HEMISTRY SIXTH EDITION JOHN E. McMURRY Cornell University ROBERT C. FAY Cornell University With Contributions by JORDAN FANTINI Denison University Prentice Hall Boston Columbus Indianapolis New York San Francisco Upper Saddle River Amsterdam Cape Town Dubai London Madrid Milan Munich Paris Montreal Toronto Delhi Mexico City Sao Paulo Sydney Hong Kong Seoul Singapore Taipei Tokyo
Contents Preface xiii 2.3 Atomic Structure: Electrons 39 Supplements xvii 2.4 Atomic Structure: Protons and Neutrons 41 2.5 Atomic Numbers 43 1 Chemistry: Matter and Measurement 1 1.1 Approaching Chemistry: Experimentation 1 1.2 Chemistry and the Elements 2 1.3 Elements and the Periodic Table 3 1.4 Some Chemical Properties of the Elements 7 1.5 Experimentation and Measurement 10 1.6 Mass and Its Measurement 11 1.7 Length and Its Measurement 12 1.8 Temperature and Its Measurement 13 1.9 Derived Units: Volume and Its Measurement 14 2.6 Atomic Masses and the Mole 45 2.7 Nuclear Chemistry: The Change of One Element into Another 48 2.8 Radioactivity 49 2.9 Nuclear Stability 52 2.10 Mixtures and Chemical Compounds; Molecules and Covalent Bonds 54 2.11 Ions and Ionic Bonds 58 2.12 Naming Chemical Compounds 60 INQUIRY Where Do Chemical Elements Come From? 67 Summary Keywords Conceptual Section Chapter 1.10 Derived Units: Density and Its Measurement 16 1.11 Derived Units: Energy and Its Measurement 17 1.12 Accuracy, Precision, and Significant Figures in Measurement 18 1.13 Rounding Numbers 20 3 Mass Relationships Reactions?4 3.1 Balancing Chemical Equations 75 in Chemical 1.14 Calculations: Converting from One Unit to Another 22 INQUIRY What Are the Risks and Benefits of Chemicals? 26 Summary Keywords Conceptual Section Chapter 3.2 Representing Chemistry on Different Levels 78 3.3 Chemical Arithmetic: Stoichiometry 79 3.4 Yields of Chemical Reactions 83 3.5 Reactions with Limiting Amounts of Reactants 85 3.6 Concentrations of Reactants in Solution: Molarity 88 2 Atoms, Molecules, and Ions 34 2.1 The Conservation of Mass and the Law of Definite Proportions 35 2.2 The Law of Multiple Proportions and Dalton's Atomic Theory 37 3.8 Solution Stoichiometry 91 3.9 Titration 92 3.10 Percent Composition and Empirical Formulas 94 3.11 Determining Empirical Formulas: Elemental Analysis 97 3.12 Determining Molecular Masses: Mass Spectrometry 100 3.7 Diluting Concentrated Solutions 90
CONTENTS V INQUIRY Did Ben Franklin Have Avogadro's Number? 102 Summary Keywords Conceptual Section Chapter 4 Reactions in Aqueous Solution 112 4.1 Some Ways that Chemical Reactions Occur 113 4.2 Electrolytes in Aqueous Solution 114 4.3 Aqueous Reactions and Net Ionic Equations 116 4.4 Precipitation Reactions and Solubility Guidelines 117 4.5 Acids, Bases, and Neutralization Reactions 120 4.6 Oxidation-Reduction (Redox) Reactions 124 4.7 Identifying Redox Reactions 127 4.8 The Activity Series of the Elements 129 4.9 Balancing Redox Reactions: The Half-Reaction Method 132 4.10 Redox Stoichiometry 136 4.11 Some Applications of Redox Reactions 139 INQUIRY How Can Chemistry Be Green? 141 Summary Keywords Conceptual Section Chapter Multiconcept 5 Periodicity and the Electronic Structure of Atoms 150 5.1 Light and the Electromagnetic Spectrum 151 5.2 Electromagnetic Energy and Atomic Line Spectra 154 5.3 Particlelike Properties of Electromagnetic Energy 157 5.4 Wavelike Properties of Matter 159 5.5 Quantum Mechanics and the Heisenberg Uncertainty Principle 160 5.6 Wave Functions and Quantum Numbers 161 5.7 The Shapes of Orbitals 164 5.8 Quantum Mechanics and Atomic Line Spectra 167 5.9 Electron Spin and the Pauli Exclusion Principle 169 5.10 Orbital Energy Levels in Multielectron Atoms 170 5.11 Electron Configurations of Multielectron Atoms 171 5.12 Some Anomalous Electron Configurations 173 5.13 Electron Configurations and the Periodic Table 175 5.14 Electron Configurations and Periodic Properties: Atomic Radii 177 INQUIRY What Do Compact Fluorescent Lights Have to Do with Atomic Line Spectra? 179 Summary Keywords Conceptual Section Chapter Multiconcept 6 Ionic Bonds and Some Main-Group Chemistry 6.1 Electron Configurations 6.2 Ionic Radii 188 6.3 Ionization Energy 190 of Ions 187 6.4 Higher Ionization Energies 192 6.5 Electron Affinity 194 6.6 The Octet Rule 196 ise 6.7 Ionic Bonds and the Formation of Ionic Solids 198 6.8 Lattice Energies in Ionic Solids 200 6.9 Some Chemistry of the Alkali Metals 203 6.10 Some Chemistry of the Alkaline-Earth Metals 205 6.11 Some Chemistry of the Halogens 206 6.12 Some Chemistry of the Noble Gases 208 INQUIRY Is Eating Salt Unhealthy? 209 Summary Keywords Conceptual Section Chapter Multiconcept 7 Covalent Bonds and Molecular Structure 216 7.1 Covalent Bonding in Molecules 217 7.2 Strengths of Covalent Bonds 218
vi CONTENTS 7.3 A Comparison of Ionic and Covalent Compounds 219 7.4 Polar Covalent Bonds: Electronegativity 220 7.5 Electron-Dot Structures 222 7.6 Electron-Dot Structures of Polyatomic Molecules 226 7.7 Electron-Dot Structures and Resonance 232 7.8 Formal Charges 234 7.9 Molecular Shapes: The VSEPR Model 236 7.10 Valence Bond Theory 243 7.11 Hybridization and sp3 Hybrid Orbitals 244 7.12 Other Kinds of Hybrid Orbitals 246 7.13 Molecular Orbital Theory: The Hydrogen Molecule 250 7.14 Molecular Orbital Theory: Other Diatomic Molecules 252 7.15 Combining Valence Bond Theory and Molecular Orbital Theory 255 INQUIRY How Does Molecular Shape Lead to Handedness in Molecules? 256 Summary Keywords Conceptual Section Chapter Multiconcept 8 Thermochemistry: Chemical Energy zee 8.1 Energy and Its Conservation 267 8.2 Internal Energy and State Functions 268 8.3 Expansion Work 270 8.4 Energy and Enthalpy 273 8.5 The Thermodynamic Standard State 274 8.6 Enthalpies of Physical and Chemical Change 276 8.7 Calorimetry and Heat Capacity 278 8.8 Hess's Law 281 8.9 Standard Heats of Formation 284 8.10 Bond Dissociation Energies 287 8.11 Fossil Fuels, Fuel Efficiency, and Heats of Combustion 289 8.12 An Introduction to Entropy 291 8.13 An Introduction to Free Energy 293 INQUIRY What Are Biofuels? 297 Summary Keywords Conceptual Section Chapter Multiconcept 9 Gases: Their Properties and Behavior 308 9.1 Gases and Gas Pressure 309 9.2 The Gas Laws 313 9.3 The Ideal Gas Law 318 9.4 Stoichiometric Relationships with Gases 320 9.5 Partial Pressure and Dalton's Law 324 9.6 The Kinetic-Molecular Theory of Gases 326 9.7 Graham's Law: Diffusion and Effusion of Gases 329 9.8 The Behavior of Real Gases 331 9.9 The Earth's Atmosphere 332 INQUIRY How Do Inhaled Anesthetics Work? 336 Summary Keywords Conceptual Section Chapter Multiconcept 10 Liquids, Solids, and Phase Changes 346 10.1 Polar Covalent Bonds and Dipole Moments 347 10.2 Intermolecular Forces 350 10.3 Some Properties of Liquids 357 10.4 Phase Changes 358 10.5 Evaporation, Vapor Pressure, and Boiling Point 362 10.6 Kinds of Solids 366 10.7 Probing the Structure of Solids: X-Ray Crystallography 368
CONTENTS vii 10.8 Unit Cells and the Packing of Spheres in Crystalline Solids 370 10.9 Structures of 5ome Ionic Solids 376 10.10 Structures of Some Covalent Network Solids 378 10.11 Phase Diagrams 380 INQUIRY Liquids Made of Ions? 383 Summary Key Words Conceptual Section Chapter Multiconcept 11 Solutions and Their Properties 392 11.1 Solutions 393 11.2 Energy Changes and the Solution Process 394 11.3 Units of Concentration 398 11.4 Some Factors Affecting Solubility 403 11.5 Physical Behavior of Solutions: Colligative Properties 406 11.6 Vapor-Pressure Lowering of Solutions: Raoult's Law 407 11.7 Boiling-Point Elevation and Freezing-Point Depression of Solutions 413 11.8 Osmosis and Osmotic Pressure 417 11.9 Some Uses of Colligative Properties 419 11.10 Fractional Distillation of Liquid Mixtures 421 INQUIRY How Does Hemodialysis Cleanse the Blood? 424 Summary Keywords Conceptual Section Chapter Multiconcept 12 Chemical Kinetics 432 12.1 Reaction Rates 433 12.2 Rate Laws and Reaction Order 437 12.3 Experimental Determination of a Rate Law 439 12.4 Integrated Rate Law for a First-Order Reaction 444 12.5 Half-Life of a First-Order Reaction 447 12.6 Radioactive Decay Rates 449 12.7 Second-Order Reactions 452 12.8 Zeroth-Order Reactions 455 12.9 Reaction Mechanisms 456 12.10 Rate Laws for Elementary Reactions 459 12.11 Rate Laws for Overall Reactions 461 12.12 Reaction Rates and Temperature: The Arrhenius Equation 465 12.13 Using the Arrhenius Equation 469 12.14 Catalysis 472 12.15 Homogeneous and Heterogeneous Catalysts 476 INQUIRY How Do Enzymes Work? 479 Summary Key Words Conceptual Section Chapter Multiconcept 13 Chemical Equilibrium 492 13.1 The Equilibrium State 493 13.2 The Equilibrium Constant Kc 495 13.3 The Equilibrium Constant Kp 499 13.4 Heterogeneous Equilibria 502 13.5 Using the Equilibrium Constant 503 13.6 Factors That Alter the Composition of an Equilibrium Mixture: Le Chatelier's Principle 511 13.7 Altering an Equilibrium Mixture: Changes in Concentration 513 13.8 Altering an Equilibrium Mixture: Changes in Pressure and Volume 516 13.9 Altering an Equilibrium Mixture: Changes in Temperature 519 13.10 The Effect of a Catalyst on Equilibrium 521 13.11 The Link between Chemical Equilibrium and Chemical Kinetics 522
viii CONTENTS INQUIRY How Does Equilibrium Affect Oxygen Transport in the Bloodstream? 525 Summary Key Words Conceptual Section Chapter Multiconcept 14 Aqueous Equilibria: Acids and Bases 53s 14.1 Acid-Base Concepts: The Bronsted-Lowry Theory 539 14.2 Acid Strength and Base Strength 542 14.3 Hydrated Protons and Hydronium Ions 545 14.4 Dissociation of Water 545 14.5 The ph Scale 547 14.6 Measuring ph 549 14.7 The ph in Solutions of Strong Acids and Strong Bases 550 14.8 Equilibria in Solutions of Weak Acids 552 14.9 Calculating Equilibrium Concentrations in Solutions 15.2 The Common-Ion Effect 590 15.3 Buffer Solutions 594 15.4 The Henderson-Hasselbalch Equation 597 15.5 ph Titration Curves 601 15.6 Strong Acid-Strong Base Titrations 602 15.7 Weak Acid-Strong Base Titrations 604 15.8 Weak Base-Strong Acid Titrations 607 15.9 Polyprotic Acid-Strong Base Titrations 608 15.10 Solubility Equilibria 611 15.11 Measuring K5p and Calculating Solubility from Ksp 612 15.12 Factors That Affect Solubility 616 15.13 Precipitation of Ionic Compounds 623 15.14 Separation of Ions by Selective Precipitation 624 15.15 Qualitative Analysis 625 INQUIRY How Does Fluoride Ion Help To Prevent Dental Cavities? 628 Summary Keywords Conceptual Section Chapter Multiconcept of Weak Acids 554 14.10 Percent Dissociation in Solutions of Weak Acids 558 14.11 Polyprotic Acids 559 14.12 Equilibria in Solutions of Weak Bases 562 14.13 Relation between Ka and 564 14.14 Acid-Base Properties of Salts 565 14.15 Factors That Affect Acid Strength 570 14.16 Lewis Acids and Bases 573 INQUIRY What Is Acid Rain and What Are Its Effects? 576 Summary Key Words Conceptual Section Chapter Multiconcept 15 Applications of Aqueous Equilibria sse 15.1 Neutralteation Reactions 587 16 Thermodynamics: Entropy, Free Energy, and Equilibrium 640 16.1 Spontaneous Processes 641 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review 642 16.3 Entropy and Probability 646 16.4 Entropy and Temperature 649 16.5 Standard Molar Entropies and Standard Entropies of Reaction 651 16.6 Entropy and the Second Law of Thermodynamics 653 16.7 Free Energy 655 16.8 Standard Free-Energy Changes for Reactions 658 16.9 Standard Free Energies of Formation 660 16.10 Free-Energy Changes and Composition of the Reaction Mixture 662 16.11 Free Energy and Chemical Equilibrium 665
CONTENTS ix INQUIRY Does Entropy Prevent the Evolution of Biological Complexity? 669 Summary Keywords Conceptual Section Chapter Multiconcept 18.5 Binary Hydrides 733 18.6 Oxygen 738 18.7 Preparation and Uses of Oxygen 738 18.8 Reactivity of Oxygen 740 18.9 Oxides 741 17 Electrochemistry eso 17.1 Galvanic Cells 681 17.2 Shorthand Notation for Galvanic Cells 685 17.3 Cell Potentials and Free-Energy Changes for Cell Reactions 687 17.4 Standard Reduction Potentials 689 18.10 Peroxides and Superoxides 744 18.11 Hydrogen Peroxide 746 18.12 Ozone 748 18.13 Water 749 18.14 Hydrates 750 INQUIRY What Role for Hydrogen in Future? 752 Our Energy 17.5 Using Standard Reduction Potentials 692 17.6 Cell Potentials and Composition of the Reaction Mixture: The Nernst Equation 695 Summary Key Words Conceptual Section Chapter Multiconcept 17.7 Electrochemical Determination of ph 698 17.8 Standard Cell Potentials and Equilibrium Constants 700 17.9 Batteries 702 17.10 Fuel Cells 706 17.11 Corrosion 707 17.12 Electrolysis and Electrolytic Cells 709 17.13 Commercial Applications of Electrolysis 712 17.14 Quantitative Aspects of Electrolysis 715 INQUIRY Why Are Some Metal Objects Brightly Colored? 718 Summary Key Words Conceptual Section Chapter Multiconcept 18 Hydrogen, Oxygen, and Water 72s 18.1 Hydrogen 729 18.2 Isotopes of Hydrogen 730 18.3 Preparation and Uses of Hydrogen 731 18.4 Reactivity of Hydrogen 733 19 The Main-Group Elements?6o 19.1 A Review of General Properties and Periodic Trends 762 19.2 Distinctive Properties of the Second-Row Elements 764 19.3 The Group 3A Elements 766 19.4 Boron 767 19.5 Aluminum 768 19.6 The Group 4A Elements 769 19.7 Carbon 770 19.8 Silicon 774 19.9 The Group 5A Elements 777 19.10 Nitrogen 779 19.11 Phosphorus 782 19.12 The Group 6A Elements 786 19.13 Sulfur 787 19.14 The Halogens: Oxoacids and Oxoacid Salts 791 INQUIRY How Do Laser Printers Work? 793 Summary Keywords Conceptual Section Chapter Multiconcept
X CONTENTS 20 Transition Elements and Coordination Chemistry 802 Summary Keywords Conceptual Section Chapter Multiconcept 20.1 Electron Configurations 804 20.2 Properties of Transition Elements 806 20.3 Oxidation States of Transition Elements 809 20.4 Chemistry of Selected Transition Elements 811 20.5 Coordination Compounds 817 20.6 Ligands 819 20.7 Naming Coordination Compounds 821 20.8 Isomers 824 20.9 Enantiomers and Molecular Handedness 830 20.10 Color of Transition Metal Complexes 832 20.11 Bonding in Complexes: Valence Bond Theory 834 20.12 Crystal Field Theory 837 INQUIRY How Do Living Things Acquire Nitrogen? 843 Summary Keywords Conceptual Section Chapter Multiconcept 22 Nuclear Chemistry sss 22.1 Energy Changes During 22.2 Nuclear Fission and Fusion 893 22.3 Nuclear Transmutation 897 Nuclear Reactions 889 22.4 Detecting and Measuring Radioactivity 898 22.5 Applications of Nuclear Chemistry 901 INQUIRY Does Nature Have Nuclear Reactors? 904 Summary Key Words Section Chapter Multiconcept 23 Organic and Biological Chemistry gos 23.1 Organic Molecules and Their Structures: Alkanes 909 23.2 Families of Organic Compounds: Functional Groups 912 21 Metals and Solid-State Materials 852 23.3 Naming Organic Compounds 914 23.4 Unsaturated Organic Compounds: Alkenes and Alkynes 917 23.5 Cyclic Organic Compounds 921 21.1 Sources of the Metallic Elements 853 21.2 Metallurgy 855 21.3 Iron and Steel 858 21.4 Bonding in Metals 859 21.5 Semiconductors 864 21.6 Semiconductor Applications 867 21.7 Superconductors 871 21.8 Ceramics 874 21.9 Composites 877 INQUIRY Why is it Said That the Next Big Thing Will Be Really Small? 879 23.6 Aromatic Compounds 923 23.7 Alcohols, Ethers, and Amines 925 23.8 Carbonyl Compounds 927 23.9 An Overview of Biological Chemistry 932 23.10 Amino Acids, Peptides, and Proteins 934 23.11 Carbohydrates 937 23.12 Lipids 939 23.13 Nucleic Acids 941 INQUIRY Which Is Better, Natural or Synthetic? 947 Summary Key Words Conceptual Section Chapter Multiconcept
CONTENTS Appendix A Mathematical Operations A-1 Appendix B Thermodynamic Properties at 25 C A-9 Appendix C Equilibrium Constants at 25 C A-14 Appendix D Standard Reduction Potentials at 25 C A-18 Appendix E Properties of Water A-20 Answers to Selected A-21 Glossary G-1 Index 1-1 Photo Credits C-1