checklist of concepts
Checklist of equations
Focus 14: Molecular interactions
Topic 14 A The electric propertiesof molecules
14A.1 Electric dipole moments
14A.2 Polarizabilities
14A.3 Polarization
14A.3(a) The mean dipole moment
14A.3(b) The frequency dependence of the polarization
14A.3(c) Molar polarization
Checklist of concepts
Checklist of equations
Topic 14B Interactions betweenmolecules
14B.1 The interactions of dipoles
14B.1(a) Charge–dipole interactions
14B.1(b) Dipole–dipole interactions
14B.1(c) Dipole–induced dipole interactions
14B.1(d) Induced dipole–induced dipole interactions
14B.2 Hydrogen bonding
14B.3 The total interaction
Checklist of concepts
Checklist of equations
Topic 14C Liquids
14C.1 Molecular interactions in liquids
14C.1(a) The radial distribution function
14C.1(b) The calculation of g(r)
14C.1(c) The thermodynamic properties of liquids
14C.2 The liquid–vapour interface
14C.2(a) Surface tension
14C.2(b) Curved surfaces
14C.2(c) Capillary action
14C.3 Surface films
14C.3(a) Surface pressure
14C.3(b) The thermodynamics of surface layers
14C.4 Condensation
Checklist of concepts
Checklist of equations
Topic 14D Macromolecules
14D.1 Average molar masses
14D.2 The different levels of structure
14D.3 Random coils
14D.3(a) Measures of size
14D.3(b) Constrained chains
14D.3(c) Partly rigid coils
14D.4 Mechanical properties
14D.4(a) Conformational entropy
14D.4(b) Elastomers
14D.5 Thermal properties
Checklist of concepts
Checklist of equations
Topic 14E Self-assembly
14E.1 Colloids
14E.1(a) Classification and preparation
14E.1(b) Structure and stability
14E.1(c) The electrical double layer
14E.2 Micelles and biological membranes
14E.2(a) The hydrophobic interaction
14E.2(b) Micelle formation
14E.2(c) Bilayers, vesicles, and membranes
Checklist of concepts
Checklist of equations
Focus 15: Solids
Topic 15A Crystal structure
15A.1 Periodic crystal lattices
15A.2 The identification of lattice planes
15A.2(a) The Miller indices
15A.2(b) The separation of neighbouring planes
Checklist of concepts
Checklist of equations
Topic 15B Diffraction techniques
15B.1 X-ray crystallography
15B.1(a) X-ray diffraction
15B.1(b) Bragg’s law
15B.1(c) Scattering factors
15B.1(d) The electron density
15B.1(e) The determination of structure
15B.2 Neutron and electron diffraction
Checklist of concepts
Checklist of equations
Topic 15C Bonding in solids
15C.1 Metals
15C.1(a) Close packing
15C.1(b) Electronic structure of metals
15C.2 Ionic solids
15C.2(a) Structure
15C.2(b) Energetics
15C.3 Covalent and molecular solids
Checklist of concepts
Checklist of equations
Topic 15D The mechanical properties of solids
Checklist of concepts
Checklist of equations
Topic 15E The electrical propertiesof solids
15E.1 Metallic conductors
15E.2 Insulators and semiconductors
15E.3 Superconductors
Checklist of concepts
Checklist of equations
Topic 15F The magnetic properties of solids
15F.1 Magnetic susceptibility
15F.2 Permanent and induced magnetic moments
15F.3 Magnetic properties of superconductors
Checklist of concepts
Checklist of equations
Topic 15G The optical propertiesof solids
15G.1 Excitons
15G.2 Metals and semiconductors
15G.2(a) Light absorption
15G.2(b) Light-emitting diodes and diode lasers
15G.3 Nonlinear optical phenomena
Checklist of concepts
Focus 16: Molecules in motion
Topic 16A Transport properties of a perfect gas
16A.1 The phenomenological equations
16A.2 The transport parameters
16A.2(a) The diffusion coefficient
16A.2(b) Thermal conductivity
16A.2(c) Viscosity
16A.2(d) Effusion
Checklist of concepts
Checklist of equations
Topic 16B Motion in liquids
16B.1 Experimental results
16B.1(a) Liquid viscosity
16B.1(b) Electrolyte solutions
16B.2 The mobilities of ions
16B.2(a) The drift speed
16B.2(b) Mobility and conductivity
16B.2(c) The Einstein relations
Checklist of concepts
Checklist of equations
Topic 16C Diffusion
16C.1 The thermodynamic view
16C.2 The diffusion equation
16C.2(a) Simple diffusion
16C.2(b) Diffusion with convection
16C.2(c) Solutions of the diffusion equation
16C.3 The statistical view
Checklist of concepts
Checklist of equations
Focus 17: Chemical kinetics
Topic 17A The rates of chemicalreactions
17A.1 Monitoring the progressof a reaction
17A.1(a) General considerations
17A.1(b) Special techniques
17A.2 The rates of reactions
17A.2(a) The definition of rate
17A.2(b) Rate laws and rate constants
17A.2(c) Reaction order
17A.2(d) The determination of the rate law
Checklist of concepts
Checklist of equations
Topic 17B Integrated rate laws
17B.1 Zeroth-order reactions
17B.2 First-order reactions
17B.3 Second-order reactions
Checklist of concepts
Checklist of equations
Topic 17C Reactions approaching equilibrium
17C.1 First-order reactions approaching equilibrium
17C.2 Relaxation methods
Checklist of concepts
Checklist of equations
Topic 17D The Arrhenius equation
17D.1 The temperature dependence of rate constants
17D.2 The interpretation of the Arrhenius parameters
17D.2(a) A first look at the energy requirements of reactions
17D.2(b) The effect of a catalyst on the activation energy
Checklist of concepts
Checklist of equations
Topic 17E Reaction mechanisms
17E.1 Elementary reactions
17E.2 Consecutive elementary reactions
17E.3 The steady-state approximation
17E.4 The rate-determining step
17E.5 Pre-equilibria
17E.6 Kinetic and thermodynamic control of reactions
Checklist of concepts
Checklist of equations
Topic 17F Examples of reaction mechanisms
17F.1 Unimolecular reactions
17F.2 Polymerization kinetics
17F.2(a) Stepwise polymerization
17F.2(b) Chain polymerization
17F.3 Enzyme-catalysed reactions
Checklist of concepts
Checklist of equations
Topic 17G Photochemistry
17G.1 Photochemical processes
17G.2 The primary quantum yield
17G.3 Mechanism of decay of excited singlet states
17G.4 Quenching
17G.5 Resonance energy transfer
Checklist of concepts
Checklist of equations
Focus 18: Reaction dynamics
Topic 18A Collision theory
18A.1 Reactive encounters
18A.1(a) Collision rates in gases
18A.1(b) The energy requirement
18A.1(c) The steric requirement
18A.2 The RRK model
Checklist of concepts
Checklist of equations
Topic 18B Diffusion-controlled reactions
18B.1 Reactions in solution
18E.1(a) Classes of reaction
18B.1(b) Diffusion and reaction
18B.2 The material-balance equation
18B.2(a) The formulation of the equation
18B.2(b) Solutions of the equation
Checklist of concepts
Checklist of equations
Topic 18C Transition-state theory
18C.1 The Eyring equation
18C.1(a) The formulation of the equation
18C.1(b) The rate of decay of the activated complex
18C.1(c) The concentration of the activated complex
18C.1(d) The rate constant
18C.2 Thermodynamic aspects
18C.2(a) Activation parameters
18C.2(b) Reactions between ions
18C.3 The kinetic isotope effect
Checklist of concepts
Checklist of equations
Topic 18D The dynamics of molecularcollisions
18D.1 Molecular beams
18D.1(a) Techniques
18D.1(b) Experimental results
18D.2 Reactive collisions
18D.2(a) Probes of reactive collisions
18D.2(b) State-to-state reaction dynamics
18D.3 Potential energy surfaces
18D.4 Some results from experiments and calculations
18D.4(a) The direction of attack and separation
18D.4(b) Attractive and repulsive surfaces
18D.4(c) Quantum mechanical scattering theory
Checklist of concepts
Checklist of equations
Topic 18E Electron transfer in homogeneous systems
18E.1 The rate law
18E.2 The role of electron tunnelling
18E.3 The rate constant
18E.4 Experimental tests of the theory
Checklist of concepts
Checklist of equations
Focus 19: Processes at solid surfaces
Topic 19 A An introduction to solid surfaces
19A.1 Surface growth
19A.2 Physisorption and chemisorption
19A.3 Experimental techniques
19A.3(a) Microscopy
19A.3(b) Ionization techniques
19A.3(c) Diffraction techniques
19A.3(d) Determination of the extent and rates of adsorption and desorption
Checklist of concepts
Checklist of equations
Topic 19B Adsorption and desorption
19B.1 Adsorption isotherms
19B.1(a) The Langmuir isotherm
19B.1(b) The isosteric enthalpy of adsorption
19B.1(c) The BET isotherm
19B.1(d) The Temkin and Freundlich Isotherms
19B.2 The rates of adsorption and desorption
19B.2(a) The precursor state
19B.2(b) Adsorption and desorption at the molecular level
19B.2(c) Mobility on surfaces
Checklist of concepts
Checklist of equations
Topic 19C Heterogeneous catalysis
19C.1 Mechanisms of heterogeneous catalysis
19C.1(a) Unimolecular reactions
19C.1(b) The Langmuir–Hinshelwood mechanism
19C.1(c) The Eley–Rideal mechanism
19C.2 Catalytic activity at surfaces
Checklist of concepts
Checklist of equations
Topic 19D Processes at electrodes
19D.1 The electrode–solution interface
19D.2 The current density at an electrode
19D.2(a) The Butler–Volmer equation
19D.2(b) Tafel plots
19D.3 Voltammetry
19D.4 Electrolysis
19D.5 Working galvanic cells
Checklist of concepts
Checklist of equations
Solutions
Available in the E-Book
Resource Section
Part 1 Mathematical resources
1.1 Integration
1.2 Differentiation
1.3 Series expansions
Part 2 Quantities and units
Part 3 Data
Part 4 Character tables
Index