T h e C e n T r a l S C i e n C e

ChemistryT h e C e n T r a l S C i e n C e

13Th ediTion aP® ediTion

A01_BROW0417_13_AP_FM.indd 1 11/13/13 11:15 PM

ChemistryT h e C e n T r a l S C i e n C e

13Th ediTion aP® 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

Boston Columbus indianapolis new York San Francisco Upper Saddle river amsterdam Cape Town dubai london Madrid Milan Munich Paris Montréal Toronto

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Editor in Chief, Chemistry: Adam JaworskiSenior Acquisitions Editor: Terry HaugenAcquisitions Editor: Chris Hess, Ph.D.Executive Marketing Manager: Jonathan CottrellAssociate Team Lead, Program Management, Chemistry and Geoscience: Jessica MoroEditorial Assistant: Lisa Tarabokjia/Caitlin FalcoMarketing Assistant: Nicola HoustonDirector of Development: Jennifer HartDevelopment Editor, Text: Carol Pritchard-MartinezTeam Lead, Project Management, Chemistry and Geosciences: Gina M. CheselkaProject Manager: Beth SweetenFull-Service Project Management/Composition: Greg Johnson, PreMediaGlobalOperations Specialist: Christy HallIllustrator: Precision GraphicsArt Director: Mark OngInterior / Cover Designer: Tamara NewnamImage Lead: Maya MelenchukPhoto Researcher: Kerri Wilson, PreMediaGlobalText Permissions Manager: Alison BrucknerText Permission Researcher: Jacqueline Bates, GEX Publishing ServicesSenior Content Producer: Kristin MayoProduction Supervisor, Media: Shannon KongElectrostatic Potential Maps: Richard Johnson, Chemistry Department, University of New HampshireCover Image Credit: “Metal-Organic Frameworks” by Omar M. Yaghi, University of California, Berkeley

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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.PearsonSchool.com/AdvancedISBN-10: 0-13-357412-1 (High School Binding)ISBN-13: 978-0-13-357412-8 (High School Binding)


To our students, whose enthusiasm and curiosity

have often inspired us, and whose questions and suggestions

have sometimes taught us.


vi

Preface xx

Tips for AP® Chemistry Exam Success xxiv

Correlation Guide for AP xxviii

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 43

Cathode Rays and Electrons 43 Radioactivity 45 The Nuclear Model of the Atom 46

2.3 The Modern View of Atomic Structure 47

Atomic Numbers, Mass Numbers, and Isotopes 49

2.4 Atomic Weights 50

The Atomic Mass Scale 50 Atomic Weight 51

2.5 The Periodic Table 52

2.6 Molecules and Molecular Compounds 56

Molecules and Chemical Formulas 56 Molecular and Empirical Formulas 56 Picturing Molecules 57

2.7 Ions and Ionic Compounds 58

Predicting Ionic Charges 59 Ionic Compounds 60

2.8 Naming Inorganic Compounds 62

Names 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 69

Alkanes 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

CONTENTS

Preface xxTips for AP® Chemistry Exam Success xxivCorrelation Guide for AP xxviii

1 Introduction: Matter and Measurement 2

1.1 The Study of Chemistry 2

The Atomic and Molecular Perspective of Chemistry 4 Why Study Chemistry? 5

1.2 Classifications of Matter 6

States of Matter 7 Pure Substances 7 Elements 7 Compounds 8 Mixtures 10

1.3 Properties of Matter 11

Physical and Chemical Changes 12 Separation of Mixtures 13

1.4 Units of Measurement 14

SI Units 15 Length and Mass 17 Temperature 17 derived SI Units 19 Volume 19 density 19

1.5 Uncertainty in Measurement 22

Precision and Accuracy 22 Significant Figures 22 Significant Figures in Calculations 22

1.6 dimensional Analysis 27

Using 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 82

Balancing Equations 82 Indicating the States of Reactants and Products 85

3.2 Simple Patterns of Chemical Reactivity 86

Combination and decomposition Reactions 86 Combustion Reactions 89

3.3 Formula Weights 89

Formula and Molecular Weights 90 Percentage Composition from Chemical Formulas 91

3.4 Avogadro’s Number and the Mole 91

Molar Mass 93 Interconverting Masses and Moles 95 Interconverting Masses and Numbers of Particles 96

3.5 Empirical Formulas from Analyses 98

Molecular Formulas from Empirical Formulas 100 Combustion Analysis 101

3.6 Quantitative Information from Balanced Equations 103

3.7 Limiting Reactants 106

Theoretical 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 128

Solubility Guidelines for Ionic Compounds 129 Exchange (Metathesis) Reactions 130 Ionic Equations and Spectator Ions 131

4.3 Acids, Bases, and Neutralization Reactions 132

Acids 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 138

Oxidation and Reduction 138 Oxidation Numbers 140 Oxidation of Metals by Acids and Salts 142 The Activity Series 143

4.5 Concentrations of Solutions 146

Molarity 146 Expressing the Concentration of an Electrolyte 147 Interconverting Molarity, Moles, and Volume 148 dilution 149

4.6 Solution Stoichiometry and Chemical Analysis 151

Titrations 152


Chemistry Put to Work Antacids 139 Strategies in Chemistry Analyzing Chemical Reactions 146

5 Thermochemistry 164

5.1 Energy 166

Kinetic 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 170

Internal Energy 171 Relating ∆E to Heat and Work 172 Endothermic and Exothermic Processes 173 State Functions 174


Contents ix

5.3 Enthalpy 175

Pressure–Volume Work 175 Enthalpy Change 177

5.4 Enthalpies of Reaction 179

5.5 Calorimetry 181

Heat 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 189

Using Enthalpies of Formation to Calculate Enthalpies of Reaction 192

5.8 Foods and Fuels 194

Foods 194 Fuels 197 Other Energy Sources 198


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 216

Hot Objects and the Quantization of Energy 216 The Photoelectric Effect and Photons 217

6.3 Line Spectra and the Bohr Model 219

Line 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 223

The Uncertainty Principle 225

6.5 Quantum Mechanics and Atomic Orbitals 226

Orbitals and Quantum Numbers 228

6.6 Representations of Orbitals 230

The s Orbitals 230 The p Orbitals 233 The d and f Orbitals 233

6.7 Many-Electron Atoms 234

Orbitals and Their Energies 234 Electron Spin and the Pauli Exclusion Principle 235

6.8 Electron Configurations 237

Hund’s Rule 237 Condensed Electron Configurations 239 Transition Metals 240 The Lanthanides and Actinides 240

6.9 Electron Configurations and the Periodic Table 241

Anomalous Electron Configurations 245


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 262

Periodic Trends in Atomic Radii 264 Periodic Trends in Ionic Radii 265

7.4 Ionization Energy 268

Variations 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 273

Metals 274 Nonmetals 276 Metalloids 277


x Contents

7.7 Trends for Group 1A and Group 2A Metals 278

Group 1A: The Alkali Metals 278 Group 2A: The Alkaline Earth Metals 281

7.8 Trends for Selected Nonmetals 282

Hydrogen 282 Group 6A: The Oxygen Group 283 Group 7A: The Halogens 284 Group 8A: The Noble Gases 286


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 300

The Octet Rule 300

8.2 Ionic Bonding 301

Energetics 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 306

Lewis Structures 307 Multiple Bonds 308

8.4 Bond Polarity and Electronegativity 309

Electronegativity 309 Electronegativity and Bond Polarity 310 dipole Moments 311 differentiating Ionic and Covalent Bonding 314

8.5 drawing Lewis Structures 315

Formal Charge and Alternative Lewis Structures 317

8.6 Resonance Structures 320

Resonance in Benzene 322

8.7 Exceptions to the Octet Rule 322

Odd 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


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 347

Effect 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 359

sp Hybrid Orbitals 360 sp2 and sp3 Hybrid Orbitals 361 Hypervalent Molecules 362 Hybrid Orbital Summary 364

9.6 Multiple Bonds 365

Resonance Structures, delocalization, and p Bonding 368 General Conclusions about s and p Bonding 372

9.7 Molecular Orbitals 373

Molecular Orbitals of the Hydrogen Molecule 373 Bond Order 375

9.8 Period 2 diatomic Molecules 376

Molecular 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


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 401

Atmospheric Pressure and the Barometer 401

10.3 The Gas Laws 404

The 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 408

Relating the Ideal-Gas Equation and the Gas Laws 410

10.5 Further Applications of the Ideal-Gas Equation 412

Gas densities and Molar Mass 413 Volumes of Gases in Chemical Reactions 414

10.6 Gas Mixtures and Partial Pressures 415

Partial Pressures and Mole Fractions 417

10.7 The Kinetic-Molecular Theory of Gases 418

distributions of Molecular Speed 419 Application of Kinetic-Molecular Theory to the Gas Laws 420

10.8 Molecular Effusion and diffusion 421

Graham’s Law of Effusion 423 diffusion and Mean Free Path 424

10.9 Real Gases: deviations from Ideal Behavior 426

The 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 446

dispersion Forces 447 dipole–dipole Forces 448 Hydrogen Bonding 449 Ion–dipole Forces 452 Comparing Intermolecular Forces 452

11.3 Select Properties of Liquids 455

Viscosity 455 Surface Tension 456 Capillary Action 456

11.4 Phase Changes 457

Energy Changes Accompanying Phase Changes 457 Heating Curves 459 Critical Temperature and Pressure 460

11.5 Vapor Pressure 461

Volatility, 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 467

Types 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 482

Crystalline and Amorphous Solids 482 Unit Cells and Crystal Lattices 483 Filling the Unit Cell 485

12.3 Metallic Solids 486

The Structures of Metallic Solids 487 Close Packing 488 Alloys 491

12.4 Metallic Bonding 494

Electron-Sea Model 494 Molecular–Orbital Model 495

12.5 Ionic Solids 498

Structures of Ionic Solids 498

12.6 Molecular Solids 502

12.7 Covalent-Network Solids 503

Semiconductors 504 Semiconductor doping 506

12.8 Polymers 507

Making Polymers 509 Structure and Physical Properties of Polymers 511

12.9 Nanomaterials 514

Semiconductors 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 530

The 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 538

Solute–Solvent Interactions 538 Pressure Effects 541 Temperature Effects 543

13.4 Expressing Solution Concentration 544

Mass Percentage, ppm, and ppb 544 Mole Fraction, Molarity, and Molality 545 Converting Concentration Units 547

13.5 Colligative Properties 548

Vapor-Pressure Lowering 548 Boiling-Point Elevation 551 Freezing-Point depression 552 Osmosis 554 determination of Molar Mass from Colligative Properties 557

13.6 Colloids 559

Hydrophilic and Hydrophobic Colloids 560 Colloidal Motion in Liquids 562


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 577

Change of Rate with Time 579 Instantaneous Rate 579 Reaction Rates and Stoichiometry 580

14.3 Concentration and Rate Laws 581

Reaction 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 587

First-Order Reactions 587 Second-Order Reactions 589 Zero-Order Reactions 591 Half-Life 591

14.5 Temperature and Rate 593

The Collision Model 593 The Orientation Factor 594 Activation Energy 594 The Arrhenius Equation 596 determining the Activation Energy 597

14.6 Reaction Mechanisms 599

Elementary 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 606

Homogeneous Catalysis 607 Heterogeneous Catalysis 608 Enzymes 609


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 632

Evaluating Kc 634 Equilibrium Constants in Terms of Pressure, Kp 635 Equilibrium Constants and Units 636

15.3 Understanding and Working with Equilibrium Constants 637

The 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 646

Predicting the direction of Reaction 646 Calculating Equilibrium Concentrations 648

15.7 Le Châtelier’s Principle 650

Change in Reactant or Product Concentration 651 Effects of Volume and Pressure Changes 652 Effect of Temperature Changes 654 The Effect of Catalysts 657


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 678

The Ion Product of Water 679

16.4 The pH Scale 680

pOH and Other “p” Scales 682 Measuring pH 683

16.5 Strong Acids and Bases 684

Strong Acids 684 Strong Bases 685

16.6 Weak Acids 686

Calculating Ka from pH 688 Percent Ionization 689 Using Ka to Calculate pH 690 Polyprotic Acids 694

16.7 Weak Bases 696

Types of Weak Bases 698

16.8 Relationship between Ka and Kb 699

16.9 Acid–Base Properties of Salt Solutions 702

An 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 705

Factors That Affect Acid Strength 705 Binary Acids 706 Oxyacids 707 Carboxylic Acids 709

16.11 Lewis Acids and Bases 710


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 729

Composition 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 738

Strong 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 748

The Solubility-Product Constant, Ksp 748 Solubility and Ksp 749

17.5 Factors That Affect Solubility 751

Common-Ion Effect 751 Solubility and pH 753 Formation of Complex Ions 756 Amphoterism 758

17.6 Precipitation and Separation of Ions 759

Selective Precipitation of Ions 760

17.7 Qualitative Analysis for Metallic Elements 762


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 776

Composition of the Atmosphere 776 Photochemical Reactions in the Atmosphere 778 Ozone in the Stratosphere 780

18.2 Human Activities and Earth’s Atmosphere 782

The 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 791

The 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 794

dissolved Oxygen and Water Quality 794 Water Purification: desalination 795 Water Purification: Municipal Treatment 796

18.5 Green Chemistry 798

Supercritical Solvents 800 Greener Reagents and Processes 800


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 814

Seeking a Criterion for Spontaneity 816 Reversible and Irreversible Processes 816

19.2 Entropy and the Second Law of Thermodynamics 818

The 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 821

Expansion 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 828

Entropy Changes in the Surroundings 830

19.5 Gibbs Free Energy 831

Standard Free Energy of Formation 834

19.6 Free Energy and Temperature 836

19.7 Free Energy and the Equilibrium Constant 838

Free 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 860

Half-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 868

Standard Reduction Potentials 869 Strengths of Oxidizing and Reducing Agents 874

20.5 Free Energy and Redox Reactions 876

Emf, Free Energy, and the Equilibrium Constant 877

20.6 Cell Potentials Under Nonstandard Conditions 880

The Nernst Equation 880 Concentration Cells 882

20.7 Batteries and Fuel Cells 886

Lead–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 891

Corrosion of Iron (Rusting) 891 Preventing Corrosion of Iron 892

20.9 Electrolysis 893

Quantitative Aspects of Electrolysis 894



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 910

Nuclear Equations 911 Types of Radioactive decay 912

21.2 Patterns of Nuclear Stability 914

Neutron-to-Proton Ratio 914 Radioactive decay Chains 916 Further Observations 916

21.3 Nuclear Transmutations 918

Accelerating Charged Particles 918 Reactions Involving Neutrons 919 Transuranium Elements 920

21.4 Rates of Radioactive decay 920

Radiometric dating 921 Calculations Based on Half-Life 923

21.5 detection of Radioactivity 926

Radiotracers 927

21.6 Energy Changes in Nuclear Reactions 929

Nuclear Binding Energies 930

21.7 Nuclear Power: Fission 932

Nuclear Reactors 934 Nuclear Waste 936

21.8 Nuclear Power: Fusion 937

21.9 Radiation in the Environment and Living Systems 938

Radiation doses 940 Radon 942


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 952

Chemical Reactions 955

22.2 Hydrogen 956

Isotopes 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 960

Noble-Gas Compounds 961

22.4 Group 7A: The Halogens 962

Properties 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 966

Properties 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 970

General 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 973

Properties 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 977

General 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 980

Elemental 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 984

General Characteristics of the Group 4A Elements 984 Occurrence and Preparation of Silicon 984 Silicates 985 Glass 986 Silicones 987

22.11 Boron 987


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 998

Physical Properties 998

Electron Configurations and Oxidation States 999 Magnetism 1001

23.2 Transition-Metal Complexes 1002

The 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 1007

Metals and Chelates in Living Systems 1009

23.4 Nomenclature and Isomerism in Coordination Chemistry 1012

Isomerism 1014 Structural Isomerism 1014 Stereoisomerism 1015

23.5 Color and Magnetism in Coordination Chemistry 1019

Color 1019 Magnetism of Coordination Compounds 1021

23.6 Crystal-Field Theory 1021

Electron Configurations in Octahedral Complexes 1024 Tetrahedral and Square-Planar Complexes 1026


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 1042

The 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 1044

Structures of Alkanes 1045 Structural Isomers 1045 Nomenclature of Alkanes 1046 Cycloalkanes 1049 Reactions of Alkanes 1049

24.3 Alkenes, Alkynes, and Aromatic Hydrocarbons 1050

Alkenes 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 1058

Alcohols 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 1068

Amino Acids 1068 Polypeptides and Proteins 1070 Protein Structure 1071


xviii Contents

24.8 Carbohydrates 1073

disaccharides 1074 Polysaccharides 1075

24.9 Lipids 1076

Fats 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


xx

PREFACE

To the Teacher

PhilosophyWe authors of Chemistry: The Central Science are delighted and honored that you have chosen us as your instructional partners for your chemistry class. We have all been active researchers who ap-preciate both the learning and the discovery aspects of the chemi-cal sciences. We have also all taught chemistry many times. Our varied, wide-ranging experiences have formed the basis of the close collaborations we have enjoyed as coauthors. In writing our book, our focus is on the students: we try to ensure that the text is not only accurate and up-to-date but also clear and readable. We strive to convey the breadth of chemistry and the excitement that scientists experience in making new discoveries that contribute to our understanding of the physical world. We want the student to appreciate that chemistry is not a body of specialized knowledge that is separate from most aspects of modern life, but central to any attempt to address a host of societal concerns, including renewable energy, environmental sustainability, and improved human health.

Publishing the thirteenth edition of this text bespeaks an exceptionally long record of successful textbook writing. We are appreciative of the loyalty and support the book has received over the years, and mindful of our obligation to justify each new edition. We begin our approach to each new edition with an in-tensive author retreat, in which we ask ourselves the deep ques-tions that we must answer before we can move forward. What justifies yet another edition? What is changing in the world not only of chemistry, but with respect to science education and the qualities of the students we serve? The answer lies only partly in the changing face of chemistry itself. The introduction of many new technologies has changed the landscape in the teach-ing of sciences at all levels. The use of the Internet in accessing information and presenting learning materials has markedly changed the role of the textbook as one element among many tools for student learning. Our challenge as authors is to main-tain the text as the primary source of chemical knowledge and practice, while at the same time integrating it with the new ave-nues for learning made possible by technology and the Internet. This edition incorporates links to a number of those new meth-odologies, including use of the Internet, computer-based class-room tools, such as Learning Catalytics™, a cloud-based active learning analytics and assessment system, and web-based tools, particularly MasteringChemistry®, which is continually evolv-ing to provide more effective means of testing and evaluating student performance, while giving the student immediate and helpful feedback. In past versions, MasteringChemistry® pro-vided feedback only on a question level. Now with Knewton-enhanced adaptive follow-up assignments, and Dynamic Study Modules, MasteringChemistry® continually adapts to each stu-dent, offering a personalized learning experience.

As authors, we want this text to be a central, indispensa-ble learning tool for students. Whether as a physical book or in electronic form, it can be carried everywhere and used at any time. It is the one place students can go to obtain the informa-tion outside of the classroom needed for learning, skill develop-ment, reference, and test preparation. The text, more effectively than any other instrument, provides the depth of coverage and coherent background in modern chemistry that students need to serve their professional interests and, as appropriate, to pre-pare for more advanced chemistry courses.

If the text is to be effective in supporting your role as an educator, it must be addressed to the students. We have done our best to keep our writing clear and interesting and the book attractive and well illustrated. The book has numerous in-text study aids for students, including carefully placed descrip-tions of problem-solving strategies. We hope that our cumula-tive experiences as teachers is evident in our pacing, choice of examples, and the kinds of study aids and motivational tools we have employed. We believe students are more enthusiastic about learning chemistry when they see its importance relative to their own goals and interests; therefore, we have highlighted many important applications of chemistry in everyday life. We hope you make use of this material.

It is our philosophy, as authors, that the text and all the supplementary materials provided to support its use must work in concert with you, the educator. A textbook is only as useful to students as the teacher permits it to be. This book is replete with features that can help students learn and that can guide them as they acquire both conceptual understanding and problem-solving skills. There is a great deal here for the students to use, too much for all of it to be absorbed by any one student. You will be the guide to the best use of the book. Only with your active help will the students be able to utilize most effectively all that the text and its supplements offer. Students care about grades, of course, and with encouragement they will also be-come interested in the subject matter and care about learning. Please consider emphasizing features of the book that can en-hance student appreciation of chemistry, such as the Chemistry Put to Work and Chemistry and Life boxes that show how chem-istry impacts modern life and its relationship to health and life processes. Learn to use, and urge students to use, the rich online resources available. Emphasize conceptual understanding and place less emphasis on simple manipulative, algorithmic prob-lem solving.

What Is New in This Edition?A great many changes have been made in producing this thir-teenth edition. We have continued to improve upon the art program, and new features connected with the art have been introduced. Many figures in the book have undergone modifi-cation, and dozens of new figures have been introduced.


PrefaCe xxi

A systematic effort has been made to place explanatory la-bels directly into figures to guide the student. New designs have been employed to more closely integrate photographic materi-als into figures that convey chemical principles.

We have continued to explore means for more clearly and directly addressing the issue of concept learning. It is well es-tablished that conceptual misunderstandings, which impede student learning in many areas, are difficult to correct. We have looked for ways to identify and correct misconceptions via the worked examples in the book, and in the accompanying prac-tice exercises. Among the more important changes made in the new edition, with this in mind, are: • Amajor new feature of this edition is the addition of a

second Practice Exercise to accompany each Sample Ex-ercise within the chapters. The majority of new Practice Exercises are all of the multiple-choice variety, which enable feedback via MasteringChemistry®. The correct answers to select Practice Exercises are given in an appendix, and guidance for correcting wrong answers is provided in Mas-teringChemistry®. The new Practice Exercise feature adds to the aids provided to students for mastering the concepts advanced in the text and rectifying conceptual misunder-standings. The enlarged practice exercise materials also further cement the relationship of the text to the online learning materials. At the same time, they offer a new sup-portive learning experience for all students, regardless of whether the MasteringChemistry® program is used.

• A second major innovation in this edition is the Design An Experiment feature, which appears as a final exercise in all chapters beginning with Chapter 3, as well as in MasteringChemistry®. The Design an Experiment exercise is a departure from the usual kinds of end-of-chapter exer-cises in that it is inquiry based, open ended, and tries to stimulate the student to “think like a scientist.” Each exer-cise presents the student with a scenario in which vari-ous unknowns require investigation. The student is called upon to ponder how experiments might be set up to pro-vide answers to particular questions about a system, and/or test plausible hypotheses that might account for a set of observations. The aim of the Design an Experiment exer-cises is to foster critical thinking. We hope that they will be effective in active learning environments, which include classroom-based work and discussions, but they are also suitable for individual student work. There is no one right way to solve these exercises, but we authors offer some ideas in an online Instructor’s Resource Manual, which will include results from class testing and analysis of stu-dent responses.

• The Go Figure exercises introduced in the twelfth edition proved to be a popular innovation, and we have expanded on its use. This feature poses a question that students can answer by examining the figure. These questions encour-age students to actually study the figure and understand its primary message. Answers to the Go Figure questions are provided in the back of the text.

• The popular Give It Some Thought (GIST) questions em-bedded in the text have been expanded by improvements

in some of the existing questions and addition of new ones. The answers to all the GIST items are provided in the back of the text.

• New end-of-chapter exercises have been added, and many of those carried over from the twelfth edition have been significantly revised. Analysis of student responses to the twelfth edition questions in MasteringChemistry® helped us identify and revise or create new questions, prompt-ing improvements and eliminations of some questions. Additionally, analysis of usage of MasteringChemistry® has enhanced our understanding of the ways in which teachers and students have used the end-of-chapter and MasteringChemistry® materials. This, in turn, has led to additional improvements to the content within the text and in the MasteringChemistry® item library. At the end of each chapter, we list the Learning Outcomes that students should be able to perform after studying each section. End-of-chapter exercises, both in the text and in Master-ingChemistry® offer ample opportunities for students to assess mastery of learning outcomes. We trust the Learning Outcomes will help you organize your class and tests as the course proceeds.

Organization and ContentsThe first five chapters give a largely macroscopic, phenomeno-logical view of chemistry. The basic concepts introduced—such as nomenclature, stoichiometry, and thermochemistry—provide necessary background for many of the laboratory experiments usually performed in chemistry. We believe that an early intro-duction to thermochemistry is desirable because so much of our understanding of chemical processes is based on considerations of energy changes. Thermochemistry is also important when we come to a discussion of bond enthalpies. We believe we have produced an effective, balanced approach to teaching thermo-dynamics in chemistry, as well as providing students with an introduction to some of the global issues involving energy pro-duction and consumption. It is no easy matter to walk the nar-row pathway between—on the one hand—trying to teach too much at too high a level and—on the other hand—resorting to oversimplifications. As with the book as a whole, the emphasis has been on imparting conceptual understanding, as opposed to presenting equations into which students are supposed to plug numbers.

The next four chapters (Chapters 6–9) deal with elec-tronic structure and bonding. We have largely retained our presentation of atomic orbitals. For more advanced students, Closer Look boxes in Chapters 6 and 9 highlight radial prob-ability functions and the phases of orbitals. Our approach of placing this latter discussion in a Closer Look box in Chapter 9 enables those who wish to cover this topic to do so, while others may wish to bypass it. In treating this topic and others in Chapters 7 and 9, we have materially enhanced the accom-panying figures to more effectively bring home their central messages.

In Chapters 10–13, the focus of the text changes to the next level of the organization of matter: examining the states of


xxii PrefaCe

matter. Chapters 10 and 11 deal with gases, liquids, and inter-molecular forces, as in earlier editions. Chapter 12 is devoted to solids, presenting an enlarged and more contemporary view of the solid state as well as of modern materials. The chapter provides an opportunity to show how abstract chemical bond-ing concepts impact real-world applications. The modular organization of the chapter allows you to tailor your coverage to focus on materials (semiconductors, polymers, nanomaterials, and so forth) that are most relevant to your students and your own interests. Chapter 13 treats the formation and properties of solutions in much the same manner as the previous edition.

The next several chapters examine the factors that determine the speed and extent of chemical reactions: kinetics (Chapter 14), equilibria (Chapters 15–17), thermodynamics (Chapter 19), and electrochemistry (Chapter 20). Also in this section is a chapter on environmental chemistry (Chapter 18), in which the concepts developed in preceding chapters are applied to a discussion of the atmosphere and hydrosphere. This chapter has increasingly come to be focused on green chemistry and the impacts of human activi-ties on Earth’s water and atmosphere.

After a discussion of nuclear chemistry (Chapter 21), the book ends with three survey chapters. Chapter 22 deals with nonmetals, Chapter 23 with the chemistry of transition metals, including coordination compounds, and Chapter 24 with the chemistry of organic compounds and elementary biochemical themes. These final four chapters are developed in a parallel fashion and can be covered in any order.

Our chapter sequence provides a fairly standard organ-ization, but we recognize that not everyone teaches all the topics in the order we have chosen. We have therefore made sure that educators can make common changes in teaching sequence with no loss in student comprehension. In partic-ular, many teachers prefer to introduce gases (Chapter 10) after stoichiometry (Chapter 3) rather than with states of matter. The chapter on gases has been written to permit this change with no disruption in the flow of material. It is also possible to treat balancing redox equations (Sections 20.1 and 20.2) earlier, after the introduction of redox reactions in Section 4.4. Finally, some teachers like to cover organic chemistry (Chapter 24) right after bonding (Chapters 8 and 9). This, too, is a largely seamless move.

We have brought students into greater contact with de-scriptive organic and inorganic chemistry by integrating exam-ples throughout the text. You will find pertinent and relevant examples of “real” chemistry woven into all the chapters to il-lustrate principles and applications. Some chapters, of course, more directly address the “descriptive” properties of elements and their compounds, especially Chapters 4, 7, 11, 18, and 22–24. We also incorporate descriptive organic and inorganic chemistry in the end-of-chapter exercises.

Changes in This EditionThe What is New in This Edition section on pp. xx–xxi details changes made throughout the new edition. Beyond a mere list-ing, however, it is worth dwelling on the general goals we set forth in formulating this new edition. Chemistry: The Central

Science has traditionally been valued for its clarity of writing, its scientific accuracy and currency, its strong end-of-chapter exercises, and its consistency in level of coverage. In making changes, we have made sure not to compromise these charac-teristics, and we have also continued to employ an open, clean design in the layout of the book.

The art program for this thirteenth edition has continued the trajectory set in the twelfth edition: to make greater and more effective use of the figures as learning tools, by drawing the reader more directly into the figure. The art itself has con-tinued to evolve, with modifications of many figures and addi-tions or replacements that teach more effectively. The Go Figure feature has been expanded greatly to include a larger number of figures. In the same vein, we have added to the Give it Some Thought feature, which stimulates more thoughtful reading of the text and fosters critical thinking.

We provide a valuable overview of each chapter under the What’s Ahead banner. Concept links ( ) continue to provide easy-to-see cross-references to pertinent material covered ear-lier in the text. The essays titled Strategies in Chemistry, which provide advice to students on problem solving and “thinking like a chemist,” continue to be an important feature. For exam-ple, the new Strategies in Chemistry essay at the end of Chapter 3 introduces the new Design an Experiment feature and provides a worked out example as guidance.

We have continued to emphasize conceptual exercises in the end-of-chapter exercise materials. The well-received Visu-alizing Concepts exercise category has been continued in this edition. These exercises are designed to facilitate concept un-derstanding through use of models, graphs, and other visual materials. They precede the regular end-of-chapter exercises and are identified in each case with the relevant chapter section number. A generous selection of Integrative Exercises, which give students the opportunity to solve problems that integrate concepts from the present chapter with those of previous chap-ters, is included at the end of each chapter. The importance of integrative problem solving is highlighted by the Sample Integrative Exercise, which ends each chapter beginning with Chapter 4. In general, we have included more conceptual end-of-chapter exercises and have made sure that there is a good representation of somewhat more difficult exercises to provide a better mix in terms of topic and level of difficulty. Many of the exercises have been restructured to facilitate their use in Mas-teringChemistry®. We have made extensive use of the metadata from student use of MasteringChemistry® to analyze end-of-chapter exercises and make appropriate changes, as well as to develop Learning Outcomes for each chapter.

New essays in our well-received Chemistry Put to Work and Chemistry and Life series emphasize world events, scientific discoveries, and medical breakthroughs that bear on topics de-veloped in each chapter. We maintain our focus on the positive aspects of chemistry without neglecting the problems that can arise in an increasingly technological world. Our goal is to help students appreciate the real-world perspective of chemistry and the ways in which chemistry affects their lives.

It is perhaps a natural tendency for chemistry text-books to grow in length with succeeding editions, but it is


PrefaCe xxiii

one that we have resisted. There are, nonetheless, many new items in this edition, mostly ones that replace other material considered less pertinent. Here is a list of several significant changes in content:

In Chapter 1, the Closer Look box on the scientific method has been rewritten. The Chemistry Put to Work box, dealing with Chemistry in the News, has been completely rewritten, with items that describe diverse ways in which chemistry intersects with the affairs of modern society. The Chapter Summary and Learning Outcomes sections at the end of the chapter have been rewritten for ease of use by both teacher and student, in this and all chapters in the text. Similarly, the exercises have been thor-oughly vetted, modified where this was called for and replaced or added to, here and in all succeeding chapters.

In Chapter 3, graphic elements highlighting the correct ap-proach to problem solving have been added to Sample Exercises on calculating an empirical formula from mass percent of the elements present, combustion analysis, and calculating a theo-retical yield.

Chapter 5 now presents a more explicit discussion of com-bined units of measurement, an improved introduction to en-thalpy, and more consistent use of color in art.

Changes in Chapter 6 include a significant revision of the discussion of the energy levels of the hydrogen atom, including greater clarity on absorption versus emission processes. There is also a new Closer Look box on Thought Experiments and Schrödinger’s Cat, which gives students a brief glimpse of some of the philosophical issues in quantum mechanics and also con-nects to the 2012 Nobel Prize in Physics.

In Chapter 7, the emphasis on conceptual thinking was en-hanced in several ways: the section on effective nuclear charge was significantly revised to include a classroom-tested analogy, the number of Go Figure features was increased substantially, and new end-of-chapter exercises emphasize critical thinking and understanding concepts. In addition, the Chemistry Put to Work box on lithium-ion batteries was updated and revised to include discussion of current issues in using these batteries. Fi-nally, the values of ionic radii were revised to be consistent with a recent research study of the best values for these radii.

In Chapter 9, which is one of the most challenging for students, we continue to refine our presentation based on our classroom experience. Twelve new Go Figure exercises will stim-ulate more student thought in a chapter with a large amount of graphic material. The discussion of molecular geometry was made more conceptually oriented. The section on delocalized bonding was completely revised to provide what we believe will be a better introduction that students will find useful in organic chemistry. The Closer Look box on phases in orbitals was re-vamped with improved artwork. We also increased the number of end-of-chapter exercises, especially in the area of molecular orbital theory. The Design an Experiment feature in this chapter gives the students the opportunity to explore color and conju-gated π systems.

Chapter 10 contains a new Sample Exercise that walks the student through the calculations that are needed to understand Torricelli’s barometer. Chapter 11 includes an improved defini-tion of hydrogen bonding and updated data for the strengths

of intermolecular attractions. Chapter 12 includes the latest up-dates to materials chemistry, including plastic electronics. New material on the diffusion and mean free path of colloids in solu-tion is added to Chapter 13, making a connection to the diffu-sion of gas molecules from Chapter 10.

In Chapter 14, ten new Go Figure exercises have been added to reinforce many of the concepts presented as figures and graphs in the chapter. The Design an Experiment exercise in the chapter connects strongly to the Closer Look box on Beer’s Law, which is often the basis for spectrometric kinetics experi-ments performed in the general chemistry laboratory.

The presentation in Chapter 16 was made more closely tied to that in Chapter 15, especially through the use of more initial/change/equilibrium (ICE) charts. The number of conceptual end-of-chapter exercises, including Visualizing Concepts fea-tures, was increased significantly.

Chapter 17 offers improved clarity on how to make buff-ers, and when the Henderson–Hasselbalch equation may not be accurate. Chapter 18 has been extensively updated to reflect changes in this rapidly evolving area of chemistry. Two Closer Look boxes have been added; one dealing with the shrinking level of water in the Ogallala aquifer and a second with the po-tential environmental consequences of hydraulic fracking. In Chapter 20, the description of Li-ion batteries has been signifi-cantly expanded to reflect the growing importance of these bat-teries, and a new Chemistry Put to Work box on batteries for hybrid and electric vehicles has been added.

Chapter 21 was updated to reflect some of the current is-sues in nuclear chemistry and more commonly used nomencla-ture for forms of radiation are now used. Chapter 22 includes an improved discussion of silicates.

In Chapter 23, the section on crystal-field theory (Section 23.6) has undergone considerable revision. The description of how the d-orbital energies of a metal ion split in a tetrahedral crystal field has been expanded to put it on par with our treat-ment of the octahedral geometry, and a new Sample Exercise that effectively integrates the links between color, magnetism, and the spectrochemical series has been added. Chapter 24’s coverage of organic chemistry and biochemistry now includes oxidation–reduction reactions that organic chemists find most relevant.

To the StudentChemistry: The Central Science, Thirteenth Edition, AP Edition has been written to introduce you to modern chemistry. As authors, we have, in effect, been engaged by your teachers to help you learn chemistry. Based on the comments of students and educators who have used this book in its previous editions, we believe that we have done that job well. Of course, we expect the text to continue to evolve through future editions. We invite you to write to tell us what you like about the book so that we will know where we have helped you most. Also, we would like to learn of any shortcomings so that we might further improve the book in subsequent editions. Our addresses are given at the end of the Preface.


xxiv PrefaCe

Advice for Learning and Studying ChemistryLearning chemistry requires both the assimilation of many con-cepts and the development of analytical skills. In this text, we have provided you with numerous tools to help you succeed in both tasks. If you are going to succeed in your chemistry course, you will have to develop good study habits. Science courses, and chemistry in particular, make different demands on your learn-ing skills than do other types of courses. We offer the following tips for success in your study of chemistry:

Don’t fall behind! As the course moves along, new top-ics will build on material already presented. If you don’t keep up in your reading and problem solving, you will find it much harder to follow the discussions on current topics. Experienced teachers know that students who read the relevant sections of the text before coming to a class learn more from the class and retain greater recall. “Cramming” just before an exam has been shown to be an ineffective way to study any subject, chemis-try included. So now you know. How important to you, in this competitive world, is a good grade in chemistry?

Focus your study. The amount of information you will be expected to learn can sometimes seem overwhelming. It is es-sential to recognize those concepts and skills that are particularly important. Pay attention to what your teacher is emphasizing. As you work through the Sample Exercises and homework assign-ments, try to see what general principles and skills they employ. Use the What’s Ahead feature at the beginning of each chapter to help orient yourself to what is important in each chapter. A sin-gle reading of a chapter will simply not be enough for successful learning of chapter concepts and problem-solving skills. You will need to go over assigned materials more than once. Don’t skip the Give It Some Thought and Go Figure features, Sample Exer-cises, and Practice Exercises. They are your guides to whether you are learning the material. They are also good preparation for test-taking. The Learning Outcomes and Key Equations at the end of the chapter should help you focus your study.

Keep good notes. Your notes will provide you with a clear and concise record of what your teacher regards as the most important material to learn. Using your lecture notes in conjunction with this text is the best way to determine which material to study.

Skim topics in the text before they are covered in class. Reviewing a topic before class will make it easier for you to take good notes. First read the What’s Ahead points and the end-of-chapter Summary; then quickly read through the chapter, skipping Sample Exercises and supplemental sections. Paying attention to the titles of sections and subsections gives you a feeling for the scope of topics. Try to avoid thinking that you must learn and understand everything right away.

You need to do a certain amount of preparation before class. More than ever, teachers are using the class period not simply as a one-way channel of communication from teacher to student. Rather, they expect students to come to class ready to work on problem solving and critical thinking. Coming to class unprepared is not a good idea for any environment, but it certainly is not an option for an active learning classroom if you aim to do well in the course.

After class, carefully read the topics covered in class. As you read, pay attention to the concepts presented and to the ap-plication of these concepts in the Sample Exercises. Once you think you understand a Sample Exercise, test your understand-ing by working the accompanying Practice Exercise.

Learn the language of chemistry. As you study chemis-try, you will encounter many new words. It is important to pay attention to these words and to know their meanings or the entities to which they refer. Knowing how to identify chemi-cal substances from their names is an important skill; it can help you avoid painful mistakes on examinations. For example, “chlorine” and “chloride” refer to very different things.

Attempt the assigned end-of-chapter exercises. Working the exercises selected by your teacher provides necessary prac-tice in recalling and using the essential ideas of the chapter. You cannot learn merely by observing; you must be a participant. In particular, try to resist checking the Student Solutions Manual (if you have one) until you have made a sincere effort to solve the exercise yourself. If you get stuck on an exercise, however, get help from your teacher or another student. Spending more than 20 minutes on a single exercise is rarely effective unless you know that it is particularly challenging.

Learn to think like a scientist. This book is written by sci-entists who love chemistry. We encourage you to develop your critical thinking skills by taking advantage of new features in this edition, such as exercises that focus on conceptual learning, and the Design an Experiment exercises.

Use online resources. Some things are more easily learned by discovery, and others are best shown in three dimensions. If your teacher has included MasteringChemistry® with your book, take advantage of the unique tools it provides to get the most out of your time in chemistry.

The bottom line is to work hard, study effectively, and use the tools available to you, including this textbook. We want to help you learn more about the world of chemistry and why chemistry is the central science. If you really learn chemistry, you can be the life of the party, impress your friends and par-ents, and … well, also pass the course with a good grade.

Tips for AP Chemistry Exam SuccessEd Waterman, Rocky Mountain High School

The Content and Nature of the AP Exam in ChemistryThe Advanced Placement Examination in Chemistry is a com-prehensive evaluation of knowledge of all areas of general chemistry at the first year college level. It consists of two equally 90 minute sessions. Section I contains 60 multiple-choice questions worth 50% of the total score. Three long and four short free-response questions, counting for another 50%, com-pose Section II. Use of calculators is allowed only on the free- response section. A periodic table and a list of pertinent formu-las and equations is available for the entire exam.


PrefaCe xxv

Pearson Education also publishes Pearson Education Test Prep Workbook for AP® Chemistry, a companion workbook to accompany Chemistry: The Central Science, AP® Edition. Thor-oughly revised and redesigned, the 2015 Test Prep Workbook for AP® Chemistry correlates to the new AP® Chemistry Curric-ulum Framework (CF) which launched in the 2013-2014 school year. The test prep workbook contains concise content summa-ries of chapters that are relevant to the AP Chemistry Exam, test taking tips, hundreds of multiple choice and free response prac-tice questions, two complete practice exams with scoring guide-lines, answers and detailed explanations of all questions. It also presents a review of spectroscopy, including mass spectrometry, photoelectron spectroscopy and UV-visible spectrophotometry. To order your own copy of the test prep workbook please visit Pearsonschool.com/Advanced or call 1-800-848-9500.

For more information and published examples of recent exams, please refer to the College Board’s Advanced Placement website at http://apcentral.collegeboard.com/.

Big Ideas and Learning ObjectivesThe AP Chemistry Curriculum Framework outlines the content of the course around six Big Ideas and 117 learning objectives. The following outline identifies the important AP Chemistry curriculum topics found in each chapter and section of this text organized by the six Big Ideas. The tables that follow correlate the 117 curriculum learning objectives to the pertinent chapters and sections of Chemistry: The Central Science.

Besides mastering content, students should be able to visu-alize and interpret atomic and molecular models, analyze data for patterns and relationships, predict atomic and molecular properties, justify their trends and select and perform chemical calculations for a variety of chemical systems.

AP Chemistry Curriculum Topics Correlated to Chemistry: The Central Science Table of ContentsBIG IDEA 1. All matter is composed of atoms. The content for Big Idea 1 is found primarily in Chapters 1, 2, 3, 6 and 7 of Chemistry: The Central Science.

1. Introduction: Matter and Measurement1.2 Classification of Matter. Gas, liquid, solid, pure substance, elements, symbols, compounds, mixtures.1.3 Properties of Matter. Physical properties, chemical proper-ties, physical change, chemical change, separation of mixtures, filtration, distillation, chromatography.

2. Atoms, Molecules and Ions2.1 The Atomic Theory of Matter. Atoms, law of constant composition, law of conservation of mass, law of multiple pro-portions, Dalton’s atomic theory.2.3 The Modern View of Atomic Structure. Nucleus, elec-trons, structure of the atom, atomic mass unit, electrical charges of subatomic particles, atomic number, mass number, isotopes, Coulomb’s law, mass spectrometry.

2.6 Molecules and Molecular Compounds. Molecules, chemi-cal formulas, molecular formulas, empirical formulas, struc-tural formulas.2.7 Ions and Ionic Compounds. Ion, cation, anion, polyatomic ions, ionic charges, ionic compounds.

3. Stoichiometry: Calculations with Chemical Formulas and Equations3.3 Formula weights. Molar mass, percentage composition.3.4 Avogadro’s Number and the Mole. Moles, Avogadro’s number, molar mass, interconverting mass, moles and number of particles.3.5 Empirical Formulas from Analysis. Calculation of empiri-cal and molecular formulas, combustion analysis.

6. Electronic Structure of Atoms6.2 Quantized Energy and Photons. Quantum, photoelectric effect.6.5 Quantum Mechanics and Atomic Orbitals. Quantum mechanical model, orbitals, electron shell, subshell.6.6 Representations of Orbitals. Shell model, orbitals desig-nated s, p, d and f, relative energies, relative distance from the nucleus, probability distributions, electron density.6.8 Electron Configurations. Electron configuration, orbital diagram, core electrons, valence electrons.6.9 Electron Configurations and the Periodic Table. Repre-sentative elements, transition elements, f-block elements.

7. Periodic Properties of the Elements7.2 Effective Nuclear Charge. Effective nuclear charge, screen-ing effect, valence electrons, inner core electrons, trends in ef-fective nuclear charge.7.3 Sizes of Ions. Atomic radius, ionic radius, trends in atomic and ionic radii, isoelectronic series.7.4 Ionization Energy. First ionization energy, successive ioni-zation energies, trends in ionization energies, shells, subshells and trends, electron configurations of ions.7.5 Electron Affinities Electron affinity as energy, trends, anomilies.7.6 Metals, Nonmetals and Metalloids. Metals, metallic char-acter, metallic properties, nonmetals, nonmetal properties, metalloids, group trends.

BIG IDEA 2. Bonding and intermolecular forces explain the physical and chemical properties of matter. The content for Big Idea 2 is found primarily in Chapters 8, 9, 10, 11, 12 and 13 of Chemistry: The Central Science.

Chapter 8. Basic Concepts of Chemical Bonding8.1 Lewis Symbols and the Octet Rule. Lewis electron-dot symbols, octet rule.8.2 Ionic Bonding. Electron transfer, lattice energy, Coulomb’s law, s- and p-block electron configurations, transition metal ions8.3 Covalent Bonding. Lewis structures, multiple bonds.8.4 Bond Polarity and Electronegativity. Bond polarity, polar and nonpolar bonds, electron density, polar molecules, dipoles, differentiating covalent and ionic bonding.


xxvi PrefaCe

8.5 Drawing Lewis Structures. Determining Lewis structures, formal charge.8.6 Resonance Structures. Resonance structures, delocalized electrons, depiction of resonance structures.8.7 Exceptions to the Octet Rule. Odd electrons, six electrons, expanded octets.8.8 Strengths of Covalent Bonds. Bond enthalpy, bond break-ing, bond forming, calculations using bond enthalpies, bond lengths.

9. Molecular Geometry and Bonding Theory9.1 Molecular Shapes. Linear, bent, trigonal planar, tetrahe-dral, trigonal pyramidal, bond angles.9.2 The VSEPR Model. Valence shell electron pair repulsion, bonding pair, electron domain, nonbonding pair, molecular ge-ometry, electron domain geometry, expanded valence shells, T-shaped, trigonal bipyramidal, see-saw, octahedral.9.3 Molecular Shape and Polarity. Bond dipole, polar mole-cules, electron densities in molecules.9.5 Hybrid Orbitals. sp, sp2 and sp3 hybridization, orbital over-lap, multiple bonds, s and p bonds, delocalized electrons.

10. Gases10.2 Pressure. Standard atmospheric pressure, atmospheres, torr.10.3 The Gas Laws. Boyle’s law (pressure-volume), Charles law (temperature-volume), Boyles law and Charles law plots, abso-lute zero, Avogadro’s law.10.4 The Ideal-Gas Equation. Ideal gas, ideal-gas constant, calculations using ideal gas law.10.5 Further Applications of the Ideal-Gas Equation. Calcula-tions of gas density, molar mass and volumes in chemical reactions.10.6 Gas Mixtures and Partial Pressures. Partial pressure, Dalton’s law, water vapor pressure.10.7 The Kinetic-Molecular Theory of Gases. Summary of KMT, molecular collisions, molecular origin of gas properties, molecular speed distributions (Maxwell-Boltzmann), tempera-ture as average kinetic energy.10.9 Real Gases: Deviations From Ideal Behavior. Real vs. ideal gases, effect of intermolecular forces, structure of particles.

11. Liquids and Intermolecular Forces11.1 A Molecular Comparison of Gases, Liquids and Solids. Properties of the states of matter, particle explanations.11.2 Intermolecular Forces. Dispersion forces, polarizability, dipole-dipole forces, hydrogen bonding, ion-dipole forces, rela-tive strengths of forces, explanation of molecular properties, so-lution formation.11.3 Select Properties of Liquids. Viscosity, surface tension, capillary action.11.4 Phase Changes. Energetics of phase changes, heat of fu-sion, heat of vaporization, heat of sublimation, heating curves, critical temperature and pressure.11.5 Vapor Pressure. Dynamic equilibrium, vapor pressure, volatility, distributions of kinetic energy, boiling point, vapor pressure plots.

12. Solids and Modern Materials12.1 Classification of Solids. Metallic, ionic, covalent-network and molecular solids, atomic and molecular explanations, polymers.12.2 Structures of Solids. Crystals, crystalline solids, amorphous solids.12.3 Metallic Solids. Metallic solids, alloys, substitutional and interstitial alloys.12.4 Metallic Bonding. Electron-sea model, delocalized electrons, thermal and electrical conductivity, malleability and ductility.12.5 Ionic Solids. Ionic crystals, ionic interactions, atomic expla-nation of properties, brittleness, melting points, boiling points.12.6 Molecular Solids. Molecules, intermolecular forces, struc-tural explanation of properties.12.7 Covalent-network solids. Diamond, graphite, semiconduc-tors, doping, p-type, n-type, atomic explanations of properties.

13. Properties of Solutions13.1 The Solution Process. Energetics of solution formation, spontaneous processes, entropy, effect of intermolecular forces, solva-tion, hydration, particle depictions.13.2 Saturated Solutions and Solubility. Crystallization, solu-bility, saturated, unsaturated, supersaturated.13.3 Factors Affecting Solubility. Miscible, immiscible, solute-solvent interactions, molecular structure, energetics, like dis-solves like, pressure effects, temperature effects.13.4 Expressing Solution Concentration. Molarity, particle views, calculations involving molarity.

BIG IDEA 3. Chemical reactions involve the rearrangement of atoms and describe how matter changes. The content for Big Idea 3 is found primarily in Chapters 3, 4, 16 and 20 of Chemistry: The Central Science.

Chapter 3. Stoichiometry: Calculations with Chemical Formulas and Equations3.1 Chemical Equations. Chemical equations, reactants, prod-ucts, balancing equations, coefficients.3.2. Some Simple Patterns of Chemical Reactivity. Combina-tion (synthesis), decomposition, combustion.3.6. Quantitative Information from Balanced Equations. Stoichiometry, using equations to interconvert mass, moles and number of particles.3.7 Limiting Reactants. Limiting reatcatnt, theoretical yield, actual yield, percentage theoretical yield.

Chapter 4. Reactions in Aqueous Solution4.1 General Properties of Aqueous Solutions. Molecules in water, non-electrolytes, ions in solution, strong electrolytes, weak electrolytes, chemical equilibrium.4.2 Precipitation Reactions. Precipitate, solubility, solubility guidelines, molecular (complete) equations, ionic equations, net ionic equations, spectator ions, writing net ionic equations.


PrefaCe xxvii

4.3 Acids, Bases, and Neutralization Reactions. Acids, proton donors, monoprotoc acids, diprotic acids, bases, proton accep-tors, hydroxides, strong and weak acids and bases, strong acids and bases as strong electrolytes, neutralization reactions, salts.4.4 Oxidation-Reduction Reactions. Oxidation, reduction, redox reactions, oxidation numbers, determining oxidation numbers, displacement reactions, activity series.4.5 Concentrations of Solutions. Molarity, calculating molar-ity, interconverting molarity, moles and solution volume, dilu-tion, preparing solution concentrations.4.6 Solution Stoichiometry and Chemical Analysis. Titration, standard solution, equivalence point, titration calculations, mass relations in a neutralization reaction.

Chapter 5. Thermochemistry5.2 The First Law of Thermodynamics. Energy diagrams, exo-thermic and endothermic reactions, temperature change, energy from foods and fuels.

Chapter 16. Acid-Base Equilibria16.2 Brønsted-Lowry Acids and BasesHydronium ion, proton transfer reactions, Brønsted-Lowry acid, Brønsted-Lowry base, conjugate acid-base pairs, relative strengths of acids and bases

Chapter 20. Electrochemistry20.1 Oxidation States and Oxidation-Reduction Reactions Electron transfer reactions, gain of electrons, loss of electrons20.2 Balancing Redox Equations Half reactions, half reaction method, redox titrations20.3 Voltaic Cells Voltaic (galvanic) cell, anode, cathode, salt bridge, direction of electron flow20.4 Cell Potentials Under Standard Conditions Cell poten-tial, electromotive force, standard emf, standard reduction po-tential, standard hydrogen electrode, calculating cell potentials20.5 Free Energy and Redox Reactions Relationship of free en-ergy (∆G) to cell potential, Faraday’s constant, predicting the direction of the reaction20.7 Batteries and Fuel Cells Electrical energy from batter-ies, lead-acid, alkaline, nickel-cadmium, nickel-metal-hydride, lithium-ion, hydrogen fuel cells20.9 Electrolysis Electrolytic cell, stoichiometry and redox reactions, calculating electrons transferred, mass, current, time and charge, electrolysis of water, electroplating

BIG IDEA 4. Molecular collisions determine the rates of chemical reactions. The content for Big Idea 4 is found primarily in Chapter 14 of Chemistry: The Central Science.

14. Chemical Kinetics14.1 Factors that Affect Reaction Rates. Effects of tempera-ture, physical state, concentration and catalysts.14.2 Reaction Rates. Reaction rate as change in concentra-tion per time, graphical representations of rate, rate and stoichiometry.

14.3 Concentration and Rate Laws. Initial rate, spectroscopic measurement of rates, rate law, rate constant, reaction order, rate constant units, method of initial rate.14.4 The Change of Concentration with Time. Integrated rate law, zeroth, first and second order reactions, graphical repre-sentations, half-life, radioactive decay.14.5 Temperature and Rate. The collision model, orientation factor, activation energy, activated complex, transition state, energy profile and reaction rate, graphical representations, Ar-rhenius equation (qualitative).14.6 Reaction Mechanisms. Mechanisms, elementary reaction, unimolecular, bimolecular and termolecular reactions, overall equation from elementary steps, intermediate, rate-determin-ing step, mechanism and rate-determining step.14.7 Catalysis. Catalyst, homogeneous and heterogeneous catal-ysis, effect of catalyst on energy profile, surface catalyst, acid-base catalysts, enzymes, active site, substrate, lock-and-key model.

Big Idea 5. Thermodynamics describes the role energy plays in chemical and physical changes. The content in Big Idea 5 is found primarily in Chapters 5 and 19 of Chemistry: The Central Science.

5. Thermochemistry5.1 The Nature of Energy. Energy, work, kinetic energy, poten-tial energy, Coulomb’s law, electrostatic potential energy, meas-urement of energy, joules, calories, system, surroundings, force, work and heat.5.2 The First Law of Thermodynamics. Internal energy (∆E), relating ∆E to work and heat, exothermic, endothermic.5.3 Enthalpy. Enthalpy, pressure-volume work (P∆V).5.4 Enthalpies of Reaction. Enthalpy of reaction (∆H), ther-mochemical equation, enthalpy diagram, signs of ∆H, relating heats to stoichiometry5.5 Calorimetry. Constant pressure calorimetry, calorimeter, heat capacity, molar heat capacity, specific heat capacity, calcu-lating heats.5.6 Hess’s Law. Heats added and subtracted like chemical equations.5.7 Enthalpies of Formation. Standard enthalpy of formation (∆Hf), formation reaction, using ∆Hf to calculate enthalpies of reaction, enthalpy diagrams.5.8 Foods and Fuels. Combustion of natural gas, fossil fuels, pe-troleum, coal, sugars and fats, renewable energy sources.

19. Chemical Thermodynamics19.1 Spontaneous Processes. Spontaneous process, direction and extent of a reaction, reversible and irreversible processes.19.2 Entropy and the Second Law ofThermodynamics. En-tropy (S), randomness, change in entropy (∆S), ∆S for phase changes, second law of thermodynamics.19.3 Molecular Interpretation of Entropy. Translational, vi-brational and rotational energy, entropy and phase, third law of thermodynamics.


xxviii PrefaCe

19.4 Entropy Change in Chemical Reactions. Standard molar entropies, entropy and temperature, molecular complexity.19.5 Gibbs Free Energy. Free energy (∆G), free energy and equilibrium, ∆G = ∆H - T∆S, standard free energy of formation.19.6 Free Energy and Temperature. Temperature and sponta-neous processes, phase changes.19.7 Free Energy and the Equilibrium Constant. Standard and nonstandard conditions, relationship between ∆G and K.

BIG IDEA 6. Equilibrium represents a balance between enthalpy and entropy for reversible physical and chemi-cal changes. The content for Big Idea 6 is found primarily in Chapters 15, 16, and 17 of Chemistry: The Central Science.

Chapter 15. Chemical Equilibrium15.1 The Concept of Equilibrium. Rates of forward and reverse reactions, equilibrium mixtures.15.2 The Equilibrium Constant. Law of mass action, equi-librium constant expression, equilibrium constant (K), Kc and Kp.15.3 Understanding and Working with Equilibrium Constants. Magnitudes of K, chemical equations and K, stoichiometry and K, calculating K.15.4 Heterogeneous Equilibria. Homogeneous and heterogeneous equilibria and K.15.5 Calculating Equilibrium Constants. K from concentra-tions, K from initial conditions, ICE tables.15.6 Applications of Equilibrium Constants. Reaction quo-tient (Q), predicting direction, calculating concentrations.15.7 LeChâtelier’s Principle. LeChâtelier’s principle, changes in concentration, volume, pressure or temperature, catalysts, optimizing a product.

Chapter 16. Acid-Base Equilibria16.2 Brønsted-Lowry Acids and Bases. Hydronium ion, pro-ton transfer reactions, Brønsted-Lowry acids, Brønsted-Lowry bases, conjugate acid-base pairs, proton acceptor, proton donor, relative acid and base strengths.16.3 The Autoionization of Water. Ion-product constant (Kw), effect of temperature.16.4 The pH Scale. pH, pOH, measuring pH, indicators.16.5 Strong Acids and Bases. Complete ionization, calculating pH.16.6 Weak Acids. Incomplete ionization, acid-dissociation con-stant (Ka), calculating concentration, Ka and pH, percent ioni-zation, polyprotic acids.16.7 Weak Bases. Base-dissociation constant (Kb), amines as weak bases, calculating pH and pOH.16.8 Relationship Between Ka and Kb. KaKb = Kw, K’s of con-jugate acid-base pairs.16.9 Acid-Base Properties of Salt Solutions. Hydrolysis, ani-ons as bases, cations as acids.16.10 Acid-Base Behavior and Chemical Structure. Fac-tors that affect acid strength, oxidation number, electronegativ-ity, oxyacids, carboxylic acids.

17. Additional Aspects of Aqueous Equilibria17.1 The Common-Ion Effect. Common ions and equilibrium.17.2 Buffered Solutions. Buffers, buffer composition, buffer action, buffer pH, buffer capacity, buffer calculations.17.3 Acid-base Titrations. Titration curve, pH of equivalence point, weak acid-strong base titrations, pKa of weak acid from titration data, polyprotic acid titrations, indicators.17.4 Solubility Equilibria. Solubility product constant (Ksp), solubility, calculating solubilities.17.5 Factors that Affect Solubility. Common ions, pH.

Correlation Guide For APAP Chemistry Topics correlated to Chemistry: The Central Science, Thirteenth Edition, AP® Edition

BIG IDEA 1. All matter is composed of atoms.

Learning Objective Science Practice Chapter/Sectio

1.1 Use atomic molecular theory to explain that the element mass ratio in any pure compound is always identical.

6.1 1.2

1.2 Use mass data to quantitatively identify or infer the compositions of pure sub-stances and mixtures.

2.2 2.1, 2.4

1.3 Use calculations of mass data to determine the identity or purity of a substance. 2.2, 6.1 1.61.4 Interconvert the number of particles, moles, mass, and volume of substances,

both qualitatively and quantitatively.7.1 3.4


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Learning Objective Science Practice Chapter/Sectio

1.5 Use data to explain electron distributions in atoms or ions. 1.5, 6.2 6.8, 6.91.6 Analyze data of electron energies for patterns and relationships. 5.1 6.8 TPWB1.7 Explain how energies of electrons vary within atomic shells using data from

photoelectron spectroscopy, ionization energy data, and Coulomb’s law.5.1, 6.2 6.8 TPWB

1.8 Analyze measured energies and explain electron configurations using Coulomb’s law.

6.2 6.8 TPWB

1.9 Explain trends in atomic properties using the shell model or location on the periodic table.

6.4 7.2, 7.3, 7.4

1.10 Use experimental evidence to explain the arrangement of the periodic table and apply periodic properties to chemical reactivity.

6.1 7.6, 7.7

1.11 Analyze and identify patterns in data of binary compounds to predict properties of related compounds.

3.1, 5.1 8.2, 8.4 T8.1, T8.2, T8.3

1.12 Explain how data sets support either the classical shell atomic model or the quantum mechanical model.

6.3 6.2, 6.3, 6.4, 6.5, 6.6

1.13 Determine if an atomic model is consistent with a given set of data. 5.3 2.1, 2.2, 2.3, 6.31.14 Use mass spectral data to identify elements and isotopes. 1.4, 1.5 2.41.15 Explain why various types of spectroscopy are used to measure vibrational and

electronic motions of molecules.4.1

1.16 Design and interpret an experiment that uses spectrophotometry to determine the concentration of a substance in a solution.

4.2, 5.1 14.3, 4.5 TPWB

1.17 Use both symbols and particle drawings to quantitatively and qualitatively ex-press the law of conservation of mass.

1.5 3.1

1.18 Apply conservation of atoms to particle views of balanced chemical reactions and physical changes.

1.4 3.1, 3.2

1.19 Design or interpret data from a gravimetric analysis experiment to determine the concentration of a substance in solution.

4.2, 5.1 3.6, 3.7

1.20 Design or interpret data from a titration experiment to determine the concentra-tion of a substance in solution.

4.2, 5.1 4.5, 4.6

BIG IDEA 2. Bonding and intermolecular forces explain the physical and chemical properties of matter.

Learning Objective Science Practice Chapter/Section

2.1 Predict and explain properties based on chemical formulas and particle views. 6.4, 7.1 8.2, 8.3, 8.4 2.2 Explain the strengths of acids and bases using molecular structure, intermolecu-

lar forces, and solution equilibrium.7.2 16.2, 16.6, 16.9, 16.10

2.3 Use particulate models to explain differences between solids and liquids. 6.4, 7.1 11.1 to 11.7 2.4 Use KMT and intermolecular forces to predict the macroscopic properties of real

and ideal gases.1.4, 6.4 10.1, 10.2, 10.3, 10.7,

10.9 2.5 Use particle representations to explain the effect of changes in the macroscopic

properties of gases.1.3, 6.4, 7.2 10.3, 10.4

2.6 Calculate temperature, pressure, volume and moles for an ideal gas. 2.2, 2.3 10.3, 10.4, 10.5, 10.6 2.7 Use intermolecular forces to explain how solutes separate by chromatography. 6.2 13.3 TPWB 2.8 Draw and interpret particle representations of solutions showing interactions

between the solute and solvent particles.1.1, 1.2, 6.4 13.1, 13.2, 13.3

2.9 Create particle views of solutions to interpret molar concentration. 1.1, 1.4 13.4, 13.5 VC 4.1–4.5 2.10 Design an experiment to separate substances using filtration, paper chromatog-

raphy, column chromatography, or distillation and explain how substances sepa-rate using intermolecular interactions.

4.2, 5.1 13.3 TPWB

2.11 Use London dispersion forces to predict properties and explain trends for non-polar substances.

6.2, 6.4 11.2


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2.12 Analyze data for real gases to identify deviations from ideal behavior and explain using molecular interactions.

5.1, 6.5 10.9

2.13 Explain how the structural features of polar molecules affect the forces of attrac-tion between them.

1.4, 6.4 11.2, 13.3

2.14 Using particle views, qualitatively apply Coulomb’s law to explain how the solu-bility of ionic compounds is affected by interactions of ions, and attractions be-tween ions and solvents.

1.4, 6.4 13.3 + VC 13.1–13.12

2.15 Explain the solubility of ionic solids and molecules in water and other solvents using particle views to show intermolecular forces and entropy.

1.4, 6.2 13.2, 13.3

2.16 Use the strengths and types of intermolecular forces to explain the properties of molecules such as phase, vapor pressure, viscosity, melting point and boiling point.

6.2 11.3

2.17 Predict the type of bonding in a binary compound based on electronegativity of the elements and position on the periodic table.

6.4 8.3, 8.4

2.18 Use location of atoms on the periodic table to rank and explain bond polarity. 6.1 8.4 2.19 Use particle views of ionic compounds to explain the effect of microscopic struc-

ture on macroscopic properties such as boiling point, solubility, hardness, brittle-ness, low volatility, and lack of malleability, ductility, and conductivity.

1.1, 1.4, 7.1 12.5

2.20 Explain how delocalized electrons affect the macroscopic properties of metals such as conductivity, malleability, ductility, and low volatility.

6.2, 7.1 12.3, 12.4

2.21 Use Lewis diagrams and VSEPR to predict geometry, hybridization, and polarity of molecules.

1.4 9.2, 9.3, 9.4, 9.5

2.22 Design and evaluate an experimental plan to collect and interpret data to deduce the types of bonding in solids.

4.2 12.1 TPWB

2.23 Create a visual representation of an ionic solid showing its structure and particle interactions.

1.1 12.5

2.24 Use a visual representation of an ionic solid to explain its structure and particle interactions.

1.1, 6.2, 7.1 12.5

2.25 Compare properties of alloys and metals, identify alloy types and explain proper-ties on the atomic level.

1.4, 7.2 12.3

2.26 Use the electron sea model to explain the macroscopic properties of metals and alloys.

6.4, 7.1 12.3, 12.4

2.27 Create a visual representation of a metallic solid showing its structure and parti-cle interactions.

1.1 12.3, 12.4

2.28 Use a visual representation of a metallic solid to explain its structure and particle interactions.

1.1, 1–2, 6.4 12.3, 12.4

2.29 Create a visual representation of a covalent solid showing its structure and par-ticle interactions.

1.1 12.7

2.30 Use a visual representation of a covalent solid to explain its structure and particle interactions.

1.1, 1.2, 6.4 12.7

2.31 Create a visual representation of a molecular solid showing its structure and par-ticle interactions.

1.1 12.6, 12.8

2.32 Use a visual representation of a molecular solid to explain its structure and par-ticle interactions.

1.1, 1.2, 6.4 12.6, 12.8

BIG IDEA 3. Chemical reactions involve the rearrangement of atoms and describe how matter changes.


3.1 Interpret macroscopic observations of change using symbols, chemical equa-tions, and particle views.

1.5, 7.1 4.1, 4.2, 4.3


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3.2 Interpret an observed chemical change using a balanced molecular (complete), ionic or net ionic equation and justify why each is used in a given situation.

1.5, 7.1 3.2, 4.1, 4.2, 4.3

3.3 Use stoichiometry calculations to model laboratory chemical reactions and ana-lyze deviations from the expected results.

2.2, 5.1 3.6, 3.7, 4.6

3.4 Apply stoichiometry calculations to convert measured quantities such as mass, volumes of solutions, or volumes and pressures of gases to other quantities in chemical reactions, including reactions with limiting reactants or unreacted products.

2.2, 5.1, 6.4 3.6, 3.7, 4.6

3.5 Design an experiment or analyze data from an experiment involving the synthe-sis or decomposition of a compound to confirm the conservation of mass and the law of definite proportions.

2.1, 2.4 3.5

3.6 Use data from synthesis or decomposition of a compound to confirm the conser-vation of mass and the law of definite proportions.

2.2, 6.1 3.5

3.7 Use proton-transfer reactions to identify compounds as Brønsted-Lowry acids and bases and conjugate acid-base pairs.

6.1 16.1, 16.2

3.8 Use electron transfer to identify redox reactions. 6.1 3.2, 4.43.9 Design or interpret the results of a redox titration experiment. 4.2, 5.1 4.4, 4.6, 4.5 TPWB3.10 Classify a process as a physical change, a chemical change, or an ambiguous

change using macroscopic observations and the formation or breaking of chemi-cal bonds or intermolecular forces.

1.4, 6.1 1.3, 4.2, 4.3, 4.4

3.11 Create symbolic and graphical representations to describe an observed change in energy associated with a chemical or physical change.

1.5, 4.4 5.2, 5.3, 5.4

3.12 Use half-cell reactions, potentials and Faraday’s laws to make quantitative pre-dictions about voltaic (galvanic) or electrolytic reactions.

2.2, 2.3, 6.4 20.3, 20.9

3.13 Analyze voltaic (galvanic) or electrolytic cell data to identify properties of redox reactions.

5.1 20.3, 20.9

BIG IDEA 4. Molecular collisions determine the rates of chemical reactions.


4.1 Design and interpret an experiment to determine the factors that affect reaction rate such as temperature, concentration, and surface area.

4.2, 5.1 14.1 TPWB 14.1

4.2 Analyze concentration vs. time data to determine the rate law for a zeroth-, first-, and second-order reaction.

5.1 14.3, 14.4

4.3 Determine half-life from the rate constant of a first-order reaction. 2.1, 2.2 14.44.4 Relate the rate law, order and rate constant for an elementary reaction to the

frequency and success of molecular collisions.7.1 14.5, 14.6

4.5 Explain effective and ineffective reactant collisions using energy distributions and molecular orientation.

6.2 14.5, TPWB 14.5

4.6 Make qualitative predictions about the temperature dependence of reaction rate using an energy profile for an elementary reaction including reactants, transition state and products.

1.4, 6.4 14.5

4.7 Evaluate alternative reaction mechanisms that correspond to rate data and infer the presence or absence of an intermediate.

6.5 14.6

4.8 Use various representations including energy profiles, particle views and chemi-cal equations to describe chemical reactions that occur with and without cata-lysts.

1.5 14.7

4.9 Explain rate changes due to acid-base, surface, and enzyme catalysts, and select appropriate mechanisms with or without catalysts.

6.2, 7.2 14.7


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BIG IDEA 5. Thermodynamics describes the role energy plays in physical and chemical changes.


5.1 Create and interpret graphical representations to explain how and why poten-tial energy varies with distance between atoms such as in bond order, strength and length in covalent bonds and in the magnitudes of intermolecular forces between polar molecules.

1.1, 1.4, 7.2 9.7

5.2 Explain how temperature relates to molecular motion using particle views of moving molecules or kinetic energy distribution (Maxwell-Boltzmann) plots.

1.1, 1.4, 7.1 10.7

5.3 Use molecular collisions to explain or predict the transfer of heat between sys-tems.

7.1 5.2

5.4 Use conservation of energy to explain energy transfer between systems including the quantity of energy transferred, the direction of energy flow, and the type of energy (heat or work).

1.4, 2.2 5.2, 5.3

5.5 Use conservation of energy to explain the quantity of energy change that occurs when two substances of different temperatures interact.

2.2 5.5

5.6 Calculate or estimate energy changes associated with chemical reactions, heating or cooling a substance or changing its phase using quantities such as enthalpy of reaction, heat capacity and heat of fusion or vaporization, and relate energy changes to P∆V work.

2.2, 2.3 5.2, 5.3, 11.4

5.7 Design and interpret a constant pressure calorimetry experiment to determine change in enthalpy of a chemical or physical process.

4.2, 5.1 5.5

5.8 Use bond energies to calculate or estimate enthalpies of reaction. 2.3, 7.1, 7.2 5.4, 8.85.9 Explain and predict the relative strengths and types of intermolecular forces act-

ing between molecules using molecular electron density distributions.6.4 11.2, 11.3

5.10 Use chemical bonds and intermolecular forces to classify and justify chemical and physical changes.

5.1 11.1, 11.2

5.11 Use the strengths of intermolecular forces, such as hydrogen bonding and Lon-don dispersions, to explain the shape and function of large molecules.

7.2 24.7 to 24.10

5.12 Use particle views and models to predict the signs and relative magnitudes of the entropy changes associated with chemical or physical processes.

1.4 19.2, 19.3, 19.4

5.13 Use the signs of both ∆H° and ∆S° and a calculation or estimation of ∆G°, to predict the favorability of a physical or chemical change.

2.2, 2.3, 6.4 19.5

5.14 Calculate the change in standard Gibbs free energy to determine the favorability of a chemical or physical change.

2.2 19.5

5.15 Explain how nonspontaneous processes, such as those in living systems, can be made favorable by coupling them with spontaneous reactions.

6.2 19.5 & p808, p814

5.16 Use LeChâtelier’s principle to predict outcomes for systems in which coupled reactions share a common intermediate.

6.4 15.7

5.17 Use the equilibrium constant for combined reactions to make predictions for systems involving coupled reactions sharing a common intermediate.

6.4 19.7

5.18 Explain how initial conditions can greatly affect product formation for unfavora-ble reactions using thermodynamic and kinetic arguments.

1.3, 7.2 19.7

BIG IDEA 6. Equilibrium represents a balance between enthalpy and entropy for reversible physical and chemical changes.


6.1 Use a given a set of experimental observations to explain the reversibility of a chemical, biological or environmental process.

6.2 15.1

6.2 Predict the effects of changing conditions on Q or K of a chemical system. 2.2 15.2, 15.3, 15.46.3 Predict the relative rates of the forward and reverse reactions using LeChâtelier’s

principle and principles of kinetics.7.2 15.2, 15.7

6.4 Given initial conditions, use Q and K to predict the direction a reaction will proceed toward equilibrium.

2.2, 6.4 15.6


PrefaCe xxxiii


6.5 Calculate the equilibrium constant, K, given the appropriate tabular or graphical data for a system at equibrium.

2.2 15.5

6.6 Given a set of initial conditions and the equilibrium constant, K, use stoichi-ometry and the law of mass action to determine qualitatively or quantitatively equilibrium concentrations or partial pressures.

2.2, 6.4 15.5, 15.6

6.7 Given an equilibrium system with a large or small K, determine which chemical species will have relatively large and small concentrations.

2.2, 2.3 15.5, 15.6

6.8 Use LeChâtelier’s principle to predict the direction a reaction at equilibrium will proceed as a result of a given change.

1.4, 6.4 15.7

6.9 Design a set of conditions that will optimize a desired result using LeChatelier’s principle.

4.2 15.7

6.10 Use LeChâtelier’s principle to explain the effect a change will have on Q or K. 1.4, 7.2 15.76.11 Construct a particle representation of a strong or weak acid to illustrate which

species will have large and small concentrations at equilibrium.1.1, 1.4, 2.3 16.6

6.12 Contrast pH, percentage ionization, concentrations and the amount of base re-quired to reach an equivalence point when comparing solutions of strong and weak acids.

1.4 16.4, 16.5, 16.6

6.13 Interpret titration data to determine concentration of a weak acid or base and its pKa or pKb.

5.1 17.3

6.14 Explain why a neutral solution requires 3H+4 = 3OH-4 rather than pH = 7, using the dependence of Kw on temperature.

2.2, 6.2 16.3, 16.4 + p713

6.15 Calculate or estimate the pH and the concentrations of all species in a mixture of strong acids and bases.

2.2, 2.3, 6.4 16.5

6.16 Identify a solution as a weak acid or base, calculate its pH and the concentration of all species in the solution, and infer its relative strength.

2.2, 6.4 16.6, 16.7

6.17 Given a mixture of weak and strong acids and bases, identify the chemical reac-tion and tell which species are present in large concentrations at equilibrium.

6.4 17.3

6.18 Select an appropriate conjugate acid-base pair to design a buffer solution with a target pH and estimate the concentrations needed to achieve a desired buffer capacity.

2.3, 4.2, 6.4 16.2, 17.1, 17.2

6.19 Given the pKa, predict the predominant form of a weak acid in a solution of a given pH.

2.3, 5.1, 6.4 16.9, 17.3

6.20 Identify a buffer solution and explain how it behaves upon addition of acid or base.

6.4 17.2

6.21 Predict and rank the solubilities of various salts, given their Ksp values. 2.2, 2.3, 6.4 17.4, 17.56.22 Interpret solubility data of various salts to determine or rank Ksp values. 2.2, 2.3, 6.4 17.4, 17.56.23 Use data to predict the influence of pH and common ions on the relative solu-

bilities of salts.5.1 17.5

6.24 Use particle representations to explain changes in enthalpy and entropy associ-ated with the dissolution of a salt.

1.4, 7.1 17.5

6.25 Use the relationship between ∆G° and K (∆G° = -RT lnK) to estimate the magnitude of K and the thermodynamic favorability of a process.

2.3 19.7

TPWB: Test Prep WorkbookVC: Visualizing Concepts

Upon publication, this text was correlated to the College Board’s AP Chemistry Curriculum Framework dated 2013-2014. We con-tinually monitor the College Board’s AP Course Description for updates to exam topics. For the most current correlation for this textbook, visit PearsonSchool.com/AdvancedCorrelations.


xxxiv PrefaCe

List of ResourcesMasteringChemistry®

(http://www.masteringchemistry.com)MasteringChemistry® is the most effective, widely used online tutorial, homework and assessment system for chemistry. It helps instructors maximize class time with customizable, easy-to-assign, and automatically graded assessments that motivate students to learn outside of class and arrive prepared for lecture. These assessments can easily be customized and personalized by instructors to suit their individual teaching style. The pow-erful gradebook provides unique insight into student and class performance even before the first test. As a result, instructors can spend class time where students need it most.

Pearson eText The integration of Pearson eText within MasteringChemistry® gives students with eTexts easy access to the electronic text when they are logged into MasteringChemistry®. Pearson eText pages look exactly like the printed text, offering powerful new functionality for students and instructors. Users can create notes, highlight text in different colors, create bookmarks, zoom, view in single-page or two-page view, and more.

Upon textbook purchase, students and teachers are granted access to MasteringChemistry®. High school teachers can obtain preview or adoption access for MasteringChemistry® in one of the following ways:

Preview Access• Teachers can request preview access online by visiting

PearsonSchool.com/Access_Request, select Initial Access then Option 2. Preview Access information will be sent to the teacher via email.

Adoption Access• With the purchase of this program, a Pearson Adoption

Access Card with Instructor Manual, will be delivered with your textbook purchase. (ISBN: 0-13-034391-9)

• Ask your sales representative for an Pearson AdoptionAccess Card with Instructor Manual. (ISBN: 0-13-034391-9)

OR• Visit PearsonSchool.com/Access_Request, select Initial

Access then Option 3. Adoption access information will be sent to the teacher via email.

Students, ask your teacher for access.

For StudentsTest Prep Workbook for AP® Chemistry By Ed Waterman, experienced AP chemistry teacher. This Test Prep Workbook for AP® Chemistry has been thoroughly revised to align with the College Board’s new AP® Chemistry Curriculum Framework. This workbook provides an overview of the AP Chemistry Curriculum Framework, test-taking tips, and strategies for preparing for peak performance. It has hundreds of practice questions for mastering each type of AP Exam question—with fully explained answers and two complete chemistry practice tests for AP.

Pearson Active Reading Guide Designed for use with the Student Edition, the Pearson Active Reading Guide helps students tackle some of the toughest aspects of an AP chemistry course—reading for understanding, active learning, and mastering vocabulary.

Students Guide Prepared by James C. Hill of California State University. This book assists students through the text material with chapter overviews, learning objectives, a review of key terms, as well as self-tests with answers and explanations. This edition also features MCAT practice questions.

Solutions to Red Exercises Prepared by Roxy Wilson of the University of Illinois, Urbana-Champaign. Full solutions to all the red-numbered exercises in the text are provided. (Short answers to red exercises are found in the appendix of the text.)

Solutions to Black Exercises Prepared by Roxy Wilson of the University of Illinois, Urbana-Champaign. Full solutions to all the black-numbered exercises in the text are provided.

Laboratory Experiments Prepared by John H. Nelson of the University of Nevada, and Michael Lufaso of the University of North Florida with contributions by Matthew Stoltzfus of The Ohio State University. This manual contains 40 finely tuned experiments chosen to introduce students to basic lab techniques and to illustrate core chemical principles. This new edition has been revised with the addition of four brand new experiments to correlate more tightly with the text.


PrefaCe xxxv

For TeachersSome of the teacher supplements and resources for this text are available electronically to qualified adopters on the Instructor Resource Center (IRC). Upon adoption or to preview, please go to www.pearsonschool.com/access_request and select Instructor Resource Center. You will be required to complete a brief one-time registration subject to verification of educator status. Upon verification, access information and instructions will be sent to you via email. Once logged into the IRC, enter ISBN 978-0-13-357412-8 in the “Search our Catalog” box to locate resources. Electronic teacher supplements are also available within the Instructor’s tab of MasteringChemistry.

ExamView® CD-ROM The ExamView computerized test bank CD-ROM includes hundreds of questions, allowing teachers to build, edit, print, and administer tests based on text objectives Algorithmically based, ExamView enables teachers to create multiple but equivalent versions of the same question or test with a click of a button.

Solutions to Exercises Prepared by Roxy Wilson of the University of Illinois, Urbana-Champaign. This manual contains all end-of-chapter exercises in the text.

Instructor Resource Center This resource provides an integrated collection of resources to help instructors make efficient and effective use of their time. It features all artwork from the text, including figures and tables in PDF format for high-resolution printing, as well as five prebuilt PowerPoint™ presentations. The first presentation contains the images embedded within PowerPoint slides. The second includes

a complete lecture outline that is modifiable by the user. The final three presentations contain worked “in-chapter” sample exercises and questions to be used with Classroom Response Systems. The Instructor Resource Center also contains movies, animations, and electronic files of the Instructor Resource Manual, as well as the Test Item File. Available on the IRC for download.

TestGen Testbank Prepared by Andrea Leonard of the University of Louisiana. The Test Item File now provides a selection of more than 4,000 test questions with 200 new questions in the thirteenth edition and 200 additional algorithmic questions. Available on the IRC for download.

Instructor Resource Manual (0-321-94929-3) Prepared by Linda Brunauer of Santa Clara University and Elzbieta Cook of Louisiana State University. Organized by chapter, this manual offers detailed lecture outlines and complete descriptions of all available lecture demonstrations, interactive media assets, common student misconceptions, and more. Available on the IRC for download.

Annotated Instructor’s Edition to Laboratory Experiments (0-321-98608-3) Prepared by John H. Nelson of the University of Nevada, and Michael Lufaso of the University of North Florida with contributions by Matthew Stoltzfus of the Ohio State University. This AIE combines the full student lab manual with appendices covering the proper disposal of chemical waste, safety instructions for the lab, descriptions of standard lab equipment, answers to questions, and more. Available on the IRC for download.

The production of a textbook is a team effort requiring the in-volvement of many people besides the authors who contributed hard work and talent to bring this edition to life. Although their names don’t appear on the cover of the book, their creativity, time, and support have been instrumental in all stages of its de-velopment and production.

Each of us has benefited greatly from discussions with colleagues and from correspondence with instructors and stu-

dents both here and abroad. Colleagues have also helped im-mensely by reviewing our materials, sharing their insights, and providing suggestions for improvements. On this edition, we were particularly blessed with an exceptional group of accuracy checkers who read through our materials looking for both tech-nical inaccuracies and typographical errors.

Acknowledgments

Theodore L. BrownDepartment of ChemistryUniversity of Illinois atUrbana-ChampaignUrbana, IL [email protected] [email protected]

H. Eugene LeMay, Jr.Department of ChemistryUniversity of NevadaReno, NV [email protected]

Bruce E. BurstenDepartment of ChemistryUniversity of TennesseeKnoxville, TN [email protected]

Catherine J. MurphyDepartment of ChemistryUniversity of Illinois atUrbana-ChampaignUrbana, IL [email protected].

Patrick M. WoodwardDepartment of Chemistryand BiochemistryThe Ohio State UniversityColumbus, OH [email protected]

Matthew W. StoltzfusDepartment of Chemistryand BiochemistryThe Ohio State UniversityColumbus, OH [email protected]


THEODORE L. BROWN received his Ph.D. from Michigan State University in 1956. Since then, he has been a member of the faculty of the University of Illinois, Urbana-Champaign, where he is now Professor of Chemistry, Emeritus. He served as Vice Chancellor for Research, and Dean of The Graduate College, from 1980 to 1986, and as Founding Director of the Arnold and Mabel Beckman Institute for Advanced Science and Technology from 1987 to 1993. Professor Brown has been an Alfred P. Sloan Foundation Research Fellow and has been awarded a Guggenheim Fellowship. In 1972 he was awarded the American Chemical Society Award for Research in Inorganic Chemistry and received the American Chemical Society Award for Distinguished Service in the Advancement of Inorganic Chemistry in 1993. He has been elected a Fellow of the American Association for the Advancement of Science, the American Academy of Arts and Sciences, and the American Chemical Society.

H. EUGENE LEMAY, JR., received his B.S. degree in Chemistry from Pacific Lutheran University (Washington) and his Ph.D. in Chemistry in 1966 from the University of Illinois, Urbana-Champaign. He then joined the faculty of the University of Nevada, Reno, where he is currently Professor of Chemistry, Emeritus. He has enjoyed Visiting Professorships at the University of North Carolina at Chapel Hill, at the University College of Wales in Great Britain, and at the University of California, Los Angeles. Professor LeMay is a popular and effective teacher, who has taught thousands of students during more than 40 years of university teaching. Known for the clarity of his lectures and his sense of humor, he has received several teaching awards, including the University Distinguished Teacher of the Year Award (1991) and the first Regents’ Teaching Award given by the State of Nevada Board of Regents (1997).

BRUCE E. BURSTEN received his Ph.D. in Chemistry from the University of Wisconsin in 1978. After two years as a National Science Foundation Postdoctoral Fellow at Texas A&M University, he joined the faculty of The Ohio State University, where he rose to the rank of Distinguished University Professor. In 2005, he moved to the University of Tennessee, Knoxville, as Distinguished Professor of Chemistry and Dean of the College of Arts and Sciences. Professor Bursten has been a Camille and Henry Dreyfus Foundation Teacher-Scholar and an Alfred P. Sloan Foundation Research Fellow, and he is a Fellow of both the American Association for the Advancement of Science and the American Chemical Society. At Ohio State he has received the University Distinguished Teaching Award in 1982 and 1996, the Arts and Sciences Student Council Outstanding Teaching Award in 1984, and the University Distinguished Scholar Award in 1990. He received the Spiers Memorial Prize and Medal of the Royal Society of Chemistry in 2003, and the Morley Medal of the Cleveland Section of the American Chemical Society in 2005. He was President of the American Chemical Society for 2008. In addition to his teaching and service activities, Professor Bursten’s research program focuses on compounds of the transition-metal and actinide elements.

About the Authors

THE BROWN/LEMAY/BURSTEN/MURpHY/WOODWARD/STOLTzfUS AUTHOR TEAM values collaboration as an integral component to overall success. While each author brings unique talent, research interests, and teaching experiences, the team works together to review and develop the entire text. It is this collaboration that keeps the content ahead of educational trends and contributes to continuous innovations in teaching and learning throughout the text and technology. Some of the new key features in the thirteenth edition and accompanying MasteringChemistry® course are highlighted on the following pages.


CATHERINE J. MURpHY received two B.S. degrees, one in Chemistry and one in Biochemistry, from the University of Illinois, Urbana-Champaign, in 1986. She received her Ph.D. in Chemistry from the University of Wisconsin in 1990. She was a National Science Foundation and National Institutes of Health Postdoctoral Fellow at the California Institute of Technology from 1990 to 1993. In 1993, she joined the faculty of the University of South Carolina, Columbia, becoming the Guy F. Lipscomb Professor of Chemistry in 2003. In 2009 she moved to the University of Illinois, Urbana-Champaign, as the Peter C. and Gretchen Miller Markunas Professor of Chemistry. Professor Murphy has been honored for both research and teaching as a Camille Dreyfus Teacher-Scholar, an Alfred P. Sloan Foundation Research Fellow, a Cottrell Scholar of the Research Corporation, a National Science Foundation CAREER Award winner, and a subsequent NSF Award for Special Creativity. She has also received a USC Mortar Board Excellence in Teaching Award, the USC Golden Key Faculty Award for Creative Integration of Research and Undergraduate Teaching, the USC Michael J. Mungo Undergraduate Teaching Award, and the USC Outstanding Undergraduate Research Mentor Award. Since 2006, Professor Murphy has served as a Senior Editor for the Journal of Physical Chemistry. In 2008 she was elected a Fellow of the American Association for the Advancement of Science. Professor Murphy’s research program focuses on the synthesis and optical properties of inorganic nanomaterials, and on the local structure and dynamics of the DNA double helix.

pATRICK M. WOODWARD received B.S. degrees in both Chemistry and Engineering from Idaho State University in 1991. He received a M.S. degree in Materials Science and a Ph.D. in Chemistry from Oregon State University in 1996. He spent two years as a postdoctoral researcher in the Department of Physics at Brookhaven National Laboratory. In 1998, he joined the faculty of the Chemistry Department at The Ohio State University where he currently holds the rank of Professor. He has enjoyed visiting professorships at the University of Bordeaux in France and the University of Sydney in Australia. Professor Woodward has been an Alfred P. Sloan Foundation Research Fellow and a National Science Foundation CAREER Award winner. He currently serves as an Associate Editor to the Journal of Solid State Chemistry and as the director of the Ohio REEL program, an NSF-funded center that works to bring authentic research experiments into the laboratories of first- and second-year chemistry classes in 15 colleges and universities across the state of Ohio. Professor Woodward’s research program focuses on understanding the links between bonding, structure, and properties of solid-state inorganic functional materials.

MATTHEW W. STOLTzfUS received his B.S. degree in Chemistry from Millersville University in 2002 and his Ph. D. in Chemistry in 2007 from The Ohio State University. He spent two years as a teaching postdoctoral assistant for the Ohio REEL program, an NSF-funded center that works to bring authentic research experiments into the general chemistry lab curriculum in 15 colleges and universities across the state of Ohio. In 2009, he joined the faculty of Ohio State where he currently holds the position of Chemistry Lecturer. In addition to lecturing general chemistry, Stoltzfus accepted the Faculty Fellow position for the Digital First Initiative, inspiring instructors to offer engaging digital learning content to students through emerging technology. Through this initiative, he developed an iTunes U general chemistry course, which has attracted over 120,000 students from all over the world. Stoltzfus has received several teaching awards, including the inaugural Ohio State University 2013 Provost’s Award for Distinguished Teaching by a Lecturer and he is recognized as an Apple Distinguished Educator.


Data-Driven AnalyticsA New Direction in Chemical Education

Authors traditionally revise roughly 25% of the end of chapter questions when producing a new edition. These changes typically involve modifying numerical variables/identities of chemical formulas to make them “new” to the next batch of students. While these changes

are appropriate for the printed version of the text, one of the strengths of MasteringChemistry® is its ability to randomize variables so that every student receives a “different” problem. Hence, the effort which authors have historically put into changing variables can now be used to improve questions.

In order to make informed decisions, the author team consulted the massive reservoir of data available through MasteringChemistry® to revise their question bank. In particular, they analyized which problems were frequently assigned and why; they paid careful attention to the amount of time it took students to work through a problem (flagging those that took longer than expected) and they observed the wrong answer submissions and hints used (a measure used to calculate the difficulty of problems). This “metadata” served as a starting point for the discussion of which end of chapter questions should be changed.

For example, the breadth of ideas presented in Chapter 9 challenges students to understand three-dimensional visualization while simultaneously introducing several new concepts (particu-larly VSEPR, hybrids, and Molecular Orbital theory) that challenge their critical thinking skills. In revising the exercises for the chapter, the authors drew on the metadata as well as their own experi-ence in assigning Chapter 9 problems in Mastering Chemistry. From these analyses, we were able to articulate two general revision guidelines.

1. Improve coverage of topic areas that were underutilized: In Chapter 9, the authors noticed that there was a particularly low usage rate for questions concerning Molecular Orbital Theory. Based on the metadata and their own teaching experience with Mastering, they recognized an opportunity to expand the coverage of MO theory. Two brand new exercises that emphasize the basics of MO theory were the result of this analysis including the example below. This strategy was replicated throughout the entire book.


2. Revise the least assigned existing problems. Much of the appeal of MasteringChemistry® for students is the immediate feedback they get when they hit submit, which also provides an opportunity to confront any misconceptions right away. For teachers, the appeal is that these problems are automatically graded. Essay questions fail to provide these advantages since they must be graded by a teacher before a student may receive feedback. Wherever possible, we revised current essay questions to include automatically graded material.

Bottom Line: The revision of the end of chapter questions in this edition is informed by robust data-driven analytics providing a new level of pedagogically-sound assessments for your students, all while making the time they spend working these problems even more valuable.


Helping Students Think Like Scientists

Design an ExperimentStarting with Chapter 3, every chapter will feature a Design an Experiment exercise. The goal of these exercises is to challenge students to think like a scientist, imagining what kind of data needs to be collected and what sort of experimental procedures will provide them the data needed to answer the question. These exercises tend to be integrative, forcing students to draw on many of the skills they have learned in the current and previous chapters.

Design an Experiment topics include: Ch 3: Formation of Sulfur OxidesCh 4: Identification of Mysterious White PowdersCh 5: Joule ExperimentCh 6: Photoelectric Effect and Electron ConfigurationsCh 7: Chemistry of Potassium SuperoxideCh 8: Benzene ResonanceCh 9: Colors of Organic Dyes Ch 10: Identification of an Unknown Noble GasCh 11: Hydraulic FluidsCh 12: PolymersCh 13: Volatile Solvent Molecules

Ch 14: Reaction Kinetics via SpectrophotometryCh 15: Beer’s Law and Visible-Light SpectroscopyCh 16: Acidity/Basicity of an Unknown LiquidCh 17: Understanding Differences in pKaCh 18: Effects of Fracking on GroundwaterCh 19: Drug Candidates and the Equilibrium ConstantCh 20: Voltaic CellsCh 21: Discovery and Properties of RadiumCh 22: Identification of UnknownsCh 23: Synthesis and Characterization of a Coordination CompoundCh 24: Quaternary Structure in Proteins

Go figureGo Figure questions encourage students to stop and analyze the artwork in the text, for conceptual understanding. “Voice Balloons” in selected figures help students break down and understand the components of the image. These questions are also available in MasteringChemistry®. The number of Go Figure questions in the thirteenth edition has increased by 25%.


Helping Students Think Like Scientists

practice ExercisesA major new feature of this edition is the addition of a second Practice Exercise to accompany each Sample Exercise within the chapters. The new Practice Exercises are multiple-choice with correct answers provided for the students in an appendix. Specific wrong answer feedback, written by the authors, will be available in MasteringChemistry® The primary goal of the new Practice Exercise feature is to provide students with an additional problem to test mastery of the concepts in the text and to address the most common conceptual misunderstandings. To ensure the questions touched on the most common student misconceptions, the authors consulted the ACS Chemistry Concept inventory before writing their questions.

Give It Some Thought (GIST) questionsThese informal, sharply-focused exercises allow students the opportunity to gauge whether they are “getting it” as they read the text. The number of GIST questions has increased throughout the text as well as in MasteringChemistry®.


Learning CatalyticsLearning Catalytics™ is a “bring your own device” student engagement, assessment, and classroom intelligence system. With Learning Catalytics™ you can: • Assess students in real time, using open-ended tasks to probe student understanding. • Understand immediately where students are and adjust your class accordingly. • Improve your students’ critical-thinking skills. • Access rich analytics to understand student performance. • Add your own questions to make Learning Catalytics™ fit your class exactly. • Manage student interactions with intelligent grouping and timing.

Learning Catalytics™ is a technology that has grown out of twenty years of cutting-edge research, innovation, and implementation of interactive teaching and peer instruction.

Learning Catalytics™ will be included with the purchase of MasteringChemistry® with eText.

The most effective learning happens when students actively participate and interact with material in order to truly internalize key concepts. The Brown/Lemay/Bursten/Murphy/Woodward/Stoltzfus author team has spent decades refining their text based on educational

research to the extent that it has largely defined how the general chemistry course is taught. With the thirteenth edition, these authors have extended this tradition by giving each student a way to personalize their learning experience through MasteringChemistry®. The MasteringChemistry® course for Brown/Lemay/Bursten/Murphy/Woodward/Stoltzfus evolves learning and technology usage far beyond the lecture-homework model. Many of these resources can be used pre-lecture, during class, and for assessment while providing each student with a personalized learning experi-ence which gives them the greatest chance of succeeding.

Active and Visual


pause and predict VideosAuthor Dr. Matt Stoltzfus created Pause and Predict Videos. These videos engage students by prompting them to submit a prediction about the outcome of an experiment or demonstration before seeing the final result. A set of assignable tutorials, based on these videos, challenge students to transfer their understanding of the demonstration to related scenarios. These videos are also available in web- and mobile-friendly formats through the study area of MasteringChemistry® and in the Pearson eText.

NEW! Simulations, assignable in MasteringChemistry®, include those developed by the PhET Chemistry Group, and the leading authors in simulation development covering some of the most difficult chemistry concepts.


AdaptiveMasteringChemistry® has always been personalized and adaptive on a question level by providing error-specific feedback based on actual student responses; however, Mastering now includes two new adaptive assignment types—Adaptive Follow-Up Assignments and Dynamic Study Modules.

Adaptive follow-Up AssignmentsTeachers have the ability to assign adaptive follow-up assignments. Content delivered to students as part of adaptive learning will be automatically personalized for each individual based on strengths and weaknesses identified by his or her performance on Mastering parent assignments.

Question sets in the Adaptive Follow-Up Assignments continu-ously adapt to each student’s needs, making efficient use of study time.


Dynamic Study ModulesNEW! Dynamic Study Modules, designed to enable students to study effectively on their own as well as help students quickly access and learn the nomenclature they need to be successful in chemistry.

These modules can be accessed on smartphones, tablets, and computers and results can be tracked in the MasteringChemistry® Gradebook. Here’s how it works:

1. Students receive an initial set of questions and benefit from the metacognition involved with asking them to indicate how confident they are with their answer.

2. After answering each set of questions, students review their answers. 3. Each question has explanation material that reinforces the correct answer response

and addresses the misconceptions found in the wrong answer choices. 4. Once students review the explanations, they are presented with a new set of

questions. Students cycle through this dynamic process of test-learn-retest until they achieve mastery of the material.


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