Physical Chemistry: Thermodynamics, Structure, and Change

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
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B Energy
B.1 Force
B.2 Energy: A first look
B.3 The relation between molecular and bulk properties
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C Waves
C.1 Harmonic waves
C.2 The electromagnetic field
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PART ONE: Thermodynamics
CHAPTER
1 The properties of gases
1A The perfect gas
1A.1 Variables of state
1A.2 Equations of state
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1B The kinetic model
1B.1 The model
1B.2 Collisions
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1C Real gases
1C.1 Deviations from perfect behaviour
1C.2 The van der Waals equation
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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
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2B Enthalpy
2B.1 The definition of enthalpy
2B.2 The variation of enthalpy with temperature
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2C Thermochemistry
2C.1 Standard enthalpy changes
2C.2 Standard enthalpies offormation
2C.3 The temperature dependence of reaction enthalpies
2C.4 Experimental techniques
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2D State functions and exact differentials
2D.1 Exact and inexact differentials
2D.2 Changes in internal energy
2D.3 The Joule–Thomson effect
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2E Adiabatic changes
2E.1 The change in temperature
2E.2 The change in pressure
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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
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3B The measurement of entropy
3B.1 The calorimetric measurement of entropy
3B.2 The Third Law
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3C Concentrating on the system
3C.1 The Helmholtz and Gibbs energies
3C.2 Standard molar Gibbs energies
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3D Combining the First and Second Laws
3D.1 Properties of the internal energy
3D.2 Properties of the Gibbs energy
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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
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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
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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
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5B The properties of solutions
5B.1 Liquid mixtures
5B.2 Colligative properties
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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
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5D Phase diagrams of ternary systems
5D.1 Triangular phase diagrams
5D.2 Ternary systems
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5E Activities
5E.1 The solvent activity
5E.2 The solute activity
5E.3 The activities of regular solutions
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5F The activities of ions
5F.1 Mean activity coefficients
5F.2 The Debye–Hückel theory
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CHAPTER 6 Chemical equilibrium
6A The equilibrium constant
6A.1 The Gibbs energy minimum
6A.2 The description of equilibrium
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6B The response of equilibriato the conditions
6B.1 The response to pressure
6B.2 The response to temperature
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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
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6D Electrode potentials
6D.1 Standard potentials
6D.2 Applications of standard potentials
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PART TWO: Structure
CHAPTER 7 Introduction to quantum theory
7A The origins of quantum mechanics
7A.1 Energy quantization
7A.2 Wave–particle duality
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7B Dynamics of microscopic systems
7B.1 The Schrödinger equation
7B.2 The Born interpretation of the wavefunction
7B.3 The probability density
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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
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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
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8B Vibrational motion
8B.1 The harmonic oscillator
8B.2 The properties of oscillators
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8C Rotational motion
8C.1 Rotation in two dimensions
8C.2 Rotation in three dimensions
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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
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9B Many-electron atoms
9B.1 The orbital approximation
9B.2 The building-up principle
9B.3 Self-consistent field orbitals
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9C Atomic spectra
9C.1 The spectra of hydrogenic atoms
9C.2 The spectra of complex atoms
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Mathematical background 5 Vectors
CHAPTER 10 Molecular structure
10A Valence-bond theory
10A.1 Diatomic molecules
10A.2 Polyatomic molecules
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10B Principles of molecular orbital theory
10B.1 Linear combinations of atomic orbitals
10B.2 Orbital notation
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10C Homonuclear diatomic molecules
10C.1 Electron configurations
10C.2 Photoelectron spectroscopy
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10D Heteronuclear diatomic molecules
10D.1 Polar bonds
10D.2 The variation principle
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10E Polyatomic molecules
10E.1 The Hückel approximation
10E.2 Applications
10E.3 Computational chemistry
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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
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11B Group theory
11B.1 The elements of group theory
11B.2 Matrix representations
11B.3 Character tables
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11C Applications of symmetry
11C.1 Vanishing integrals
11C.2 Applications to orbitals
11C.3 Selection rules
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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
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12B Molecular rotation
12B.1 Moments of inertia
12B.2 The rotational energy levels
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12C Rotational spectroscopy
12C.1 Microwave spectroscopy
12C.2 Rotational Raman spectroscopy
12C.3 Nuclear statistics and rotational states
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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
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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
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CHAPTER 13 Electronic transitions
13A Electronic spectra
13A.1 Diatomic molecules
13A.2 Polyatomic molecules
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13B Decay of excited states
13B.1 Fluorescence and phosphorescence
13B.2 Dissociation and predissociation
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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
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CHAPTER 14 Magnetic resonance
14A General principles
14A.1 Nuclear magnetic resonance
14A.2 Electron paramagnetic resonance
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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
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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
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14D Electron paramagnetic resonance
14D.1 The g-value
14D.2 Hyperfine structure
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CHAPTER 15 Statistical thermodynamics
15A The Boltzmann distribution
15A.1 Configurations and weights
15A.2 The derivation of the Boltzmann distribution
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15B Molecular partition functions
15B.1 The significance of the partition function
15B.2 Contributions to the partition function
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15C Molecular energies
15C.1 The basic equations
15C.2 Contributions of the fundamental modes of motion
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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
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15E The internal energy and the entropy
15E.1 The internal energy
15E.2 The entropy
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15F Derived functions
15F.1 The derivations
15F.2 Equilibrium constants
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CHAPTER 16 Molecular interactions
16A Electric properties of molecules
16A.1 Electric dipole moments
16A.2 Polarizabilities
16A.3 Polarization
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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
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16C Liquids
16C.1 Molecular interactions in liquids
16C.2 The liquid–vapour interface
16C.3 Surface films
16C.4 Condensation
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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
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17B Properties of macromolecules
17B.1 Mechanical properties
17B.2 Thermal properties
17B.3 Electrical properties
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17C Self-assembly
17C.1 Colloids
17C.2 Micelles and biological membranes
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17D Determination of size and shape
17D.1 Mean molar masses
17D.2 The techniques
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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
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18B Bonding in solids
18B.1 Metallic solids
18B.2 Ionic solids
18B.3 Covalent and molecular solids
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18C Mechanical, electrical, and magnetic properties of solids
18C.1 Mechanical properties
18C.2 Electrical properties
18C.3 Magnetic properties
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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
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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
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19B Motion in liquids
19B.1 Experimental results
19B.2 The mobilities of ions
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19C Diffusion
19C.1 The thermodynamic view
19C.2 The diffusion equation
19C.3 The statistical view
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CHAPTER 20 Chemical kinetics
20A The rates of chemical reactions
20A.1 Monitoring the progress of a reaction
20A.2 The rates of reactions
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20B Integrated rate laws
20B.1 First-order reactions
20B.2 Second-order reactions
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20C Reactions approaching equilibrium
20C.1 First-order reactions approaching equilibrium
20C.2 Relaxation methods
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20D The Arrhenius equation
20D.1 The temperature dependence of reaction rates
20D.2 The interpretation of the Arrhenius parameters
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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
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20F Examples of reaction mechanisms
20F.1 Unimolecular reactions
20F.2 Polymerization kinetics
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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
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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
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CHAPTER 21 Reaction dynamics
21A Collision theory
21A.1 Reactive encounters
21A.2 The RRK model
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21B Diffusion-controlled reactions
21B.1 Reactions in solution
21B.2 The material-balance equation
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21C Transition-state theory
21C.1 The Eyring equation
21C.2 Thermodynamic aspects
21C.3 The kinetic isotope effect
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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
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21E Electron transfer in homogeneous systems
21E.1 The electron transfer rate law
21E.2 The rate constant
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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
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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
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22B Adsorption and desorption
22B.1 Adsorption isotherms
22B.2 The rates of adsorption and desorption
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22C Heterogeneous catalysis
22C.1 Mechanisms of heterogeneous catalysis
22C.2 Catalytic activity at surfaces
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Resource Section
PART 1 Common integrals
PART 2 Units
PART 3 Data
PART 4 Character tables
Index