HEMISTRY. McMURRY ROBERT C. FAY JOHN E. JORDAN FANTINI EDITION SIXTH. With Contributions by. Cornell University. Denison University

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1 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

2 Contents Preface xiii 2.3 Atomic Structure: Electrons 39 Supplements xvii 2.4 Atomic Structure: Protons and Neutrons Atomic Numbers 43 1 Chemistry: Matter and Measurement Approaching Chemistry: Experimentation Chemistry and the Elements Elements and the Periodic Table Some Chemical Properties of the Elements Experimentation and Measurement Mass and Its Measurement Length and Its Measurement Temperature and Its Measurement Derived Units: Volume and Its Measurement Atomic Masses and the Mole Nuclear Chemistry: The Change of One Element into Another Radioactivity Nuclear Stability Mixtures and Chemical Compounds; Molecules and Covalent Bonds Ions and Ionic Bonds 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 Derived Units: Energy and Its Measurement Accuracy, Precision, and Significant Figures in Measurement 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 Chemical Arithmetic: Stoichiometry Yields of Chemical Reactions Reactions with Limiting Amounts of Reactants Concentrations of Reactants in Solution: Molarity 88 2 Atoms, Molecules, and Ions The Conservation of Mass and the Law of Definite Proportions The Law of Multiple Proportions and Dalton's Atomic Theory Solution Stoichiometry Titration Percent Composition and Empirical Formulas Determining Empirical Formulas: Elemental Analysis Determining Molecular Masses: Mass Spectrometry Diluting Concentrated Solutions 90

3 CONTENTS V INQUIRY Did Ben Franklin Have Avogadro's Number? 102 Summary Keywords Conceptual Section Chapter 4 Reactions in Aqueous Solution Some Ways that Chemical Reactions Occur Electrolytes in Aqueous Solution Aqueous Reactions and Net Ionic Equations Precipitation Reactions and Solubility Guidelines Acids, Bases, and Neutralization Reactions Oxidation-Reduction (Redox) Reactions Identifying Redox Reactions The Activity Series of the Elements Balancing Redox Reactions: The Half-Reaction Method Redox Stoichiometry 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 Light and the Electromagnetic Spectrum Electromagnetic Energy and Atomic Line Spectra Particlelike Properties of Electromagnetic Energy Wavelike Properties of Matter Quantum Mechanics and the Heisenberg Uncertainty Principle Wave Functions and Quantum Numbers The Shapes of Orbitals Quantum Mechanics and Atomic Line Spectra Electron Spin and the Pauli Exclusion Principle Orbital Energy Levels in Multielectron Atoms Electron Configurations of Multielectron Atoms Some Anomalous Electron Configurations Electron Configurations and the Periodic Table 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 Ionization Energy 190 of Ions Higher Ionization Energies Electron Affinity The Octet Rule 196 ise 6.7 Ionic Bonds and the Formation of Ionic Solids Lattice Energies in Ionic Solids Some Chemistry of the Alkali Metals Some Chemistry of the Alkaline-Earth Metals Some Chemistry of the Halogens 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 Covalent Bonding in Molecules Strengths of Covalent Bonds 218

4 vi CONTENTS 7.3 A Comparison of Ionic and Covalent Compounds Polar Covalent Bonds: Electronegativity Electron-Dot Structures Electron-Dot Structures of Polyatomic Molecules Electron-Dot Structures and Resonance Formal Charges Molecular Shapes: The VSEPR Model Valence Bond Theory Hybridization and sp3 Hybrid Orbitals Other Kinds of Hybrid Orbitals Molecular Orbital Theory: The Hydrogen Molecule Molecular Orbital Theory: Other Diatomic Molecules 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 Internal Energy and State Functions Expansion Work Energy and Enthalpy The Thermodynamic Standard State Enthalpies of Physical and Chemical Change Calorimetry and Heat Capacity Hess's Law Standard Heats of Formation Bond Dissociation Energies Fossil Fuels, Fuel Efficiency, and Heats of Combustion An Introduction to Entropy An Introduction to Free Energy 293 INQUIRY What Are Biofuels? 297 Summary Keywords Conceptual Section Chapter Multiconcept 9 Gases: Their Properties and Behavior Gases and Gas Pressure The Gas Laws The Ideal Gas Law Stoichiometric Relationships with Gases Partial Pressure and Dalton's Law The Kinetic-Molecular Theory of Gases Graham's Law: Diffusion and Effusion of Gases The Behavior of Real Gases The Earth's Atmosphere 332 INQUIRY How Do Inhaled Anesthetics Work? 336 Summary Keywords Conceptual Section Chapter Multiconcept 10 Liquids, Solids, and Phase Changes Polar Covalent Bonds and Dipole Moments Intermolecular Forces Some Properties of Liquids Phase Changes Evaporation, Vapor Pressure, and Boiling Point Kinds of Solids Probing the Structure of Solids: X-Ray Crystallography 368

5 CONTENTS vii 10.8 Unit Cells and the Packing of Spheres in Crystalline Solids Structures of 5ome Ionic Solids Structures of Some Covalent Network Solids Phase Diagrams 380 INQUIRY Liquids Made of Ions? 383 Summary Key Words Conceptual Section Chapter Multiconcept 11 Solutions and Their Properties Solutions Energy Changes and the Solution Process Units of Concentration Some Factors Affecting Solubility Physical Behavior of Solutions: Colligative Properties Vapor-Pressure Lowering of Solutions: Raoult's Law Boiling-Point Elevation and Freezing-Point Depression of Solutions Osmosis and Osmotic Pressure Some Uses of Colligative Properties Fractional Distillation of Liquid Mixtures 421 INQUIRY How Does Hemodialysis Cleanse the Blood? 424 Summary Keywords Conceptual Section Chapter Multiconcept 12 Chemical Kinetics Reaction Rates Rate Laws and Reaction Order Experimental Determination of a Rate Law Integrated Rate Law for a First-Order Reaction Half-Life of a First-Order Reaction Radioactive Decay Rates Second-Order Reactions Zeroth-Order Reactions Reaction Mechanisms Rate Laws for Elementary Reactions Rate Laws for Overall Reactions Reaction Rates and Temperature: The Arrhenius Equation Using the Arrhenius Equation Catalysis Homogeneous and Heterogeneous Catalysts 476 INQUIRY How Do Enzymes Work? 479 Summary Key Words Conceptual Section Chapter Multiconcept 13 Chemical Equilibrium The Equilibrium State The Equilibrium Constant Kc The Equilibrium Constant Kp Heterogeneous Equilibria Using the Equilibrium Constant Factors That Alter the Composition of an Equilibrium Mixture: Le Chatelier's Principle Altering an Equilibrium Mixture: Changes in Concentration Altering an Equilibrium Mixture: Changes in Pressure and Volume Altering an Equilibrium Mixture: Changes in Temperature The Effect of a Catalyst on Equilibrium The Link between Chemical Equilibrium and Chemical Kinetics 522

6 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 Acid Strength and Base Strength Hydrated Protons and Hydronium Ions Dissociation of Water The ph Scale Measuring ph The ph in Solutions of Strong Acids and Strong Bases Equilibria in Solutions of Weak Acids Calculating Equilibrium Concentrations in Solutions 15.2 The Common-Ion Effect Buffer Solutions The Henderson-Hasselbalch Equation ph Titration Curves Strong Acid-Strong Base Titrations Weak Acid-Strong Base Titrations Weak Base-Strong Acid Titrations Polyprotic Acid-Strong Base Titrations Solubility Equilibria Measuring K5p and Calculating Solubility from Ksp Factors That Affect Solubility Precipitation of Ionic Compounds Separation of Ions by Selective Precipitation Qualitative Analysis 625 INQUIRY How Does Fluoride Ion Help To Prevent Dental Cavities? 628 Summary Keywords Conceptual Section Chapter Multiconcept of Weak Acids Percent Dissociation in Solutions of Weak Acids Polyprotic Acids Equilibria in Solutions of Weak Bases Relation between Ka and Acid-Base Properties of Salts Factors That Affect Acid Strength 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 Thermodynamics: Entropy, Free Energy, and Equilibrium Spontaneous Processes Enthalpy, Entropy, and Spontaneous Processes: A Brief Review Entropy and Probability Entropy and Temperature Standard Molar Entropies and Standard Entropies of Reaction Entropy and the Second Law of Thermodynamics Free Energy Standard Free-Energy Changes for Reactions Standard Free Energies of Formation Free-Energy Changes and Composition of the Reaction Mixture Free Energy and Chemical Equilibrium 665

7 CONTENTS ix INQUIRY Does Entropy Prevent the Evolution of Biological Complexity? 669 Summary Keywords Conceptual Section Chapter Multiconcept 18.5 Binary Hydrides Oxygen Preparation and Uses of Oxygen Reactivity of Oxygen Oxides Electrochemistry eso 17.1 Galvanic Cells Shorthand Notation for Galvanic Cells Cell Potentials and Free-Energy Changes for Cell Reactions Standard Reduction Potentials Peroxides and Superoxides Hydrogen Peroxide Ozone Water Hydrates 750 INQUIRY What Role for Hydrogen in Future? 752 Our Energy 17.5 Using Standard Reduction Potentials 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 Standard Cell Potentials and Equilibrium Constants Batteries Fuel Cells Corrosion Electrolysis and Electrolytic Cells Commercial Applications of Electrolysis 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 Isotopes of Hydrogen Preparation and Uses of Hydrogen Reactivity of Hydrogen The Main-Group Elements?6o 19.1 A Review of General Properties and Periodic Trends Distinctive Properties of the Second-Row Elements The Group 3A Elements Boron Aluminum The Group 4A Elements Carbon Silicon The Group 5A Elements Nitrogen Phosphorus The Group 6A Elements Sulfur The Halogens: Oxoacids and Oxoacid Salts 791 INQUIRY How Do Laser Printers Work? 793 Summary Keywords Conceptual Section Chapter Multiconcept

8 X CONTENTS 20 Transition Elements and Coordination Chemistry 802 Summary Keywords Conceptual Section Chapter Multiconcept 20.1 Electron Configurations Properties of Transition Elements Oxidation States of Transition Elements Chemistry of Selected Transition Elements Coordination Compounds Ligands Naming Coordination Compounds Isomers Enantiomers and Molecular Handedness Color of Transition Metal Complexes Bonding in Complexes: Valence Bond Theory 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 Nuclear Transmutation 897 Nuclear Reactions Detecting and Measuring Radioactivity 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 Families of Organic Compounds: Functional Groups Metals and Solid-State Materials Naming Organic Compounds Unsaturated Organic Compounds: Alkenes and Alkynes Cyclic Organic Compounds Sources of the Metallic Elements Metallurgy Iron and Steel Bonding in Metals Semiconductors Semiconductor Applications Superconductors Ceramics Composites 877 INQUIRY Why is it Said That the Next Big Thing Will Be Really Small? Aromatic Compounds Alcohols, Ethers, and Amines Carbonyl Compounds An Overview of Biological Chemistry Amino Acids, Peptides, and Proteins Carbohydrates Lipids Nucleic Acids 941 INQUIRY Which Is Better, Natural or Synthetic? 947 Summary Key Words Conceptual Section Chapter Multiconcept

9 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