Basic Physical Chemistry

by Smith, E. Brian

• ISBN13: 9781848168725
• ISBN10: 1848168721
• Format: Paperback
• Copyright: 2012-08-30
• Publisher: Imperial College Pr

Summary

This elegant book provides a student-friendly introduction to the subject of physical chemistry. It is concise and more compact than standard textbooks on the subject and it emphasises the two important concepts underpinning physical chemistry: quantum mechanics and the second law of thermodynamics. the principles are challenging to students because they both focus on uncertainty and probability. the book explains these fundamental concepts clearly and shows how they offer the key to understanding the wide range of chemical phenomena including atomic and molecular spectra, the structure and properties of solids, liquids and gases, chemical equilibrium, and the rates of chemical reactions.

Author Biography

Sir Brian Smith received his first degree and his doctorate at Liverpool University. After two years at the University of California, Berkeley, he was appointed Lecturer in Physical Chemistry and Fellow of St Catherine's College, Oxford. Later, he was elected Master of the College. Subsequently he was Vice-Chancellor of Cardiff University. His research interests include intermolecular forces and the biological effects of simple gases. In the latter area he has contributed to the understanding of the mechanisms of general anaesthesia, inert gas narcosis and decompression sickness, and he has been active in applying the results of his investigations to the Science of deep-sea diving.

Table of Contents

Preface	p. vii
Notation	p. xv
Acknowledgements and Credits	p. xix
Background	p. 1
Introduction	p. 1
The building blocks	p. 3
The periodic table	p. 5
Isotopes	p. 5
Molecules	p. 6
The mole	p. 8
Waves	p. 8
Electromagnetic radiation	p. 10
The perfect gas	p. 11
Chemical equilibrium	p. 12
Ionic equilibria	p. 14
The next steps	p. 16
Energy	p. 17
Kinetic and potential energy	p. 17
Kinetic theory of gases	p. 19
Equipartition of energy	p. 21
Heat and work	p. 23
Conservation of energy - The First Law	p. 25
State functions	p. 25
Enthalpy	p. 27
Hess's law	p. 29
Calorimetry	p. 31
Coulombic energy	p. 33
Summary of key principles	p. 35
The First Principle: Energy is Not Continuous	p. 37
The failures of classical physics	p. 37
Basic ideas of quantum mechanics	p. 39
The uncertainty principle	p. 42
Summary of important principles	p. 43
Translational motion: Particle in a box	p. 44
Rotational motion	p. 48
Vibrational motion	p. 50
The hydrogen-like atom	p. 51
Hydrogen atom spectra	p. 53
The Schrödinger wave equation	p. 56
Quantum mechanics - further considerations	p. 58
Electrons in Atoms	p. 61
Limitations of the simple model	p. 61
Solution of the Schrödinger equation for many-electron atoms	p. 61
Electron spin	p. 63
Many-electron atoms	p. 64
Pauli exclusion principle and the Aufbau principle	p. 66
The shielding of outer electrons and atomic properties	p. 69
Estimating atomic properties	p. 74
Solving the Schrödinger equation for atoms	p. 77
The ground state of the helium atom	p. 78
Summary of key principles	p. 81
Chemical Bonding and Molecular Structure	p. 83
The chemical bond - a historical digression	p. 83
Valence bond theory	p. 85
Molecular orbitals	p. 89
Homonuclear diatomic molecules	p. 93
Heteronuclear molecules	p. 96
Hybridisation	p. 97
Delocalised orbitals	p. 100
Ab initio calculations	p. 103
Summary of key principles	p. 105
Atomic and Molecular Spectra	p. 107
Spectroscopy	p. 107
The intensities of spectroscopic lines	p. 110
Spectroscopic line widths	p. 113
Atomic spectra	p. 114
Two-electron spectra	p. 116
Russell-Saunders coupling	p. 118
Molecular spectra	p. 119
Rotational spectra	p. 120
Vibrational spectra	p. 124
Vibrational-rotational spectra	p. 126
Vibrations of polyatomic molecules	p. 129
Low-resolution infrared spectra	p. 130
Raman spectra	p. 132
Molecular electronic spectra	p. 133
Low-resolution electronic spectra	p. 137
The fate of excited electronic states	p. 139
Nuclear magnetic resonance (NMR)	p. 140
Electron spin resonance spectroscopy	p. 145
Summary of key principles	p. 145
The Second Principle: The Higher, the Fewer	p. 147
Equilibrium	p. 147
Why we need a second principle	p. 149
The second factor	p. 151
Microstates	p. 152
The Boltzmann factor	p. 153
Entropy	p. 157
Defining the position of equilibrium	p. 159
Entropy as a function of pressure and temperature	p. 160
Partition functions	p. 162
Determination of thermodynamic functions from partition functions	p. 165
Summary of key principles	p. 172
Chemical Equilibrium	p. 175
Free energy	p. 175
Gibbs free energy	p. 176
The pressure and temperature dependence of Gibbs free energy	p. 177
Chemical potential	p. 179
Equilibrium between gaseous reactants	p. 180
The temperature dependence of the equilibrium constant	p. 183
The effect of pressure on equilibrium constants	p. 185
Equilibrium calculations using thermodynamic tables	p. 187
Equilibrium constants from free energy functions	p. 191
Equilibrium constants and partition functions	p. 192
Summary of the basic equations of chemical thermodynamics	p. 196
The States of Matter	p. 199
Gases, liquids and solids	p. 199
The thermodynamics of phase changes	p. 201
Intermolecular energy	p. 203
The origins of intermolecular energy	p. 205
Gas imperfection	p. 211
Critical behaviour	p. 213
Corresponding states	p. 214
The liquid state	p. 215
The solid state	p. 217
Crystal structure	p. 218
X-ray diffraction	p. 221
Molecular structures by diffraction methods	p. 224
Solid surfaces	p. 226
Summary of key principles	p. 229
Mixtures and Solutions	p. 231
The ideal solution	p. 231
Truly ideal solutions	p. 233
Ideal solutions of solids in liquids	p. 235
Ideal dilute solutions	p. 237
Non-ideal solutions	p. 241
Molecular basis of ideality	p. 243
Ions in solution	p. 245
Debye-Hückel theory	p. 246
Electrochemical cells	p. 249
Summary of key principles	p. 252
Rates of Chemical Reactions	p. 255
The order of reactions	p. 255
First-order reactions	p. 256
Second-order reactions	p. 258
Determination of reaction order	p. 259
Effect of temperature on reaction rates	p. 260
Collision theory	p. 261
Activated complex theory	p. 264
Thermodynamic interpretation of activated complexes	p. 268
Unimolecular reactions	p. 269
Chain reactions	p. 272
Explosions	p. 275
Reactions in solution	p. 277
Catalysis	p. 278
Reaction dynamics	p. 282
Photochemical reactions	p. 284
Summary of key principles	p. 286
Answers to Problems	p. 289
Thermochemical Data at 298.15 K	p. 290
Hydrogen-Like Wave Functions	p. 292
Symmetry	p. 294
Units and Fundamental Constants	p. 295
Further Reading	p. 297
The Periodic Table	p. 299
Index	p. 301
Table of Contents provided by Ingram. All Rights Reserved.