The Central Science 14TH EDITION, AP® Edition

chemistry The Central Science 14TH EDITION, AP® Edition

Theodore L. Brown University of Illinois at Urbana-Champaign

H. Eugene LeMay, Jr. University of Nevada, Reno

Bruce E. Bursten Worcester Polytechnic Institute

Catherine J. Murphy University of Illinois at Urbana-Champaign

Patrick M. Woodward The Ohio State University

Matthew W. Stoltzfus The Ohio State University

With contributions by Michael W. Lufaso University of North Florida

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Library of Congress Cataloging-in-Publication Data Names: Brown, Theodore L. (Theodore Lawrence), 1928- Title: Chemistry : the central science / Theodore L. Brown, University of Illinois at Urbana-Champaign [and five others]. Description: 14th edition. | New York : Pearson, 2017. | Includes bibliographical references and index. Identifiers: LCCN 2016046345 | ISBN 9780134414232 Subjects: LCSH: Chemistry—Textbooks. Classification: LCC QD31.3 .C43145 2017 | DDC 540—dc23 LC record available at https://lccn.loc.gov/2016046345

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ISBN 10: 0-13-465095-6 (High School Binding) www.PearsonSchool.com/Advanced ISBN 13: 978-0-13-465095-1 (High School Binding)

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Preface xvii

2 Atoms, Molecules, and Ions 42

1 Introduction: 2.1 The Atomic Theory of Matter 44 Matter, Energy, 2.2 The Discovery of Atomic Structure 45 and Measurement 2 Cathode Rays and Electrons 45 radioactivity 47 The Nuclear Model of the Atom 48 1.1 The Study of Chemistry 4 The Atomic and Molecular Perspective of Chemistry 4 2.3 The Modern View of Atomic Why Study Chemistry? 5 Structure 49 1.2 Classifications of Matter 7 Atomic Numbers, Mass Numbers, and Isotopes 51 States of Matter 7 Pure Substances 7 2.4 Atomic Weights 53 Elements 8 Compounds 9 Mixtures 10 The Atomic Mass Scale 53 atomic Weight 53 1.3 Properties of Matter 12 2.5 The Periodic Table 55 Physical and Chemical Changes 12 Separation of 2.6 Molecules and Molecular Mixtures 13 Compounds 58 1.4 The Nature of Energy 15 Molecules and Chemical Formulas 58 Molecular and Kinetic Energy and Potential Energy 15 Empirical Formulas 58 Picturing Molecules 59 1.5 Units of Measurement 17 2.7 Ions and Ionic Compounds 60 SI Units 17 length and Mass 19 Predicting Ionic Charges 61 ionic Compounds 62 Temperature 19 Derived SI Units 20 Volume 20 2.8 Naming Inorganic Compounds 65 Density 21 Units of Energy 21 Names and Formulas of Ionic Compounds 65 1.6 Uncertainty in Measurement 24 Names and Formulas of Acids 69 names and Precision and Accuracy 24 Significant Figures 25 Formulas of Binary Molecular Compounds 70 Significant Figures in Calculations 26 2.9 Some Simple Organic 1.7 Dimensional Analysis 28 Compounds 71 Conversion Factors 28 Using Two or More Conversion Alkanes 71 Some Derivatives of Alkanes 72 Factors 30 Conversions Involving Volume 31 Chapter Summary and Key Terms 74 Chapter Summary and Key Terms 33 Learning Outcomes 74 Key Equations 75 Learning Outcomes 34 Key Equations 34 Exercises 75 Additional Exercises 80 Exercises 35 Additional Exercises 39 A Closer Look Basic Forces 51 Chemistry Put to Work Chemistry and the Chemical A Closer Look The Mass Spectrometer 54 Industry 6 A Closer Look What Are Coins Made Of? 57 A Closer Look The Scientific Method 17 Chemistry and Life Elements Required by Living Chemistry Put to Work Chemistry in the News 23 Organisms 64 Strategies for Success Estimating Answers 30 Strategies for Success How to Take a Test 73 Strategies for Success The Importance of Practice 32 Strategies for Success The Features of This Book 32

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How Compounds Dissolve in Water 123 Strong and Weak Electrolytes 124 4.2 Precipitation Reactions 126 Solubility Guidelines for Ionic Compounds 126 Exchange (Metathesis) Reactions 127 ionic 3 Chemical Reactions and Equations and Spectator Ions 129 4.3 Acids, Bases, and Neutralization 82 Reaction Stoichiometry Reactions 130 3.1 Chemical Equations 84 Acids 130 Bases 131 Strong and Weak Acids and Bases 132 identifying Strong and Weak Balancing Equations 84 a Step-by-Step Example of Electrolytes 132 neutralization Reactions and Balancing a Chemical Equation 85 indicating the Salts 134 neutralization Reactions with Gas States of Reactants and Products 87 Formation 136 3.2 Simple Patterns of Chemical 4.4 Oxidation-Reduction Reactions 137 Reactivity 88 Oxidation and Reduction 137 Oxidation Combination and Decomposition Reactions 88 Numbers 138 Oxidation of Metals by Acids and Combustion Reactions 90 Salts 140 The Activity Series 141 3.3 Formula Weights 90 4.5 Concentrations of Solutions 144 Formula and Molecular Weights 91 Percentage Molarity 144 expressing the Concentration of an Composition from Chemical Formulas 92 Electrolyte 145 interconverting Molarity, Moles, and 3.4 Avogadro’s Number and the Mole 93 Volume 146 Dilution 147 Molar Mass 94 interconverting Masses and 4.6 Solution Stoichiometry and Moles 96 interconverting Masses and Numbers of Chemical Analysis 148 Particles 97 Titrations 150 3.5 Empirical Formulas from Chapter Summary and Key Terms 153 Analyses 98 Learning Outcomes 154 Key Equations 154 Molecular Formulas from Empirical Formulas 100 Exercises 154 Additional Exercises 159 Combustion Analysis 101 Integrative Exercises 160 Design an 3.6 Quantitative Information from Experiment 161 Balanced Equations 102 Chemistry Put to Work Antacids 136 3.7 106 Limiting Reactants Strategies for Success Analyzing Chemical Theoretical and Percent Yields 108 Reactions 144 Chapter Summary and Key Terms 110 Learning Outcomes 110 Key Equations 110 Exercises 111 Additional Exercises 117 Integrative Exercises 118 Design an Experiment 119

Strategies for Success Problem Solving 92 Glucose Monitoring Chemistry and Life 96 5 Thermochemistry 162 Strategies for Success Design an Experiment 109 5.1 The Nature of Chemical Energy 164 5.2 The First Law of Thermodynamics 166 System and Surroundings 166 internal Energy 167 Relating ∆E to Heat and Work 168 endothermic and Exothermic Processes 170 State Functions 170 4 Reactions in Aqueous 5.3 Enthalpy 172 Pressure–Volume Work 172 enthalpy Change 174 Solution 120 5.4 Enthalpies of Reaction 176 4.1 General Properties of Aqueous 5.5 Calorimetry 178 Solutions 122 Heat Capacity and Specific Heat 179 Constant-Pressure Calorimetry 180 Electrolytes and Nonelectrolytes 122 Bomb Calorimetry (Constant-Volume Calorimetry) 182

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5.6 Hess’s Law 183 6.9 Electron Configurations and the 5.7 Enthalpies of Formation 186 Periodic Table 241 Using Enthalpies of Formation to Calculate Enthalpies Anomalous Electron Configurations 244 of Reaction 188 Chapter Summary and Key Terms 246 5.8 Bond Enthalpies 190 Learning Outcomes 247 Key Equations 248 Bond Enthalpies and the Enthalpies of Reactions 192 Exercises 248 Additional Exercises 253 Integrative Exercises 255 Design an 5.9 Foods and Fuels 194 Experiment 255 Foods 194 Fuels 196 Other Energy Sources 197 Measurement and the Uncertainty Chapter Summary and Key Terms 200 A Closer Look Principle Learning Outcomes 201 Key Equations 201 226 Exercises 202 Additional Exercises 208 A Closer Look Thought Experiments and Integrative Exercises 210 Design an Schrödinger’s Cat 229 Experiment 211 A Closer Look Probability Density and Radial Probability Functions 233 A Closer Look Energy, Enthalpy, and P-V Work 175 Chemistry and Life Nuclear Spin and Magnetic A Closer Look Using Enthalpy as a Guide 178 Resonance Imaging 237 Chemistry and Life The Regulation of Body Temperature 183 Chemistry Put to Work The Scientific and Political Challenges of Biofuels 198

7 Periodic Properties of the Elements 256 6 Electronic Structure 7.1 Development of the Periodic Table 258 of Atoms 212 7.2 Effective Nuclear Charge 259 6.1 The Wave Nature of Light 214 7.3 Sizes of Atoms and Ions 262 Periodic Trends in Atomic Radii 264 Periodic Trends 216 6.2 Quantized Energy and Photons in Ionic Radii 264 Hot Objects and the Quantization of Energy 216 The Photoelectric Effect and Photons 217 7.4 Ionization Energy 268 Variations in Successive Ionization Energies 268 219 6.3 Line Spectra and the Bohr Model Periodic Trends in First Ionization Energies 269 Line Spectra 219 Bohr’s Model 220 The Energy Electron Configurations of Ions 270 States of the Hydrogen Atom 221 limitations of the Bohr Model 224 7.5 Electron Affinity 272 Periodic Trends in Electron Affinity 273 6.4 The Wave Behavior of Matter 224 The Uncertainty Principle 226 7.6 Metals, Nonmetals, and Metalloids 273 6.5 Quantum Mechanics and Atomic Metals 274 Nonmetals 276 Metalloids 278 Orbitals 227 Orbitals and Quantum Numbers 228 7.7 Trends for Group 1A and Group 2A Metals 278 6.6 Representations of Orbitals 231 Group 1A: The Alkali Metals 278 Group 2A: The The s Orbitals 231 The p Orbitals 233 The d and f Alkaline Earth Metals 282 Orbitals 234 7.8 Trends for Selected Nonmetals 283 6.7 Many-Electron Atoms 234 Hydrogen 283 Group 6A: The Oxygen Group 284 Orbitals and Their Energies 235 electron Spin and Group 7A: The Halogens 285 Group 8A: The Noble the Pauli Exclusion Principle 236 Gases 287 6.8 Electron Configurations 236 Chapter Summary and Key Terms 288 Hund’s Rule 238 Condensed Electron Learning Outcomes 289 Key Equations 289 Configurations 240 Transition Metals 240 Exercises 290 Additional Exercises 294 The Lanthanides and Actinides 241

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Integrative Exercises 296 Design an Experiment 297

A Closer Look Effective Nuclear Charge 262 Chemistry Put to Work Ionic Size and Lithium-Ion Batteries 267 9 Molecular Geometry and Chemistry and Life The Improbable Development of (R)-naproxen Lithium Drugs 281 Bonding Theories 338

9.1 Molecular Shapes 340 9.2 The VSEPR Model 342 Applying the VSEPR Model to Determine Molecular Shapes 343 effect of Nonbonding Electrons and Multiple Bonds on Bond Angles 347 Molecules with Expanded Valence Shells 347 Shapes of Larger 8 Basic Concepts of Molecules 350 9.3 Molecular Shape and Molecular Chemical Bonding 298 Polarity 352 8.1 Lewis Symbols and the Octet Rule 300 9.4 Covalent Bonding and Orbital The Octet Rule 300 Overlap 354 8.2 Ionic Bonding 301 9.5 Hybrid Orbitals 355 2 3 Energetics of Ionic Bond Formation 302 electron sp Hybrid Orbitals 355 sp and sp Hybrid Configurations of Ions of the s- and p-Block Orbitals 357 hypervalent Molecules 359 Elements 304 Transition Metal Ions 305 Hybrid Orbital Summary 359 8.3 Covalent Bonding 306 9.6 Multiple Bonds 361 Lewis Structures 307 Multiple Bonds 308 Resonance Structures, Delocalization, and p Bonding 365 General Conclusions about s and p 8.4 Bond Polarity and Bonding 367 Electronegativity 309 9.7 Molecular Orbitals 368 Electronegativity 309 electronegativity and Bond Molecular Orbitals of the Hydrogen Molecule 368 Polarity 310 Dipole Moments 311 Comparing Bond Order 370 Ionic and Covalent Bonding 314 9.8 8.5 Drawing Lewis Structures 315 Bonding in Period 2 Diatomic 371 Formal Charge and Alternative Lewis Structures 317 Molecules

Molecular Orbitals for li2 and Be2 372 8.6 Resonance Structures 319 Molecular Orbitals from 2p Atomic Orbitals 373 Resonance in Benzene 321 Electron Configurations for B2 through ne2 376 8.7 Exceptions to the Octet Rule 322 Electron Configurations and Molecular Properties 377 Odd Number of Electrons 323 less Than an Octet Heteronuclear Diatomic Molecules 380 of Valence Electrons 323 More Than an Octet of Chapter Summary and Key Terms 382 Valence Electrons 324 Learning Outcomes 383 Key Equations 384 8.8 Strengths and Lengths of Covalent Exercises 384 Additional Exercises 389 Integrative Exercises 392 Design an Bonds 325 Experiment 393 Chapter Summary and Key Terms 328 Learning Outcomes 329 Key Equations 329 Chemistry and Life The Chemistry of Vision 367 Exercises 329 Additional Exercises 334 A Closer Look Phases in Atomic and Molecular Integrative Exercises 335 Design an Orbitals 374 Experiment 337 Chemistry Put to Work Orbitals and Energy 381 A Closer Look Calculation of Lattice Energies: The Born–Haber Cycle 305 A Closer Look Oxidation Numbers, Formal Charges, and Actual Partial Charges 319

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10 Gases 394 11 Liquids and 10.1 Characteristics of Gases 396 Intermolecular Forces 434 10.2 Pressure 397 Atmospheric Pressure and the Barometer 397 11.1 A Molecular Comparison of Gases, Liquids, and Solids 436 10.3 The Gas Laws 400 The Pressure–Volume Relationship: Boyle’s Law 400 11.2 Intermolecular Forces 438 The Temperature–Volume Relationship: Charles’s Dispersion Forces 439 Dipole–Dipole Law 401 The Quantity–Volume Relationship: Interactions 440 hydrogen Bonding 441 Avogadro’s Law 402 Ion–Dipole Forces 444 Comparing Intermolecular Forces 444 10.4 The Ideal-Gas Equation 403 Relating the Ideal-Gas Equation and the Gas 11.3 Select Properties of Liquids 445 Laws 406 Viscosity 446 Surface Tension 447 Capillary Action 448 10.5 Further Applications of the Ideal-Gas Equation 407 11.4 Phase Changes 449 Energy Changes Accompany Phase Changes 449 Gas Densities and Molar Mass 407 Volumes of Gases Heating Curves 450 Critical Temperature and in Chemical Reactions 409 Pressure 451 10.6 Gas Mixtures and Partial 11.5 Vapor Pressure 453 Pressures 410 Volatility, Vapor Pressure, and Temperature 454 Partial Pressures and Mole Fractions 411 Vapor Pressure and Boiling Point 455 10.7 The Kinetic-Molecular Theory 11.6 Phase Diagrams 456 of Gases 412 The Phase Diagrams of h2O and CO2 457 Distributions of Molecular Speed 413 application of Kinetic-Molecular Theory to the Gas Laws 414 11.7 Liquid Crystals 459 Types of Liquid Crystals 459 10.8 Molecular Effusion and Diffusion 415 Graham’s Law of Effusion 416 Diffusion and Mean Chapter Summary and Key Terms 462 Learning Free Path 417 Outcomes 463 Exercises 463 Additional Exercises 468 Integrative Exercises 470 Design 10.9 Real Gases: Deviations from Ideal an Experiment 471 Behavior 419 The van der Waals Equation 421 Chemistry Put to Work Ionic Liquids 447 Chapter Summary and Key Terms 423 A Closer Look The Clausius–Clapeyron Learning Outcomes 424 Key Equations 424 Equation 455 Exercises 424 Additional Exercises 430 Integrative Exercises 432 Design an Experiment 433

Strategies for Success Calculations Involving Many Variables 405 A Closer Look The Ideal-Gas Equation 414 Chemistry Put to Work Gas Separations 418 12 Solids and Modern Materials 472

12.1 Classification of Solids 474 12.2 Structures of Solids 475 Crystalline and Amorphous Solids 475 Unit Cells and Crystal Lattices 475 Filling the Unit Cell 477

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12.3 Metallic Solids 478 13.5 Colligative Properties 542 The Structures of Metallic Solids 479 Close Vapor–Pressure Lowering 542 Boiling-Point Packing 480 Alloys 483 Elevation 544 Freezing-Point Depression 545 12.4 Metallic Bonding 486 Osmosis 547 Determination of Molar Mass from Colligative Properties 550 Electron-Sea Model 486 Molecular Orbital Model 487 13.6 Colloids 552 12.5 Ionic Solids 489 Hydrophilic and Hydrophobic Colloids 553 Structures of Ionic Solids 490 Colloidal Motion in Liquids 555 12.6 Molecular Solids 494 Chapter Summary and Key Terms 556 12.7 Covalent-Network Solids 494 Learning Outcomes 557 Key Equations 558 Semiconductors 495 Semiconductor Doping 497 Exercises 558 Additional Exercises 564 Integrative Exercises 565 Design an 12.8 Polymers 500 Experiment 567 Making Polymers 501 Structure and Physical Properties of Polymers 504 Chemistry and Life Fat-Soluble and Water-Soluble 12.9 Nanomaterials 506 Vitamins 533 Semiconductors on the Nanoscale 506 Metals on the Chemistry and Life Blood Gases and Deep-Sea Nanoscale 507 Carbon on the Nanoscale 509 Diving 537 Chapter Summary and Key Terms 512 A Closer Look Ideal Solutions with Two or More Learning Outcomes 513 Key Equations 513 Volatile Components 544 Exercises 514 Additional Exercises 521 A Closer Look The van’t Hoff Factor 551 Integrative Exercises 522 Design an Chemistry and Life Sickle-Cell Anemia 555 Experiment 523

A Closer Look X-ray Diffraction 478 Chemistry Put to Work Alloys of Gold 485 Chemistry Put to Work Solid-State Lighting 499 Chemistry Put to Work Modern Materials in the Automobile 503 Chemistry Put to Work Microporous and 14 Chemical Kinetics 568 Mesoporous Materials 508 14.1 Factors That Affect Reaction Rates 570 14.2 Reaction Rates 571 Change of Rate with Time 572 instantaneous Rate 573 reaction Rates and Stoichiometry 574 14.3 Concentration and Rate Laws 575 13 Properties of Reaction Orders: The Exponents in the Rate Law 577 Magnitudes and Units of Rate Constants 579 Solutions 524 Using Initial Rates to Determine Rate Laws 580 14.4 The Change of Concentration with 13.1 The Solution Process 526 Time 581 The Natural Tendency toward Mixing 526 The Effect First-Order Reactions 581 Second-Order of Intermolecular Forces on Solution Formation 527 Reactions 583 Zero-Order Reactions 585 Energetics of Solution Formation 528 Solution Half-Life 585 Formation and Chemical Reactions 530 14.5 Temperature and Rate 587 13.2 Saturated Solutions and The Collision Model 587 The Orientation Factor 588 530 Solubility Activation Energy 588 The Arrhenius Equation 590 13.3 Factors Affecting Solubility 532 Determining the Activation Energy 591 Solute–Solvent Interactions 532 Pressure 14.6 Reaction Mechanisms 593 Effects 534 Temperature Effects 537 Elementary Reactions 593 Multistep 13.4 Expressing Solution Mechanisms 593 rate Laws for Elementary Concentration 538 Reactions 595 The Rate-Determining Step for a Mass Percentage, ppm, and ppb 538 Mole Fraction, Multistep Mechanism 596 Mechanisms with a Slow Molarity, and Molality 539 Converting Concentration Initial Step 597 Mechanisms with a Fast Initial Units 540 Step 598

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14.7 Catalysis 600 Chemistry Put to Work The Haber Process 628 Homogeneous Catalysis 600 heterogeneous A Closer Look Temperature Changes and Catalysis 602 Enzymes 603 Le Châtelier’s Principle 651 Chapter Summary and Key Terms 608 Chemistry Put to Work Controlling Nitric Oxide Learning Outcomes 608 Key Equations 609 Emissions 654 Exercises 609 Additional Exercises 617 Integrative Exercises 620 Design an Experiment 621

A Closer Look Using Spectroscopic Methods to Measure Reaction Rates: Beer’s Law 576 Chemistry Put to Work Methyl Bromide in the Atmosphere 586 16 Acid–Base Equilibria 664 Chemistry Put to Work Catalytic Converters 604 Chemistry and Life Nitrogen Fixation and 16.1 Arrhenius Acids and Bases 666 Nitrogenase 606 16.2 Brønsted–Lowry Acids and Bases 667 The h+ Ion in Water 667 Proton-Transfer Reactions 667 Conjugate Acid–Base Pairs 668 Relative Strengths of Acids and Bases 670 16.3 The Autoionization of Water 672 The Ion Product of Water 672 16.4 The pH Scale 674 15 Chemical Equilibrium 622 pOH and Other “p” Scales 676 Measuring pH 677 16.5 Strong Acids and Bases 678 15.1 The Concept of Equilibrium 625 Strong Acids 678 Strong Bases 679 15.2 The Equilibrium Constant 627 16.6 Weak Acids 680 Evaluating 629 equilibrium Constants in Terms Kc Calculating K from pH 681 Percent Ionization 682 of Pressure, 630 equilibrium Constants and a Kp Using K to Calculate pH 683 Polyprotic Acids 687 Units 631 a 16.7 Weak Bases 690 15.3 Understanding and Working with Types of Weak Bases 690 Equilibrium Constants 632 693 The Magnitude of Equilibrium Constants 632 16.8 Relationship between Ka and Kb The Direction of the Chemical Equation and K 633 16.9 Acid–Base Properties of Salt Relating Chemical Equation Stoichiometry and Solutions 696 Equilibrium Constants 634 An Anion’s Ability to React with Water 696 15.4 Heterogeneous Equilibria 636 A Cation’s Ability to React with Water 696 Combined Effect of Cation and Anion in Solution 697 15.5 Calculating Equilibrium Constants 638 16.10 Acid–Base Behavior and Chemical 699 15.6 Applications of Equilibrium Structure Factors That Affect Acid Strength 699 Binary Constants 640 Acids 700 Oxyacids 701 Carboxylic Acids 703 Predicting the Direction of Reaction 641 Calculating Equilibrium Concentrations 642 16.11 Lewis Acids and Bases 704 15.7 Le Châtelier’s Principle 644 Chapter Summary and Key Terms 707 Learning Outcomes 707 Key Equations 708 Change in Reactant or Product Concentration 646 Exercises 708 Additional Exercises 713 Effects of Volume and Pressure Changes 647 effect Integrative Exercises 715 Design an of Temperature Changes 649 The Effect of Experiment 715 Catalysts 651 Chapter Summary and Key Terms 654 A Closer Look Polyprotic Acids 689 655 655 Learning Outcomes Key Equations Chemistry Put to Work Amines and Amine Exercises 656 Additional Exercises 661 Hydrochlorides 695 Integrative Exercises 662 Design an The Amphiprotic Behavior of Experiment 663 Chemistry and Life Amino Acids 703

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Photochemical Reactions in the Atmosphere 770 Ozone in the Stratosphere 773 18.2 Human Activities and Earth’s Atmosphere 774 The Ozone Layer and Its Depletion 774 Sulfur 17 Additional Aspects of Compounds and Acid Rain 776 nitrogen Oxides and Photochemical Smog 779 Greenhouse Gases: Water Aqueous Equilibria 716 Vapor, Carbon Dioxide, and Climate 780

17.1 The Common-Ion Effect 718 18.3 Earth’s Water 784 The Global Water Cycle 784 Salt Water: 17.2 721 Buffers Earth’s Oceans and Seas 785 Freshwater and Composition and Action of Buffers 721 Calculating Groundwater 786 the pH of a Buffer 723 Buffer Capacity and pH Range 726 addition of Strong Acids or Bases to 18.4 Human Activities and Water Buffers 726 Quality 787 17.3 Acid–Base Titrations 729 Dissolved Oxygen and Water Quality 788 Water Purification: Desalination 788 Water Purification: Strong Acid–Strong Base Titrations 730 Weak Acid– Municipal Treatment 789 Strong Base Titrations 732 Titrating with an Acid– Base Indicator 736 Titrations of Polyprotic Acids 738 18.5 Green Chemistry 792 17.4 Solubility Equilibria 739 Supercritical Solvents 794 Greener Reagents and Processes 794 The Solubility-Product Constant, Ksp 740 Solubility and Ksp 741 Chapter Summary and Key Terms 797 Learning Outcomes 797 Exercises 798 17.5 Factors That Affect Solubility 743 Additional Exercises 803 Integrative The Common-Ion Effect 743 Solubility and pH 744 Exercises 804 Design an Experiment 805 Formation of Complex Ions 746 amphoterism 749 17.6 Precipitation and Separation A Closer Look Other Greenhouse Gases 783 of Ions 751 A Closer Look The Ogallala Aquifer—A Shrinking Resource 787 Selective Precipitation of Ions 752 A Closer Look Fracking and Water Quality 790 17.7 Qualitative Analysis for Metallic Ocean Acidification 792 Elements 753 Chemistry and Life Chapter Summary and Key Terms 756 Learning Outcomes 757 Key Equations 757 Exercises 758 Additional Exercises 763 Integrative Exercises 764 Design an Experiment 765

Chemistry and Life Blood as a Buffered Solution 729 19 Chemical A Closer Look Limitations of Solubility Products 743 Thermodynamics 806 Chemistry and Life Tooth Decay and 19.1 Spontaneous Processes 808 Fluoridation 746 Seeking a Criterion for Spontaneity 809 reversible Lead Contamination in Drinking A Closer Look and Irreversible Processes 810 Water 750 19.2 Entropy and the Second Law of Thermodynamics 812 The Relationship between Entropy and Heat 812 ∆S for Phase Changes 813 The Second Law of Thermodynamics 814 19.3 The Molecular Interpretation of Entropy and the Third Law of 18 Chemistry of the Thermodynamics 815 Expansion of a Gas at the Molecular Level 815 Environment 766 Boltzmann’s Equation and Microstates 816 Molecular Motions and Energy 818 18.1 Earth’s Atmosphere 768 Making Qualitative Predictions about ∆S 819 Composition of the Atmosphere 769 The Third Law of Thermodynamics 821

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19.4 Entropy Changes in Chemical 20.7 Batteries and Fuel Cells 877 Reactions 822 Lead–Acid Battery 878 alkaline Battery 878 Temperature Variation of Entropy 822 Standard Nickel–Cadmium and Nickel–Metal Hydride Molar Entropies 823 Calculating the Standard Batteries 878 Lithium-Ion Batteries 879 Hydrogen Entropy Change for a Reaction 824 entropy Changes Fuel Cells 879 in the Surroundings 824 20.8 Corrosion 882 19.5 Gibbs Free Energy 825 Corrosion of Iron (Rusting) 882 Preventing Corrosion Standard Free Energy of Formation 828 of Iron 883 19.6 Free Energy and Temperature 830 20.9 Electrolysis 884 19.7 Free Energy and the Equilibrium Quantitative Aspects of Electrolysis 886 Constant 832 Chapter Summary and Key Terms 889 Free Energy under Nonstandard Conditions 832 Learning Outcomes 890 Key Equations 890 Relationship between ∆G ° and K 834 Exercises 890 Additional Exercises 897 Integrative Exercises 898 Design an Chapter Summary and Key Terms 836 Experiment 899 Learning Outcomes 837 Key Equations 837 Exercises 838 Additional Exercises 844 A Closer Look Electrical Work 871 Integrative Exercises 846 Design an Chemistry and Life Heartbeats and Experiment 847 Electrocardiography 876 A Closer Look The Entropy Change When a Gas Chemistry Put to Work Batteries for Hybrid and Expands Isothermally 814 Electric Vehicles 880 Chemistry and Life Entropy and Human Chemistry Put to Work Electrometallurgy of Society 822 Aluminum 887 A Closer Look What’s “Free” About Free Energy? 829 Chemistry and Life Driving Nonspontaneous Reactions: Coupling Reactions 835

21 Nuclear Chemistry 900 21.1 Radioactivity and Nuclear Equations 902 20 Electrochemistry 848 Nuclear Equations 902 Types of Radioactive Decay 903 20.1 Oxidation States and Oxidation– 21.2 Patterns of Nuclear Stability 905 Reduction Reactions 850 Neutron-to-Proton Ratio 905 radioactive Decay 20.2 Balancing Redox Equations 852 Chains 907 Further Observations 908 Half-Reactions 852 Balancing Equations by the 21.3 Nuclear Transmutations 909 Method of Half-Reactions 852 Balancing Equations Accelerating Charged Particles 910 reactions for Reactions Occurring in Basic Solution 855 Involving Neutrons 911 Transuranium Elements 911 20.3 Voltaic Cells 857 21.4 Rates of Radioactive Decay 912 20.4 Cell Potentials under Standard Radiometric Dating 913 Calculations Based on Half- Conditions 860 Life 915 Standard Reduction Potentials 861 Strengths of 21.5 Detection of Radioactivity 917 Oxidizing and Reducing Agents 866 Radiotracers 917 20.5 Free Energy and Redox Reactions 868 21.6 Energy Changes in Nuclear Emf, Free Energy, and the Equilibrium Constant 869 Reactions 919 20.6 Cell Potentials under Nonstandard Nuclear Binding Energies 921 Conditions 871 21.7 Nuclear Power: Fission 922 The Nernst Equation 872 Concentration Cells 874 Nuclear Reactors 925 nuclear Waste 927

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21.8 Nuclear Power: Fusion 928 22.8 The Other Group 5A Elements: P, As, 21.9 Radiation in the Environment Sb, and Bi 965 and Living Systems 930 Occurrence, Isolation, and Properties of Radiation Doses 931 Phosphorus 966 Phosphorus Halides 966 Oxy Compounds of Phosphorus 967 Chapter Summary and Key Terms 933 Learning Outcomes 934 Key Equations 935 22.9 Carbon 969 Exercises 935 Additional Exercises 939 Elemental Forms of Carbon 969 Oxides of Integrative Exercises 940 Design an Carbon 970 Carbonic Acid and Carbonates 971 Experiment 941 Carbides 972 22.10 The Other Group 4A Elements: Chemistry and Life Medical Applications Si, Ge, Sn, and Pb 972 of Radiotracers 918 General Characteristics of the Group 4A Elements 972 A Closer Look The Dawning of the Nuclear Age 925 Occurrence and Preparation of Silicon 973 A Closer Look Nuclear Synthesis of the Silicates 973 Glass 975 Silicones 976 Elements 929 22.11 Boron 976 Chemistry and Life Radiation Therapy 932 Chapter Summary and Key Terms 978 Learning Outcomes 979 Exercises 979 Additional Exercises 983 Integrative Exercises 984 Design an Experiment 985

A Closer Look The Hydrogen Economy 948 Chemistry and Life Nitroglycerin, Nitric Oxide, and Heart Disease 965 22 Chemistry of the Chemistry and Life Arsenic in Drinking Water 968 942 Chemistry Put to Work Carbon Fibers and Nonmetals Composites 970 22.1 Periodic Trends and Chemical Reactions 944 Chemical Reactions 945 22.2 Hydrogen 946 Isotopes of Hydrogen 946 Properties of Hydrogen 947 Production of Hydrogen 948 Uses of Hydrogen 949 Binary Hydrogen Compounds 949 23 Transition Metals 22.3 Group 8A: The Noble Gases 950 Noble-Gas Compounds 951 and Coordination 22.4 Group 7A: The Halogens 952 Chemistry 986 Properties and Production of the Halogens 952 Uses of the Halogens 954 The Hydrogen Halides 954 23.1 The Transition Metals 988 Interhalogen Compounds 954 Oxyacids and Physical Properties 989 electron Configurations and Oxyanions 954 Oxidation States 990 Magnetism 991 22.5 Oxygen 955 23.2 Transition-Metal Complexes 992 Properties of Oxygen 955 Production of Oxygen 956 The Development of Coordination Chemistry: Werner’s Uses of Oxygen 956 Ozone 956 Oxides 956 Theory 993 The Metal–Ligand Bond 995 Peroxides and Superoxides 958 Charges, Coordination Numbers, and Geometries 996 22.6 The Other Group 6A Elements: S, Se, 23.3 Common Ligands in Coordination Te, and Po 958 Chemistry 997 Occurrence and Production of S, Se, and Te 959 Metals and Chelates in Living Systems 999 Properties and Uses of Sulfur, Selenium, and Tellurium 959 Sulfides 959 Oxides, Oxyacids, and 23.4 Nomenclature and Isomerism in Oxyanions of Sulfur 960 Coordination Chemistry 1003 22.7 Nitrogen 962 Isomerism 1005 Structural Isomerism 1005 Stereoisomerism 1006 Properties of Nitrogen 962 Production and Uses of Nitrogen 962 hydrogen Compounds of Nitrogen 962 Oxides and Oxyacids of Nitrogen 963

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23.5 Color and Magnetism in 24.4 Organic Functional Groups 1048 Coordination Chemistry 1009 Alcohols 1048 Ethers 1050 Aldehydes and Color 1009 Magnetism of Coordination Ketones 1050 Carboxylic Acids and Esters 1051 Compounds 1011 Amines and Amides 1054 23.6 Crystal-Field Theory 1011 24.5 Chirality in Organic Chemistry 1055 Electron Configurations in Octahedral 24.6 Introduction to Biochemistry 1057 Complexes 1015 Tetrahedral and Square-Planar 24.7 Proteins 1057 Complexes 1017 Amino Acids 1057 Polypeptides and Proteins 1059 Chapter Summary and Key Terms 1021 Protein Structure 1060 Learning Outcomes 1021 Exercises 1022 24.8 Carbohydrates 1062 Additional Exercises 1026 Integrative Exercises 1028 Design an Experiment 1029 Disaccharides 1063 Polysaccharides 1064 24.9 Lipids 1065 A Closer Look Entropy and the Chelate Effect 1001 Fats 1065 Phospholipids 1066 Chemistry and Life The Battle for Iron in Living 24.10 Nucleic Acids 1067 Systems 1002 Chapter Summary and Key Terms 1071 A Closer Look Charge-Transfer Color 1019 Learning Outcomes 1072 Exercises 1072 Additional Exercises 1077 Integrative Exercises 1078 Design an Experiment 1079

Chemistry Put to Work Gasoline 1040 A Closer Look Mechanism of Addition Reactions 1045 Strategies for Success What Now? 1070 24 The Chemistry of Life: Organic and Biological APPENDICES Chemistry 1030 A Mathematical Operations 1080 B Properties of Water 1087 24.1 General Characteristics of Organic Molecules 1032 C Thermodynamic Quantities for Selected The Structures of Organic Molecules 1032 Substances at 298.15 K (25 °C) 1088 The Stability of Organic Compounds 1033 Solubility D Aqueous Equilibrium Constants 1092 and Acid–Base Properties of Organic Compounds 1033 E Standard Reduction Potentials at 25 °C 1094

24.2 Introduction to Hydrocarbons 1034 Answers to Selected Exercises A-1 Structures of Alkanes 1035 Structural Isomers 1035 nomenclature of Alkanes 1036 Answers to Give It Some Thought A-31 Cycloalkanes 1039 reactions of Alkanes 1039 Answers to Go Figure A-37 24.3 Alkenes, Alkynes, and Aromatic Hydrocarbons 1041 Answers to Selected Practice Exercises A-43 Alkenes 1041 Alkynes 1043 Addition Glossary G-1 Reactions of Alkenes and Alkynes 1044 aromatic Hydrocarbons 1045 Stabilization of p Electrons Photo and Art Credits P-1 by Delocalization 1046 Substitution Reactions of Aromatic Hydrocarbons 1046 Index I-1

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A Closer Look The Scientific Method 17 Phases in Atomic and Molecular Other Greenhouse Gases 783 Basic Forces 51 Orbitals 374 The Ogallala Aquifer—A Shrinking The Mass Spectrometer 54 The Ideal-Gas Equation 414 Resource 787 What Are Coins Made Of? 57 The Clausius–Clapeyron Equation 455 Fracking and Water Quality 790 Energy, Enthalpy, and P–V Work 175 X-ray Diffraction 478 The Entropy Change When a Gas Using Enthalpy as a Guide 178 Ideal Solutions with Two or More Expands Isothermally 814 Measurement and the Uncertainty Volatile Components 544 What’s “Free” About Free Energy? 829 Principle 226 The van’t Hoff Factor 551 Electrical Work 871 Thought Experiments and Using Spectroscopic Methods to The Dawning of the Nuclear Age 925 Schrödinger’s Cat 229 Measure Reaction Rates: Nuclear Synthesis of the Elements 929 Probability Density and Radial Beer’s Law 576 The Hydrogen Economy 948 Probability Functions 233 Temperature Changes and Le Entropy and the Chelate Effect 1001 Effective Nuclear Charge 262 Châtelier’s Principle 651 Charge-Transfer Color 1019 Calculation of Lattice Energies: Polyprotic Acids 689 Mechanism of Addition The Born–Haber Cycle 305 Limitations of Solubility Products 743 Reactions 1045 Oxidation Numbers, Formal Charges, Lead Contamination in Drinking and Actual Partial Charges 319 Water 750

Chemistry Put to Work Chemistry and the Chemical Ionic Liquids 447 The Haber Process 628 Industry 6 Alloys of Gold 485 Controlling Nitric Oxide Chemistry in the News 23 Solid-State Lighting 499 Emissions 654 Antacids 136 Modern Materials in the Amines and Amine The Scientific and Political Challenges Automobile 503 Hydrochlorides 695 of Biofuels 198 Microporous and Mesoporous Batteries for Hybrid and Electric Ionic Size and Lithium-Ion Materials 508 Vehicles 880 Batteries 267 Methyl Bromide in the Electrometallurgy of Aluminum 887 Orbitals and Energy 381 Atmosphere 586 Carbon Fibers and Composites 970 Gas Separations 418 Catalytic Converters 604 Gasoline 1040

Chemistry and Life Elements Required by Living Blood Gases and Deep-Sea Diving 537 Heartbeats and Organisms 64 Sickle-Cell Anemia 555 Electrocardiography 876 Glucose Monitoring 96 Nitrogen Fixation and Medical Applications of The Regulation of Body Nitrogenase 606 Radiotracers 918 Temperature 183 The Amphiprotic Behavior of Amino Radiation Therapy 932 Nuclear Spin and Magnetic Resonance Acids 703 Nitroglycerin, Nitric Oxide, and Heart Imaging 237 Blood as a Buffered Solution 729 Disease 965 The Improbable Development of Tooth Decay and Fluoridation 746 Arsenic in Drinking Water 968 Lithium Drugs 281 Ocean Acidification 792 The Battle for Iron in Living The Chemistry of Vision 367 Entropy and Human Society 822 Systems 1002 Fat-Soluble and Water-Soluble Driving Nonspontaneous Reactions: Vitamins 533 Coupling Reactions 835

Strategies for Success Estimating Answers 30 Problem Solving 92 Calculations Involving Many The Importance of Practice 32 Design an Experiment 109 Variables 405 The Features of This Book 32 Analyzing Chemical Reactions 144 What Now? 1070 How to Take a Test 73 xiv

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Smart Figures Figures 3.4 Methane reacts with oxygen in a Bunsen Figure 10.12 Distribution of molecular speeds for and 3.5 burner and balanced chemical nitrogen gas

equation for the combustion of CH4 Figure 13.2 Intermolecular interactions involved in Figure 3.6 Combustion of magnesium metal in air, a solutions combination reaction Figure 13.3 Dissolution of the ionic solid NaCl in water Figure 4.4 A precipitation reaction Figure 13.4 Enthalpy changes accompanying the Figure 4.14 Reaction of copper metal with silver ion solution process Figures 5.2 Electrostatic potential energy and ionic Figure 14.16 Energy profile for conversion of methyl

and 5.3 bonding isonitrile H3CNC to its isomer Figure 5.23 Enthalpy diagram for propane combustion acetonitrile H CCN 1 3 2 Figure 5.24 Using bond enthalpies to estimate ∆Hrxn Figure 15.2 Equilibrium between NO and N O 1 2 2 4 Figure 6.25 General energy ordering of orbitals for a Figure 15.9 Predicting the direction of a reaction many-electron atom by comparing Q and K at a given Figure 8.5 Periodic trends in lattice energy as a temperature function of cation or anion radius Le Châtelier’s Le Châtelier’s principle Figure 9.12 Covalent bonds in H2, HCl, and Cl2 box, pg 645 Figure 9.13 Formation of the H2 molecule as atomic Figure 17.7 Titration of a strong acid with a strong base orbitals overlap Figure 17.9 Titration of a weak acid with a strong base Figure 9.14 Formation of sp hybrid orbitals Figure 20.3 Spontaneous oxidation–reduction reaction Figure 9.16 Formation of sp2 hybrid orbitals involving zinc and copper Figure 9.17 Formation of sp3 hybrid orbitals Figure 20.5 A voltaic cell that uses a salt bridge to Figure 9.22 Hybrid orbital bonding in ethylene complete the electrical circuit Figure 9.23 Formation of p bond in acetylene, C2H2

Interactive Sample Exercises Sample Exercise 1.1 Distinguishing among Elements, Sample Exercise 4.13 Using Molarity to Calculate Grams of Compounds, and Mixtures Solute Sample Exercise 1.2 Using SI Prefixes Sample Exercise 5.1 Relating Heat and Work to Changes of Sample Exercise 1.6 Assigning Appropriate Significant Internal Energy Figures Sample Exercise 5.4 Relating ∆ H to Quantities of Reactants Sample Exercise 1.8 Determining the Number of Significant and Products Figures in a Calculated Quantity Sample Exercise 5.6 Measuring ∆ H Using a Coffee-Cup Sample Exercise 1.11 Converting Units Using Two or More Calorimeter

Conversion Factors Sample Exercise 5.7 Measuring qrxn Using a Bomb Sample Exercise 1.13 Conversions Involving Density Calorimeter Sample Exercise 2.1 Atomic Size Sample Exercise 5.8 Using Hess’s Law to Calculate ∆ H Sample Exercise 2.3 Writing Symbols for Atoms Sample Exercise 5.10 Equations Associated with Enthalpy of Sample Exercise 2.4 Calculating the Atomic Weight of an Formation Element from Isotopic Abundance Sample Exercise 6.6 Subshells of the Hydrogen Atom Sample Exercise 2.5 Using the Periodic Table Sample Exercise 6.7 Orbital Diagrams and Electron Sample Exercise 2.9 Identifying Ionic and Molecular Configurations Compounds Sample Exercise 6.8 Electron Configurations for a Group Sample Exercise 3.2 Balancing Chemical Equations Sample Exercise 7.2 Predicting Relative Sizes of Atomic Radii Sample Exercise 3.5 Calculating Formula Weights Sample Exercise 8.2 Charges on Ions Sample Exercise 3.8 Converting Moles to Number of Atoms Sample Exercise 8.6 Drawing a Lewis Structure Sample Exercise 3.18 Calculating the Amount of Product Sample Exercise 9.1 Using the VSEPR Model Formed from a Limiting Reactant Sample Exercise 10.3 Evaluating the Effects of Changes in P, Sample Exercise 4.1 Relating Relative Numbers of Anions V, n, and T on a Gas and Cations to Chemical Formulas Sample Exercise 10.4 Using the Ideal-Gas Equation Sample Exercise 4.3 Predicting a Metathesis Reaction Sample Exercise 11.4 Relating Boiling Point to Vapor Pressure Sample Exercise 4.4 Writing a Net Ionic Equation Sample Exercise 12.4 Identifying Types of Semiconductors

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Sample Exercise 13.6 Calculation of Molarity Using the Sample Exercise 19.1 Identifying Spontaneous Processes Density of the Solution Sample Exercise 20.2 Balancing Redox Equations Sample Exercise 14.3 Relating Rates at Which Products in Acidic Solution Appear and Reactants Disappear Sample Exercise 21.1 Predicting the Product of a Sample Exercise 15.1 Writing Equilibrium-Constant Nuclear Reaction Expressions Sample Exercise 22.4 Predicting Chemical Reactions among Sample Exercise 16.1 Identifying Conjugate Acids and Bases the Halogens

Sample Practice 17.11 Calculating Ksp from Solubility Sample Exercise 23.2 Determining the Oxidation Number of Sample Exercise 18.1 Calculating Concentration from a Metal in a Complex Partial Pressure Sample Exercise 24.1 Naming Alkanes

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To the Instructor feedback. MasteringChemistryTM not only provides feedback on a question by question basis, but using Knewton-enhanced adaptive follow-up assignments and Dynamic Study Modules, Philosophy it now continually adapts to each student, offering a personalized learning experience. We authors of Chemistry: The Central Science are delighted and As authors, we want this text to be a central, indispensable honored that you have chosen us as your instructional partners learning tool for students. Whether as a physical book or in elec- for your general chemistry class. Collectively we have taught tronic form, it can be carried everywhere and used at any time. It general chemistry to multiple generations of students. So we is the best place students can go to obtain the information out- understand the challenges and opportunities of teaching a class side of the classroom needed for learning, skill development, ref- that so many students take. We have also been active research- erence, and test preparation. The text, more effectively than any ers who appreciate both the learning and the discovery aspects other instrument, provides the depth of coverage and coherent of the chemical sciences. Our varied, wide-ranging experiences background in modern chemistry that students need to serve have formed the basis of the close collaborations we have enjoyed their professional interests and, as appropriate, to prepare for as coauthors. In writing our book, our focus is on the students: more advanced chemistry courses. we try to ensure that the text is not only accurate and up-to-date If the text is to be effective in supporting your role as instruc- but also clear and readable. We strive to convey the breadth of tor, it must be addressed to the students. We have done our best to chemistry and the excitement that scientists experience in mak- keep our writing clear and interesting and the book attractive and ing new discoveries that contribute to our understanding of the well illustrated. The book has numerous in-text study aids for stu- physical world. We want the student to appreciate that chemis- dents, including carefully placed descriptions of problem-solving try is not a body of specialized knowledge that is separate from strategies. We hope that our cumulative experiences as teachers is most aspects of modern life, but central to any attempt to address evident in our pacing, choice of examples, and the kinds of study a host of societal concerns, including renewable energy, environ- aids and motivational tools we have employed. We believe stu- mental sustainability, and improved human health. dents are more enthusiastic about learning chemistry when they Publishing the fourteenth edition of this text bespeaks see its importance relative to their own goals and interests; there- an exceptionally long record of successful textbook writing. fore, we have highlighted many important applications of chem- We are appreciative of the loyalty and support the book has istry in everyday life. We hope you make use of this material. received over the years, and mindful of our obligation to jus- It is our philosophy, as authors, that the text and all the sup- tify each new edition. We begin our approach to each new plementary materials provided to support its use must work in edition with an intensive author retreat, in which we ask our- concert with you, the instructor. A textbook is only as useful to selves the deep questions that we must answer before we can students as the instructor permits it to be. This book is replete move forward. What justifies yet another edition? What is with features that help students learn and that can guide them changing in the world not only of chemistry, but with respect as they acquire both conceptual understanding and problem- to science education and the qualities of the students we solving skills. There is a great deal here for the students to use, serve? How can we help your students not only learn the prin- too much for all of it to be absorbed by any student in a one- ciples of chemistry, but also become critical thinkers who can year course. You will be the guide to the best use of the book. think more like chemists? The answers lie only partly in the Only with your active help will the students be able to uti- changing face of chemistry itself. The introduction of many lize most effectively all that the text and its supplements offer. new technologies has changed the landscape in the teaching Students care about grades, of course, and with encouragement of sciences at all levels. The use of the Internet in accessing they will also become interested in the subject matter and care information and presenting learning materials has mark- about learning. Please consider emphasizing features of the edly changed the role of the textbook as one element among book that can enhance student appreciation of chemistry, such many tools for student learning. Our challenge as authors is as the Chemistry Put To Work and Chemistry and Life boxes that to maintain the text as the primary source of chemical knowl- show how chemistry impacts modern life and its relationship to edge and practice, while at the same time integrating it with health and life processes. Also consider emphasizing conceptual the new avenues for learning made possible by technology. understanding (placing less emphasis on simple manipulative, This edition incorporates a number of those new methodolo- algorithmic problem solving) and urging students to use the gies, including use of computer-based classroom tools, such rich on-line resources available. as Learning CatalyticsTM, a cloud-based active learning analytics and assessment system, and web-based tools, particularly MasteringChemistryTM, which is continually evolving to pro- Organization and Contents vide more effective means of testing and evaluating student The first five chapters give a largely macroscopic, phenomeno- performance, while giving the student immediate and helpful logical view of chemistry. The basic concepts introduced—such

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A01_BROW0951_14_AP_FM.indd 17 19/11/16 1:12 AM xviii Preface

as nomenclature, stoichiometry, and thermochemistry—pro- Our chapter sequence provides a fairly standard organiza- vide necessary background for many of the laboratory experi- tion, but we recognize that not everyone teaches all the topics ments usually performed in general chemistry. We believe that in the order we have chosen. We have therefore made sure that an early introduction to thermochemistry is desirable because instructors can make common changes in teaching sequence so much of our understanding of chemical processes is based with no loss in student comprehension. In particular, many on considerations of energy changes. By incorporating bond instructors prefer to introduce gases (Chapter 10) after stoi- enthalpies in the Thermochemistry chapter we aim to empha- chiometry (Chapter 3) rather than with states of matter. The size the connection between the macroscopic properties of chapter on gases has been written to permit this change with substances and the submicroscopic world of atoms and bonds. no disruption in the flow of material. It is also possible to treat We believe we have produced an effective, balanced approach balancing redox equations (Sections 20.1 and 20.2) earlier, to teaching thermodynamics in general chemistry, as well as after the introduction of redox reactions in Section 4.4. Finally, providing students with an introduction to some of the global some instructors like to cover organic chemistry (Chapter 24) issues involving energy production and consumption. It is no right after bonding (Chapters 8 and 9). This, too, is a largely easy matter to walk the narrow pathway between—on the one seamless move. hand—trying to teach too much at too high a level and—on We have brought students into greater contact with descrip- the other hand—resorting to oversimplifications. As with the tive organic and inorganic chemistry by integrating examples book as a whole, the emphasis has been on imparting conceptual throughout the text. You will find pertinent and relevant exam- understanding, as opposed to presenting equations into which ples of “real” chemistry woven into all the chapters to illustrate students are supposed to plug numbers. principles and applications. Some chapters, of course, more The next four chapters (Chapters 6–9) deal with electronic directly address the “descriptive” properties of elements and structure and bonding. For more advanced students, A Closer their compounds, especially Chapters 4, 7, 11, 18, and 22–24. We Look boxes in Chapters 6 and 9 highlight radial probability func- also incorporate descriptive organic and inorganic chemistry in tions and the phases of orbitals. Our approach of placing this the end-of-chapter exercises. 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 New in This Edition bypass it. In treating this topic and others in Chapters 7 and 9, As with every new edition of Chemistry: The Central Science the we have materially enhanced the accompanying figures to more book has undergone a great many changes as we strive to keep effectively bring home their central messages. the content current, and to improve the clarity and effectiveness In Chapters 10–13, the focus of the text changes to the of the text, the art, and the exercises. Among the myriad changes next level of the organization of matter: examining the states there are certain points of emphasis that we use to organize and of matter. Chapters 10 and 11 deal with gases, liquids, and inter- guide the revision process. In creating the fourteenth edition molecular forces, while Chapter 12 is devoted to solids, present- our revision was organized around the following points: ing a contemporary view of the solid state as well as of modern • Our treatment of energy and thermochemistry has been materials accessible to general chemistry students. The chapter significantly revised. The concept of energy is now intro- provides an opportunity to show how abstract chemical bonding duced in Chapter 1, whereas previously it did not appear concepts impact real-world applications. The modular organiza- until Chapter 5. This change allows instructors greater tion of the chapter allows you to tailor your coverage to focus on freedom in the order in which they cover the material. For the materials (semiconductors, polymers, nanomaterials, and example, this change would facilitate coverage of Chap- so forth) that are most relevant to your students and your own ters 6 and 7 immediately following Chapter 2, a sequence interests. This section of the book concludes with Chapter 13 that is in line with an atoms-first approach to teaching which covers the formation and properties of solutions. general chemistry. More importantly, bond enthalpies The next several chapters examine the factors that deter- are now integrated into Chapter 5 to emphasize the con- mine the speed and extent of chemical reactions: kinetics nection between macroscopic quantities, like reaction (Chapter 14), equilibria (Chapters 15–17), thermodynamics enthalpies, and the submicroscopic world of atoms and (Chapter 19), and electrochemistry (Chapter 20). Also in this bonds. We feel this change leads to a better integration of section is a chapter on environmental chemistry (Chapter 18), in thermochemical concepts with the surrounding chapters. which the concepts developed in preceding chapters are applied Bond enthalpies are revisited in Chapter 8 after students to a discussion of the atmosphere and hydrosphere. This chapter have developed a more sophisticated view of chemical has increasingly come to be focused on green chemistry and the bonding. impacts of human activities on Earth’s water and atmosphere. After a discussion of nuclear chemistry (Chapter 21), the • Considerable effort was made to provide students with a book ends with three survey chapters. Chapter 22 deals with clear discussion, superior problem sets, and better real- nonmetals, Chapter 23 with the chemistry of transition met- time feedback on their understanding of the material. The als, including coordination compounds, and Chapter 24 with author team used an interactive e-book platform to view the chemistry of organic compounds and elementary bio- passages that students highlighted in their reading along chemical themes. These final four chapters are developed in with the related notes and questions that detailed what an independent, modular fashion and can be covered in any they did not understand. In response, numerous passages order. were revised for greater clarity.

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• Extensive effort has gone into creating enhanced content The art program for the fourteenth edition continues the for the eText version of the book. These features make the trajectory set in the previous two editions: to make greater and eText so much more than just an electronic copy of the more effective use of the figures as learning tools, by drawing physical textbook. New Smart Figures take key figures from the reader more directly into the figure. The style of the art has the text and bring them to life through animation and nar- been revised throughout for enhanced clarity and a cleaner ration. Likewise, new Smart Sample Exercises animate key more modern look. This includes: new white-background anno- sample exercises from the text, offering students a more in tation boxes with crisp, thin leaders; richer and more saturated depth and detailed discussion than can be provided in the colors in the art, and expanded use of 3D renderings. An edito- printed text. These interactive features will also include rial review of every figure in the text resulted in numerous minor follow-up questions, which can be assigned in Master- revisions to the art and its labels in order to increase clarity. The ingChemistryTM. Go Figure questions have been carefully scrutinized. Using sta- TM • We used metadata from MasteringChemistryTM to inform tistics from MasteringChemistry , many have been modified our revisions. In the thirteenth edition a second Practice or changed entirely to engage and challenge students to think Exercise was added to accompany each Sample Exercise. critically about the concept(s) that underlie each figure. The Nearly all of the additional practice exercises were mul- Give it Some Thought feature has been revised in a similar vein to tiple choice questions with wrong answer distractors stimulate more thoughtful reading of the text and foster critical written to identify student misconceptions and common thinking. mistakes. As implemented in MasteringChemistryTM, We provide a valuable overview of each chapter under the feedback was provided with each wrong answer to help What’s Ahead banner. Concept links ( ) continue to provide students recognize their misconceptions. In this new easy-to-see cross-references to pertinent material covered earlier edition we have carefully scrutinized the metadata from in the text. The essays titled Strategies in Chemistry, which pro- MasteringChemistryTM to identify practice exercises that vide advice to students on problem solving and “thinking like a either were not challenging the students or were not chemist,” have been renamed Strategies for Success to better con- being used. Those exercises have either been modified or vey their usefulness to the student. changed entirely. A similar effort was made to revise Give We have continued to emphasize conceptual exercises It Some Thought and Go Figure questions to make them in the end-of-chapter problems. In each chapter we begin more effective and amenable to use in MasteringChemis- the exercises with the well-received Visualizing Concepts cat- tryTM. Finally, the number of end-of-chapter exercises that egory. These exercises are designed to facilitate conceptual have wrong answer feedback in MasteringChemistryTM understanding through use of models, graphs, photographs, has been dramatically expanded. We have also replaced and other visual materials. They precede the regular end- outdated or little-used end-of-chapter exercises (~10 per of-chapter exercises and are identified in each case with the chapter). relevant chapter section number. A generous selection of Inte- grative Exercises, which give students the opportunity to solve • Finally, subtle but important changes have been made to problems that integrate concepts from the present chap- allow students to quickly reference important concepts and ter with those of previous chapters, is included at the end of assess their knowledge of the material. Key points are now each chapter. The importance of integrative problem solving set in italic with line spaces above and below for greater em- is highlighted by the Sample Integrative Exercise, which ends phasis. New skills-based How To . . . features offer step-by- each chapter beginning with Chapter 4. In general, we have step guidance for solving specific types of problems such included more conceptual end-of-chapter exercises and have as Drawing Lewis Structures, Balancing Redox Equations, made sure that there is a good representation of somewhat and Naming Acids. These features, with numbered steps more difficult exercises to provide a better mix in terms of encased by a thin rule, are integrated into the main discus- topic and level of difficulty. Many of the exercises have been sion and are easy to find. Finally, each Learning Objective restructured to facilitate their use in MasteringChemistryTM. is now correlated to specific end-of-chapter exercises. This We have made extensive use of the metadata from student use allows students to test their mastery of each learning objec- of MasteringChemistryTM to analyze end-of-chapter exercises tive when preparing for quizzes and exams. and make appropriate changes, as well as to develop Learning Changes in This Edition Outcomes for each chapter. New essays in our well-received Chemistry Put To Work and The New in This Edition section details changes made Chemistry and Life series emphasize world events, scientific dis- throughout this edition. Beyond a mere listing, however, it is coveries, and medical breakthroughs relevant to topics devel- worth dwelling on the general goals we set forth in formulating oped in each chapter. We maintain our focus on the positive this new edition. Chemistry: The Central Science has tradition- aspects of chemistry without neglecting the problems that can ally been valued for its clarity of writing, its scientific accuracy arise in an increasingly technological world. Our goal is to help and currency, its strong end-of-chapter exercises, and its con- students appreciate the real-world perspective of chemistry and sistency in level of coverage. In making changes, we have made the ways in which chemistry affects their lives. sure not to compromise these characteristics, and we have also It is perhaps a natural tendency for chemistry textbooks continued to employ an open, clean design in the layout of the to grow in length with succeeding editions, but it is one that book. we have resisted. There are, nonetheless, many new items in

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this edition, mostly ones that replace other material consid- In Chapter 17 a new A Closer Look box entitled Lead Con- ered less pertinent. Here is a list of several significant changes tamination in Drinking Water explores the chemistry behind the in content: water quality crisis in Flint, Michigan. Chapter 1, and every chapter that follows, begins with a Chapter 18 has been revised to reflect the most up-to-date

new chapter opening photo and backstory to provide a real data on atmospheric CO2 levels and the ozone hole. Figure 18.4, world context for the material that follows. A new section on showing the UV absorption spectrum of ozone, has been added the nature of energy (Section 1.4) has been added to Chapter 1. so students can understand its role in filtering out harmful UV The inclusion of energy in the opening chapter provides much radiation from the sun. A new Sample Exercise (18.3) walks stu-

greater flexibility for the order in which subsequent chapters dents through the steps needed to calculate the amount of CO2 can be covered. The Chemistry Put To Work box, dealing with produced from combustion of a hydrocarbon. Chemistry in the News, has been completely rewritten, with items In Chapter 19 we have substantially rewritten the early sec- that describe diverse ways in which chemistry intersects with tions to help students better understand the concepts of spon- the affairs of modern society. taneous, nonspontaneous, reversible, and irreversible processes In Chapter 2 the figures depicting the key experiments that and their relationships. These improvements have led to a led to the discovery of the structure of the atom—Millikan’s Oil clearer definition of entropy. Drop experiment and Rutherford’s Gold Foil experiment—have been enhanced. This is also the first occurrence of the periodic table which has been updated throughout the text to reflect the To the Student acceptance and naming of elements 113 (Nihonium), 115 (Mus- covium), 117 (Tennessine), and 118 (Oganesson). Chemistry: The Central Science, Fourteenth Edition, has been Chapter 5 has undergone the most extensive revision written to introduce you to modern chemistry. As authors, in the book. Early parts of the chapter have been modified to we have, in effect, been engaged by your instructor to help reflect the fact that basic concepts of energy are now introduced you learn chemistry. Based on the comments of students and in Chapter 1. Two new figures have been added. Figure 5.3 quali- instructors who have used this book in its previous editions, we tatively relates electrostatic potential energy to changes in the believe that we have done that job well. Of course, we expect bonding of an ionic solid, while Figure 5.16 provides a real- the text to continue to evolve through future editions. We world analogy to help students understand the relationship invite you to write to tell us what you like about the book so that between spontaneity and reaction enthalpy. The figure illus- we will know where we have helped you most. Also, we would trating exothermic and endothermic reactions (Figure 5.8) has like to learn of any shortcomings so we may further improve the been modified to show before and after images of the reaction. book in subsequent editions. Our addresses are given at the end Finally, to stress the atomistic origins of reaction enthalpies, a of the Preface. new section (Section 5.8) on bond enthalpies has been added, as discussed earlier. Advice for Learning and A new Sample Exercise has been added to Chapter 6 that Studying Chemistry shows how the radii of orbits in the Bohr model of the hydrogen atom depend on the principal quantum number and how the Learning chemistry requires both the assimilation of many con- electron behavior changes when a photon is emitted or absorbed. cepts and the development of analytical skills. In this text, we Chapter 8 has seen some of its content on bond enthalpies have provided you with numerous tools to help you succeed in moved to Chapter 5. The concepts there are now reinforced here. both tasks. If you are going to succeed in your chemistry course, In Chapter 11, attention has been paid to the text regarding you will have to develop good study habits. Science courses, and various intermolecular forces to make clear that chemists usu- chemistry in particular, make different demands on your learn- ally think about them in units of energy, not units of force. A ing skills than do other types of courses. We offer the following new checklist art piece replaces old Figure 11.14 in order to make tips for success in your study of chemistry: it clear that intermolecular interaction energies are additive. Don’t fall behind! As the course moves along, new top- Chapter 12 has a new A Closer Look box entitled Modern ics will build on material already presented. If you don’t keep Materials in the Automobile which discusses the wide range of up in your reading and problem solving, you will find it much materials used in a hybrid automobile, including semiconduc- harder to follow the lectures and discussions on current topics. tors, ionic solids, alloys, polymers, and more. A new Chemistry Experienced teachers know that students who read the relevant Put To Work entitled Microporous and Mesoporous Materials exam- sections of the text before coming to a class learn more from the ines materials with different pore sizes and their application in class and retain greater recall. “Cramming” just before an exam ion exchange and catalytic converters. has been shown to be an ineffective way to study any subject, In Chapter 15 a new A Closer Look box on Temperature chemistry included. So now you know. How important to you, Changes and Le Châtelier’s Principle explains the theoretical in this competitive world, is a good grade in chemistry? underpinnings of the empirical rules that successfully predict Focus your study. The amount of information you will how temperature changes influence the equilibrium constants be expected to learn may seem overwhelming. It is essential of exothermic and endothermic reactions. to recognize those concepts and skills that are particularly In Chapter 16 a new A Closer Look box on Polyprotic Acids important. Pay attention to what your instructor is emphasiz- explicitly shows the speciation of ions as a function of pH. ing. As you work through the Sample Exercises and homework

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assignments, try to see what general principles and skills they critical thinking skills by taking advantage of features in this employ. Use the What’s Ahead feature at the beginning of each new edition, such as exercises that focus on conceptual learning, chapter to help orient yourself to what is important in each and the Design an Experiment exercises. chapter. A single reading of a chapter will generally not be Use online resources. Some things are more easily enough for successful learning of chapter concepts and prob- learned by discovery, and others are best shown in three dimen- lem-solving skills. You will often need to go over assigned sions. If your instructor has included MasteringChemistryTM materials more than once. Don’t skip the Give It Some Thought with your book, take advantage of the unique tools it provides to and Go Figure features, Sample Exercises, and Practice Exercises. get the most out of your time in chemistry. These are your guides to whether you are learning the material. The bottom line is to work hard, study effectively, and use They are also good preparation for test-taking. The Learning the tools available to you, including this textbook. We want Outcomes and Key Equations at the end of the chapter will also to help you learn more about the world of chemistry and why help you focus your study. chemistry is the central science. If you really learn chemistry, Keep good lecture notes. Your lecture notes will pro- you can be the life of the party, impress your friends and parents, vide you with a clear and concise record of what your instructor and . . . well, also pass the course with a good grade. 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. Tips for AP Chemistry Exam Skim topics in the text before they are covered in lecture. Reviewing a topic before lecture will make it easier for Success you to take good notes. First read the What’s Ahead points and Ed Waterman, Rocky Mountain High School 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 The Content and Nature of the AP Exam you a feeling for the scope of topics. Try to avoid thinking that in Chemistry you must learn and understand everything right away. The Advanced Placement Examination in Chemistry is a com- You need to do a certain amount of preparation prehensive evaluation of knowledge of all areas of general before lecture. More than ever, instructors are using the lec- chemistry at the first year college level. It consists of two equally ture period not simply as a one-way channel of communica- weighted 90 minute sessions. Section I contains 60 multiple- tion from teacher to student. Rather, they expect students to choice questions worth 50% of the total score. Three long and come to class ready to work on problem solving and critical four short free-response questions, counting for another 50%, thinking. Coming to class unprepared is not a good idea for compose Section II. Use of calculators is allowed only on the any lecture environment, but it certainly is not an option for free-response section. A periodic table similar to the one found an active learning classroom if you aim to do well in the course. on the end paper of this text, and a list of pertinent formulas and After lecture, carefully read the topics covered in equations is available for the entire exam. class. As you read, pay attention to the concepts presented and Pearson Education also publishes Pearson Education Test Prep: to the application of these concepts in the Sample Exercises. Once For AP® Chemistry, a companion test prep workbook to accompany you think you understand a Sample Exercise, test your under- Chemistry: The Central Science, AP Edition. Thoroughly revised and standing by working the accompanying Practice Exercise. redesigned, the Pearson Test Prep for AP Workbook correlates to Learn the language of chemistry. As you study the current AP Chemistry Curriculum Framework (CF). The test chemistry, you will encounter many new words. It is impor- prep workbook contains concise content summaries of chapters tant to pay attention to these words and to know their mean- from Chemistry: The Central Science that are relevant to the AP ings or the entities to which they refer. Knowing how to Chemistry Exam, test-taking tips, hundreds of multiple-choice identify chemical substances from their names is an impor- and free-response practice questions, two complete practice tant skill; it can help you avoid painful mistakes on examina- exams with scoring guidelines, answers and detailed explanations tions. For example, “chlorine” and “chloride” refer to very of all questions. It also presents a review of spectroscopy, includ- different things. ing mass spectrometry, photoelectron spectroscopy and UV- Attempt the assigned end-of-chapter exercises. Work- visible spectrophotometry. To order your own copy of the test ing the exercises selected by your instructor provides necessary prep workbook please visit Pearsonschool.com/Advanced. practice in recalling and using the essential ideas of the chapter. For more information and published examples of test ques- You cannot learn merely by observing; you must be a participant. tions, please refer to the College Board’s Advanced Placement In particular, try to resist checking the Solutions Manual (if you website at http://apcentral.collegeboard.com/. have one) until you have made a sincere effort to solve the exercise yourself. If you get stuck on an exercise, however, get help Big Ideas and Learning Objectives from your instructor, your teaching assistant, or another student. Spending more than 20 minutes on a single exercise is rarely The AP Chemistry Curriculum Framework outlines the content effective unless you know that it is particularly challenging. of the course around six Big Ideas and 117 learning objectives. Learn to think like a scientist. This book is written by The following outline identifies the important AP Chemistry scientists who love chemistry. We encourage you to develop your curriculum topics found in each chapter and section of this text

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organized by the six Big Ideas. The tables that follow correlate 6.5 Quantum Mechanics and Atomic Orbitals the 117 curriculum learning objectives to the pertinent chapters Quantum mechanical model, orbitals, electron shell, and sections of Chemistry: The Central Science. subshell Besides mastering content, students should be able to visu- 6.6 Representations of Orbitals alize and interpret atomic and molecular models, analyze data Shell model, orbitals designated s, p, d, and f, relative for patterns and relationships, predict atomic and molecular energies, relative distance from the nucleus, probability properties, justify trends, and select and perform chemical cal- distributions, electron density culations for a variety of chemical systems. 6.8 Electron Configurations Electron configuration, orbital diagram, core electrons, AP Chemistry Curriculum Framework valence electrons 6.9 Electron Configurations and the Periodic Table Correlated to Chemistry: The Central Representative elements, transition elements, f-block Science Table of Contents elements Chapter 7. Periodic Properties of the Elements Big Idea 1. All matter is composed of atoms. 7.2 Effective nuclear charge The content for Big Idea 1 is found primarily in Chapters 1, 2, 3, Effective nuclear charge, screening effect, valence electrons, 6, and 7 of Chemistry: The Central Science. inner core electrons, trends in effective nuclear charge Chapter 1. Matter and Measurement 7.3 Sizes of Ions 1.1 The Study of Chemistry Atomic radius, ionic radius, trends in atomic and ionic Elements, atoms, molecules radii, isoelectronic series 1.2 Classification of Matter 7.4 Ionization energy Gas, liquid, solid, pure substance, elements, symbols, First ionization energy, successive ionization energies, compounds, mixtures trends in ionization energies, shells, subshells and trends, 1.3 Properties of Matter electron configurations of ions Physical properties, chemical properties, physical change, 7.6 Metals, Nonmetals, and Metalloids chemical change, separation of mixtures, filtration, Metals, metallic character, metallic properties, distillation, chromatography nonmetals, nonmetal properties, metalloids, 1.5 Units of Measurement group trends 1.6 Dimensional Analysis Big Idea 2. Bonding and intermolecular forces Chapter 2. Atoms, Molecules, and Ions explain the chemical and physical properties of 2.1 The Atomic Theory of Matter matter. Atoms, law of constant composition, law of conservation of The content for Big Idea 2 is found primarily in Chapters 8, 9, mass, law of multiple proportions, Dalton’s atomic theory 10, 11, 12 and 13 of Chemistry: The Central Science. 2.3 The Modern View of Atomic Structure Chapter 8. Basic Concepts of Chemical Bonding Nucleus, electrons, structure of the atom, atomic mass 8.1 Lewis Symbols and the Octet Rule unit, electrical charges of subatomic particles, atomic Lewis electron-dot symbols, octet rule number, mass number, isotopes, Coulomb’s law, mass 8.2 Ionic Bonding spectrometry Electron transfer, lattice energy, Coulomb’s law, energies 2.6 Molecules and Molecular Compounds of ionic bond formation, s- and p-block electron configu- Molecules, chemical formulas, molecular formulas, em- rations, transition metal ions pirical formulas, structural formulas 8.3 Covalent Bonding 2.7 Ions and Ionic Compounds Lewis structures, multiple bonds Ion, cation, anion, polyatomic ions, ionic charges, ionic 8.4 Bond Polarity and Electronegativity compounds Bond polarity, polar and nonpolar bonds, electron den- Chapter 3. Stoichiometry: Calculations with Chemical sity, polar molecules, dipoles, differentiating covalent and Formulas and Equations ionic bonding 3.3 Formula weights 8.5 Drawing Lewis Structures Molar mass, percentage composition Determining Lewis structures, formal charge 3.4 Avogadro’s Number and the Mole 8.6 Resonance Structures Moles, Avogadro’s number, molar mass, interconverting Resonance structures, delocalized electrons, depiction of mass, moles, and number of particles resonance structures 3.5 Empirical Formulas from Analysis 8.7 Exceptions to the Octet Rule Calculation of empirical and molecular formulas, Odd electrons, six electrons, expanded octets combustion analysis 8.8 Strengths and Lengths of Covalent Bonds Chapter 6. Electronic Structure of Atoms Average bond enthalpies of single and multiple bonds, 6.2 Quantized Energy and Photons bond lengths Quantum, photoelectric effect

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Chapter 9. Molecular Geometry and Bonding Theories 12.2 Structures of Solids 9.1 Molecular Shapes Crystals, crystalline solids, amorphous solids Linear, bent, trigonal planar, tetrahedral, trigonal pyrami- 12.3 Metallic Solids dal, bond angles Metallic solids, alloys, substitutional and interstitial alloys 9.2 The VSEPR Model 12.4 Metallic Bonding Valence shell electron pair repulsion, bonding pair, Electron-sea model, delocalized electrons, thermal and electron domain, nonbonding pair, molecular geometry, electrical conductivity, malleability and ductility electron domain geometry, expanded valence shells, 12.5 Ionic Solids T-shaped, trigonal bipyramidal, see-saw, octahedral Ionic crystals, ionic interactions, atomic explanation 9.3 Molecular Shape and Polarity of properties, brittleness, melting points, boiling Bond dipole, polar molecules, electron densities in mol- points ecules 12.6 Molecular Solids 9.5 Hybrid Orbitals Molecules, intermolecular forces, structural explanation sp, sp2, and sp3 hybridization, orbital overlap, multiple of properties bonds, sigma and pi bonds, delocalized electrons 12.7 Covalent-network solids Chapter 10. Gases Diamond, graphite, semiconductors, doping, p-type, 10.2 Pressure n-type, atomic explanations of properties Standard atmospheric pressure, atmospheres, torr, Chapter 13. Properties of Solutions 10.3 The Gas Laws 13.1 The Solution Process Boyle’s law (pressure-volume), Charles’s law (temperature- Energetics of solution formation, spontaneous processes, volume), Boyle’s law and Charles law plots, absolute zero, entropy, effect of intermolecular forces, solvation, hydra- Avogadro’s law tion, particle depictions 10.4 The Ideal-Gas Equation 13.2 Saturated Solutions and Solubility Ideal gas, ideal-gas constant, calculations using ideal gas law Crystallization, solubility, saturated, unsaturated, super- 10.5 Further Applications of the Ideal-Gas Equation saturated Calculations of gas density, molar mass, and volumes in 13.3 Factors Affecting Solubility chemical reactions Miscible, immiscible, solute-solvent interactions, mo- 10.6 Gas Mixtures and Partial Pressures lecular structure, energetics, like dissolves like, pressure Partial pressure, Dalton’s law, water vapor pressure effects, temperature effects 10.7 The Kinetic-Molecular Theory of Gases 13.4 Expressing Solution Concentration Summary of KMT, molecular collisions, molecular origin Molarity, particle views, calculations involving molarity of gas properties, molecular speed distributions (Maxwell- 13.6 Colloids Boltzmann), temperature as average kinetic energy Energetics of colloidal dispersions, Tyndall effect, hydro- 10.9 Real Gases: Deviations from Ideal Behavior philic, hydrophobic, examples of colloids Real vs. ideal gases, effect of intermolecular forces, struc- Big Idea 3. Chemical reactions involve the ture of particles rearrangement of atoms and describe how matter Chapter 11. Liquids and Intermolecular Forces changes. 11.1 A Molecular Comparison of Gases, Liquids and Solids The content for Big Idea 3 is found primarily in Chapters 3, 4, 16, Properties of the states of matter, particle explanations and 20 of Chemistry: The Central Science. 11.2 Intermolecular Forces Chapter 3. Stoichiometry: Calculations with Chemical Dispersion forces, polarizability, dipole-dipole forces, Formulas and Equations hydrogen bonding, ion-dipole forces, relative strengths 3.1 Chemical Equations of forces, explanation of molecular properties, solution Chemical equations, reactants, products, balancing equa- formation tions, coefficients 11.3 Select Properties of Liquids 3.2. Some Simple Patterns of Chemical Reactivity Viscosity, surface tension, capillary action Combination (synthesis), decomposition, combustion 11.4 Phase Changes 3.6. Quantitative Information from Balanced Equations Energetics of phase changes, heat of fusion, heat of Stoichiometry, using equations to interconvert mass, vaporization, heat of sublimation, heating curves, critical moles, and number of particles temperature and pressure 3.7 Limiting reactants 11.5 Vapor Pressure Limiting reatcatnt, theoretical yield, actual yield, percent- Dynamic equilibrium, vapor pressure, volatility, distribu- age theoretical yield tions of kinetic energy, boiling point, vapor pressure plots Chapter 4. Reactions in Aqueous Solution Chapter 12. Solids and Modern Materials 4.1 General Properties of Aqueous Solutions 12.1 Classification of Solids Molecules in water, non-electrolytes, ions in solution, Metallic, ionic, covalent-network and molecular solids, strong electrolytes, weak electrolytes, chemical atomic and molecular explanations, polymers equilibrium

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4.2 Precipitation Reactions Chapter 14. Chemical Kinetics Precipitate, solubility, solubility guidelines, molecular 14.1 Factors that Affect Reaction Rates (complete) equations, ionic equations, net ionic equa- Effects of temperature, physical state, concentration and tions, spectator ions, writing net ionic equations catalysts 4.3 Acids, Bases, and Neutralization Reactions 14.2 Reaction Rates Acids, proton donors, monoprotoc acids, diprotic acids, Reaction rate as change in concentration per time, bases, proton acceptors, hydroxides, strong and weak graphical representations of rate, rate, and stoichiometry acids and bases, strong acids and bases as strong electro- 14.3 Concentration and Rate Laws lytes, neutralization reactions, salts Initial rate, spectroscopic measurement of rates, rate law, 4.4 Oxidation–Reduction reactions rate constant, reaction order, rate constant units, method Oxidation, reduction, redox reactions, oxidation num- of initial rate bers, determining oxidation numbers, displacement 14.4 The Change of Concentration with Time reactions, activity series Integrated rate law, zeroth, first and second order reactions, 4.5 Concentrations of Solutions graphical representations, half-life, radioactive decay Molarity, calculating molarity, interconverting molarity, 14.5 Temperature and Rate moles, and solution volume, dilution, preparing solution The collision model, orientation factor, activation en- concentrations ergy, activated complex, transition state, energy profile 4.6 Solution Stoichiometry and Chemical Analysis and reaction rate, graphical representations, Arrhenius Titration, standard solution, equivalence point, titration equation (qualitative), calculations, mass relations in a neutralization reaction 14.6 Reaction Mechanisms Chapter 5. Thermochemistry Mechanisms, elementary reaction, unimolecular, bimo- 5.2 The First Law of Thermodynamics lecular and termolecular reactions, overall equation from Energy diagrams, exothermic and endothermic reactions, elementary steps, intermediate, rate-determining step, temperature change, energy from foods and fuels mechanism and rate-determining step 14.7 Catalysis Chapter 16. Acid–Base Equilibria Catalyst, homogeneous and heterogeneous catalysis, effect 16.2 Brønsted–Lowry Acids and Bases of catalyst on energy profile, surface catalyst, acid–base cat- Hydronium ion, proton transfer reactions, Brønsted– alysts, enzymes, active site, substrate, lock-and-key model Lowry acid, Brønsted–Lowry base, conjugate acid–base pairs, relative strengths of acids and bases Big Idea 5. Thermodynamics describes the role energy Chapter 20. Electrochemistry plays in physical and chemical changes. 20.1 Oxidation States and Oxidation–Reduction Reactions The content for Big Idea 5 is found primarily in Chapters 5 and Electron transfer reactions, gain of electrons, loss of 19 of Chemistry: The Central Science. electrons Chapter 5. Thermochemistry 20.2 Balancing Redox Equations 1.4 The Nature of Energy Half reactions, half reaction method, redox titrations Energy, work, heat, kinetic energy, potential energy 20.3 Voltaic Cells 5.1 The Nature of Chemical Energy Voltaic (galvanic) cell, anode, cathode, salt bridge, direc- Coulomb’s law, electrostatic potential energy, energy tion of electron flow stored in chemical bonds measurement of energy, joules, 20.4 Cell Potentials under Standard Conditions calories, force, work and heat Cell potential, electromotive force, standard emf, stan- 5.2 The First Law of Thermodynamics dard reduction potential, standard hydrogen electrode, System, surroundings internal energy (∆E), relating ∆E to calculating cell potentials work and heat, exothermic, endothermic 20.5 Free Energy and Redox Reactions 5.3 Enthalpy Relationship of free energy (∆G) to cell potential, Fara- Enthalpy, pressure-volume work (P∆V), enthalpy change day’s constant, predicting the direction of the reaction 5.4 Enthalpies of Reaction 20.7 Batteries and Fuel Cells Enthalpy of reaction (∆H), thermochemical equation, Electrical energy from batteries, lead-acid, alkaline, enthalpy diagram, signs of ∆H, relating heats to nickel–cadmium, nickel–metal hydride, lithium-ion, stoichiometry hydrogen fuel cells 5.5 Calorimetry 20.9 Electrolysis Constant pressure calorimetry, calorimeter, heat capacity, Electrolytic cell, stoichiometry and redox reactions, molar heat capacity, specific heat capacity, calculating heats calculating electrons transferred, mass, current, time and 5.6 Hess’s Law charge, electrolysis of water, electroplating Heats added and subtracted like chemical equations Big Idea 4. Molecular dynamics and collisions deter- 5.7 Enthalpies of Formation mine the rates of chemical reactions. Standard enthalpy of formation (∆Hff), formation The content for Big Idea 4 is found primarily in Chapter 14 of reaction, using ∆Hf to calculate enthalpies of reaction, Chemistry: The Central Science. enthalpy diagrams

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5.8 Bond Enthalpies 15.6 Applications of Equilibrium Constants Bond enthalpies, average bond enthalpies, bond break- Reaction quotient (Q), predicting direction, calculating ing, bond forming, using bond enthalpies to calculate concentrations enthalpies of reaction 15.7 LeChâtelier’s Principle 5.9 Foods and Fuels LeChâtelier’s principle, changes in concentration, Combustion of natural gas, fossil fuels, petroleum, coal, volume, pressure or temperature, catalysts, optimizing a sugars and fats, renewable energy sources product Chapter 19. Chemical Thermodynamics Chapter 16. Acid–Base Equilibria 19.1 Spontaneous Processes 16.2 Brønsted–Lowry Acids and Bases Spontaneous process, direction and extent of a reaction, Hydronium ion, proton transfer reactions, Brønsted– reversible and irreversible processes Lowry acids, Brønsted–Lowry bases, conjugate acid–base 19.2 Entropy and the Second Law ofThermodynamics pairs, proton acceptor, proton donor, relative acid and Entropy (S), randomness, change in entropy (∆S), ∆S for base strengths phase changes, second law of thermodynamics 16.3 The Autoionization of Water

19.3 Molecular Interpretation of Entropy Ion-product constant (Kw), effect of temperature Translational, vibrational and rotational energy, entropy 16.4 The pH Scale and phase, third law of thermodynamics pH, pOH, measuring pH, indicators 19.4 Entropy Change in Chemical Reactions 16.5 Strong Acids and Bases Standard molar entropies, entropy and temperature, Complete ionization, calculating pH molecular complexity 16.6 Weak Acids

19.5 Gibbs Free Energy Incomplete ionization, acid-dissociation constant (Ka), Free energy (∆G), free energy and equilibrium, calculating concentration, Ka and pH, percent ionization, ∆G = ∆H - T∆S, standard free energy of formation polyprotic acids 19.6 Free Energy and Temperature 16.7 Weak Bases

Temperature and spontaneous processes, phase changes Base-dissociation constant (Kb), amines as weak bases, cal- 19.7 Free Energy and the Equilibrium Constant culating pH and pOH

Standard and nonstandard conditions, relationship 16.8 Relationship Between Ka and Kb between ∆G and K Ka Kb = Kw, K’s of conjugate acid–base pairs Big Idea 6. Equilibrium represents a balance between 16.9 Acid–Base Properties of Salt Solutions enthalpy and entropy for reversible physical and Hydrolysis, anions as bases, cations as acids chemical changes. 16.10 Acid–Base Behavior and Chemical Structure The content for Big Idea 6 is found primarily in Chapters 15, 16, Factors that affect acid strength, oxidation number, elec- and 17 of Chemistry: The Central Science. tronegativity, oxyacids, carboxylic acids Chapter 15. Chemical Equilibrium Chapter 17. Additional Aspects of Aqueous Equilibria 15.1 The Concept of Equilibrium 17.1 The Common-Ion Effect Rates of forward and reverse reactions, equilibrium Common ions and equilibrium mixtures 17.2 Buffered Solutions 15.2 The Equilibrium Constant Buffers, buffer composition, buffer action, buffer pH, buf- Law of mass action, equilibrium constant expression, fer capacity, buffer calculations 17.3 Acid–base Titrations equilibrium constant (K), Kc, and Kp 15.3 Understanding and Working with Equilibrium Constants Titration curve, pH of equivalence point, weak acid– Magnitudes of K, chemical equations and K, stoichiom- strong base titrations, pKa of weak acid from titration etry and K, calculating K data, polyprotic acid titrations, indicators 15.4 Heterogeneous Equilibria 17.4 Solubility Equilibria Homogeneous and heterogeneous equilibria and K Solubility product constant (Ksp), solubility, calculating 15.5 Calculating Equilibrium Constants solubilities K from concentrations, K from initial conditions, ICE 17.5 Factors that Affect Solubility tables Common ions, pH

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AP Chemistry Learning Objectives and Science Practices Correlated to Chemistry: The Central Science, Fourteenth Edition, AP® Edition Big Idea 1. All matter is composed of atoms. Learning Objective Science Practice Chapter/Section 1.1 Justify using atomic molecular theory that the element mass ratio of any pure compound is 6.1 1.2 always identical. 1.2 Identify or infer the quantitative compositions of pure substances and mixtures using mass data. 2.2 2.1, 2.4 1.3 Justify the identity or purity of a substance using calculations of mass data. 2.2, 6.1 1.7 1.4 Interconvert the number of particles, moles, mass, and volume of substances, both qualitatively 7.1 3.4 and quantitatively. 1.5 Explain electron distributions in atoms or ions using data. 1.5, 6.2 6.8, 6.9 1.6 Analyze data of electron energies for patterns and relationships. 5.1 6.8, 6.9 APTP 1.7 Describe atomic electron structure and explain how energies of electrons vary within atomic shells 5.1, 6.2 6.8, 6.9 APTP using data from photoelectron spectroscopy, ionization energy data, and Coulomb’s law. 1.8 Explain electron configurations by using Coulomb’s law to analyze measured energies. 6.2 6.9 APTP 1.9 Predict and justify trends in atomic properties using the shell model or atomic location on the 6.4 7.2, 7.3, 7.4 periodic table. 1.10 Justify with experimental evidence the arrangement of the periodic table and apply periodic 6.1 7.6, 7.7 properties to chemical reactivity. 1.11 Analyze and identify patterns in data for binary compounds to predict properties of related 3.1, 5.1 8.2, 8.4 T8.1, compounds. T8.2, T8.3 1.12 Explain how data sets support either the classical shell atomic model or the quantum 6.3 6.2, 6.3, 6.4, mechanical model. 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, 6.3 1.14 Identify elements and isotopes and their masses using mass spectral data. 1.4, 1.5 2.4 1.15 Explain why various types of spectroscopy are used to measure vibrational and electronic 4.1 14.3, 6.9 APTP motions of molecules. 1.16 Design and interpret an experiment that uses spectrophotometry to determine the 4.2, 5.1 14.3, 4.5 APTP concentration of a substance in a solution. 1.17 Express the law of conservation of mass quantitatively and qualitatively using both symbols 1.5 3.1 and particle drawings. 1.18 Apply conservation of atoms to particle views of balanced chemical reactions and physical 1.4 3.1, 3.2 changes. 1.19 Design or interpret data from a gravimetric analysis experiment to determine the 4.2, 5.1 3.6, 3.7 concentration of a substance in solution. 1.20 Design or interpret data from a titration experiment to determine the concentration of a 4.2, 5.1 4.5, 4.6 substance in solution.

Big Idea 2. Bonding and intermolecular forces explain the chemical and physical properties of matter. Learning Objective Science Practice Chapter/Section 2.1 Predict properties of substances based on their chemical formulas and explain properties using 6.4, 7.1 8.2, 8.3, 8.4 particle views. 2.2 Explain the strengths of acids and bases using molecular structure, interparticle forces, and 7.2 16.2, 16.6, 16.9, solution equilibrium. 16.10 2.3 Explain differences between solids and liquids using particulate models. 6.4, 7.1 11.1 to 11.7 2.4 Predict the macroscopic properties of real and ideal gases using kinetic molecular theory and 1.4, 6.4 10.1, 10.2, 10.3, intermolecular forces. 10.7, 10.9 2.5 Explain the effect of changes in the macroscopic properties of gases using particle representations. 1.3, 6.4, 7.2 10.3, 10.4 2.6 Calculate temperature, pressure, volume, and moles for ideal gases. 2.2, 2.3 10.3, 10.4, 10.5, 10.6

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Learning Objective Science Practice Chapter/Section 2.7 Explain how solutes separate by chromatography using intermolecular forces. 6.2 13.3 APTP 2.8 Draw and interpret particle representations of solutions showing interactions between the solute 1.1, 1.2, 6.4 13.1, 13.2, 13.3 and solvent particles. 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 chromatography, 4.2, 5.1 APTP 13.3 column chromatography, or distillation and explain how substances separate using intermolecular interactions. 2.11 Predict properties and explain trends for nonpolar substances Using London dispersion forces. 6.2, 6.4 11. 2 2.12 Identify and explain deviations from ideal behavior for real gases by analyzing data using 5.1, 6.5 10.9 molecular interactions. 2.13 Explain how the structural features of polar molecules affect the forces of attraction between 1.4, 6.4 11.2, 13.3 them. 2.14 Explain how the solubility of ionic compounds is affected by interactions of ions, and 1.4, 6.4 13.3 + VC attractions between ions and solvents using particle views and the qualitative application of 13.1–13.12 Coulomb’s law. 2.15 Explain the solubility of ionic solids and molecules in water and other solvents using particle 1.4, 6.2 13.2, 13.3 views showing intermolecular forces and entropy. 2.16 Explain properties of molecules such as phase, vapor pressure, viscosity, melting point, and 6.2 11. 3 boiling point using the strengths and types of intermolecular forces. 2.17 Predict the type of bonding in a binary compound based on the electronegativities and the 6.4 8.3, 8.4 locations of the elements on the periodic table. 2.18 Rank and explain bond polarity using location of the bonded atoms on the periodic table. 6.1 8.4 2.19 Explain, using particle views, the effect of microscopic structure on the macroscopic properties 1.1, 1.4, 7.1 12.5 of ionic compounds such as boiling point, solubility, hardness, brittleness, low volatility, lack of malleability, ductility, and conductivity. 2.20 Explain how delocalized electrons affect the macroscopic properties of metals such as 6.2, 7.1 12.3, 12.4 conductivity, malleability, ductility, and low volatility. 2.21 Predict geometry, hybridization, and polarity of molecules using Lewis diagrams. 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 4.2 APTP 12.1 bonding in solids. 2.23 Create a visual representation of an ionic solid showing its structure and particle interactions. 1.1 12.5 2.24 Explain the structure and particle interactions of an ionic solid using visual representations. 1.1, 6.2, 7.1 12.5 2.25 Compare properties of alloys and metals, identify alloy types and explain properties on the 1.4, 7.2 12.3 atomic level. 2.26 Predict and explain the macroscopic properties of metals and alloys using the electron sea model 6.4, 7.1 12.3, 12.4 2.27 Create a visual representation of a metallic solid showing its structure and particle interactions. 1.1 12.3, 12.4 2.28 Explain the structure and particle interactions of a metallic solid using a visual representation. 1.1, 1.2, 6.4 12.3, 12.4 2.29 Create a visual representation of a covalent solid showing its structure and particle interactions. 1.1 12.7 2.30 Explain the structure and particle interactions of a covalent solid using a visual representation. 1.1, 1.2, 6.4 12.7 2.31 Create a visual representation of a molecular solid showing its structure and particle 1.1 12.6, 12.8 interactions. 2.32 Explain the structure and particle interactions of a molecular solid using a visual 1.1, 1.2, 6.4 12.6, 12.8 representation.

Big Idea 3. Chemical reactions involve the rearrangement of atoms and describe how matter changes. Learning Objective Science Practice Chapter/Section 3.1 Interpret macroscopic observations of change using symbols, chemical equations, and particle 1.5, 7.1 4.1, 4.2, 4.3 views. 3.2 Interpret an observed chemical change using a balanced molecular (complete), ionic or net 1.5, 7.1 3.2, 4.1, 4.2, 4.3 ionic equation and justify why each is used in a given situation. 3.3 Model laboratory chemical reactions and analyze deviations from the expected results using 2.2, 5.1 3.6, 3.7, 4.6 stoichiometry calculations.

Continued

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Learning Objective Science Practice Chapter/Section 3.4 Convert, using stoichiometry calculations, measured quantities such as mass, volumes of 2.2, 5.1, 6.4 3.6, 3.7, 4.6 solutions, or volumes and pressures of gases to other quantities in chemical reactions, including reactions with limiting reactants or unreacted products. 3.5 Design an experiment or analyze data from an experiment involving the synthesis or 2.1, 2.4 3.5 decomposition of a compound to confirm the conservation of mass and the law of definite proportions. 3.6 Confirm the conservation of mass and the law of definite proportions using data from the 2.2, 6.1 3.5 synthesis or decomposition of a compound. 3.7 Identify compounds as Brønsted–Lowry acids, bases, and conjugate acid–base pairs using 6.1 16.1, 16.2 proton-transfer reactions. 3.8 Identify redox reactions from electron transfer. 6.1 3.2, 4.4 3.9 Design and interpret the results of a redox titration experiment. 4.2, 5.1 4.4, 4.6, APTP 4.5 3.10 Classify a process as a physical change, a chemical change, or an ambiguous change using 1.4, 6.1 1.3, 4.2, 4.3, 4.4 macroscopic observations and the making and breaking of chemical bonds or intermolecular forces. 3.11 Create a symbolic and a graphical representation to describe an observed change in energy 1.5, 4.4 5.2, 5.3, 5.4 associated with a chemical or physical change. 3.12 Make qualitative and quantitative predictions about voltaic (galvanic) and electrolytic reactions 2.2, 2.3, 6.4 20.3, 20.9 using half-cell reactions and potentials and Faraday’s laws. 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 dynamics and collisions determine the rates of chemical reactions. Learning Objective Science Practice Chapter/Section 4.1 Design and interpret an experiment to determine the factors that affect reaction rate such as 4.2, 5.1 14.1 APTP 14.1 temperature, concentration, and surface area. 4.2 Determine the rate law for a zeroth-, first-, and second-order reaction by analyzing 5.1 14.3, 14.4 concentration vs. time data. 4.3 Determine half-life from the rate constant of a first-order reaction. 2.1, 2.2 14.4 4.4 Explain the relationship among the rate law, order, and rate constant for an elementary reaction 7.1 14.5, 14.6 and the frequency and success of molecular collisions. 4.5 Explain effective and ineffective reactant collisions using energy distributions and molecular 6.2 14.5, APTP 14.5 orientation. 4.6 Explain the relative temperature dependence of reaction rate using an energy profile for an 1.4, 6.4 14.5 elementary reaction showing reactants, transition state, and products. 4.7 Evaluate alternative reaction mechanisms to match reaction rate data and infer the presence of 6.5 14.6 an intermediate. 4.8 Describe chemical reactions that occur with and without catalysts using various representations 1.5 14.7 including energy profiles, particle views, and chemical equations. 4.9 Explain rate changes due to acid–base, surface, and enzyme catalysts, and select appropriate 6.2, 7.2 14.7 mechanisms with or without catalysts.

Big Idea 5. Thermodynamics describes the role energy plays in physical and chemical changes. Learning Objective Science Practice Chapter/Section 5.1 Create and interpret graphical representations to explain how and why potential energy varies 1.1, 1.4, 7.2 9.7 with distance between atoms such as in bond order, strength and length in covalent bonds, and the magnitudes of intermolecular forces between polar molecules. 5.2 Explain how temperature relates to molecular motion using particle views of moving 1.1, 1.4, 7.1 10.7 molecules or kinetic energy distribution (Maxwell-Boltzmann) plots. 5.3 Explain and predict the transfer of heat between systems using molecular collisions. 7.1 5.2 5.4 Explain energy transfer between systems using the conservation of energy to include the 1.4, 2.2 5.2, 5.3 quantity of energy transferred, the direction of energy flow, and the type of energy (heat or work). 5.5 Explain, using the conservation of energy, the quantity of energy change that occurs when 2.2 5.5 two substances of different temperatures interact.

A01_BROW0951_14_AP_FM.indd 28 19/11/16 1:12 AM Preface xxix

Learning Objective Science Practice Chapter/Section 5.6 Calculate or estimate energy changes associated with chemical reactions, heating or 2.2, 2.3 5.2, 5.3, 11.4 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 PΔV work. 5.7 Design and interpret a constant pressure calorimetry experiment to determine change in 4.2, 5.1 5.5 enthalpy of a chemical or physical process. 5.8 Calculate or estimate enthalpies of reaction using bond energies. 2.3, 7.1, 7.2 5.4, 5.8 5.9 Explain and predict the relative strengths and types of intermolecular forces acting between 6.4 11.2, 11.3 molecules using molecular electron density distributions. 5.10 Classify and justify chemical and physical changes citing changes in chemical bonds and 5.1 11.1, 11. 2 intermolecular forces. 5.11 Explain the shapes and functions of large molecules using the strengths of intermolecular forces, 7.2 24.7 through such as hydrogen bonding and London dispersions. 24.10 5.12 Predict the signs and relative magnitudes of the entropy changes associated with chemical or 1.4 19.2, 19.3, 19.4 physical processes using particle views and models. 5.13 Predict the thermodynamic favorability of a physical or chemical change using the signs of both 2.2, 2.3, 6.4 19.5 ΔH° and ΔS° and a calculation or estimation of ΔG°. 5.14 Calculate the change in standard Gibbs free energy to determine the thermodynamic 2.2 19.5 favorability of a chemical or physical change. 5.15 Explain how thermodynamically unfavorable processes, such as those in living systems, 6.2 19.5 & pp 836, can be made thermodynamically favorable by coupling them with favorable reactions. pp 842 5.16 Make predictions for systems in which coupled reactions share a common intermediate using 6.4 15.7 LeChatelier’s principle. 5.17 Make predictions for systems involving coupled reactions sharing a common intermediate using 6.4 19.7 the equilibrium constant for the combined reactions. 5.18 Explain how initial conditions can greatly affect product formation for unfavorable reactions 1.3, 7.2 19.7 using thermodynamic and kinetic arguments.

Big Idea 6. Equilibrium represents a balance between enthalpy and entropy for physical and chemical changes. Learning Objective Science Practice Chapter/Section 6.1 Explain the reversibility of a chemical, biological, or environmental process, given a set of 6.2 15.1 experimental observations. 6.2 Predict the effects of manipulating a chemical equation or set of equations on Q or K of that 2.2 15.2, 15.3, 15.4 chemical system. 6.3 Predict the relative rates of the forward and reverse reactions using LeChatelier’s principle and 7.2 15.2, 15.7 principles of kinetics. 6.4 Predict the direction a reaction will proceed toward equilibrium, given initial conditions and 2.2, 6.4 15.6 considering Q and K. 6.5 Calculate the equilibrium constant, K, given the appropriate tabular or graphical data for a 2.2 15.5 system at equibrium. 6.6 Calculate or estimate equilibrium concentrations or partial pressures from stoichiometry and the 2.2, 6.4 15.5, 15.6 law of mass action, given a set of initial conditions and the equilibrium constant, K. 6.7 Determine which chemical species will have relatively large and small concentrations, given an 2.2, 2.3 15.5, 15.6 equilibrium system with a large or small K. 6.8 Predict the direction a reaction at equilibrium will proceed as a result of a given change using 1.4, 6.4 15.7 LeChatelier’s principle. 6.9 Design a set of conditions that will optimize a desired result, such as product yield, using 4.2 15.7 LeChatelier’s principle. 6.10 Explain the effect a change of conditions will have on Q or K of an equilibrium system using Use 1.4, 7.2 15.7 LeChatelier’s principle. 6.11 Construct a particle representation of a strong or weak acid to illustrate which species will have 1.1, 1.4, 2.3 16.6 large and small concentrations at equilibrium. 6.12 Compare and contrast properties of strong and weak acid solutions including pH, percentage 1.4 16.4, 16.5, 16.6 ionization, concentrations and the amount of base required to reach an equivalence.

Continued

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Learning Objective Science Practice Chapter/Section 6.13 Interpret data for a weak acid or weak base titration to determine the concentration of titrant, the 5.1 17.3 pKa or pKb and the equivalence point. 6.14 Explain why a neutral solution requires [H+] = [OH-] rather than pH = 7, using the dependence 2.2, 6.2 16.3, 16.4, of Kw on temperature. pp 737 6.15 Calculate or estimate the pH and concentrations of all chemical species in a mixture of strong 2.2, 2.3, 6.4 16.5 acids and/or bases. 6.16 Identify a solution as a weak acid or base, calculate its pH and the concentration of all species 2.2, 6.4 16.6, 16.7 in the solution, and infer its relative strength. 6.17 Determine the chemical reaction that results in a given mixture of weak and strong acids 6.4 17.3 and bases, and identify which species are present in large concentrations at equilibrium. 6.18 Select an appropriate conjugate acid–base pair to design a buffer solution with a target pH and 2.3, 4.2, 6.4 16.2, 17.1, 17.2 estimate the concentrations needed to achieve a desired buffer capacity.

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, 17.5

6.22 Interpret solubility data of various salts to determine or rank Ksp values. 2.2, 2.3, 6.4 17.4, 17.5 6.23 Interpret data to predict the influence of pH and common ions on the relative solubilities of 5.1 17.5 salts. 6.24 Identify and explain changes in enthalpy and entropy associated with the dissolution of a salt 1.4, 7.1 17.5 using particle representations. 6.25 Estimate the magnitude of K and the thermodynamic favorability of a process using the 2.3 19.7 relationship between ΔG° and K (ΔG° = -RT lnK). APTP: AP Test Prep VC: Visualizing Concepts p: page number Upon publication, this text was correlated to the College Board’s AP Chemistry Curriculum Framework Revised Edition—Effective Fall 2014. We continually 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.

A01_BROW0951_14_AP_FM.indd 30 19/11/16 1:12 AM Aob ut 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 fourteenth edition and accompanying MasteringChemistryTM course are highlighted on the upcoming pages.

Theodore L. Brown received his Ph.D. enjoyed Visiting Professorships at the University of North from Michigan State University in 1956. Carolina at Chapel Hill, at the University College of Wales in Since then, he has been a member of the Great Britain, and at the University of California, Los Angeles. faculty of the University of Illinois, Urbana- Professor LeMay is a popular and effective teacher, who has Champaign, where he is now Professor of taught thousands of students during more than 40 years of uni- Chemistry, Emeritus. He served as Vice versity teaching. Known for the clarity of his lectures and his Chancellor for Research, and Dean of The sense of humor, he has received several teaching awards, includ- Graduate College, from 1980 to 1986, and ing the University Distinguished Teacher of the Year Award as Founding Director of the Arnold and Mabel Beckman (1991) and the first Regents’ Teaching Award given by the State Institute for Advanced Science and Technology from 1987 to of Nevada Board of Regents (1997). 1993. Professor Brown has been an Alfred P. Sloan Foundation Research Fellow and has been awarded a Guggenheim Bruce E. Bursten received his Ph.D. in Fellowship. In 1972 he was awarded the American Chemical Chemistry from the University of Wisconsin Society Award for Research in Inorganic Chemistry and received in 1978. After two years as a National Science the American Chemical Society Award for Distinguished Service Foundation Postdoctoral Fellow at Texas in the Advancement of Inorganic Chemistry in 1993. He has A&M University, he joined the faculty of been elected a Fellow of the American Association for the The Ohio State University, where he rose to Advancement of Science, the American Academy of Arts and the rank of Distinguished University Profes- Sciences, and the American Chemical Society. sor. In 2005, he moved to the University of Tennessee, Knoxville, as Distinguished Pro- H. Eugene Lemay, Jr., received his B.S. fessor of Chemistry and Dean of the College of Arts and Sciences. degree in Chemistry from Pacific Lutheran In 2015, he moved to Worcester Polytechnic Institute as Provost University (Washington) and his Ph.D. in and Professor of Chemistry and Biochemistry. Professor Bursten Chemistry in 1966 from the University of has been a Camille and Henry Dreyfus Foundation Teacher- Illinois, Urbana-Champaign. He then Scholar and an Alfred P. Sloan Foundation Research Fellow, and joined the faculty of the University of he is a Fellow of both the American Association for the Advance- Nevada, Reno, where he is currently ment of Science and the American Chemical Society. At Ohio Professor of Chemistry, Emeritus. He has State he received the University Distinguished Teaching Award in

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A01_BROW0951_14_AP_FM.indd 31 19/11/16 1:12 AM xxxii About the Authors

1982 and 1996, the Arts and Sciences Student Council Outstand- Professor. He has enjoyed visiting professorships at the Universi- ing Teaching Award in 1984, and the University Distinguished ty of Bordeaux in France and the University of Sydney in Austra- Scholar Award in 1990. He received the Spiers Memorial Prize lia. Professor Woodward has been an Alfred P. Sloan Foundation and Medal of the Royal Society of Chemistry in 2003, and the Research Fellow and a National Science Foundation CAREER Morley Medal of the Cleveland Section of the American Chemi- Award winner. He has served as Vice Chair for Undergraduate cal Society in 2005. He was President of the American Chemical Studies in the Department of Chemistry and Biochemistry at Society for 2008 and Chair of the Section on Chemistry of the Ohio State University, and director of the Ohio REEL program. American Association for the Advancement of Science in 2015. In He is currently the Vice President of the Neutron Scattering Soci- addition to his teaching and service activities, Professor Bursten’s ety of America. Professor Woodward’s research program focuses research program focuses on compounds of the transition-metal on understanding the links between bonding, structure, and and actinide elements. properties of solid-state inorganic materials.

Catherine J. Murphy received two B.S. Matthew W. Stoltzfus received his B.S. degrees, one in Chemistry and one in Bio- degree in Chemistry from Millersville Uni- chemistry, from the University of Illinois, versity in 2002 and his Ph. D. in Chemistry Urbana-Champaign, in 1986. She received in 2007 from The Ohio State University. He her Ph.D. in Chemistry from the University spent two years as a teaching postdoctoral of Wisconsin in 1990. She was a National assistant for the Ohio REEL program, an Science Foundation and National Institutes NSF-funded center that works to bring au- of Health Postdoctoral Fellow at the Califor- thentic research experiments into the gener- nia Institute of Technology from 1990 to 1993. In 1993, she al chemistry lab curriculum in 15 colleges joined the faculty of the University of South Carolina, Colum- and universities across the state of Ohio. In 2009, he joined the bia, becoming the Guy F. Lipscomb Professor of Chemistry in faculty of Ohio State where he currently holds the position of 2003. In 2009 she moved to the University of Illinois, Urbana- Chemistry Lecturer. In addition to lecturing general chemistry, Champaign, as the Peter C. and Gretchen Miller Markunas Pro- Stoltzfus served as a Faculty Fellow for the Digital First Initiative, fessor of Chemistry. Professor Murphy has been honored for inspiring instructors to offer engaging digital learning content both research and teaching as a Camille Dreyfus Teacher- to students through emerging technology. Through this initia- Scholar, an Alfred P. Sloan Foundation Research Fellow, a Cot- tive, he developed an iTunes U general chemistry course, which trell Scholar of the Research Corporation, a National Science has attracted over 200,000 students from all over the world. The Foundation CAREER Award winner, and a subsequent NSF iTunes U course, along with the videos at www.drfus.com, are Award for Special Creativity. She has also received a USC Mortar designed to supplement the text and can be used by any general Board Excellence in Teaching Award, the USC Golden Key Fac- chemistry student. Stoltzfus has received several teaching ulty Award for Creative Integration of Research and Undergrad- awards, including the inaugural Ohio State University 2013 Pro- uate Teaching, the USC Michael J. Mungo Undergraduate vost’s Award for Distinguished Teaching by a Lecturer and he is Teaching Award, and the USC Outstanding Undergraduate Re- recognized as an Apple Distinguished Educator. search Mentor Award. From 2006–2011, Professor Murphy served as a Senior Editor for the Journal of Physical Chemistry; in Michael W. Lufaso received his B.S. de- 2011 she became the Deputy Editor for the Journal of Physical gree in Chemistry from Youngstown State Chemistry C. She is an elected Fellow of the American Associa- University in 1998 and his Ph.D. in Chem- tion for the Advancement of Science (2008), the American istry from the Ohio State University in Chemical Society (2011), the Royal Society of Chemistry (2014), 2002. He was a National Research Council and the U.S. National Academy of Sciences (2015). Professor Postdoctoral Fellow at the National Insti- Murphy’s research program focuses on the synthesis, optical tute for Standards and Technology and a properties, surface chemistry, biological applications, and envi- postdoctoral fellow at the University of ronmental implications of colloidal inorganic nanomaterials. South Carolina. In 2006 he joined the University of North Florida where he currently holds the rank of Associate Profes- Patrick M. Woodward received B.S. de- sor in the Department of Chemistry. He was a Brian Andreen grees in both Chemistry and Engineering Cottrell College Science Award winner from Research Corpo- from Idaho State University in 1991. He re- ration. He was named a Munoz Presidential Professor in 2011 ceived a M.S. degree in Materials Science and and received an Outstanding Faculty Scholarship award in a Ph.D. in Chemistry from Oregon State Uni- 2014. He has authored laboratory manuals and taught ten dif- versity in 1996. He spent two years as a post- ferent undergraduate courses primarily in the areas of general, doctoral researcher in the Department of inorganic, and solid state chemistry. His undergraduate re- Physics at Brookhaven National Laboratory. search program focuses on structure prediction, synthesis, and In 1998, he joined the faculty of the Chemistry Department at characterization of the structure and properties of solid state The Ohio State University where he currently holds the rank of materials.

A01_BROW0951_14_AP_FM.indd 32 19/11/16 1:12 AM New Levels of Student Interaction for Improved Conceptual Understanding

Embedded in eText 2.0, as well as assignable in MasteringChemistryTM, new features engage students through interactivity to enhance the reading experience and help them learn challenging chemistry concepts.

NEW! 50 Interactive Sample Exercises bring key Sample Exercises in the text to life through animation and narration. Author Matt Stoltzfus uses the text’s Analyze/Plan/Solve/ Check technique to guide students through the problem-solving process. Play icons within the text identify each Interactive Sample Exercise. Clicking the icon in the eText launches a visual and conceptual presentation which goes beyond the static page. The Practice Exercises within each Sample Exercise can also be assigned in MasteringChemistryTM where students will receive answer-specific feedback.

NEW! 27 Smart Figures walk students through complex visual representations, dispelling common misconceptions before they take root. Each Smart Figure converts a static in-text figure into a dynamic process narrated by author Matt Stoltzfus. Play icons within the text identify each Smart Figure. Clicking the icon in the eText launches the animation. Smart Figures are assignable in MasteringChemistryTM where they are accompanied by a multiple-choice question with answer-specific video feedback. Selecting the correct answer launches a brief wrap-up video that highlights the key concepts behind the answer.

A02_BROW0951_14_AP_VWT.indd 1 19/11/16 1:10 AM Visually Revised to Better Help Students Build General Chemistry

The visual program has been revised for enhanced clarity and to create a clean, modern look. Style changes include: expanded use of 3D renderings, new white annotation boxes with crisp leader lines, and a more saturated art palette.

Phenolphthalein indicator Methyl red indicator Color-change interval 8.3 < pH < 10.0 Color-change interval 4.2 < pH < 6.0 14 14

12 12 REVISED! Annotations Equivalence point Equivalence point 10 10 offer expanded 8 8 explanations; additional pH pH 6 6 new leaders emphasize key relationships and key 4 4 points in figures. 2 2

0 0 10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80 mL NaOH mL NaOH

Good choice. Suitable indicator for titration of a Poor choice. Unsatisfactory indicator for titration of a weak acid with a strong base because equivalence weak acid with a strong base because color point falls within the color-change interval changes before reaching equivalence point

NEW! Before and after photos clearly show characteristics of endothermic and exothermic reactions. Added reaction equations connect the chemistry to what’s happening in the photos.

A02_BROW0951_14_AP_VWT.indd 2 19/11/16 1:10 AM Knowledge and Understanding

The authors used the wealth of student data in MasteringChemistryTM to identify the areas where students struggle most, revising discussions, figures, and exercises throughout the text to address misconceptions and encourage thinking about the real-world use of chemistry.

NEW! The author team utilized Mastering metadata to edit and clarify in- chapter Go Figure and Give It Some Thought questions, as well as end-of-chapter problems. User data helped them to identify problematic questions and then modify, replace, or delete—resulting in a more diverse and polished set of problems.

UPDATED! A Closer Look features have been updated to reflect recent news and discoveries in the field of chemistry, providing relevance and applications for students. End-of- chapter questions give students the chance to test whether they understood the concept or not.

A02_BROW0951_14_AP_VWT.indd 3 19/11/16 1:10 AM Continuous Learning Before, During, and After Class

NEW! eText 2.0 • Full eReader functionality includes page navigation, search, glossary, highlighting, note taking, annotations, and more. • A responsive design allows the eText to reflow and resize to your device or screen. eText 2.0 now works on supported smartphones, tablets, and laptop/desktop computers. • In-context glossary offers students instant access to definitions by simply hovering over key terms. • Seamlessly integrated eInteractives engage students through interactivity to further enhance their learning experience. * New! 50 Interactive Sample Exercises bring key Sample Exercises in the text to life through animation and narration. * New! 27 SmartFigures walk students through complex visual representations, dispelling common misconceptions before they take root. • Accessible (screen-reader ready). • Configurable eadingr settings, including resizable type and night reading mode.

A02_BROW0951_14_AP_VWT.indd 4 19/11/16 1:10 AM with MasteringChemistryTM

Before Class

NEW! 66 Dynamic Study Modules help students study effectively on their own by continuously assessing their activity and performance in real time. Students complete a set of questions with a unique answer format that also asks them to indicate their confidence level. Questions repeat until the student can answer them all correctly and confidently. Once completed, Dynamic Study Modules explain the concept using materials from the text. These are available as graded assignments prior to class, and accessible on smartphones, tablets, and computers.

NEW! The Chemistry Primer helps students remediate their chemistry math skills and prepare for their first college chemistry course. • Pre-built Assignments get students up to speed at the beginning of the course. • Math is covered in the context of chemistry, basic chemical literacy, balancing chemical equations, mole theory, and stoichiometry. • Scaled to students’ needs, remediation is only suggested to students that perform poorly on initial assessment. • Remediation includes tutorials, wrong-answer specific feedback, video instruction, and step-wise scaffolding to build students’ abilities.

A02_BROW0951_14_AP_VWT.indd 5 19/11/16 1:10 AM MasteringChemistry™ MasteringChemistryTM delivers engaging, dynamic learning opportunities—focusing on course objectives and responsive to each student’s progress—that are proven to help students absorb course material and understand challenging chemistry processes and concepts.

During Class

Learning Catalytics™ With questions specific to Chemistry: The Central Science 14e, Learning Catalytics generates class discussion, guides your lecture, and promotes peer-to-peer learning with real-time analytics. MasteringChemistryTM with eText now provides Learning Catalytics—an interactive student response tool that uses students’ smartphones, tablets, or laptops to engage them in more sophisticated tasks and individual and group problem- solving. Instructors can: • Upload a full PowerPoint® deck for easy creation of slide questions. • Help your students develop critical thinking skills. • Monitor responses to find out where your students are struggling. • Rely on real-time data to adjust your teaching strategy. • Automatically group students for discussion, teamwork, and peer-to-peer learning.

Book-specific questions embedded in library

A02_BROW0951_14_AP_VWT.indd 6 19/11/16 1:10 AM www.MasteringChemistry.com

After Class Hundreds of new Enhanced EOC questions with wrong-answer-response feedback

Design An Experiment feature provides a departure from the usual kinds of end-of-chapter exercises with an inquiry-based, open-ended approach that tries to stimulate the student to “think like a scientist.” Designed to foster critical thinking, each exercise presents the student with a scenario in which various unknowns require investigation. The student is called upon to ponder how experiments might be set up to provide answers to particular questions about observations.

Adaptive Follow-Up Assignments allow instructors to deliver content to students–automatically personalized for each individual based on the strengths and weaknesses identified by his or her performance on initial Mastering assignments.

A02_BROW0951_14_AP_VWT.indd 7 19/11/16 1:10 AM MasteringChemistryTM Access/Resources

Access Upon textbook purchase, students and teachers are granted access to MasteringChemistryTM. High school teachers can obtain preview or adoption access to MasteringBiology in one of the following ways: Preview Access • Teachers can request preview access online by visiting www.PearsonSchool.com/Access_Request. Select Science, choose Initial Access, and complete the form under Option 2. Preview Access information will be sent to the teacher via e-mail. Adoption Access • With the purchase of this program, a Pearson Adoption Access Card with Instructor Manual will be delivered with your textbook purchase. (ISBN: 978-0-13-353986-8) • Ask your sales representative for a Pearson Adoption Access Card with Instructor Manual. (ISBN: 978-0-13-353986-8) OR • Visit PearsonSchool.com/Access_Request, select Science, choose Initial Access, and complete the form under Option 3— MyLab/Mastering Class Adoption Access. Adoption access information will be sent to the teacher via e-mail. Students, ask your teacher for access. Resources For the Students For the Instructor The following resources are available for purchase. Most of the teacher supplements and resources for this text are Test Prep Workbook for AP® Chemistry available electronically to qualified adopters on the Instructor By Ed Waterman, experienced AP chemistry teacher. Resource Center (IRC). Upon adoption or to preview, please go to www.pearsonschool.com/access_request and select This Test Prep Workbook for AP® Chemistry is aligned Instructor Resource Center. You will be required to complete a with the College Board’s new AP® Chemistry Curriculum brief one-time registration subject to verification of educator Framework. This workbook provides an overview of the status. Upon verification, access information and instructions AP Chemistry Curriculum Framework, test-taking tips, will be sent to you via e-mail. Once logged into the IRC, enter and strategies for preparing for peak performance. It has 978-0-13-465095-1 in the “Search our Catalog” box to locate hundreds of practice questions for mastering each type of resources. Electronic Instructor supplements are also available AP Exam question—with fully explained answers and two within the Instructor’s tab of MasteringChemistry. complete chemistry practice tests for AP. TestGen Test Bank/ExamView® Students Guide Computerized test generators let educators view and edit This book assists students through the text material with Test Bank questions, transfer questions to tests, and print chapter overviews, learning objectives, a review of key tests in a variety of customized formats. This Test Bank terms, as well as self-tests with answers and explanations. includes over 3,000 multiple choice, true/false, and answer/ This edition also features MCAT practice questions. essay questions. Questions are rated by difficulty and are Solutions to Red Exercises correlated to the book’s Learning Outcomes. Full solutions to all the red-numbered exercises in the text Instructor Manual are provided. Organized by chapter, this useful guide includes objectives, Solutions to Black Exercises lecture outlines, references to figures and solved problems, Full solutions to all the black-numbered exercises in the text as well as teaching tips. are provided. Instructor Resource Materials Laboratory Experiments The material available for download includes all This manual contains 43 finely-tuned experiments chosen to illustrations, tables, and photos from the text in JPEG introduce students to basic lab techniques and to illustrate format, Pre-built PowerPoint™ Presentations (lecture, core chemical principles. worked examples, images), TestGen computerized software with the TestGen version of the Testbank and Word files of the Test Item File. Solutions Manual Full solutions to all of the exercises (both red and black) in the text are provided. Annotated Instructor’s Edition to Laboratory Experiments Instructor’s companion to the Laboratory Experiments.

A02_BROW0951_14_AP_VWT.indd 8 19/11/16 1:10 AM chemistry The Central Science 14TH EDITION, AP® Edition

A02_BROW0951_14_AP_VWT.indd 9 19/11/16 1:10 AM