MODERN CHEMISTRY AND ITS WONDERS
UNIT I Introduction to the Study of Modern Chemistry xxviii con t e n t s 1 The Atom in Modern Chemistry 2 11 The Nature of Modern Chemistry 2 12 Elements: The Building Blocks of Matter 5 13 Indirect Evidence for the Existence of Atoms: Laws of Chemical Combination 8 14 The Physical Structure of Atoms 15 15 Mass Spectrometry, Isotopes, and the Measurement of Relative Mass 23 16 The Mole: Counting Molecules by Weighing 26 2 Chemical Formulas, Equations, and Reaction Yields 35 21 Empirical and Molecular Formulas 36 22 Chemical Formula and Percentage Composition 37 23 Writing Balanced Chemical Equations 39 24 Mass Relationships in Chemical Reactions 43 25 Limiting Reactant and Percentage Yield 45 UNIT II Chemical Bonding and Molecular Structure 50 3 Atomic Shells and Classical Models of Chemical Bonding 52 31 Representations of Molecules 54 32 The Periodic Table 59 33 Forces and Potential Energy in Atoms 62 34 Ionization Energies, the Shell Model of the Atom, and Shielding 70 35 Electron Affinity 77 36 Electronegativity: The Tendency of Atoms to Attract Electrons in Molecules 79 37 Forces and Potential Energy in Molecules: Formation of Chemical Bonds 83 38 Ionic Bonding 85 39 Covalent and Polar Covalent Bonding 90 310 Electron Pair Bonds and Lewis Diagrams for Molecules 99 311 The Shapes of Molecules: Valence Shell Electron-Pair Repulsion Theory 106 312 Oxidation Numbers 112 313 Inorganic Nomenclature 114 4 Introduction to Quantum Mechanics 124 41 Preliminaries: Wave Motion and Light 126 42 Evidence for Energy Quantization in Atoms 130 43 The Bohr Model: Predicting Discrete Energy Levels in Atoms 139 44 Evidence for Wave–Particle Duality 142 45 The Schrödinger Equation 154 46 Quantum Mechanics of Particle-in-a-Box Models 158 47 A DEEPER LOOK Wave Functions for Particles in Two- and Three-Dimensional Boxes 166 5 Quantum Mechanics and Atomic Structure 177 51 The Hydrogen Atom 178 52 Shell Model for Many-Electron Atoms 196 53 Aufbau Principle and Electron Configurations 201 54 Shells and the Periodic Table: Photoelectron Spectroscopy 206 55 Periodic Properties and Electronic Structure 209 6 Quantum Mechanics and Molecular Structure 219 61 Quantum Picture of the Chemical Bond 221 62 Exact Molecular Orbitals for the Simplest Molecule: H12 225 63 Molecular Orbital Theory and the Linear Combination of Atomic Orbitals Approximation for H12 231 64 Homonuclear Diatomic Molecules: First-Period Atoms 235 65 Homonuclear Diatomic Molecules: Second- Period Atoms 237 66 Heteronuclear Diatomic Molecules 246 67 Summary Comments for the LCAO Method and Diatomic Molecules 252 68 Valence Bond Theory and the Electron Pair Bond 253 69 Orbital Hybridization for Polyatomic Molecules 259 610 Predicting Molecular Structures and Shapes 266 611 Using the LCAO and Valence Bond Methods Together 270 612 Summary and Comparison of the LCAO and Valence Bond Methods 275 613 A DEEPER LOOK Properties of the Exact Molecular Orbitals for H12 278 7 Bonding in Organic Molecules 289 71 Petroleum Refining and the Hydrocarbons 290 72 The Alkanes 291 73 The Alkenes and Alkynes 297 74 Aromatic Hydrocarbons 300 75 Fullerenes 303 76 Functional Groups and Organic Reactions 304 77 Pesticides and Pharmaceuticals 316 8 Bonding in Transition Metal Compounds and Coordination Complexes 325 81 Chemistry of the Transition Metals 326 82 Introduction to Coordination Chemistry 333 83 Structures of Coordination Complexes 339 84 Crystal Field Theory: Optical and Magnetic Properties 345 85 Optical Properties and the Spectrochemical Series 352 86 Bonding in Coordination Complexes 355 UNIT III Kinetic Molecular Description of the States of Matter 368 9 The Gaseous State 370 91 The Chemistry of Gases 371 92 Pressure and Temperature of Gases 373 93 The Ideal Gas Law 380 94 Mixtures of Gases 383 95 The Kinetic Theory of Gases 385 96 Real Gases: Intermolecular Forces 394 97 A DEEPER LOOK Molecular Collisions and Rate Processes 399 10 Solids, Liquids, and Phase Transitions 414 101 Bulk Properties of Gases, Liquids, and Solids: Molecular Interpretation 415 102 Intermolecular Forces: Origins in Molecular Structure 421 103 Intermolecular Forces in Liquids 426 104 Phase Equilibrium 430 105 Phase Transitions 432 106 Phase Diagrams 434 11 Solutions 441 111 Composition of Solutions 442 112 Nature of Dissolved Species 445 113 Reaction Stoichiometry in Solutions: Acid–Base Titrations 448 114 Reaction Stoichiometry in Solutions: Oxidation– Reduction Titrations 452 115 Phase Equilibrium in Solutions: Nonvolatile Solutes 459 116 Phase Equilibrium in Solutions: Volatile Solutes 467 117 Colloidal Suspensions 472 UNIT IV Equilibrium in Chemical Reactions 478 12 Thermodynamic Processes and Thermochemistry 480 121 Systems, States, and Processes 482 122 The First Law of Thermodynamics: Internal Energy, Work, and Heat 485 123 Heat Capacity, Calorimetry, and Enthalpy 492 124 The First Law and Ideal Gas Processes 495 125 Molecular Contributions to Internal Energy and Heat Capacity 498 126 Thermochemistry 504 127 Reversible Processes in Ideal Gases 512 128 A DEEPER LOOK Distribution of Energy among Molecules 517 13 Spontaneous Processes and Thermodynamic Equilibrium 526 131 The Nature of Spontaneous Processes 527 132 Entropy and Spontaneity: A Molecular Statistical Interpretation 530 133 Entropy and Heat: Macroscopic Basis of the Second Law of Thermodynamics 535 134 Entropy Changes in Reversible Processes 537 135 Entropy Changes and Spontaneity 541 136 The Third Law of Thermodynamics 544 137 The Gibbs Free Energy 547 138 A DEEPER LOOK Carnot Cycles, Efficiency, and Entropy 552 14 Chemical Equilibrium 563 141 The Nature of Chemical Equilibrium 564 142 The Empirical Law of Mass Action 568 143 Thermodynamic Description of the Equilibrium State 574 144 The Law of Mass Action for Related and Simultaneous Equilibria 581 145 Equilibrium Calculations for Gas-Phase and Heterogeneous Reactions 583 146 The Direction of Change in Chemical Reactions: Empirical Description 589 147 The Direction of Change in Chemical Reactions: Thermodynamic Explanation 598 148 Distribution of a Single Species between Immiscible Phases: Extraction and Separation Processes 602 15 Acid–Base Equilibria 611 151 Classifications of Acids and Bases 612 152 Properties of Acids and Bases in Aqueous Solutions: The Brønsted–Lowry Scheme 619 153 Acid and Base Strength 622 154 Equilibria Involving Weak Acids and Bases 630 155 Buffer Solutions 635 156 Acid–Base Titration Curves 640 157 Polyprotic Acids 645 158 Organic Acids and Bases: Structure and Reactivity 649 159 A DEEPER LOOK Exact Treatment of Acid–Base Equilibria 655 16 Solubility and Precipitation Equilibria 667 161 The Nature of Solubility Equilibria 668 162 Ionic Equilibria between Solids and Solutions 671 163 Precipitation and the Solubility Product 674 164 The Effects of pH on Solubility 678 165 Complex Ions and Solubility 680 166 A DEEPER LOOK Selective Precipitation of Ions 685 17 Electrochemistry 693 171 Electrochemical Cells 694 172 Cell Potentials and the Gibbs Free Energy 700 173 Concentration Effects and the Nernst Equation 708 174 Molecular Electrochemistry 715 175 Batteries and Fuel Cells 728 176 Corrosion and Corrosion Prevention 736 177 Electrometallurgy 738 178 A DEEPER LOOK Electrolysis of Water and Aqueous Solutions 744 UNIT V Rates of Chemical and Physical Processes 752 18 Chemical Kinetics 754 181 Rates of Chemical Reactions 755 182 Rate Laws 758 183 Reaction Mechanisms 766 184 Reaction Mechanisms and Rate 769 185 Effect of Temperature on Reaction Rates 775 186 Molecular Theories of Elementary Reactions 780 187 Reactions in Solution 792 188 Catalysis 794 19 Nuclear Chemistry 807 191 Mass–Energy Relationships in Nuclei 808 192 Nuclear Decay Processes 812 193 Kinetics of Radioactive Decay 818 194 Radiation in Biology and Medicine 822 195 Nuclear Fission 827 196 Nuclear Fusion and Nucleosynthesis 832 20 Molecular Spectroscopy and Photochemistry 839 201 Introduction to Molecular Spectroscopy 840 202 Experimental Methods in Molecular Spectroscopy 844 203 Rotational and Vibrational Spectroscopy 850 204 Nuclear Magnetic Resonance Spectroscopy 869 205 Electronic Spectroscopy and Excited State Relaxation Processes 873 206 Introduction to Atmospheric Chemistry 880 207 Photosynthesis 889 208 A DEEPER LOOK Lasers 895 UNIT VI Materials 902 21 Structure and Bonding in Solids 904 211 Crystal Symmetry and the Unit Cell 905 212 Crystal Structure 911 213 Cohesion in Solids 916 214 Defects and Amorphous Solids 923 215 A DEEPER LOOK Lattice Energies of Crystals 927 22 Inorganic Materials 935 221 Minerals: Naturally Occurring Inorganic Materials 936 222 Properties of Ceramics 941 223 Silicate Ceramics 943 224 Nonsilicate Ceramics 948 225 Electrical Conduction in Materials 953 226 Band Theory of Conduction 957 227 Semiconductors 959 228 Pigments and Phosphors: Optical Displays 962 23 Polymeric Materials and Soft Condensed Matter 967 231 Polymerization Reactions for Synthetic Polymers 968 232 Applications for Synthetic Polymers 972 233 Liquid Crystals 979 234 Natural Polymers 982 Appendices A1 A Scientific Notation and Experimental Error A2 B SI Units, Unit Conversions, and Physics for General Chemistry A8 C Mathematics for General Chemistry A21 D Standard Chemical Thermodynamic Properties A37 E Standard Reduction Potentials at 25°C A45 F Physical Properties of the Elements A47 G Answers to Odd-Numbered Problems A56