Chemistry & chemical reactivity 7th ed., enhanced ed

PART 1 CONCEPTS OF CHEMISTRY 1 Basic Concepts of Chemistry | 1 Sport Drinks | 1 1.1 Chemistry and Its Methods | 3 Hypotheses, Laws, and Theories | 4 Goals of Science | 6 Dilemmas and Integrity in Science | 6 Chemical Perspectives: Moral Issues in Science | 7 1.2 Classifying Matter | 7 States of Matter and Kinetic-Molecular Theory | 7 Matter at the Macroscopic and Particulate Levels | 9 Pure Substances | 10 Mixtures: Homogeneous and Heterogeneous | 11 1.3 Elements and Atoms | 12 1.4 Compounds and Molecules | 13 1.5 Physical Properties | 14 Chemical Perspectives: Thermophilic Bacteria | 16 Extensive and Intensive Properties | 16 1.6 Physical and Chemical Changes | 17 Case Study: Ancient and Modern Hair Coloring | 18 CHAPTER GOALS REVISITED | 20 KEY EQUATIONS | 20 STUDY QUESTIONS | 20 Let’s Review: The Tools of Quantitative Chemistry | 24 Copper | 24 1 Units of Measurement | 25 Temperature Scales | 26 Length, Volume, and Mass | 27 This text is available in these student versions: • Complete text ISBN 978-0-495-38703-9 • Volume 1 (Chapters 1–11) ISBN 978-0-495-38711-4 • Volume 2 (Chapters 11–23) ISBN 978-0-495-38712-1 • Complete Enhanced Edition ISBN 978-0-495-39029-9 Contents 2 Making Measurements: Precision, Accuracy, Experimental Error, and Standard Deviation | 30 Experimental Error | 30 Standard Deviation | 31 3 Mathematics of Chemistry | 32 Exponential or Scientifi c Notation | 32 Signifi cant Figures | 35 Problem Solving by Dimensional Analysis | 38 Graphing | 39 Case Study: Out of Gas! | 41 Problem Solving and Chemical Arithmetic | 42 STUDY QUESTIONS | 43 2 Atoms, Molecules, and Ions | 50 The Periodic Table, the Central Icon of Chemistry | 50 2.1 Atomic Structure—Protons, Electrons, and Neutrons | 51 2.2 Atomic Number and Atomic Mass | 51 Atomic Number | 51 Atomic Weight and the Atomic Mass Unit | 52 Mass Number | 52 2.3 Isotopes | 53 Isotope Abundance | 54 Determining Atomic Mass and Isotope Abundance | 54 2.4 Atomic Weight | 55 Case Study: Catching Cheaters with Isotopes | 58 2.5 The Periodic Table | 58 Developing the Periodic Table | 58 Historical Perspectives: The Story of the Periodic Table | 59 Features of the Periodic Table | 60 A Brief Overview of the Periodic Table and the Chemical Elements | 62 2.6 Molecules, Compounds, and Formulas | 67 Formulas | 68 Molecular Models | 69 v The interchapters found in the standard edition are available on this book’s companion website at www.cengage.com/chemistry/kotz vi | Contents 2.7 Ionic Compounds: Formulas, Names, and Properties | 70 Ions | 71 Formulas of Ionic Compounds | 74 Names of Ions | 76 Names of Ionic Compounds | 77 Properties of Ionic Compounds | 78 2.8 Molecular Compounds: Formulas and Names | 80 2.9 Atoms, Molecules, and the Mole | 82 Historical Perspectives: Amedeo Avogadro and His Number | 83 Atoms and Molar Mass | 83 Molecules, Compounds, and Molar Mass | 85 2.10 Describing Compound Formulas | 88 Percent Composition | 88 Empirical and Molecular Formulas from Percent Composition | 90 Determining a Formula from Mass Data | 93 A Closer Look: Mass Spectrometry, Molar Mass, and Isotopes | 95 2.11 Hydrated Compounds | 96 Case Study: What’s in Those French Fries? | 96 CHAPTER GOALS REVISITED | 98 KEY EQUATIONS | 100 STUDY QUESTIONS | 100 3 Chemical Reactions | 112 Black Smokers | 112 3.1 Introduction to Chemical Equations | 113 Historical Perspectives: Antoine Laurent Lavoisier, 1743– 1794 | 114 3.2 Balancing Chemical Equations | 116 3.3 Introduction to Chemical Equilibrium | 118 3.4 Chemical Reactions in Aqueous Solution | 121 3.5 Ions and Molecules in Aqueous Solution | 122 Solubility of Ionic Compounds in Water | 125 3.6 Precipitation Reactions | 127 Predicting the Outcome of a Precipitation Reaction | 127 Net Ionic Equations | 129 3.7 Acids and Bases | 131 Acids and Bases: The Arrhenius Defi nition | 132 Acids and Bases: The Brønsted-Lowry Defi nition | 133 A Closer Look: The Hydronium Ion—The H+ Ion in Water | 134 Chemical Perspectives: Sulfuric Acid | 135 Reactions of Acids and Bases | 136 Oxides of Nonmetals and Metals | 138 3.8 Gas-Forming Reactions | 139 3.9 Oxidation-Reduction Reactions | 141 Oxidation-Reduction Reactions and Electron Transfer | 142 Oxidation Numbers | 144 A Closer Look: Are Oxidation Numbers “Real”? | 144 Recognizing Oxidation-Reduction Reactions | 146 Case Study: Killing Bacteria with Silver | 148 3.10 Classifying Reactions in Aqueous Solution | 149 CHAPTER GOALS REVISITED | 151 STUDY QUESTIONS | 152 4 Stoichiometry: Quantitative Information About Chemical Reactions | 158 The Chemistry of a Sparkler | 158 4.1 Mass Relationships in Chemical Reactions: Stoichiometry | 159 4.2 Reactions in Which One Reactant Is Present in Limited Supply | 163 A Stoichiometry Calculation with a Limiting Reactant | 163 4.3 Percent Yield | 168 4.4 Chemical Equations and Chemical Analysis | 169 Quantitative Analysis of a Mixture | 169 Determining the Formula of a Compound by Combustion | 171 4.5 Measuring Concentrations of Compounds in Solution | 174 Solution Concentration: Molarity | 174 Preparing Solutions of Known Concentration | 177 4.6 pH, a Concentration Scale for Acids and Bases | 179 A Closer Look: Serial Dilutions | 180 4.7 Stoichiometry of Reactions in Aqueous Solution | 182 Solution Stoichiometry | 182 Titration: A Method of Chemical Analysis | 183 Case Study: How Much Salt Is There in Seawater? | 186 Standardizing an Acid or Base | 186 Determining Molar Mass by Titration | 187 Titrations Using Oxidation-Reduction Reactions | 188 Case Study: Forensic Chemistry: Titrations and Food Tampering | 188 4.8 Spectrophotometry, Another Method of Analysis | 189 Transmittance, Absorbance, and the Beer–Lambert Law | 190 Spectrophotometric Analysis | 192 CHAPTER GOALS REVISITED | 194 KEY EQUATIONS | 195 STUDY QUESTIONS | 195 Contents | vii 5 Principles of Chemical Reactivity: Energy and Chemical Reactions | 208 A Hot Air Balloon | 208 5.1 Energy: Some Basic Principles | 209 Conservation of Energy | 211 Temperature and Heat | 211 Systems and Surroundings | 212 Directionality and Extent of Transfer of Heat: Thermal Equilibrium | 212 A Closer Look: What Is Heat? | 213 Energy Units | 214 Chemical Perspectives: Food and Calories | 215 5.2 Specifi c Heat Capacity: Heating and Cooling | 215 Quantitative Aspects of Energy Transferred as Heat | 217 5.3 Energy and Changes of State | 219 Case Study: Abba’s Refrigerator | 222 5.4 The First Law of Thermodynamics | 222 Enthalpy | 225 A Closer Look: P–V Work | 225 State Functions | 226 5.5 Enthalpy Changes for Chemical Reactions | 227 5.6 Calorimetry | 229 Constant Pressure Calorimetry, Measuring H | 229 Constant Volume Calorimetry, Measuring U | 231 5.7 Enthalpy Calculations | 233 Hess’s Law | 233 Energy Level Diagrams | 234 Standard Enthalpies of Formation | 236 Enthalpy Change for a Reaction | 237 A Closer Look: Hess’s Law and Equation 5.6 | 238 5.8 Product- or Reactant-Favored Reactions and Thermodynamics | 239 Case Study: The Fuel Controversy: Alcohol and Gasoline | 240 CHAPTER GOALS REVISITED | 241 KEY EQUATIONS | 241 STUDY QUESTIONS | 242 Let’s Review Chapters 1–5 | 254 The Purpose of Let’s Review | 254 Preparing for an Examination | 254 Key Points to Know | 255 Examination Preparation Questions | 255 Answers and Solutions to Examination Preparation Questions | 261 PART 2 ATOMS AND MOLECULES 6 The Structure of Atoms | 268 Aurora Borealis | 268 6.1 Electromagnetic Radiation | 269 6.2 Quantization: Planck, Einstein, Energy, and Photons | 271 Planck’s Equation | 271 Einstein and the Photoelectric Effect | 273 Energy and Chemistry: Using Planck’s Equation | 273 6.3 Atomic Line Spectra and Niels Bohr | 275 The Bohr Model of the Hydrogen Atom | 276 The Bohr Theory and the Spectra of Excited Atoms | 278 Case Study: What Makes the Colors in Fireworks? | 281 6.4 Particle–Wave Duality: Prelude to Quantum Mechanics | 282 6.5 The Modern View of Electronic Structure: Wave or Quantum Mechanics | 283 Quantum Numbers and Orbitals | 285 Shells and Subshells | 286 6.6 The Shapes of Atomic Orbitals | 287 s Orbitals | 287 A Closer Look: H Atom Orbital Shapes—Wave Functions and Nodes | 289 p Orbitals | 290 d Orbitals | 291 f Orbitals | 291 6.7 One More Electron Property: Electron Spin | 291 The Electron Spin Quantum Number, ms | 291 A Closer Look: Paramagnetism and Ferromagnetism | 292 Diamagnetism and Paramagnetism | 293 Chemical Perspectives: Quantized Spins and MRI | 294 CHAPTER GOALS REVISITED | 295 KEY EQUATIONS | 296 STUDY QUESTIONS | 297 7 The Structure of Atoms and Periodic Trends | 304 The Chromium-Bearing Mineral Crocoite, PbCrO4 | 304 7.1 The Pauli Exclusion Principle | 305 7.2 Atomic Subshell Energies and Electron Assignments | 306 Order of Subshell Energies and Assignments | 307 Effective Nuclear Charge, Z * | 308 viii | Contents 7.3 Electron Confi gurations of Atoms | 309 Electron Confi gurations of the Main Group Elements | 309 Elements of Period 3 | 313 Electron Confi gurations of the Transition Elements | 315 7.4 Electron Confi gurations of Ions | 316 A Closer Look: Questions About Transition Element Electron Confi gurations | 317 7.5 Atomic Properties and Periodic Trends | 319 Atomic Size | 319 Ionization Energy | 321 Electron Affi nity | 324 Trends in Ion Sizes | 326 Case Study: Metals in Biochemistry and Medicine | 327 7.6 Periodic Trends and Chemical Properties | 328 CHAPTER GOALS REVISITED | 331 STUDY QUESTIONS | 332 INTERCHAPTER Milestones in the Development of Chemistry and the Modern View of Atoms and Molecules | 338 Greek Philosophers and Medieval Alchemists | 339 Chemists of the 18th–19th Centuries | 340 Atomic Structure—Remarkable Discoveries—1890s and Beyond | 342 Historical Perspectives: 20th-Century Giants of Science | 346 The Nature of the Chemical Bond | 347 SUGGESTED READINGS | 347 STUDY QUESTIONS | 347 8 Bonding and Molecular Structure | 348 Chemical Bonding in DNA | 348 8.1 Chemical Bond Formation | 349 8.2 Covalent Bonding and Lewis Structures | 350 Valence Electrons and Lewis Symbols for Atoms | 350 Lewis Electron Dot Structures and the Octet Rule | 352 Drawing Lewis Electron Dot Structures | 353 Predicting Lewis Structures | 355 8.3 Atom Formal Charges in Covalent Molecules and Ions | 359 A Closer Look: Comparing Formal Charge and Oxidation Number | 360 8.4 Resonance | 361 8.5 Exceptions to the Octet Rule | 364 Compounds in Which an Atom Has Fewer Than Eight Valence Electrons | 364 Compounds in Which an Atom Has More Than Eight Valence Electrons | 364 Molecules with an Odd Number of Electrons | 366 Case Study: The Importance of an Odd-Electron Molecule, NO | 367 8.6 Molecular Shapes | 367 Central Atoms Surrounded Only by Single-Bond Pairs | 368 Central Atoms with Single-Bond Pairs and Lone Pairs | 370 Multiple Bonds and Molecular Geometry | 373 8.7 Bond Polarity and Electronegativity | 375 Charge Distribution: Combining Formal Charge and Electronegativity | 377 A Closer Look: Electronegativity | 378 8.8 Bond and Molecular Polarity | 380 A Closer Look: Visualizing Charge Distributions and Molecular Polarity—Electrostatic Potential Surfaces and Partial Charge | 382 8.9 Bond Properties: Order, Length, Energy | 386 Bond Order | 386 Bond Length | 387 Bond Dissociation Enthalpy | 388 Historical Perspectives: DNA—Watson, Crick, and Franklin | 392 8.10 DNA, Revisited | 392 CHAPTER GOALS REVISITED | 393 KEY EQUATIONS | 395 STUDY QUESTIONS | 395 9 Bonding and Molecular Structure: Orbital Hybridization and Molecular Orbitals | 404 The Chemistry of the Noble Gases | 404 9.1 Orbitals and Theories of Chemical Bonding | 405 9.2 Valence Bond Theory | 406 The Orbital Overlap Model of Bonding | 406 Hybridization of Atomic Orbitals | 408 Multiple Bonds | 416 Benzene: A Special Case of  Bonding | 421 9.3 Molecular Orbital Theory | 422 Principles of Molecular Orbital Theory | 422 A Closer Look: Molecular Orbitals for Compounds Formed from p-Block Elements | 429 Electron Confi gurations for Heteronuclear Diatomic Molecules | 429 Case Study: Two Chemical Bonding Mysteries | 430 Resonance and MO Theory | 431 CHAPTER GOALS REVISITED | 433 KEY EQUATIONS | 433 STUDY QUESTIONS | 434 Contents | ix 10 Carbon: More Than Just Another Element | 442 Camphor, an “Aromatic” Molecule | 442 10.1 Why Carbon? | 443 Structural Diversity | 443 Isomers | 444 A Closer Look: Writing Formulas and Drawing Structures | 445 Stability of Carbon Compounds | 446 Chemical Perspectives: Chirality and Elephants | 447 10.2 Hydrocarbons | 447 Alkanes | 448 A Closer Look: Flexible Molecules | 453 Alkenes and Alkynes | 453 Aromatic Compounds | 458 A Closer Look: Petroleum Chemistry | 461 10.3 Alcohols, Ethers, and Amines | 461 Alcohols and Ethers | 462 Properties of Alcohols and Ethers | 464 Amines | 466 Historical Perspectives: Mauveine | 467 10.4 Compounds with a Carbonyl Group | 468 Aldehydes and Ketones | 469 Carboxylic Acids | 471 Esters | 472 A Closer Look: Glucose and Sugars | 473 Amides | 475 A Closer Look: Fats and Oils | 476 10.5 Polymers | 478 Classifying Polymers | 478 Case Study: Biodiesel—A Fuel for the Future? | 479 Addition Polymers | 480 Condensation Polymers | 484 Chemical Perspectives: Super Diapers | 487 CHAPTER GOALS REVISITED | 488 STUDY QUESTIONS | 488 Let’s Review Chapters 6–10 | 496 The Purpose of Let’s Review | 496 Preparing for an Examination | 496 Key Points to Know | 497 Examination Preparation Questions | 497 Answers and Solutions to Examination Preparation Questions | 506 PART 3 STATES OF MATTER 11 Gases and Their Properties | 514 The Atmosphere and Altitude Sickness | 514 11.1 Gas Pressure | 516 A Closer Look: Measuring Gas Pressure | 517 11.2 Gas Laws: The Experimental Basis | 517 Boyle’s Law: The Compressibility of Gases | 517 The Effect of Temperature on Gas Volume: Charles’s Law | 519 Combining Boyle’s and Charles’s Laws: The General Gas Law | 521 Avogadro’s Hypothesis | 522 11.3 The Ideal Gas Law | 524 The Density of Gases | 525 Calculating the Molar Mass of a Gas from P, V, and T Data | 526 11.4 Gas Laws and Chemical Reactions | 527 11.5 Gas Mixtures and Partial Pressures | 530 11.6 The Kinetic-Molecular Theory of Gases | 532 Historical Perspectives: Studies on Gases: Robert Boyle and Jacques Charles | 533 Molecular Speed and Kinetic Energy | 533 Chemical Perspectives: The Earth’s Atmosphere | 534 Kinetic-Molecular Theory and the Gas Laws | 537 11.7 Diffusion and Effusion | 538 11.8 Some Applications of the Gas Laws and Kinetic- Molecular Theory | 540 Separating Isotopes | 540 Deep Sea Diving | 540 Case Study: You Stink! | 541 11.9 Nonideal Behavior: Real Gases | 542 CHAPTER GOALS REVISITED | 544 KEY EQUATIONS | 544 STUDY QUESTIONS | 546 12 Intermolecular Forces and Liquids | 554 Antarctica Scene—Icebergs, Penguins, Snow, Ice, and Fog | 554 12.1 States of Matter and Intermolecular Forces | 555 12.2 Intermolecular Forces Involving Polar Molecules | 557 Interactions Between Ions and Molecules with a Permanent Dipole | 557 Interactions Between Molecules with Permanent Dipoles | 558 A Closer Look: Hydrated Salts | 559 x | Contents Hydrogen Bonding | 561 Hydrogen Bonding and the Unusual Properties of Water | 563 A Closer Look: Hydrogen Bonding in Biochemistry | 565 12.3 Intermolecular Forces Involving Nonpolar Molecules | 565 Dipole/Induced Dipole Forces | 565 London Dispersion Forces: Induced Dipole/Induced Dipole Forces | 566 A Closer Look: Methane Hydrates: An Answer to World Fuel Supplies? | 567 Summary of Intermolecular Forces | 568 12.4 Properties of Liquids | 570 Vaporization and Condensation | 570 Vapor Pressure | 573 Vapor Pressure, Enthalpy of Vaporization, and the Clausius-Clapeyron Equation | 575 Boiling Point | 576 Critical Temperature and Pressure | 577 Surface Tension, Capillary Action, and Viscosity | 578 Case Study: The Mystery of the Disappearing Fingerprints | 579 CHAPTER GOALS REVISITED | 580 KEY EQUATION | 581 STUDY QUESTIONS | 581 13 The Chemistry of Solids | 588 Graphite to Graphene | 588 13.1 Crystal Lattices and Unit Cells | 589 A Closer Look: Packing Oranges | 595 13.2 Structures and Formulas of Ionic Solids | 596 13.3 Bonding in Ionic Compounds: Lattice Energy | 599 Lattice Energy | 599 Calculating a Lattice Enthalpy from Thermodynamic Data | 600 13.4 The Solid State: Other Kinds of Solid Materials | 602 Molecular Solids | 602 Network Solids | 602 Amorphous Solids | 603 13.5 Phase Changes Involving Solids | 604 Melting: Conversion of Solid into Liquid | 604 Sublimation: Conversion of Solid into Vapor | 606 13.6 Phase Diagrams | 606 Water | 606 Case Study: The World’s Lightest Solid | 607 Phase Diagrams and Thermodynamics | 608 Carbon Dioxide | 608 CHAPTER GOALS REVISITED | 610 STUDY QUESTIONS | 610 14 Solutions and Their Behavior | 616 Safe Flying | 616 14.1 Units of Concentration | 618 14.2 The Solution Process | 620 A Closer Look: Supersaturated Solutions | 620 Liquids Dissolving in Liquids | 621 Solids Dissolving in Water | 622 Enthalpy of Solution | 623 Enthalpy of Solution: Thermodynamic Data | 625 14.3 Factors Affecting Solubility: Pressure and Temperature | 626 Dissolving Gases in Liquids: Henry’s Law | 626 Temperature Effects on Solubility: Le Chatelier’s Principle | 627 14.4 Colligative Properties | 628 Changes in Vapor Pressure: Raoult’s Law | 629 Chemical Perspectives: Henry’s Law and the Killer Lakes of Cameroon | 630 Boiling Point Elevation | 632 Freezing Point Depression | 634 Osmotic Pressure | 635 Colligative Properties and Molar Mass Determination | 637 Colligative Properties of Solutions Containing Ions | 639 A Closer Look: Osmosis and Medicine | 639 Case Study: Henry’s Law in a Soda Bottle | 641 14.5 Colloids | 642 Types of Colloids | 643 Surfactants | 645 CHAPTER GOALS REVISITED | 646 KEY EQUATIONS | 647 STUDY QUESTIONS | 648 Let’s Review Chapters 11–14 | 656 The Purpose of Let’s Review | 656 Preparing for an Examination | 656 Key Points to Know | 657 Examination Preparation Questions | 657 Answers and Solutions to Examination Preparation Questions | 664 Contents | xi PART 4 CONTROL OF REACTIONS 15 Chemical Kinetics: The Rates of Chemical Reactions | 670 Where Did the Indicator Go? | 670 15.1 Rates of Chemical Reactions | 671 15.2 Reaction Conditions and Rate | 676 15.3 Effect of Concentration on Reaction Rate | 677 Rate Equations | 678 The Order of a Reaction | 679 The Rate Constant, k | 679 Determining a Rate Equation | 680 15.4 Concentration–Time Relationships: Integrated Rate Laws | 683 First-Order Reactions | 683 A Closer Look: Rate Laws, Rate Constants, and Reaction Stoichiometry | 684 Second-Order Reactions | 686 Zero-Order Reactions | 687 Graphical Methods for Determining Reaction Order and the Rate Constant | 687 Half-Life and First-Order Reactions | 690 15.5 A Microscopic View of Reaction Rates | 692 Concentration, Reaction Rate, and Collision Theory | 692 Temperature, Reaction Rate, and Activation Energy | 693 Activation Energy | 694 Effect of a Temperature Increase | 695 Effect of Molecular Orientation on Reaction Rate | 695 The Arrhenius Equation | 696 A Closer Look: Reaction Coordinate Diagrams | 697 Effect of Catalysts on Reaction Rate | 699 15.6 Reaction Mechanisms | 701 Case Study: Enzymes: Nature’s Catalysts | 702 Molecularity of Elementary Steps | 703 Rate Equations for Elementary Steps | 704 Molecularity and Reaction Order | 704 Reaction Mechanisms and Rate Equations | 705 CHAPTER GOALS REVISITED | 710 KEY EQUATIONS | 711 STUDY QUESTIONS | 712 16 Principles of Reactivity: Chemical Equilibria | 724 Dynamic and Reversible! | 724 16.1 Chemical Equilibrium: A Review | 725 16.2 The Equilibrium Constant and Reaction Quotient | 726 Writing Equilibrium Constant Expressions | 728 A Closer Look: Equilibrium Constant Expressions for Gases— Kc and Kp | 730 The Meaning of the Equilibrium Constant, K | 730 The Reaction Quotient, Q | 732 16.3 Determining an Equilibrium Constant | 734 16.4 Using Equilibrium Constants in Calculations | 737 Calculations Where the Solution Involves a Quadratic Expression | 738 16.5 More About Balanced Equations and Equilibrium Constants | 741 16.6 Disturbing a Chemical Equilibrium | 744 Effect of the Addition or Removal of a Reactant or Product | 745 Effect of Volume Changes on Gas-Phase Equilibria | 746 Effect of Temperature Changes on Equilibrium Composition | 748 Case Study: Applying Equilibrium Concepts: The Haber- Bosch Process | 749 CHAPTER GOALS REVISITED | 750 KEY EQUATIONS | 751 STUDY QUESTIONS | 752 17 The Chemistry of Acids and Bases | 760 Aspirin Is Over 100 Years Old! | 760 17.1 Acids and Bases: A Review | 761 17.2 The Brønsted–Lowry Concept of Acids and Bases Extended | 762 Conjugate Acid–Base Pairs | 764 17.3 Water and the pH Scale | 765 Water Autoionization and the Water Ionization Constant, Kw | 765 The pH Scale | 767 Calculating pH | 768 17.4 Equilibrium Constants for Acids and Bases | 768 Ka Values for Polyprotic Acids | 772 Aqueous Solutions of Salts | 773 A Logarithmic Scale of Relative Acid Strength, pKa | 775 Relating the Ionization Constants for an Acid and Its Conjugate Base | 775 17.5 Predicting the Direction of Acid–Base Reactions | 776 17.6 Types of Acid–Base Reactions | 778 The Reaction of a Strong Acid with a Strong Base | 779 The Reaction of a Weak Acid with a Strong Base | 779 The Reaction of a Strong Acid with a Weak Base | 779 The Reaction of a Weak Acid with a Weak Base | 780 xii | Contents 17.7 Calculations with Equilibrium Constants | 780 Determining K from Initial Concentrations and Measured pH | 780 What Is the pH of an Aqueous Solution of a Weak Acid or Base? | 782 17.8 Polyprotic Acids and Bases | 787 17.9 The Lewis Concept of Acids and Bases | 789 Case Study: Uric Acid, Gout, and Bird Droppings | 789 Cationic Lewis Acids | 790 Molecular Lewis Acids | 791 Molecular Lewis Bases | 793 17.10 Molecular Structure, Bonding, and Acid–Base Behavior | 793 Acid Strength of the Hydrogen Halides, HX | 793 Comparing Oxoacids, HNO2 and HNO3 | 794 A Closer Look: Acid Strengths and Molecular Structure | 795 Why Are Carboxylic Acids Brønsted Acids? | 796 Why Are Hydrated Metal Cations Brønsted Acids? | 797 Why Are Anions Brønsted Bases? | 798 Why Are Ammonia and Its Derivatives Brønsted and Lewis Bases? | 798 CHAPTER GOALS REVISITED | 799 KEY EQUATIONS | 800 STUDY QUESTIONS | 801 18 Principles of Reactivity: Other Aspects of Aqueous Equilibria | 810 Minerals and Gems—The Importance of Solubility | 810 18.1 The Common Ion Effect | 811 18.2 Controlling pH: Buffer Solutions | 814 General Expressions for Buffer Solutions | 816 Preparing Buffer Solutions | 818 How Does a Buffer Maintain pH? | 820 18.3 Acid–Base Titrations | 821 Case Study: Take A Deep Breath! | 822 Titration of a Strong Acid with a Strong Base | 822 Titration of a Weak Acid with a Strong Base | 824 Titration of Weak Polyprotic Acids | 827 Titration of a Weak Base with a Strong Acid | 828 pH Indicators | 830 18.4 Solubility of Salts | 832 The Solubility Product Constant, Ksp | 832 Relating Solubility and Ksp | 834 A Closer Look: Solubility Calculations | 837 Solubility and the Common Ion Effect | 838 The Effect of Basic Anions on Salt Solubility | 840 18.5 Precipitation Reactions | 842 Ksp and the Reaction Quotient, Q | 843 Ksp, the Reaction Quotient, and Precipitation Reactions | 844 18.6 Equilibria Involving Complex Ions | 846 18.7 Solubility and Complex Ions | 847 CHAPTER GOALS REVISITED | 849 KEY EQUATIONS | 850 STUDY QUESTIONS | 850 19 Principles of Reactivity: Entropy and Free Energy | 860 Can Ethanol Contribute to Energy and Environmental Goals? | 860 19.1 Spontaneity and Energy Transfer as Heat | 862 19.2 Dispersal of Energy: Entropy | 863 A Closer Look: Reversible and Irreversible Processes | 864 19.3 Entropy: A Microscopic Understanding | 864 Dispersal of Energy | 864 Dispersal of Matter: Dispersal of Energy Revisited | 866 A Summary: Entropy, Entropy Change, and Energy Dispersal | 868 19.4 Entropy Measurement and Values | 868 Standard Entropy Values, So | 868 Determining Entropy Changes in Physical and Chemical Processes | 870 19.5 Entropy Changes and Spontaneity | 871 In Summary: Spontaneous or Not? | 874 19.6 Gibbs Free Energy | 876 The Change in the Gibbs Free Energy, G | 876 Gibbs Free Energy, Spontaneity, and Chemical Equilibrium | 877 A Summary: Gibbs Free Energy (rG and rGo), the Reaction Quotient (Q) and Equilibrium Constant (K ), and Reaction Favorability | 879 What Is “Free” Energy? | 879 19.7 Calculating and Using Free Energy | 879 Standard Free Energy of Formation | 879 Calculating rGo, the Free Energy Change for a Reaction Under Standard Conditions | 880 Free Energy and Temperature | 881 Case Study: Thermodynamics and Living Things | 884 Using the Relationship Between rGo and K | 885 CHAPTER GOALS REVISITED | 886 KEY EQUATIONS | 887 STUDY QUESTIONS | 887 20 Principles of Reactivity: Electron Transfer Reactions | 896 Don’t Hold onto That Money! | 896 20.1 Oxidation–Reduction Reactions | 898 Balancing Oxidation–Reduction Equations | 899 Contents | xiii 20.2 Simple Voltaic Cells | 905 Voltaic Cells with Inert Electrodes | 908 Electrochemical Cell Notations | 909 20.3 Commercial Voltaic Cells | 909 Historical Perspectives: Frogs and Voltaic Piles | 910 Primary Batteries: Dry Cells and Alkaline Batteries | 911 Secondary or Rechargeable Batteries | 912 Fuel Cells and Hybrid Cars | 914 20.4 Standard Electrochemical Potentials | 915 Electromotive Force | 915 Measuring Standard Potentials | 916 Standard Reduction Potentials | 917 A Closer Look: EMF, Cell Potential, and Voltage | 918 Tables of Standard Reduction Potentials | 918 Using Tables of Standard Reduction Potentials | 921 Relative Strengths of Oxidizing and Reducing Agents | 923 Chemical Perspectives: An Electrochemical Toothache! | 925 20.5 Electrochemical Cells Under Nonstandard Conditions | 925 The Nernst Equation | 925 20.6 Electrochemistry and Thermodynamics | 928 Work and Free Energy | 928 E o and the Equilibrium Constant | 929 20.7 Electrolysis: Chemical Change Using Electrical Energy | 931 Case Study: Manganese in the Oceans | 932 Electrolysis of Molten Salts | 932 Electrolysis of Aqueous Solutions | 933 20.8 Counting Electrons | 937 Historical Perspectives: Electrochemistry and Michael Faraday | 937 CHAPTER GOALS REVISITED | 939 KEY EQUATIONS | 940 STUDY QUESTIONS | 940 Let’s Review Chapters 15–20 | 948 The Purpose of Let’s Review | 948 Preparing for an Examination | 949 Key Points to Know | 949 Examination Preparation Questions | 949 Answers and Solutions to Examination Preparation Questions | 956 PART 5 CHEMISTRY OF THE ELEMENTS 21 The Chemistry of the Main Group Elements | 962 Carbon and Silicon | 962 21.1 Element Abundances | 963 21.2 The Periodic Table: A Guide to the Elements | 964 Valence Electrons | 964 Ionic Compounds of Main Group Elements | 965 Molecular Compounds of Main Group Elements | 966 A Closer Look: Hydrogen, Helium, and Balloons | 968 21.3 Hydrogen | 968 Chemical and Physical Properties of Hydrogen | 968 Preparation of Hydrogen | 969 21.4 The Alkali Metals, Group 1A | 971 Preparation of Sodium and Potassium | 971 Properties of Sodium and Potassium | 972 A Closer Look: The Reducing Ability of the Alkali Metals | 973 Important Lithium, Sodium, and Potassium Compounds | 974 21.5 The Alkaline Earth Elements, Group 2A | 975 Properties of Calcium and Magnesium | 976 Metallurgy of Magnesium | 976 Chemical Perspectives: Alkaline Earth Metals and Biology | 977 Calcium Minerals and Their Applications | 978 Chemical Perspectives: Of Romans, Limestone, and Champagne | 978 21.6 Boron, Aluminum, and the Group 3A Elements | 979 Chemistry of the Group 3A Elements | 979 Case Study: Hard Water | 980 Boron Minerals and Production of the Element | 981 Metallic Aluminum and Its Production | 981 Boron Compounds | 983 Aluminum Compounds | 985 21.7 Silicon and the Group 4A Elements | 986 Silicon | 986 Silicon Dioxide | 987 Silicate Minerals with Chain and Ribbon Structures | 988 Silicates with Sheet Structures and Aluminosilicates | 989 Silicone Polymers | 990 Case Study: Lead, Beethoven, and a Mystery Solved | 991 xiv | Contents 21.8 Nitrogen, Phosphorus, and the Group 5A Elements | 991 Properties of Nitrogen and Phosphorus | 992 Nitrogen Compounds | 992 Case Study: A Healthy Saltwater Aquarium and the Nitrogen Cycle | 994 A Closer Look: Making Phosphorus | 997 Hydrogen Compounds of Phosphorus and Other Group 5A Elements | 997 Phosphorus Oxides and Sulfi des | 997 Phosphorus Oxoacids and Their Salts | 999 21.9 Oxygen, Sulfur, and the Group 6A Elements | 1001 Preparation and Properties of the Elements | 1001 Sulfur Compounds | 1003 A Closer Look: Snot-tites and Sulfur Chemistry | 1004 21.10 The Halogens, Group 7A | 1005 Preparation of the Elements | 1005 Fluorine Compounds | 1007 Chlorine Compounds | 1008 CHAPTER GOALS REVISITED | 1010 STUDY QUESTIONS | 1011 22 The Chemistry of the Transition Elements | 1018 Memory Metal | 1018 22.1 Properties of the Transition Elements | 1019 Electron Confi gurations | 1021 Oxidation and Reduction | 1021 Chemical Perspectives: Corrosion of Iron | 1023 Periodic Trends in the d-Block: Size, Density, Melting Point | 1024 22.2 Metallurgy | 1025 Pyrometallurgy: Iron Production | 1026 Hydrometallurgy: Copper Production | 1028 22.3 Coordination Compounds | 1029 Complexes and Ligands | 1029 Formulas of Coordination Compounds | 1032 A Closer Look: Hemoglobin | 1033 Naming Coordination Compounds | 1034 22.4 Structures of Coordination Compounds | 1036 Common Coordination Geometries | 1036 Isomerism | 1036 22.5 Bonding in Coordination Compounds | 1040 The d Orbitals: Ligand Field Theory | 1040 Electron Confi gurations and Magnetic Properties | 1041 22.6 Colors of Coordination Compounds | 1045 Color | 1045 The Spectrochemical Series | 1046 22.7 Organometallic Chemistry: The Chemistry of Low-Valent Metal–Organic Complexes | 1048 Case Study: Accidental Discovery of a Chemotherapy Agent | 1049 Carbon Monoxide Complexes of Metals | 1049 The Effective Atomic Number Rule and Bonding in Organometallic Compounds | 1050 Ligands in Organometallic Compounds | 1051 Case Study: Ferrocene—The Beginning of a Chemical Revolution | 1052 CHAPTER GOALS REVISITED | 1054 STUDY QUESTIONS | 1054 23 Nuclear Chemistry | 1060 A Primordial Nuclear Reactor | 1060 23.1 Natural Radioactivity | 1061 23.2 Nuclear Reactions and Radioactive Decay | 1062 Equations for Nuclear Reactions | 1062 Radioactive Decay Series | 1063 Other Types of Radioactive Decay | 1066 23.3 Stability of Atomic Nuclei | 1067 The Band of Stability and Radioactive Decay | 1068 Nuclear Binding Energy | 1069 23.4 Rates of Nuclear Decay | 1072 Half-Life | 1072 Kinetics of Nuclear Decay | 1073 Radiocarbon Dating | 1075 23.5 Artifi cial Nuclear Reactions | 1077 A Closer Look: The Search for New Elements | 1079 23.6 Nuclear Fission | 1080 23.7 Nuclear Fusion | 1081 23.8 Radiation Health and Safety | 1082 Units for Measuring Radiation | 1082 Radiation: Doses and Effects | 1083 A Closer Look: What Is a Safe Exposure? | 1084 23.9 Applications of Nuclear Chemistry | 1084 Nuclear Medicine: Medical Imaging | 1085 Nuclear Medicine: Radiation Therapy | 1086 Analytical Methods: The Use of Radioactive Isotopes as Tracers | 1086 Analytical Methods: Isotope Dilution | 1086 A Closer Look: Technetium-99m | 1087 Space Science: Neutron Activation Analysis and the Moon Rocks | 1088 Food Science: Food Irradiation | 1088 Case Study: Nuclear Medicine and Hyperthyroidism | 1089 CHAPTER GOALS REVISITED | 1090 KEY EQUATIONS | 1090 STUDY QUESTIONS | 1091 A Appendices | A-1 A Using Logarithms and the Quadratic Equation | A-2 B Some Important Physical Concepts | A-7 C Abbreviations and Useful Conversion Factors | A-10 D Physical Constants | A-14 E A Brief Guide to Naming Organic Compounds | A-17 F Values for the Ionization Energies and Electron Affi nities of the Elements | A-21 G Vapor Pressure of Water at Various Temperatures | A-22 H Ionization Const