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CHEMISTRYT H E C E N T R A L S C I E N C E 13TH EDITION
CHEMISTRYT H E C E N T R A L S C I E N C E 13TH EDITION
Theodore L. BrownUniversity of Illinois at Urbana-Champaign
H. Eugene LeMay, Jr.University of Nevada, Reno
Bruce E. BurstenUniversity of Tennessee, Knoxville
Catherine J. MurphyUniversity of Illinois at Urbana-Champaign
Patrick M. WoodwardThe Ohio State University
Matthew W. StoltzfusThe Ohio State University
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Library of Congress Cataloging-In Publication Data
Brown, Theodore L. (Theodore Lawrence), 1928- author.
Chemistry the central science.—Thirteenth edition / Theodore L. Brown, University of Illinois at Urbana-Chanmpaign, H. Euguene LeMay, Jr., University of Nevada, Reno, Bruce E. Bursten, University of Tennessee, Knoxville, Catherine J. Murphy, University of Illinois at Urbana-Chanmpaign, Patrick M. Woodward, The Ohio State University, Matthew W. Stoltzfus, The Ohio State University.
pages cm Includes index. ISBN-13: 978-0-321-91041-7 ISBN-10: 0-321-91041-9 1. Chemistry--Textbooks. I. Title. QD31.3.B765 2014 540—dc23 2013036724
1 2 3 4 5 6 7 8 9 10—CRK— 17 16 15 14
www.pearsonhighered.comStudent Edition: 0-321-91041-9 / 978-0-321-91041-7Instructor’s Resource Copy: 0-321-96239-7 / 978-0-321-96239-3
To our students, whose enthusiasm and curiosity
have often inspired us, and whose questions and suggestions
have sometimes taught us.
vi
Preface XX
1 Introduction: Matter and Measurement 2 2 Atoms, Molecules, and Ions 40
3 Chemical Reactions and Reaction Stoichiometry 80
4 Reactions in Aqueous Solution 122
5 Thermochemistry 164
6 Electronic Structure of Atoms 212
7 Periodic Properties of the Elements 256
8 Basic Concepts of Chemical Bonding 298
9 Molecular Geometry and Bonding Theories 342
10 Gases 398
11 Liquids and Intermolecular Forces 442
12 Solids and Modern Materials 480
13 Properties of Solutions 530
14 Chemical Kinetics 574
15 Chemical Equilibrium 628
16 Acid–Base Equilibria 670
17 Additional Aspects of Aqueous Equilibria 724
18 Chemistry of the Environment 774
19 Chemical Thermodynamics 812
20 Electrochemistry 856
21 Nuclear Chemistry 908
22 Chemistry of the Nonmetals 952
23 Transition Metals and Coordination Chemistry 996
24 The Chemistry of Life: Organic and Biological Chemistry 1040
APPENDICES
A Mathematical Operations 1092 B Properties of Water 1099 C Thermodynamic Quantities for Selected Substances at
298.15 K (25 °C) 1100 D Aqueous Equilibrium Constants 1103 E Standard Reduction Potentials at 25 °C 1105
Answers to Selected Exercises A-1
Answers to Give It Some Thought A-31
Answers to Go Figure A-38
Answers to Selected Practice Exercises A-44
Glossary G-1
Photo/Art Credits P-1
Index I-1
BRIEF CONTENTS
vii
2 Atoms, Molecules, and Ions 40
2.1 The Atomic Theory of Matter 42
2.2 The Discovery of Atomic Structure 43Cathode Rays and Electrons 43 Radioactivity 45 The Nuclear Model of the Atom 46
2.3 The Modern View of Atomic Structure 47Atomic Numbers, Mass Numbers, and Isotopes 49
2.4 Atomic Weights 50The Atomic Mass Scale 50 Atomic Weight 51
2.5 The Periodic Table 52
2.6 Molecules and Molecular Compounds 56Molecules and Chemical Formulas 56 Molecular and Empirical Formulas 56 Picturing Molecules 57
2.7 Ions and Ionic Compounds 58Predicting Ionic Charges 59 Ionic Compounds 60
2.8 Naming Inorganic Compounds 62Names and Formulas of Ionic Compounds 62 Names and Formulas of Acids 67 Names and Formulas of Binary Molecular Compounds 68
2.9 Some Simple Organic Compounds 69Alkanes 69 Some Derivatives of Alkanes 70
Chapter Summary and Key Terms 72 Learning Outcomes 72 Key Equations 73 Exercises 73 Additional Exercises 78
A Closer Look Basic Forces 49
A Closer Look The Mass Spectrometer 52
A Closer Look What Are Coins Made Of? 54 Chemistry and Life Elements Required by Living Organisms 61
Strategies in Chemistry How to Take a Test 71
CONTENTSPreface xx
1 Introduction: Matter and Measurement 2
1.1 The Study of Chemistry 2The Atomic and Molecular Perspective of Chemistry 4 Why Study Chemistry? 5
1.2 Classifications of Matter 6States of Matter 7 Pure Substances 7 Elements 7 Compounds 8 Mixtures 10
1.3 Properties of Matter 11Physical and Chemical Changes 12 Separation of Mixtures 13
1.4 Units of Measurement 14SI Units 15 Length and Mass 17 Temperature 17 Derived SI Units 19 Volume 19 Density 19
1.5 Uncertainty in Measurement 22Precision and Accuracy 22 Significant Figures 22 Significant Figures in Calculations 22
1.6 Dimensional Analysis 27Using Two or More Conversion Factors 28 Conversions Involving Volume 29
Chapter Summary and Key Terms 32 Learning Outcomes 32 Key Equations 32 Exercises 32 Additional Exercises 37
Chemistry Put to Work Chemistry and the Chemical Industry 6
A Closer Look The Scientific Method 14 Chemistry Put to Work Chemistry in the News 20
Strategies in Chemistry Estimating Answers 28 Strategies in Chemistry The Importance of Practice 31
Strategies in Chemistry The Features of This Book 32
viii CONTENTS
3 Chemical Reactions and Reaction Stoichiometry 80
3.1 Chemical Equations 82Balancing Equations 82 Indicating the States of Reactants and Products 85
3.2 Simple Patterns of Chemical Reactivity 86Combination and Decomposition Reactions 86 Combustion Reactions 89
3.3 Formula Weights 89Formula and Molecular Weights 90 Percentage Composition from Chemical Formulas 91
3.4 Avogadro’s Number and the Mole 91Molar Mass 93 Interconverting Masses and Moles 95 Interconverting Masses and Numbers of Particles 96
3.5 Empirical Formulas from Analyses 98Molecular Formulas from Empirical Formulas 100 Combustion Analysis 101
3.6 Quantitative Information from Balanced Equations 103
3.7 Limiting Reactants 106Theoretical and Percent Yields 109
Chapter Summary and Key Terms 111 Learning Outcomes 111 Key Equations 112 Exercises 112 Additional Exercises 118 Integrative Exercises 120 Design an Experiment 120
Strategies in Chemistry Problem Solving 92
Chemistry and Life Glucose Monitoring 95 Strategies in Chemistry Design an Experiment 110
4 Reactions in Aqueous Solution 122
4.1 General Properties of Aqueous Solutions 124
Electrolytes and Nonelectrolytes 124 How Compounds Dissolve in Water 125 Strong and Weak Electrolytes 126
4.2 Precipitation Reactions 128Solubility Guidelines for Ionic Compounds 129 Exchange (Metathesis) Reactions 130 Ionic Equations and Spectator Ions 131
4.3 Acids, Bases, and Neutralization Reactions 132Acids 132 Bases 133 Strong and Weak Acids and Bases 133 Identifying Strong and Weak Electrolytes 135 Neutralization Reactions and Salts 135 Neutralization Reactions with Gas Formation 138
4.4 Oxidation–Reduction Reactions 138Oxidation and Reduction 138 Oxidation Numbers 140 Oxidation of Metals by Acids and Salts 142 The Activity Series 143
4.5 Concentrations of Solutions 146Molarity 146 Expressing the Concentration of an Electrolyte 147 Interconverting Molarity, Moles, and Volume 148 Dilution 149
4.6 Solution Stoichiometry and Chemical Analysis 151Titrations 152
Chapter Summary and Key Terms 155 Learning Outcomes 156 Key Equations 156 Exercises 156 Additional Exercises 161 Integrative Exercises 161 Design an Experiment 163
Chemistry Put to Work Antacids 139 Strategies in Chemistry Analyzing Chemical Reactions 146
5 Thermochemistry 164
5.1 Energy 166Kinetic Energy and Potential Energy 166 Units of Energy 168 System and Surroundings 169 Transferring Energy: Work and Heat 169
5.2 The First Law of Thermodynamics 170Internal Energy 171 Relating ∆E to Heat and Work 172 Endothermic and Exothermic Processes 173 State Functions 174
CONTENTS ix
5.3 Enthalpy 175Pressure–Volume Work 175 Enthalpy Change 177
5.4 Enthalpies of Reaction 179
5.5 Calorimetry 181Heat Capacity and Specific Heat 181 Constant-Pressure Calorimetry 183 Bomb Calorimetry (Constant-Volume Calorimetry) 185
5.6 Hess’s Law 187
5.7 Enthalpies of Formation 189Using Enthalpies of Formation to Calculate Enthalpies of Reaction 192
5.8 Foods and Fuels 194Foods 194 Fuels 197 Other Energy Sources 198
Chapter Summary and Key Terms 200 Learning Outcomes 201 Key Equations 202 Exercises 202 Additional Exercises 209 Integrative Exercises 210 Design an Experiment 211
A Closer Look Energy, Enthalpy, and P–V Work 178
Strategies in Chemistry Using Enthalpy as a Guide 181
Chemistry and Life The Regulation of Body Temperature 186
Chemistry Put to Work The Scientific and Political Challenges of Biofuels 198
6 Electronic Structure of Atoms 212
6.1 The Wave Nature of Light 214
6.2 Quantized Energy and Photons 216Hot Objects and the Quantization of Energy 216 The Photoelectric Effect and Photons 217
6.3 Line Spectra and the Bohr Model 219Line Spectra 219 Bohr’s Model 220 The Energy States of the Hydrogen Atom 221 Limitations of the Bohr Model 223
6.4 The Wave Behavior of Matter 223The Uncertainty Principle 225
6.5 Quantum Mechanics and Atomic Orbitals 226
Orbitals and Quantum Numbers 228
6.6 Representations of Orbitals 230The s Orbitals 230 The p Orbitals 233 The d and f Orbitals 233
6.7 Many-Electron Atoms 234Orbitals and Their Energies 234 Electron Spin and the Pauli Exclusion Principle 235
6.8 Electron Configurations 237Hund’s Rule 237 Condensed Electron Configurations 239 Transition Metals 240 The Lanthanides and Actinides 240
6.9 Electron Configurations and the Periodic Table 241Anomalous Electron Configurations 245
Chapter Summary and Key Terms 246 Learning Outcomes 247 Key Equations 247 Exercises 248 Additional Exercises 252 Integrative Exercises 255 Design an Experiment 255
A Closer Look Measurement and the Uncertainty Principle 225
A Closer Look Thought Experiments and Schrödinger’s Cat 227
A Closer Look Probability Density and Radial Probability Functions 232
Chemistry and Life Nuclear Spin and Magnetic Resonance Imaging 236
7 Periodic Properties of the Elements 256
7.1 Development of the Periodic Table 258
7.2 Effective Nuclear Charge 259
7.3 Sizes of Atoms and Ions 262Periodic Trends in Atomic Radii 264 Periodic Trends in Ionic Radii 265
7.4 Ionization Energy 268Variations in Successive Ionization Energies 268 Periodic Trends in First Ionization Energies 268 Electron Configurations of Ions 271
7.5 Electron Affinity 272
7.6 Metals, Nonmetals, and Metalloids 273Metals 274 Nonmetals 276 Metalloids 277
x CONTENTS
7.7 Trends for Group 1A and Group 2A Metals 278Group 1A: The Alkali Metals 278 Group 2A: The Alkaline Earth Metals 281
7.8 Trends for Selected Nonmetals 282Hydrogen 282 Group 6A: The Oxygen Group 283 Group 7A: The Halogens 284 Group 8A: The Noble Gases 286
Chapter Summary and Key Terms 288 Learning Outcomes 289 Key Equations 289 Exercises 289 Additional Exercises 294 Integrative Exercises 296 Design an Experiment 297
A Closer Look Effective Nuclear Charge 261 Chemistry Put to Work Ionic Size and Lithium-Ion Batteries 267
Chemistry and Life The Improbable Development of Lithium Drugs 281
8 Basic Concepts of Chemical Bonding 298
8.1 Lewis Symbols and the Octet Rule 300The Octet Rule 300
8.2 Ionic Bonding 301Energetics of Ionic Bond Formation 302 Electron Configurations of Ions of the s- and p-Block Elements 305 Transition Metal Ions 306
8.3 Covalent Bonding 306Lewis Structures 307 Multiple Bonds 308
8.4 Bond Polarity and Electronegativity 309Electronegativity 309 Electronegativity and Bond Polarity 310 Dipole Moments 311 Differentiating Ionic and Covalent Bonding 314
8.5 Drawing Lewis Structures 315Formal Charge and Alternative Lewis Structures 317
8.6 Resonance Structures 320Resonance in Benzene 322
8.7 Exceptions to the Octet Rule 322Odd Number of Electrons 323 Less Than an Octet of Valence Electrons 323 More Than an Octet of Valence Electrons 324
8.8 Strengths and Lengths of Covalent Bonds 325
Bond Enthalpies and the Enthalpies of Reactions 327 Bond Enthalpy and Bond Length 329
Chapter Summary and Key Terms 332 Learning Outcomes 333 Key Equations 333 Exercises 333 Additional Exercises 338 Integrative Exercises 340 Design an Experiment 341
A Closer Look Calculation of Lattice Energies: The Born–Haber Cycle 304
A Closer Look Oxidation Numbers, Formal Charges, and Actual Partial Charges 319
Chemistry Put to Work Explosives and Alfred Nobel 330
9 Molecular Geometry and Bonding Theories 342
9.1 Molecular Shapes 344
9.2 The VSEPR Model 347Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles 351 Molecules with Expanded Valence Shells 352 Shapes of Larger Molecules 355
9.3 Molecular Shape and Molecular Polarity 356
9.4 Covalent Bonding and Orbital Overlap 358
9.5 Hybrid Orbitals 359sp Hybrid Orbitals 360 sp2 and sp3 Hybrid Orbitals 361 Hypervalent Molecules 362 Hybrid Orbital Summary 364
9.6 Multiple Bonds 365Resonance Structures, Delocalization, and p Bonding 368 General Conclusions about s and p Bonding 372
9.7 Molecular Orbitals 373Molecular Orbitals of the Hydrogen Molecule 373 Bond Order 375
9.8 Period 2 Diatomic Molecules 376Molecular Orbitals for Li2 and Be2 377 Molecular Orbitals from 2p Atomic Orbitals 377 Electron Configurations for B2 through Ne2 381 Electron Configurations and Molecular Properties 383 Heteronuclear Diatomic Molecules 384
CONTENTS xi
Chapter Summary and Key Terms 386 Learning Outcomes 387 Key Equations 388 Exercises 388 Additional Exercises 393 Integrative Exercises 396 Design an Experiment 397
Chemistry and Life The Chemistry of Vision 372 A Closer Look Phases in Atomic and Molecular Orbitals 379
Chemistry Put to Work Orbitals and Energy 385
10 Gases 398
10.1 Characteristics of Gases 400
10.2 Pressure 401Atmospheric Pressure and the Barometer 401
10.3 The Gas Laws 404The Pressure–Volume Relationship: Boyle’s Law 404 The Temperature–Volume Relationship: Charles’s Law 406 The Quantity–Volume Relationship: Avogadro’s Law 406
10.4 The Ideal-Gas Equation 408Relating the Ideal-Gas Equation and the Gas Laws 410
10.5 Further Applications of the Ideal-Gas Equation 412Gas Densities and Molar Mass 413 Volumes of Gases in Chemical Reactions 414
10.6 Gas Mixtures and Partial Pressures 415Partial Pressures and Mole Fractions 417
10.7 The Kinetic-Molecular Theory of Gases 418Distributions of Molecular Speed 419 Application of Kinetic-Molecular Theory to the Gas Laws 420
10.8 Molecular Effusion and Diffusion 421Graham’s Law of Effusion 423 Diffusion and Mean Free Path 424
10.9 Real Gases: Deviations from Ideal Behavior 426The van der Waals Equation 428
Chapter Summary and Key Terms 431 Learning Outcomes 431 Key Equations 432
Exercises 432 Additional Exercises 438 Integrative Exercises 440 Design an Experiment 441
Strategies in Chemistry Calculations Involving Many Variables 410
A Closer Look The Ideal-Gas Equation 421
Chemistry Put to Work Gas Separations 425
11 Liquids and Intermolecular Forces 442
11.1 A Molecular Comparison of Gases, Liquids, and Solids 444
11.2 Intermolecular Forces 446Dispersion Forces 447 Dipole–Dipole Forces 448 Hydrogen Bonding 449 Ion–Dipole Forces 452 Comparing Intermolecular Forces 452
11.3 Select Properties of Liquids 455Viscosity 455 Surface Tension 456 Capillary Action 456
11.4 Phase Changes 457Energy Changes Accompanying Phase Changes 457 Heating Curves 459 Critical Temperature and Pressure 460
11.5 Vapor Pressure 461Volatility, Vapor Pressure, and Temperature 462 Vapor Pressure and Boiling Point 463
11.6 Phase Diagrams 464
The Phase Diagrams of H2O and CO2 465
11.7 Liquid Crystals 467Types of Liquid Crystals 467
Chapter Summary and Key Terms 470 Learning Outcomes 471 Exercises 471 Additional Exercises 477 Integrative Exercises 478 Design an Experiment 479
Chemistry Put to Work Ionic Liquids 454
A Closer Look The Clausius–Clapeyron Equation 463
xii CONTENTS
12 Solids and Modern Materials 480
12.1 Classification of Solids 480
12.2 Structures of Solids 482Crystalline and Amorphous Solids 482 Unit Cells and Crystal Lattices 483 Filling the Unit Cell 485
12.3 Metallic Solids 486The Structures of Metallic Solids 487 Close Packing 488 Alloys 491
12.4 Metallic Bonding 494Electron-Sea Model 494 Molecular–Orbital Model 495
12.5 Ionic Solids 498Structures of Ionic Solids 498
12.6 Molecular Solids 502
12.7 Covalent-Network Solids 503Semiconductors 504 Semiconductor Doping 506
12.8 Polymers 507Making Polymers 509 Structure and Physical Properties of Polymers 511
12.9 Nanomaterials 514Semiconductors on the Nanoscale 514 Metals on the Nanoscale 515 Carbons on the Nanoscale 516
Chapter Summary and Key Terms 519 Learning Outcomes 520 Key Equation 520 Exercises 521 Additional Exercises 527 Integrative Exercises 528 Design an Experiment 529
A Closer Look X-ray Diffraction 486
Chemistry Put to Work Alloys of Gold 494 Chemistry Put to Work Solid-State Lighting 508
Chemistry Put to Work Recycling Plastics 511
13 Properties of Solutions 530
13.1 The Solution Process 530The Natural Tendency toward Mixing 532 The Effect of Intermolecular Forces on Solution Formation 532 Energetics of Solution Formation 533 Solution Formation and Chemical Reactions 535
13.2 Saturated Solutions and Solubility 536
13.3 Factors Affecting Solubility 538Solute–Solvent Interactions 538 Pressure Effects 541 Temperature Effects 543
13.4 Expressing Solution Concentration 544Mass Percentage, ppm, and ppb 544 Mole Fraction, Molarity, and Molality 545 Converting Concentration Units 547
13.5 Colligative Properties 548Vapor-Pressure Lowering 548 Boiling-Point Elevation 551 Freezing-Point Depression 552 Osmosis 554 Determination of Molar Mass from Colligative Properties 557
13.6 Colloids 559Hydrophilic and Hydrophobic Colloids 560 Colloidal Motion in Liquids 562
Chapter Summary and Key Terms 564 Learning Outcomes 565 Key Equations 565 Exercises 566 Additional Exercises 571 Integrative Exercises 572 Design an Experiment 573
Chemistry and Life Fat-Soluble and Water-Soluble Vitamins 539
Chemistry and Life Blood Gases and Deep-Sea Diving 544
A Closer Look Ideal Solutions with Two or More Volatile Components 550
A Closer Look The Van’t Hoff Factor 558
Chemistry and Life Sickle-Cell Anemia 562
CONTENTS xiii
14 Chemical Kinetics 574
14.1 Factors that Affect Reaction Rates 576
14.2 Reaction Rates 577Change of Rate with Time 579 Instantaneous Rate 579 Reaction Rates and Stoichiometry 580
14.3 Concentration and Rate Laws 581Reaction Orders: The Exponents in the Rate Law 584 Magnitudes and Units of Rate Constants 585 Using Initial Rates to Determine Rate Laws 586
14.4 The Change of Concentration with Time 587First-Order Reactions 587 Second-Order Reactions 589 Zero-Order Reactions 591 Half-Life 591
14.5 Temperature and Rate 593The Collision Model 593 The Orientation Factor 594 Activation Energy 594 The Arrhenius Equation 596 Determining the Activation Energy 597
14.6 Reaction Mechanisms 599Elementary Reactions 599 Multistep Mechanisms 600 Rate Laws for Elementary Reactions 601 The Rate-Determining Step for a Multistep Mechanism 602 Mechanisms with a Slow Initial Step 603 Mechanisms with a Fast Initial Step 604
14.7 Catalysis 606Homogeneous Catalysis 607 Heterogeneous Catalysis 608 Enzymes 609
Chapter Summary and Key Terms 614 Learning Outcomes 614 Key Equations 615 Exercises 615 Additional Exercises 624 Integrative Exercises 626 Design an Experiment 627
A Closer Look Using Spectroscopic Methods to Measure Reaction Rates: Beer’s Law 582
Chemistry Put to Work Methyl Bromide in the Atmosphere 592
Chemistry Put to Work Catalytic Converters 610 Chemistry and Life Nitrogen Fixation and Nitrogenase 612
15 Chemical Equilibrium 628
15.1 The Concept of Equilibrium 630
15.2 The Equilibrium Constant 632Evaluating Kc 634 Equilibrium Constants in Terms of Pressure, Kp 635 Equilibrium Constants and Units 636
15.3 Understanding and Working with Equilibrium Constants 637The Magnitude of Equilibrium Constants 637 The Direction of the Chemical Equation and K 639 Relating Chemical Equation Stoichiometry and Equilibrium Constants 639
15.4 Heterogeneous Equilibria 641
15.5 Calculating Equilibrium Constants 644
15.6 Applications of Equilibrium Constants 646Predicting the Direction of Reaction 646 Calculating Equilibrium Concentrations 648
15.7 Le Châtelier’s Principle 650Change in Reactant or Product Concentration 651 Effects of Volume and Pressure Changes 652 Effect of Temperature Changes 654 The Effect of Catalysts 657
Chapter Summary and Key Terms 660 Learning Outcomes 660 Key Equations 661 Exercises 661 Additional Exercises 666 Integrative Exercises 668 Design an Experiment 669
Chemistry Put to Work The Haber Process 633 Chemistry Put to Work Controlling Nitric Oxide Emissions 659
16 Acid–Base Equilibria 670
16.1 Acids and Bases: A Brief Review 672
16.2 BrØnsted–Lowry Acids and Bases 673
xiv CONTENTS
The H+ Ion in Water 673 Proton-Transfer Reactions 673 Conjugate Acid–Base Pairs 674 Relative Strengths of Acids and Bases 676
16.3 The Autoionization of Water 678The Ion Product of Water 679
16.4 The pH Scale 680pOH and Other “p” Scales 682 Measuring pH 683
16.5 Strong Acids and Bases 684Strong Acids 684 Strong Bases 685
16.6 Weak Acids 686Calculating Ka from pH 688 Percent Ionization 689 Using Ka to Calculate pH 690 Polyprotic Acids 694
16.7 Weak Bases 696Types of Weak Bases 698
16.8 Relationship between Ka and Kb 699
16.9 Acid–Base Properties of Salt Solutions 702An Anion’s Ability to React with Water 702 A Cation’s Ability to React with Water 702 Combined Effect of Cation and Anion in Solution 704
16.10 Acid–Base Behavior and Chemical Structure 705Factors That Affect Acid Strength 705 Binary Acids 706 Oxyacids 707 Carboxylic Acids 709
16.11 Lewis Acids and Bases 710
Chapter Summary and Key Terms 713 Learning Outcomes 714 Key Equations 714 Exercises 715 Additional Exercises 720 Integrative Exercises 722 Design an Experiment 723
Chemistry Put to Work Amines and Amine Hydrochlorides 701
Chemistry and Life The Amphiprotic Behavior of Amino Acids 709
17 Additional Aspects of Aqueous Equilibria 724
17.1 The Common-Ion Effect 726
17.2 Buffers 729Composition and Action of Buffers 729 Calculating the pH of a Buffer 731 Buffer Capacity and pH Range 734 Addition of Strong Acids or Bases to Buffers 735
17.3 Acid–Base Titrations 738Strong Acid–Strong Base Titrations 738 Weak Acid–Strong Base Titrations 740 Titrating with an Acid–Base Indicator 744 Titrations of Polyprotic Acids 746
17.4 Solubility Equilibria 748The Solubility-Product Constant, Ksp 748 Solubility and Ksp 749
17.5 Factors That Affect Solubility 751Common-Ion Effect 751 Solubility and pH 753 Formation of Complex Ions 756 Amphoterism 758
17.6 Precipitation and Separation of Ions 759Selective Precipitation of Ions 760
17.7 Qualitative Analysis for Metallic Elements 762
Chapter Summary and Key Terms 765 Learning Outcomes 765 Key Equations 766 Exercises 766 Additional Exercises 771 Integrative Exercises 772 Design an Experiment 773
Chemistry and Life Blood as a Buffered Solution 737
A Closer Look Limitations of Solubility Products 751
Chemistry and Life Ocean Acidification 753 Chemistry and Life Tooth Decay and Fluoridation 755
18 Chemistry of the Environment 774
18.1 Earth’s Atmosphere 776Composition of the Atmosphere 776 Photochemical Reactions in the Atmosphere 778 Ozone in the Stratosphere 780
18.2 Human Activities and Earth’s Atmosphere 782The Ozone Layer and Its Depletion 782 Sulfur Compounds and Acid Rain 784 Nitrogen Oxides and Photochemical Smog 786 Greenhouse Gases: Water Vapor, Carbon Dioxide, and Climate 787
18.3 Earth’s Water 791The Global Water Cycle 791 Salt Water: Earth’s Oceans and Seas 792 Freshwater and Groundwater 792
CONTENTS xv
18.4 Human Activities and Water Quality 794Dissolved Oxygen and Water Quality 794 Water Purification: Desalination 795 Water Purification: Municipal Treatment 796
18.5 Green Chemistry 798Supercritical Solvents 800 Greener Reagents and Processes 800
Chapter Summary and Key Terms 803 Learning Outcomes 803 Exercises 804 Additional Exercises 808 Integrative Exercises 809 Design an Experiment 811
A Closer Look Other Greenhouse Gases 790 A Closer Look The Ogallala Aquifer—A Shrinking Resource 794
A Closer Look Fracking and Water Quality 797
19 Chemical Thermodynamics 812
19.1 Spontaneous Processes 814Seeking a Criterion for Spontaneity 816 Reversible and Irreversible Processes 816
19.2 Entropy and the Second Law of Thermodynamics 818The Relationship between Entropy and Heat 818 ∆S for Phase Changes 819 The Second Law of Thermodynamics 820
19.3 The Molecular Interpretation of Entropy and the Third Law of Thermodynamics 821Expansion of a Gas at the Molecular Level 821 Boltzmann’s Equation and Microstates 823 Molecular Motions and Energy 824 Making Qualitative Predictions about ∆S 825 The Third Law of Thermodynamics 827
19.4 Entropy Changes in Chemical Reactions 828Entropy Changes in the Surroundings 830
19.5 Gibbs Free Energy 831Standard Free Energy of Formation 834
19.6 Free Energy and Temperature 836
19.7 Free Energy and the Equilibrium Constant 838Free Energy under Nonstandard Conditions 838 Relationship between ∆G° and K 840
Chapter Summary and Key Terms 844
Learning Outcomes 844 Key Equations 845 Exercises 845 Additional Exercises 851 Integrative Exercises 853 Design an Experiment 855
A Closer Look The Entropy Change When a Gas Expands Isothermally 820
Chemistry and Life Entropy and Human Society 828
A Closer Look What’s “Free” about Free Energy? 836 Chemistry and Life Driving Nonspontaneous Reactions: Coupling Reactions 842
20 Electrochemistry 856
20.1 Oxidation States and Oxidation–Reduction Reactions 858
20.2 Balancing Redox Equations 860Half-Reactions 860 Balancing Equations by the Method of Half-Reactions 860 Balancing Equations for Reactions Occurring in Basic Solution 863
20.3 Voltaic Cells 865
20.4 Cell Potentials Under Standard Conditions 868Standard Reduction Potentials 869 Strengths of Oxidizing and Reducing Agents 874
20.5 Free Energy and Redox Reactions 876Emf, Free Energy, and the Equilibrium Constant 877
20.6 Cell Potentials Under Nonstandard Conditions 880The Nernst Equation 880 Concentration Cells 882
20.7 Batteries and Fuel Cells 886Lead–Acid Battery 886 Alkaline Battery 887 Nickel–Cadmium and Nickel–Metal Hydride Batteries 887 Lithium-Ion Batteries 887 Hydrogen Fuel Cells 889
20.8 Corrosion 891Corrosion of Iron (Rusting) 891 Preventing Corrosion of Iron 892
20.9 Electrolysis 893Quantitative Aspects of Electrolysis 894
Chapter Summary and Key Terms 897 Learning Outcomes 898 Key Equations 899 Exercises 899 Additional Exercises 905 Integrative Exercises 907 Design an Experiment 907
xvi CONTENTS
A Closer Look Electrical Work 879 Chemistry and Life Heartbeats and Electrocardiography 884
Chemistry Put to Work Batteries for Hybrid and Electric Vehicles 889
Chemistry Put to Work Electrometallurgy of Aluminum 895
21 Nuclear Chemistry 908
21.1 Radioactivity and Nuclear Equations 910Nuclear Equations 911 Types of Radioactive Decay 912
21.2 Patterns of Nuclear Stability 914Neutron-to-Proton Ratio 914 Radioactive Decay Chains 916 Further Observations 916
21.3 Nuclear Transmutations 918Accelerating Charged Particles 918 Reactions Involving Neutrons 919 Transuranium Elements 920
21.4 Rates of Radioactive Decay 920Radiometric Dating 921 Calculations Based on Half-Life 923
21.5 Detection of Radioactivity 926Radiotracers 927
21.6 Energy Changes in Nuclear Reactions 929Nuclear Binding Energies 930
21.7 Nuclear Power: Fission 932Nuclear Reactors 934 Nuclear Waste 936
21.8 Nuclear Power: Fusion 937
21.9 Radiation in the Environment and Living Systems 938Radiation Doses 940 Radon 942
Chapter Summary and Key Terms 944 Learning Outcomes 945 Key Equations 945 Exercises 946 Additional Exercises 949 Integrative Exercises 951 Design an Experiment 951
Chemistry and Life Medical Applications of Radiotracers 928
A Closer Look The Dawning of the Nuclear Age 934
A Closer Look Nuclear Synthesis of the Elements 939
Chemistry and Life Radiation Therapy 943
22 Chemistry of the Nonmetals 952
22.1 Periodic Trends and Chemical Reactions 952Chemical Reactions 955
22.2 Hydrogen 956Isotopes of Hydrogen 956 Properties of Hydrogen 957 Production of Hydrogen 958 Uses of Hydrogen 959 Binary Hydrogen Compounds 959
22.3 Group 8A: The Noble Gases 960Noble-Gas Compounds 961
22.4 Group 7A: The Halogens 962Properties and Production of the Halogens 962 Uses of the Halogens 964 The Hydrogen Halides 964 Interhalogen Compounds 965 Oxyacids and Oxyanions 966
22.5 Oxygen 966Properties of Oxygen 967 Production of Oxygen 967 Uses of Oxygen 967 Ozone 967 Oxides 968 Peroxides and Superoxides 969
22.6 The Other Group 6A Elements: S, Se, Te, and Po 970General Characteristics of the Group 6A Elements 970 Occurrence and Production of S, Se, and Te 970 Properties and Uses of Sulfur, Selenium, and Tellurium 971 Sulfides 971 Oxides, Oxyacids, and Oxyanions of Sulfur 971
22.7 Nitrogen 973Properties of Nitrogen 973 Production and Uses of Nitrogen 973 Hydrogen Compounds of Nitrogen 973 Oxides and Oxyacids of Nitrogen 975
22.8 The Other Group 5A Elements: P, As, Sb, and Bi 977General Characteristics of the Group 5A Elements 977 Occurrence, Isolation, and Properties of Phosphorus 977 Phosphorus Halides 978 Oxy Compounds of Phosphorus 978
22.9 Carbon 980Elemental Forms of Carbon 980 Oxides of Carbon 981 Carbonic Acid and Carbonates 983 Carbides 983
CONTENTS xvii
22.10 The Other Group 4A Elements: Si, Ge, Sn, and Pb 984General Characteristics of the Group 4A Elements 984 Occurrence and Preparation of Silicon 984 Silicates 985 Glass 986 Silicones 987
22.11 Boron 987
Chapter Summary and Key Terms 989 Learning Outcomes 990 Exercises 990 Additional Exercises 994 Integrative Exercises 994 Design an Experiment 995
A Closer Look The Hydrogen Economy 958 Chemistry and Life Nitroglycerin, Nitric Oxide, and Heart Disease 976
Chemistry and Life Arsenic in Drinking Water 980
Chemistry Put to Work Carbon Fibers and Composites 982
23 Transition Metals and Coordination Chemistry 996
23.1 The Transition Metals 998Physical Properties 998Electron Configurations and Oxidation States 999 Magnetism 1001
23.2 Transition-Metal Complexes 1002The Development of Coordination Chemistry: Werner’s Theory 1003 The Metal–Ligand Bond 1005 Charges, Coordination Numbers, and Geometries 1006
23.3 Common Ligands in Coordination Chemistry 1007Metals and Chelates in Living Systems 1009
23.4 Nomenclature and Isomerism in Coordination Chemistry 1012Isomerism 1014 Structural Isomerism 1014 Stereoisomerism 1015
23.5 Color and Magnetism in Coordination Chemistry 1019Color 1019 Magnetism of Coordination Compounds 1021
23.6 Crystal-Field Theory 1021
Electron Configurations in Octahedral Complexes 1024 Tetrahedral and Square-Planar Complexes 1026
Chapter Summary and Key Terms 1030 Learning Outcomes 1031 Exercises 1031 Additional Exercises 1035 Integrative Exercises 1037 Design an Experiment 1039
A Closer Look Entropy and the Chelate Effect 1010
Chemistry and Life The Battle for Iron in Living Systems 1011
A Closer Look Charge-Transfer Color 1028
24 The Chemistry of Life: Organic and Biological Chemistry 1040
24.1 General Characteristics of Organic Molecules 1042The Structures of Organic Molecules 1042 The Stabilities of Organic Substances 1043 Solubility and Acid–Base Properties of Organic Substances 1042
24.2 Introduction to Hydrocarbons 1044Structures of Alkanes 1045 Structural Isomers 1045 Nomenclature of Alkanes 1046 Cycloalkanes 1049 Reactions of Alkanes 1049
24.3 Alkenes, Alkynes, and Aromatic Hydrocarbons 1050Alkenes 1051 Alkynes 1053 Addition Reactions of Alkenes and Alkynes 1054 Aromatic Hydrocarbons 1056 Stabilization of p Electrons by Delocalization 1056 Substitution Reactions 1057
24.4 Organic Functional Groups 1058Alcohols 1058 Ethers 1061 Aldehydes and Ketones 1061 Carboxylic Acids and Esters 1062 Amines and Amides 1066
24.5 Chirality in Organic Chemistry 1067
24.6 Introduction to Biochemistry 1067
24.7 Proteins 1068Amino Acids 1068 Polypeptides and Proteins 1070 Protein Structure 1071
xviii CONTENTS
24.8 Carbohydrates 1073Disaccharides 1074 Polysaccharides 1075
24.9 Lipids 1076Fats 1076 Phospholipids 1077
24.10 Nucleic Acids 1077
Chapter Summary and Key Terms 1082 Learning Outcomes 1083 Exercises 1083 Additional Exercises 1089
Integrative Exercises 1090
Design an Experiment 1091
Chemistry Put to Work Gasoline 1050 A Closer Look Mechanism of Addition Reactions 1055
Strategies in Chemistry What Now? 1081
Appendices
A Mathematical Operations 1092
B Properties of Water 1099
C Thermodynamic Quantities for Selected Substances AT 298.15 K (25 °C) 1100
D Aqueous Equilibrium Constants 1103
E Standard Reduction Potentials at 25 °C 1105
Answers to Selected Exercises A-1
Answers to Give It Some Thought A-31
Answers to Go Figure A-38
Answers to Selected Practice Exercises A-44
Glossary G-1
Photo/Art Credits P-1
Index I-1
xix
Chemistry Put to Work Chemistry and the Chemical Industry 6 Chemistry in the News 20 Antacids 139The Scientific and Political Challenges of Biofuels 198Ionic Size and Lithium-Ion Batteries 267Explosives and Alfred Nobel 330Orbitals and Energy 385Gas Separations 425Ionic Liquids 454Alloys of Gold 494Solid-State Lighting 508Recycling Plastics 511Methyl Bromide in the Atmosphere 592Catalytic Converters 610The Haber Process 633Controlling Nitric Oxide Emissions 659Amines and Amine Hydrochlorides 701Batteries for Hybrid and Electric Vehicles 889Electrometallurgy of Aluminum 895Carbon Fibers and Composites 982Gasoline 1050
A Closer Look The Scientific Method 14 Basic Forces 49 The Mass Spectrometer 52What Are Coins Made Of? 54Energy, Enthalpy, and P–V Work 178Measurement and the Uncertainty Principle 225Thought Experiments and Schrödinger’s Cat 226Probability Density and Radial Probability Functions 232Effective Nuclear Charge 261Calculation of Lattice Energies: The Born–Haber Cycle 304Oxidation Numbers, Formal Charges, and Actual Partial
Charges 319Phases in Atomic and Molecular Orbitals 379The Ideal-Gas Equation 421The Clausius–Clapeyron Equation 463X-ray Diffraction 486Ideal Solutions with Two or More Volatile Components 550The Van’t Hoff Factor 558Using Spectroscopic Methods to Measure Reaction Rates:
Beer’s Law 582Limitations of Solubility Products 751Other Greenhouse Gases 790
The Ogallala Aquifer—A Shrinking Resource 794Fracking and Water Quality 797The Entropy Change When a Gas Expands Isothermally 820What’s “Free” about Free Energy? 836Electrical Work 879The Dawning of the Nuclear Age 934Nuclear Synthesis of the Elements 939The Hydrogen Economy 958Entropy and the Chelate Effect 1010Charge-Transfer Color 1028Mechanism of Addition Reactions 1055
Chemistry and Life Elements Required by Living Organisms 61 Glucose Monitoring 95 The Regulation of Body Temperature 186Nuclear Spin and Magnetic Resonance Imaging 236The Improbable Development of Lithium Drugs 281The Chemistry of Vision 372Fat-Soluble and Water-Soluble Vitamins 539Blood Gases and Deep-Sea Diving 544Sickle-Cell Anemia 562Nitrogen Fixation and Nitrogenase 612The Amphiprotic Behavior of Amino Acids 709Blood as a Buffered Solution 737Ocean Acidification 753Tooth Decay and Fluoridation 755Entropy and Human Society 828Driving Nonspontaneous Reactions: Coupling Reactions 842Heartbeats and Electrocardiography 884Medical Applications of Radiotracers 928Radiation Therapy 943Nitroglycerin, Nitric Oxide, and Heart Disease 976Arsenic in Drinking Water 980The Battle for Iron in Living Systems 1011
Strategies in Chemistry Estimating Answers 28 The Importance of Practice 31 The Features of This Book 32How to Take a Test 71Problem Solving 92Design an Experiment 110Analyzing Chemical Reactions 146Using Enthalpy as a Guide 181Calculations Involving Many Variables 410What Now? 1081
CHEMICAL APPLICATIONS AND ESSAYS
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