Elements of Physical Chemistry 7th Edition by Peter Atkins, Julio de Paula ISBN 0198727879 978-0198727873

Focus 1 The properties of gases

1A The perfect gas

1A.1 The perfect gas equation of state

1A.2 Using the perfect gas law

1A.3 Mixtures of gases: partial pressures

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1B The kinetic model of gases

1B.1 The pressure of a gas according to the kinetic model

1B.2 The root-mean-square speed of gas molecules

1B.3 The Maxwell distribution of speeds

1B.4 Diffusion and effusion

1B.5 Molecular collisions

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1C Real gases

1C.1 Molecular interactions

1C.2 The critical temperature

1C.3 The compression factor

1C.4 The virial equation of state

1C.5 The van der Waals equation of state

1C.6 The liquefaction of gases

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Focus 2 The First Law of thermodynamics

2A Work

2A.1 Systems and surroundings

2A.2 Expansion work

2A.3 Reversible expansion

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2B Heat

2B.1 Conventions

2B.2 Heat capacity

2B.3 Calorimetry

2B.4 Heat influx during expansion

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2C Internal energy

2C.1 The internal energy

2C.2 The internal energy as a state function

2C.3 Changes in the internal energy

2C.4 The molecular basis of the internal energy

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2D Enthalpy

2D.1 The definition of enthalpy

2D.2 Changes in enthalpy

2D.3 The temperature dependence of the enthalpy

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2E Physical change

2E.1 The enthalpy of phase transition

2E.2 Ionization and electron attachment

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2F Chemical change

2F.1 Bond dissociation

2F.2 Enthalpies of combustion

2F.3 The combination of reaction enthalpies

2F.4 Standard enthalpies of formation

2F.5 The variation of reaction enthalpy with temperature

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Focus 3 The Second Law of thermodynamics

3A Entropy

3A.1 The direction of spontaneous change

3A.2 Entropy and the Second Law

3A.3 Heat engines, refrigerators, and heat pumps

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3B Entropy changes

3B.1 The entropy change accompanying a change in volume

3B.2 The entropy change accompanying a change in temperature

3B.3 The entropy change accompanying a phase transition

3B.4 Entropy changes in the surroundings

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3C Absolute entropy

3C.1 The Third Law of thermodynamics

3C.2 The molecular interpretation of entropy

3C.3 Residual entropy

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3D The Gibbs energy

3D.1 The standard reaction entropy

3D.2 The spontaneity of chemical reactions

3D.3 Focusing on the system

3D.4 Properties of the Gibbs energy

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Focus 4 Physical transformations

4A The thermodynamics of transition

4A.1 The condition of stability

4A.2 The variation of Gibbs energy with pressure

4A.3 The variation of Gibbs energy with temperature

4A.4 The Gibbs–Helmholtz equation

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4B Phase diagrams of pure substances

4B.1 Phase boundaries

4B.2 The location of phase boundaries

4B.3 Characteristic points

4B.4 The phase rule

4B.5 Phase diagrams of typical materials

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4C Partial molar quantities

4C.1 Partial molar volume

4C.2 The chemical potential

4C.3 Spontaneous mixing

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4D Solutions

4D.1 Ideal solutions

4D.2 The chemical potential of the solvent

4D.3 Ideal–dilute solutions

4D.4 The chemical potential of the solute

4D.5 Real solutions: activities

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4E Colligative properties

4E.1 The modification of boiling and freezing points

4E.2 Osmosis

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4F Phase diagrams of mixtures

4F.1 Mixtures of volatile liquids

4F.2 Liquid–liquid phase diagrams

4F.3 Liquid–solid phase diagrams

4F.4 Zone refining

4F.5 The Nernst distribution law

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Focus 5 Chemical change

5A The thermodynamics of reaction

5A.1 The reaction Gibbs energy

5A.2 The variation of ΔrG with composition

5A.3 Reactions at equilibrium

5A.4 The standard reaction Gibbs energy

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5B The equilibrium constant

5B.1 The composition at equilibrium

5B.2 The equilibrium constant in terms of concentration

5B.3 The molecular interpretation of equilibrium constants

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5C Response to conditions

5C.1 The effect of temperature

5C.2 The effect of compression

5C.3 The presence of a catalyst

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5D Proton transfer equilibria

5D.1 Brønsted–Lowry theory

5D.2 Protonation and deprotonation

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5E Polyprotic acids

5E.1 Successive deprotonation

5E.2 Speciation

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5F Acid–base equilibria of salts in water

5F.1 The pH of salt solutions

5F.2 Acid–base titrations

5F.3 Buffer action

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5G Solubility equilibria

5G.1 The solubility constant

5G.2 The common-ion effect

5G.3 The effect of added salts on solubility

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5H Ions in solution

5H.1 Mean activity coefficients

5H.2 The Debye–Hückel theory

5H.3 The migration of ions

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5I Electrochemical cells

5I.1 Half-reactions and electrodes

5I.2 Reactions at electrodes

5I.3 Varieties of cell

5I.4 The cell reaction

5I.5 The cell potential

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5J Standard potentials

5J.1 The contributions of individual electrodes

5J.2 Equilibrium constants from standard potentials

5J.3 The variation of potential with pH

5J.4 The electrochemical series

5J.5 The combination of standard potentials

5J.6 Thermodynamic data from standard potentials

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Focus 6 Chemical kinetics

6A Empirical chemical kinetics

6A.1 The definition of rate

6A.2 Experimental techniques

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6B Rate laws

6B.1 The rate constant

6B.2 Reaction order

6B.3 The determination of the rate law

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6C Integrated rate laws

6C.1 Zeroth-order reactions

6C.2 First-order reactions

6C.3 Second-order reactions of the type A → products

6C.4 Second-order reactions of the type A + B → products

6C.5 Half-lives

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6D The temperature dependence of reaction rates

6D.1 The Arrhenius parameters

6D.2 Collision theory of gas-phase reactions

6D.3 Transition-state theory

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6E The approach to equilibrium

6E.1 Equilibria and rates

6E.2 Relaxation

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6F Reaction mechanisms

6F.1 Elementary reactions

6F.2 The formulation of rate laws

6F.3 Consecutive reactions

6F.4 Pre-equilibrium

6F.5 The steady-state approximation

6F.6 The rate-determining step

6F.7 Kinetic control

6F.8 Unimolecular reactions

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6G Reactions in solution

6G.1 Activation control and diffusion control

6G.2 Diffusion

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6H Homogeneous catalysis

6H.1 The Michaelis–Menten mechanism of enzyme catalysis

6H.2 The analysis of rates of enzyme-catalysed reactions

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6I Heterogeneous catalysis

6I.1 Physisorption and chemisorption

6I.2 Adsorption isotherms

6I.3 Mechanisms of surface-catalysed reactions

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Focus 7 Quantum theory

7A The emergence of quantum theory

7A.1 The evidence for discrete energies

7A.2 The evidence for radiation as particles

7A.3 The evidence for particles as waves

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7B The dynamics of microscopic systems

7B.1 The Schrödinger equation

7B.2 The Born interpretation

7B.3 The uncertainty principle

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7C Translation

7C.1 Motion in one dimension

7C.2 Tunnelling

7C.3 Motion in two dimensions

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7D Rotation

7D.1 Rotation in two dimensions

7D.2 Rotation in three dimensions

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7E Vibration

7E.1 The harmonic oscillator

7E.2 The quantum mechanical treatment

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Focus 8 Atomic structure

8A Hydrogenic atoms

8A.1 The permitted energies of hydrogenic atoms

8A.2 Quantum numbers

8A.3 The s orbitals

8A.4 The p and d orbitals

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8B Many-electron atoms

8B.1 The orbital approximation

8B.2 Electron spin

8B.3 The Pauli principle

8B.4 Penetration and shielding

8B.5 The building-up principle

8B.6 The occupation of d orbitals

8B.7 The configurations of cations and anions

8B.8 Self-consistent field orbitals

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8C Periodic trends of atomic properties

8C.1 Atomic and ionic radii

8C.2 Ionization energy and electron affinity

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8D Atomic spectroscopy

8D.1 The spectra of hydrogenic atoms

8D.2 The energies of many-electron atoms

8D.3 Spin–orbit coupling

8D.4 Selection rules for many-electron atoms

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Focus 9 The chemical bond

9A Valence bond theory

9A.1 Diatomic molecules

9A.2 Polyatomic molecules

9A.3 Promotion and hybridization

9A.4 Resonance

9A.5 The language of valence bond theory

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9B Molecular orbital theory: homonuclear diatomics

9B.1 The construction of molecular orbitals

9B.2 Bonding and antibonding orbitals

9B.3 Inversion symmetry

9B.4 The chemical bond in molecular orbital theory

9B.5 Many-electron homonuclear diatomics

9B.6 The configurations of Period 2 homonuclear diatomics

9B.7 The criteria for building molecular orbitals

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9C Molecular orbital theory: heteronuclear diatomics

9C.1 Polar bonds

9C.2 The formulation of molecular orbitals

9C.3 Molecular orbital diagrams

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9D Molecular orbital theory: polyatomic molecules

9D.1 The molecular orbitals of H2O

9D.2 The Hückel method

9D.3 The molecular orbitals of benzene

9D.4 Computational chemistry

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Focus 10 Molecular interactions

10A Electric properties of molecules

10A.1 Electric dipole moments

10A.2 Dipole moments of polyatomic molecules

10A.3 Polarizabilities

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10B Interactions between molecules

10B.1 Interactions between partial charges

10B.2 Charge–dipole interactions

10B.3 Dipole–dipole interactions

10B.4 Dipole–induced dipole interactions

10B.5 Dispersion interactions

10B.6 Hydrogen bonding

10B.7 The hydrophobic effect

10B.8 Modelling the total interaction

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Focus 11 Molecular spectroscopy

11A General features of molecular spectroscopy

11A.1 Spectrometers

11A.2 Absorption and emission

11A.3 Raman scattering

11A.4 Linewidths

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11B Rotational spectroscopy

11B.1 The rotational energy levels of molecules

11B.2 Forbidden and allowed rotational states

11B.3 Populations at thermal equilibrium

11B.4 Microwave spectroscopy

11B.5 Rotational Raman spectra

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11C Vibrational spectroscopy

11C.1 The vibrations of molecules

11C.2 Vibrational transitions

11C.3 Anharmonicity

11C.4 Vibrational Raman spectra of diatomic molecules

11C.5 The vibrations of polyatomic molecules

11C.6 Vibration–rotation spectra

11C.7 Vibrational Raman spectra of polyatomic molecules

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11D Electronic spectroscopy

11D.1 Ultraviolet and visible spectra

11D.2 Specific types of transitions

11D.3 Analysis of mixtures by electronic spectroscopy

11D.4 Photoelectron spectroscopy

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11E The decay of excited states

11E.1 Fluorescence and phosphorescence

11E.2 Mechanism of decay of excited states

11E.3 Quenching

11E.4 Resonance energy transfer

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Focus 12 Statistical thermodynamics

12A The Boltzmann distribution

12A.1 The population of states

12A.2 The general form of the Boltzmann distribution

12A.3 The origins of the Boltzmann distribution

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12B The partition function

12B.1 The interpretation of the partition function

12B.2 The molecular partition function

12B.3 The translational partition function

12B.4 The rotational partition function

12B.5 The vibrational partition function

12B.6 The electronic partition function

12B.7 The significance of the molecular partition function

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12C The origin of thermodynamic properties

12C.1 The internal energy

12C.2 The heat capacity

12C.3 The entropy

12C.4 The Gibbs energy

12C.5 The equilibrium constant

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Resource section

Part 1 Common integrals

Part 2 Units

Part 3 Data

Index