Catching Fire

The exceptional quality of previous editions has been built upon to make the twelfth edition of Atkins' Physical Chemistry even more closely suited to the needs of both lecturers and students. The writing style has been refreshed in collaboration with current students of physical chemistry in order to retain the clarity for which the book is recognised while mirroring the way you read and engage with information. The new edition is now available as an enhanced e-book, which offers you a richer, more dynamic learning experience. It does this by incorporating digital enhancements that are carefully curated and thoughtfully inserted at meaningful points to enhance the learning experience. In addition, it offers formative auto-graded assessment materials to provide you with regular opportunities to test their understanding. Digital enhancements introduced for the new edition include dynamic graphs, which you can interact with to explore how the manipulation of variables affects the results of the graphs; self-check questions at the end of every Topic; video content from physical chemists; and video tutorials to accompany each Focus, which dig deeper into the key equations introduced. There is also a new foundational prologue entitled 'Energy: A First Look', which summarizes key concepts that are best kept in mind right from the beginning of your physical chemistry studies. The coupling of the broad coverage of the subject with a structure and use of pedagogy that is even more innovative will ensure Atkins' Physical Chemistry remains the textbook of choice for studying 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