Physical Chemistry: Thermodynamics, Structure, and Change Tenth Ed

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Cover FUNDAMENTAL CONSTANTS Title page Copyright page PREFACE USING THE BOOK BOOK COMPANION SITE ACKNOWLEDGEMENTS CONTENTS TABLES CHEMIST’S TOOLKITS Foundations A Matter A.1 Atoms A.2 Molecules A.3 Bulk matter Checklist of concepts Checklist of equations B Energy B.1 Force B.2 Energy: A first look B.3 The relation between molecular and bulk properties Checklist of concepts Checklist of equations C Waves C.1 Harmonic waves C.2 The electromagnetic field Checklist of concepts Checklist of equations PART ONE: Thermodynamics CHAPTER 1 The properties of gases 1A The perfect gas 1A.1 Variables of state 1A.2 Equations of state Checklist of concepts Checklist of equations 1B The kinetic model 1B.1 The model 1B.2 Collisions Checklist of concepts Checklist of equations 1C Real gases 1C.1 Deviations from perfect behaviour 1C.2 The van der Waals equation Checklist of concepts Checklist of equations Mathematical background 1 Differentiation and integration CHAPTER 2 The First Law 2A Internal energy 2A.1 Work, heat, and energy 2A.2 The definition of internal energy 2A.3 Expansion work 2A.4 Heat transactions Checklist of concepts Checklist of equations 2B Enthalpy 2B.1 The definition of enthalpy 2B.2 The variation of enthalpy with temperature Checklist of concepts Checklist of equations 2C Thermochemistry 2C.1 Standard enthalpy changes 2C.2 Standard enthalpies offormation 2C.3 The temperature dependence of reaction enthalpies 2C.4 Experimental techniques Checklist of concepts Checklist of equations 2D State functions and exact differentials 2D.1 Exact and inexact differentials 2D.2 Changes in internal energy 2D.3 The Joule–Thomson effect Checklist of concepts Checklist of equations 2E Adiabatic changes 2E.1 The change in temperature 2E.2 The change in pressure Checklist of concepts Checklist of equations Mathematical background 2 Multivariate calculus CHAPTER 3 The Second and Third Laws 3A Entropy 3A.1 The Second Law 3A.2 The definition of entropy 3A.3 The entropy as a state function 3A.4 Entropy changes accompanying specific processes Checklist of concepts Checklist of equations 3B The measurement of entropy 3B.1 The calorimetric measurement of entropy 3B.2 The Third Law Checklist of concepts Checklist of equations 3C Concentrating on the system 3C.1 The Helmholtz and Gibbs energies 3C.2 Standard molar Gibbs energies Checklist of concepts Checklist of equations 3D Combining the First and Second Laws 3D.1 Properties of the internal energy 3D.2 Properties of the Gibbs energy Checklist of concepts Checklist of equations CHAPTER 4 Physical transformations of pure substances 4A Phase diagrams of pure substances 4A.1 The stabilities of phases 4A.2 Phase boundaries 4A.3 Three representative phasediagrams Checklist of concepts Checklist of equations 4B Thermodynamic aspects of phase transitions 4B.1 The dependence of stability on the conditions 4B.2 The location of phase boundaries 4B.3 The Ehrenfest classification of phase transitions Checklist of concepts Checklist of equations CHAPTER 5 Simple mixtures 5A The thermodynamic description of mixtures 5A.1 Partial molar quantities 5A.2 The thermodynamics of mixing 5A.3 The chemical potentials of liquids Checklist of concepts Checklist of equations 5B The properties of solutions 5B.1 Liquid mixtures 5B.2 Colligative properties Checklist of concepts Checklist of equations 5C Phase diagrams of binary systems 5C.1 Vapour pressure diagrams 5C.2 Temperature–composition diagrams 5C.3 Liquid–liquid phase diagrams 5C.4 Liquid–solid phase diagrams Checklist of concepts Checklist of equations 5D Phase diagrams of ternary systems 5D.1 Triangular phase diagrams 5D.2 Ternary systems Checklist of concepts 5E Activities 5E.1 The solvent activity 5E.2 The solute activity 5E.3 The activities of regular solutions Checklist of concepts Checklist of equations 5F The activities of ions 5F.1 Mean activity coefficients 5F.2 The Debye–Hückel theory Checklist of concepts Checklist of equations CHAPTER 6 Chemical equilibrium 6A The equilibrium constant 6A.1 The Gibbs energy minimum 6A.2 The description of equilibrium Checklist of concepts Checklist of equations 6B The response of equilibriato the conditions 6B.1 The response to pressure 6B.2 The response to temperature Checklist of concepts Checklist of equations 6C Electrochemical cells 6C.1 Half-reactions and electrodes 6C.2 Varieties of cells 6C.3 The cell potential 6C.4 The determination of thermodynamic functions Checklist of concepts Checklist of equations 6D Electrode potentials 6D.1 Standard potentials 6D.2 Applications of standard potentials Checklist of concepts Checklist of equations PART TWO: Structure CHAPTER 7 Introduction to quantum theory 7A The origins of quantum mechanics 7A.1 Energy quantization 7A.2 Wave–particle duality Checklist of concepts Checklist of equations 7B Dynamics of microscopic systems 7B.1 The Schrödinger equation 7B.2 The Born interpretation of the wavefunction 7B.3 The probability density Checklist of concepts Checklist of equations 7C The principles of quantum theory 7C.1 Operators 7C.2 Superpositions and expectation values 7C.3 The uncertainty principle 7C.4 The postulates of quantum mechanics Checklist of concepts Checklist of equations Mathematical background 3 Complex numbers CHAPTER 8 The quantum theory of motion 8A Translation 8A.1 Free motion in one dimension 8A.2 Confined motion in one dimension 8A.3 Confined motion in two or more dimensions 8A.4 Tunnelling Checklist of concepts Checklist of equations 8B Vibrational motion 8B.1 The harmonic oscillator 8B.2 The properties of oscillators Checklist of concepts Checklist of equations 8C Rotational motion 8C.1 Rotation in two dimensions 8C.2 Rotation in three dimensions Checklist of concepts Checklist of equations Mathematical background 4 Differential equations CHAPTER 9 Atomic structure and spectra 9A Hydrogenic atoms 9A.1 The structure of hydrogenic atoms 9A.2 Atomic orbitals and their energies Checklist of concepts Checklist of equations 9B Many-electron atoms 9B.1 The orbital approximation 9B.2 The building-up principle 9B.3 Self-consistent field orbitals Checklist of concepts Checklist of equations 9C Atomic spectra 9C.1 The spectra of hydrogenic atoms 9C.2 The spectra of complex atoms Checklist of concepts Checklist of equations Mathematical background 5 Vectors CHAPTER 10 Molecular structure 10A Valence-bond theory 10A.1 Diatomic molecules 10A.2 Polyatomic molecules Checklist of concepts Checklist of equations 10B Principles of molecular orbital theory 10B.1 Linear combinations of atomic orbitals 10B.2 Orbital notation Checklist of concepts Checklist of equations 10C Homonuclear diatomic molecules 10C.1 Electron configurations 10C.2 Photoelectron spectroscopy Checklist of concepts Checklist of equations 10D Heteronuclear diatomic molecules 10D.1 Polar bonds 10D.2 The variation principle Checklist of concepts Checklist of equations 10E Polyatomic molecules 10E.1 The Hückel approximation 10E.2 Applications 10E.3 Computational chemistry Checklist of concepts Checklist of equations Mathematical background 6 Matrices CHAPTER 11 Molecular symmetry 11A Symmetry elements 11A.1 Symmetry operations and symmetry elements 11A.2 The symmetry classification of molecules 11A.3 Some immediate consequences of symmetry Checklist of concepts Checklist of operations and elements 11B Group theory 11B.1 The elements of group theory 11B.2 Matrix representations 11B.3 Character tables Checklist of concepts Checklist of equations 11C Applications of symmetry 11C.1 Vanishing integrals 11C.2 Applications to orbitals 11C.3 Selection rules Checklist of concepts Checklist of equations CHAPTER 12 Rotational and vibrational spectra 12A General features of molecular spectroscopy 12A.1 The absorption and emission of radiation 12A.2 Spectral linewidths 12A.3 Experimental techniques Checklist of concepts Checklist of equations 12B Molecular rotation 12B.1 Moments of inertia 12B.2 The rotational energy levels Checklist of concepts Checklist of equations 12C Rotational spectroscopy 12C.1 Microwave spectroscopy 12C.2 Rotational Raman spectroscopy 12C.3 Nuclear statistics and rotational states Checklist of concepts Checklist of equations 12D Vibrational spectroscopy of diatomic molecules 12D.1 Vibrational motion 12D.2 Infrared spectroscopy 12D.3 Anharmonicity 12D.4 Vibration–rotation spectra 12D.5 Vibrational Raman spectra Checklist of concepts Checklist of equations 12E Vibrational spectroscopy of polyatomic molecules 12E.1 Normal modes 12E.2 Infrared absorption spectra 12E.3 Vibrational Raman spectra 12E.4 Symmetry aspects of molecular vibrations Checklist of concepts Checklist of equations CHAPTER 13 Electronic transitions 13A Electronic spectra 13A.1 Diatomic molecules 13A.2 Polyatomic molecules Checklist of concepts Checklist of equations 13B Decay of excited states 13B.1 Fluorescence and phosphorescence 13B.2 Dissociation and predissociation Checklist of concepts 13C Lasers 13C.1 Population inversion 13C.2 Cavity and mode characteristics 13C.3 Pulsed lasers 13C.4 Time-resolved spectroscopy 13C.5 Examples of practical lasers Checklist of concepts Checklist of equations CHAPTER 14 Magnetic resonance 14A General principles 14A.1 Nuclear magnetic resonance 14A.2 Electron paramagnetic resonance Checklist of concepts Checklist of equations 14B Features of NMR spectra 14B.1 The chemical shift 14B.2 The origin of shielding constants 14B.3 The fine structure 14B.4 Conformational conversion and exchange processes Checklist of concepts Checklist of equations 14C Pulse techniques in NMR 14C.1 The magnetization vector 14C.2 Spin relaxation 14C.3 Spin decoupling 14C.4 The nuclear Overhauser effect 14C.5 Two-dimensional NMR 14C.6 Solid-state NMR Checklist of concepts Checklist of equations 14D Electron paramagnetic resonance 14D.1 The g-value 14D.2 Hyperfine structure Checklist of concepts Checklist of equations CHAPTER 15 Statistical thermodynamics 15A The Boltzmann distribution 15A.1 Configurations and weights 15A.2 The derivation of the Boltzmann distribution Checklist of concepts Checklist of equations 15B Molecular partition functions 15B.1 The significance of the partition function 15B.2 Contributions to the partition function Checklist of concepts Checklist of equations 15C Molecular energies 15C.1 The basic equations 15C.2 Contributions of the fundamental modes of motion Checklist of concepts Checklist of equations 15D The canonical ensemble 15D.1 The concept of ensemble 15D.2 The mean energy of a system 15D.3 Independent molecules revisited 15D.4 The variation of energy with volume Checklist of concepts Checklist of equations 15E The internal energy and the entropy 15E.1 The internal energy 15E.2 The entropy Checklist of concepts Checklist of equations 15F Derived functions 15F.1 The derivations 15F.2 Equilibrium constants Checklist of concepts Checklist of equations CHAPTER 16 Molecular interactions 16A Electric properties of molecules 16A.1 Electric dipole moments 16A.2 Polarizabilities 16A.3 Polarization Checklist of concepts Checklist of equations 16B Interactions between molecules 16B.1 Interactions between partial charges 16B.2 The interactions of dipoles 16B.3 Hydrogen bonding 16B.4 The hydrophobic interaction 16B.5 The total interaction Checklist of concepts Checklist of equations 16C Liquids 16C.1 Molecular interactions in liquids 16C.2 The liquid–vapour interface 16C.3 Surface films 16C.4 Condensation Checklist of concepts Checklist of equations CHAPTER 17 Macromolecules and self-assembly 17A The structures of macromolecules 17A.1 The different levels of structure 17A.2 Random coils 17A.3 Biological macromolecules Checklist of concepts Checklist of equations 17B Properties of macromolecules 17B.1 Mechanical properties 17B.2 Thermal properties 17B.3 Electrical properties Checklist of concepts Checklist of equations 17C Self-assembly 17C.1 Colloids 17C.2 Micelles and biological membranes Checklist of concepts Checklist of equations 17D Determination of size and shape 17D.1 Mean molar masses 17D.2 The techniques Checklist of concepts Checklist of equations CHAPTER 18 Solids 18A Crystal structure 18A.1 Periodic crystal lattices 18A.2 The identification of lattice planes 18A.3 X-ray crystallography 18A.4 Neutron and electron diffraction Checklist of concepts Checklist of equations 18B Bonding in solids 18B.1 Metallic solids 18B.2 Ionic solids 18B.3 Covalent and molecular solids Checklist of concepts Checklist of equations 18C Mechanical, electrical, and magnetic properties of solids 18C.1 Mechanical properties 18C.2 Electrical properties 18C.3 Magnetic properties Checklist of concepts Checklist of equations 18D The optical properties of solids 18D.1 Light absorption by excitonsin molecular solids 18D.2 Light absorption by metalsand semiconductors 18D.3 Light-emitting diodes and diode lasers 18D.4 Nonlinear optical phenomena Checklist of concepts Mathematical background 7 Fourier series and Fourier transforms PART THREE: Change CHAPTER 19 Molecules in motion 19A Transport in gases 19A.1 The phenomenological equations 19A.2 The transport parameters Checklist of concepts Checklist of equations 19B Motion in liquids 19B.1 Experimental results 19B.2 The mobilities of ions Checklist of concepts Checklist of equations 19C Diffusion 19C.1 The thermodynamic view 19C.2 The diffusion equation 19C.3 The statistical view Checklist of concepts Checklist of equations CHAPTER 20 Chemical kinetics 20A The rates of chemical reactions 20A.1 Monitoring the progress of a reaction 20A.2 The rates of reactions Checklist of concepts Checklist of equations 20B Integrated rate laws 20B.1 First-order reactions 20B.2 Second-order reactions Checklist of concepts Checklist of equations 20C Reactions approaching equilibrium 20C.1 First-order reactions approaching equilibrium 20C.2 Relaxation methods Checklist of concepts Checklist of equations 20D The Arrhenius equation 20D.1 The temperature dependence of reaction rates 20D.2 The interpretation of the Arrhenius parameters Checklist of concepts Checklist of equations 20E Reaction mechanisms 20E.1 Elementary reactions 20E.2 Consecutive elementary reactions 20E.3 The steady-state approximation 20E.4 The rate-determining step 20E.5 Pre-equilibria 20E.6 Kinetic and thermodynamic control of reactions Checklist of concepts Checklist of equations 20F Examples of reaction mechanisms 20F.1 Unimolecular reactions 20F.2 Polymerization kinetics Checklist of concepts Checklist of equations 20G Photochemistry 20G.1 Photochemical processes 20G.2 The primary quantum yield 20G.3 Mechanism of decay of excited singlet states 20G.4 Quenching 20G.5 Resonance energy transfer Checklist of concepts Checklist of equations 20H Enzymes 20H.1 Features of enzymes 20H.2 The Michaelis–Menten mechanism 20H.3 The catalytic efficiencyof enzymes 20H.4 Mechanisms of enzyme inhibition Checklist of concepts Checklist of equations CHAPTER 21 Reaction dynamics 21A Collision theory 21A.1 Reactive encounters 21A.2 The RRK model Checklist of concepts Checklist of equations 21B Diffusion-controlled reactions 21B.1 Reactions in solution 21B.2 The material-balance equation Checklist of concepts Checklist of equations 21C Transition-state theory 21C.1 The Eyring equation 21C.2 Thermodynamic aspects 21C.3 The kinetic isotope effect Checklist of concepts Checklist of equations 21D The dynamics of molecular collisions 21D.1 Molecular beams 21D.2 Reactive collisions 21D.3 Potential energy surfaces 21D.4 Some results from experiments and calculations Checklist of concepts Checklist of equations 21E Electron transfer in homogeneous systems 21E.1 The electron transfer rate law 21E.2 The rate constant Checklist of concepts Checklist of equations 21F Processes at electrodes 21F.1 The electrode–solution interface 21F.2 The rate of electron transfer 21F.3 Voltammetry 21F.4 Electrolysis 21F.5 Working galvanic cells Checklist of concepts Checklist of equations CHAPTER 22 Processes on solid surfaces 22A An introduction to solid surfaces 22A.1 Surface growth 22A.2 Physisorption and chemisorption 22A.3 Experimental techniques Checklist of concepts Checklist of equations 22B Adsorption and desorption 22B.1 Adsorption isotherms 22B.2 The rates of adsorption and desorption Checklist of concepts Checklist of equations 22C Heterogeneous catalysis 22C.1 Mechanisms of heterogeneous catalysis 22C.2 Catalytic activity at surfaces Checklist of concepts Checklist of equations Resource Section PART 1 Common integrals PART 2 Units PART 3 Data PART 4 Character tables Index Copyright Title Page Dedication Contents Chapter 1: ‘I’m thinking’ – Oh, but are you? Chapter 2: Renegade perception Chapter 3: The Pushbacker sting Chapter 4: ‘Covid’: The calculated catastrophe Chapter 5: There is no ‘virus’ Chapter 6: Sequence of deceit Chapter 7: War on your mind Chapter 8: ‘Reframing’ insanity Chapter 9: We must have it? So what is it? Chapter 10: Human 2.0 Chapter 11: Who controls the Cult? Chapter 12: Escaping Wetiko Postscript Appendix: Cowan-Kaufman-Morell Statement on Virus Isolation Bibliography Index