Chemistry

Chapter 1 Elements and Compounds 1 1.1 Chemistry: A Definition, 2 1.2 Elements, Compounds, and Mixtures, 3 1.3 Atomic Symbols, 4 1.4 Chemical Formulas, 5 1.5 Evidence for the Existence of Atoms, 6 1.6 The Role of Measurement in Chemistry, 7 1.7 The Structure of Atoms, 9 1.8 Atomic Number and Mass Number, 11 1.9 Isotopes, 12 1.10 The Difference Between Atoms and Ions, 14 1.11 Polyatomic Ions, 16 1.12 The Periodic Table, 16 1.13 The Macroscopic, Atomic and Symbolic Worlds of Chemistry, 18 1.14 The Mass of an Atom, 19 1.15 Chemical Reactions and the Law of Conservation of Atoms, 21 1.16 Chemical Equations as a Representation of Chemical Reactions, 21 1.17 Balancing Chemical Equations, 22 Chapter 2 The Mole: The Link between the Macroscopic and the Atomic Worlds of Chemistry 31 2.1 The Mole as the Bridge Between the Macroscopic and Atomic Scales, 32 2.2 The Mole as a Collection of Atoms, 33 2.3 Converting Grams into Moles and Number of Atoms, 35 2.4 The Mole as a Collection of Molecules, 37 2.5 Percent by Mass, 40 2.6 Determining the Formula of a Compound, 41 2.7 Two Views of Chemical Equations: Molecules Versus Moles, 45 2.8 Mole Ratios and Chemical Equations, 46 2.9 Stoichiometry, 48 2.10 The Stoichiometry of the Breathalyzer, 49 2.11 The Nuts and Bolts of Limiting Reagents, 50 2.12 Density, 53 2.13 Solute, Solvent, and Solution, 54 2.14 Concentration, 55 2.15 Molarity as a Way to Count Particles in a Solution, 56 2.16 Dilution Calculations, 58 2.17 Solution Stoichiometry, 59 Problems, 63 Chapter 3 The Structure of the Atom 71 3.1 Rutherford’s Model of the Atom, 72 3.2 Particles and Waves, 73 3.3 Light and Other Forms of Electromagnetic Radiation, 74 3.4 Atomic Spectra, 76 3.5 The Wave-Packet Model of Electromagnetic Radiation, 77 3.6 The Bohr Model of the Atom, 79 3.7 The Energy States of the Hydrogen Atom, 80 3.8 Electromagnetic Radiation and Color, 82 3.9 The First Ionization Energy, 83 3.10 The Shell Model, 85 3.11 The Shell Model and the Periodic Table, 87 3.12 Photoelectron Spectroscopy and the Structure of Atoms, 88 3.13 Electron Configurations from Photoelectron Spectroscopy, 89 3.14 Allowed Combinations of Quantum Numbers, 95 3.15 Shells and Subshells of Orbitals, 96 3.16 Orbitals and the Pauli Exclusion Principle, 98 3.17 Predicting Electron Configurations, 100 3.18 Electron Configurations and the Periodic Table, 101 3.19 Electron Configurations and Hund’s Rules, 102 3.20 The Sizes of Atoms: Metallic Radii, 104 3.21 The Sizes of Atoms: Covalent Radii, 104 3.22 The Relative Sizes of Atoms and Their Ions, 105 3.23 Patterns in Ionic Radii, 107 3.24 Second, Third, Fourth, and Higher Ionization Energies, 108 3.25 Average Valence Electron Energy (AVEE), 110 3.26 AVEE and Metallicity, 111 Problems, 113 Chapter 4 The Covalent Bond 123 4.1 Valence Electrons, 124 4.2 The Covalent Bond, 125 4.3 How Does the Sharing of Electrons Bond Atoms?, 126 4.4 Using Lewis Structures to Understand the Formation of Bonds, 127 4.5 Drawing Skeleton Structures, 128 4.6 A Step-by-Step Approach to Writing Lewis Structures, 129 4.7 Molecules That Don’t Seem to Satisfy the Octet Rule, 131 4.8 Bond Lengths, 134 4.9 Resonance Hybrids, 136 4.10 Electronegativity, 139 4.11 Partial Charge, 141 4.12 Formal Charge, 142 4.13 The Shapes of Molecules, 145 4.14 Predicting the Shapes of Molecules (The Electron Domain Model), 148 4.15 The Role of Nonbonding Electrons in the ED Model, 151 4.16 Bond Angles, 154 4.17 The Difference Between Polar Bonds and Polar Molecules, 156 Problems, 158 Special Topics 4A.1 Valence Bond Theory, 165 4A.2 Hybrid Atomic Orbitals, 166 4A.3 Molecules with Double and Triple Bonds, 169 4A.4 Molecular Orbital Theory, 170 Problems, 176 Chapter 5 Ionic and Metallic Bonds 177 5.1 Metals, Nonmetals, and Semimetals, 178 5.2 The Active Metals, 178 5.3 Main-Group Metals and Their Ions, 180 5.4 Main-Group Nonmetals and Their Ions, 181 5.5 Transition Metals and Their Ions, 184 5.6 Chemistry and Color, 184 5.7 Predicting the Formulas of Ionic Compounds, 185 5.8 Predicting the Products of Reactions That Produce Ionic Compounds, 186 5.9 Oxides, Peroxides, and Superoxides, 188 5.10 The Ionic Bond, 189 5.11 Structures of Ionic Compounds, 190 5.12 Metallic Bonds, 191 5.13 The Relationship among Ionic, Covalent, and Metallic Bonds, 192 5.14 Bond-Type Triangles, 197 5.15 Properties of Metallic, Covalent, and Ionic Compounds, 201 5.16 Oxidation Numbers, 201 5.17 Calculating Oxidation Numbers, 204 5.18 Oxidation–Reduction Reactions, 207 5.19 Nomenclature, 209 Problems, 213 Chapter 6 Gases 221 6.1 Temperature, 222 6.2 Temperature as a Property of Matter, 223 6.3 The States of Matter, 224 6.4 Elements or Compounds That Are Gases at Room Temperature, 225 6.5 The Properties of Gases, 226 6.6 Pressure versus Force, 227 6.7 Atmospheric Pressure, 229 6.8 Boyle’s Law, 231 6.9 Amontons’ Law, 232 6.10 Charles’ Law, 233 6.11 Gay-Lussac’s Law, 234 6.12 Avogadro’s Hypothesis, 234 6.13 The Ideal Gas Equation, 236 6.14 Dalton’s Law of Partial Pressures, 237 6.15 Ideal Gas Calculations: Part I, 240 6.16 Ideal Gas Calculations: Part II, 244 6.17 The Kinetic Molecular Theory, 246 6.18 How the Kinetic Molecular Theory Explains the Gas Laws, 247 6.19 Graham’s Laws of Diffusion and Effusion, 250 Problems, 252 Special Topics 6A.1 Deviations from Ideal Gas Law Behavior: The van der Waals Equation, 259 6A.2 Analysis of the van der Waals Constants, 262 Problems, 263 Chapter 7 Making and Breaking of Bonds 264 7.1 Energy, 265 7.2 Heat, 268 7.3 Heat and the Kinetic Molecular Theory, 268 7.4 Specific Heat, 269 7.5 State Functions, 273 7.6 The First Law of Thermodynamics, 274 7.7 Work, 276 7.8 The Enthalpy of a System, 280 7.9 Enthalpies of Reaction, 282 7.10 Enthalpy as a State Function, 285 7.11 Standard-State Enthalpies of Reaction, 287 7.12 Calculating Enthalpies of Reaction, 288 7.13 Enthalpies of Atom Combination, 289 7.14 Using Enthalpies of Atom Combination to Probe Chemical Reactions, 296 7.15 Bond Length and the Enthalpy of Atom Combination, 299 7.16 Hess’s Law, 300 7.17 Enthalpies of Formation, 301 Problems, 305 Chapter 8 Liquids and Solutions 313 8.1 The Structure of Gases, Liquids, and Solids, 314 8.2 Intermolecular Forces, 316 8.3 Relative Strengths of Intermolecular Forces, 320 8.4 The Kinetic Theory of Liquids, 324 8.5 The Vapor Pressure of a Liquid, 325 8.6 Melting Point and Freezing Point, 328 8.7 Boiling Point, 330 8.8 Phase Diagrams, 332 8.9 Hydrogen Bonding and the Anomalous Properties of Water, 333 8.10 Solutions: Like Dissolves Like, 334 8.11 Hydrophilic and Hydrophobic Molecules, 337 8.12 Soaps, Detergents, and Dry-Cleaning Agents, 339 8.13 Why Do Some Solids Dissolve in Water?, 341 8.14 Solubility Equilibria, 344 8.15 Solubility Rules, 346 8.16 Net Ionic Equations, 347 Problems, 349 Special Topics 8A.1 Colligative Properties, 357 8A.2 Depression of the Partial Pressure of a Solvent, 358 8A.3 Boiling Point Elevation, 361 8A.4 Freezing Point Depression, 363 Problems, 365 Chapter 9 Solids 367 9.1 Types of Solids, 368 9.2 Molecular and Network Covalent Solids, 369 9.3 The Physical Properties of Molecular and Network Covalent Solids, 372 9.4 Metallic Solids, 373 9.5 Physical Properties That Result from the Structure of Metals, 374 9.6 The Structure of Metals, 375 9.7 Coordination Numbers and the Structures of Metals, 378 9.8 Unit Cells: The Simplest Repeating Unit in a Crystal, 379 9.9 Solid Solutions and Intermetallic Compounds, 380 9.10 Semimetals, 381 9.11 Ionic Solids, 382 9.12 The Search for New Materials, 385 9.13 Measuring the Distance Between Particles in a Unit Cell, 388 9.14 Determining the Unit Cell of a Crystal, 389 9.15 Calculating the Size of an Atom or Ion, 391 Problems, 392 Special Topics 9A.1 Defects, 397 9A.2 Metals, Semiconductors, and Insulators, 398 9A.3 Thermal Conductivity, 401 9A.4 Thermal Expansion, 402 9A.5 Glass and Other Ceramics, 403 Problems, 407 Chapter 10 The Connection Between Kinetics and Equilibrium 408 10.1 Reactions That Don’t Go to Completion, 409 10.2 Gas-Phase Reactions, 411 10.3 The Rate of a Chemical Reaction, 413 10.4 The Collision Theory Model of Gas-Phase Reactions, 415 10.5 Equilibrium Constant Expressions, 418 10.6 Reaction Quotients: A Way to Decide Whether a Reaction is at Equilibrium, 423 10.7 Changes in Concentration That Occur as a Reaction Comes to Equilibrium, 425 10.8 Hidden Assumptions That Make Equilibrium Calculations Easier, 430 10.9 What Do We Do When the Assumption Fails?, 434 10.10 The Effect of Temperature on an Equilibrium Constant, 436 10.11 Le Châtelier’s Principle, 437 10.12 Le Châtelier’s Principle and the Haber Process, 443 10.13 What Happens When a Solid Dissolves in Water?, 445 10.14 The Solubility Product Expression, 446 10.15 The Relationship Between Ksp and the Solubility of a Salt, 448 10.16 The Role of the Ion Product (Qsp) in Solubility Calculations, 451 10.17 The Common-Ion Effect, 453 Problems, 458 Chapter 11 Acids and Bases 468 11.1 Properties of Acids and Bases, 469 11.2 The Arrhenius Definition of Acids and Bases, 469 11.3 The Brønsted–Lowry Definition of Acids and Bases, 470 11.4 Conjugate Acid–Base Pairs, 472 11.5 The Role of Water in the Brønsted Model, 474 11.6 To What Extent Does Water Dissociate to Form Ions?, 475 11.7 pH as a Measure of the Concentration of the H3O+ Ion, 478 11.8 Relative Strengths of Acids and Bases, 481 11.9 Relative Strengths of Conjugate Acid–Base Pairs, 485 11.10 Relative Strengths of Different Acids and Bases, 486 11.11 Relationship of Structure to Relative Strengths of Acids and Bases, 490 11.12 Strong Acid pH Calculations, 494 11.13 Weak Acid pH Calculations, 494 11.14 Base pH Calculations, 500 11.15 Mixtures of Acids and Bases: Buffers, 504 11.16 Buffers and Buffer Capacity, 506 11.17 Buffers in the Body, 510 11.18 Acid–Base Reactions, 511 11.19 pH Titration Curves, 513 Problems, 520 Special Topics 11A.1 Diprotic Acids, 530 11A.2 Diprotic Bases, 534 11A.3 Compounds That Could Be Either Acids or Bases, 536 Problems, 539 Chapter 12 Oxidation–Reduction Reactions 540 12.1 Common Oxidation–Reduction Reactions, 541 12.2 Determining Oxidation Numbers, 542 12.3 Recognizing Oxidation–Reduction Reactions, 544 12.4 Voltaic Cells, 548 12.5 Standard Cell Potentials, 551 12.6 Oxidizing and Reducing Agents, 553 12.7 Relative Strengths of Oxidizing and Reducing Agents, 554 12.8 Batteries, 559 12.9 Electrochemical Cells at Nonstandard Conditions: The Nernst Equation, 563 12.10 Electrolysis and Faraday’s Law, 567 12.11 Electrolysis of Molten NaCl, 571 12.12 Electrolysis of Aqueous NaCl, 572 12.13 Electrolysis of Water, 574 12.14 The Hydrogen Economy, 575 Problems, 576 Special Topics 12.A1 Balancing Oxidation–Reduction Equations, 585 12.A2 Redox Reactions in Acidic Solutions, 585 12.A3 Redox Reactions in Basic Solutions, 589 12.A4 Molecular Redox Reactions, 590 Problems, 592 Chapter 13 Chemical Thermodynamics 594 13.1 Spontaneous Chemical and Physical Processes, 595 13.2 Entropy and Disorder, 596 13.3 Entropy and the Second Law of Thermodynamics, 597 13.4 Standard-State Entropies of Reaction, 600 13.5 The Third Law of Thermodynamics, 600 13.6 Calculating Entropy Changes for Chemical Reactions, 601 13.7 Gibbs Free Energy, 606 13.8 The Effect of Temperature on the Free Energy of a Reaction, 612 13.9 Beware of Oversimplifications, 613 13.10 Standard-State Free Energies of Reaction, 613 13.11 Equilibria Expressed in Partial Pressures, 615 13.12 Interpreting Standard-State Free Energy of Reaction Data, 619 13.13 The Relationship between Free Energy and Equilibrium Constants, 620 13.14 The Temperature Dependence of Equilibrium Constants, 626 13.15 Gibbs Free Energies of Formation and Absolute Entropies, 630 Problems, 632 Chapter 14 Kinetics 640 14.1 The Forces That Control a Chemical Reaction, 641 14.2 Chemical Kinetics, 642 14.3 Is the Rate of Reaction Constant?, 642 14.4 Instantaneous Rates of Reaction, 644 14.5 Rate Laws and Rate Constants, 645 14.6 The Rate Law Versus the Stoichiometry of a Reaction, 646 14.7 Order and Molecularity, 647 14.8 A Collision Theory Model of Chemical Reactions, 650 14.9 The Mechanisms of Chemical Reactions, 652 14.10 Zero-Order Reactions, 654 14.11 Determining the Order of a Reaction from Rates of Reaction, 655 14.12 The Integrated Form of Zero-, First-, and Second-Order Rate Laws, 658 14.13 Determining the Order of a Reaction with the Integrated Form of Rate Laws 663 14.14 Reactions That Are First-Order in Two Reactants, 666 14.15 The Activation Energy of Chemical Reactions, 667 14.16 Catalysts and the Rates of Chemical Reactions, 669 14.17 Determining the Activation Energy of a Reaction, 671 14.18 The Kinetics of Enzyme-Catalyzed Reactions, 673 Problems, 675 Special Topics 14A.1 Deriving the Integrated Rate Laws, 686 Chapter 15 Nuclear Chemistry 688 15.1 Radioactivity, 689 15.2 The Structure of the Atom, 690 15.3 Modes of Radioactive Decay, 692 15.4 Neutron-Rich Versus Neutron-Poor Nuclides, 694 15.5 Binding Energy Calculations, 697 15.6 The Kinetics of Radioactive Decay, 700 15.7 Dating by Radioactive Decay, 703 15.8 Ionizing Versus Nonionizing Radiation, 705 15.9 Biological Effects of Ionizing Radiation, 706 15.10 Natural Versus Induced Radioactivity, 709 15.11 Nuclear Fission, 713 15.12 Nuclear Fusion, 715 15.13 Nuclear Synthesis, 717 15.14 Nuclear Medicine, 719 Problems, 720 Chapter 16 Organic Chemistry 723 16.1 What Is an Organic Compound?, 724 16.2 The Saturated Hydrocarbons or Alkanes, 726 16.3 Rotation Around C—C Bonds, 729 16.4 The Nomenclature of Alkanes, 730 16.5 The Unsaturated Hydrocarbons: Alkenes and Alkynes, 733 16.6 Aromatic Hydrocarbons and Their Derivatives, 735 16.7 The Chemistry of Petroleum Products, 737 16.8 The Chemistry of Coal, 740 16.9 Functional Groups, 742 16.10 Oxidation-Reduction Reactions, 746 16.11 Alkyl Halides, 750 16.12 Alcohols and Ethers, 752 16.13 Aldehydes and Ketones, 755 16.14 Reactions at the Carbonyl Group, 757 16.15 Carboxylic Acids and Carboxylate Ions, 759 16.16 Esters, 761 16.17 Amines, Alkaloids, and Amides, 763 16.18 Alkene Stereoisomers, 765 16.19 Stereogenic Atoms, 768 16.20 Optical Activity, 771 Problems, 774 Appendix A A.1 Systems of Units A-2 The English Units of Measurement A-2 SI Units of Measurement A-3 Derived SI Units A-4 Non-SI Units A-4 Conversion Factors A-5 A.2 Uncertainty in Measurement A-6 Systematic and Random Errors A-6 Accuracy and Precision A-7 A.3 Significant figures A-8 Addition and Subtraction with Significant Figures A-9 Multiplication and Division with Significant Figures A-10 Rounding Off A-10 A.4 Scientific Notation A-10 A.5 The Graphical Treatment of Data A-12 A.6 Significant Figures and Unit Conversion Worksheet A-15 Significant Figures A-15 Counting Significant Figures in a Measurement A-15 Measurements versus Definitions A-18 Unit Conversions A-19 Appendix B Table B.1 Values of Selected Fundamental Constants B-2 Table B.2 Selected Conversion Factors B-2 Table B.3 The Vapor Pressure of Water B-3 Table B.4 Radii of Atoms and Ions B-4 Table B.5 Ionization Energies B-6 Table B.6 Electron Affinities B-8 Table B.7 Electronegativities B-9 Table B.8 Acid-Dissociation Equilibrium Constants B-10 Table B.9 Base-Ionization Equilibrium Constants B-11 Table B.10 Solubility Product Equilibrium Constants B-12 Table B.11 Complex Formation Equilibrium Constants B-13 Table B.12 Standard Reduction Potentials B-14 Table B.13 Standard-State Enthalpies, Free Energies and Entropies of Atom Combination B- 17 Table B.14 Bond-Dissociation Enthalpies B-25 Table B.15 Electron Configuration of the First 86 Elements B-26 Table B.16 Standard-State Enthalpy of Formation, Free Energy of Formation and Absolute Entropy Data B-28 Appendix C Answers to Selected Problems C-1 Appendix D Answers to Checkpoints D-1 Photo Credits P-1 Index I-1 Modules (available at www.wiley.com/college/spencer) Module 1 Chemistry of the Nonmetals Module 2 Transition Metal Chemistry Module 3 Complex Ion Equilibria Module 4 Organic Chemistry: Structure and Nomenclature of Hydrocarbons Module 5 Organic Chemistry: Functional Groups Module 6 Organic Chemistry: Reaction Mechanisms Module 7 Polymer Chemistry Module 8 Biochemistry Module 9 Chemical Analysis