Physical Chemistry: Thermodynamics, Structure, and Change

✍ Scribed by Peter Atkins, Julio de Paula

• Publisher: Freeman
• Year: 2014
• Tongue: English
• Edition: 10
• Category: Library

✦ Synopsis

Edition after edition, Atkins and de Paula's #1 bestseller remains the most contemporary, most effective full-length textbook for courses covering thermodynamics in the first semester and quantum mechanics in the second semester. Its molecular view of physical chemistry, contemporary applications, student friendly pedagogy, and strong problem-solving emphasis make it particularly well-suited for pre-meds, engineers, physics, and chemistry students. Now organized into briefer, more manageable topics, and featuring additional applications and mathematical guidance, the new edition helps students learn more effectively, while allowing instructors to teach the way they want.
For maximum flexibility in your physical chemistry course, this text is now offered as a traditional text or in two volumes:
Volume 1: Thermodynamics and Kinetics: 1-4641-2451-5
Volume 2: Quantum Chemistry: 1-4641-2452-3

✦ Table of Contents

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
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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
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
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8C Rotational motion
8C.1 Rotation in two dimensions
8C.2 Rotation in three dimensions
Checklist of concepts
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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
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
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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
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
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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
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
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15C Molecular energies
15C.1 The basic equations
15C.2 Contributions of the fundamental modes of motion
Checklist of concepts
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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
Checklist of concepts
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15E The internal energy and the entropy
15E.1 The internal energy
15E.2 The entropy
Checklist of concepts
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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
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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
Checklist of concepts
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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
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17D Determination of size and shape
17D.1 Mean molar masses
17D.2 The techniques
Checklist of concepts
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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
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
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20D The Arrhenius equation
20D.1 The temperature dependence of reaction rates
20D.2 The interpretation of the Arrhenius parameters
Checklist of concepts
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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
Checklist of concepts
Checklist of equations
20F Examples of reaction mechanisms
20F.1 Unimolecular reactions
20F.2 Polymerization kinetics
Checklist of concepts
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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
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
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21C Transition-state theory
21C.1 The Eyring equation
21C.2 Thermodynamic aspects
21C.3 The kinetic isotope effect
Checklist of concepts
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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
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
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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
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
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22B Adsorption and desorption
22B.1 Adsorption isotherms
22B.2 The rates of adsorption and desorption
Checklist of concepts
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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
Cover
Fundamental Constants
Title
Copyright
About the Book
Using the Book
Organizing the information
Presenting the mathematics
Setting up and solving problems
The Book Companion Site
Acknowledgements
Brief Contents
Full Contents
List of the Chemist's Toolkits
F1 Foundations
1 Matter
1.1 Atoms
1.2 Molecules
1.3 Bulk matter
Checklist of concepts
Checklist of equations
2 Energy
2.1 Force
2.2 Energy: a first look
2.3 The relation between molecular and bulk properties
Checklist of concepts
Checklist of equations
3 Waves
3.1 Harmonic waves
3.2 The electromagnetic field
Checklist of concepts
Checklist of equations
Exercises and problems
1 Matter
2 Energy
3 Waves
Integrated activities
MB1 Differentiation and integration
F2 The principles of quantum mechanics
4 The emergence of quantum theory
4.1 The quantization of energy
4.2 Wave–particle duality
4.3 Retrospect and summary
Checklist of concepts
Checklist of equations
5 The wavefunction
5.1 Postulate I: the wavefunction
5.2 Postulate II: the Born interpretation
Checklist of concepts
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6 Extracting information from the wavefunction
6.1 Postulate III: quantum mechanical operators
6.2 Postulate IV: eigenvalues and eigenfunctions
Checklist of concepts
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7 Predicting the outcome of experiments
7.1 Wavefunctions as linear combinations
7.2 Mean values as expectation values
7.3 The orthogonality of eigenfunctions
7.4 The expectation value of a linear combination of eigenfunctions
Checklist of concepts
Checklist of equations
8 The uncertainty principle
8.1 Complementarity
8.2 The Heisenberg uncertainty principle
8.3 Commutation and complementarity
Checklist of concepts
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Exercises and problems
4 The emergence of quantum theory
5 The wavefunction
6 Extracting information from the wavefunction
7 Predicting the outcome of experiments
8 The uncertainty principle
Integrated activities
MB2 Differential equations
F3 The quantum mechanics of motion
9 Translational motion in one dimension
9.1 Free motion
9.2 Confined motion: the particle in a box
Checklist of concepts
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10 Tunnelling
10.1 The rectangular potential energy barrier
10.2 The Eckart potential energy barrier
10.3 The double-well potential
Checklist of concepts
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11 Translational motion in several dimensions
11.1 Motion in two dimensions
11.2 Motion in three dimensions
Checklist of concepts
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12 Vibrational motion
12.1 The energy levels
12.2 The wavefunctions
12.3 The properties of oscillators
12.4 Applications of the harmonic oscillator model in chemistry
Checklist of concepts
Checklist of equations
13 Rotational motion in two dimensions
13.1 A particle on a ring
13.2 Quantization of angular momentum
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14 Rotational motion in three dimensions
14.1 A particle on a sphere
14.2 Angular momentum
Checklist of concepts
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Exercises and problems
9 Translational motion in one dimension
10 Tunnelling
11 Translational motion in several dimensions
12 Vibrational motion
13 Rotational motion in two dimensions
14 Rotational motion in three dimensions
Integrated activities
MB3 Complex numbers
F4 Approximation methods
15 Time-independent perturbation theory
15.1 Perturbation expansions
15.2 The first-order correction to the energy
15.3 The first-order correction to the wavefunction
15.4 The second-order correction to the energy
Checklist of concepts
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16 Transitions
16.1 Time-dependent perturbation theory
16.2 The absorption and emission of radiation
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Exercises and problems
15 Time-independent perturbation theory
16 Transitions
F5 Atomic structure and spectra
17 Hydrogenic atoms
17.1 The structure of hydrogenic atoms
17.2 The atomic orbitals and their energies
Checklist of concepts
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18 Hydrogenic atomic orbitals
18.1 Shells and subshells
18.2 Radial distribution functions
Checklist of concepts
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19 Many-electron atoms
19.1 The orbital approximation
19.2 Factors affecting electronic structure
19.3 Self-consistent field calculations
Checklist of concepts
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20 Periodicity
20.1 The building-up principle
20.2 The configurations of the elements
20.3 The periodicity of atomic properties
Checklist of concepts
21 Atomic spectroscopy
21.1 The spectrum of hydrogen
21.2 Term symbols
21.3 Selection rules of many-electron atoms
Checklist of concepts
Checklist of equations
Exercises and problems
17 Hydrogenic atoms
18 Hydrogenic atomic orbitals
19 Many-electron atoms
20 Periodicity
21 Atomic spectroscopy
Integrated activities
MB4 Vectors
F6 Molecular structure
22 Valence-bond theory
22.1 Diatomic molecules
22.2 Polyatomic molecules
Checklist of concepts
Checklist of equations
23 The principles of molecular orbital theory
23.1 Linear combinations of atomic orbitals
23.2 Orbital notation
Checklist of concepts
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24 Homonuclear diatomic molecules
24.1 Electron configurations
24.2 Photoelectron spectroscopy
Checklist of concepts
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25 Heteronuclear diatomic molecules
25.1 Polar bonds
25.2 The variation principle
Checklist of concepts
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26 Polyatomic molecules
26.1 The Hückel approximation
26.2 Applications
Checklist of concepts
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27 Self-consistent fields
27.1 The central challenge
27.2 The Hartree–Fock formalism
27.3 The Roothaan equations
27.4 Basis sets
Checklist of concepts
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28 Semi-empirical methods
28.1 The Hückel approximation revisited
28.2 Differential overlap
Checklist of concepts
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29 Ab initio methods
29.1 Configuration interaction
29.2 Many-body perturbation theory
Checklist of concepts
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30 Density functional theory
30.1 The Kohn–Sham equations
30.2 The exchange–correlation energy
Checklist of concepts
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Exercises and problems
22 Valence-bond theory
23 The principles of molecular orbital theory
24 Homonuclear diatomic molecules
25 Heteronuclear diatomic molecules
26 Polyatomic molecules
27 Self-consistent fields
28 Semi-empirical methods
29 Ab initio methods
30 Density functional theory
Integrated activities
MB5 Matrices
F7 Molecular symmetry
31 The analysis of molecular shape
31.1 Symmetry operations and symmetry elements
31.2 The symmetry classification of molecules
31.3 Some immediate consequences of symmetry
Checklist of concepts
32 Group theory
32.1 The elements of group theory
32.2 Matrix representations
32.3 Character tables
Checklist of concepts
Checklist of equations
33 Applications of symmetry
33.1 Vanishing integrals
33.2 Applications to orbitals
33.3 Selection rules
Checklist of concepts
Checklist of equations
Exercises and problems
31 The analysis of molecular shape
32 Group theory
33 Applications of symmetry
F8 Interactions
34 Electric properties of molecules
34.1 Electric dipole moments
34.2 Polarizabilities
Checklist of concepts
Checklist of equations
35 Interactions between molecules
35.1 Interactions between partial charges
35.2 The interactions of dipoles
35.3 Hydrogen bonding
35.4 The total interaction
Checklist of concepts
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36 Real gases
36.1 Molecular interactions in gases
36.2 The virial equation of state
36.3 The van der Waals equation
36.4 Thermodynamic considerations
Checklist of concepts
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37 Crystal structure
37.1 Periodic crystal lattices
37.2 The identification of lattice planes
37.3 X-ray crystallography
37.4 Neutron and electron diffraction
Checklist of concepts
Checklist of equations
38 Bonding in solids
38.1 Metallic solids
38.2 Ionic solids
38.3 Molecular solids and covalent networks
Checklist of concepts
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39 Electrical, optical, and magnetic properties of solids
39.1 Electrical properties
39.2 Optical properties
39.3 Magnetic properties
39.4 Superconductivity
Checklist of concepts
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Exercises and problems
34 Electric properties of molecules
35 Interactions between molecules
36 Real Gases
37 Crystal structure
38 Bonding in solids
39 Electrical, optical, and magnetic properties of solids
Integrated activities
MB6 Fourier series and Fourier transforms
F9 Molecular spectroscopy
40 General features
40.1 Spectrometers
40.2 Absorption spectroscopy
40.3 Emission spectroscopy
40.4 Raman spectroscopy
40.5 Spectral linewidths
Checklist of concepts
Checklist of equations
41 Molecular rotation
41.1 Moments of inertia
41.2 The rotational energy levels
Checklist of concepts
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42 Rotational spectroscopy
42.1 Microwave spectroscopy
42.2 Rotational Raman spectroscopy
42.3 Nuclear statistics and rotational states
Checklist of concepts
Checklist of equations
43 Vibrational spectroscopy: diatomic molecules
43.1 Vibrational motion of diatomic molecules
43.2 Infrared spectroscopy
43.3 Anharmonicity
43.4 Vibration–rotation spectra
43.5 Vibrational Raman spectra of diatomic molecules
Checklist of concepts
Checklist of equations
44 Vibrational spectroscopy: polyatomic molecules
44.1 Normal modes
44.2 Infrared absorption spectra of polyatomic molecules
44.3 Vibrational Raman spectra of polyatomic molecules
44.4 Symmetry aspects of molecular vibrations
Checklist of concepts
Checklist of equations
45 Electronic spectroscopy
45.1 The electronic spectra of diatomic molecules
45.2 The electronic spectra of polyatomic molecules
Checklist of concepts
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46 Decay of excited states
46.1 Fluorescence and phosphorescence
46.2 Dissociation and predissociation
46.3 Laser action
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Exercises and problems
40 General features
41 Molecular rotation
42 Rotational spectroscopy
43 Vibrational spectroscopy: diatomic molecules
44 Vibrational spectroscopy: polyatomic molecules
45 Electronic spectroscopy
46 Decay of excited states
Integrated activities
F10 Magnetic resonance
47 General principles
47.1 Nuclear magnetic resonance
47.2 Electron paramagnetic resonance
Checklist of concepts
Checklist of equations
48 Features of NMR spectra
48.1 The chemical shift
48.2 The origin of shielding constants
48.3 The fine structure
48.4 Conformational conversion and exchange processes
Checklist of concepts
Checklist of equations
49 Pulse techniques in NMR
49.1 The magnetization vector
49.2 Spin relaxation
49.3 The nuclear Overhauser effect
49.4 Two-dimensional NMR
49.5 Solid-state NMR
Checklist of concepts
Checklist of equations
50 Electron paramagnetic resonance
50.1 The g-value
50.2 Hyperfine structure
Checklist of concepts
Checklist of equations
Exercises and problems
47 General principles
48 Features of NMR spectra
49 Pulse techniques in NMR
50 Electron paramagnetic resonance
Integrated activities
F11 Statistical thermodynamics
51 The Boltzmann distribution
51.1 Configurations and weights
51.2 The derivation of the Boltzmann distribution
Checklist of concepts
Checklist of equations
52 Molecular partition functions
52.1 The significance of the partition function
52.2 Contributions to the partition function
Checklist of concepts
Checklist of equations
53 Molecular energies
53.1 The basic equations
53.2 The translational contribution
53.3 The rotational contribution
53.4 The vibrational contribution
53.5 The electronic contribution
Checklist of concepts
Checklist of equations
54 The canonical ensemble
54.1 The concept of ensemble
54.2 The mean energy of a system
54.3 Independent molecules revisited
54.4 The variation of energy with volume
Checklist of concepts
Checklist of equations
Exercises and problems
51 The Boltzmann distribution
52 Partition functions
53 Molecular energies
54 The canonical ensemble
Integrated activities
MB7 Probability theory
F12 The First Law of thermodynamics
55 The First Law
55.1 Work, heat, and energy
55.2 Internal energy
55.3 Expansion work
Checklist of concepts
Checklist of equations
56 Enthalpy
56.1 The definition of enthalpy
56.2 Heat capacity at constant pressure
56.3 Changes in enthalpy with pressure and temperature
56.4 The Joule–Thomson effect
Checklist of concepts
Checklist of equations
57 Thermochemistry
57.1 Calorimetry
57.2 Standard enthalpy changes
57.3 Standard enthalpies of formation
57.4 The temperature dependence of reaction enthalpies
Checklist of concepts
Checklist of equations
58 Internal energy
58.1 Changes in internal energy
58.2 The molecular basis of heat capacity
58.3 Adiabatic processes
Checklist of concepts
Checklist of equations
Exercises and problems
55 The First Law
56 Enthalpy
57 Thermochemistry
58 Internal energy
Integrated activities
MB8 Multivariate calculus
F13 The Second and Third Laws of thermodynamics
59 The Second Law
59.1 The recognition of spontaneous change
59.2 The direction of spontaneous change
59.3 Entropy
Checklist of concepts
60 The statistical entropy
60.1 The statistical definition of entropy
60.2 The entropy in terms of the partition function
Checklist of concepts
Checklist of equations
61 The thermodynamic entropy
61.1 The entropy as a state function
61.2 The thermodynamic temperature
61.3 The Clausius inequality
61.4 Entropy changes in the surroundings
Checklist of concepts
Checklist of equations
62 Entropy changes for specific processes
62.1 Isothermal expansion of a perfect gas
62.2 Phase transitions
62.3 Entropy changes on heating
Checklist of concepts
Checklist of equations
63 The Third Law
63.1 The calorimetric measurement of entropy
63.2 The Nernst heat theorem and the Third Law
63.3 Third-Law entropies
63.4 The standard reaction entropy
Checklist of concepts
Checklist of equations
64 Spontaneous processes
64.1 Criteria of spontaneity
64.2 The Helmholtz and Gibbs energies
64.3 Maximum work
Checklist of concepts
Checklist of equations
65 Standard Gibbs energies
65.1 Gibbs energies of formation
65.2 Ions in solution
Checklist of concepts
Checklist of equations
66 Combining the First and Second Laws
66.1 The fundamental equation
66.2 Properties of the internal energy
66.3 Properties of the Gibbs energy
66.4 Properties of the Helmholtz energy
Checklist of concepts
Checklist of equations
Exercises and problems
59 The Second Law
60 The statistical entropy
61 The thermodynamic entropy
62 Entropy changes for specific processes
63 The Third Law
64 Spontaneous processes
65 Standard Gibbs energies
66 Combining the First and Second Laws
Integrated activities
F14 Physical equilibria
67 Phase diagrams: one-component systems
67.1 The phase rule
67.2 The Ehrenfest classification
67.3 One-component systems
Checklist of concepts
Checklist of equations
68 Phase diagrams: two-component systems
68.1 Liquid–vapour systems
68.2 Liquid–liquid systems
68.3 Liquid–solid systems
Checklist of concepts
Checklist of equations
69 Physical transformations
69.1 Partial molar quantities
69.2 The chemical potential
69.3 The structure of one-component phase diagrams
Checklist of concepts
Checklist of equations
70 Ideal mixtures
70.1 The mixing of perfect gases
70.2 The mixing of liquids
Checklist of concepts
Checklist of equations
71 Colligative properties
71.1 The origin of colligative properties
71.2 Osmosis
Checklist of concepts
Checklist of equations
72 Real solutions
72.1 Activities
72.2 Model systems: regular solutions
72.3 Model systems: ionic solutions
Checklist of concepts
Checklist of equations
Exercises and problems
67 Phase diagrams: one-component systems
68 Phase diagrams: two-component systems
69 Physical transformations
70 Ideal mixtures
71 Colligative properties
72 Real solutions
Integrated activities
F15 Chemical equilibria
73 Chemical transformations
73.1 The reaction Gibbs energy
73.2 The thermodynamic description of equilibrium
73.3 Exergonic and endergonic reactions
Checklist of concepts
Checklist of equations
74 The statistical description of equilibrium
74.1 The relation between K and the partition function
74.2 Contributions to the equilibrium constant
Checklist of concepts
Checklist of equations
75 The response of equilibria to the conditions
75.1 The response of equilibria to pressure
75.2 The response of equilibria to temperature
Checklist of concepts
Checklist of equations
76 Electrochemical cells
76.1 Half-reactions and electrodes
76.2 Varieties of cells
76.3 The cell potential
Checklist of concepts
Checklist of equations
77 Standard electrode potentials
77.1 The conventions
77.2 Applications of standard potentials
Checklist of concepts
Checklist of equations
Exercises and problems
73 Chemical transformations
74 The statistical description of equilibrium
75 The response of equilibria to the conditions
76 Electrochemical cells
77 Standard electrode potentials
Integrated activities
F16 Molecular motion
78 The kinetic theory of gases
78.1 The kinetic model
78.2 Collisions with walls and surfaces
Checklist of concepts
Checklist of equations
79 Transport properties of gases
79.1 The phenomenological equations
79.2 The transport parameters
Checklist of concepts
Checklist of equations
80 Motion in liquids
80.1 Pure liquids
80.2 Electrolyte solutions
Checklist of concepts
Checklist of equations
81 Diffusion
81.1 The thermodynamic view
81.2 The diffusion equation
81.3 The statistical view
Checklist of concepts
Checklist of equations
Exercises and problems
78 The kinetic theory of gases
79 Transport properties of gases
80 Motion in liquids
81 Diffusion
Integrated activities
F17 Chemical kinetics
82 Reaction rates
82.1 Monitoring the progress of a reaction
82.2 The rates of reactions
Checklist of concepts
Checklist of equations
83 Integrated rate laws
83.1 First-order reactions
83.2 Second-order reactions
Checklist of concepts
Checklist of equations
84 Reactions approaching equilibrium
84.1 First-order reactions close to equilibrium
84.2 Relaxation methods
Checklist of concepts
Checklist of equations
85 The Arrhenius equation
85.1 The temperature dependence of reaction rates
85.2 The interpretation of the Arrhenius parameters
86 Reaction mechanisms
86.1 Elementary reactions
86.2 Consecutive elementary reactions
86.3 The steady-state approximation
86.4 The rate-determining step
86.5 Pre-equilibria
86.6 Kinetic and thermodynamic control of reactions
Checklist of concepts
Checklist of equations
Exercises and problems
82 Reaction rates
83 Integrated rate laws
84 Reactions approaching equilibrium
85 The Arrhenius equation
86 Reaction mechanisms
Integrated activities
F18 Reaction dynamics
87 Collision theory
87.1 Collision rates in gases
87.2 The energy requirement
87.3 The steric requirement
Checklist of concepts
Checklist of equations
88 Diffusion-controlled reactions
88.1 Reaction in solution
88.2 The material-balance equation
Checklist of concepts
Checklist of equations
89 Transition-state theory
89.1 The Eyring equation
89.2 Thermodynamic aspects
Checklist of concepts
Checklist of equations
90 The dynamics of molecular collisions
90.1 Molecular beams
90.2 Reactive collisions
90.3 Potential energy surfaces
90.4 Some results from experiments and calculations
Checklist of concepts
Checklist of equations
Exercises and problems
87 Collision theory
88 Diffusion-controlled reactions
89 Transition-state theory
90 The dynamics of molecular collisions
Integrated activity
F19 Processes in fluid systems
91 Unimolecular reactions
91.1 The Lindemann–Hinshelwood mechanism
91.2 The RRK model
Checklist of concepts
Checklist of equations
92 Enzymes
92.1 Features of enzymes
92.2 The Michaelis–Menten mechanism
92.3 The catalytic efficiency of enzymes
92.4 Mechanisms of enzyme inhibition
Checklist of concepts
Checklist of equations
93 Photochemistry
93.1 Photochemical processes
93.2 The primary quantum yield
93.3 Mechanism of decay of excited singlet states
93.4 Quenching
93.5 Resonance energy transfer
Checklist of concepts
Checklist of equations
94 Electron transfer in homogeneous systems
94.1 The rate law
94.2 The rate constant
Checklist of concepts
Checklist of equations
Exercises and problems
91 Unimolecular reactions
92 Enzymes
93 Photochemistry
94 Electron transfer in homogeneous systems
Integrated activities
F20 Processes on solid surfaces
95 Solid surfaces
95.1 Surface growth
95.2 Physisorption and chemisorption
95.3 Experimental techniques
Checklist of concepts
Checklist of equations
96 Adsorption and desorption
96.1 Adsorption isotherms
96.2 The rates of adsorption and desorption
Checklist of concepts
Checklist of equations
97 Heterogeneous catalysis
97.1 Mechanisms of heterogeneous catalysis
97.2 Catalytic activity at surfaces
Checklist of concepts
Checklist of equations
Exercises and problems
95 Solid surfaces
96 Adsorption and desorption
97 Heterogeneous catalysis
Integrated activities
Resource Section
PART 1 Common integrals
Algebraic functions
Exponential functions
Gaussian functions
Trigonometric functions
PART 2 Quantum numbers and operators
A. Common quantum numbers
B. Common operators in quantum mechanics
PART 3 Units
Some common units
Common SI prefixes
The SI base units
A selection of derived units
PART 4 Data
PART 5 Character tables
The groups C1, Cs, Ci
The groups Cnv
The groups Dn
The groups Dnh
The cubic groups
The icosahedral group
Index
A
B
C
D
E
F
G
H
I
J
K
L
M
N
O
P
Q
R
S
T
U
V
W
X
Y
Z
Back Cover
Cover Page
Half-title Page
Copyright Page
Title Page
About the book
Using the book
Organizing the information
Checklist of key ideas
Impact sections
Notes on good practice
Justifications
interActivities
Further information
Synoptic tables and the Resource section
Part 1: Data section
Mathematics support
A brief comment
Mathematical background
Problem solving
A brief illustration
Worked examples
Self-tests
Discussion questions
Exercises and Problems
The Book Companion Site
Living graphs
Artwork
Tables of data
Group theory tables
Weblinks
Other resources
Explorations in Physical Chemistry
Solutions manuals
About the authors
Acknowledgements
Summary of contents
Contents
Fundamentals
F.1: Atoms
F.2: Molecules
F.3: Bulk matter
F.4: Thermodynamic properties
F.5: The relation between molecular and bulk properties
F.6: Particles
F.7: Waves
F.8: Units
Exercises
MATHEMATICAL BACKGROUND 1: Differentiation and integration
MB1.1: Differentiation: definitions
MB1.2: Differentiation: manipulations
MB1.3: Partial derivatives
MB1.4: Series expansions
MB1.5: Integration: definitions
MB1.6: Integration: manipulations
MB1.7: Multiple integrals
PART 1: Quantum theory
Chapter 1: The principles of quantum theory
Three crucial experiments
1.1: Quantization of energy
1.2: The particle character of electromagnetic radiation
1.3: The wave character of particles
I1.1: Impact on biology:Electron microscopy
The postulates
1.4: Postulate I: the wavefunction
1.5: Postulate II: the Born interpretation
1.6: Postulate III: quantum mechanical operators
1.7: Postulate IV: eigenvalues and eigenfunctions
1.8: Postulate V: superpositions and expectation values
Complementary observables
1.9: The Heisenberg uncertainty principle
1.10: The general form of the uncertainty principle
Checklist of key ideas
Further information 1.1: Dirac notation
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 2: Differential equations
MB2.1: The structure of differential equations
MB2.2: The solution of ordinary differential equations
MB2.3: The solution of partial differentiale quations
Chapter 2: Nanosystems 1: motion in one dimension
Translational motion
2.1: Free motion
2.2: A particle in a box
2.3: Tunnelling
I2.1: Impact on nanoscienceScanning probe microscopy
Vibrational motion
2.4: The energy levels
2.5: The wavefunctions
Techniques of approximation
2.6: An overview of approximation techniques
2.7: Time-independent perturbation theory
Checklist of key ideas
Further information 2.1: Time-independent perturbation theory
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 3: Complex numbers
MB3.1: Definitions
MB3.2: Polar representation
MB3.3: Operations
Chapter 3: Nanosystems 2: motion in several dimensions
Translational motion
3.1: Motion in two dimensions
3.2: Motion in three dimensions
I3.1: Impact on nanoscienceQuantum dots
Rotational motion
3.3: Rotation in two dimensions: a particle on a ring
3.4: Rotation in three dimensions: the particle on a sphere
3.5: Spin
Checklist of key ideas
Discussion questions
Exercises
Problems
PART 2: Atoms, molecules, and assemblies
Chapter 4: Atomic structure and spectra
Hydrogenic atoms
4.1: The structure of hydrogenic atoms
4.2: Atomic orbitals and their energies
4.3: Spectroscopic transitions
Many-electron atoms
I4.1: The spectroscopy of stars
4.4: The orbital approximation
4.5: Term symbols
Checklist of key ideas
Further information 4.1: The separation of internal and external motion
Further information 4.2: Time-dependent perturbation theory
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 4: Vectors
MB4.1: Definitions
MB4.2: Operations
MB4.3: The graphical representation of vector operations
MB4.4: Vector differentiation
Chapter 5: The chemical bond
The Born–Oppenheimer approximation
Valence-bond theory
5.1: Homonuclear diatomic molecules
5.2: Polyatomic molecules
Molecular orbital theory
5.3: The hydrogen molecule-ion
5.4: Homonuclear diatomic molecules
5.5: Heteronuclear diatomic molecules
I5.1: Impact on biochemistry:The biochemical reactivity of O2, N2, and NO
Polyatomic molecules: the Hückelapproximation
5.6: Ethene
5.7: The matrix formulation of the Hückel method
5.8: Butadiene and p-electron binding energy
5.9: Benzene and aromatic stability
Checklist of key ideas
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 5: Matrices
MB5.1: Definitions
MB5.2: Matrix addition and multiplication
MB5.3: Eigenvalue equations
Chapter 6: Computational chemistry
The central challenge
6.1: The Hartree–Fock formalism
6.2: The Roothaan equations
6.3: Basis sets
The first approach: semiempirical methods
6.4: The Hückel method revisited
6.5: Differential overlap
The second approach: ab initio methods
6.6: Configuration interaction
6.7: Many-body perturbation theory
The third approach: density functional theory
6.8: The Kohn–Sham equations
6.9: The exchange–correlation energy
Current achievements
6.10: Comparison of calculations and experiments
6.11: Applications to larger molecules
I6.1: Impact on nanoscience:The structures of nanoparticles
I6.2: Impact on medicine:Molecular recognition and drug design
Checklist of key ideas
Discussion questions
Exercises
Problems
Chapter 7: Molecular symmetry
The symmetry elements of objects
7.1: Operations and symmetry elements
7.2: The symmetry classification of molecules
7.3: Some immediate consequences of symmetry
Applications
7.4: Character tables and symmetry labels
7.5: Vanishing integrals and orbital overlap
7.6: Vanishing integrals and selection rules
Checklist of key ideas
Discussion questions
Exercises
Problems
Chapter 8: Molecular assemblies
Interactions between molecules
8.1: Interactions between partial charges
8.2: Electric dipole moments
8.3: Interactions between dipoles
8.4: Induced dipole moments
8.5: Hydrogen bonding
I8.1: Impact on Biochemistry:Proteins and nucleic acids
8.6: The total interaction
I8.2: Impact on nanoscience:Colloidal nanoparticles
Gases and liquids
8.7: Molecular interactions in gases
8.8: Molecular interactions in liquids
I8.3: Impact on materials science:Liquid crystals
Checklist of key ideas
Further information 8.1: The dipole–dipole interaction
Further information 8.2: The basic principles of molecular beams
Discussion questions
Exercises
Problems
Chapter 9: Solids
Crystal lattices
9.1: Lattices and unit cells
9.2: The identification of lattice planes
9.3: The investigation of structure
I9.1: Impact on biochemistry:X-ray crystallography of biological macromolecules
9.4: Neutron and electron diffraction
Crystal structure
9.5 Metallic solids
9.6: Ionic solids
9.7: Molecular solids and covalent networks
The properties of solids
9.8: Mechanical properties
9.9: Electrical properties
I9.2: Impact on technology:Conducting polymers
I9.3: Impact on nanoscience:Nanowires
9.10: Optical properties
9.11: Magnetic properties
9.12: Superconductors
Checklist of key ideas
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 6: Fourier series and Fourier transforms
MB6.1: Fourier series
MB6.2: Finite approximations and Parseval’stheorem
MB6.3: Fourier transforms
MB6.4: The convolution theorem
PART 3: Molecular spectroscopy
Chapter 10: Rotational and vibrational spectra
Pure rotational spectra
10.1: Moments of inertia
10.2: Rotational energy levels
10.3: Rotational transitions
10.4: Rotational Raman spectra
10.5: Nuclear statistics and rotational states
I10.1: Impact on Astrophysics:Rotational spectroscopy of interstellarmolecules
The vibrations of diatomic molecules
10.6: Techniques
10.7: Molecular vibrations
10.8: Selection rules
10.9: Anharmonicity
10.10: Vibration–rotation spectra
10.11: Vibrational Raman spectra of diatomic molecules
The vibrations of polyatomic molecules
10.12: Normal modes
10.13: Infrared absorption spectra of polyatomic molecules
I10.2: Impact on environmental science:Climate
10.14: Vibrational Raman spectra of polyatomic molecules
I10.3: Impact on biochemistry:Vibrational microscopy
10.15: Symmetry aspects of molecular vibrations
Checklist of key ideas
Further information 10.1: The Einstein coefficients
Further information 10.2: Selection rules for rotational and vibrational spectroscopy
Discussion questions
Exercises
Problems
Chapter 11: Electronic spectroscopy
Experimental techniques
11.1:Spectrometers
11.2:The Beer–Lambert law
The characteristics of electronictransitions
11.3:The electronic spectra of diatomic molecules
11.4: The electronic spectraof polyatomic molecules
I11.1:Impact on Biochemistry:Vision
The fates of electronicallyexcited states
11.5:Fluorescence and phosphorescence
I11.2: Impact on Nanoscience:Single-molecule spectroscopy
11.6:Dissociation and predissociation
11.7:General principles of laser action
11.8:Examples of practical lasers
Checklist of key ideas
Discussion questions
Exercises
Problems
Chapter 12:Magnetic resonance
The effect of magnetic fields on electronsand nuclei
12.1:The energies of electrons in magnetic fields
12.2:The energies of nuclei in magnetic fields
12.3:Magnetic resonance spectroscopy
Nuclear magnetic resonance
12.4:The NMR spectrometer
12.5:The chemical shift
12.6:The fine structure
12.7:Conformational conversion and exchangeprocesses
Pulse techniques in NMR
12.8:The magnetization vector
12.9:Spin relaxation
I12.1: Impact on medicine:Magnetic resonance imaging
12.10:Spin decoupling
12.11:The nuclear Overhauser effect
12.12:Two-dimensional NMR
12.13: Solid-state NMR
Electron paramagnetic resonance
12.14:The EPR spectrometer
12.15:The g-value
12.16:Hyperfine structure
I12.2:Impact on biochemistrySpin probes
Checklist of key ideas
Discussion questions
Exercises
Problems
PART 4: Molecularthermodynamics
Chapter 13:The Boltzmann distribution
The distribution of molecular states
13.1:Configurations and weights
13.2:The molecular partition function
13.3:Contributions to the molecular partition function
I13.1:Impact on biochemistry: The helix–coil transition in polypeptides
13.4:The mean energy
The canonical partition function
13.5:The canonical ensemble
13.6:The mean energy of a system
13.7:Independent molecules
Checklist of key ideas
Further information 13.1: The derivation of theBoltzmann distribution
Further information 13.2:The partition functions of polyatomic rotors
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 7:Probability theory
MB7.1:Discrete distributions
MB7.2:Continuous distributions
Chapter 14: The First Law ofthermodynamics
The internal energy
14.1:Work, heat, and energy
14.2:The First Law
14.3:Expansion work
14.4:Heat transactions
14.5:Enthalpy
l14.1:Impact on biochemistry: Differential scanning calorimetry
14.6:Adiabatic changes
Thermochemistry
14.7:Standard enthalpy changes
14.8:Standard enthalpies of formation
14.9:The temperature dependence of reaction enthalpies
Properties of the internal energyand the enthalpy
14.10:Changes in internal energy
14.11:The Joule–Thomson effect
Checklist of key ideas
Further information 14.1:Adiabatic processes
Discussion questions
Exercises
Problems
MATHEMATICAL BACKGROUND 8:Multivariate calculus
MB8.1:Partial derivatives
MB8.2:Exact differentials
Chapter 15:The Second Law of thermodynamics
The direction of spontaneouschange
15.1:The dispersal of energy
15.2:Entropy
I15.1:Impact on Technology:Refrigeration
15.3: Entropy changes accompanying specificprocesses
15.4:The Third Law of thermodynamics
Concentrating on the system
15.5:The Helmholtz and Gibbs energies
15.6:Standard molar Gibbs energies
Combining the First andSecond Laws
15.7:The fundamental equation
15.8:Properties of the internal energy
15.9:Properties of the Gibbs energy
Checklist of key ideas
Further information 15.1:The Born equation
Discussion questions
Exercises
Problems
Chapter 16:Physical equilibria
Phase diagrams
16.1:One-component systems
16.2:Two-component systems
I16.1: Impact on biochemistry:Biological membranes
Thermodynamic interpretation
16.3:Properties of the chemical potential
16.4:The structure of one-component phasediagrams
16.5: The structure of two-component phasediagrams
I16.2: Impact on biochemistry:Osmosis and the structure of biological cells
16.6:Real solutions
Checklist of key ideas
Further information 16.1:The phase rule
Further information 16.2:The Ehrenfest classification
Further information 16.3:The Debye–Hückel theory of ionic solutions
Discussion questions
Exercises
Problems
Chapter 17:Chemical equilibrium
Spontaneous chemical reactions
17.1:The Gibbs energy minimum and the reactionGibbs energy
17.2: The thermodynamic descriptionof equilibrium
I17.1: Impact on biology:Energy conversion in biological cells
17.3:The statistical description of equilibrium
The response of equilibria to theconditions
17.4:How equilibria respond to pressure
17.5:The response of equilibria to temperature
Electrochemistry
17.6:Half-reactions and electrodes
17.7:Varieties of cells
17.8:The cell potential
I17.2: Impact on Engineering:Fuel cells
17.9:Standard electrode potentials
17.10:Applications of standard potentials
I17.3: Impact on biology:The respiratory chain
Checklist of key ideas
Discussion questions
Exercises
Problems
PART 5:Chemical dynamics
Chapter 18:Molecular motion
Motion in gases
18.1:The kinetic model of gases
18.2:Collisions with walls and surfaces
18.3:The rate of effusion
18.4:Transport properties of a perfect gas
Motion in liquids
18.5:Experimental results
18.6:The conductivities of electrolyte solutions
18.7:The mobilities of ions
I18.1: Impact on biochemistry:Gel electrophoresis in genomics and proteomics
Diffusion
18.8:The thermodynamic view
18.9:The diffusion equation
18.10:Diffusion probabilities
18.11:The statistical view
I18.2: Impact on biochemistry:Transport across membranes
Checklist of key ideas
Further information 18.1: The transport characteristics of aperfect gas
Further information 18.2:Random coils
Discussion questions
Exercises
Problems
Chapter 19:Chemical kinetics
Empirical chemical kinetics
19.1:Experimental techniques
19.2:The rates of reactions
19.3:Integrated rate laws
19.4:Reactions approaching equilibrium
Accounting for the rate laws
19.5:Elementary reactions
19.6:Consecutive elementary reactions
The kinetics of complex reactions
19.7: The Lindemann–Hinshelwood mechanismof unimolecular reactions
19.8:Polymerization kinetics
19.9:Photochemistry
I19.1: Impact on biochemistry:Harvesting of light during plant photosynthesis
Checklist of key ideas
Further information 19.1:Förster theory of resonance energy transfer
Discussion questions
Exercises
Problems
Chapter 20:Molecular reaction dynamics
The temperature dependence of reaction rates
20.1:The Arrhenius equation
20.2:The activation energy of a composite reaction
Reactive encounters
20.3:Collision theory
20.4:Diffusion-controlled reactions
20.5:The material balance equation
Transition state theory
20.6:The Eyring equation
20.7:Thermodynamic aspects
20.8:Electron transfer in homogeneous systems
The dynamics of molecularcollisions
20.9:Reactive collisions
20.10:Potential energy surfaces
20.11: Some results from experiments andcalculations
Checklist of key ideas
Further information 20.1: The RRK model of unimolecularreactions
Further information 20.2: The Gibbs energy of activation ofelectron transfer
Discussion questions
Exercises
Problems
Chapter 21:Catalysis
Homogeneous catalysis
21.1:Acid and base catalysis
21.2:Enzymes
Heterogeneous catalysis
21.3:The growth and structure of surfaces
21.4:The extent of adsorption
21.5:The rates of surface processes
I21.1:Impact on biochemistry:Biosensor analysis
21.6:Mechanisms of heterogeneous catalysis
21.7:Catalytic activity at surfaces
I21.2: Impact on technology:Catalysis in the chemical industry
Checklist of key ideas
Further information 21.1:The BET isotherm
Discussion questions
Exercises
Problems
Resource section
Contents
Part 1:Data section
Part 2:Common operators in quantum mechanics
Part 3:Character tables
The groups C1, Cs, Ci
The groups Cnv
The groups Dn
The groups Dnh
The cubic groups
The icosahedral group
Solutions to a) exercises
Fundamentals
Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
Chapter 12
Chapter 13
Chapter 14
Chapter 15
Chapter 16
Chapter 17
Chapter 18
Chapter 19
Chapter 20
Chapter 21
Solutions to odd-numbered problems
Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
Chapter 12
Chapter 13
Chapter 14
Chapter 15
Chapter 16
Chapter 17
Chapter 18
Chapter 19
Chapter 20
Chapter 21
Index
A
B
C
D
E
F
G
H
I
J
K
L
M
N
O
P
Q
R
S
T
U
V
W
X
Y
Z