Atkins' Physical Chemistry

Description

Atkins' Physical Chemistry is widely acknowledged by both students and lecturers around the globe to be the textbook of choice for studying physical chemistry. Now in its eleventh edition, the text has been enhanced with additional learning features and maths support, re-organised into discrete Topics, to make the text more flexible to teach from and more readable for students. Cover PREFACE USING THE BOOK ABOUT THE AUTHORS ACKNOWLEDGEMENTS BRIEF CONTENTS FULL CONTENTS CONVENTIONS LIST OF TABLES LIST OF THE CHEMIST’S TOOLKITS LIST OF MATERIAL PROVIDED AS A DEEPER LOOK LIST OF IMPACTS PROLOGUE Energy, temperature, and chemistry FOCUS 1 The properties of gases TOPIC 1A The perfect gas 1A.1 Variables of state (a) Pressure (b) Temperature 1A.2 Equations of state (a) The empirical basis (b) Mixtures of gases Checklist of concepts Checklist of equations TOPIC 1B The kinetic model 1B.1 The model (a) Pressure and molecular speeds (b) The Maxwell–Boltzmann distribution of speeds (c) Mean values 1B.2 Collisions (a) The collision frequency (b) The mean free path Checklist of concepts Checklist of equations TOPIC 1C Real gases 1C.1 Deviations from perfect behaviour (a) The compression factor (b) Virial coefficients (c) Critical constants 1C.2 The van der Waals equation (a) Formulation of the equation (b) The features of the equation (c) The principle of corresponding states Checklist of concepts Checklist of equations FOCUS 2 The First LawThe TOPIC 2A Internal energy 2A.1 Work, heat, and energy (a) Operational definitions (b) The molecular interpretation of heat and work 2A.2 The definition of internal energy (a) Molecular interpretation of internal energy (b) The formulation of the First Law 2A.3 Expansion work (a) The general expression for work (b) Expansion against constant pressure (c) Reversible expansion (d) Isothermal reversible expansion of a perfect gas 2A.4 Heat transactions (a) Calorimetry (b) Heat capacity Checklist of concepts Checklist of equations TOPIC 2B Enthalpy 2B.1 The definition of enthalpy (a) Enthalpy change and heat transfer (b) Calorimetry 2B.2 The variation of enthalpy with temperature (a) Heat capacity at constant pressure (b) The relation between heat capacities Checklist of concepts Checklist of equations TOPIC 2C Thermochemistry 2C.1 Standard enthalpy changes (a) Enthalpies of physical change (b) Enthalpies of chemical change (c) Hess’s law 2C.2 Standard enthalpies of formation 2C.3 The temperature dependence of reaction enthalpies 2C.4 Experimental techniques (a) Differential scanning calorimetry (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 (a) General considerations (b) Changes in internal energy at constant pressure 2D.3 Changes in enthalpy 2D.4 The Joule–Thomson effect (a) The observation of the Joule–Thomson effect (b) The molecular interpretation of 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 (a) The thermodynamic definition of entropy (b) The statistical definition of entropy 3A.3 The entropy as a state function (a) The Carnot cycle (b) The thermodynamic temperature (c) The Clausius inequality Checklist of concepts Checklist of equations TOPIC 3B Entropy changes accompanyingspecific 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 (a) The Nernst heat theorem (b) Third-Law entropies (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 (a) Criteria of spontaneity (b) Some remarks on the Helmholtz energy (c) Maximum work (d) Some remarks on the Gibbs energy (e) Maximum non-expansion work 3D.2 Standard molar Gibbs energies (a) Gibbs energies of formation (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 (a) The Maxwell relations (b) The variation of internal energy with volume 3E.2 Properties of the Gibbs energy (a) General considerations (b) The variation of the Gibbs energy with temperature (c) The variation of the Gibbs energy 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 (a) The number of phases (b) Phase transitions (c) Thermodynamic criteria of phase stability 4A.2 Phase boundaries (a) Characteristic properties related to phase transitions (b) The phase rule 4A.3 Three representative phase diagrams (a) Carbon dioxide (b) Water (c) Helium Checklist of concepts Checklist of equations TOPIC 4B Thermodynamic aspects of phase transitions 4B.1 The dependence of stability on the conditions (a) The temperature dependence of phase stability (b) The response of melting to applied pressure (c) The vapour pressure of a liquid subjected to pressure 4B.2 The location of phase boundaries (a) The slopes of the phase boundaries (b) The solid–liquid boundary (c) The liquid–vapour boundary Checklist of concepts Checklist of equations FOCUS 5 Simple mixtures TOPIC 5A The thermodynamic description of mixtures 5A.1 Partial molar quantities (a) Partial molar volume (b) Partial molar Gibbs energies (c) The wider significance of the chemical potential (d) The Gibbs–Duhem equation 5A.2 The thermodynamics of mixing (a) The Gibbs energy of mixing of perfect gases (b) Other thermodynamic mixing functions 5A.3 The chemical potentials of liquids (a) Ideal solutions (b) Ideal–dilute solutions Checklist of concepts Checklist of equations TOPIC 5B The properties of solutions 5B.1 Liquid mixtures (a) Ideal solutions (b) Excess functions and regular solutions 5B.2 Colligative properties (a) The common features of colligative properties (b) The elevation of boiling point (c) The depression of freezing point (d) Solubility (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 (a) The construction of the diagrams (b) The interpretation of the diagrams 5C.3 Distillation (a) Simple and fractional distillation (b) Azeotropes (c) Immiscible liquids 5C.4 Liquid–liquid phase diagrams (a) Phase separation (b) Critical solution temperatures (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 (a) Partially miscible liquids (b) Ternary solids Checklist of concepts TOPIC 5F Activities 5F.1 The solvent activity 5F.2 The solute activity (a) Ideal–dilute solutions (b) Real solutes (c) Activities in terms of molalities 5F.3 The activities of regular solutions 5F.4 The activities of ions (a) Mean activity coefficients (b) The Debye–Hückel limiting law (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 (a) The reaction Gibbs energy (b) Exergonic and endergonic reactions 6A.2 The description of equilibrium (a) Perfect gas equilibria (b) The general case of a reaction (c) The relation between equilibrium constants (d) Molecular interpretation of the equilibrium constant Checklist of concepts Checklist of equations TOPIC 6B The response of equilibriato the conditions 6B.1 The response to pressure 6B.2 The response to temperature (a) The van ’t Hoff equation (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 cells (a) Liquid junction potentials (b) Notation 6C.3 The cell potential (a) The Nernst equation (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 (a) The measurement procedure (b) Combining measured values 6D.2 Applications of standard potentials (a) The electrochemical series (b) The determination of activity coefficients (c) The determination of equilibrium constants Checklist of concepts Checklist of equations FOCUS 7 Quantum theory TOPIC 7A The origins of quantum mechanics 7A.1 Energy quantization (a) Black-body radiation (b) Heat capacity (c) Atomic and molecular spectra 7A.2 Wave–particle duality (a) The particle character of electromagnetic radiation (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 (a) Normalization (b) Constraints on the wavefunction (c) Quantization Checklist of concepts Checklist of equations TOPIC 7C Operators and observables 7C.1 Operators (a) Eigenvalue equations (b) The construction of operators (c) Hermitian operators (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 (a) The acceptable solutions (b) The properties of the wavefunctions (c) The properties of the energy 7D.3 Confined motion in two and more dimensions (a) Energy levels and wavefunctions (b) Degeneracy 7D.4 Tunnelling Checklist of concepts Checklist of equations TOPIC 7E Vibrational motion 7E.1 The harmonic oscillator (a) The energy levels (b) The wavefunctions 7E.2 Properties of the harmonic oscillator (a) Mean values (b) Tunnelling Checklist of concepts Checklist of equations TOPIC 7F Rotational motion 7F.1 Rotation in two dimensions (a) The solutions of the Schrödinger equation (b) Quantization of angular momentum 7F.2 Rotation in three dimensions (a) The wavefunctions and energy levels (b) Angular momentum (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 (a) The separation of variables (b) The radial solutions 8A.2 Atomic orbitals and their energies (a) The specification of orbitals (b) The energy levels (c) Ionization energies (d) Shells and subshells (e) s Orbitals (f) Radial distribution functions (g) p Orbitals (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 (a) Spin (b) The Pauli principle 8B.3 The building-up principle (a) Penetration and shielding (b) Hund’s rules (c) Atomic and ionic radii (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 (a) Singlet and triplet terms (b) Spin–orbit coupling (c) Term symbols (d) Hund’s rules (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 (a) Promotion (b) Hybridization Checklist of concepts Checklist of equations TOPIC 9B Molecular orbital theory: the hydrogen molecule-ion 9B.1 Linear combinations of atomic orbitals (a) The construction of linear combinations (b) Bonding orbitals (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 (a) σ Orbitals and π orbitals (b) The overlap integral (c) 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 (a) The procedure (b) The features of the solutions Checklist of concepts Checklist of equations TOPIC 9E Molecular orbital theory: polyatomicmolecules 9E.1 The Hückel approximation (a) An introduction to the method (b) The matrix formulation of the method 9E.2 Applications (a) π-Electron binding energy (b) Aromatic stability 9E.3 Computational chemistry (a) Semi-empirical and ab initio methods (b) Density functional theory (c) Graphical representations Checklist of concepts Checklist of equations FOCUS 10 Molecular symmetry TOPIC 10A Shape and symmetry 10A.1 Symmetry operations andsymmetry elements 10A.2 The symmetry classification of molecules (a) The groups C1, Ci, and Cs (b) The groups Cn, Cnv, and Cnh (c) The groups Dn, Dnh, and Dnd (d) The groups Sn (e) The cubic groups (f) The full rotation group 10A.3 Some immediate consequences of symmetry (a) Polarity (b) Chirality Checklist of concepts Checklist of operations and elements TOPIC 10B Group theory 10B.1 The elements of group theory 10B.2 Matrix representations (a) Representatives of operations (b) The representation of a group (c) Irreducible representations (d) Characters 10B.3 Character tables (a) The symmetry species of atomic orbitals (b) The symmetry species of linear combinations of orbitals (c) Character tables and degeneracy Checklist of concepts Checklist of equations TOPIC 10C Applications of symmetry 10C.1 Vanishing integrals (a) Integrals of the product of functions (b) Decomposition of a representation 10C.2 Applications to molecular orbital theory (a) Orbital overlap (b) Symmetry-adapted linear combinations 10C.3 Selection rules Checklist of concepts Checklist of equations FOCUS 11 Molecular spectroscopy TOPIC 11A General features of molecular spectroscopy 11A.1 The absorption and emission of radiation (a) Stimulated and spontaneous radiative processes (b) Selection rules and transition moments (c) The Beer–Lambert law 11A.2 Spectral linewidths (a) Doppler broadening (b) Lifetime broadening 11A.3 Experimental techniques (a) Sources of radiation (b) Spectral analysis (c) Detectors (d) Examples of spectrometers Checklist of concepts Checklist of equations TOPIC 11B Rotational spectroscopy 11B.1 Rotational energy levels (a) Spherical rotors (b) Symmetric rotors (c) Linear rotors (d) Centrifugal distortion 11B.2 Microwave spectroscopy (a) Selection rules (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 (a) The convergence of energy levels (b) The Birge–Sponer plot 11C.4 Vibration–rotation spectra (a) Spectral branches (b) Combination differences 11C.5 Vibrational Raman spectra Checklist of concepts Checklist of equations TOPIC 11D Vibrational spectroscopy of polyatomic 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 vibrational spectra 11E.1 Classification of normal modes according to symmetry 11E.2 Symmetry of vibrational wavefunctions (a) Infrared activity of normal modes (b) Raman activity of normal modes (c) The symmetry basis of the exclusion rule Checklist of concepts TOPIC 11F Electronic spectra 11F.1 Diatomic molecules (a) Term symbols (b) Selection rules (c) Vibrational fine structure (d) Rotational fine structure 11F.2 Polyatomic molecules (a) d-Metal complexes (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 (a) The energies of nuclei in magnetic fields (b) The NMR spectrometer 12A.2 Electron paramagnetic resonance (a) The energies of electrons in magnetic fields (b) The EPR spectrometer Checklist of concepts Checklist of equations TOPIC12B Features of NMR spectra 12B.1 The chemical shift 12B.2 The origin of shielding constants (a) The local contribution (b) Neighbouring group contributions (c) The solvent contribution 12B.3 The fine structure (a) The appearance of the spectrum (b) The magnitudes of coupling constants (c) The origin of spin–spin coupling (d) Equivalent nuclei (e) Strongly coupled nuclei 12B.4 Exchange processes 12B.5 Solid-state NMR Checklist of concepts Checklist of equations TOPIC 12C Pulse techniques in NMR 12C.1 The magnetization vector (a) The effect of the radiofrequency field (b) Time- and frequency-domain signals 12C.2 Spin relaxation (a) The mechanism of relaxation (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 (a) The effects of nuclear spin (b) The McConnell equation (c) 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 (a) Instantaneous configurations (b) The most probable distribution (b) The values of the constants 13A.2 The relative population 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 (a) The translational contribution (b) The rotational contribution (c) The vibrational contribution (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 (a) The translational contribution (b) The rotational contribution (c) The vibrational contribution (d) The electronic contribution (e) The spin contribution Checklist of concepts Checklist of equations TOPIC 13D The canonical ensemble 13D.1 The concept of ensemble (a) Dominating configurations (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 (a) The calculation of internal energy (b) Heat capacity 13E.2 The entropy (a) Entropy and the partition function (b) The translational contribution (c) The rotational contribution (d) The vibrational contribution (e) Residual entropies Checklist of concepts Checklist of equations TOPIC 13F Derived functions 13F.1 The derivations 13F.2 Equilibrium constants (a) The relation between K and the partition function (b) A dissociation equilibrium (c) Contributions to the equilibrium constant Checklist of concepts Checklist of equations FOCUS 14 Molecular interactions TOPIC 14A The electric properties of molecules 14A.1 Electric dipole moments 14A.2 Polarizabilities 14A.3 Polarization (a) The frequency dependence of the polarization (b) Molar polarization Checklist of concepts Checklist of equations TOPIC 14B Interactions between molecules 14B.1 The interactions of dipoles (a) Charge–dipole interactions (b) Dipole–dipole interactions (c) Dipole–induced dipole interactions (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 (a) The radial distribution function (b) The calculation of g(r) (c) The thermodynamic properties of liquids 14C.2 The liquid–vapour interface (a) Surface tension (b) Curved surfaces (c) Capillary action 14C.3 Surface films (a) Surface pressure (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 (a) Measures of size (b) Constrained chains (c) Partly rigid coils 14D.4 Mechanical properties (a) Conformational entropy (b) Elastomers 14D.5 Thermal properties Checklist of concepts Checklist of equations TOPIC 14E Self-assembly 14E.1 Colloids (a) Classification and preparation (b) Structure and stability (c) The electrical double layer 14E.2 Micelles and biological membranes (a) The hydrophobic interaction (b) Micelle formation (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 (a) The Miller indices (b) The separation of neighbouring planes Checklist of concepts Checklist of equations TOPIC 15B Diffraction techniques 15B.1 X-ray crystallography (a) X-ray diffraction (b) Bragg’s law (c) Scattering factors (d) The electron density (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 (a) Close packing (b) Electronic structure of metals 15C.2 Ionic solids (a) Structure (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 properties of 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 properties of solids 15G.1 Excitons 15G.2 Metals and semiconductors (a) Light absorption (b) Light-emitting diodes and diode lasers 15G.3 Nonlinear optical phenomena Checklist of concepts FOCUS 16 Molecules in motio TOPIC 16A Transport properties of a perfect gas 16A.1 The phenomenologicalequations 16A.2 The transport parameters (a) The diffusion coefficient (b) Thermal conductivity (c) Viscosity (d) Effusion Checklist of concepts Checklist of equations TOPIC 16B Motion in liquids 16B.1 Experimental results (a) Liquid viscosity (b) Electrolyte solutions 16B.2 The mobilities of ions (a) The drift speed (b) Mobility and conductivity (c) The Einstein relations Checklist of concepts Checklist of equations FOCUS 16C Diffusion 16C.1 The thermodynamic view 16C.2 The diffusion equation (a) Simple diffusion (b) Diffusion with convection (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 chemical reactions 17A.1 Monitoring the progress of a reaction (a) General considerations (b) Special techniques 17A.2 The rates of reactions (a) The definition of rate (b) Rate laws and rate constants (c) Reaction order (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 reaction rates 17D.2 The interpretation of the Arrhenius parameters (a) A first look at the energy requirements of reactions (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 (a) Stepwise polymerization (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 (a) Collision rates in gases (b) The energy requirement (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 (a) Classes of reaction (b) Diffusion and reaction 18B.2 The material-balance equation (a) The formulation of the equation (b) Solutions of the equation Checklist of concepts Checklist of equations TOPIC 18C Transition-state theory 18C.1 The Eyring equation (a) The formulation of the equation (b) The rate of decay of the activated complex (c) The concentration of the activated complex (d) The rate constant 18C.2 Thermodynamic aspects (a) Activation parameters (b) Reactions between ions 18C.3 The kinetic isotope effect Checklist of concepts Checklist of equations TOPIC 18D The dynamics of molecular collisions 18D.1 Molecular beams (a) Techniques (b) Experimental results 18D.2 Reactive collisions (a) Probes of reactive collisions (b) State-to-state reaction dynamics 18D.3 Potential energy surfaces 18D.4 Some results from experiments and calculations (a) The direction of attack and separation (b) Attractive and repulsive surfaces (c) Quantum mechanical scattering theory Checklist of concepts Checklist of equations TOPIC 18E Electron transfer in homogeneoussystems 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 19A An introduction to solid surfaces 19A.1 Surface growth 19A.2 Physisorption and chemisorption 19A.3 Experimental techniques (a) Microscopy (b) Ionization techniques (c) Diffraction techniques (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 (a) The Langmuir isotherm (b) The isosteric enthalpy of adsorption (c) The BET isotherm (d) The Temkin and Freundlich isotherms 19B.2 The rates of adsorption and desorption (a) The precursor state (b) Adsorption and desorption at the molecular level (c) Mobility on surfaces Checklist of concepts Checklist of equations TOPIC 19C Heterogeneous catalysis 19C.1 Mechanisms of heterogeneous catalysis (a) Unimolecular reactions (b) The Langmuir–Hinshelwood mechanismIn (c) The Eley–Rideal mechanism 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 (a) The Butler–Volmer equation (b) Tafel plots 19D.3 Voltammetry 19D.4 Electrolysis 19D.5 Working galvanic cells Checklist of concepts Checklist of equations RESOURCE SECTION PART 1 Common integrals PART 2 Units PART 3 Data PART 4 Character tables INDEX