ChemistryT h e C e n T r a l S C i e n C e 13Th ediTion

ChemistryT h e C e n T r a l S C i e n C e 13Th ediTion

Theodore L. BrownUniversity of illinois at Urbana-Champaign

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

Bruce E. BurstenUniversity of tennessee, Knoxville

Catherine J. MurphyUniversity of illinois at Urbana-Champaign

Patrick M. Woodwardthe Ohio state University

Matthew W. Stoltzfusthe Ohio state University

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Library of Congress Cataloging-In Publication Data

Brown, Theodore L. (Theodore Lawrence), 1928- author.

Chemistry the central science.—Thirteenth edition / Theodore L. Brown, University of Illinois at Urbana-Chanmpaign, H. Euguene LeMay, Jr., University of Nevada, Reno, Bruce E. Bursten, University of Tennessee, Knoxville, Catherine J. Murphy, University of Illinois at Urbana-Chanmpaign, Patrick M. Woodward, The Ohio State University, Matthew W. Stoltzfus, The Ohio State University.

pages cm Includes index. ISBN-13: 978-0-321-91041-7 ISBN-10: 0-321-91041-9 1. Chemistry--Textbooks. I. Title. QD31.3.B765 2014 540—dc23 2013036724

1 2 3 4 5 6 7 8 9 10—CRK— 17 16 15 14

www.pearsonhighered.comStudent Edition: 0-321-91041-9 / 978-0-321-91041-7Instructor’s Resource Copy: 0-321-96239-7 / 978-0-321-96239-3

To our students, whose enthusiasm and curiosity

have often inspired us, and whose questions and suggestions

have sometimes taught us.

Student Edition: 0-321-91041-9 / 978-0-321-91041-7Instructor’s Resource Copy: 0-321-96239-7 / 978-0-321-96239-3

vi

Preface  xx

1 Introduction: Matter and Measurement  2 2 Atoms, Molecules, and Ions  40

3 Chemical Reactions and Reaction Stoichiometry  80

4 Reactions in Aqueous Solution  122

5 Thermochemistry  164

6 Electronic Structure of Atoms  212

7 Periodic Properties of the Elements  256

8 Basic Concepts of Chemical Bonding  298

9 Molecular Geometry and Bonding Theories  342

10 Gases  398

11 Liquids and Intermolecular Forces  442

12 Solids and Modern Materials  480

13 Properties of Solutions  530

14 Chemical Kinetics  574

15 Chemical Equilibrium  628

16 Acid–Base Equilibria  670

17 Additional Aspects of Aqueous Equilibria  724

18 Chemistry of the Environment  774

19 Chemical Thermodynamics  812

20 Electrochemistry  856

21 Nuclear Chemistry  908

22 Chemistry of the Nonmetals  952

23 Transition Metals and Coordination Chemistry  996

24 The Chemistry of Life: Organic and Biological Chemistry  1040

APPENdICES  

A Mathematical Operations  1092 B Properties of Water  1099 C Thermodynamic Quantities for Selected Substances at

298.15 K (25 °C)  1100 D Aqueous Equilibrium Constants  1103 E Standard Reduction Potentials at 25 °C  1105

Answers to Selected Exercises  A-1

Answers to Give It Some Thought  A-31

Answers to Go Figure  A-38

Answers to Selected Practice Exercises  A-44

Glossary  G-1

Photo/Art Credits  P-1

Index  I-1

BRIEF CONTENTS

vii

2 Atoms, Molecules, and Ions  40

2.1 The Atomic Theory of Matter  42

2.2 The discovery of Atomic Structure  43

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

2.3 The Modern View of Atomic Structure  47

Atomic Numbers, Mass Numbers, and Isotopes  49

2.4 Atomic Weights  50

The Atomic Mass Scale  50 Atomic Weight  51

2.5 The Periodic Table  52

2.6 Molecules and Molecular Compounds  56

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

2.7 Ions and Ionic Compounds  58

Predicting Ionic Charges  59 Ionic Compounds  60

2.8 Naming Inorganic Compounds  62

Names and Formulas of Ionic Compounds  62 Names and Formulas of Acids  67 Names and Formulas of Binary Molecular Compounds  68

2.9 Some Simple Organic Compounds  69

Alkanes  69 Some derivatives of Alkanes  70

Chapter Summary and Key Terms  72 Learning Outcomes  72 Key Equations  73 Exercises  73 Additional Exercises  78

A Closer Look Basic Forces  49

A Closer Look The Mass Spectrometer  52

A Closer Look What Are Coins Made Of?  54 Chemistry and Life Elements Required by Living Organisms  61

Strategies in Chemistry How to Take a Test  71

CONTENTS

Preface  xx

1 Introduction: Matter and Measurement  2

1.1 The Study of Chemistry  2

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

1.2 Classifications of Matter  6

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

1.3 Properties of Matter  11

Physical and Chemical Changes  12 Separation of Mixtures  13

1.4 Units of Measurement  14

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

1.5 Uncertainty in Measurement  22

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

1.6 dimensional Analysis  27

Using Two or More Conversion Factors  28 Conversions Involving Volume  29

Chapter Summary and Key Terms  32 Learning Outcomes  32 Key Equations  32 Exercises  32 Additional Exercises  37

Chemistry Put to Work Chemistry and the Chemical Industry  6

A Closer Look The Scientific Method  14 Chemistry Put to Work Chemistry in the News  20

Strategies in Chemistry Estimating Answers  28 Strategies in Chemistry The Importance of Practice  31

Strategies in Chemistry The Features of This Book  32

viii Contents

3 Chemical Reactions and Reaction Stoichiometry  80

3.1 Chemical Equations  82

Balancing Equations  82 Indicating the States of Reactants and Products  85

3.2 Simple Patterns of Chemical Reactivity  86

Combination and decomposition Reactions  86 Combustion Reactions  89

3.3 Formula Weights  89

Formula and Molecular Weights  90 Percentage Composition from Chemical Formulas  91

3.4 Avogadro’s Number and the Mole  91

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

3.5 Empirical Formulas from Analyses  98

Molecular Formulas from Empirical Formulas  100 Combustion Analysis  101

3.6 Quantitative Information from Balanced Equations  103

3.7 Limiting Reactants  106

Theoretical and Percent Yields  109

Chapter Summary and Key Terms  111 Learning Outcomes  111 Key Equations  112 Exercises  112 Additional Exercises  118 Integrative Exercises  120 design an Experiment  120

Strategies in Chemistry Problem Solving  92

Chemistry and Life Glucose Monitoring  95 Strategies in Chemistry Design an Experiment  110

4 Reactions in Aqueous Solution  122

4.1 General Properties of Aqueous Solutions  124

Electrolytes and Nonelectrolytes  124 How Compounds dissolve in Water  125 Strong and Weak Electrolytes  126

4.2 Precipitation Reactions  128

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

4.3 Acids, Bases, and Neutralization Reactions  132

Acids  132 Bases  133 Strong and Weak Acids and Bases  133 Identifying Strong and Weak Electrolytes  135 Neutralization Reactions and Salts  135 Neutralization Reactions with Gas Formation  138

4.4 Oxidation–Reduction Reactions  138

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

4.5 Concentrations of Solutions  146

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

4.6 Solution Stoichiometry and Chemical Analysis  151

Titrations  152

Chapter Summary and Key Terms  155 Learning Outcomes  156 Key Equations  156 Exercises  156 Additional Exercises  161 Integrative Exercises  161 design an Experiment  163

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

5 Thermochemistry  164

5.1 Energy  166

Kinetic Energy and Potential Energy  166 Units of Energy  168 System and Surroundings  169 Transferring Energy: Work and Heat  169

5.2 The First Law of Thermodynamics  170

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

Contents ix

5.3 Enthalpy  175

Pressure–Volume Work  175 Enthalpy Change  177

5.4 Enthalpies of Reaction  179

5.5 Calorimetry  181

Heat Capacity and Specific Heat  181 Constant-Pressure Calorimetry  183 Bomb Calorimetry (Constant-Volume Calorimetry)  185

5.6 Hess’s Law  187

5.7 Enthalpies of Formation  189

Using Enthalpies of Formation to Calculate Enthalpies of Reaction  192

5.8 Foods and Fuels  194

Foods  194 Fuels  197 Other Energy Sources  198

Chapter Summary and Key Terms  200 Learning Outcomes  201 Key Equations  202 Exercises  202 Additional Exercises  209 Integrative Exercises  210 design an Experiment  211

A Closer Look Energy, Enthalpy, and P–V Work  178

Strategies in Chemistry Using Enthalpy as a Guide  181

Chemistry and Life The Regulation of Body Temperature  186

Chemistry Put to Work The Scientific and Political Challenges of Biofuels  198

6 Electronic Structure of Atoms  212

6.1 The Wave Nature of Light  214

6.2 Quantized Energy and Photons  216

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

6.3 Line Spectra and the Bohr Model  219

Line Spectra  219 Bohr’s Model  220 The Energy States of the Hydrogen Atom  221 Limitations of the Bohr Model  223

6.4 The Wave Behavior of Matter  223

The Uncertainty Principle  225

6.5 Quantum Mechanics and Atomic Orbitals  226

Orbitals and Quantum Numbers  228

6.6 Representations of Orbitals  230

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

6.7 Many-Electron Atoms  234

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

6.8 Electron Configurations  237

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

6.9 Electron Configurations and the Periodic Table  241

Anomalous Electron Configurations  245

Chapter Summary and Key Terms  246 Learning Outcomes  247 Key Equations  247 Exercises  248 Additional Exercises  252 Integrative Exercises  255 design an Experiment  255

A Closer Look Measurement and the Uncertainty Principle  225

A Closer Look Thought Experiments and Schrödinger’s Cat  227

A Closer Look Probability Density and Radial Probability Functions  232

Chemistry and Life Nuclear Spin and Magnetic Resonance Imaging  236

7 Periodic Properties of the Elements  256

7.1 development of the Periodic Table  258

7.2 Effective Nuclear Charge  259

7.3 Sizes of Atoms and Ions  262

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

7.4 Ionization Energy  268

Variations in Successive Ionization Energies  268 Periodic Trends in First Ionization Energies  268 Electron Configurations of Ions  271

7.5 Electron Affinity  272

7.6 Metals, Nonmetals, and Metalloids  273

Metals  274 Nonmetals  276 Metalloids  277