Preface xi
About the Companion Website xiii
1 The Metric System and Mathematical Tools 1
1.1 Scientific Notation and Significant Figures 1
1.2 The Metric System 2
1.3 Manipulations of Exponential Expressions 4
1.4 Equations, Proportionality, and Graphs 5
1.5 Quadratic, Cubic, and Quartic Equations 7
1.6 Exponential Functions and Logarithms 8
1.7 Radial and Spherical Polar Coordinates 11
1.8 Differential and Integral Calculus 12
1.9 Differential Equations 14
1.10 Complex Numbers 15
2 Atoms, Elements, and the Periodic System 17
2.1 Subatomic Particles and Atoms 17
2.2 Elements, Isotopes, and Ions 18
2.3 The Periodic Chart and Periodic Properties of the Elements 21
2.4 Definition of Atomic Masses, Avogadro's Number, and the Mole 26
Further Reading 28
3 Molecules, Compounds, Bonding, and Percent Composition 29
3.1 Ionic Compounds 29
3.2 Molecules with Covalent Bonds 30
3.3 Molecules with Polar Covalent Bonds and Lewis Structures 31
3.4 Molecular Compounds and the (Gram) Molecular Mass 37
3.5 Percent Composition and Empirical Formulae 38
Further Reading 39
4 Chemical Reactions 41
4.1 Chemical Reaction and Stoichiometry 41
4.2 Limiting Reagents, Theoretical Yield, and Percent Yield 42
4.3 Solutions: General Aspects 43
4.4 Solution Stoichiometry: Molarity, Molality, Mole Fraction, Dilutions 45
4.5 Precipitation Reactions 47
Further Reading 49
5 Electronic Structure of Atoms 51
5.1 Description of Light as an Electromagnetic Wave 51
5.2 Particle Properties of Light and Wave-particle Duality 52
5.3 The Hydrogen Atom Emission Spectrum: Stationary Atomic States 55
5.4 Hydrogen Atom Orbitals 58
5.5 Atoms with Multiple Electrons: The Aufbau Principle Revisited 62
Further Reading 67
6 Chemical Bonding: Covalent Bonding, Molecular Geometries, and Polarity 69
6.1 General Aspects of Covalent Bonding 69
6.2 Lewis and VB Theory 69
6.3 Hybridization and Multiple Bonding 70
6.4 VSEPR Model 73
6.5 Molecular Polarity 75
6.6 MO Theory 76
Further Reading 81
7 Solids and Liquids: Bonding and Characteristics 83
7.1 Metals and Semiconductors 83
7.2 Ionic Solids 85
7.3 Covalent Solids 86
7.4 Intermolecular Forces 87
7.4.1 Hydrogen Bonding 87
7.4.2 Dipole-Dipole Interactions 88
7.4.3 London Dispersion Forces (Induced Dipole Forces) 89
7.5 Macromolecular Solids 89
7.6 Liquids and Solutions 90
7.6.1 General Aspects of Solutions and Solvation 90
7.6.2 Colligative Properties 90
Further Reading 93
8 The Gaseous State 95
8.1 General Properties of Gases 95
8.2 Empirical Gas Laws 97
8.3 The Ideal Gas Law 99
8.4 Real Gases 100
8.5 Gaseous Mixtures and Partial Pressures 101
8.6 Kinetic Theory of Gases 102
8.7 Diffusion and Effusion of Gases 104
Further Reading 106
9 Chemical Equilibrium 107
9.1 What Is a System "at Equilibrium"? 107
9.2 Liquid-Vapor Phase Equilibrium: Vapor Pressure 108
9.3 Temperature Dependence of Vapor Pressure 110
9.4 Chemical Equilibrium and the Equilibrium Constant 113
9.5 Equilibrium Calculations 115
9.6 Direction of a Chemical Reaction and the Concentration Quotient Q 119
9.7 Numerical Determination of Equilibrium Constants from Experimental Data 120
9.8 Perturbations of Equilibria: Le Chatelier's Principle 120
9.9 Solubility and Solubility Product 122
9.9.1 The Solubility Product Constant, Ksp 123
9.9.2 Solubility Calculations 123
9.9.3 Common Ion Effect 124
9.9.4 Experimental Determination of Ksp 125
9.9.5 Precipitation Reactions 126
Further Reading 127
10 Acids and Bases 129
10.1 What Are Acids/Bases? 129
10.2 Strong Acids and Bases; Definition of pH and pOH 130
10.3 Weak Acids/Bases 131
10.4 The Relationship Between pH and pOH: Self-dissociation of Water 134
10.5 Common Ion Effect 135
10.6 Acidic and Basic Salts 136
10.7 Buffers 138
10.8 Acid-Base Titrations 140
10.8.1 Titration of a Strong Acid with a Strong Base 141
10.8.2 Titration of a Weak Acid with a Strong Base 143
10.8.3 Acid-Base Indicators 145
Further Reading 146
11 Thermodynamics: Energy, Energy Conversions, and Spontaneity 147
11.1 Energetics of Chemical Reactions 147
11.2 Thermochemistry 147
11.2.1 Definition of Energy, Work, and Heat 147
11.2.2 Calorimetry: Measurement of Heat Flow 150
11.3 The First Law of Thermodynamics 152
11.4 State Functions 153
11.5 Definition of Enthalpy 153
11.6 Hess' Law and Reaction Enthalpies 154
11.6.1 Enthalpy of Crystal Formation: Lattice Energy of MgO 156
11.7 Enthalpy of Phase Transitions 157
11.8 Entropy 158
11.8.1 Entropy and Probability 161
11.8.2 Entropy and Heat Flow 162
11.8.3 Entropy as an Indicator of Energy Exhaustion 163
11.9 Free Enthalpy 164
11.10 Free Enthalpy and Equilibrium 165
Further Reading 168
12 Reduction-Oxidation (Redox) Reactions and Electrochemistry 169
12.1 Oxidation State and Oxidation Numbers: Balancing Redox Equations 170
12.2 Galvanic Cells, Electric Work, and Electromotive Force 173
12.3 Batteries 177
12.3.1 Alkaline Dry Cell (AA Battery) 177
12.3.2 Lead-Acid Battery 178
12.3.3 Lithium-ion Battery 180
12.4 Relationship Between Cell Potential and Free Enthalpy 181
12.5 Concentration and Temperature Dependence of EMF 181
Further Reading 183
13 Chemical Kinetics: Rates of Reactions and Reaction Mechanisms 185
13.1 Scope of Kinetics Discussion 185
13.2 Elementary Steps and Chemical Reactions 185
13.2.1 Kinetic Model of Chemical Reactions 185
13.2.2 Basics of Chemical Kinetics: Rate Law and Rate Constant 187
13.2.3 Time Dependence of the Reaction Rate 188
13.2.4 Integrated Rate Law 189
13.3 Rates of Multistep Reactions, and Equilibria 191
13.4 Reaction Rates for Reactions That Are Nonlinear in Concentrations 194
13.5 Reaction Path and Catalysis 195
Further Reading 198
14 Nuclear Reactions 199
14.1 Nuclear Reactions and Transmutations 199
14.2 The Structure of Atomic Nuclei 199
14.3 Radioactive Decay and Decay Chains 200
14.3.1 ?-Decay 200
14.3.2 ?-Decay 200
14.3.3 ?-Emission (?-Decay) 201
14.3.4 Positron Emission 202
14.3.5 Nuclear Decay Chains 202
14.3.6 Nuclear Dating 203
14.4 Nuclear Fission and Nuclear Fusion 204
14.4.1 Nuclear Binding Energy 205
14.4.2 Nuclear Fusion 205
14.4.3 Nuclear Fission 206
Further Reading 207
15 Fundamentals of Quantum Chemistry, Spectroscopy, and Structural Chemistry 209
15.1 Wavefunctions and the 1D and 2D Particle in a Box 209
15.2 Spherical Harmonics, Hydrogen Atom Wavefunctions, and Hydrogen Atomic Orbitals 213
15.3 Atomic Energy Levels and Atomic Emission Spectroscopy 217
15.4 Molecular Energy Levels, Spectroscopy, and Structural Methods 219
15.4.1 Electronic Energy Levels and UV-vis Absorption Spectroscopy 219
15.4.2 Vibrational Energy Levels and Infrared Spectroscopy 221
15.4.3 Rotational Energy Levels and Microwave Spectroscopy 225
15.4.4 Nuclear Magnetic Resonance Spectroscopy 226
15.4.5 X-ray Diffraction 228
15.5 Mass Spectrometry 230
Further Reading 230
Epilogue 231
Appendix 233
List of Constants 233
List of Abbreviations and Symbols 234
Index 235
