Principios de Química

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ChemicalPrinciples

Sixth Edition

Steven S. ZumdahlUniversity of Illinois

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Contents

Learning to Think Like a Chemist xv

About the Author xxiv

1 Chemists and Chemistry 11.1 Thinking Like a Chemist 2

1.2 A Real-World Chemistry Problem 3

■ Chemistry Explorers: Alice Williams’s Focus: The Structure of Nucleic Acids 4

■ Chemistry Explorers: Stephanie Burns: Chemist, Executive 5

1.3 The Scientific Method 7

■ Chemical Insights: Critical Units! 9

1.4 Industrial Chemistry 10

■ Chemical Insights: A Note-able Achievement 11

1.5 Polyvinyl Chloride (PVC): Real-World Chemistry 12

2 Atoms, Molecules, and Ions 152.1 The Early History of Chemistry 16

2.2 Fundamental Chemical Laws 17

2.3 Dalton’s Atomic Theory 19

2.4 Cannizzaro’s Interpretation 21

■ Chemical Insights: Seeing Atoms 22

2.5 Early Experiments to Characterize the Atom 24

■ Chemical Insights: Marie Curie: Founder of Radioactivity 26

2.6 The Modern View of Atomic Structure: An Introduction 29

2.7 Molecules and Ions 30

2.8 An Introduction to the Periodic Table 34

■ Chemical Insights: Hassium Fits Right In 36

2.9 Naming Simple Compounds 36

■ Chemical Insights: Playing Tag 42

Discussion Questions and Exercises 45

3 Stoichiometry 523.1 Atomic Masses 53

■ Chemical Insights: Elemental Analysis Catches Elephant Poachers 54

3.2 The Mole 56

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3.3 Molar Mass 58

■ Chemical Insights: Measuring the Masses of Large Molecules or MakingElephants Fly 59

3.4 Percent Composition of Compounds 60

3.5 Determining the Formula of a Compound 62

3.6 Chemical Equations 66

3.7 Balancing Chemical Equations 68

3.8 Stoichiometric Calculations: Amounts of Reactants and Products 70

■ Chemical Insights: High Mountains—Low Octane 71

3.9 Calculations Involving a Limiting Reactant 73


4 Types of Chemical Reactions and Solution Stoichiometry 904.1 Water, the Common Solvent 91

4.2 The Nature of Aqueous Solutions: Strong and Weak Electrolytes 93

4.3 The Composition of Solutions 97

4.4 Types of Chemical Reactions 101

4.5 Precipitation Reactions 101

4.6 Describing Reactions in Solution 106

4.7 Selective Precipitation 108

■ Chemical Insights: Chemical Analysis of Cockroaches 109

4.8 Stoichiometry of Precipitation Reactions 110

4.9 Acid–Base Reactions 113

4.10 Oxidation–Reduction Reactions 117

■ Chemical Insights: State-of-the-Art Analysis 119

4.11 Balancing Oxidation–Reduction Equations 123

4.12 Simple Oxidation–Reduction Titrations 130


5 Gases 1415.1 Early Experiments 142

5.2 The Gas Laws of Boyle, Charles, and Avogadro 143

5.3 The Ideal Gas Law 146

■ Chemical Insights: Cold Atoms 147

5.4 Gas Stoichiometry 150

5.5 Dalton’s Law of Partial Pressures 152

■ Chemical Insights: The Chemistry of Air Bags 153

5.6 The Kinetic Molecular Theory of Gases 155

■ Chemical Insights: Separating Gases 156

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5.7 Effusion and Diffusion 164

5.8 Collisions of Gas Particles with the Container Walls 167

5.9 Intermolecular Collisions 169

5.10 Real Gases 171

■ Chemistry Explorers: Kenneth Suslick Practices Sound Chemistry 174

■ Chemical Insights: Cool Sounds 175

5.11 Characteristics of Several Real Gases 176

5.12 Chemistry in the Atmosphere 176

■ Chemical Insights: The Importance of Oxygen 178

■ Chemistry Explorers: Kristie A. Boering and Ronald C. Cohen Study the Earth’sAtmosphere 179

■ Chemical Insights: Acid Rain: An Expensive Problem 180


6 Chemical Equilibrium 1966.1 The Equilibrium Condition 197

6.2 The Equilibrium Constant 200

6.3 Equilibrium Expressions Involving Pressures 203

6.4 The Concept of Activity 205

6.5 Heterogeneous Equilibria 206

6.6 Applications of the Equilibrium Constant 208

6.7 Solving Equilibrium Problems 211

6.8 Le Châtelier’s Principle 216

6.9 Equilibria Involving Real Gases 222


7 Acids and Bases 2337.1 The Nature of Acids and Bases 234

7.2 Acid Strength 236

7.3 The pH Scale 239

7.4 Calculating the pH of Strong Acid Solutions 241

7.5 Calculating the pH of Weak Acid Solutions 242

7.6 Bases 248

■ Chemical Insights: Amines 253

7.7 Polyprotic Acids 254

7.8 Acid–Base Properties of Salts 263

7.9 Acid Solutions in Which Water Contributes to the H� Concentration 270

7.10 Strong Acid Solutions in Which Water Contributes to the H� Concentration 275

7.11 Strategy for Solving Acid–Base Problems: A Summary 276


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8 Applications of Aqueous Equilibria 2868.1 Solutions of Acids or Bases Containing a Common Ion 287

8.2 Buffered Solutions 289

8.3 Exact Treatment of Buffered Solutions 297

8.4 Buffer Capacity 300

8.5 Titrations and pH Curves 303

8.6 Acid–Base Indicators 319

8.7 Titration of Polyprotic Acids 324

8.8 Solubility Equilibria and the Solubility Product 328

8.9 Precipitation and Qualitative Analysis 335

■ Chemistry Explorers: Yi Lu Researches the Role of Metals in Biological Systems 339

8.10 Complex Ion Equilibria 341


9 Energy, Enthalpy, and Thermochemistry 3589.1 The Nature of Energy 359

■ Chemical Insights: Bees Are Hot 362

9.2 Enthalpy 365

9.3 Thermodynamics of Ideal Gases 366

9.4 Calorimetry 374

9.5 Hess’s Law 380

■ Chemical Insights: Firewalking: Magic or Science? 383

9.6 Standard Enthalpies of Formation 384

9.7 Present Sources of Energy 390

■ Chemical Insights: Hiding Carbon Dioxide 392

■ Chemical Insights: Super Greenhouse Gas 394

9.8 New Energy Sources 394

■ Chemical Insights: Farming the Wind 396

■ Chemical Insights: Heat Packs 400


10 Spontaneity, Entropy, and Free Energy 41010.1 Spontaneous Processes 411

10.2 The Isothermal Expansion and Compression of an Ideal Gas 417

10.3 The Definition of Entropy 425

■ Chemical Insights: Entropy: An Organizing Force? 426

10.4 Entropy and Physical Changes 427

10.5 Entropy and the Second Law of Thermodynamics 429

10.6 The Effect of Temperature on Spontaneity 430

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10.7 Free Energy 433

10.8 Entropy Changes in Chemical Reactions 436

10.9 Free Energy and Chemical Reactions 440

10.10 The Dependence of Free Energy on Pressure 444

10.11 Free Energy and Equilibrium 448

10.12 Free Energy and Work 453

10.13 Reversible and Irreversible Processes: A Summary 455

10.14 Adiabatic Processes 457


11 Electrochemistry 47211.1 Galvanic Cells 473

■ Chemical Insights: Dental Resistance 474

11.2 Standard Reduction Potentials 476

11.3 Cell Potential, Electrical Work, and Free Energy 482

11.4 Dependence of the Cell Potential on Concentration 485

11.5 Batteries 492

■ Chemical Insights: Electrochemical Window Shades 494

■ Chemical Insights: Fuel Cells—Portable Energy 496

11.6 Corrosion 497

■ Chemical Insights: Refurbishing the Lady 498

■ Chemical Insights: Paint That Stops Rust—Completely 501

11.7 Electrolysis 502

■ Chemical Insights: The Chemistry of Sunken Treasure 505

11.8 Commercial Electrolytic Processes 506


12 Quantum Mechanics and Atomic Theory 52112.1 Electromagnetic Radiation 522

■ Chemical Insights: New-Wave Sunscreens 524

12.2 The Nature of Matter 525

12.3 The Atomic Spectrum of Hydrogen 530

12.4 The Bohr Model 531

■ Chemical Insights: The New, Improved Atomic Clock 534

■ Chemical Insights: Fireworks 536

12.5 The Quantum Mechanical Description of the Atom 536

■ Chemical Insights: Electrons as Waves 540

12.6 The Particle in a Box 541

■ Chemistry Explorers: Charles Sykes Researches Surface Architecture 543

12.7 The Wave Equation for the Hydrogen Atom 548

12.8 The Physical Meaning of a Wave Function 550

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12.9 The Characteristics of Hydrogen Orbitals 551

12.10 Electron Spin and the Pauli Principle 556

12.11 Polyelectronic Atoms 556

12.12 The History of the Periodic Table 559

12.13 The Aufbau Principle and the Periodic Table 561

12.14 Further Development of the Polyelectronic Model 568

12.15 Periodic Trends in Atomic Properties 571

■ Chemical Insights: Why Is Mercury a Liquid? 574

12.16 The Properties of a Group: The Alkali Metals 578

■ Chemical Insights: Lithium: Behavior Medicine 582


13 Bonding: General Concepts 59213.1 Types of Chemical Bonds 593

■ Chemical Insights: No Lead Pencils 596

13.2 Electronegativity 597

13.3 Bond Polarity and Dipole Moments 599

13.4 Ions: Electron Configurations and Sizes 603

13.5 Formation of Binary Ionic Compounds 607

13.6 Partial Ionic Character of Covalent Bonds 611

13.7 The Covalent Chemical Bond: A Model 612

13.8 Covalent Bond Energies and Chemical Reactions 616

13.9 The Localized Electron Bonding Model 619

13.10 Lewis Structures 620

13.11 Resonance 625

13.12 Exceptions to the Octet Rule 626

■ Chemical Insights: Hyperconjugation—The Octet Rules 632

13.13 Molecular Structure: The VSEPR Model 636

■ Chemical Insights: Chemical Structure and Communication: Semiochemicals 646

■ Chemical Insights: Smelling and Tasting Electronically 648


14 Covalent Bonding: Orbitals 66014.1 Hybridization and the Localized Electron Model 661

14.2 The Molecular Orbital Model 673

14.3 Bonding in Homonuclear Diatomic Molecules 677

14.4 Bonding in Heteronuclear Diatomic Molecules 684

14.5 Combining the Localized Electron and Molecular Orbital Models 685

■ Chemical Insights: The Always Interesting NO 686

14.6 Orbitals: Human Inventions 688

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14.7 Molecular Spectroscopy: An Introduction 690

■ Chemistry Explorers: Jonathan E. Kenny Looks at Spectroscopy in the Real World 690

14.8 Electronic Spectroscopy 692

14.9 Vibrational Spectroscopy 694

14.10 Rotational Spectroscopy 698

14.11 Nuclear Magnetic Resonance Spectroscopy 700

■ Chemical Insights: NMR and Oenology 704


15 Chemical Kinetics 71415.1 Reaction Rates 715

■ Chemical Insights: Femtochemistry 718

15.2 Rate Laws: An Introduction 719

15.3 Determining the Form of the Rate Law 722

15.4 The Integrated Rate Law 726

15.5 Rate Laws: A Summary 735

15.6 Reaction Mechanisms 737

■ Chemistry Explorers: Christopher Rose-Petruck Studies Ultrafast X-raySpectroscopy 738

■ Chemical Insights: Seeing Reaction Mechanisms 742

15.7 The Steady-State Approximation 743

15.8 A Model for Chemical Kinetics 747

15.9 Catalysis 751

■ Chemical Insights: TiO2—One of Nature’s Most Versatile Materials 752

■ Chemistry Explorers: Christopher Arumainayagam Researches the Interactions ofMolecules with Surfaces 754

■ Chemical Insights: Enzymes: Nature’s Catalysts 756

■ Chemical Insights: Hot, New Enzymes 760


16 Liquids and Solids 77716.1 Intermolecular Forces 778

16.2 The Liquid State 781

■ Chemical Insights: Getting a Grip 782

■ Chemical Insights: Smart Fluids 784

16.3 An Introduction to Structures and Types of Solids 785

■ Chemical Insights: Conch Clues 789

16.4 Structure and Bonding in Metals 790

■ Chemical Insights: Closest Packing of M & Ms 792

■ Chemical Insights: Seething Surfaces 793

16.5 Carbon and Silicon: Network Atomic Solids 799

■ Chemical Insights: Superconductivity 802

■ Chemical Insights: Greenhouse Glass 804

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■ Chemical Insights: Explosive Sniffer 806

■ Chemical Insights: Gallium Arsenide Lasers 807

■ Chemical Insights: Transistors and Integrated Circuits 810

16.6 Molecular Solids 812

16.7 Ionic Solids 813

16.8 Structures of Actual Ionic Solids 817

16.9 Lattice Defects 818

16.10 Vapor Pressure and Changes of State 819

16.11 Phase Diagrams 826

■ Chemical Insights: Making Diamonds at Low Pressures: Fooling Mother Nature 828

16.12 Nanotechnology 831

■ Chemical Insights: Smaller Can Be Better 832

■ Chemical Insights: Minimotor Molecule 834


17 Properties of Solutions 84617.1 Solution Composition 847

17.2 The Thermodynamics of Solution Formation 847

■ Chemical Insights: An Energy Solution 848

■ Chemical Insights: Miracle Solvents 852

17.3 Factors Affecting Solubility 854

■ Chemical Insights: Ionic Liquids? 857

■ Chemical Insights: The Lake Nyos Tragedy 859

17.4 The Vapor Pressures of Solutions 859

17.5 Boiling-Point Elevation and Freezing-Point Depression 864

17.6 Osmotic Pressure 867

17.7 Colligative Properties of Electrolyte Solutions 871

17.8 Colloids 873

■ Chemical Insights: Organisms and Ice Formation 874


18 The Representative Elements 88518.1 A Survey of the Representative Elements 886

18.2 The Group 1A Elements 891

18.3 The Chemistry of Hydrogen 893




■ Chemical Insights: Beethoven: Hair Is the Story 901


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18.8 The Chemistry of Nitrogen 903

■ Chemical Insights: An Explosive Discovery 905

■ Chemical Insights: Nitrous Oxide: Laughing Gas That Propels Whipped Cream and Cars 910

18.9 The Chemistry of Phosphorus 911


18.11 The Chemistry of Oxygen 915

18.12 The Chemistry of Sulfur 916



■ Chemical Insights: Automatic Sunglasses 924

Exercises 925

19 Transition Metals and Coordination Chemistry 93319.1 The Transition Metals: A Survey 934

19.2 The First-Row Transition Metals 940

■ Chemical Insights: Titanium Makes Great Bicycles 942

19.3 Coordination Compounds 946

19.4 Isomerism 951

■ Chemical Insights: Alfred Werner: Coordination Chemist 953

■ Chemical Insights: The Importance of Being cis 956

■ Chemical Insights: Chirality: Why Is It Important? 957

19.5 Bonding in Complex Ions: The Localized Electron Model 958

19.6 The Crystal Field Model 959

■ Chemical Insights: Transition Metal Ions Lend Color to Gems 965

19.7 The Molecular Orbital Model 966

19.8 The Biologic Importance of Coordination Complexes 969


20 The Nucleus: A Chemist’s View 98120.1 Nuclear Stability and Radioactive Decay 982

■ Chemical Insights: Does Antimatter Matter? 986

20.2 The Kinetics of Radioactive Decay 987

■ Chemical Insights: Stellar Nucleosynthesis 988

20.3 Nuclear Transformations 991

20.4 Detection and Uses of Radioactivity 993

20.5 Thermodynamic Stability of the Nucleus 996

20.6 Nuclear Fission and Nuclear Fusion 1000

20.7 Effects of Radiation 1004

■ Chemical Insights: Nuclear Physics: An Introduction 1005

Exercises 1007

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21 Organic and Biochemical Molecules 101321.1 Alkanes: Saturated Hydrocarbons 1014

■ Chemical Insights: Chemistry in the Garden 1015

21.2 Alkenes and Alkynes 1023

21.3 Aromatic Hydrocarbons 1026

21.4 Hydrocarbon Derivatives 1028

21.5 Polymers 1035

■ Chemical Insights: Wallace Hume Carothers 1041

■ Chemical Insights: Heal Thyself 1043

21.6 Natural Polymers 1044

■ Chemical Insights: Tanning in the Shade 1052

Exercises 1060

Appendix 1 Mathematical Procedures A1A1.1 Exponential Notation A1

A1.2 Logarithms A3

A1.3 Graphing Functions A4

A1.4 Solving Quadratic Equations A5

A1.5 Uncertainties in Measurements A8

A1.6 Significant Figures A13

Appendix 2 Units of Measurement and Conversions Among Units A15A2.1 Measurements A15

A2.2 Unit Conversions A17

Appendix 3 Spectral Analysis A17

Appendix 4 Selected Thermodynamic Data A21

Appendix 5 Equilibrium Constants and Reduction Potentials A24

Glossary A27

Answers to Selected Exercises A41

Photo Credits A75

Index A78

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Learning to Think Like a Chemist

Chemistry is a fascinating and important subject that is challenging to teachand even more challenging to learn. Making this complex subject accessible tostudents without distortion is the challenge of the chemical educator, especiallyat the introductory level. Chemical Principles, Sixth Edition, provides a rigor-ous but understandable introduction to chemistry. It emphasizes conceptual un-derstanding, the importance of models, and thoughtful problem solving.

Chemical Principles is based on my experience at the University of Illi-nois teaching an accelerated general chemistry course for chemical sciencesmajors and other students who require a rigorous introductory course. Thesestudents typically have excellent credentials and a genuine aptitude for chem-istry, but have only limited understanding of the fundamental concepts ofchemistry. Although they may know how to solve stoichiometry and gas prob-lems when they arrived in my course, these students typically lacked a thor-ough appreciation for the chemical principles that underlie these applications.This is not because they had inadequate preparation in high school; instead,I believe it results from the nature of chemistry itself—a subject that requiresseveral passes before real mastery can take place.

My mission in writing this text was to produce a book that does not as-sume that students already know how to think like chemists. These studentswill do complicated and rigorous thinking eventually, but they must be broughtto that point gradually. Thus this book covers the advanced topics (in gases,atomic theory, thermodynamics, and so on) that one expects in a course forchemical sciences majors, but it starts with the fundamentals, and then buildsto the level required for more complete understanding. Chemistry is not theresult of an inspired vision. It is the product of countless observations andmany attempts, using logic and trial and error, to account for these observa-tions. In this book I try to develop key chemical concepts in the same way—to show the observations first and then discuss the models that have been con-structed to explain the observed behavior. I hope students will practice“thinking like a chemist” by carefully studying the observations to see if theycan follow the thought process, rather than just jumping ahead to the equa-tion or model that will follow.

In Chemical Principles, Sixth Edition, I take advantage of the excellentmath skills that these students typically possess. As a result, there are fewerworked-out examples than would be found in most mainstream books. Theend-of-chapter problems cover a wide range—from drill exercises to difficultproblems, some of which would challenge the average senior chemistry major.Thus instructors can tailor the problem assignments to the level appropriatefor their students.

This text maintains a student-friendly approach without being patroniz-ing. In addition, to demonstrate the importance of chemistry in real life, I haveincorporated throughout the book a number of applications and recentadvances in essay form.

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New to This EditionI continue to be pleased that the previous editions of the text have been wellreceived. In response to comments from users, however, we have made somesignificant changes for the sixth edition.

• Eight new Chemistry Explorers boxes have been added, which featurechemists who are doing cutting-edge research. The purpose of these boxesis to provide human faces to the study of chemistry and show potential rolemodels to the students.

• The boxed essays that connect chemical concepts to the real world havebeen renamed Chemical Insights. Fifteen new Chemical Insights boxes havebeen added throughout the text, including The Importance of Oxygen(Chapter 6), New-Wave Sunscreens (Chapter 12), NMR and Oenology(Chapter 14) and Closest Packing of M&Ms (Chapter 16).

• Two new sections have been added. Section 5.11, “Characteristics of RealGases,” emphasizes the properties of several real gases. Section 16.12, “Nano-technology,” provides an introduction to a very important new area of chem-istry and technology.

• Former Chapter 19 has been combined with Chapter 18 and the materialedited to provide a more focused and usable treatment of descriptivechemistry.

• 20% of the end-of-chapter problems have been revised and new prob-lems added, as appropriate. In particular we have added more ChallengeProblems to each chapter. We have also added art to the end-of-chapterproblems where appropriate.

OrganizationThe early chapters in this book deal with chemical reactions. Stoichiometryis covered in Chapters 3 and 4, with special emphasis on reactions in aque-ous solutions. The properties of gases are treated in Chapter 5, followed bycoverage of gas phase equilibria in Chapter 6. Acid–base equilibria are cov-ered in Chapter 7, and Chapter 8 deals with additional aqueous equilibria.Thermodynamics is covered in two chapters: Chapter 9 deals with thermo-chemistry and the first law of thermodynamics; Chapter 10 treats the topicsassociated with the second law of thermodynamics. The discussion of elec-trochemistry follows in Chapter 11. Atomic theory and quantum mechanicsare covered in Chapter 12, followed by two chapters on chemical bondingand modern spectroscopy (Chapters 13 and 14). Chemical kinetics is discussedin Chapter 15, followed by coverage of solids and liquids in Chapter 16, andthe physical properties of solutions in Chapter 17. A systematic treatment ofthe descriptive chemistry of the representative elements is given in Chapter18, and of the transition metals in Chapter 19. Chapter 20 covers topics innuclear chemistry and Chapter 21 provides an introduction to organic chem-istry and to the most important biomolecules.

Flexibility of Topic OrderWe recognize that the order of the chapters in this text may not fit the orderof the topics in your course. Therefore, we have tried to make the order asflexible as possible. In the courses that I have taught using the text, I have

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successfully used it in a very different order from the one the text follows. Iwould encourage you to use it in whatever order that serves your purposes.

Instructors have several options for arranging the material to complementtheir syllabi. For example, the section on gas phase and aqueous equilibria(Chapters 6–8) could be moved to any point later in the course. The chapterson thermodynamics can be separated: Chapter 9 can be used early in thecourse, with Chapter 10 later. In addition, the chapters on atomic theory andbonding (Chapters 12–14) can be used near the beginning of the course. Insummary, an instructor who wants to cover atomic theory early and equilib-rium later might prefer the following order of chapters: 1–5, 9, 12, 13, 14,10, 11, 6, 7, 8, 15–21. An alternative order might be: 1–5, 9, 12, 13, 14, 6,7, 8, 10, 11, 15–21. The point is that the chapters on atomic theory and bond-ing (12–14), thermodynamics (9, 10), and equilibrium (6, 7, 8) can be movedaround quite easily. In addition, the kinetics chapter (Chapter 15) can be cov-ered at any time after bonding. It is also possible to use Chapter 20 (on nuclearchemistry) much earlier—after Chapter 12, for example—if desired.

APPROACH 1

Chapter 1 Chemists and ChemistryChapter 2 Atoms, Molecules, and IonsChapter 3 StoichiometryChapter 4 Types of Chemical Reactions and SolutionStoichiometryChapter 5 GasesChapter 9 Energy, Enthalpy, and ThermochemistryChapter 12 Quantum Mechanics and Atomic TheoryChapter 13 Bonding: General ConceptsChapter 14 Covalent Bonding: OrbitalsChapter 10 Spontaneity, Entropy, and Free EnergyChapter 11 ElectrochemistryChapter 6 Chemical EquilibriumChapter 7 Acids and BasesChapter 8 Applications of Aqueous EquilibriaChapter 15 Chemical KineticsChapter 16 Liquids and SolidsChapter 17 Properties of SolutionsChapter 18 The Representative ElementsChapter 19 Transition Metals and CoordinationChemistryChapter 20 The Nucleus: A Chemist’s ViewChapter 21 Organic and Biochemical Molecules

APPROACH 2

Chapter 1 Chemists and ChemistryChapter 2 Atoms, Molecules, and IonsChapter 3 StoichiometryChapter 4 Types of Chemical Reactions and SolutionStoichiometryChapter 5 GasesChapter 9 Energy, Enthalpy, and ThermochemistryChapter 12 Quantum Mechanics and Atomic TheoryChapter 13 Bonding: General ConceptsChapter 14 Covalent Bonding: OrbitalsChapter 6 Chemical EquilibriumChapter 7 Acids and BasesChapter 8 Applications of Aqueous EquilibriaChapter 10 Spontaneity, Entropy, and Free EnergyChapter 11 ElectrochemistryChapter 15 Chemical KineticsChapter 16 Liquids and SolidsChapter 17 Properties of SolutionsChapter 18 The Representative ElementsChapter 19 Transition Metals and CoordinationChemistryChapter 20 The Nucleus: A Chemist’s ViewChapter 21 Organic and Biochemical Molecules

Mathematical LevelThis text assumes a solid background in algebra. All of the mathematical op-erations required are described in Appendix One or are illustrated in worked-out examples. A knowledge of calculus is not required for use of this text.Differential and integral notions are used only where absolutely necessary andare explained where they are used.

Two approaches for teaching atomic theory earlier and equilibrium later in the course

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Complete Instructional PackageFor the InstructorA complete suite of customizable teaching tools accompanies Chemical Princi-ples, Sixth Edition. Whether available in print, online, or via CD, these integratedresources are designed to save you time and help make class preparation, pre-sentation, assessment, and course management more efficient and effective.

HM Testing™ (powered by Diploma®) combines a flexible test-editing pro-gram with a comprehensive gradebook function for easy administration andtracking. With HM Testing instructors can administer tests via print, networkserver, or the Web. Questions can be selected based on chapter/section, levelof difficulty, question format, functionality, or five levels of keywords. In-structors also have the option of accessing the Test Bank content from HMChemSPACE™ with Eduspace®. With HM Testing you can:

• Choose from over 1600 static test items designed to measure the conceptsand principles covered in the text.

• Ensure that each student gets a different version of the problem by select-ing from the 350 algorithmic questions within the computerized Test Bank.

• Author your own questions, which can integrate into the existing Test Bank,becoming part of the question database for future use.

• Choose problems designated as single-skill (easy), multi-skill (moderate),and challenging and multi-skill (difficult).

• Customize tests to assess the specific content from the text.

• Create several forms of the same test in which questions and answers arescrambled.

The complete Solutions Manual files are included on this CD.

HM ClassPresent General Chemistry CD-ROM provides a library of molec-ular animations and lab demonstration videos covering core chemistry con-cepts arranged by chapter and topic. The resources can be browsed by thumb-nail and description or searched by chapter, title, or keyword. Full transcriptsaccompany all audio commentary, to reinforce visual presentations and to ac-commodate different learning styles.

HM ChemSPACE (college.hmco.com/pic/zumdahlCP6e) is a Website designedto be a “turnkey” solution that students can access and use quickly withoutany instructor setup. The instructor version of the HM ChemSPACE Websiteincludes much of the content found in the Eduspace version but without anyof the accompanying course-management tools and services. It requires no in-structor setup and includes all the digital resources instructors need to developlectures:

• Virtually all of the text figures, tables, and photos available in PowerPointslides and in digital format

• Instructor’s Resource Guide

• Transparencies (PDF format)

• Animations and videos

• Classroom Response System (CRS) “clicker” content, by Don DeCoste (Uni-versity of Illinois), offers a dynamic way to facilitate interactive learning

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with students. This text-specific content is comprised of multiple-choicequestions to test common misunderstandings, core objectives, and difficultconcepts—all with an average time of 1 minute for feedback. Students’ re-sponses display anonymously in a bar graph, pie chart, or other graphicand can be exported to a gradebook. (Additional hardware and softwarerequired; contact your Houghton Mifflin sales representative for moreinformation.)

HM ChemSPACE with Eduspace is an instructor’s one-stop resource for allcourse material. Through Eduspace, instructors can access:

• Instructor and student media included within HM ChemSPACE

• Online homework problems from WebAssign®

• ChemWork interactive assignments, which help students learn the processof problem solving through a series of interactive hints. These exercises aregraded automatically.

• SMARTHINKING®—live, online tutoring for students

• Powerful course-management tools from Blackboard®—gradebook, white-board—that enhance teaching and learning.

• Customized functions—select, create, and post homework assignments andtests—that allow instructors to tailor these materials to their specific needs.

Online Course Content for Blackboard, WebCT®, eCollege, and ANGEL allowsonline delivery of text-specific content using your institution’s local course-management system. Through these course-management systems, HoughtonMifflin offers access to all assets such as Test Bank content, tutorials, andvideo lessons. Additionally, qualified adoptions can use PowerCartridges forBlackboard and PowerPacks for WebCT to allow access to all HM ChemSPACEwith Eduspace course content, including ChemWork and end-of-chapter prob-lems, from your institution’s local Blackboard or WebCT system.

WebAssign is a Houghton Mifflin partner offering an online homework sys-tem with text-specific end-of-chapter problems. WebAssign was developed byteachers, for teachers. For information on this system, contact your HM rep-resentative. With WebAssign, you can

• Create assignments from a ready-to-use database of textbook questions orwrite and customize your own exercises

• Create, post, and review assignments 24 hours a day, 7 days a week

• Deliver, collect, grade, and record assignments instantly

• Offer more practice exercises, quizzes, and homework

• Assess student performance to keep abreast of individual progress

• Control tolerance and significant figures settings on a global and per-questionbasis

The WebAssign gradebook gives you complete control over every aspect ofstudent grades. In addition, if you choose to enable it, your students will beable to see their own grades and homework, quiz, and test averages as the se-mester progresses, and even compare their scores with the class averages.

Complete Solutions Guide, Thomas J. Hummel and Steven S. Zumdahl, pre-sents detailed solutions for all end-of-chapter exercises in the text for the

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convenience of faculty and staff involved in instruction and for instructorswho wish their students to have solutions for all exercises. Available from theHM Testing CD.

For the StudentAn extensive print and media package has been designed to assist students inworking problems, visualizing molecular-level interactions, and building studystrategies to fully comprehend concepts.

Technology Supplements for StudentsHM ChemSPACE is the portal to online student media resources (college.hmco.com/pic/zumdahlCP6e) to help students prepare for class, study for quizzesand exams, and improve their grade. Students will have access to the following:

• Online Multimedia eBook integrates reading textbook content with em-bedded links to media activities and supports highlighting, note taking,zooming, printing, and easy navigation by chapter or page.

• Visualizations (molecular animations and lab demonstration videos) give stu-dents the opportunity to review and test their knowledge of key concepts.

• Interactive tutorials allow students to dynamically review and interact withkey concepts from the text.

• Electronic flashcards

• ACE practice tests

• Over 45 hours of video lessons from Thinkwell, segmented into 8–10 minutemini-lectures by a chemistry professor that combines video, audio, andwhiteboard to demonstrate key concepts.

• General Chemistry resources: interactive periodic table, molecule library ofchemical structures, and Careers in Chemistry

HM ChemSPACE accompanies every new copy of the text. Students who havebought a used textbook can purchase access to HM ChemSPACE separately.

HM ChemSPACE with Eduspace, Houghton Mifflin’s Complete Online Learn-ing Tool, features all of the student resources available in HM ChemSPACEas well as ChemWork assignments and SMARTHINKING—live, online tutor-ing. This dynamic suite of products gives students many options for practiceand communication.

ChemWork AssignmentsChemWork is a homework system we, Steven and Susan Zumdahl,developed. It is different from the end-of-chapter homework providedin the text and online. These problems are designed to use as a stand-alone learning system in one of two ways: students can learn theproblem solving process (while doing actual homework problems) or asa capstone assignment to determine whether they understand how tosolve problems (perhaps in final preparation for an exam).

If students can solve a particular problem with no assistance,they can proceed directly to the answer, and receive congratulations.However, if students need help, assistance is available through a seriesof hints. The procedure for assisting students is modeled after the wayinstructors would help students with a homework problem in their

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offices. The hints are usually in the form of interactive questions thatnudge students in the right direction without telling them how to solvethe problem; the goal is to help students figure out how to successfullycomplete the problem themselves. Often computer-based homeworkgives up and gives the correct solution after students fail two or threetimes. Students realize this and often just push buttons until the rightanswer comes up. ChemWork never gives up on students; it never revealsthe right answer—rather it helps students get to the correct solution.

When we were first developing this approach we were concernedthat students would become irritated at not having the answer easilyrevealed. However, we observed that students actually appreciateddoing the problems in a supportive yet demanding environment. Thegood news is that this approach really helps them learn how to thinklike a chemist. When we started to use this system, we saw a significantincrease in our exam scores.

Another important feature of ChemWork is that each student inthe course receives a unique set of problems. This is accomplished byusing a combination of algorithmic, datapool, and version questionsand problems that are randomly selected by the computer. If all thestudents have the same problems, they tend to “farm out” the problemsinstead of doing all of them themselves. If students are assigned similarbut unique problems they can help each other, but everyone has to dotheir own problem set.

ChemWork also has the capability to check for significant figuresin calculations. Since it is a homework system, it is designed to tellstudents if the significant figures are incorrect in their answer withoutmarketing the answer wrong. This feature encourages students to payattention to the significant figures without frustrating them so muchthat they give up.

The development of ChemWork over 10 years while being used bythousands of students has resulted in a system that dramaticallyenhances students’ problem-solving skills.

SMARTHINKING—Live, Online TutoringSMARTHINKING provides personalized, text-specific tutoring duringtypical study hours when students need it most.* With SMARTHINKINGstudents can submit a question to get a response from a qualified e-structor within 24 hours; use the whiteboard with full scientificnotation and graphics; view past online sessions, questions, or essays in an archive on their personal academic homepage; and view theirtutoring schedule. E-structors help students with the process of problemsolving rather than supply answers. SMARTHINKING is availablethrough Eduspace or, upon instructor request, with new copies of thestudent textbook.

Print Supplements for StudentsStudy Guide, by Paul Kelter (Northern Illinois University)—a comprehensiveself-study aid for students containing alternative strategies for solving prob-lems, supplemental explanations for the most difficult material, and self-tests.

*Terms and conditions subject to change; some limits apply.

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There are approximately 400 worked examples and 1200 practice problems(with answers) designed to give students mastery and confidence with the con-cepts covered in the text. (ISBN: 978-0-618-94658-7)

Student Solutions Manual, by Tom Hummel (University of Illinois)—providesdetailed solutions for half of the end-of-chapter exercises using the strategiesemphasized in the text. (ISBN: 978-0-618-95336-3)

AcknowledgementsThe successful completion of this book is due to the efforts of many people.Charles Hartford, Vice President and Publisher, has extensive experience incrafting effective chemistry texts and was always supportive and furnishedmany creative ideas for the revision. I greatly appreciate the efforts of RebeccaBerardy Schwartz, who did an excellent job as Development Editor on thisproject. Also, I wish to thank Nicole Moore, Marketing Manager, and KrisBishop, Marketing Assistant, for their creative ideas and knowledge of themarket to promote this title. In addition I am grateful to Cathy Brooks, SeniorProject Editor, for managing the production of a very complex project. Cathyis the best project editor in the business.

I greatly appreciate the efforts of Tom Hummel from the University ofIllinois who managed the revision of the end-of-chapter exercises and prob-lems and the solutions manuals. Tom’s extensive knowledge of general chem-istry and high standards of accuracy assure the quality of the problems andsolutions in this text. I am grateful to Don DeCoste of the University of Illi-nois for many discussion about how students learn chemistry and for creat-ing the discussion questions and new Challenge Problems. I want to extendspecial thanks to Professor Eric Scerri from UCLA for his valuable input onthe phases of atomic orbitals. Finally, I am deeply grateful to my multitalentedwife, Susan Arena Zumdahl, for her cheerful help on all facets of this projectand for making my life fun. My thanks and love go to our children and grand-children for their love and support.

Thanks to others who supplied valuable assistance on this edition: JillHaber, Art and Design Manager; Sharon Donahue, Photo Researcher; CiaBoynton, Designer; Jessyca Broekman, Art Editor; Estelle Lebeau, CentralMichigan University, for her keen eye for accuracy; and Marjorie SingerAnderson for her developmental editing. I would also like to especially thankthe following people for their hospitality during our trip to Europe and theirconstructive feedback as users of the fifth edition.

Matti Näsäkkälä, University of Helsinki, FinlandArnold Maliniak and Sven Hovmöller, Stockholm University, SwedenUlf Henriksson, The Royal Institute of Technology (KTH), Stockholm,

SwedenLennart Sjölin and Sture Nordholm, Gothenburg University, SwedenSerge Hoste, Gerrit Herman, Isabel Van Driessche, and André Goeminne,

University of Gent, BelgiumPhilippe Bogaerts, Université Libre de Bruxelles, Belgium

My special appreciation goes to the following people who reviewed allor part of the manuscript in its various stages, in this edition as well as pre-vious ones.

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Sixth Edition ReviewersElizabeth Day, University of the PacificIvan J. Dmochowski, University of PennsylvaniaBrian Enderle, University of California, DavisRegina Frey, Washington University, St. LouisBrian Frost, University of NevadaDerek Gragson, California Polytechnic State UniversityKeith Griffiths, University of Western OntarioRobert Kerber, State University of New York, Stony BrookCarl Hoeger, University of California, San DiegoK. C. McGill, Georgia College and State UniversityThomas G. Minehan, California State University, NorthridgeJohn H. Nelson, University of NevadaRobert Price, City College of San FranciscoDouglas Raynie, South Dakota State UniversityPhilip J. Reid, University of WashingtonThomas Schleich, University of California, Santa CruzRobert Sharp, University of MichiganMark Sulkes, Tulane UniversityJohn H. Terry, Cornell UniversityMichael R. Topp, University of PennsylvaniaMark Thachuk, University of British ColumbiaMeishan Zhao, University of Chicago

Fifth Edition ReviewersAlan L. Balch, University of California, DavisDavid Erwin, Rose-Hulman Institute of TechnologyMichael Hecht, Princeton UniversityRosemary Marusak, Kenyon CollegePatricia B. O’Hara, Amherst CollegeRuben D. Parra, DePaul UniversityPhilip J. Reid, University of WashingtonEric Scerri, University of California, Los AngelesRobert Sharp, University of Michigan

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About the Author

STEVEN S. ZUMDAHL received his B.S. degree in Chemistry from WheatonCollege (Illinois) in 1964 and his Ph.D. in Chemistry from the University ofIllinois, Urbana, in 1968.

In over 35 years of teaching he has been a faculty member at the Uni-versity of Colorado, Boulder; Parkland College (Illinois); and the Universityof Illinois, where he served as Professor and Associate Head and Director ofUndergraduate Programs in Chemistry until he became Professor Emeritus in2003. In 1994 Dr. Zumdahl received the National Catalyst Award from theChemical Manufacturers Association in recognition of his contribution tochemical education in the United States.

Professor Zumdahl is known at the University of Illinois for his rapportwith students and for his outstanding teaching ability. During his tenure atthe University, he received the University of Illinois Award for Excellence inTeaching, the Liberal Arts and Sciences College Award for DistinguishedTeaching, and the School of Chemical Sciences Teaching Award (five times).

Dr. Z., as he is known to his students, greatly enjoys “mechanical things,”including bicycles and cars. He collects and restores classic automobiles, hav-ing a special enthusiasm for vintage Corvettes and Packards.

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A1

Exponential NotationThe numbers characteristic of scientific measurements are often very large orvery small; thus it is convenient to express them by using powers of 10. Forexample, the number 1,300,000 can be expressed as 1.3 � 106, which meansmultiply 1.3 by 10 six times:

1.3 � 106 � 1.3 � 10 � 10 � 10 � 10 � 10 � 10106 � 1 million

Note that each multiplication by 10 moves the decimal point one place to theright, and the easiest way to interpret the notation 1.3 � 106 is that it meansmove the decimal point in 1.3 to the right six times.

In this notation the number 1985 can be expressed as 1.985 � 103. Notethat the usual convention is to write the number that appears before the powerof 10 as a number between 1 and 10. Some other examples are given below.

A1.1

Number Exponential Notation

5.6 5.6 � 100 or 5.6 � 139 3.9 � 101

943 9.43 � 102

1126 1.126 � 103

To represent a number smaller than 1 in exponential notation, start witha number between 1 and 10 and divide by the appropriate power of 10:

0.0034 � � � 3.4 � 10�3

Division by 10 moves the decimal point one place to the left. Thus the number0.00000014 can be written as 1.4 � 10�7.

To summarize, we can write any number in the form

N � 10�n

where N is between 1 and 10 and the exponent n is an integer. If the sign pre-ceding n is positive, it means the decimal point in N should be moved n placesto the right. If a negative sign precedes n, the decimal point in N should bemoved n places to the left.

3.4�103

3.4��10 � 10 � 10

Appendix OneMathematical Procedures

Appendixes

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A2 Appendix One Mathematical Procedures

Multiplication and DivisionWhen two numbers expressed in exponential notation are multiplied, the ini-tial numbers are multiplied and the exponents of 10 are added:

(M � 10m)(N � 10n) � (MN) � 10m�n

For example,

(3.2 � 104)(2.8 � 103) � 9.0 � 107

When the numbers are multiplied, if a result greater than 10 is obtained forthe initial number, the number is adjusted to conventional notation:

(5.8 � 102)(4.3 � 108) � 24.9 � 1010 � 2.49 � 1011 � 2.5 � 1011

Division of two numbers expressed in exponential notation involvesnormal division of the initial numbers and subtraction of the exponent of thedivisor from that of the dividend. For example,

� � 10(8�3) � 2.3 � 105

Addition and SubtractionWhen we add or subtract numbers expressed in exponential notation, theexponents of the numbers must be the same. For example, to add 1.31 � 105

and 4.2 � 104, rewrite one number so that the exponents of both are the same:

13.1 � 104

� 4.2 � 104

17.3 � 104

In correct exponential notation the result is expressed as 1.73 � 105.

Powers and RootsWhen a number expressed in exponential notation is taken to some power,the initial number is taken to the appropriate power and the exponent of 10is multiplied by that power:

(N � 10n)m � Nm � 10m�n

For example,*

(7.5 � 102)3 � 7.53 � 103�2 � 422 � 106 � 4.22 � 108

� 4.2 � 108 (rounded to 2 significant figures)

When a root is taken of a number expressed in exponential notation, theroot of the initial number is taken and the exponent of 10 is divided by thenumber representing the root:

�N� �� 1�0�n� � (N � 10n)1/2 � �N� � 10n/2

Divisor

4.8�2.1

4.8 � 108

��2.1 � 103

*Refer to the instruction booklet for your calculator for directions concerning how to take rootsand powers of numbers.



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A1.2 Logarithms A3

For example, (2.9 � 106)1/2 � �2�.9� � 106/2 � 1.7 � 103

Because the exponent of the result must be an integer, we may sometimes haveto change the form of the number so that the power divided by the root equalsan integer; for example,

�1�.9� �� 1�0�3� � (1.9 � 103)1/2 � (0.19 � 104)1/2

� �0�.1�9� � 102 � 0.44 � 102

� 4.4 � 101

The same procedure is followed for roots other than square roots; for example,

�3

4�.6� �� 1�0�10� � (4.6 � 1010)1/3 � (46 � 109)1/3

� �3

4�6� � 103 � 3.6 � 103

LogarithmsA logarithm is an exponent. Any number N can be expressed as follows:

N � 10x

For example, 1000 � 103

100 � 102

10 � 101

1 � 100

The common, or base 10, logarithm of a number is the power to which 10must be taken to yield that number. Thus, since 1000 � 103,

log 1000 � 3

Similarly, log 100 � 2

log 10 � 1

log 1 � 0

For a number between 10 and 100, the required exponent of 10 will be be-tween 1 and 2. For example, 65 � 101.8129; that is, log 65 � 1.8129. For anumber between 100 and 1000, the exponent of 10 will be between 2 and 3.For example, 650 � 102.8129 and log 650 � 2.8129.

A number N greater than 0 and less than 1 can be expressed as follows:

N � 10�x �

For example, 0.001 � � � 10�3

0.01 � � � 10�2

0.1 � � � 10�11�101

1�10

1�102

1�100

1�103

1�1000

1�10x

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Thus log 0.001 � �3

log 0.01 � �2

log 0.1 � �1

Although common logs are often tabulated, the most convenient methodfor obtaining such logs is to use a calculator.

Since logs are simply exponents, they are manipulated according to the rulesfor exponents. For example, if A � 10x and B � 10y, then their product is

A � B � 10x � 10y � 10x�y

and log AB � x � y � log A � log B

For division we have � � 10x�y

and log � x � y � log A � log B

For a number raised to a power we have

An � (10x)n � 10nx

and log An � nx � n log A

It follows that log � log A�n � �n log A

or for n � 1, log � �log A

When a common log is given, to find the number it represents, we mustcarry out the process of exponentiation. For example, if the log is 2.673, thenN � 102.673. The process of exponentiation is also called taking the antilog,or the inverse logarithm, and is easily carried out by using a calculator.

A second type of logarithm, the natural logarithm, is based on the num-ber 2.7183, which is referred to as e. In this case a number is represented asN � ex � 2.7183x. For example,

N � 7.15 � ex

ln 7.15 � x � 1.967

If a natural logarithm is given, to find the number it represents, we mustcarry out exponentiation to the base e (2.7183) by using a calculator.

Graphing FunctionsIn the interpretation of the results of a scientific experiment, it is often usefulto make a graph. It is usually most convenient to graph the function in a formthat gives a straight line. The equation for a straight line (a linear equation)can be represented by the general form

y � mx � b

where y is the dependent variable, x is the independent variable, m is the slope,and b is the intercept with the y axis.

1�A

1�An

A�B

10x

�10y

A�B

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As an illustration of the characteristics of a linear equation, the functiony � 3x � 4 is plotted in Fig. A1.1. For this equation, m � 3 and b � 4. Notethat the y intercept occurs when x � 0. In this case the intercept is 4, as canbe seen from the equation (b � 4).

The slope of a straight line is defined as the ratio of the rate of changein y to that in x:

m � slope �

For the equation y � 3x � 4, y changes three times as fast as x (since x hasa coefficient of 3). Thus the slope in this case is 3. This can be verified fromthe graph. For the triangle shown in Fig. A1.1:

Slope � � � 3

Sometimes an equation that is not in standard form can be changed to theform y � mx � b by rearrangement or mathematical manipulation. An exam-ple is the equation k � Ae�Ea/RT, where A, Ea, and R are constants, k is thedependent variable, and 1/T is the independent variable. This equation can bechanged to standard form by taking the natural logarithm of both sides,

ln k � ln Ae�Ea/RT � ln A � ln e�Ea/RT � ln A �

noting that the log of a product is equal to the sum of the logs of the indi-vidual terms and that the natural log of e�Ea/RT is simply the exponent �Ea/RT.Thus in standard form the equation k � Ae�Ea/RT is written

ln k � � � � � ln A�

� ��

ym x

b

A plot of ln k versus 1/T (see Fig. A1.2) gives a straight line with slope �Ea/Rand intercept ln A.

Of course, many relationships that arise from the description of naturalsystems are nonlinear, and the “slope” of a curve is continuously changing.In this case the instantaneous slope is given by the tangent to the curve at thatpoint, which is described by a new function obtained by taking the derivativeof the original function. For example, for the function in x, f � ax2, the deriv-ative (df/dx) is 2ax. Thus the slope at each point on the curve defined by thefunction ax2 is given by 2ax.

Solving Quadratic EquationsA quadratic equation, a polynomial in which the highest power of x is 2, canbe written as

ax2 � bx � c � 0

One method for finding the two values of x that satisfy a quadratic equationis to use the quadratic formula:

x ��b � �b�2�� 4�a�c��

2a

1�T

Ea�R

Ea�RT

24�8

y�x

y�x

FIGURE A1.1

Graph of the linear equation y � 3x � 4.

Intercept

60

50

40

30

20

10

0

y

x

y�3x�4

y

x

10 20 30 40

Slope = −Ea

R

Intercept = ln A

1T

ln k

FIGURE A1.2

Graph of ln k versus 1/T.

A1.4



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where a, b, and c represent the coefficients of x2 and x and the constant,respectively. For example, in the determination of [H�] in a solution of 1.0 �10�4 M acetic acid, the following expression arises:

1.8 � 10�5 �

which yields x2 � (1.8 � 10�5)x � 1.8 � 10�9 � 0

where a � 1, b � 1.8 � 10�5, and c � �1.8 � 10�9. Using the quadratic for-mula, we have

x �

�

and x � � 3.5 � 10�5

or x � � �5.2 � 10�5

Note that there are two roots, as there always will be for a polynomial in x2.In this case x represents a concentration of H� (see Section 7.5). Thus thepositive root is the one that solves the problem, since a concentration cannotbe a negative number.

A second method for solving quadratic equations is by successive approx-imations, a systematic method of trial and error. A value of x is guessed andsubstituted into the equation everywhere x (or x2) appears, except for oneplace. For example, for the equation

x2 � (1.8 � 10�5)x � 1.8 � 10�9 � 0

we might guess x � 2 � 10�5. Substituting that value into the equation gives

x2 � (1.8 � 10�5)(2 � 10�5) � 1.8 � 10�9 � 0

or x2 � 1.8 � 10�9 � 3.6 � 10�10 � 1.4 � 10�9

Thus x � 3.7 � 10�5

Note that the guessed value of x (2 � 10�5) is not the same as the value of xthat is calculated (3.7 � 10�5) after inserting the estimated value. This meansthat x � 2 � 10�5 is not the correct solution, and we must try another guess.

We take the calculated value (3.7 � 10�5) as our next guess:

x2 � (1.8 � 10�5)(3.7 � 10�5) � 1.8 � 10�9 � 0

x2 � 1.8 � 10�9 � 6.7 � 10�10 � 1.1 � 10�9

Thus x � 3.3 � 10�5

Now we compare the two values of x again:

Guessed: x � 3.7 � 10�5

Calculated: x � 3.3 � 10�5

These values are closer but still not identical.

�10.5 � 10�5

��2

6.9 � 10�5

��2

�1.8 � 10�5 � �3�.2�4� �� 1�0��10� �� (�4�)(�1�)(��1�.8� �� 1�0��9)��

2(1)

�b � �b�2�� 4�a�c��

2a

x2

��1.0 � 10�4 � x



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Next, we try 3.3 � 10�5 as our guess:

x2 � (1.8 � 10�5)(3.3 � 10�5) � 1.8 � 10�9 � 0

x2 � 1.8 � 10�9 �5.9 � 10�10 � 1.2 � 10�9

Thus x � 3.5 � 10�5

Compare:

Guessed: x � 3.3 � 10�5

Calculated: x � 3.5 � 10�5

Next, we guess x � 3.5 � 10�5, which leads to

x2 � (1.8 � 10�5)(3.5 � 10�5) � 1.8 � 10�9 � 0

x2 � 1.8 � 10�9 � 6.3 � 10�10 � 1.2 � 10�9

Thus x � 3.5 � 10�5

Now the guessed value and the calculated value are the same; we have foundthe correct solution. Note that this agrees with one of the roots found withthe quadratic formula in the first method above.

To further illustrate the method of successive approximations, we willsolve Example 7.9 by using this procedure. In solving for [H�] for 0.010 MH2SO4, we obtain the following expression:

1.2 � 10�2 �

which can be rearranged to give

x � (1.2 � 10�2)� �We will guess a value for x, substitute it into the right side of the equation,and then calculate a value for x. In guessing a value for x, we know it mustbe less than 0.010, since a larger value would make the calculated value forx negative and the guessed and calculated values will never match. We startby guessing x � 0.005.

The results of the successive approximations are shown in the followingtable:

0.010 � x��0.010 � x

x(0.010 � x)��

0.010 � x

Guessed CalculatedTrial Value for x Value for x

1 0.0050 0.00402 0.0040 0.00513 0.00450 0.004554 0.00452 0.00453

Note that the first guess was close to the actual value and that there wasoscillation between 0.004 and 0.005 for the guessed and calculated values.For trial 3, an average of these values was used as the guess, and this led rapidlyto the correct value (0.0045 to the correct number of significant figures). Alsonote that it is useful to carry extra digits until the correct value is obtained,which is then rounded off to the correct number of significant figures.



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The method of successive approximations is especially useful for solvingpolynomials containing x to a power of 3 or higher. The procedure is the sameas for quadratic equations: Substitute a guessed value for x into the equationfor every x term but one, and then solve for x. Continue this process until theguessed and calculated values agree.

Uncertainties in MeasurementsThe number associated with a measurement is obtained by using some measur-ing device. For example, consider the measurement of the volume of a liquidin a buret, as shown in Fig. A1.3, where the scale is greatly magnified. Thevolume is about 22.15 mL. Note that the last number must be estimated byinterpolating between the 0.1-mL marks. Since the last number is estimated,its value may vary depending on who makes the measurement. If five differ-ent people read the same volume, the results might be as follows:

Person Result of Measurement

1 22.15 mL2 22.14 mL3 22.16 mL4 22.17 mL5 22.16 mL

A1.5

Note from these results that the first three numbers (22.1) remain the same re-gardless of who makes the measurement; these are called certain digits. How-ever, the digit to the right of the 1 must be estimated and thus varies; it is calledan uncertain digit. We customarily report a measurement by recording all thecertain digits plus the first uncertain digit. In our example it would not makeany sense to try to record the volume to thousandths of a milliliter because thevalue for hundredths of a milliliter must be estimated when using the buret.

It is very important to realize that a measurement always has some degreeof uncertainty. The uncertainty of a measurement depends on the precision ofthe measuring device. For example, using a bathroom scale, you might estimatethat the mass of a grapefruit is about 1.5 pounds. Weighing the same grapefruiton a highly precise balance might produce a result of 1.476 pounds. In the firstcase the uncertainty occurs in the tenths of a pound place; in the second casethe uncertainty occurs in the thousandths of a pound place. Suppose we weightwo similar grapefruit on the two devices and obtain the following results:

50

40

30

20

10

0

22

23

Buret

FIGURE A1.3

Measurement of volume using a buret. The volume is read at the bottom of the liquid curve (called the meniscus).

Bathroom Scale Balance

Grapefruit 1 1.5 lb 1.476 lbGrapefruit 2 1.5 lb 1.518 lb

Do the two grapefruits have the same mass? The answer depends on whichset of results you consider. Thus a conclusion based on a series of measure-ments depends on the certainty of those measurements. For this reason, it isimportant to indicate the uncertainty in any measurement. This is done byalways recording the certain digits and the first uncertain digit (the estimatednumber). These numbers are called the significant figures of a measurement.



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The convention of significant figures automatically gives an indication ofthe uncertainty in a measurement. The uncertainty in the last number (the es-timated number) is usually assumed to be �1 unless otherwise indicated. Forexample, the measurement 1.86 kilograms can be interpreted to mean 1.86 �0.01 kilograms.

Precision and AccuracyTwo terms often used to describe uncertainty in measurements are precisionand accuracy. Although these words are frequently used interchangeably ineveryday life, they have different meanings in the scientific context. Accuracyrefers to the agreement of a particular value with the true value. Precisionrefers to the degree of agreement among several measurements of the samequantity. Precision reflects the reproducibility of a given type of measurement.The difference between these terms is illustrated by the results of three dif-ferent target practices shown in Fig. A1.4.

Two different types of errors are also introduced in Fig. A1.4. A randomerror (also called an indeterminate error) means that a measurement has anequal probability of being high or low. This type of error occurs in estimat-ing the value of the last digit of a measurement. The second type of error iscalled systematic error (or determinate error). This type of error occurs in thesame direction each time; it is either always high or always low. Figure A1.4(a)indicates large random errors (poor technique). Figure A1.4(b) indicates smallrandom errors but a large systematic error, and Fig. A1.4(c) indicates smallrandom errors and no systematic error.

In quantitative work precision is often used as an indication of accuracy;we assume that the average of a series of precise measurements (which should“average out” the random errors because of their equal probability of beinghigh or low) is accurate, or close to the “true” value. However, this assump-tion is valid only if systematic errors are absent. Suppose we weigh a piece ofbrass five times on a very precise balance and obtain the following results:

Weighing Result

1 2.486 g2 2.487 g3 2.485 g4 2.484 g5 2.488 g

Normally, we would assume that the true mass of the piece of brass is veryclose to 2.486 grams, which is the average of the five results. However, if thebalance has a defect causing it to give a result that is consistently 1.000 gramtoo high (a systematic error of �1.000 gram), then 2.486 grams would beseriously in error. The point here is that high precision among several mea-surements is an indication of accuracy only if you can be sure that systematicerrors are absent.

Expression of Experimental ResultsThe accuracy of a measurement refers to how close it is to the true value. Aninaccurate result occurs as a result of some flaw (systematic error) in the

(a)

(b)

(c)

FIGURE A1.4

Shooting targets show the difference between precise and accurate. (a) Neither accurate nor precise (large random errors). (b) Precise but not accurate(small random errors, large systematic error).(c) Bull’s-eye! Both precise and accurate(small random errors, no systematic error).



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measurement: the presence of an interfering substance, incorrect calibration ofan instrument, operator error, and so on. The goal of chemical analysis is toeliminate systematic error, but random errors can only be minimized. In prac-tice, an experiment is almost always done in order to find an unknown value(the true value is not known—someone is trying to obtain that value by doingthe experiment). In this case the precision of several replicate determinationsis used to assess the accuracy of the result. The results of the replicate exper-iments are expressed as an average (which we assume is close to the true value)with an error limit that gives some indication of how close the average valuemay be to the true value. The error limit represents the uncertainty of theexperimental result.

To illustrate this procedure, consider a situation that might arise in thepharmaceutical industry. Assume that the specification for a commercial 500-mgacetaminophen (the active painkiller in Tylenol) tablet is that each batch oftablets must contain 450 to 550 mg of acetaminophen per tablet. Supposethat chemical analysis gave the following results for a batch of acetaminophentablets: 428, 479, 442, and 435 mg. How can these results be used to decidewhether the batch of tablets meets the specification? Although the details ofhow to draw such conclusions from measured data are beyond the scope ofthis discussion, we will consider some aspects of this process. We will focushere on the types of experimental uncertainty, the expression of experimentalresults, and a simplified method for estimating experimental uncertainty whenseveral types of measurements contribute to the final result.

There are two common ways of expressing an average: the mean and themedian. The mean (x�) is the arithmetic average of the results, or

Mean � x� � �n

i�1�

where means take the sum of the values. The mean is equal to the sum ofall the measurements divided by the number of measurements. For the aceta-minophen results given previously, the mean is

x� � � 446 mg

The median is the value that lies in the middle among the results. Halfof the measurements are above the median and half are below the median.For results of 465, 485, and 492 mg, the median is 485 mg. When there isan even number of results, the median is the average of the two middle results.For the acetaminophen results, the median is

� 439 mg

There are several advantages to using the median. If a small number ofmeasurements is made, one value can greatly affect the mean. Consider theresults for the analysis of acetaminophen: 428, 479, 442, and 435 mg. Themean is 446 mg, which is larger than three of the four results. The median is439 mg, which lies near the three values that are relatively close to one another.

In addition to expressing an average value for a series of results, we mustalso express the uncertainty. This usually means expressing either the preci-sion of the measurements or the observed range of the measurements. Therange of a series of measurements is defined by the smallest value and the

442 � 435��

2

428 � 479 � 442 � 435��

4

x1 � x2 � �� xn��n

xi�n



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largest value. For the analytical results on the acetaminophen tablets, the rangeis from 428 to 479 mg. Using this range, we can express the results by sayingthat the true value lies between 428 and 479 mg. That is, we can express theamount of acetaminophen in a typical tablet as 446 � 33 mg, where the errorlimit is chosen to give the observed range (approximately).

The most common way to specify precision is by the standard deviations, which for a small number of measurements is given by the formula

s � � �1/2

where xi is an individual result, x� is the average (either mean or median), and nis the total number of measurements. For the acetaminophen example wehave

s � � �1/2

� 23

Thus we can say that the amount of acetaminophen in a typical tablet in thebatch of tablets is 446 mg with a sample standard deviation of 23 mg. Sta-tistically, this means that any additional measurement has a 68% probability(68 chances out of 100) of being between 423 mg (446 � 23) and 469 mg(446 � 23). Thus the standard deviation is a measure of the precision of agiven type of measurement.

In scientific calculations it is also useful to be able to estimate the preci-sion of a procedure that involves several measurements by combining the pre-cisions of the individual steps. That is, we want to answer the following ques-tion: How do the uncertainties propagate when we combine the results ofseveral different types of measurements? There are many ways to deal withthe propagation of uncertainty. We will discuss one simple method below.

Worst-Case Method for Estimating Experimental UncertaintyTo illustrate this method, we will consider the determination of the density ofan irregularly shaped solid. In this determination we make three measure-ments. First, we measure the mass of the object on a balance. Next, wemust obtain the volume of the solid. The easiest method for doing this is topartially fill a graduated cylinder with a liquid and record the volume. Thenwe add the solid and record the volume again. The difference in the measuredvolumes is the volume of the solid. We can then calculate the density of thesolid from the equation

D �

where M is the mass of the solid, V1 is the initial volume of liquid in the grad-uated cylinder, and V2 is the volume of liquid plus solid. Suppose we get thefollowing results:

M � 23.06 g

V1 � 10.4 mL

V2 � 13.5 mL

M�V2 � V1

(428 � 446)2 � (479 � 446)2 � (442 � 446)2 � (435 � 446)2

��4 � 1

�n

i�1 (xi � x�)2

��n � 1



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The calculated density is

� 7.44 g/mL

Now suppose that the precision of the balance used is �0.02 g and thatthe volume measurements are precise to �0.05 mL. How do we estimate theuncertainty of the density? We can do this by assuming a worst case. That is,we assume the largest uncertainties in all measurements, and we see what com-binations of measurements will give the largest and smallest possible results(the greatest range). Since the density is the mass divided by the volume, thelargest value of the density will be that obtained by using the largest possiblemass and the smallest possible volume:

Largest possible mass � 23.06 � 0.02o

Dmax � � 7.69 g/mL

p rSmallest possible V2 Largest possible V1

The smallest value of the density is

Smallest possible masso

Dmin � � 7.20 g/mL

p rLargest possible V2 Smallest possible V1

Thus the calculated range is from 7.20 to 7.69, and the average of these valuesis 7.45. The error limit is the number that gives the high and low range valueswhen added and subtracted from the average. Therefore, we can express thedensity as 7.45 � 0.25 g/mL, which is the average value plus or minus thequantity that gives the range calculated by assuming the largest uncertainties.

Analysis of the propagation of uncertainties is useful in drawing qualitativeconclusions from the analysis of measurements. For example, suppose that weobtained the preceding results for the density of an unknown alloy and wewant to know if it is one of the following alloys:

Alloy A: D � 7.58 g/mL

Alloy B: D � 7.42 g/mL

Alloy C: D � 8.56 g/mL

We can safely conclude that the alloy is not C. But the values of the densities foralloys A and B are both within the inherent uncertainty of our method. To dis-tinguish between A and B, we need to improve the precision of our determina-tion. The obvious choice is to improve the precision of the volume measurement.

The worst-case method is useful for estimating the maximum uncertaintyexpected when the results of several measurements are combined to obtain aresult. We assume the maximum uncertainty in each measurement and thencalculate the minimum and maximum possible results. These extreme valuesdescribe the range and thus the maximum error limit associated with a par-ticular determination.

23.04��13.55 � 10.35

23.08��13.45 � 10.45

23.06 g��13.5 mL � 10.4 mL



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A1.6 Significant Figures A13

Confidence LimitsA more sophisticated method for estimating the uncertainty of a particulartype of determination involves the use of confidence limits. A confidence limitis defined as

Confidence limit � �

where t � a weighting factor based on statistical analysis

s � the standard deviation

n � the number of experiments carried out

In this context an experiment may refer to a single type of measurement(for example, weighing an object) or to a procedure that requires various typesof measurements to obtain a given final result (for example, obtaining thepercentage of iron in a particular sample of iron ore). Some representativevalues of t are listed in Table A1.1.

A 95% confidence level means that the true value (the average obtainedif the experiment were repeated an infinite number of times) will lie within�ts/�n� of the observed average (obtained from n experiments) with a 95%probability (95 of 100 times). Thus the factor �ts/�n� represents an errorlimit for a given set of results from a particular type of experiment. Thus wemight represent the result of n determinations as

x� �

where x� is the average of the results from the n experiments. This type oferror limit is expected to be considerably smaller than that obtained from aworst-case analysis.

Significant FiguresCalculating the final result for an experiment usually involves adding, sub-tracting, multiplying, or dividing the results of various types of measurements.Thus it is important to be able to estimate the uncertainty in the final result.In the previous section we have considered this process in some detail. Aclosely related matter concerns the number of digits that should be retainedin the result of a given calculation. In other words, how many of the digits inthe result are significant (meaningful) relative to the uncertainty expected inthe result? From statistical analyses of how uncertainties accumulate whenarithmetic operations are carried out, rules have been developed for deter-mining the correct number of significant figures in a final result. First, wemust consider how to count the number of significant figures (digits) repre-sented in a particular number.

Rules for Counting Significant Figures (Digits)1. Nonzero integers. Nonzero integers always count as significant figures.

2. Zeros. There are three classes of zeros:

a. Leading zeros are zeros that precede all the nonzero digits. They do notcount as significant figures. In the number 0.0025 the three zeros simply

ts��n�

ts��n�

A1.6

TABLE A1.1

Values of t for 90% and 95% Confi-dence Levels

Values of t forConfidence Intervals

n 90% 95%

2 6.31 12.73 2.92 4.304 2.35 3.185 2.13 2.786 2.02 2.577 1.94 2.458 1.90 2.369 1.86 2.31

10 1.83 2.26



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indicate the position of the decimal point. This number has only twosignificant figures.

b. Captive zeros are zeros between nonzero digits. They always count assignificant figures. The number 1.008 has four significant figures.

c. Trailing zeros are zeros at the right end of the number. They are sig-nificant only if the number contains a decimal point. The number 100has only one significant figure, whereas the number 1.00 � 102 has threesignificant figures. The number one hundred written as 100. also hasthree significant figures.

3. Exact numbers. Many times calculations involve numbers that were notobtained by using measuring devices but were determined by counting: 10experiments, 3 apples, 8 molecules. Such numbers are called exact num-bers. They can be assumed to have an infinite number of significant figures.Other examples of exact numbers are the 2 in 2�r (the circumference of acircle) and the 4 and the 3 in �

43

��r3 (the volume of a sphere). Exact numberscan also arise from definitions. For example, one inch is defined as exactly2.54 centimeters. Thus, in the statement 1 in � 2.54 cm, neither the 2.54 northe 1 limits the number of significant figures when used in a calculation.

The following rules apply for determining the number of significant fig-ures in the result of a calculation.

Rules for Significant Figures in Mathematical Operations*1. For multiplication or division the number of significant figures in the re-

sult is the same as the number in the least precise measurement used in thecalculation. For example, consider this calculation:

4.56 � 1.4 � 6.38 6.4�

Limiting term has Two significanttwo significant figures

figures

The correct product has only two significant figures, since 1.4 has two sig-nificant figures.

2. For addition or subtraction the result has the same number of decimalplaces as the least precise measurement used in the calculation. For exam-ple, consider the following sum:

12.11

18.0 � Limiting term has one decimal place

1.013

31.123 31.1�

One decimal place

The correct result is 31.1, since 18.0 has only one decimal place.

Corrected888888n

Corrected888888n

*Although these rules work well for most cases, they can give misleading results in certain cases.For a discussion of this, see L. M. Schwartz, “Propagation of Significant Figures,” J. Chem. Ed.62 (1985):693.



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A2.1 Measurements A15

Note that for multiplication and division significant figures are counted.For addition and subtraction the decimal places are counted.

In most calculations you will need to round off numbers to obtain thecorrect number of significant figures. The following rules should be appliedfor rounding.

Rules for Rounding1. In a series of calculations, carry the extra digits through to the final result,

then round off.*

2. If the digit to be removed†

a. is less than 5, the preceding digit stays the same. For example, 1.33rounds to 1.3.

b. is equal to or greater than 5, the preceding digit is increased by 1. Forexample, 1.36 rounds to 1.4.

When rounding, use only the first number to the right of the last signif-icant figure. Do not round off sequentially. For example, the number 4.348when rounded to two significant figures is 4.3, not 4.4.

*This practice will not usually be followed in the examples in this text because we want to showthe correct number of significant figures in each step. However, in the answers to the end-of-chapter exercises, only the final answer is rounded.

†This procedure is consistent with the operation of calculators.

A2.1

Appendix TwoUnits of Measurement and Conversions Among Units

MeasurementsMaking observations is fundamental to all science. A quantitative observa-tion, or measurement, always consists of two parts: a number and a scale (aunit). Both parts must be present for the measurement to be meaningful.

The two most widely used systems of units are the English system usedin the United States and the metric system used by most of the rest of theindustrialized world. This duality obviously causes a good deal of trouble; forexample, parts as simple as bolts are not interchangeable between machinesbuilt using the different systems. As a result, the United States has begun toadopt the metric system.

For many years, most scientists worldwide have used the metric system.In 1960 an international agreement established a system of units called theInternational System (le Système International in French), abbreviated SI. Thissystem is based on the metric system and the units derived from the metricsystem. The fundamental SI units are listed in Table A2.1.



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A16 Appendix Two Units of Measurement and Conversions Among Units

Because the fundamental units are not always convenient (expressing themass of a pin in kilograms is awkward), the SI system uses prefixes to changethe size of the unit. These prefixes are listed in Table A2.2.

One physical quantity that is very important in chemistry is volume, whichis not a fundamental SI unit; it is derived from length. A cube with dimensionsof 1 m on each edge has a volume of (1 m)3 � 1 m3. Then, recognizing thatthere are 10 decimeters (dm) in a meter, the volume of the cube is (10 dm)3 �1000 dm3. A cubic decimeter, dm3, is commonly called a liter (L), which is aunit of volume slightly larger than a quart. Similarly, since 1 dm equals 10centimeters (cm), the liter (1 dm)3 contains 1000 cm3, or 1000 milliliters (mL).

TABLE A2.1

The Fundamental SI Units

Physical Quantity Name of Unit Abbreviation

Mass kilogram kgLength meter mTime second sTemperature Kelvin KElectric current ampere AAmount of substance mole molLuminous intensity candela cd

TABLE A2.2

The Prefixes Used in the SI System

ExponentialPrefix Symbol Meaning Notation*

exa E 1,000,000,000,000,000,000 1018

peta P 1,000,000,000,000,000 1015

tera T 1,000,000,000,000 1012

giga G 1,000,000,000 109

mega M 1,000,000 106

kilo k 1000 103

hecto h 100 102

deka da 10 101

— — 1 100

deci d 0.1 10�1

centi c 0.01 10�2

milli m 0.001 10�3

micro � 0.000001 10�6

nano n 0.000000001 10�9

pico p 0.000000000001 10�12

femto f 0.000000000000001 10�15

atto a 0.000000000000000001 10�18

*The most common notations are shown in bold. See Appendix A1.1 if you need a review of expo-nential notation.



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Spectral Analysis A17

Unit ConversionsIt is often necessary to convert results from one system of units to another.The most common way of converting units is by the unit factor method, morecommonly called dimensional analysis. To illustrate the use of this method,we will look at a simple unit conversion.

Consider a pin measuring 2.85 cm in length. What is its length in inches?To solve this problem, we must use the equivalence statement

2.54 cm � 1 in (exactly)

If we divide both sides of this equation by 2.54 cm, we get

� 1 �

Note that the expression 1 in/2.54 cm equals 1. This expression is called aunit factor. Since 1 in and 2.54 cm are exactly equivalent, multiplying anyexpression by this unit factor will not change its value.

The pin has a length of 2.85 cm. Multiplying this length by the unit factorgives

2.85 cm � � in � 1.12 in

Note that the centimeter units cancel to give inches for the result. This is exactlywhat we wanted to accomplish. Note also that the result has three significantfigures, as required by the number 2.85. Recall that the 1 and 2.54 in the con-version factor are exact numbers by definition.

2.85�2.54

1 in�2.54 cm

1 in�2.54 cm

2.54 cm�2.54 cm

A2.2

Steps Converting from One Unit to Another

1 To convert from one unit to another, use the equivalence statement thatrelates the two units.

2 Derive the appropriate unit factor by noting the direction of the requiredchange (to cancel the unwanted units).

3 Multiply the quantity to be converted by the unit factor to give the quan-tity with the desired units.

In dimensional analysis your verification that everything has been donecorrectly is that the correct units are obtained in the end. In doing chemistryproblems, you should always include the units for the quantities used. Alwayscheck to see that the units cancel to give the correct units for the final result.This provides a very valuable check, especially for complicated problems.

Appendix ThreeSpectral Analysis

Although volumetric and gravimetric analyses are still commonly used, spec-troscopy is the technique most often used for modern chemical analysis. Spec-troscopy is the study of electromagnetic radiation emitted or absorbed by a



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A18 Appendix Three Spectral Analysis

given chemical species. Since the quantity of radiation absorbed or emittedcan be related to the quantity of the absorbing or emitting species present,this technique can be used for quantitative analysis. There are many spectro-scopic techniques, since electromagnetic radiation spans a wide range of en-ergies to include microwaves, X rays, and ultraviolet, infrared, and visiblelight, to name a few of its familiar forms. However, we will consider here onlyone procedure, which is based on the absorption of visible light.

If a liquid is colored, it is because some component of the liquid absorbsvisible light. In a solution the greater the concentration of the light-absorbingsubstance, the more light is absorbed, and the more intense is the color ofthe solution.

The quantity of light absorbed by a substance can be measured by a spec-trophotometer, shown schematically in Fig. A3.1. This instrument consists ofa source that emits all wavelengths of light in the visible region (wavelengthsof 400–700 nm); a monochromator, which selects a given wavelength oflight; a sample holder for the solution being measured; and a detector, whichcompares the intensity of incident light I0 with the intensity of light after ithas passed through the sample I. The ratio I/I0, called the transmittance, is ameasure of the fraction of light that passes through the sample. The amountof light absorbed is given by the absorbance A, where

A � �log

The absorbance can be expressed by the Beer-Lambert law:

A � �lc

where � is the molar absorptivity or the molar extinction coefficient (in L mol�1

cm�1), l is the distance the light travels through the solution (in cm), and c isthe concentration of the absorbing species (in mol/L). The Beer-Lambert lawis the basis for using spectroscopy in quantitative analysis. If � and l are known,determining A for a solution allows us to calculate the concentration of theabsorbing species in the solution.

Suppose we have a pink solution containing an unknown concentrationof Co2�(aq) ions. A sample of this solution is placed in a spectrophotometer,and the absorbance is measured at a wavelength where � for Co2�(aq) isknown to be 12 L mol�1 cm�1. The absorbance A is found to be 0.60. Thewidth of the sample tube is 1.0 cm. We want to determine the concentrationof Co2�(aq) in the solution. This problem can be solved by a straightforwardapplication of the Beer-Lambert law,

A � �lc

I�I0

Source Monochromator Sample Detector

I0 I

lFIGURE A3.1

A schematic diagram of a simple spectropho-tometer. The source emits all wavelengths ofvisible light, which are dispersed by using aprism or grating and then focused, one wave-length at a time, onto the sample. The detec-tor compares the intensity of the incident light(l0) with the intensity of the light after it haspassed through the sample (l ).



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Spectral Analysis A19

where A � 0.60

� �

l � light path � 1.0 cm

Solving for the concentration gives

c � � � 5.0 � 10�2 mol/L

To obtain the unknown concentration of an absorbing species from themeasured absorbance, we must know the product �l, since

c �

We can obtain the product �l by measuring the absorbance of a solution ofknown concentration, since

o Measured using ao spectrophotometer

�l �

r Known from makingr up the solution

However, a more accurate value of the product �l can be obtained by plot-ting A versus c for a series of solutions. Note that the equation A � �lc givesa straight line with slope �l when A is plotted against c.

For example, consider the following typical spectroscopic analysis. A sam-ple of steel from a bicycle frame is to be analyzed to determine its manganesecontent. The procedure involves weighing out a sample of the steel, dissolving itin strong acid, treating the resulting solution with a very strong oxidizing agentto convert all the manganese to permanganate ion (MnO4

�), and then usingspectroscopy to determine the concentration of the intensely purple MnO4

� ionsin the solution. To do this, however, the value of �l for MnO4

� must be deter-mined at an appropriate wavelength. The absorbance values for four solutionswith known MnO4

� concentrations were measured to give the following data:

A�c

A��l

0.60��

�12 �mo

Ll cm��(1.0 cm)

A��l

12 L�mol cm

Concentration ofSolution MnO4

� (mol/L) Absorbance

1 7.00 � 10�5 0.1752 1.00 � 10�4 0.2503 2.00 � 10�4 0.5004 3.50 � 10�4 0.875

A plot of absorbance versus concentration for the solutions of known con-centration is shown in Fig. A3.2. The slope of this line (change in A/changein c) is 2.48 � 103 L/mol. This quantity represents the product �l.

A sample of the steel weighing 0.1523 g was dissolved, and the unknownamount of manganese was converted to MnO4

� ions. Water was then addedto give a solution with a final volume of 100.0 mL. A portion of this solu-tion was placed in a spectrophotometer, and its absorbance was found to be0.780. We can use these data to calculate the percent manganese in the steel.



Licensed to:

A20 Appendix Three Spectral Analysis

The MnO4� ions from the manganese in the dissolved steel sample show an

absorbance of 0.780. Using the Beer-Lambert law, we calculate the concen-tration of MnO4

� in this solution:

c � � � 3.15 � 10�4 mol/L

However, there is a more direct way for finding c. Using a graph such asthat in Fig. A3.2 (often called a Beer’s law plot), we can read the concentra-tion that corresponds to A � 0.780. This interpolation is shown by dashedlines on the graph. By this method, c � 3.15 � 10�4 mol/L, which agrees withthe value obtained above.

Recall that the original 0.1523-g steel sample was dissolved, the manganesewas converted to permanganate, and the volume was adjusted to 100.0 mL.We now know that the [MnO4

�] in that solution is 3.15 � 10�4 M. Usingthis concentration, we can calculate the total number of moles of MnO4

� inthat solution:

Mol of MnO4� � 100.0 mL � � 3.15 � 10�4

� 3.15 � 10�5 mol

Each mole of manganese in the original steel sample yields a mole of MnO4�.

That is,

1 mol of Mn 1 mol of MnO4�

so the original steel sample must have contained 3.15 � 10�5 mol of man-ganese. The mass of manganese present in the sample is

3.15 � 10�5 mol of Mn � � 1.73 � 10�3 g of Mn

Since the steel sample weighed 0.1523 g, the percent manganese in the steel is

� 100% � 1.14%1.73 � 10�3 g of Mn��1.523 � 10�1 g of sample

54.938 g of Mn��

1 mol of Mn

Oxidation8888888n

mol�

L1 L

��1000 mL

0.780��2.48 � 103 L/mol

A��l

1.0 × 10– 4 2.0 × 10– 4

Concentration (mol/L)

3.0 × 10– 4

0.10

0

0.20

0.30

0.40Abs

orba

nce

0.50

0.60

0.70

0.800.780

Slope =

0.90

1.00

3.15 × 10– 4

0.5582.25 × 10– 4

= 2.48 × 103

C = 2.25 × 10– 4

A = 0.558

FIGURE A3.2

A plot of absorbance versus concentration ofMnO4

� in a series of solutions of knownconcentration.



Licensed to:

Selected Thermodynamic Data A21

This example illustrates a typical use of spectroscopy in quantitativeanalysis. The steps commonly involved are as follows:

1. Preparation of a calibration plot (a Beer’s law plot) from the measured ab-sorbance values of a series of solutions with known concentrations.

2. Measurement of the absorbance of the solution of unknown concentration.

3. Use of the calibration plot to determine the unknown concentration.

Substance H�f G�f S�and State (kJ/mol) (kJ/mol) (J K�1 mol�1)


AluminumAl(s) 0 0 28Al2O3(s) �1676 �1582 51Al(OH)3(s) �1277 — —AlCl3(s) �704 �629 111

BariumBa(s) 0 0 67BaCO3(s) �1219 �1139 112BaO(s) �582 �552 70Ba(OH)2(s) �946 — —BaSO4(s) �1465 �1353 132

BerylliumBe(s) 0 0 10BeO(s) �599 �569 14Be(OH)2(s) �904 �815 47

BromineBr2(l) 0 0 152Br2(g) 31 3 245Br2(aq) �3 4 130Br�(aq) �121 �104 82HBr(g) �36 �53 199

CadmiumCd(s) 0 0 52CdO(s) �258 �228 55Cd(OH)2(s) �561 �474 96CdS(s) �162 �156 65CdSO4(s) �935 �823 123

CalciumCa(s) 0 0 41CaC2(s) �63 �68 70CaCO3(s) �1207 �1129 93CaO(s) �635 �604 40Ca(OH)2(s) �987 �899 83Ca3(PO4)2(s) �4126 �3890 241CaSO4(s) �1433 �1320 107CaSiO3(s) �1630 �1550 84

CarbonC(s) (graphite) 0 0 6C(s) (diamond) 2 3 2CO(g) �110.5 �137 198CO2(g) �393.5 �394 214CH4(g) �75 �51 186CH3OH(g) �201 �163 240CH3OH(l) �239 �166 127H2CO(g) �116 �110 219HCOOH(g) �363 �351 249HCN(g) 135.1 125 202C2H2(g) 227 209 201C2H4(g) 52 68 219CH3CHO(g) �166 �129 250C2H5OH(l) �278 �175 161C2H6(g) �84.7 �32.9 229.5C3H6(g) 20.9 62.7 266.9C3H8(g) �104 �24 270C2H4O(g)

(ethylene oxide) �53 �13 242CH2PCHCN(g) 185.0 195.4 274CH3COOH(l) �484 �389 160C6H12O6(s) �1275 �911 212CCl4(l) �135 �65 216

ChlorineCl2(g) 0 0 223Cl2(aq) �23 7 121Cl�(aq) �167 �131 57HCl(g) �92 �95 187

ChromiumCr(s) 0 0 24Cr2O3(s) �1128 �1047 81CrO3(s) �579 �502 72

CopperCu(s) 0 0 33CuCO3(s) �595 �518 88

*All values are assumed precise to at least �1.

(continued)

Appendix FourSelected Thermodynamic Data*



Licensed to:

A22 Appendix Four Selected Thermodynamic Data



Cu2O(s) �170 �148 93CuO(s) �156 �128 43Cu(OH)2(s) �450 �372 108CuS(s) �49 �49 67

FluorineF2(g) 0 0 203F�(aq) �333 �279 �14HF(g) �271 �273 174

HydrogenH2(g) 0 0 131H(g) 217 203 115H�(aq) 0 0 0OH�(aq) �230 �157 �11H2O(l) �286 �237 70H2O(g) �242 �229 189

IodineI2(s) 0 0 116I2(g) 62 19 261I2(aq) 23 16 137I�(aq) �55 �52 106

IronFe(s) 0 0 27Fe3C(s) 21 15 108Fe0.95O(s)

(wustite) �264 �240 59FeO(s) �272 �255 61Fe3O4(s)

(magnetite) �1117 �1013 146Fe2O3(s)

(hematite) �826 �740 90FeS(s) �95 �97 67FeS2(s) �178 �166 53FeSO4(s) �929 �825 121

LeadPb(s) 0 0 65PbO2(s) �277 �217 69PbS(s) �100 �99 91PbSO4(s) �920 �813 149

MagnesiumMg(s) 0 0 33MgCO3(s) �1113 �1029 66MgO(s) �602 �569 27Mg(OH)2(s) �925 �834 64

ManganeseMn(s) 0 0 32MnO(s) �385 �363 60

Mn3O4(s) �1387 �1280 149Mn2O3(s) �971 �893 110MnO2(s) �521 �466 53MnO4

�(aq) �543 �449 190

MercuryHg(l) 0 0 76Hg2Cl2(s) �265 �211 196HgCl2(s) �230 �184 144HgO(s) �90 �59 70HgS(s) �58 �49 78

NickelNi(s) 0 0 30NiCl2(s) �316 �272 107NiO(s) �241 �213 38Ni(OH)2(s) �538 �453 79NiS(s) �93 �90 53

NitrogenN2(g) 0 0 192NH3(g) �46 �17 193NH3(aq) �80 �27 111NH4

�(aq) �132 �79 113NO(g) 90 87 211NO2(g) 34 52 240N2O(g) 82 104 220N2O4(g) 10 98 304N2O4(l) �20 97 209N2O5(s) �42 134 178N2H4(l) 51 149 121N2H3CH3(l) 54 180 166HNO3(aq) �207 �111 146HNO3(l) �174 �81 156NH4ClO4(s) �295 �89 186NH4Cl(s) �314 �203 96

OxygenO2(g) 0 0 205O(g) 249 232 161O3(g) 143 163 239

PhosphorusP(s) (white) 0 0 41P(s) (red) �18 �12 23P(s) (black) �39 �33 23P4(g) 59 24 280PF5(g) �1578 �1509 296PH3(g) 5 13 210H3PO4(s) �1279 �1119 110H3PO4(l) �1267 — —

Appendix Four (continued)



Licensed to:

Selected Thermodynamic Data A23



H3PO4(aq) �1288 �1143 158P4O10(s) �2984 �2698 229

PotassiumK(s) 0 0 64KCl(s) �436 �408 83KClO3(s) �391 �290 143KClO4(s) �433 �304 151K2O(s) �361 �322 98K2O2(s) �496 �430 113KO2(s) �283 �238 117KOH(s) �425 �379 79KOH(aq) �481 �440 9.20

SiliconSiO2(s) (quartz) �911 �856 42SiCl4(l) �687 �620 240

SilverAg(s) 0 0 43Ag�(aq) 105 77 73AgBr(s) �100 �97 107AgCN(s) 146 164 84AgCl(s) �127 �110 96Ag2CrO4(s) �712 �622 217AgI(s) �62 �66 115Ag2O(s) �31 �11 122Ag2S(s) �32 �40 146

SodiumNa(s) 0 0 51Na�(aq) �240 �262 59NaBr(s) �360 �347 84Na2CO3(s) �1131 �1048 136NaHCO3(s) �948 �852 102NaCl(s) �411 �384 72NaH(s) �56 �33 40NaI(s) �288 �282 91NaNO2(s) �359 — —NaNO3(s) �467 �366 116Na2O(s) �416 �377 73Na2O2(s) �515 �451 95NaOH(s) �427 �381 64NaOH(aq) �470 �419 50

SulfurS(s) (rhombic) 0 0 32S(s) (monoclinic) 0.3 0.1 33

S2�(aq) 33 86 �15S8(g) 102 50 431SF6(g) �1209 �1105 292H2S(g) �21 �34 206SO2(g) �297 �300 248SO3(g) �396 �371 257SO4

2�(aq) �909 �745 20H2SO4(l) �814 �690 157H2SO4(aq) �909 �745 20

TinSn(s) (white) 0 0 52Sn(s) (gray) �2 0.1 44SnO(s) �285 �257 56SnO2(s) �581 �520 52Sn(OH)2(s) �561 �492 155

TitaniumTiCl4(g) �763 �727 355TiO2(s) �945 �890 50

UraniumU(s) 0 0 50UF6(s) �2137 �2008 228UF6(g) �2113 �2029 380UO2(s) �1084 �1029 78U3O8(s) �3575 �3393 282UO3(s) �1230 �1150 99

XenonXe(g) 0 0 170XeF2(g) �108 �48 254XeF4(s) �251 �121 146XeF6(g) �294 — —XeO3(s) 402 — —

ZincZn(s) 0 0 42ZnO(s) �348 �318 44Zn(OH)2(s) �642 — —ZnS(s)

(wurtzite) �193 — —ZnS(s)

(zinc blende) �206 �201 58ZnSO4(s) �983 �874 120

Appendix Four (continued)



Licensed to:

A24 Appendix Five Equilibrium Constants and Reduction Potentials

Appendix FiveEquilibrium Constants and Reduction Potentials

TABLE A5.1

Values of Ka for Some Common Monoprotic Acids

Name Formula Value of Ka

Hydrogen sulfate ion HSO4� 1.2 � 10�2

Chlorous acid HClO2 1.2 � 10�2

Monochloracetic acid HC2H2ClO2 1.35 � 10�3

Hydrofluoric acid HF 7.2 � 10�4

Nitrous acid HNO2 4.0 � 10�4

Formic acid HCO2H 1.8 � 10�4

Lactic acid HC3H5O3 1.38 � 10�4

Benzoic acid HC7H5O2 6.4 � 10�5

Acetic acid HC2H3O2 1.8 � 10�5

Hydrated aluminum(III) ion [Al(H2O)6]3� 1.4 � 10�5

Propanoic acid HC3H5O2 1.3 � 10�5

Hypochlorous acid HOCl 3.5 � 10�8

Hypobromous acid HOBr 2 � 10�9

Hydrocyanic acid HCN 6.2 � 10�10

Boric acid H3BO3 5.8 � 10�10

Ammonium ion NH4� 5.6 � 10�10

Phenol HOC6H5 1.6 � 10�10

Hypoiodous acid HOI 2 � 10�11

TABLE A5.2

Stepwise Dissociation Constants for Several Common Polyprotic Acids

Name Formula Ka1Ka2

Ka3

Phosphoric acid H3PO4 7.5 � 10�3 6.2 � 10�8 4.8 � 10�13

Arsenic acid H3AsO4 5 � 10�3 8 � 10�8 6 � 10�10

Carbonic acid H2CO3 4.3 � 10�7 4.8 � 10�11

Sulfuric acid H2SO4 Large 1.2 � 10�2

Sulfurous acid H2SO3 1.5 � 10�2 1.0 � 10�7

Hydrosulfuric acid H2S 1.0 � 10�7 10�19

Oxalic acid H2C2O4 6.5 � 10�2 6.1 � 10�5

Ascorbic acid H2C6H6O6 7.9 � 10�5 1.6 � 10�12

(vitamin C)

Citric acid H3C6H5O7 8.4 � 10�4 1.8 � 10�5 4.0 � 10�6



Licensed to:

Equilibrium Constants and Reduction Potentials A25

TABLE A5.3

Values of Kb for Some Common Weak Bases

Name Formula Conjugate Acid Kb

Ammonia NH3 NH4� 1.8 � 10�5

Methylamine CH3NH2 CH3NH3� 4.38 � 10�4

Ethylamine C2H5NH2 C2H5NH3� 5.6 � 10�4

Diethylamine (C2H5)2NH (C2H5)2NH2� 1.3 � 10�3

Triethylamine (C2H5)3N (C2H5)3NH� 4.0 � 10�4

Hydroxylamine HONH2 HONH3� 1.1 � 10�8

Hydrazine H2NNH2 H2NNH3� 3.0 � 10�6

Aniline C6H5NH2 C6H5NH3� 3.8 � 10�10

Pyridine C5H5N C5H5NH� 1.7 � 10�9

TABLE A5.4

Values of Ksp at 25�C for Common Ionic Solids

Ionic Solid Ksp (at 25�C) Ionic Solid Ksp (at 25�C) Ionic Solid Ksp (at 25�C)

Fluorides Chromates (continued) Hydroxides (continued)BaF2 2.4 � 10�5 Hg2CrO4* 2 � 10�9 Co(OH)3 2.5 � 10�16

MgF2 6.4 � 10�9 BaCrO4 8.5 � 10�11 Ni(OH)2 1.6 � 10�16

PbF2 4 � 10�8 Ag2CrO4 9.0 � 10�12 Zn(OH)2 4.5 � 10�17

SrF2 7.9 � 10�10 PbCrO4 2 � 10�16 Cu(OH)2 1.6 � 10�19

CaF2 4.0 � 10�11 Hg(OH)2 3 � 10�26

Carbonates Sn(OH)2 3 � 10�27

Chlorides NiCO3 1.4 � 10�7 Cr(OH)3 6.7 � 10�31

PbCl2 1.6 � 10�5 CaCO3 8.7 � 10�9 Al(OH)3 2 � 10�32

AgCl 1.6 � 10�10 BaCO3 1.6 � 10�9 Fe(OH)3 4 � 10�38

Hg2Cl2* 1.1 � 10�18 SrCO3 7 � 10�10 Co(OH)3 2.5 � 10�43

CuCO3 2.5 � 10�10

Bromides ZnCO3 2 � 10�10 SulfidesPbBr2 4.6 � 10�6 MnCO3 8.8 � 10�11 MnS 2.3 � 10�13

AgBr 5.0 � 10�13 FeCO3 2.1 � 10�11 FeS 3.7 � 10�19

Hg2Br2* 1.3 � 10�22 Ag2CO3 8.1 � 10�12 NiS 3 � 10�21

CdCO3 5.2 � 10�12 CoS 5 � 10�22

Iodides PbCO3 1.5 � 10�15 ZnS 2.5 � 10�22

PbI2 1.4 � 10�8 MgCO3 1 � 10�15 SnS 1 � 10�26

AgI 1.5 � 10�16 Hg2CO3* 9.0 � 10�15 CdS 1.0 � 10�28

Hg2I2* 4.5 � 10�29 PbS 7 � 10�29

Hydroxides CuS 8.5 � 10�45

Sulfates Ba(OH)2 5.0 � 10�3 Ag2S 1.6 � 10�49

CaSO4 6.1 � 10�5 Sr(OH)2 3.2 � 10�4 HgS 1.6 � 10�54

Ag2SO4 1.2 � 10�5 Ca(OH)2 1.3 � 10�6

SrSO4 3.2 � 10�7 AgOH 2.0 � 10�8 PhosphatesPbSO4 1.3 � 10�8 Mg(OH)2 8.9 � 10�12 Ag3PO4 1.8 � 10�18

BaSO4 1.5 � 10�9 Mn(OH)2 2 � 10�13 Sr3(PO4)2 1 � 10�31

Cd(OH)2 5.9 � 10�15 Ca3(PO4)2 1.3 � 10�32

Chromates Pb(OH)2 1.2 � 10�15 Ba3(PO4)2 6 � 10�39

SrCrO4 3.6 � 10�5 Fe(OH)2 1.8 � 10�15 Pb3(PO4)2 1 � 10�54

*Contains Hg22� ions. Ksp � [Hg2

2�][X�]2 for Hg2X2 salts.



Licensed to:

A26 Appendix Five Equilibrium Constants and Reduction Potentials

TABLE A5.5

Standard Reduction Potentials at 25�C (298 K) for Many Common Half-Reactions

Half-Reaction �° (V) Half-Reaction �° (V)

F2 � 2e� 88n 2F� 2.87 O2 � 2H2O � 4e� 88n 4OH� 0.40Ag2� � e� 88n Ag� 1.99 Cu2� � 2e� 88n Cu 0.34Co3� � e� 88n Co2� 1.82 Hg2Cl2 � 2e� 88n 2Hg � 2Cl� 0.27H2O2 � 2H� � 2e� 88n 2H2O 1.78 AgCl � e� 88n Ag � Cl� 0.22Ce4� � e� 88n Ce3� 1.70 SO4

2� � 4H� � 2e� 88n H2SO3 � H2O 0.20PbO2 � 4H� � SO4

2� � 2e� 88n PbSO4 � 2H2O 1.69 Cu2� � e� 88n Cu� 0.16MnO4

� � 4H� � 3e� 88n MnO2 � 2H2O 1.68 2H� � 2e� 88n H2 0.00IO4

� � 2H� � 2e� 88n IO3� � H2O 1.60 Fe3� � 3e� 88n Fe �0.036

MnO4� � 8H� � 5e� 88n Mn2� � 4H2O 1.51 Pb2� � 2e� 88n Pb �0.13

Au3� � 3e� 88n Au 1.50 Sn2� � 2e� 88n Sn �0.14PbO2 � 4H� � 2e� 88n Pb2� � 2H2O 1.46 Ni2� � 2e� 88n Ni �0.23Cl2 � 2e� 88n 2Cl� 1.36 PbSO4 � 2e� 88n Pb � SO4

2� �0.35Cr2O7

2� � 14H� � 6e� 88n 2Cr3� � 7H2O 1.33 Cd2� � 2e� 88n Cd �0.40O2 � 4H� � 4e� 88n 2H2O 1.23 Fe2� � 2e� 88n Fe �0.44MnO2 � 4H� � 2e� 88n Mn2� � 2H2O 1.21 Cr3� � e� 88n Cr2� �0.50IO3

� � 6H� � 5e� 88n �12

�I2 � 3H2O 1.20 Cr3� � 3e� 88n Cr �0.73Br2 � 2e� 88n 2Br� 1.09 Zn2� � 2e� 88n Zn �0.76VO2

� � 2H� � e� 88n VO2� � H2O 1.00 2H2O � 2e� 88n H2 � 2OH� �0.83AuCl4

� � 3e� 88n Au � 4Cl� 0.99 Mn2� � 2e� 88n Mn �1.18NO3

� � 4H� � 3e� 88n NO � 2H2O 0.96 Al3� � 3e� 88n Al �1.66ClO2 � e� 88n ClO2

� 0.954 H2 � 2e� 88n 2H� �2.232Hg2� � 2e� 88n Hg2

2� 0.91 Mg2� � 2e� 88n Mg �2.37Ag� � e� 88n Ag 0.80 La3� � 3e� 88n La �2.37Hg2

2� � 2e� 88n 2Hg 0.80 Na� � e� 88n Na �2.71Fe3� � e� 88n Fe2� 0.77 Ca2� � 2e� 88n Ca �2.76O2 � 2H� � 2e� 88n H2O2 0.68 Ba2� � 2e� 88n Ba �2.90MnO4

� � e� 88n MnO42� 0.56 K� � e� 88n K �2.92

I2 � 2e� 88n 2I� 0.54 Li� � e� 88n Li �3.05Cu� � e� 88n Cu 0.52



Licensed to:

Note to the Student: The Glossary includes brief definitions ofsome of the fundamental terms used in chemistry. It does notinclude complex concepts that require detailed explanation forunderstanding. Please refer to the appropriate sections of thetext for complete discussion of particular topics or concepts.

Accuracy: the agreement of a particular value with the truevalue. (A1.5)

Acid: a substance that produces hydrogen ions in solution;a proton donor. (4.2)

Acid–base indicator: a substance that marks the endpoint ofan acid–base titration by changing color. (8.6)

Acid dissociation constant (Ka): the equilibrium constant fora reaction in which a proton is removed from an acid byH2O to form the conjugate base and H3O�. (7.1)

Acid rain: a result of air pollution by sulfur dioxide. (5.11)Actinide series: a group of 14 elements following actinium

in the periodic table, in which the 5f orbitals are beingfilled. (12.13; 18.1)

Activated complex (transition state): the arrangement of atomsfound at the top of the potential energy barrier as a re-action proceeds from reactants to products. (15.8)

Activation energy: the threshold energy that must be over-come to produce a chemical reaction. (15.8)

Addition polymerization: a type of polymerization in whichthe monomers simply add together to form the polymer,with no other products. (21.5)

Addition reaction: a reaction in which atoms add to acarbon–carbon multiple bond. (21.2)

Adiabatic process: a process that occurs without the trans-fer of energy as heat. (10.14)

Adsorption: the collection of one substance on the surfaceof another. (15.9)

Air pollution: contamination of the atmosphere, mainly bythe gaseous products of transportation and production ofelectricity. (5.11)

Alcohol: an organic compound in which the hydroxyl groupis a substituent on a hydrocarbon. (21.4)

Aldehyde: an organic compound containing the carbonylgroup bonded to at least one hydrogen atom. (21.4)

Alkali metal: a Group 1A metal. (2.8; 18.2)Alkaline earth metal: a Group 2A metal. (2.8; 18.4)Alkane: a saturated hydrocarbon with the general formula

CnH2n�2. (21.1)Alkene: an unsaturated hydrocarbon containing a carbon–

carbon double bond. The general formula is CnH2n. (21.2)Alkyne: an unsaturated hydrocarbon containing a triple

carbon–carbon bond. The general formula is CnH2n�2.(21.2)

Alloy: a substance that contains a mixture of elements andhas metallic properties. (16.4)

Alloy steel: a form of steel containing carbon plus other met-als such as chromium, cobalt, manganese, and molybde-num. (19.2)

Alpha (�) particle: a helium nucleus. (20.1)Alpha-particle production: a common mode of decay for ra-

dioactive nuclides in which the mass number changes.(20.1)

Amine: an organic base derived from ammonia in which oneor more of the hydrogen atoms are replaced by organicgroups. (7.6; 21.4)

�-Amino acid: an organic acid in which an amino group andan R group are attached to the carbon atom next to thecarboxyl group. (21.6)

Amorphous solid: a solid with considerable disorder in itsstructure. (16.3)

Ampere: the unit of electric current equal to one coulombof charge per second. (11.7)

Amphoteric substance: a substance that can behave either asan acid or as a base. (7.2)

Angular momentum quantum number (�): the quantumnumber relating to the shape of an atomic orbital, whichcan assume any integral value from 0 to n � 1 for eachvalue of n. (12.9)

Anion: a negative ion. (2.7)Anode: the electrode in a galvanic cell at which oxidation

occurs. (11.1)Antibonding molecular orbital: an orbital higher in energy

than the atomic orbitals of which it is composed. (14.2)Aqueous solution: a solution in which water is the dissolv-

ing medium or solvent. (4)Aromatic hydrocarbon: one of a special class of cyclic un-

saturated hydrocarbons, the simplest of which is benzene.(21.3)

Arrhenius concept: a concept postulating that acids producehydrogen ions in aqueous solution, whereas bases pro-duce hydroxide ions. (7.1)

Arrhenius equation: the equation representing the rate con-stant as k � Ae�Ea/RT where A represents the product ofthe collision frequency and the steric factor, and e�Ea/RT

is the fraction of collisions with sufficient energy to pro-duce a reaction. (15.8)

Atmosphere: the mixture of gases that surrounds the earth’ssurface. (5.11)

Atomic mass (average): the weighted average mass of theatoms in a naturally occurring element. (2.3)

Atomic number: the number of protons in the nucleus of anatom. (2.6)

Glossary

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A28 Glossary

Atomic radius: half the distance between the nuclei in a mol-ecule consisting of identical atoms. (12.15)

Atomic solid: a solid that contains atoms at the lattice points.(16.3)

Aufbau principle: the principle stating that as protons areadded one by one to the nucleus to build up the elements,electrons are similarly added to hydrogenlike orbitals.(12.13)

Autoionization: the transfer of a proton from one moleculeto another of the same substance. (7.2)

Avogadro’s law: equal volumes of gases at the same temper-ature and pressure contain the same number of particles.(5.2)

Avogadro’s number: the number of atoms in exactly 12 gramsof pure 12C, equal to 6.022 � 1023. (3.2)

Ball-and-stick model: a molecular model that distorts thesizes of atoms, but shows bond relationships clearly. (2.7)

Band model: a molecular model for metals in which the elec-trons are assumed to travel around the metal crystal inmolecular orbitals formed from the valence atomic or-bitals of the metal atoms. (16.4)

Barometer: a device for measuring atmospheric pressure. (5.1)Base: a substance that produces hydroxide ions in aqueous

solution, a proton acceptor. (7.2)Base dissociation constant (Kb): the equilibrium constant for

the reaction of a base with water to produce the conju-gate acid and hydroxide ion. (7.6)

Basic oxide: an ionic oxide that dissolves in water to pro-duce a basic solution. (18.4)

Battery: a group of galvanic cells connected in series. (11.5)Beta (�) particle: an electron produced in radioactive decay.

(20.1)Beta-particle production: a decay process for radioactive nu-

clides in which the mass number remains constant andthe atomic number changes. The net effect is to changea neutron to a proton. (20.1)

Bidentate ligand: a ligand that can form two bonds to ametal ion. (19.3)

Bimolecular step: a reaction involving the collision of twomolecules. (15.6)

Binary compound: a two-element compound. (2.9)Binding energy (nuclear): the energy required to decompose

a nucleus into its component nucleons. (20.5)Biomolecule: a molecule responsible for maintaining and/or

reproducing life. (22)Bond energy: the energy required to break a given chemical

bond. (13.1)Bond length: the distance between the nuclei of the two

atoms connected by a bond; the distance where the totalenergy of a diatomic molecule is minimal. (13.1)

Bond order: the difference between the number of bondingelectrons and the number of antibonding electrons, di-vided by two. It is an index of bond strength. (14.2)

Bonding molecular orbital: an orbital lower in energy thanthe atomic orbitals of which it is composed. (14.2)

Bonding pair: an electron pair found in the space betweentwo atoms. (13.9)

Borane: a covalent hydride of boron. (18.5)Boyle’s law: the volume of a given sample of gas at constant

temperature varies inversely with the pressure. (5.2)Breeder reactor: a nuclear reactor in which fissionable fuel

is produced while the reactor runs. (20.6)Brønsted–Lowry definition (model): a model proposing that

an acid is a proton donor, and a base is a proton accep-tor. (7.1)

Buffer capacity: the ability of a buffered solution to absorbprotons or hydroxide ions without a significant changein pH; determined by the magnitudes of [HA] and [A�]in the solution. (8.4)

Buffered solution: a solution that resists a change in its pHwhen either hydroxide ions or protons are added. (8.2)

Calorimetry: the science of measuring heat flow. (9.4)Capillary action: the spontaneous rising of a liquid in a nar-

row tube. (16.2)Carbohydrate: a polyhydroxyl ketone or polyhydroxyl alde-

hyde or a polymer composed of these. (21.6)Carboxyhemoglobin: a stable complex of hemoglobin and

carbon monoxide that prevents normal oxygen uptake inthe blood. (19.8)

Carboxyl group: the OCOOH group in an organic acid.(7.2; 21.4)

Carboxylic acid: an organic compound containing the car-boxyl group; an acid with the general formula RCOOH.(21.4)

Catalyst: a substance that speeds up a reaction without be-ing consumed. (15.9)

Cathode: the electrode in a galvanic cell at which reductionoccurs. (11.1)

Cathode rays: the “rays” emanating from the negative elec-trode (cathode) in a partially evacuated tube; a stream ofelectrons. (2.5)

Cathodic protection: a method in which an active metal,such as magnesium, is connected to steel to protect it fromcorrosion. (11.6)

Cation: a positive ion. (2.7)Cell potential (electromotive force): the driving force in a

galvanic cell that pulls electrons from the reducing agentin one compartment to the oxidizing agent in the other.(11.1)

Ceramic: a nonmetallic material made from clay and hard-ened by firing at high temperature; it contains minutesilicate crystals suspended in a glassy cement. (16.5)

Chain reaction (nuclear): a self-sustaining fission processcaused by the production of neutrons that proceed to splitother nuclei. (20.6)

Charge balance: the positive and negative charges carried bythe ions in an aqueous solution must balance. (7.9)

Charles’s law: the volume of a given sample of gas at con-stant pressure is directly proportional to the temperaturein kelvins. (5.2)



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Glossary A29

Chelating ligand (chelate): a ligand having more than oneatom with a lone pair that can be used to bond to a metalion. (19.3)

Chemical bond: the energy that holds two atoms together ina compound. (2.7)

Chemical equation: a representation of a chemical reactionshowing the relative numbers of reactant and productmolecules. (3.6)

Chemical equilibrium: a dynamic reaction system in whichthe concentrations of all reactants and products remainconstant as a function of time. (6)

Chemical formula: the representation of a molecule in whichthe symbols for the elements are used to indicate the typesof atoms present and subscripts are used to show therelative numbers of atoms. (2.7)

Chemical kinetics: the area of chemistry that concerns reac-tion rates. (15)

Chemical stoichiometry: the calculation of the quantities ofmaterial consumed and produced in chemical reactions. (3)

Chirality: the quality of having nonsuperimposable mirrorimages. (19.4)

Chlor-alkali process: the process for producing chlorine andsodium hydroxide by electrolyzing brine in a mercury cell.(11.8)

Coagulation: the destruction of a colloid by causing parti-cles to aggregate and settle out. (17.8)

Codons: organic bases in sets of three that form the geneticcode. (21.6)

Colligative properties: properties of a solution that depend onthe number, and not on the identity, of the solute particles.(17.5)

Collision model: a model based on the idea that moleculesmust collide to react; used to account for the observedcharacteristics of reaction rates. (15.8)

Colloid: a suspension of particles in a dispersing medium.(17.8)

Combustion reaction: the vigorous and exothermic reactionthat takes place between certain substances, particularlyorganic compounds, and oxygen. (21.1)

Common ion effect: the shift in an equilibrium positioncaused by the addition or presence of an ion involved inthe equilibrium reaction. (8.1)

Complete ionic equation: an equation that shows all sub-stances that are strong electrolytes as ions. (4.6)

Complex ion: a charged species consisting of a metal ion sur-rounded by ligands. (8.9; 19.1)

Compound: a substance with constant composition that canbe broken down into elements by chemical processes. (2.7)

Concentration cell: a galvanic cell in which both compart-ments contain the same components, but at different con-centrations. (11.4)

Condensation: the process by which vapor molecules re-form a liquid. (16.10)

Condensation polymerization: a type of polymerization inwhich the formation of a small molecule, such as water,accompanies the extension of the polymer chain. (21.5)

Condensed states of matter: liquids and solids. (16.1)Conduction bands: the molecular orbitals that can be occu-

pied by mobile electrons, which are free to travel through-out a metal crystal to conduct electricity or heat. (16.4)

Conjugate acid: the species formed when a proton is addedto a base. (7.1)

Conjugate acid–base pair: two species related to each otherby the donating and accepting of a single proton. (7.1)

Conjugate base: what remains of an acid molecule after aproton is lost. (7.1)

Continuous spectrum: a spectrum that exhibits all the wave-lengths of visible light. (12.3)

Control rods: rods in a nuclear reactor composed of sub-stances that absorb neutrons. These rods regulate thepower level of the reactor. (20.6)

Coordinate covalent bond: a metal–ligand bond resultingfrom the interaction of a Lewis base (the ligand) and aLewis acid (the metal ion). (19.3)

Coordination compound: a compound composed of a com-plex ion and counter ions sufficient to give no net charge.(19.3)

Coordination isomerism: isomerism in a coordination com-pound in which the composition of the coordinationsphere of the metal ion varies. (19.4)

Coordination number: the number of bonds formed betweenthe metal ion and the ligands in a complex ion. (19.3)

Copolymer: a polymer formed from the polymerization ofmore than one type of monomer. (21.5)

Core electron: an inner electron in an atom; one not in theoutermost (valence) principal quantum level. (12.13)

Corrosion: the process by which metals are oxidized in theatmosphere. (11.6)

Coulomb’s law: E � 2.31 � 10�19 (Q1Q2/r), where E is theenergy of interaction between a pair of ions, expressed injoules; r is the distance between the ion centers in nm;and Q1 and Q2 are the numerical ion charges. (13.1)

Counter ions: anions or cations that balance the charge onthe complex ion in a coordination compound. (19.3)

Covalent bonding: a type of bonding in which electrons areshared by atoms. (2.7; 13.1)

Critical mass: the mass of fissionable material required toproduce a self-sustaining chain reaction. (20.6)

Critical point: the point on a phase diagram at which thetemperature and pressure have their critical values; theendpoint of the liquid–vapor line. (16.11)

Critical pressure: the minimum pressure required to produceliquefaction of a substance at the critical temperature.(16.11)

Critical reaction (nuclear): a reaction in which exactly oneneutron from each fission event causes another fissionevent, thus sustaining the chain reaction. (20.6)

Critical temperature: the temperature above which vaporcannot be liquefied, no matter what pressure is applied.(16.11)

Crosslinking: the existence of bonds between adjacent chainsin a polymer, thus adding strength to the material. (21.5)



Licensed to:

A30 Glossary

Crystal field model: a model used to explain the magnetismand colors of coordination complexes through the split-ting of the d orbital energies. (19.6)

Crystalline solid: a solid with a regular arrangement of itscomponents. (16.3)

Cubic closest packed (ccp) structure: a solid modeled by theclosest packing of spheres with an abcabc arrangementof layers; the unit cell is face-centered cubic. (16.4)

Cyclotron: a type of particle accelerator in which an ion in-troduced at the center is accelerated in an expanding spi-ral path by use of alternating electric fields in the presenceof a magnetic field. (20.3)

Cytochromes: a series of iron-containing species composed ofheme and a protein. Cytochromes are the principal electron-transfer molecules in the respiratory chain. (19.8)

Dalton’s law of partial pressures: for a mixture of gases ina container, the total pressure exerted is the sum of thepressures that each gas would exert if it were alone. (5.5)

Degenerate orbitals: a group of orbitals with the same en-ergy. (12.9)

Dehydrogenation reaction: a reaction in which two hydro-gen atoms are removed from adjacent carbons of a satu-rated hydrocarbon, giving an unsaturated hydrocarbon.(21.1)

Delocalization: the condition where the electrons in a mole-cule are not localized between a pair of atoms but canmove throughout the molecule. (13.9)

Denaturation: the breaking down of the three-dimensionalstructure of a protein resulting in the loss of its function.(21.6)

Denitrification: the return of nitrogen from decomposedmatter to the atmosphere by bacteria that change nitratesto nitrogen gas. (18.8)

Deoxyribonucleic acid (DNA): a huge nucleotide polymerhaving a double-helical structure with complementarybases on the two strands. Its major functions are pro-tein synthesis and the storage and transport of geneticinformation. (21.6)

Desalination: the removal of dissolved salts from an aque-ous solution. (17.6)

Dialysis: a phenomenon in which a semipermeable mem-brane allows transfer of both solvent molecules and smallsolute molecules and ions. (17.6)

Diamagnetism: a type of magnetism, associated with pairedelectrons, that causes a substance to be repelled from theinducing magnetic field. (14.3)

Differential rate law: an expression that gives the rate of areaction as a function of concentrations; often called therate law. (15.2)

Diffraction: the scattering of light from a regular array ofpoints or lines, producing constructive and destructive in-terference. (12.2)

Diffusion: the mixture of gases. (5.7)Dilution: the process of adding solvent to lower the con-

centration of solute in a solution. (4.3)

Dimer: a molecule formed by the joining of two identicalmonomers. (21.5)

Dipole–dipole attraction: the attractive force resulting whenpolar molecules line up so that the positive and negativeends are close to each other. (16.1)

Dipole moment: a property of a molecule whose charge dis-tribution can be represented by a center of positive chargeand a center of negative charge. (13.3)

Disaccharide: a sugar formed from two monosaccharidesjoined by a glycoside linkage. (21.6)

Disproportionation reaction: a reaction in which a given el-ement is both oxidized and reduced. (18.13)

Disulfide linkage: a SOS bond that stabilizes the tertiarystructure of many proteins. (21.6)

Double bond: a bond in which two pairs of electrons areshared by two atoms. (13.8)

Downs cell: a cell used for electrolyzing molten sodium chlo-ride. (11.8)

Dry cell battery: a common battery used in calculators,watches, radios, and portable audio players. (11.5)

Dual nature of light: the statement that light exhibits bothwave and particulate properties. (12.2)

E � mc2: Einstein’s equation proposing that energy has mass;E is energy, m is mass, and c is the speed of light. (12.2)

Effective nuclear charge: the apparent nuclear charge exertedon a particular electron, equal to the actual nuclear chargeminus the effect of electron repulsions. (12.11)

Effusion: the passage of a gas through a tiny orifice into anevacuated chamber. (5.7)

Electrical conductivity: the ability to conduct an electric cur-rent. (4.2)

Electrochemistry: the study of the interchange of chemicaland electrical energy. (11)

Electrolysis: a process that involves forcing a current througha cell to cause a nonspontaneous chemical reaction tooccur. (11.7)

Electrolyte: a material that dissolves in water to give a so-lution that conducts an electric current. (4.2)

Electrolytic cell: a cell that uses electrical energy to producea chemical change that would otherwise not occur spon-taneously. (11.7)

Electromagnetic radiation: radiant energy that exhibitswavelike behavior and travels through space at the speedof light in a vacuum. (12.1)

Electron: a negatively charged particle that moves aroundthe nucleus of an atom. (2.5)

Electron affinity: the energy change associated with the ad-dition of an electron to a gaseous atom. (12.15)

Electron capture: a process in which one of the inner-orbitalelectrons in an atom is captured by the nucleus. (20.1)

Electron sea model: a model for metals postulating a regu-lar array of cations in a “sea” of electrons. (16.4)

Electron spin quantum number: a quantum number repre-senting one of the two possible values for the electronspin; either ��

12

� or ��12

�. (12.10)



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Glossary A31

Electronegativity: the tendency of an atom in a molecule toattract shared electrons to itself. (13.2)

Element: a substance that cannot be decomposed into sim-pler substances by chemical or physical means. (2.1)

Elementary step: a reaction whose rate law can be writtenfrom its molecularity. (15.6)

Empirical formula: the simplest whole number ratio ofatoms in a compound. (3.5)

Enantiomers: isomers that are nonsuperimposable mirrorimages of each other. (19.4)

Endpoint: the point in a titration at which the indicatorchanges color. (4.9)

Endothermic: refers to a reaction where energy (as heat)flows into the system. (9.1)

Energy: the capacity to do work or to cause heat flow. (9.1)Enthalpy: a property of a system equal to E � PV, where E

is the internal energy of the system, P is the pressure ofthe system, and V is the volume of the system. At con-stant pressure, where only PV work is allowed, the changein enthalpy equals the energy flow as heat. (9.2)

Enthalpy of fusion: the enthalpy change that occurs to melta solid at its melting point. (16.10)

Entropy: a thermodynamic function that measures random-ness or disorder. (10.1)

Enzyme: a large molecule, usually a protein, that catalyzesbiological reactions. (15.9)

Equilibrium (thermodynamic definition): the position wherethe free energy of a reaction system has its lowest possi-ble value. (10.11)

Equilibrium constant: the value obtained when equilibriumconcentrations of the chemical species are substituted inthe equilibrium expression. (6.2)

Equilibrium expression: the expression (from the law ofmass action) obtained by multiplying the product con-centrations and dividing by the multiplied reactant con-centrations, with each concentration raised to a powerrepresented by the coefficient in the balanced equation.(6.2)

Equilibrium position: a particular set of equilibrium con-centrations. (6.2)

Equivalence point (stoichiometric point): the point in a titra-tion when enough titrant has been added to react exactlywith the substance in solution being titrated. (4.9; 8.4)

Exothermic: refers to a reaction where energy (as heat) flowsout of the system. (9.1)

Exponential notation: expresses a number as N � 10M, aconvenient method for representing a very large or verysmall number and for easily indicating the number of sig-nificant figures. (A1.1)

Faraday: a constant representing the charge on one mole ofelectrons; 96,485 coulombs. (11.3)

First law of thermodynamics: the energy of the universe isconstant; same as the law of conservation of energy. (9.1)

Fission: the process of using a neutron to split a heavy nu-cleus into two nuclei with smaller mass numbers. (20.6)

Formal charge: the charge assigned to an atom in a mole-cule or polyatomic ion derived from a specific set of rules.(13.12)

Formation constant (stability constant): the equilibrium con-stant for each step of the formation of a complex ion bythe addition of an individual ligand to a metal ion orcomplex ion in aqueous solution. (8.9)

Fossil fuel: coal, petroleum, or natural gas; consists of carbon-based molecules derived from decomposition of once-living organisms. (9.7)

Frasch process: the recovery of sulfur from underground de-posits by melting it with hot water and forcing it to thesurface by air pressure. (18.12)

Free energy: a thermodynamic function equal to the enthalpy(H) minus the product of the entropy (S) and the kelvintemperature (T); G � H � TS. Under certain conditionsthe change in free energy for a process is equal to themaximum useful work. (10.7)

Free radical: a species with an unpaired electron. (21.5)Frequency: the number of waves (cycles) per second that pass

a given point in space. (12.1)Fuel cell: a galvanic cell for which the reactants are contin-

uously supplied. (11.5)Functional group: an atom or group of atoms in hydrocar-

bon derivatives that contains elements in addition to car-bon and hydrogen. (21.4)

Fusion: the process of combining two light nuclei to form aheavier, more stable nucleus. (20.6)

Galvanic cell: a device in which chemical energy from a spon-taneous redox reaction is changed to electrical energy thatcan be used to do work. (11.1)

Galvanizing: a process in which steel is coated with zinc toprevent corrosion. (11.6)

Gamma (�) ray: a high-energy photon. (20.1)Geiger-Müller counter (Geiger counter): an instrument that

measures the rate of radioactive decay based on the ionsand electrons produced as a radioactive particle passesthrough a gas-filled chamber. (20.4)

Gene: a given segment of the DNA molecule that containsthe code for a specific protein. (21.6)

Geometrical (cis-trans) isomerism: isomerism in which atomsor groups of atoms can assume different positions arounda rigid ring or bond. (19.4; 21.2)

Glass: an amorphous solid obtained when silica is mixedwith other compounds, heated above its melting point,and then cooled rapidly. (16.5)

Glass electrode: an electrode for measuring pH from the po-tential difference that develops when it is dipped into anaqueous solution containing H� ions. (11.4)

Glycosidic linkage: a COOOC bond formed between therings of two cyclic monosaccharides by the elimination ofwater. (21.6)

Graham’s law of effusion: the rate of effusion of a gas is in-versely proportional to the square root of the mass of itsparticles. (5.7)



Licensed to:

A32 Glossary

Gravimetric analysis: a method for determining the amountof a given substance in a solution by precipitation, fil-tration, drying, and weighing. (4.8)

Greenhouse effect: a warming effect exerted by the earth’satmosphere (particularly CO2 and H2O) due to thermalenergy retained by absorption of infrared radiation. (9.7)

Ground state: the lowest possible energy state of an atom ormolecule. (12.4)

Group (of the periodic table): a vertical column of elementshaving the same valence electron configuration and show-ing similar properties. (2.8)

Haber process: the manufacture of ammonia from nitrogenand hydrogen, carried out at high pressure and high tem-perature with the aid of a catalyst. (3.9; 6.1; 18.8)

Half-life (of a radioactive sample): the time required for thenumber of nuclides in a radioactive sample to reach halfof the original value. (20.2)

Half-life (of a reaction): the time required for a reactant toreach half of its original concentration. (15.4)

Half-reactions: the two parts of an oxidation–reduction re-action, one representing oxidation, the other reduction.(4.11; 11.1)

Halogen: a Group 7A element. (2.8; 18.13)Halogenation: the addition of halogen atoms to unsaturated

hydrocarbons. (21.2)Hard water: water from natural sources that contains rela-

tively large concentrations of calcium and magnesiumions. (18.4)

Heat: energy transferred between two objects caused by atemperature difference between them. (9.1)

Heat capacity: the amount of energy required to raise thetemperature of an object by one degree Celsius. (9.4)

Heat of fusion: the enthalpy change that occurs to melt asolid at its melting point. (16.10)

Heat of hydration: the enthalpy change associated with plac-ing gaseous molecules or ions in water; the sum of theenergy needed to expand the solvent and the energy re-leased from the solvent–solute interactions. (17.2)

Heat of solution: the enthalpy change associated with dis-solving a solute in a solvent; the sum of the energiesneeded to expand both solvent and solute in a solutionand the energy released from the solvent–solute interac-tions. (17.2)

Heat of vaporization: the energy required to vaporize onemole of a liquid at a pressure of one atmosphere. (16.10)

Heating curve: a plot of temperature versus time for a sub-stance where energy is added at a constant rate. (16.10)

Heisenberg uncertainty principle: a principle stating thatthere is a fundamental limitation to how precisely boththe position and momentum of a particle can be knownat a given time. (12.5)

Heme: an iron complex. (19.8)Hemoglobin: a biomolecule composed of four myoglobin-

like units (proteins plus heme) that can bind and trans-port four oxygen molecules in the blood. (19.8)

Henderson–Hasselbalch equation: an equation giving the re-lationship between the pH of an acid–base system andthe concentrations of base and acid

pH � pKa � log� �. (8.2)

Henry’s law: the amount of a gas dissolved in a solution isdirectly proportional to the pressure of the gas above thesolution. (17.3)

Hess’s law: in going from a particular set of reactants to aparticular set of products, the enthalpy change is the samewhether the reaction takes place in one step or in a se-ries of steps; in summary, enthalpy is a state function.(9.5)

Heterogeneous equilibrium: an equilibrium involving reac-tants and/or products in more than one phase. (6.5)

Hexagonal closest packed (hcp) structure: a structure com-posed of closest packed spheres with an ababab arrange-ment of layers; the unit cell is hexagonal. (16.4)

Homogeneous equilibrium: an equilibrium system where allreactants and products are in the same phase. (6.5)

Homopolymer: a polymer formed from the polymerizationof only one type of monomer. (21.5)

Hund’s rule: the lowest-energy configuration for an atom isthe one having the maximum number of unpaired elec-trons allowed by the Pauli exclusion principle in a par-ticular set of degenerate orbitals, with all unpaired elec-trons having parallel spins. (12.13)

Hybrid orbitals: a set of atomic orbitals adopted by an atomin a molecule different from those of the atom in the freestate. (14.1)

Hybridization: a mixing of the native orbitals on a givenatom to form special atomic orbitals for bonding. (14.1)

Hydration: the interaction between solute particles and wa-ter molecules. (4.1)

Hydride: a binary compound containing hydrogen. The hy-dride ion, H�, exists in ionic hydrides. The three classesof hydrides are covalent, interstitial, and ionic. (18.3)

Hydrocarbon: a compound composed of carbon and hy-drogen. (23.1)

Hydrocarbon derivative: an organic molecule that containsone or more elements in addition to carbon and hydro-gen. (21.4)

Hydrogen bonding: unusually strong dipole–dipole attrac-tions that occur among molecules in which hydrogen isbonded to a highly electronegative atom. (16.1)

Hydrogenation reaction: a reaction in which hydrogen isadded, with a catalyst present, to a carbon–carbon mul-tiple bond. (21.2)

Hydrohalic acid: an aqueous solution of a hydrogen halide.(18.13)

Hydronium ion: the H3O� ion; a hydrated proton. (7.1)Hypothesis: one or more assumptions put forth to explain

the observed behavior of nature. (1.3)

Ideal gas: a gas that obeys the equation, PV � nRT. (5.2)

[base]�[acid]



Licensed to:

Glossary A33

Ideal gas law: an equation of state for a gas, where the stateof the gas is its condition at a given time; expressed byPV � nRT, where P � pressure, V � volume, n � molesof the gas, R � the universal gas constant, and T � ab-solute temperature. This equation expresses behavior ap-proached by real gases at high T and low P. (5.3)

Ideal solution: a solution whose vapor pressure is directlyproportional to the mole fraction of solvent present. (17.4)

Indicator: a chemical that changes color and is used to markthe endpoint of a titration. (4.9; 8.5)

Inert pair effect: the tendency for the heavier Group 3A el-ements to exhibit the �1 as well as the expected �3 ox-idation states, and Group 4A elements to exhibit the �2as well as the �4 oxidation states. (18.5)

Integrated rate law: an expression that shows the concen-tration of a reactant as a function of time. (15.2)

Intermediate: a species that is neither a reactant nor a productbut that is formed and consumed in the reaction sequence.(15.6)

Intermolecular forces: relatively weak interactions that oc-cur between molecules. (16.1)

Internal energy: a property of a system that can be changedby a flow of work, heat, or both; �E � q � w, where�E is the change in the internal energy of the system, qis heat, and w is work. (9.1)

Ion: an atom or a group of atoms that has a net positive ornegative charge. (2.7)

Ion exchange (water softening): the process in which an ion-exchange resin removes unwanted ions (for example,Ca2� and Mg2�) and replaces them with Na� ions, whichdo not interfere with soap and detergent action. (18.4)

Ion pairing: a phenomenon occurring in solution when op-positely charged ions aggregate and behave as a singleparticle. (17.7)

Ion-product constant (Kw): the equilibrium constant for theautoionization of water; Kw � [H�][OH�]. At 25�C, Kw

equals 1.0 � 10�14. (7.2)Ion-selective electrode: an electrode sensitive to the concen-

tration of a particular ion in solution. (11.4)Ionic bonding: the electrostatic attraction between oppo-

sitely charged ions. (2.7; 13.1)Ionic compound (binary): a compound that results when a

metal reacts with a nonmetal to form a cation and an an-ion. (13.1)

Ionic solid: a solid containing cations and anions that dis-solves in water to give a solution containing the separatedions, which are mobile and thus free to conduct electriccurrent. (16.3)

Ionization energy: the quantity of energy required to removean electron from a gaseous atom or ion. (12.15)

Irreversible process: any real process. When a system un-dergoes the changes State 1 → State 2 → State 1 by anyreal pathway, the universe is different than before thecyclic process took place in the system. (10.2)

Isoelectronic ions: ions containing the same number of elec-trons. (13.4)

Isomers: species with the same formula but different prop-erties. (19.4)

Isothermal process: a process in which the temperature re-mains constant. (10.2)

Isotonic solutions: solutions having identical osmotic pres-sures. (17.6)

Isotopes: atoms of the same element (the same number ofprotons) with different numbers of neutrons. They haveidentical atomic numbers but different mass numbers.(2.6)

Ketone: an organic compound containing the carbonyl group

bonded to two carbon atoms. (21.4)Kinetic energy (�

12

� mv2): energy resulting from the motion ofan object; dependent on the mass of the object and thesquare of its velocity. (9.1)

Kinetic molecular theory: a model that assumes that an idealgas is composed of tiny particles (molecules) in constantmotion. (5.6)

Lanthanide contraction: the decrease in the atomic radii ofthe lanthanide series elements, going from left to right inthe periodic table. (19.1)

Lanthanide series: a group of 14 elements following lan-thanum in the periodic table, in which the 4f orbitals arebeing filled. (12.13; 18.1; 19.1)

Lattice: a three-dimensional system of points designating thepositions of the centers of the components of a solid(atoms, ions, or molecules). (16.3)

Lattice energy: the energy change occurring when separatedgaseous ions are packed together to form an ionic solid.(13.5)

Law of conservation of energy: energy can be converted fromone form to another but can be neither created nor de-stroyed. (9.1)

Law of conservation of mass: mass is neither created nor de-stroyed. (2.2)

Law of definite proportion: a given compound always con-tains exactly the same proportion of elements by mass.(2.2)

Law of mass action: a general description of the equilib-rium condition; it defines the equilibrium constant ex-pression. (6.2)

Law of multiple proportions: when two elements form aseries of compounds, the ratios of the masses of the sec-ond element that combine with one gram of the first el-ement can always be reduced to small whole numbers.(2.2)

Lead storage battery: a battery (used in cars) in which theanode is lead, the cathode is lead coated with lead diox-ide, and the electrolyte is a sulfuric acid solution. (11.5)

B

G DC

O��



Licensed to:

A34 Glossary

Le Châtelier’s principle: if a change is imposed on a systemat equilibrium, the position of the equilibrium will shiftin a direction that tends to reduce the effect of that change.(6.8)

Lewis acid: an electron-pair acceptor. (19.3)Lewis base: an electron-pair donor. (19.3)Lewis structure: a diagram of a molecule showing how the

valence electrons are arranged among the atoms in themolecule. (13.10)

Ligand: a neutral molecule or ion having a lone pair of elec-trons that can be used to form a bond to a metal ion; aLewis base. (19.3)

Lime-soda process: a water-softening method in which limeand soda ash are added to water to remove calcium andmagnesium ions by precipitation. (7.6)

Limiting reactant (limiting reagent): the reactant that is com-pletely consumed when a reaction is run to completion.(3.9)

Line spectrum: a spectrum showing only certain discretewavelengths. (12.3)

Linear accelerator: a type of particle accelerator in which achanging electric field is used to accelerate a positive ionalong a linear path. (20.3)

Linkage isomerism: isomerism involving a complex ion wherethe ligands are all the same but the point of attachmentof at least one of the ligands differs. (19.4)

Liquefaction: the transformation of a gas into a liquid.(18.1)

Localized electron (LE) model: a model that assumes that amolecule is composed of atoms that are bound togetherby sharing pairs of electrons using the atomic orbitals ofthe bound atoms. (13.9)

London dispersion forces: the forces, existing among noblegas atoms and nonpolar molecules, that involve an acci-dental dipole that induces a momentary dipole in a neigh-bor. (16.1)

Lone pair: an electron pair that is localized on a given atom;an electron pair not involved in bonding. (13.9)

Magnetic quantum number (m�): the quantum number re-lating to the orientation of an orbital in space relative tothe other orbitals with the same � quantum number. Itcan have integral values between � and ��, includingzero. (12.9)

Main-group (representative) elements: elements in thegroups labeled 1A, 2A, 3A, 4A, 5A, 6A, 7A, and 8A inthe periodic table. The group number gives the sum ofvalence s and p electrons. (12.13; 18.1)

Major species: the components present in relatively largeamounts in a solution. (7.4)

Manometer: a device for measuring the pressure of a gas ina container. (5.1)

Mass defect: the change in mass occurring when a nucleusis formed from its component nucleons. (20.5)

Mass number: the total number of protons and neutrons inthe atomic nucleus of an atom. (2.6)

Mass percent: the percent by mass of a component of a mix-ture (17.1) or of a given element in a compound. (3.4)

Mass spectrometer: an instrument used to determine the rel-ative masses of atoms by the deflection of their ions in amagnetic field. (3.1)

Matter: the material of the universe.Mean free path: the average distance a molecule in a given

gas sample travels between collisions with other mole-cules. (5.6; 5.9)

Measurement: a quantitative observation. (A1.5)Messenger RNA (mRNA): a special RNA molecule built in

the cell nucleus that migrates into the cytoplasm and par-ticipates in protein synthesis. (21.6)

Metal: an element that gives up electrons relatively easilyand is lustrous, malleable, and a good conductor of heatand electricity. (2.8)

Metalloids (semimetals): elements along the division line inthe periodic table between metals and nonmetals. Theseelements exhibit both metallic and nonmetallic proper-ties. (12.16; 18.1)

Metallurgy: the process of separating a metal from its oreand preparing it for use. (18.1)

Millimeters of mercury (mm Hg): a unit of pressure, alsocalled a torr; 760 mm Hg � 760 torr � 101,325 Pa �1 standard atmosphere. (5.1)

Mixture: a material of variable composition that containstwo or more substances.

Model (theory): a set of assumptions put forth to explainthe observed behavior of matter. The models of chemistryusually involve assumptions about the behavior of indi-vidual atoms or molecules. (1.3)

Moderator: a substance used in a nuclear reactor to slowdown the neutrons. (20.6)

Molal boiling-point elevation constant: a constant charac-teristic of a particular solvent that gives the change inboiling point as a function of solution molality; used inmolecular weight determinations. (17.5)

Molal freezing-point depression constant: a constant charac-teristic of a particular solvent that gives the change infreezing point as a function of the solution molality; usedin molecular weight determinations. (17.5)

Molality: the number of moles of solute per kilogram of sol-vent in a solution. (17.1)

Molar heat capacity: the energy required to raise the tem-perature of one mole of a substance by one degree Cel-sius. (9.3; 9.4)

Molar mass: the mass in grams of one mole of molecules orformula units of a substance; also called molecularweight. (3.3)

Molar volume: the volume of one mole of an ideal gas; equalto 22.42 liters at STP. (5.4)

Molarity: moles of solute per volume of solution in liters.(4.3; 17.1)

Mole (mol): the number equal to the number of carbonatoms in exactly 12 grams of pure 12C; Avogadro’s num-ber. One mole represents 6.022 � 1023 units. (3.2)



Licensed to:

Glossary A35

Mole fraction: the ratio of the number of moles of a givencomponent in a mixture to the total number of moles inthe mixture. (5.5; 17.1)

Mole ratio (stoichiometry): the ratio of moles of one sub-stance to moles of another substance in a balanced chem-ical equation. (3.8)

Molecular equation: an equation representing a reaction insolution showing the reactants and products in undisso-ciated form, whether they are strong or weak electrolytes.(4.6)

Molecular formula: the exact formula of a molecule, givingthe types of atoms and the number of each type. (3.5)

Molecular orbital (MO) model: a model that regards a mol-ecule as a collection of nuclei and electrons, where theelectrons are assumed to occupy orbitals much as they doin atoms, but having the orbitals extend over the entiremolecule. In this model the electrons are assumed to bedelocalized rather than always located between a givenpair of atoms. (14.2)

Molecular orientations (kinetics): orientations of moleculesduring collisions, some of which can lead to a reactionand some of which cannot. (15.8)

Molecular solid: a solid composed of neutral molecules atthe lattice points. (16.3)

Molecular structure: the three-dimensional arrangement ofatoms in a molecule. (13.13)

Molecular weight: the mass in grams of one mole of mole-cules or formula units of a substance; also called molarmass. (3.3)

Molecularity: the number of species that must collide to pro-duce the reaction represented by an elementary step in areaction mechanism. (15.6)

Molecule: a bonded collection of two or more atoms of thesame or different elements. (2.7)

Monodentate (unidentate) ligand: a ligand that can form onebond to a metal ion. (19.3)

Monoprotic acid: an acid with one acidic proton. (7.2)Monosaccharide (simple sugar): a polyhydroxy ketone or alde-

hyde containing from three to nine carbon atoms. (21.6)Myoglobin: an oxygen-storing biomolecule consisting of a

heme complex and a protein. (19.8)

Natural law: a statement that expresses generally observedbehavior. (1.3)

Nernst equation: an equation relating the potential of an elec-trochemical cell to the concentrations of the cell compo-nents

� � �° � log(Q) at 25°C. (11.4)

Net ionic equation: an equation for a reaction in solution,where strong electrolytes are written as ions, showingonly those components that are directly involved in thechemical change. (4.6)

Network solid: an atomic solid containing strong directionalcovalent bonds. (16.5)

0.0591�

n

Neutralization reaction: an acid–base reaction. (4.9)Neutron: a particle in the atomic nucleus with mass virtu-

ally equal to the proton’s but with no charge. (2.6)Nitrogen cycle: the conversion of N2 to nitrogen-containing

compounds, followed by the return of nitrogen gas to theatmosphere by natural decay processes. (18.8)

Nitrogen fixation: the process of transforming N2 to nitrogen-containing compounds useful to plants. (18.8)

Nitrogen-fixing bacteria: bacteria in the root nodules ofplants that can convert atmospheric nitrogen to ammo-nia and other nitrogen-containing compounds useful toplants. (18.8)

Noble gas: a Group 8A element. (2.8; 18.14)Node: an area of an orbital having zero electron probability.

(12.9)Nonelectrolyte: a substance that, when dissolved in water,

gives a nonconducting solution. (4.2)Nonmetal: an element not exhibiting metallic characteris-

tics. Chemically, a typical nonmetal accepts electronsfrom a metal. (2.8)

Normal boiling point: the temperature at which the vaporpressure of a liquid is exactly one atmosphere. (16.10)

Normal melting point: the temperature at which the solidand liquid states have the same vapor pressure under con-ditions where the total pressure on the system is one at-mosphere. (16.10)

Normality: the number of equivalents of a substance dis-solved in a liter of solution. (17.1)

Nuclear atom: an atom having a dense center of positivecharge (the nucleus) with electrons moving around theoutside. (2.5)

Nuclear transformation: the change of one element into an-other. (20.3)

Nucleon: a particle in an atomic nucleus, either a neutronor a proton. (2.6)

Nucleotide: a monomer of the nucleic acids composed of afive-carbon sugar, a nitrogen-containing base, and phos-phoric acid. (21.6)

Nucleus: the small, dense center of positive charge in anatom. (2.5)

Nuclide: the general term applied to each unique atom; rep-resented by A

ZX, where X is the symbol for a particularelement. (20.2)

Octet rule: the observation that atoms of nonmetals tend toform the most stable molecules when they are surroundedby eight electrons (to fill their valence orbitals). (13.10)

Optical isomerism: isomerism in which the isomers have op-posite effects on plane-polarized light. (19.4)

Orbital: a specific wave function for an electron in an atom.The square of this function gives the probability distrib-ution for the electron. (12.5)

d-Orbital splitting: a splitting of the d orbitals of the metalion in a complex such that the orbitals pointing at theligands have higher energies than those pointing betweenthe ligands. (19.6)



Licensed to:

A36 Glossary

Order (of reactant): the positive or negative exponent, de-termined by experiment, of the reactant concentration ina rate law. (15.2)

Organic acid: an acid with a carbon-atom backbone; oftencontains the carboxyl group. (7.2)

Organic chemistry: the study of carbon-containing com-pounds (typically chains of carbon atoms) and their prop-erties. (21)

Osmosis: the flow of solvent into a solution through a semi-permeable membrane. (17.6)

Osmotic pressure (�): the pressure that must be applied toa solution to stop osmosis; � MRT. (17.6)

Ostwald process: a commercial process for producing nitricacid by the oxidation of ammonia. (18.8)

Oxidation: an increase in oxidation state (a loss of electrons).(4.10; 11.1)

Oxidation–reduction (redox) reaction: a reaction in whichone or more electrons are transferred. (4.4; 4.10; 11.1)

Oxidation states: a concept that provides a way to keep trackof electrons in oxidation–reduction reactions accordingto certain rules. (4.10)

Oxidizing agent (electron acceptor): a reactant that acceptselectrons from another reactant. (4.10; 11.1)

Oxyacid: an acid in which the acidic proton is attached toan oxygen atom. (7.2)

Ozone: O3, the form of elemental oxygen in addition to themuch more common O2. (18.11)

Paramagnetism: a type of induced magnetism, associatedwith unpaired electrons, that causes a substance to be at-tracted into the inducing magnetic field. (14.3)

Partial pressures: the independent pressures exerted by dif-ferent gases in a mixture. (5.5)

Particle accelerator: a device used to accelerate nuclear par-ticles to very high speeds. (20.3)

Pascal: the SI unit of pressure; equal to newtons per metersquared. (5.1)

Pauli exclusion principle: in a given atom no two electronscan have the same set of four quantum numbers. (12.10)

Penetration effect: the effect whereby a valence electron pen-etrates the core electrons, thus reducing the shielding ef-fect and increasing the effective nuclear charge. (12.14)

Peptide linkage: the bond resulting from the condensationreaction between amino acids; represented by

(22.6)

Percent dissociation: the ratio of the amount of a substancethat is dissociated at equilibrium to the initial concentra-tion of the substance in a solution, multiplied by 100.(7.5)

Percent yield: the actual yield of a product as a percentageof the theoretical yield. (3.9)

Periodic table: a chart showing all the elements arranged incolumns with similar chemical properties. (2.8)

AON

BO

C

H

OO

pH curve (titration curve): a plot showing the pH of a so-lution being analyzed as a function of the amount oftitrant added. (8.5)

pH scale: a log scale based on 10 and equal to �log[H�]; aconvenient way to represent solution acidity. (7.3)

Phase diagram: a convenient way of representing the phasesof a substance in a closed system as a function of tem-perature and pressure. (16.11)

Phenyl group: the benzene molecule minus one hydrogenatom. (21.3)

Photochemical smog: air pollution produced by the actionof light on oxygen, nitrogen oxides, and unburned fuelfrom auto exhaust to form ozone and other pollutants.(5.11)

Photon: a quantum of electromagnetic radiation. (12.2)Physical change: a change in the form of a substance, but

not in its chemical composition; chemical bonds are notbroken in a physical change.

Pi (�) bond: a covalent bond in which parallel p orbitalsshare an electron pair occupying the space above and be-low the line joining the atoms. (14.1)

Planck’s constant: the constant relating the change in energyfor a system to the frequency of the electromagnetic ra-diation absorbed or emitted; equal to 6.626 � 10�34 J s.(12.2)

Polar covalent bond: a covalent bond in which the electronsare not shared equally because one atom attracts themmore strongly than the other. (13.1)

Polar molecule: a molecule that has a permanent dipole mo-ment. (4.1)

Polyatomic ion: an ion containing a number of atoms. (2.7)Polyelectronic atom: an atom with more than one electron.

(12.11)Polymer: a large, usually chainlike molecule built from many

small molecules (monomers). (21.5)Polymerization: a process in which many small molecules

(monomers) are joined together to form a large molecule.(21.2)

Polypeptide: a polymer formed from amino acids joined to-gether by peptide linkages. (21.6)

Polyprotic acid: an acid with more than one acidic proton.It dissociates in a stepwise manner, one proton at a time.(7.7)

Porous disk: a disk in a tube connecting two different solu-tions in a galvanic cell that allows ion flow withoutextensive mixing of the solutions. (11.1)

Porphyrin: a planar ligand with a central ring structureand various substituent groups at the edges of the ring.(19.8)

Positional probability: a type of probability that depends onthe number of arrangements in space that yield a partic-ular state. (10.1)

Positron production: a mode of nuclear decay in which a par-ticle is formed having the same mass as an electron butopposite charge. The net effect is to change a proton to aneutron. (20.1)



Licensed to:

Glossary A37

Potential energy: energy resulting from position or compo-sition. (9.1)

Precipitation reaction: a reaction in which an insoluble sub-stance forms and separates from the solution. (4.5)

Precision: the degree of agreement among several measure-ments of the same quantity; the reproducibility of a mea-surement. (A1.5)

Primary structure (of a protein): the order (sequence) ofamino acids in the protein chain. (21.6)

Principal quantum number: the quantum number relating tothe size and energy of an orbital; it can have any positiveinteger value. (12.9)

Probability distribution: the square of the wave function in-dicating the probability of finding an electron at a par-ticular point in space. (12.8)

Product: a substance resulting from a chemical reaction. It isshown to the right of the arrow in a chemical equation.(3.6)

Protein: a natural high-molecular-weight polymer formed bycondensation reactions between amino acids. (21.6)

Proton: a positively charged particle in an atomic nucleus.(2.6; 20)

Qualitative analysis: the separation and identification of in-dividual ions from a mixture. (4.7; 8.9)

Quantization: the concept that energy can occur only in dis-crete units called quanta. (12.2)

Rad: a unit of radiation dosage corresponding to 10�2 J ofenergy deposited per kilogram of tissue (from radiationabsorbed dose). (20.7)

Radioactive decay (radioactivity): the spontaneous decom-position of a nucleus to form a different nucleus. (20.1)

Radiocarbon dating (carbon-14 dating): a method for dat-ing ancient wood or cloth based on the rate of radioac-tive decay of the nuclide 14

6C. (20.4)Radiotracer: a radioactive nuclide, introduced into an or-

ganism for diagnostic purposes, whose pathway can betraced by monitoring its radioactivity. (20.4)

Random error: an error that has an equal probability of be-ing high or low. (A1.5)

Raoult’s law: the vapor pressure of a solution is directly pro-portional to the mole fraction of solvent present. (17.4)

Rate constant: the proportionality constant in the relation-ship between reaction rate and reactant concentrations.(15.2)

Rate of decay: the change in the number of radioactive nu-clides in a sample per unit time. (20.2)

Rate-determining step: the slowest step in a reaction mech-anism, the one determining the overall rate. (15.6)

Rate law (differential rate law): an expression that showshow the rate of reaction depends on the concentration ofreactants. (15.2)

Reactant: a starting substance in a chemical reaction. Itappears to the left of the arrow in a chemical equation.(3.6)

Reaction mechanism: the series of elementary steps involvedin a chemical reaction. (15.6)

Reaction quotient: a quotient obtained by applying the lawof mass action to initial concentrations rather than toequilibrium concentrations. (6.6)

Reaction rate: the change in concentration of a reactant orproduct per unit time. (15.1)

Reactor core: the part of a nuclear reactor where the fissionreaction takes place. (20.6)

Reducing agent (electron donor): a reactant that donateselectrons to another substance to reduce the oxidationstate of one of its atoms. (4.10; 11.1)

Reduction: a decrease in oxidation state (a gain of electrons).(4.10; 11.1)

Rem: a unit of radiation dosage that accounts for both theenergy of the dose and its effectiveness in causing bio-logical damage (from roentgen equivalent for man).(20.7)

Resonance: a condition occurring when more than one validLewis structure can be written for a particular molecule.The actual electronic structure is not represented by anyone of the Lewis structures but by the average of all ofthem. (13.11)

Reverse osmosis: the process occurring when the externalpressure on a solution causes a net flow of solvent througha semipermeable membrane from the solution to the sol-vent. (17.6)

Reversible process: a cyclic process carried out by a hypo-thetical pathway, which leaves the universe exactly thesame as it was before the process. No real process isreversible. (10.2)

Ribonucleic acid (RNA): a nucleotide polymer that transmitsthe genetic information stored in DNA to the ribosomesfor protein synthesis. (21.6)

Root mean square velocity: the square root of the averageof the squares of the individual velocities of gas particles.(5.6)

Salt: an ionic compound. (7.8)Salt bridge: a U-tube containing an electrolyte that connects

the two compartments of a galvanic cell, allowing ionflow without extensive mixing of the different solutions.(11.1)

Scientific method: the process of studying natural phenom-ena, involving observations, forming laws and theories,and testing of theories by experimentation. (1.3)

Scintillation counter: an instrument that measures radioac-tive decay by sensing the flashes of light produced in asubstance by the radiation. (20.4)

Second law of thermodynamics: in any spontaneous process,there is always an increase in the entropy of the universe.(10.5)

Secondary structure (of a protein): the three-dimensionalstructure of the protein chain (for example, -helix, ran-dom coil, or pleated sheet). (21.6)



Licensed to:

A38 Glossary

Selective precipitation: a method of separating metal ionsfrom an aqueous mixture by using a reagent whose an-ion forms a precipitate with only one or a few of the ionsin the mixture. (4.7; 8.8)

Semiconductor: a substance conducting only a slight electriccurrent at room temperature, but showing increased con-ductivity at higher temperatures. (16.5)

Semipermeable membrane: a membrane that allows solventbut not solute molecules to pass through. (17.6)

Shielding: the effect by which the other electrons screen, orshield, a given electron from some of the nuclear charge.(12.14)

SI units: International System of units based on the metricsystem and units derived from the metric system. (A2.1)

Side chain (of amino acid): the hydrocarbon group on anamino acid represented by H, CH3, or a more complexsubstituent. (21.6)

Sigma (�) bond: a covalent bond in which the electron pairis shared in an area centered on a line running betweenthe atoms. (14.1)

Significant figures: the certain digits and the first uncertaindigit of a measurement. (A1.5)

Silica: the fundamental silicon–oxygen compound, whichhas the empirical formula SiO2, and forms the basis ofquartz and certain types of sand. (16.5)

Silicates: salts that contain metal cations and polyatomicsilicon–oxygen anions that are usually polymeric. (16.5)

Single bond: a bond in which one pair of electrons is sharedby two atoms. (13.8)

Solubility: the amount of a substance that dissolves in a givenvolume of solvent at a given temperature. (4.2)

Solubility product constant: the constant for the equilibriumexpression representing the dissolving of an ionic solid inwater. (8.8)

Solute: a substance dissolved in a liquid to form a solution.(4.2; 17.1)

Solution: a homogeneous mixture. (17)Solvent: the dissolving medium in a solution. (4.2)Somatic damage: radioactive damage to an organism result-

ing in its sickness or death. (20.7)Space-filling model: a model of a molecule showing the rel-

ative sizes of the atoms and their relative orientations.(2.7)

Specific heat capacity: the energy required to raise the tem-perature of one gram of a substance by one degree Cel-sius. (9.4)

Spectator ions: ions present in solution that do not partici-pate directly in a reaction. (4.6)

Spectrochemical series: a listing of ligands in order based ontheir ability to produce d-orbital splitting. (19.6)

Spectroscopy: the study of the interaction of electromagneticradiation within matter. (14.7)

Spontaneous fission: the spontaneous splitting of a heavy nu-clide into two lighter nuclides. (20.1)

Spontaneous process: a process that occurs without outsideintervention. (10.1)

Standard atmosphere: a unit of pressure equal to 760 mmHg. (5.1)

Standard enthalpy of formation: the enthalpy change thataccompanies the formation of one mole of a compoundat 25�C from its elements, with all substances in theirstandard states at that temperature. (9.6)

Standard free energy change: the change in free energy that willoccur for one unit of reaction if the reactants in their stan-dard states are converted to products in their standardstates. (10.9)

Standard free energy of formation: the change in free energythat accompanies the formation of one mole of a sub-stance from its constituent elements with all reactants andproducts in their standard states. (10.9)

Standard hydrogen electrode: a platinum conductor in con-tact with 1 M H� ions and bathed by hydrogen gas atone atmosphere. (11.2)

Standard reduction potential: the potential of a half-reactionunder standard state conditions, as measured against thepotential of the standard hydrogen electrode. (11.2)

Standard solution: a solution whose concentration is accu-rately known. (4.3)

Standard state: a reference state for a specific substance de-fined according to a set of conventional definitions. (9.6)

Standard temperature and pressure (STP): the condition 0�Cand 1 atm of pressure. (5.4)

Standing wave: a stationary wave as on a string of a musi-cal instrument; in the wave mechanical model, the elec-tron in the hydrogen atom is considered to be a standingwave. (12.5)

State function: a property that is independent of the path-way. (9.1)

States of matter: the three different forms in which mattercan exist: solid, liquid, and gas. (5)

Stereoisomerism: isomerism in which all the bonds in the iso-mers are the same but the spatial arrangements of theatoms are different. (19.4)

Steric factor: the factor (always less than one) that reflectsthe fraction of collisions with orientations that can pro-duce a chemical reaction. (15.8)

Stoichiometric quantities: quantities of reactants mixed inexactly the correct amounts so that all are used up at thesame time. (3.9)

Strong acid: an acid that completely dissociates to producea H� ion and the conjugate base. (4.2; 7.2)

Strong base: a metal hydroxide salt that completely dissoci-ates into its ions in water. (4.2; 7.6)

Strong electrolyte: a material that, when dissolved in water,gives a solution that conducts an electric current very ef-ficiently. (4.2)

Structural formula: the representation of a molecule in whichthe relative positions of the atoms are shown and thebonds are indicated by lines. (2.7)

Structural isomerism: isomerism in which the isomers con-tain the same atoms but one or more bonds differ. (19.4;21.1)



Licensed to:

Glossary A39

Subcritical reaction (nuclear): a reaction in which less thanone neutron causes another fission event and the processdies out. (20.6)

Sublimation: the process by which a substance goes directlyfrom the solid to the gaseous state without passingthrough the liquid state. (16.10)

Subshell: a set of orbitals with a given angular momentumquantum number. (12.9)

Substitution reaction (hydrocarbons): a reaction in which anatom, usually a halogen, replaces a hydrogen atom in ahydrocarbon. (21.1)

Supercooling: the process of cooling a liquid below its freez-ing point without its changing to a solid. (16.10)

Supercritical reaction (nuclear): a reaction in which morethan one neutron from each fission event causes anotherfission event. The process rapidly escalates to a violentexplosion. (20.6)

Superheating: the process of heating a liquid above its boil-ing point without its boiling. (16.10)

Superoxide: a compound containing the O2� anion. (18.2)

Surface tension: the resistance of a liquid to an increase inits surface area. (16.2)

Surroundings: everything in the universe surrounding a ther-modynamic system. (9.1)

Syngas: synthetic gas, a mixture of carbon monoxide andhydrogen, obtained by coal gasification. (9.8)

System (thermodynamic): that part of the universe on whichattention is to be focused. (9.1)

Systematic error: an error that always occurs in the same di-rection. (A1.5)

Termolecular step: a reaction involving the simultaneous col-lision of three molecules. (15.6)

Tertiary structure (of a protein): the overall shape of a pro-tein, long and narrow or globular, maintained by differ-ent types of intramolecular interactions. (21.6)

Theoretical yield: the maximum amount of a given productthat can be formed when the limiting reactant is com-pletely consumed. (3.9)

Theory: a set of assumptions put forth to explain some as-pect of the observed behavior of matter. (1.3)

Thermal pollution: the oxygen-depleting effect on lakes andrivers of using water for industrial cooling and returningit to its natural source at a higher temperature. (17.3)

Thermodynamic stability (nuclear): the potential energy ofa particular nucleus as compared with the sum of the po-tential energies of its component protons and neutrons.(20.1)

Thermodynamics: the study of energy and its interconver-sions. (9.1)

Third law of thermodynamics: the entropy of a perfect crys-tal at 0 K is zero. (10.8)

Titration: a technique in which one solution is used to ana-lyze another. (4.9)

Torr: another name for millimeter of mercury (mm Hg).(5.1)

Transfer RNA (tRNA): a small RNA fragment that finds spe-cific amino acids and attaches them to the protein chainas dictated by the codons in mRNA. (21.6)

Transition metals: several series of elements in which innerorbitals (d or f orbitals) are being filled. (12.13; 18.1)

Transuranium elements: the elements beyond uranium thatare made artificially by particle bombardment. (20.3)

Triple bond: a bond in which three pairs of electrons areshared by two atoms. (13.8)

Triple point: the point on a phase diagram at which all threestates of a substance are present. (16.11)

Tyndall effect: the scattering of light by particles in a sus-pension. (17.8)

Uncertainty (in measurement): the characteristics that anymeasurement involves estimates and cannot be exactly re-produced. (A1.5)

Unimolecular step: a reaction step involving only one mol-ecule. (15.6)

Unit cell: the smallest repeating unit of a lattice. (16.3)Unit factor: an equivalence statement between units used for

converting from one unit to another. (A2.2)Universal gas constant: the combined proportionality con-

stant in the ideal gas law; 0.08206 L atm/K mol or 8.3145J/K mol. (5.3)

Valence electrons: the electrons in the outermost principalquantum level of an atom. (12.13)

Valence shell electron-pair repulsion (VSEPR) model: amodel whose main postulate is that the structure arounda given atom in a molecule is determined principally byminimizing electron-pair repulsions. (13.13)

van der Waals’s equation: a mathematical expression for de-scribing the behavior of real gases. (5.10)

van’t Hoff factor: the ratio of moles of particles in solutionto moles of solute dissolved. (17.7)

Vapor pressure: the pressure of the vapor over a liquid atequilibrium. (16.10)

Vaporization: the change in state that occurs when a liquidevaporates to form a gas. (16.10)

Viscosity: the resistance of a liquid to flow. (16.2)Volt: the unit of electrical potential defined as one joule of

work per coulomb of charge transferred. (11.1)Voltmeter: an instrument that measures cell potential by draw-

ing electric current through a known resistance. (11.1)Volumetric analysis: a process involving titration of one

solution with another. (4.9)

Wave function: a function of the coordinates of an electron’sposition in three-dimensional space that describes theproperties of the electron. (12.5)

Wave mechanical model: a model for the hydrogen atom inwhich the electron is assumed to behave as a standingwave. (12.7)

Wavelength: the distance between two consecutive peaks ortroughs in a wave. (12.1)



Licensed to:

A40 Glossary

Weak acid: an acid that dissociates only slightly in aqueoussolution. (4.2; 7.2)

Weak base: a base that reacts with water to produce hy-droxide ions to only a slight extent in aqueous solution.(4.2; 7.6)

Weak electrolyte: a material that, when dissolved in water,gives a solution that conducts only a small electric cur-rent. (4.2)

Weight: the force exerted on an object by gravity. (2.3)Work: force acting over a distance. (9.1)

X-ray diffraction: a technique for establishing the structuresof crystalline solids by directing X rays of a single wave-length at a crystal and obtaining a diffraction patternfrom which interatomic spaces can be determined. (16.3)

Zone of nuclear stability: the area encompassing the stablenuclides on a plot of their positions as a function of thenumber of protons and the number of neutrons in the nu-cleus. (20.1)



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Chapter 1: p. 1, © Beathan/Corbis Royalty Free; p. 2, Will &Deni McIntyre/Photo Researchers, Inc.; p. 3, Kristen Brochmann,Fundamental Photographs; p. 4, Denise Applewhite/Office ofCommunications/Princeton University; p. 5, Courtesy, DowCorning Corporation; p. 9, NASA; p. 10, Simon Fraser/SciencePhoto Library/Photo Researchers, Inc., p. 13, Brownie Harris/Stock Market/Corbis.

Chapter 2: p. 15, Dr. Dennis Marinus Hansen; p. 16, RoaldHoffman/Cornell University; p. 17 (Detail), Antoine LaurentLavoisier & His Wife by Jacques Louis David, The Metro-politan Museum of Art; p. 18, Manchester Literary & Philo-sophical Society; p. 20, The Granger Collection; p. 22 (both),Courtesy, IBM Corporation, Research Division, Almaden Re-search Center; p. 24 (top), Bettmann/Corbis; p. 24 (bottom),Richard Megna/Fundamental Photographs; p. 26: Bettmann/Corbis, p. 28, Portrait of Ernest Rutherford, 1932 by OswaldHornby Birley, Royal Society, London, UK/Bridgeman Art Li-brary; p. 31 (left, center), Frank Cox/Photograph © HoughtonMifflin Company. All rights reserved; p. 31 (right), KenO’Donoghue/Photograph © Houghton Mifflin Company. Allrights reserved; p. 33 (left), Ken O’Donoghue/Photograph ©Houghton Mifflin Company. All rights reserved; p. 33 (center,left, and right), Photograph © Houghton Mifflin Company.All rights reserved; p. 33 (right), Charles D. Winters/PhotoResearchers; p. 33 (bottom), Ken O’Donoghue/Photograph ©Houghton Mifflin Company. All rights reserved; p. 35 (top),Tom Pantages; p. 35 (bottom), Photograph © HoughtonMifflin Company. All rights reserved; p. 39, Richard Megna/Fundamental Photographs/Photograph © Houghton MifflinCompany. All rights reserved; p. 43 (both), Microtrace, LLC.

Chapter 3: p. 52, Jim Sugar/Science Faction; p. 53, Agricul-tural Research Service/USDA Photo by Scott Baur; p. 54,Kennan Ward/Stock Market/Corbis; p. 56, Ken O’Donoghue/Photograph © Houghton Mifflin Company. All rights reserved;p. 61 (top), Phil Degginger/Stone/Getty Images; p. 61 (bot-tom), The Nobel Foundation; p. 65 (top), Ken O’Donoghue/Photograph © Houghton Mifflin Company. All rights reserved;p. 65 (bottom), Frank Cox/Photograph © Houghton MifflinCompany. All rights reserved; p. 67 (top), Owen Franken/StockBoston; p. 67 (bottom), Photograph © Houghton MifflinCompany. All rights reserved; p. 70 (both), Photograph ©Houghton Mifflin Company. All rights reserved; p. 73, LarryLarimer/Artville/PictureQuest.

Chapter 4: p. 90, Photograph © Houghton Mifflin Company.All rights reserved; p. 94 (all), Ken O’Donoghue/Photograph© Houghton Mifflin Company. All rights reserved; p. 101,

Richard Megna/Fundamental Photographs/Photograph ©Houghton Mifflin Company. All rights reserved; p. 102, Pho-tograph © Houghton Mifflin Company. All rights reserved;p. 103, Photograph © Houghton Mifflin Company. All rightsreserved; p. 104 (all), Photograph © Houghton Mifflin Com-pany. All rights reserved; p. 105, Ken O’Donoghue/Photograph© Houghton Mifflin Company. All rights reserved; p. 106,Photograph © Houghton Mifflin Company. All rights re-served; p. 110, Photograph © Houghton Mifflin Company.All rights reserved; p. 112, Jeff Daly/Visuals Unlimited; p. 114(all), Richard Megna/Fundamental Photographs/Photograph© Houghton Mifflin Company. All rights reserved; p. 115,AFP Photo/Toru Yamanaka/Corbis; p. 118 (left), Photograph© Houghton Mifflin Company. All rights reserved; p. 118(center two), Ken O’Donoghue/Photograph © HoughtonMifflin Company. All rights reserved; p. 118 (right), Photo-graph © Houghton Mifflin Company. All rights reserved;p. 119, Tammy Peluso/Tom Stack and Associates; p. 120,Richard Megna/Fundamental Photographs/Photograph ©Houghton Mifflin Company. All rights reserved; p. 130, Pho-tograph © Houghton Mifflin Company. All rights reserved.

Chapter 5: p. 141, AP Photo/Keystone/Martial Trezzini/AP/Wide World Photos; p. 153, Ford Motor Company; p. 160(all), Ken O’Donoghue; p. 165, Ken O’Donoghue; p. 167, U.S.Department of Energy; p. 174, Jim Gray/Courtesy of KennethS. Suslick; p. 179 (top two), Michael Barnes; p. 179 (bottom),John Lawlor; p. 180, M. Edwards/Peter Arnold, Inc.; p. 181(both), Field Museum, Chicago, #CSGN40263 and#GN83213_6c.

Chapter 6: p. 196, Lee Foster/Taxi/Getty Images; p. 198,Photograph © Houghton Mifflin Company. All rights re-served; p. 203, Danny Eilers/Alamy; p. 206, Larry AndreMaslennikov/Peter Arnold, Inc.; p. 216, Science Photo Library/Photo Researchers; p. 217, Photograph © Houghton MifflinCompany. All rights reserved; p. 220 (all), Ken O’Donoghue;p. 221 (both), Photograph © Houghton Mifflin Company. Allrights reserved; p. 227 (all), Photograph © Houghton MifflinCompany. All rights reserved.

Chapter 7: p. 233, Sinclair Stammers/Photo Researchers, Inc.;p. 240 (both), Ken O’Donoghue/Photograph © HoughtonMifflin Company. All rights reserved; p. 248, PatrickWard/Corbis; p. 249, Rick Poley/Visuals Unlimited; p. 253,R. Konig/Jacana/Photo Researchers; p. 261, Dan Loh/AP/WideWorld Photos; p. 266, Photograph © Houghton Mifflin Com-pany. All rights reserved; p. 267, Photograph © HoughtonMifflin Company. All rights reserved.

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Chapter 9: p. 358, Jeremy Holden; p. 376 (both), Photo-graph © Houghton Mifflin Company. All rights reserved;p. 379, Phil Degginger/Color-Pic, Inc.; p. 381, Argonne Na-tional Laboratory; p. 383, Itsuo Inouye/AP/Wide World Pho-tos; p. 391, Klaus Andrews/Argus Fotoarchiv/Peter Arnold,Inc.; p. 396, Courtesy FPL Energy, LLC; p. 400, The ImageBank/Getty.

Chapter 10: p. 410, Matt Meadows/Science Photo Library/Photo Researchers; p. 417, Stephen Frisch/Stock Boston;p. 425, Photograph © Houghton Mifflin Company. All rightsreserved; p. 431, Inga Spence/Visuals Unlimited; p. 432, Pho-tograph © Houghton Mifflin Company. All rights reserved;p. 443, Phil A. Harrington/Peter Arnold, Inc.; p. 451, MichaelS. Yamashita/Corbis.

Chapter 11: p. 472, Fog Stock/Tips Images; p. 478, RichardMegna/Fundamental Photographs/Photograph © HoughtonMifflin Company. All rights reserved; p. 483, Royal Institution/London; p. 485, Photograph © Houghton Mifflin Company.All rights reserved; p. 486, Bettmann/Corbis; p. 488, Photo-graph © Houghton Mifflin Company. All rights reserved;p. 489, Ken O’Donoghue/Photograph © Houghton MifflinCompany. All rights reserved; p. 496, © Car Culture/Corbis;p. 499, Ron Watts/Corbis; p. 504, Yoav Levy/Corbis; p. 506,Oberlin College Archives/Oberlin College; p. 508, TomHollyman/Photo Researchers.

Chapter 12: p. 521, Tetra Images/Alamy; p. 526, Photograph© Houghton Mifflin Company. All rights reserved; p. 527,The Granger Collection; p. 529, Lester V. Bergman/Corbis;p. 532, The Granger Collection; p. 534, James Bergquist andD. Wineland/National Institute of Standards and Technology;p. 537, Photodisc/Getty Images; p. 540 (both), ResearchDivision, Almaden Research Center/IBM Corporation; p. 543(left), Stephen Jensen/Tufts University/Charles Sykes; p. 543(right), M. El Kouedi/Charles Sykes; p. 559: Bettmann/Corbis;p. 560, Annalen der Chemie und Pharmacia, VIII, Supple-

mentary Volume for 1872; p. 574, Charles D. Winters/PhotoResearchers; p. 582, E.R. Degginger/Color-Pic, Inc.

Chapter 13: p. 592, Kenneth Eward/Science Photo Library/Photo Researchers; p. 593 (top), Photograph © HoughtonMifflin Company. All rights reserved; p. 593 (bottom), Pho-todisc Red/Getty Images; p. 602 (all), Ken O’Donoghue/Photograph © Houghton Mifflin Company. All rights reserved;p. 612, Ken O’Donoghue/Photograph © Houghton MifflinCompany. All rights reserved; p. 614, Will & Deni McIntyre/Photo Researchers; p. 615, Ken Eward/Science Source/PhotoResearchers; p. 620 (left), The Bancroft Library; p. 620 (right),From G.N. Lewis, Valence, Dover Publications, Inc. New York,1966; p. 627, Tom Pantages; p. 638: Steve Borick/AmericanColor; p. 641 (all), Ken O’Donoghue/Photograph © HoughtonMifflin Company. All rights reserved; p. 644, Argonne NationalLaboratory; p. 647, Scott Camazine/Photo Researchers;p. 648: Courtesy, Cyrano Science, Inc. p. 650, Ken O’Donoghue/Photograph © Houghton Mifflin Company. All rights reserved.

Chapter 14: p. 660, Russell Kightley/Science Photo Library/Photo Researchers, Inc.; p. 664, Comstock Images/RoyaltyFree/Comstock Mountainside, NJ; p. 682 (both), DonaldClegg; p. 690, Courtesy of Tim Kenny/Jonathan E. Kenny;p. 692, Joseph Nettis/Stock Boston/PictureQuest; p. 694,Naturelle/Alamy Images; p. 704, Joshua Lutz/Redux Pictures;p. 705 (left), SIU/Visuals Unlimited; p. 705 (right), AlfredPasieka/Science Photo Library/Photo Researchers.

Chapter 15: p. 714, Mike Powell/Allsports Concepts/GettyImages; p. 718, Ahmed Zewail/California Institute of Tech-nology; p. 725 (both), Photograph © Houghton Mifflin Com-pany. All rights reserved; p. 727, Photograph © HoughtonMifflin Company. All rights reserved; p. 738, Courtesy ofGabriela Petruck/Christopher Rose-Petruck; p. 739, Photo-graph © Houghton Mifflin Company. All rights reserved;p. 742, Dr. Wilson Ho/University of California, Irvine; p. 752,Phil Degginger/Color-Pic, Inc.; p. 754, Graham MacIndoe/Wellesley College; p. 755, Delphi Automotive Systems; p. 760,Alfred Pasieka/Science Photo Library/Photo Researchers, Inc.

Chapter 16: p. 777, Artform No. 1 by Mark Ho; p. 782,Paul D. Stewart/Dr. Kellar Autumn/Lewis and Clark College;p. 783 (top two), Photograph © Houghton Mifflin Company.All rights reserved; p. 783 (bottom), Ray Massey/Stone/GettyImages; p. 784 (both), Courtesy, Lord Corporation; p. 786 (topleft, top right), Photograph © Houghton Mifflin Company.All rights reserved; p. 786 (bottom left), Jose Manuel SanchisCalvete/Corbis; p. 786 (bottom right), Brian Parker/Tom Stackand Associates; p. 789 (bottom left): Joanna Aizenberg; p. 789(top right), Kevin Schafer/Vireo; p. 789 (bottom right), Cour-tesy, Dr. Marc A. Meyers/University of California, San Diego;p. 792, Denise Applewhite/Princeton University; p. 793, Pho-tograph © Houghton Mifflin Company. All rights reserved;p. 798, Chip Clark; p. 800, Ken Eward/Photo Researchers;p. 803, Yoav Levy/Phototake; p. 806, Dr. Thomas Thundat/OakRidge National Laboratory; p. 812 (top), IBM Corporation;p. 812 (bottom left), Ken O’Donoghue/Photograph © HoughtonMifflin Company. All rights reserved; p. 812 (bottom right),



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Chapter 17: p. 846, Charles D. Winters/Photo Researchers,Inc.; p. 848, Richard Nowitz; p. 851, AP Photo/David Adema/POOL/AP/Wide World Photos; p. 852 (both), USDA; p. 854(both), Frank Cox/Photograph © Houghton Mifflin Company.All rights reserved; p. 855, Photograph © Houghton MifflinCompany. All rights reserved; p. 858 (bottom left and right),Betz/Visuals Unlimited; p. 859, T. Orban/Sygma/Corbis; p. 871,Courtesy, PUR/Recovery Engineering, Inc., Minneapolis, MN;p. 873, Stephen Frisch/Stock Boston.

Chapter 18: p. 885, Science Photo Library/Photo Research-ers, Inc.; p. 890, John Chard/Stone/Getty Images; p. 891,Larry Stepanowicz/Fundamental Photographs; p. 892, KenO’Donoghue; p. 893 (both), Richard Megna/FundamentalPhotographs/Photograph © Houghton Mifflin Company. Allrights reserved; p. 895, Photograph © Houghton Mifflin Com-pany. All rights reserved; p. 898 (top), The Advertizing Archive,London; p. 898 (bottom), Photograph © Houghton MifflinCompany. All rights reserved; p. 900, Photodisc Green/GettyImages, Royalty Free; p. 901, The Granger Collection; p. 903,Roger Ressmeyer/Corbis; p. 906, Hugh Spencer/Photo Re-searchers; p. 907, Photograph © Houghton Mifflin Company.All rights reserved; p. 908, Richard Megna/FundamentalPhotographs; p. 911, Stephen Frisch/Stock Boston; p. 914,Eyebyte/Royalty Free Image/Alamy Images; p. 915, Fred J.Maroon/Photo Researchers; p. 916, E.R. Degginger/Color-Pic,Inc.; p. 917, Farrell Grehan/Photo Researchers; p. 918 (topleft), Ken O’Donoghue/Photograph © Houghton Mifflin Com-pany. All rights reserved; p. 918 (top right), E.R. Degginger/Color-Pic, Inc.; p. 918 (bottom), Ken O’Donoghue/Photograph© Houghton Mifflin Company. All rights reserved; p. 919, Pho-tograph © Houghton Mifflin Company. All rights reserved;p. 920, Yoav Levy/Phototake; p. 934, AP Photo/DonnaMcWilliam/AP/Wide World Photos.

Chapter 19: p. 933, Walter Bibikow/Getty Images; p. 935(top left), Paul Silverman/Fundamental Photographs; p. 935

(top right and bottom left), Photograph © Houghton MifflinCompany. All rights reserved; p. 935 (bottom right), KenO’Donoghue/Photograph © Houghton Mifflin Company. Allrights reserved; p. 936, Photograph © Houghton Mifflin Com-pany. All rights reserved; p. 940, James King-Holmes/SciencePhoto Library/Photo Researchers; p. 941, Ken O’Donoghue/Photograph © Houghton Mifflin Company. All rights re-served; p. 942, Jodi Jacobson/Peter Arnold, Inc.; p. 943,John Cunningham/Visuals Unlimited; p. 945, Photograph ©Houghton Mifflin Company. All rights reserved; p. 946, KeithWeller/USDA Photo; p. 950 (both), Photograph © HoughtonMifflin Company. All rights reserved; p. 954, Martin Bough/Fundamental Photographs/Photograph © Houghton MifflinCompany. All rights reserved; p. 965 (both), Courtesy, Inter-national Colored Gemstone Association; p. 972, Stanley Flegler/Visuals Unlimited; p. 974 (all), Photograph © Houghton MifflinCompany. All rights reserved.

Chapter 20: p. 981, NASA; p. 986, Courtesy, CERN/Geneva,Switzerland; p. 988, Jeff Hester/Arizona State University/NASA;p. 990, U.S. Department of Energy/Science Photo Library/PhotoResearchers; p. 991, James A. Sugar/Corbis; p. 994, UniversityMuseum/University of Pennsylvania Photo Archives; p. 996(both), SIU/Visuals Unlimited; p. 1003, Peter Arnold, Inc.;p. 1005, Courtesy, Fermilab Visual Media/Batavia, IL.

Chapter 21: p. 1013, Food Image Source/Getty Images;p. 1015, Iris Kappers/Koppert Biological Systems; p. 1028,Digital Vision/Royalty Free/Getty Images; p. 1030, APPhoto/Nati Harnik/AP/Wide World Photos; p. 1032, IngaSpence/Visuals Unlimited; p. 1034, Laguna Design/SciencePhoto Library/Photo Researchers; p. 1035 (top), AP Photo/Indianapolis Star/Karen Ducey/AP/Wide World Photos; p. 1035(bottom), Phil Nelson, Woodinville, WA, p. 1036, RonBoardman/Frank Lane Picture Agency/Corbis; p. 1037, APPhoto/Elise Amendola/AP/Wide World Photos; p. 1039, Pho-tograph © Houghton Mifflin Company. All rights reserved;p. 1041, Courtesy Dupont/Dupont, Wilmington, Delaware;p. 1043, Scott White/University of Illinois, Urbana-Champaign;p. 1047, Ken Eward/Biografx/Science Source/Photo Researchers;p. 1052 (both), Photograph © Houghton Mifflin Company.All rights reserved; p. 1058, Alfred Pasieka/Science Source/PhotoResearchers.



Licensed to:

A78

aba arrangement, 790, 791,794

abc arrangement, 791, 792ABS (acrylonitrile-butadiene-

styrene), 1044Absolute entropy, 438–440Absolute zero, 146, 147Absorbance, 697, A17–A21Absorption, 753Absorptivity, molar, A18Accelerators, 36, 986, 991,

1005Acclimatization, high-altitude,

972Accuracy, A9–A10Acetate ion, 263–264Acetic acid, 1033

aspirin derived from, 1034in buffered solution,

289–291, 294, 300–302conjugate base of, 263–264glacial, 920percent dissociation, 247reaction with strong

base, 113titration with strong base,

308–312, 314–315, 324as weak acid, 95–96, 236

Acetone–water solution, 863Acetylene, 1024Acetylsalicylic acid, 1034Acid–base equilibria problems

hydrogen ions from waterin, 270–276

major species in, 241, 276polyprotic acids in, 254–263salts in, 263–270strategies for, 240–241,

244, 276–277strong acids in, 241–242,

275–276strong bases in, 249–250,

276validity of approximations,

243–244, 272–273weak acids in, 242–248,

270–275weak bases in, 251–252,

254, 265See also pH

Acid–base indicators, 114,115, 319–324

chart of pH ranges, 322

Acid–base reactions, 101,113–117

in buffered solution,290–291, 292, 296, 297

Acid–base titrations,114–117, 313–318

for determining Ka, 315–316indicators for, 114, 115,

319–324of polyprotic acids, 324–328strong acid–strong base,

304–307, 321, 323weak acid–strong base,

307–316, 323–324weak base–strong acid,

316–318Acid decomposition of paper,

3–7Acid dissociation constant

(Ka), 235accuracy of, 243determination of, 315–316log form of, 294, 302percent dissociation and,

247–248of polyprotic acids, 256, A24relation to Kb, 264–265of strong acids, 236–237tables of values, A24of weak acids, 237, 238

Acidic solutionsdefined, 239hydrogen ions from water

in, 270–276oxidation–reduction in,

125–127, 130–131of salts, 265–268solubility of salts in, 287,

334–335, 338Acid rain, 179, 180–181, 392,

499, 755Acids, 234–235

Arrhenius concept, 94–95,113, 234

Brønsted–Lowry concept,113, 234, 235

conjugate, 234, 235, 251,265

diprotic, 236hydrogens in formulas for,

95–96hydrohalic, 236, 920–921Lewis concept, 947, 958

naming of, 44–45nucleic, 4, 1056–1060organic, 236, 1033polyprotic, 254–263, 288,

324–328strength of, 236–237triprotic, 256–260, 324–328water as, 237–239See also Amphoteric

substances; Oxyacids;pH; Strong acids; Weakacids

Acid salts, of amines, 253Acoustic refrigeration, 175Acrylonitrile-butadiene-styrene

(ABS), 1044Actinide series, 565, 566,

886, 934, 935Activated complex, 748Activation energy, 747–751

catalysis and, 753for diamond production,

828Active site, of enzyme, 756Activity, 205–206

of ions in solution, 334of pure liquid or solid,

207–208of real gases, 223of species in solution, 242of water, 235

Activity coefficients, 223Actual yield, 77Addition

in exponential notation, A2significant figures, A14–A15

Addition polymerization,1037–1038

Addition reactions, 1026Adhesive forces

of geckos, 782between liquid and glass,

783Adhesives, 11Adiabatic processes, 457–460Adrenaline, 253Adsorption, 753, 754, 755Air

composition of, 176liquefaction of, 890–891,

915See also Atmosphere

Air bags, 153

Air pollution, 177–182catalytic converters and,

391, 755, 758, 759electrostatic precipitator

and, 875fossil fuels and, 359, 758,

916nitrogen dioxide and, 177,

180, 693, 905ozone and, 177, 693See also Acid rain

-al (suffix), 1032Alchemy, 16, 142, 985Alcohols, 1028–1031

esters derived from,1033–1034

oxidation of, 1033See also Ethanol; Methanol

Aldehydes, 1032–1033Alkali metals (Group 1A), 35,

580–582, 891–892atomic radii, 580, 887–888in biological systems, 892crystal structures of, 796flame test for, 340, 341halides of, crystal

structures, 609, 817–818hydroxides of, 248–249,

250ionization energies, 573,

580, 581See also specific elements

Alkaline battery, 493–494Alkaline earth metals (Group

2A), 35, 895–897hydroxides of, 249–250ionic radii, 577oxides of, 888, 895See also specific elements

Alkalis. See BasesAlkanes, 1014–1023

cyclic, 1022–1023isomers of, 1016–1021nomenclature, 1018–1021reactions, 1021–1022

Alkenes, 1023–1024, 1025,1026. See also Ethylene

Alkynes, 1024–1026Allen, Leland C., 599Allomones, 646Allotropes of carbon. See

Diamond; Fullerenes;Graphite

Index

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Index A79

Allotropes of tin, 900Alloys, 798–799

of aluminum, 507cobalt in, 944copper in, 945corrosion-resistant, 501of magnesium, 895silicon in, 899of tin, 899–900See also Steel

Alloy steels, 799�-helix, 1048, 1049Alpha (�) particles, 984, 985

biological effects, 1004,1006, 1007

early experiments, 26–28,991

Altitudeatmospheric pressure

and, 176boiling point of water

and, 830octane ratings and, 71oxygen concentration and,

972Alum, in paper

manufacturing, 4Alumina, 506–507. See also

Aluminum oxideAluminosilicates, 806Aluminum

abundance, 889alloys of, 507for bicycles, 942electron configuration, 563ionization energies, 571physical properties,

897, 898production of, 506–507

Aluminum chloride, aqueoussolution, 266, 267

Aluminum oxideamphoteric nature of,

506, 898in bauxite, 506–507corrosion inhibited by, 497electron configurations in,

604–605in gemstones, 965

Amides, 1045Amines, 253, 1034–1035Amino acids, 1045, 1046,

1052protein synthesis and,

1058, 1060p-Aminobenzoic acid, 524Amino group, 1035Ammine ligand, 950, 953Ammonia, 906

acid salt of, 253autoionization of, 238

as base, 96, 251, 906in buffered solution, 289,

295–297combustion of, 387–389dipole moment, 601in fertilizers, 905, 906hydrogen bonding in, 906as ligand, 341–343, 345,

347, 948naming of, 40in nitric acid production,

910–911nitrogen-fixing bacteria

and, 906paper decomposition and, 6in qualitative analysis, 346,

347reaction with hydrogen

chloride, 165, 235sp3 orbitals for, 663substituted, 251, 253titration with strong acid,

316–318VSEPR model, 638–640

Ammonia synthesisbacterial, 906entropy change, 436–437equilibrium in, 200–205,

208–209, 216–217, 221, 222

free energy change, 440,445, 450–451

limiting reactant in, 74–76temperature dependence of

equilibrium constant,221, 452, 453

See also Haber processAmmonium chloride, 253,

265, 266–267Ammonium dichromate,

decomposition of, 69–70Ammonium dihydrogen

phosphate, 913Ammonium ion, 33Ammonium salts, 906

solubility in water, 105, 341Amorphous solids, 785

red phosphorus, 912See also Glass

Ampere (amp), 503Amphoteric substances

aluminum oxide, 506, 898beryllium oxide, 888, 895defined, 237gallium oxide, 898in polyprotic acid titration,

325–327water as, 237–239

Amplified signal, 810amu (atomic mass units), 53

conversion to grams, 56–57

Amylopectin, 1054–1055Amylose, 1054Analytical chemistry. See

Chemical analysis-ane (suffix), 1018Angular momentum, in Bohr

model, 532Angular momentum quantum

number, 548, 549, 552Anions

as effective bases, 335formation of, 32names of, 36, 37, 39–40oxyanions, 39–40, 922periodic table and, 887

Annihilation of particles, 985, 986

Anode, 475, 481Anodic regions, 500Anslyn, Eric V., 648Antacids, 249, 334Anthracene, 1028Antibiotics, 646Antibonding molecular

orbitals, 675, 676electronic transitions from,

692of octahedral complex, 967

Anticodon, 1060Antifreeze, 867, 1030Antihydrogen, 986Antimatter, 985, 986Antimony, 902, 903

in additives for PVC, 13–14Antiparticles, 985, 986Antiproton, 986, 1005Antlerite, 499Approximations

5% rule, 243–244for logarithms, 240significant figures, A8–A9,

A13–A15for solving quadratic

equations, A6–A8See also Models

Aqua regia, 346, 485, 942Aqueous solutions

defined, 91electrolytes, 93–96,

871–873of gases, 855, 857–858importance of, 90–91nonelectrolytes, 93, 96phase diagram for,

864–865, 866polarity of water and,

91–92reactions in (see Acid–base

reactions; Oxidation–reduction reactions;Precipitation reactions)

symbol for, 67, 92, 95See also Acid–base

equilibria problems;Hydration; Solubility;Solutions; Water

Aragonite, 789Argon, 35, 790, 915, 923

electron configuration, 563freezing point, 781in Geiger counter, 993

Aristotle, 782Arnold, Michael S., 833Aromatic alcohols, 1030Aromatic amines, 1035Aromatic hydrocarbons,

1026–1028. See alsoBenzene

Arrhenius, Svante, 93–95,234, 747

Arrhenius acid–base concept,94–95, 113, 234, 248

Arrhenius equation, 749–750Arsenic, 902–903

in semiconductors, 807, 808

Arumainayagam, Christopher,754

Aspirin, 1034Astatine, 35, 919Atactic chain, 1042-ate (suffix), 40, 44, 949atm (unit of pressure),

142–143Atmosphere, 176–182

carbon dioxide in, 359,392, 393–394

composition of, 176layers of, 176–177oxygen in, 176, 177, 178research on chemistry of,

179water in, 393See also Air pollution

Atom(s)ancient Greek ideas on,

16, 522Dalton’s theory of, 18,

19–21, 522, 953early experiments on, 24–28modern view of, 29–30, 522trapping of, 147See also Hydrogen atom;

Quantum mechanicsAtomic clock, 534Atomic force microscopy

(AFM), 22Atomic masses, 53–56

early research on, 19–24,560

Atomic mass units (amu), 53conversion to grams, 56–57



Licensed to:

A80 Index

Atomic number, 30, 34, 982,983, 984

Atomic radii, 577–578group anomalies and,

887–889polarizability and, 781of transition metals, 939

Atomic solids, 790. See alsoMetals; Network solids

Atomic weights, 19–20, 54, 55

Aufbau principle, 561, 615Autoionization

of liquid ammonia, 238of water, 237–239,

241–242, 250Automobiles

air bags, 153alcohol fuels, 401, 1030catalytic converters, 391,

755, 758, 759fuel cells for, 496hydrogen fuel, 399–400,

496irreversible processes in,

455–457lead storage batteries,

492–493, 900nitrogen fixation by, 905nitrous oxide power for,

910sensor for exhaust gases,

119work of engine, 363See also Air pollution;

GasolineAutumn, Kellar, 782Average, A10, A13Avogadro, Amedeo, 20, 21Avogadro’s law (hypothesis),

20, 21, 146Avogadro’s number, 56Axial hybrid orbitals, 668Azeotrope, of nitric acid and

water, 911Azide ion, 905Azobenzenes, 834

Baekeland, Leo H., 1036Bakelite, 1036Balancing chemical equations,

67, 68–70for galvanic cell, 479–480for oxidation–reduction,

123–130, 479–480Ball-and-stick models, 31, 33Band model, 797–798Bar (unit of pressure), 143,

205Barium, 35, 895, 896Barium sulfate, insolubility of,

328, 849

Barometer, 142for vapor pressure

measurement, 820Bartlett, Neil, 923Bases, 234–235, 248–254

amines as, 253Arrhenius concept, 113,

234, 248Brønsted–Lowry concept,

113, 234, 235, 248conjugate, 234–235, 236,

237, 251, 263–264Kb of, 251–252, 263–265,

266, 267–268, A25Lewis concept, 902, 936,

946, 947, 958in nucleic acids, 1057,

1058, 1059, 1060paper decomposition and,

5–6reaction with water, 251,

252, 333strength of, 237, 265strong, 94, 95, 248–250,

263, 276water as, 234, 236,

237–239, 265weak, 96, 251–252, 254,

265, 289, 295–297, A25See also Acid–base

equilibria problems;Acid–base reactions;Acid–base titrations;Amphoteric substances

Basic solutionsdefined, 239of Group 2A oxides, 888,

895oxidation–reduction in,

127–129of salts, 263–265, 267–268,

270Basis set, for molecular

orbitals, 674Batteries, 492–497

dead, 487, 493work done by, 455–456

Bauer, Georg, 16Bauxite, 506–507bcc (body-centered cubic) unit

cell, 787, 796–797Becquerel, Henri, 26, 27Beer–Lambert law, A18–A21Beethoven, Ludwig van, 901Bell, Valerie, 156Bent, Henry, 456Benzene, 251, 1026–1028

molecular orbital model,687–688

Benzene solutionaqueous, 853with toluene, 864

Benzoic acid, 236Benzpyrene, 1028Berquist, John C., 534Beryllium, 35, 895, 896

electron configuration, 562electron-deficient

compounds, 628ionization energy, 573molecular orbital model,

677–678Beryllium chloride, 636–637Beryllium oxide, 888, 895Berzelius, Jöns Jakob, 21, 24Beta (�) particles, 26,

982, 984biological effects, 1004,

1006in breeder reactor, 1003half-life and, 989radiocarbon dating and,

993, 994in supernova explosion,

988Bicarbonate ions, 858

in human body, 752in ocean, 505

Bicycle frames, 942Bidentate ligands, 948Big bang theory, 988Bimolecular step, 737Binary covalent compounds

bonding in, 603naming of, 40, 41

Binary ionic compoundsbonding in, 603formation of, 607–611naming of, 36–39, 41

Binding energy per nucleon,998–999

Binning, Gerd K., 22Biodiesel oil, 401Biological systems

alkali metal ions in, 892alkaline earth metal ions in,

582, 895dispersion forces in, 782elements in human body,

889entropic forces in, 426ice and, 874nitrogen in, 905–906selenium in, 914semiochemicals in, 646–647strong materials in, 789water in, 894See also Medicine

Biomolecules, 1014carbohydrates, 1051–1056chirality in, 957–958, 1051,

1053–1054coordination complexes,

969–973

nucleic acids, 4, 1056–1060radiation damage to, 1004,

1006, 1050See also Enzymes; Proteins

Biosensors, 119Biot, Jean, 953Bismuth, 902Blackbody radiation, 525–526Black phosphorus, 912Black powder, 536, 537Blood, pH of, 289Blowing agents, 907Boat form of cyclohexane,

1022Body-centered cubic (bcc) unit

cell, 787, 796–797Boering, Kristie A., 179Bohr, Niels, 531Bohr model, 531–533, 535,

536, 538, 549, 551Bohr radius, 551Boiler scale, 858Boiling chips, 826Boiling point, 824

entropy change at, 429free energy and, 435–436hydrogen bonding and,

780normal, 825, 827pressure dependence of,

830vapor pressure at, 825

Boiling-point elevation,864–866

of electrolyte solutions, 872Boltzmann, Ludwig E.,

163, 425Boltzmann’s constant

entropy and, 425molecular velocities and,

163Bomb calorimeter, 378–380Bombs. See ExplosivesBond angles, 637, 638,

639–640, 650Bond energy, 594, 595–596,

613, 616–617bond order and, 677, 682chemical reactions and,

361–362, 617–619electronegativity and,

597–598of hydrogen halides, 921table of values, 617

Bondingdefined, 593, 612in metals, 797–798three-center, 897–898types of, 30–33, 593–597See also Covalent bonding;

Hydrogen bonding; Ionicbonding



Licensed to:

Index A81

Bonding molecular orbitals,675–676

electronic transitions from,692

of octahedral complex, 966

Bonding pairs, 620, 622Bond length, 595, 617

bond order and, 682rotational spectrum and,

698, 699–700vibration and, 694–695

Bond order, 676–677, 680,681, 682, 683, 684

Bond polarity. See Polarcovalent bonds

Bond strength, 676–677. Seealso Bond energy

Boranes, 897–898Boron, 897–898

atomic radius, 888as atomic solid, 788electron configuration, 562electron-deficient

compounds, 626–627,628, 897–898

ionization energy, 573molecular orbital model,

678–680paramagnetism, 680–682silicon doped with,

808–809, 811Boron tetrafluoride ion, 672Boron trifluoride, 626–627,

637Boundary conditions, 544,

545, 546Boyle, Robert, 16Boyle’s law, 143–145,

146, 149Bragg, William Henry,

786–787Bragg, William Lawrence,

786–787Bragg equation, 786Brass, 798Breeder reactors, 1003Brenner, R. J., 109Brine, electrolysis of, 509–510Brittle tin, 900Brochantite, 499Bromine, 35, 919–920,

921, 922electron affinity, 577

Bromoethane, NMR spectrumof, 701, 703

Bromthymol blue, 320, 321Brønsted, Johannes N., 234Brønsted–Lowry acid–base

concept, 113, 234, 235, 248

Brown phosphorus, 683

Bubblesboiling and, 826cavitation and, 174

Buckminsterfullerenes. SeeFullerenes

Buffer capacity, 300–303Buffered solutions, 289–297

exact treatment of, 297–300how it works, 292–297selecting weak acid for,

302–303summary, 297

Bumping, 826Buret, 114, A8Burns, Stephanie, 5Burton, William, 391Butane, 1015, 1016–1017,

10212-Butanone, 703–704

Cadmium, 564, 567–568Calcium, 35, 895–897

electron configuration, 563Calcium carbonate

as boiler scale, 975in conch shell, 789as marble, 180–181solubility in acid, 287, 335on sunken treasure, 505thermal decomposition of,

206–207, 221from water softening, 250See also Limestone

Calcium fluoride, crystalstructure, 818

Calcium hydroxide, 249–250Calcium oxide (lime)

commercial preparation of,206–207

electron configurations in,604

in scrubbing, 179, 181in water softening, 250

Calorimetry, 374–380Cancer

drugs for, 956nanotechnology

applications for, 833, 835radiation therapy for, 996selenium and, 914in smokers, 914sunscreens and, 524

Cannizzaro, Stanislao, 21–24Capillary action, 783Captive zeros, A14Carbohydrates, 1051–1056Carbon, 899

atomic mass, 53, 54–55atomic radius, 888as atomic solid, 788, 790bonding properties, 888,

1013–1014

as diamond, 442–443, 788,790, 799–800, 801,828–829

diatomic, 681–682electron affinity, 576electron configuration, 562as fullerenes, 788, 799,

812, 833as graphite, 442–443, 788,

799, 800–801, 828–829ionization energy, 573in metallurgy, 890phase diagram, 828–829in steel, 799See also Biomolecules;

HydrocarbonsCarbon-14, 54, 982, 993–994Carbonate salts

qualitative analysis, 341solubility in water, 105

Carbon dioxide, 5amorphous solid form of,

804in carbonated beverages,

855climate and, 359, 392,

393–394Dalton’s atomic theory

and, 18fire extinguisher with, 831fossil fuels and, 392, 393,

857hybrid orbitals for, 666–667Lake Nyos tragedy, 859Lewis structure, 623,

635–636metabolism of, 752phase diagram, 831polar bonds in, 601radiocarbon dating and,

994as real gas, 176sequestration of, 392solid state of, 812, 813,

823, 831sublimation of, 823, 831supercritical, 852water solution of, 254, 287,

335Carbon fiber composites,

942Carbonia, 804Carbonic acid, 254–255Carbonic anhydrase, 752Carbon monoxide

catalytic converter and,755, 758

dipole moment, 600methanol synthesis from,

1030molecular structure, 672oxidation mechanism, 742

reaction with nitrogendioxide, 737, 739–740

in syngas, 395, 397toxicity of, 973

Carbon nanotubes, 833–834,835

Carbonyl group, 1032characteristic vibration, 697

Carboxyhemoglobin, 973Carboxyl group, 236, 1033Carboxylic acids, 1033. See

also Acetic acidCarboxypeptidase-A, 756Carlson, D. A., 109Carotene, 693Carothers, Wallace H., 1036,

1041Cars. See AutomobilesCatalysis, 751–761

defined, 753by enzymes, 752, 756–757,

760, 1030, 1056in Haber process, 905heterogeneous, 753–755,

758homogeneous, 753,

756–757, 758–759, 761by nanosized metallic

particles, 833by platinum group metals,

940in polyethylene synthesis,

1040in substitution reactions,

1027by titanium dioxide, 752

Catalytic converters, 391,755, 758, 759

Cathode, 475, 481Cathode-ray tubes, 24–25Cathodic protection, 501–502Cathodic regions, 500Cations, 32

names of, 36–40, 41, 43–44periodic table and, 886–887qualitative analysis, 108–110,

339–341, 344, 346–347See also Complex ions

Cavitation, 174ccp (cubic closest packed)

structureholes in, 817–818in ionic solids, 813in metals, 791, 794–796

Cell potential, 475–476of battery, 492, 493concentration and, 485–492as intensive property,

479–480standard values, 476–482thermodynamics and,

482–485



Licensed to:

A82 Index

Cellulose, 1054, 1056coal and, 391in paper, 3–4, 5

Cellulose nitrate, 1035Celsius temperature,

conversion to Kelvin, 146Ceramics, 805–806, 808

grain sizes and propertiesof, 832

superconducting, 802–803Cerium hydrogen sulfate, 130Certain digits, A8Cesium, 35, 580, 581, 891,

892. See also Alkalimetals

Cesium atomic clock, 534Cesium chloride, 818Cesium fluoride, 817–818CFCs. See Chlorofluorocarbons

(CFCs)Chain reaction, nuclear, 1001Chain theory, of coordination

complexes, 953Chair form of cyclohexane,

1022Changes of state, 823–826

entropy and, 428–429,430–431, 438–439

free energy and, 434–436intermolecular forces and,

779positional probability and,

416, 430See also Boiling point;

Melting point; Phasediagrams; Sublimation

Chargeelectrochemical work and,

482–484formal, 630–631, 633–636partial (fractional), 92, 597,

600Charge balance, 271Charge density, hydration

and, 581, 853Charge-to-mass ratio, of

electron, 25–26Charles, Jacques, 145Charles’s law, 145–146, 149Chelating ligands, 948Chemical analysis

gravimetric, 112qualitative, 109–110,

339–341, 344, 346–347state-of-the-art, 119volumetric, 114See also Spectroscopy

Chemical bond. See BondingChemical energy, 360–362

interchanged with electricalenergy, 473, 474

See also Bond energy

Chemical equations, 66–68balancing, 67, 68–70for oxidation–reduction,

123–130for reactions in solution,

106–108Chemical equilibrium. See

Equilibrium, chemicalChemical formula, 30

determination of, 62–66for hydrated salt, 112from name of compound,

43–44Chemical kinetics. See

Kinetics, chemicalChemical reactions. See

Reactions, chemicalChemical shift, 701–702Chemical vapor deposition

(CVD), 829Chemistry

defined, 1fundamental laws of, 17–19history of, 16–24industrial, 10–14

Chemists, 2–3Chirality, 954–958

in monosaccharides, 1051,1053–1054

Chlor-alkali process, 510Chlorate ion, 922Chlorate salts, 922Chloride ions, 32, 35Chloride salts, solubility, 105,

339, 344–345, 346Chlorinated hydrocarbons,

1021–1022Chlorine, 35, 919–922

attraction for electrons,120, 889

commercial production of,509–510

electron affinity, 577reaction with sodium, 32water purification by, 915

Chlorite ion, 922Chlorofluorocarbons

(CFCs), 693, 759, 761, 1021–1022

replacements for, 175Chlorophyll, 969Christe, Karl O., 905Chromate ion, 943Chromium

coordination compoundsof, 951, 963

electron configuration, 564,566, 579, 615, 936–937

in gemstones, 965physical properties, 937, 938reactions of, 941, 943steel plated with, 508, 941

Chromous ion, 941cis–trans isomerism, 952,

955–957, 1024Clausius–Clapeyron equation,

823Clays, 804, 805–806, 808,

875Cleaning solution, 943Climate, carbon dioxide and,

359, 392, 393–394Closest packing

alloy structures and, 799in ionic solids, 813–818in metals, 790–792,

794–797of M & Ms, 792

Coagulation, 875Coal, 391–392

air pollution and, 178–179,181–182, 392

Coal conversion, 395, 397Coal gasification, 395, 397Coal slurries, 397Cobalt

compounds of, 944coordination compounds

of, 944, 946, 949–953,955–958, 960–961, 968

physical properties, 937Cockroach identification, 109Codons, 1058, 1060Coefficients, of chemical

equation, 67–68Coffee cup calorimeter, 374Cohen, Ronald C., 179Cohesive forces, of liquid, 783Colligative properties,

864–873boiling-point elevation,

864–866, 872of electrolyte solutions,

871–873freezing-point depression,

866–867, 871, 872osmotic pressure, 867–871,

872–873, 1055–1056Collision model, for kinetics,

747–751Collisions of gas molecules

equilibrium and, 198–199intermolecular, 169–171with walls, 157–160,

167–169Colloids, 873–875Colors

of complex ions, 936,962–963

of fireworks, 526, 536–537of gems, 965in spectroscopy, 693, A18wavelength of light and,

962–963

Combustionof alkanes, 1021of ammonia, 387–389calorimetry of, 378–380early experiments with,

16–17entropy and, 456–457of methane, 118, 122,

360–361, 380, 385–386,411, 495–496

of methanol, 389–390, 443as oxidation–reduction, 118of propane, 70–72

Common ion effect, 287–289in buffered solutions,

289–297solubility and, 332–333

Common names, 36, 40of organic compounds,

1021Communication, chemical,

646–647Complementary color, 962Complete ionic equation,

106–108Complex ions, 936, 946–947

colors of, 936, 962–963crystal field model,

959–966equilibria involving, 334,

341–347isomerism of, 951–958ligand field model, 968localized electron model,

958–959magnetic properties,

960–962, 968molecular orbital model,

966–968nomenclature, 948–951solubility and, 334,

344–347VSEPR model and, 958See also Coordination

compoundsComplex orbitals, 549–550,

552, 568Composites

carbon fiber, 942in conch shell, 789

Compositionpercent, 60–61of solutions, 97–100, 847

CompoundsDalton’s atomic theory and,

19–20, 953formula determination,

62–66fundamental chemical laws

and, 17–19names of, 36–45percent composition, 60–61



Licensed to:

Index A83

Compressibilityof real gas, 176of states of matter, 778

Compression of a gasadiabatic, 457–459isothermal, 422–425work associated with,

363–364Compton, Arthur, 528Computer chips, 810–811Concentrated solution, 847Concentration

cell potential and, 485–492equilibrium position and,

216–218free energy and, 444gas pressure and, 203–204of solution, 97–100

Concentration cells, 490–492Conch shell, 789Condensation, 431, 819Condensation polymerization,

1039–1040of nucleic acids, 1057of proteins, 1045

Condensed states, 778. Seealso Liquids; Solids

Conduction bands, 798, 800,801, 808

Conductors. See Electricalconductivity;Semiconductors; Thermalconductivity

Confidence limits, A13Conjugate acid, 234, 235, 251

of weak base, 265Conjugate acid–base pair, 235Conjugate base, 234–235, 251

of strong acid, 236, 237of weak acid, 236, 237,

263–264Conjugated molecules, 693Conservation of energy, 359,

361, 362, 411Conservation of mass, 9, 17Constant pressure

enthalpy change at,365–366, 370, 374, 455

heat capacity at, 367–370Constant-pressure calorimetry,

374–378Constant volume

heat capacity at, 367–370heat flow at, 370, 378

Constant-volume calorimetry,378–380

Constructive interference,529, 785

Contact potential, 809Contact process, 918Conté, Nicolas-Jacques, 596Continuous flow processes, 10

Continuous spectrum, 530Control rods, 1002Cooling, by water, 819,

857, 894Coordinate covalent bond,

947, 958Coordination compounds,

946–951biological importance,

969–973early theories of, 953isomerism of, 951–958magnetic properties,

960–962nomenclature, 948–951See also Complex ions

Coordination isomerism, 951Coordination number, 341,

946–947, 958Coordination theory, 953Copolymers, 1039–1040,

1044Copper, 34–35

electron configuration, 564,566, 579, 615, 937

electrorefining of, 507–508patina on, 498, 499, 945physical properties, 790,

937plating with, 503polycrystalline structure,

832reactions of, 945surface properties, 793

Core electrons, 563, 570,572–573, 622

Corrosion, 497–502equilibrium constant for,

451prevention of, 500–502, 508of silver, 498, 505

Coulomb’s lawion interaction energy

and, 594lattice energy and, 609

Counter ionsof coordination compound,

946in galvanic cell, 481

Covalent atomic radii. SeeAtomic radii

Covalent bonding, 30, 597coordinate, 947, 958as model, 612–615nonmetals and, 35, 603See also Bond energy;

Hybrid orbitals; Lewisstructures; Localizedelectron (LE) model;Molecular orbitals(MOs); Polar covalentbonds; VSEPR model

Covalent compounds, namingof, 40, 41

Covalent hydrides, 894boiling points of, 780of boron, 897–898of Group 6A elements, 914

Cracking, 391, 893Crenation, 870Critical mass, 1001Critical nuclear process, 1001Critical point

of carbon dioxide, 831of water, 829

Critical pressure, 829Critical temperature, 829

supercritical fluid and, 852

Crommie, Michael, 540Crosslinking, 1036Cryolite, 506, 507Crystal field model, 959–966Crystalline solids, 785

diffraction by, 529–530,785–788

grain structure of, 832molecular, 788, 812–813types of, 788, 790See also Ionic compounds;

Metals; Network solidsCubic closest packed (ccp)

structureholes in, 817–818in ionic solids, 813in metals, 791, 794–796

Cubic holes, 816, 818Cubic lattice, simple,

787, 796of cesium chloride, 818

Curie, Irene, 991Curie, Marie, 26–27, 914Curie, Pierre, 26–27, 914Current. See Electric currentCVD (chemical vapor

deposition), 829Cyanide ion

in aqueous solution, 237,265

Lewis structure, 623–624toxicity of, 973

Cycles per second, 523Cyclic hydrocarbons

aromatic, 1026–1028saturated, 1022–1023unsaturated, 1025See also Benzene

Cyclobutane, 1022decomposition, 718

Cyclohexane, 1022Cyclopropane, 1022Cyclotron, 991Cysteine, 1046, 1050Cytochromes, 969, 973

Dacron, 1039–1040Dalton, John, 18–21, 152,

522, 953Dalton’s law of partial

pressures, 152–155Dating artifacts and rocks,

993–995Davis, James H., 857Davisson–Germer experiment,

530Davy, Humphry, 910DDT, fat solubility of, 849de Broglie, Louis, 528–529,

530, 536–537, 538Debye (unit of dipole

moment), 599Decay rate, 987Decay series, 986Decimal point

in exponential notation, A1significant figures and,

A14–A15Definite proportion, law of, 18Degenerate orbitals, 554, 562Dehydrating agents

sulfuric acid, 911, 918tetraphosphorus decoxide,

912Delocalization of electrons, 615

in methane, 689molecular orbitals and,

685–688resonance and, 626

Democritus, 16, 522Denaturation of proteins, 1050Denitrification, 906Density

crystal structure and,794–795

determination of, A11–A12of gas, molar mass and,

151–152within group of elements,

580of nucleus, 982of states of matter, 778

Dental cavities, 328, 474Deoxyribonucleic acid (DNA),

1056–1058entropic ordering of, 426of extremophiles, 760

Dependent variable, A4Depletion force, 426Derivative, as slope, A5Desalination, 870–871Desorption, 755Destructive interference, 529,

785Detergents, hard water and,

250, 895–896Deuterium, fusion of,

1003–1004



Licensed to:

A84 Index

Dextrorotatory isomer, 955DHA (dihydroxyacetone),

1052Dialysis, 869Diamagnetism, 680, 681, 684

of complex ions, 961of hemoglobin, 971

Diamond, 788, 790, 799–800,801

manufacture of, 442–443,801, 828–829

Diaphragm cell, 510Diatomic molecules

bond order, 676–677heat capacity and, 368heteronuclear, 684–685,

698–700homonuclear, 677–684moment of inertia, 698,

700potential energy, 694–695

Diborane, 897Dichromate ion, 943Dicyclopentadiene, 1043Diethyl ether, vaporization of,

821–822Diethyl zinc, paper

decomposition and, 6Differential rate law, 721,

722–726, 735, 736Diffraction, 529–530,

785–788Diffractometer, 787Diffusion, 164, 165–167Digital voltmeter, 476, 483Dihydroxyacetone (DHA),

1052Dilute solution, 847Dilution of solutions, 99–100Dimensional analysis, A17Dimer, 1039Dimethylamine, 251Dinitrogen monoxide. See

Nitrous oxideDinitrogen pentoxide, 909

decomposition rate,722–723, 726–729, 750

Dinitrogen tetroxide, 907,909

Dinitrogen trioxide, 908, 909Dinosaurs, 178Dioxygen difluoride, 923Dipeptide, 1045Dipole–dipole forces,

779–780in proteins, 1050See also Hydrogen bonding

Dipole moments, 599–603induced, 780instantaneous, 780, 781percent ionic character

and, 611

rotational transitions and,698

VSEPR model and, 649Diprotic acids, 236Dirac, Paul, 575Disaccharides, 1054Dispersion forces. See London

dispersion forcesDispersions, colloidal,

873–875Disproportionation reaction,

922Dissociation constant. See

Acid dissociationconstant (Ka); Ion-product constant (Kw)

Disulfide linkage, 1050Division

in exponential notation,A1, A2

significant figures, A14,A15

DNA (deoxyribonucleic acid),1056–1058

entropic ordering of, 426of extremophiles, 760

Dobereiner, Johann, 559Doping of semiconductors,

808–809, 811d orbitals, 552, 554, 570

in coordination compounds,958, 959–968

in Group 6A bonding, 914hybrid orbitals and,

668–670octet rule and, 627–628,

630, 632, 634, 668of transition metals, 934,

935, 936–938, 939–940Double bonds

in alkenes, 1023–1024,1025, 1026

alternating, 693bond energies, 617bond lengths, 617sigma and pi bonds of, 665vibrational frequency of,

697in VSEPR model, 645–647,

649See also Ethylene

Doublet, 702Downs cell, 509Drake, Edwin, 390Dry cell batteries, 493–495Dry ice

lattice structure, 812sublimation, 823, 831

d2sp3 hybridization, 670in complex ions, 958

dsp3 hybridization, 668–669Dual nature of light, 528

Ductility of metals, 34, 790,797

steels, 799Duet rule, 621, 622du Pont, Eleuthère, 536

Ecamsule, 524EDTA

(ethylenediaminetetraacet-ate), 948

Effective nuclear charge,557–558

atomic radius and, 577Effective pairs, 647, 649, 650

hybrid orbitals and, 664,665, 666, 668, 671

Efficiency, of galvanic cell,484

Effusion, 164–165, 166Eiffel, Gustave, 498Einstein, Albert, 526–528,

530, 574, 997, 1005Ekasilicon, 559Elastic collisions, 157,

158–159Electrical conductivity

of aqueous solutions, 93–96band model and, 798of carbon nanotubes,

833–834of graphite, 801of metals, 34, 790, 797of molten ionic compounds,

612of silicon, 808superconductivity, 802–803See also Electric current;

SemiconductorsElectrical insulator, 800Electrical potential. See Cell

PotentialElectric charge. See ChargeElectric current

in electrolytic cell, 502–503in galvanic cell, 473–474,

482–483in molten ionic compound,

612in motor, 455–456See also Electrical

conductivityElectric field

bond polarity and, 597, 601

colloid in, 873–874of electromagnetic

radiation, 522Electric power. See Energy

sourcesElectrochemistry

batteries, 455–456, 487,492–497

corrosion and, 497–502,505, 508

defined, 473dental application of, 474standard reduction

potentials, 476–482, A26window application of,

494–495See also Electrolysis;

Galvanic cellsElectrodes

of galvanic cell, 474–475,481

ion-selective, 488–489Electrolysis, 502–506

in alkali metal production,890

in aluminum production,506–507

for cleaning silver, 505defined, 502in electrorefining, 507–508in metal plating, 503, 504,

508of mixtures of ions, 504,

506of sodium chloride, 508–510of water, 398, 503–504,

893Electrolytes, 93–96

coagulation by, 875colligative properties of,

871–873ion pairing in, 872

Electromagnetic force, 1005Electromagnetic radiation,

522–525blackbody, 525–526classification of, 524diffraction of, 529, 785–788hydrogen spectrum,

530–531, 532, 533, 535quantum theory of,

525–527, 528, 530See also Gamma rays;

Infrared radiation;Lasers; Light; Microwaveradiation; Photons;Spectroscopy; Ultravioletradiation

Electromotive force (emf),475, 482. See also Cellpotential

Electron(s), 29early experiments on, 24–26photoelectric emission of,

526–527relativistic mass of, 574–575wave properties of,

529–530, 537, 538, 540See also Beta (�) particles;

Valence electrons



Licensed to:

Index A85

Electron acceptor, 122Electron affinity, 576–577, 580Electron capture, 985Electron configurations,

561–568Electron correlation problem

for atoms, 557, 558, 568for molecules, 674

Electron-deficient compoundsof beryllium, 628of boron, 626–627, 628,

897–898Electron delocalization, 615

in methane, 689molecular orbitals and,

685–688resonance and, 626

Electron density map, 550Electron donor, 122Electronegativity, 597–599

bonding in covalenthydrides and, 780

formal charge and, 634,635, 636

of halogens, 919percent ionic character

and, 611Electronic spectroscopy, 690,

691–694Electronic transitions, 690,

691–692in Bohr model, 532–533,

535Electron-pair acceptor, 947Electron-pair donor, 947Electron sea model, 797Electron spin, 556, 575

chemical shift and, 703Electron spin quantum

number, 556Electron-volts (eV), 571Electrorefining, 507–508Electrostatic precipitator, 875Electrostatic repulsion, in

colloids, 873–874Elementary steps, 737–738,

741Elements

abundances of, 889ancient Greek system,

16, 142Boyle’s definition of, 16Dalton’s atomic theory

and, 19enthalpy of formation,

386, 387in human body, 889oxidation state of, 120representative, 565,

578–579, 886–891standard free energy of

formation, 443, A21–A23

standard state, 384, 386,387

symbols for, 30, 982synthesis in stars, 988,

1003transformations of,

991–992transuranium, 992See also Groups; Isotopes;

Periodic tableElephant poaching, 54Elevation. See Altitudeemf (electromotive force),

475, 482. See also Cellpotential

Emission spectrumelectron spin and, 556of fireworks, 536–537of hydrogen, 530–531, 532,

533, 535Empirical formula, 63–65, 66en (ethylenediamine), 948Enantiomers, 954–955, 957Endothermic process, 361,

362enthalpy change in, 366entropy change, 430, 432equilibrium constant for,

221, 452equilibrium positions of,

221–222vaporization as, 819

Endpoint of indicator, 115,319–321, 323

in oxidation–reduction, 130See also Equivalence point

-ene (suffix), 1024Energy, 359–365

of activation, 747–751chemical, 360–362conservation of, 359, 361,

362, 411constant-volume

calorimetry and, 378–380defined, 359of electromagnetic

radiation, 524–525equivalence to mass,

527–528, 984–985,997–999, 1005

as form of matter, 530internal, 362–366,

368–373, 378–380minimized in bonding, 595,

663, 670–671, 676quantization of, 525–527,

528, 530–531, 535, 538,544, 546

as state function, 360, 373,425

transfer of, 359–360useful, 411

See also Bond energy; Freeenergy; Heat; Ionizationenergies; Kinetic energy;Potential energy

Energy crisis, 456–457Energy levels

hybridization and, 662,663, 664, 666

of hydrogen atom,530–531, 532–533, 535,548–549, 554

of molecular orbitals, 675molecular spectroscopy

and, 690–693, 695–696,698–699

of particle in a box,545–547, 693

of polyelectronic atoms,569–570

Energy sourceshydrogen as, 380, 396,

397–400new, 394–401present, 390–394solar ponds, 848See also Batteries; Fossil

fuelsEnglish system, 9, A15Enthalpy, 365–366

calorimetry and, 374–378entropy change and, 432,

433heat at constant pressure

and, 366, 455of ideal gas, 369–373, 444as state function, 365, 373

Enthalpy of formation,384–390

bond energies and, 618defined, 384of element, 386, 387table of values, A21–A23

Enthalpy of fusion, 823compared to heat of

vaporization, 778entropy change and, 428

Enthalpy of hydration, 850of halide ions, 921

Enthalpy of reaction, 366bond energies and,

617–619calorimetry and, 374–378from enthalpies of

formation, 385–390as extensive property, 381from Hess’s law, 380–384key concepts, 387

Enthalpy of solution,849–851

Raoult’s law and, 862,863–864

temperature and, 856

Enthalpy of vaporization,819, 821–823

compared to heat of fusion,778

entropy change at, 429Entropy

absolute, 438–440changes of state and,

428–429, 430–431,438–439

in chemical reactions,436–440

defined, 425–427disorder and, 413–414,

436, 438in electrochemical process,

483of ideal gas, 425–427,

444–445molecular structure and,

439–440as organizing force, 426pressure dependence of,

444–445probability and, 413–417,

425–427, 430, 437–438,444–445

second law and, 426,429–430, 456–457

spontaneity and, 413–417,429–433, 483

standard values, 439, 440,A21–A23

as state function, 439temperature dependence of,

428, 438Entropy of hydration, 851,

853of halide ions, 921

Entropy of solution, 416–417,850–851, 853

Entropy of vaporization, 429,430–431, 822

Enzymes, 752, 756–757, 760

in fermentation, 1030in polysaccharide digestion,

1056See also Proteins

Ephedrine, 253Equation of state, 147Equations, chemical,

66–68balancing, 67, 68–70for oxidation–reduction,

123–130for reactions in solution,

106–108Equations, radioactive decay,

982Equatorial hybrid orbitals,

668



Licensed to:

A86 Index

Equilibrium, chemicalcharacteristics of, 197–200defined, 197of electrochemical cell,

487, 489entropy and, 430, 435free energy and, 435, 444,

447–452heterogeneous, 206–208homogeneous, 206law of mass action,

200–203, 206, 208Le Châtelier’s principle and,

216–222of real gases, 222–223

Equilibrium constant (K),200–203

applications of, 208–211electrochemical

measurement of,489–490, 491–492

extent of reaction and, 208free energy change and,

449–452reaction quotient and,

208–209, 210, 211, 217, 449

for redox reactions,489–490

small, 214–216for sum of stepwise

reactions, 345temperature dependence of,

220–221, 452–453in terms of pressures,

203–206, 207, 222–223units of, 202, 205–206See also Acid dissociation

constant (Ka)Equilibrium expression,

200–201, 202involving pressures,

203–205, 207involving pure solids or

liquids, 206–208Equilibrium partial pressures,

204–206Equilibrium position

concentration and, 216–218defined, 203free energy and, 447–448pressure and, 218–220solubility and, 329summary, 222temperature and, 220–221volume and, 218–219, 220

Equilibrium problems,208–216

finding concentrations orpressures, 210–211

reaction quotients in,208–209, 210, 211, 217

with small equilibriumconstants, 214–216

summary of procedure, 211See also Acid–base

equilibria problemsEquilibrium vapor pressure,

820. See also Vaporpressure

Equivalence point, 114, 115,306

indicator endpoint and,115, 319, 321, 323–324

methods for determining,319

pH value at, 306, 311, 312,314–315

for polyprotic acid, 324,325, 327

Error limit, A10, A11, A13Esters, 1033–1034Ethane, 1015Ethanol, 1030

as fuel, 401, 1030as nonelectrolyte, 96reactions of, 1033solubility in water, 93vapor pressure, 820, 821

Ethene, 1024Ethylamine, 251Ethylene, 1014, 1023–1024

bonding in, 663–665, 1024from cyclobutane, 718ethanol synthesis from,

1030hydrogenation of, 754polymers based on,

1037–1038, 1040–1042,1044

Ethylenediamine (en), 948Ethylenediaminetetraacetate

(EDTA), 948Ethylene glycol, 867, 1030,

1039Ethyl group, 1018Ethyne, 1024eV (electron-volts), 571Evaporation. See VaporizationExact numbers, A14Excited states

of hydrogen atom, 530,532, 533, 554

of molecules, 693, 694of nuclei, 985

Excluded-volume force, 426Exclusion principle, 556, 562Exothermic process, 361–362

enthalpy change, 366entropy change, 430,

431–432, 433, 435equilibrium constant, 221,

452, 453free energy change, 435–436

Expansion of a gasisothermal, 418–422,


425–427work associated with,

363–364See also PV work

Expected bond energy,597–598

Experimental uncertainty,A8–A13

Experiments, 8Explosives

in fireworks, 536–537nitrogen compounds, 10,

119, 200, 682, 806, 904, 905

plastic, detection of, 806screening of luggage, 119tagging of, 42–43

Exponential notation, A1–A3Extensive property

enthalpy change as, 381entropy as, 439free energy as, 442

Extinction coefficient, A18Extremophiles, 760Extremozymes, 760

Face-centered cubic lattice,787, 791, 792, 794–796

holes in, 817–818Families. See Groups of

periodic tableFaraday (unit of charge), 483Faraday, Michael, 483Fat-soluble vitamins, 854–855Feldspar, 806Femtochemistry, 718Fermentation, 401, 1030Ferric ion, 37Ferrochrome, 941Ferrous ion, 37Ferrovanadium, 941Fertilizers

nitrogen in, 10, 905phosphorus in, 913, 918

Fibrous proteins, 1045, 1048Fire extinguisher, 831Fire retardants, for PVC, 14Firewalking, 383Fireworks, 526, 536–537First ionization energy,

571–575First law of thermodynamics,

362, 363, 411, 456First-order rate laws

for chemical reactions, 723,726–730

for radioactive decay, 987,989, 995

Fisher, Mel, 505Fission, nuclear, 984,

1000–10025% rule, 243–244Flame test, for alkali metal

ions, 340, 341Fluids, supercritical, 852Fluorapatite, 328Fluoride ion

hydration of, 921tooth decay and, 328

Fluorine, 35atomic radius, 889electron affinity, 577, 889electron configuration, 562ionization energy, 573molecular structure,

621–622, 681, 682, 889oxidation state, 120oxygen compounds with,

922, 923physical properties, 919,

920preparation of, 920sources of, 920

Fluorite structure, 818f orbitals

of hydrogen atom, 552,554

of polyelectronic atoms,565, 566, 570

of transition elements, 934,935, 939

Forcechemical bond and, 597,

612, 695–696defined, 158electromagnetic, 1005entropic, 426gravitational, 20, 1005nuclear, 1003–1004, 1005pressure and, 143, 157,

159, 363–364work done by, 360,

363–364See also Intermolecular

forcesFormal charge, 630–631,

633–636Formation constants, 341Formula, 30–31

determination of, 62–66for hydrated salt, 112from name of compound,

43–44Formula weight, 60Forward bias, 810, 812Fossil fuels, 358–359, 390–392

air pollution and, 359, 758, 916

carbon dioxide and, 392,393, 857



Licensed to:

Index A87

entropy and, 457See also Coal; Petroleum

Fractional (partial) charge,92, 597, 600. See alsoPolar covalent bonds

Francium, 35, 580Franklin, Benjamin, 16Frasch, Herman, 916Frasch process, 916Free energy, 433–436

chemical reactions and,440–444, 445–451

electrochemical, 484–485,486, 487, 489

equilibrium and, 435, 444,447–452

of formation, 443–444,A21–A23

hydrogen halidedissociation and, 921

pressure dependence of,444–447

solubility and, 850–851standard, 440–444as state function, 441work and, 453–455

Free expansion, of ideal gas,418

Free radicalsin polymerization,

1037–1038radiation-induced, 1006titanium dioxide and, 752

Freezing pointof noble gases, 781See also Ice; Melting point

Freezing-point depression,866–867

of electrolyte solutions,871, 872

Frenkel defects, 818–819Freons, 759, 761,

1021–1022. See alsoChlorofluorocarbons(CFCs)

Frequencyof molecular vibration,

695–696of quantized radiation,

525–527of rotational transitions,

699of wave, 522–523

Frequency factor, in rateconstant, 749

Frictional heating, 360in galvanic cell, 483in motor, 455

Fructose, 1051, 1053, 1054Fry, Art, 11Fuel cells, 495–497Full, Robert J., 782

Fullerenes, 788, 799, 812,833

Functional groups, 1028Fusion, nuclear, 1000,

1003–1004in stars, 988, 1003

Galileo, 10, 142Gallium, 564, 580, 897, 898Gallium arsenide lasers, 807Galvani, Luigi, 476Galvanic cells, 473–476

batteries, 455–456, 487,492–497

compared to electrolyticcells, 502

concentration cells, 490–492concentrations and, 485–492defined, 474equilibrium state of, 487,

489fuel cells, 495–497full description of, 480–482standard reduction

potentials of, 476–482,A26

thermodynamics of,482–485

work done by, 475,482–484

Galvanizing, 500, 946Gamma rays, 26, 985

cellular damage by, 1004,1006

in radiation therapy, 996in thermal neutron analysis,

119Garrett, Steven L., 175Gas chromatography, 109Gas constant, 147, 161Gaseous diffusion, 164,

165–167Gases, 141–182

Avogadro’s law(hypothesis), 20, 21, 146

Boyle’s law, 143–145, 146, 149

Charles’s law, 145–146,149

in chemical equation, 67Dalton’s law of partial

pressures, 152–155diffusion of, 164, 165–167early experiments, 142effusion of, 164–165, 166equilibria involving,

203–206, 207, 218–220,222–223

kinetic molecular theory of,155–163, 164–165,167–169, 172–175

mixing of, 164, 165–167

mixtures of, 152–155molar concentration, 204molar mass, 151–152molar volume, 150PV work and, 364–367,

376–378, 424, 454, 455real, 145, 150, 169–176,

222–223separating with molecular

sieve, 156solubility of, 855–856,

857–858standard state, 384standard temperature and

pressure, 150, 151state of, 147stoichiometry of, 150–152See also Atmosphere; Ideal

gas; PressureGasohol, 401, 1030Gasoline, 390–391

air pollution and, 177hydrogen as by-product of,

893lead in, 391, 758, 900methanol compared to,

389–390methanol converted to, 397octane ratings, 71viscosity of, 783

Gaub, Hermann E., 834Gay-Lussac, Joseph, 20, 21Geckos, 782Geiger–Müller counter, 993Gemstones, 965Gene, 1058General theory of relativity,

528Genetic radiation damage,

1006Geometrical isomerism, 952,

955–957, 1024Germanium, 559–560, 886,

899, 901Geubelle, Philippe, 1043Gibbs, Josiah Willard, 433Glass

carbon dioxide in form of,804

composition of, 804etching of, 921liquid meniscus in, 783photochromic, 924structure of, 785, 804

Glass electrode, 488–489Global warming, 179, 359,

393–394nitrous oxide and, 908sequestration of carbon

dioxide and, 392Globular proteins, 1045,

1049–1050

Glucosecyclization of, 1054fermentation of, 1030polymers of, 1054–1056radiolabeled, 996in sucrose, 1054

Gluons, 1005Glycerol, viscosity of, 783Glycogen, 1054, 1056Glycoside linkages, 1054–1056Gold

acid solution of, 485electron configuration, 575nanoparticles of, 833oxidation and, 497, 498relativistic effects in,

574–575Goodyear, Charles, 1036Gorelli, Federico, 804Goudsmit, Samuel, 556Grafting, of polymers, 1044Graham, Thomas, 164Graham’s law of effusion,

164–165, 166Grains, crystalline, 832Granquist, Claes-Goran, 494Graphing functions, A4–A5Graphite, 788, 799, 800–801

diamonds made from,442–443, 801, 828–829

in pencils, 596Gravimetric analysis, 112Gravitons, 1005Gravity

as fundamental force, 1005photons affected by, 528weight and, 20

Gray (unit of radiation dose),1006

Gray tin, 900Greenhouse effect, 392, 393,

394, 857nitrous oxide and, 908

Gresham, T. L., 13Ground state

of hydrogen atom, 532,535, 554

zero-point energy of, 547Group 1A elements. See

Alkali metals; HydrogenGroup 2A elements. See

Alkaline earth metalsGroup 3A elements, 897–898.

See also Aluminum; BoronGroup 4A elements, 899–901.

See also Carbon; Lead;Silicon; Tin

Group 5A elements, 902–903.See also Nitrogen;Phosphorus

Group 6A elements, 914. Seealso Oxygen; Sulfur



Licensed to:

A88 Index

Group 7A elements. SeeHalogens

Group 8A elements. SeeNoble gases

Groups of periodic table, 35,579, 886

atomic radii in, 577–578,887–889

ionization energies in, 573metallic character in, 887valence electrons and,

563, 565Guericke, Otto von, 142Guldberg, Cato Maximilian,

200–201Gypsum, 916

acid rain and, 181

Haber, Fritz, 200, 216, 753Haber process, 200, 904–905

biological nitrogen fixationand, 906

catalysis in, 753diagram of, 904equilibrium of, 200,

201–202, 216–217production of hydrogen for,

73, 893See also Ammonia synthesis

Hadrons, 1005Hafnium, 568, 939–940Half-cell potential. See Cell

potentialHalf-life

first-order reaction, 729–730radioactive sample, 989–990second-order reaction, 731,

733transuranium elements, 992zero-order reaction, 734

Half-reaction method,124–130

Half-reactions, 124in galvanic cell, 473,

476–482Halide ions, hydration of, 921Hall, Charles Martin, 506Hall–Heroult process,

506–507Halogenation

of saturated hydrocarbons,1021

of unsaturated hydrocarbons,1026

Halogens (Group 7A), 35,919–923

electron affinities, 577oxyacids of, 922, 923physical properties,

919, 920preparation of, 920sources of, 920

See also Chlorine; Fluorine;Hydrochloric acid;Hydrofluoric acid

Hamiltonian operator, 538,541, 542

Hard water, 250, 895–897Harmonic oscillator, 695Hassium, 36hcp (hexagonal closest

packed) structurein ionic solids, 813in metals, 791, 794, 796

HDPE (high-densitypolyethylene), 1040

Heatadiabatic process and, 457calorimetry, 374–380conduction by metals, 790,

797, 798at constant pressure, 366,

370, 374, 455at constant volume, 370,

378in cyclic expansion–

compression, 424–425energy transfer and, 359,

360frictional, 360, 455, 483internal energy and, 363,

364–365pathway-dependence of, 425pollution by, 857sign convention for, 363vs. temperature, 360as wasted energy, 455, 483See also Exothermic

process; TemperatureHeat capacity

at constant pressure,367–370

at constant volume, 367–370defined, 374firewalking and, 383of ideal gas, 366–373molar, 366–370, 374of polyatomic gas, 367–368specific, 374temperature dependence

of, 438Heating curve, 823–824Heat of fusion, 823

compared to heat ofvaporization, 778

entropy change and, 428Heat of hydration, 850

of halide ions, 921Heat of reaction. See

Enthalpy of reactionHeat of solution, 849–851

Raoult’s law and, 862,863–864

temperature and, 856

Heat of vaporization, 819,821–823

compared to heat of fusion,778

entropy change at, 429Heat packs, 400Heisenberg, Werner, 536, 539Heisenberg uncertainty

principle, 539–541wave function and, 550,

556zero-point energy and, 547

Helical structureof DNA, 1057–1058, 1059of proteins, 1048, 1049

Helium, 35, 923electron configuration, 561Lewis structure, 621molecular orbital model,

676–677from nuclear fusion, 1003quantum mechanical model

of, 556–558, 568Helium ion, 557, 677Helium nuclei

fusion in stars, 988from radioactive decay, 984See also Alpha (�) particles

Heme complex, 969, 970–971Hemoglobin, 971–973

nitric oxide and, 686Henderson–Hasselbalch

equation, 294indicator color change and,

320–321Henry, William, 855Henry’s law, 855–856

Lake Nyos tragedy and,859

Heroult, Paul, 506Hertz (Hz), 523Hess’s law, 380–384Heterogeneous catalysis,

753–755, 758Heterogeneous equilibria,

206–208Heteronuclear diatomic

molecules, 684–685rotational spectra, 698–700

Heuer, Arthur, 789Hexadentate ligand, 948Hexagonal closest packed

(hcp) structurein ionic solids, 813in metals, 791, 794, 796

Hexoses, 1051, 1053High altitude. See AltitudeHigh-altitude sickness, 972High-spin case, 961,

964, 968Hill, Julian, 1036Ho, Wilson, 742

Hodgkin, Dorothy, 61Holes

in closest packing,813–816, 817–818

of semiconductor, 808–809on surface of copper, 793

Homogeneous catalysis, 753,756–757, 758–759, 761

Homogeneous equilibria, 206Homogeneous mixtures. See

SolutionsHomonuclear diatomic

molecules, 677–684Homopolymer, 1039Honeybees, 362Hund, F. H., 562Hund’s rule, 562Hybridization, 662Hybrid orbitals, 661–673

in complex ions, 958–959d2sp3, 670dsp3, 668–669sp, 666–667sp2, 663–665, 666sp3, 661–663, 669, 689summary, 671

Hydrated salt, formula for,112

Hydration, 92acidity of hydrated ion,

266, 267of alkali metal ions, 581enthalpy of, 850entropy of, 851, 853of halide ions, 921of proton, 234, 235, 238

Hydrazine, 907Hydride ion, 894Hydrides, 894–895

boiling points of, 780of boron, 897–898of Group 6A elements,

914metallic, 400, 894–895

hydro- (prefix), 44Hydrocarbon derivatives,

1028–1035alcohols, 1028–1031 (see

also Ethanol; Methanol)aldehydes, 1032–1033amines, 253, 1034–1035carboxylic acids, 1033esters, 1033–1034ketones, 1032–1033

Hydrocarbonsaromatic, 1026–1028 (see

also Benzene)in petroleum, 390–391saturated, 1014–1023unsaturated, 754, 1014,

1023–1028 (see alsoEthylene)



Licensed to:

Index A89

Hydrochloric acid, 95, 234,236, 920–921

in aqua regia, 346, 485,942

pH calculations, 241–242reaction with sodium

hydroxide, 113See also Hydrogen chloride

Hydrofluoric acid, 920–921equilibria with, 242–243See also Hydrogen fluoride

Hydrogenchemical properties,

893–895commercial preparation of,

891, 893as diatomic ion, 677as diatomic molecule,

bonding in, 595–597,621, 673–676

as fuel, 380, 396, 397–400,496–497, 895

in interstitial hydrides,894–895

isotopes, 55, 1003–1004nonmetallic character of,

35, 580, 886, 887, 894nuclear magnetic resonance

with, 700–704oxidation state of, 120physical properties, 893as real gas, 176in stars, 988, 1003

Hydrogenation reactions, 754,1026

Hydrogen atomBohr model, 531–533, 535,

536, 538, 549, 551electron configuration, 561emission spectrum,

530–531, 532, 533, 535energy levels, 530–531,

532–533, 535, 548–549,554

orbitals, 538–539, 541,550–556

particle in a box and,541–542

quantum numbers,548–550, 551–552

summary, 556uncertainty principle and,

539–541, 550, 556wave equation, 548–550

Hydrogen bonding, 779–780in alcohols, 1030in ammonia, 906in hydrazine, 907in hydrogen fluoride, 920in nonideal solutions, 862,

863in nucleic acids, 1057, 1060

in nylon, 1036in proteins, 1047–1048,

1050viscosity and, 783in water, 779, 780, 813,

819, 821, 822, 823, 894Hydrogen chloride, 919–921

dipole moment, 602dissolved in water, 234, 856infrared spectrum of, 696microwave spectrum of,

699–700reaction with ammonia,

165, 235See also Hydrochloric acid

Hydrogen–chlorine cannon,919

Hydrogen electrode, standard,477

Hydrogen fluoride, 919–921bond polarity, 597,

599–600, 685enthalpy of formation,

617–618molecular orbital model,

684–685Hydrogen halides, 919–921.

See also Hydrogenchloride; Hydrogenfluoride

Hydrogen ionsArrhenius acid concept and,

95, 113, 234in decomposition

of paper, 4–6hydrated, 234, 235, 238from water, 238–239,

270–276, 297–300See also Acids

Hydrogen sulfidedipole moment, 603solubility equilibria and,

338, 339–340, 346Hydrogen sulfites, 918Hydrohalic acids, 236,

920–921. See alsoHydrochloric acid;Hydrofluoric acid

Hydronium ion, 234, 235, 238Hydrophilic side chains, 1045Hydrophilic substances, 855Hydrophobic side chains, 1045Hydrophobic substances, 855Hydroxide ions

from autoionization ofwater, 238–239, 250

from base reacting withwater, 96, 251, 263–264

reaction with weak acid,113, 117

from strong base, 95, 113,248–249

Hydroxidesof alkali metals, 248–249,

250of alkaline earth metals,

249–250solubility in water, 105

Hydroxyapatite, 328Hydroxyl group, 1028

characteristic vibration, 697

Hydroxyl radical, 752, 1037Hyperconjugation, 630, 632Hypertonic solutions, 870Hypervitaminosis, 855hypo- (prefix), 40Hypochlorite ion, 922Hypochlorous acid, 236, 922Hypofluorous acid, 922, 923Hypophosphorous acid, 913Hypotheses, 3, 8, 9Hypotonic solution, 870Hz (Hertz), 523

-ic (suffix), 37, 44Ice

biological effects of, 874density, 830, 894melting, 434–435, 778,

823–824, 827, 830structure of, 812, 813,

894sublimation, 827–828, 831vapor pressure, 824

Ice skating, 830ICE table, 211Ideal gas

adiabatic expansion–compression, 457–460

defined, 145enthalpy of, 369–373, 444entropy of, 425–427,

444–445expansion into vacuum,

414–416free energy of, 444–447free expansion of, 418heat capacity, 366–370internal energy of, 368–373isothermal expansion and

compression, 417–427kinetic energy of, 157,

160–161, 366, 368kinetic molecular theory of,

155–163, 167–169molar mass, 151–152molar volume, 150partial pressures, 152–155

Ideal gas law, 146–150derivation of, 157–161

Ideal solutions, 862, 863Ilmenite, 940–941Independent variable, A4

Indicators, acid–base, 114,115, 319–324

chart of pH ranges, 322Indium, 560, 897, 898Industrial chemistry, 10–14Inert atmosphere box, 903Inert gases

in acoustic refrigerator, 175nitrogen as, 903, 905noble gases and, 643See also Noble gases

Infrared radiation, 524–525climate and, 393, 394vibrational spectroscopy

and, 690, 696, 697Initial rates, method of,

723–726, 736Insects

cockroach identification,109

plant cooperation with,1015

plant defenses against, 646semiochemicals and,

646–647“Insoluble,” 104Instantaneous rate, 717Insulators, electrical, 800Integrated circuits, 810–811Integrated rate law, 721, 722,

726–737first-order, 726–730, 987,

989, 995with multiple reactants,

734–735for radioactive decay, 987,

989, 995second-order, 731–733summary, 735–737zero-order, 733–734

Intensive property, 479–480Intercept, A4–A5Interference of waves,

529, 785Intermediate, 737, 741

femtosecond studies of, 718scanning tunneling

microscope studies of, 742

in steady-stateapproximation, 743–746

Intermolecular collisions,169–171

Intermolecular forces, 778–781dipole–dipole, 779–780in liquids, 781–783, 785in molecular solids,

812–813in real gases, 176vapor pressure and, 821See also Hydrogen bonding;

London dispersion forces



Licensed to:

A90 Index

Internal energy, 362–365constant-volume

calorimetry and, 378–380enthalpy and, 365–366of ideal gas, 368–373as state function, 373

Interstitial alloys, 799of titanium, 942

Interstitial hydrides, 894–895Iodine, 35, 919–920, 921, 922

electron affinity, 577oxidation state, 120sublimation, 823

Iodine-131, 984, 995, 996Ion(s), 31–33

electrolysis of mixtures of,504, 506

in electrolytes, 93–96energy of interaction

of, 594independence in solution,

92–93, 101naming of, 36–40oxidation states of, 120polyatomic, 33, 39–40separating mixtures of,

108–110, 337–341,346–347

sizes of, 605–607spectator, 107, 108See also Complex ions;

HydrationIon-exchange resin, 896–897Ionic bonding, 32, 594, 597

electronegativity and,598–599

hyperconjugation and, 632partial ionic character,

611–612in proteins, 1050

Ionic compounds, 31, 32–33,594

crystal structures, 788, 790,813–818

defined, 612electron configurations in,

603–605formation of, 607–611gas phase of, 604, 611, 612hydrides, 894lattice defects, 818–819lattice energy, 607–611Lewis structures, 621names of, 36–40, 41,

43–44polar solvents for, 849, 851predicting formulas of,

604–605solubility in water, 92–93,

851, 853X-ray diffraction by, 529See also Salts; Solubility

Ionic equationcomplete, 106–108net, 107, 108

Ionic hydrides, 894Ionic liquids, 857Ionic radii, 605–607Ionic solids. See Ionic

compounds; SaltsIon interchange, 105Ionization energies, 571–575

of alkali metals, 573, 580,581

electronegativity and, 599of metals vs. nonmetals,

579–580of transition metals, 938

Ionization potential, 571Ion pairing, 333–334, 872Ion product, 335–336Ion-product constant (Kw),

238–239relation to Ka and Kb,

264–265weak acid solutions and,

271–276Ion-selective electrodes,

488–489Iridium, 940, 996Iron, 937, 944

abundance, 889in biological systems,

969–973corrosion, 451, 497,

498–502, 944electron configuration, 564formed in stars, 988in heat packs, 400ores of, 130–131protective oxide coating

on, 498Iron oxide

in Haber process catalyst,905

protective coating of, 498as rust, 500, 944

Irreversible processes, 424,425, 455–457. See alsoSpontaneous processes

Isobutane, 1016, 1017Isoelectronic ions, sizes of,

606–607Isomer, defined, 951Isomerism

in alkanes, 1016–1021in alkenes, 1024cis–trans, 952, 955–958,

1024in complex ions, 951–958coordination, 951geometrical, 952, 955–957,

1024linkage, 951–952

optical, 952–958, 1051,1053–1054

of pharmaceuticals, 956,957–958

stereoisomerism, 952–958,1024, 1051, 1053–1054

structural, 951–952,1016–1021

Isotactic chain, 1042Isothermal process

defined, 417expansion and compression,

417–427, 460Isotonic solutions, 869, 870Isotopes, 30, 982

atomic masses and, 53–56for labeling explosives,

42–43mass spectrometry of, 53, 55separation of, 166–167

-ite (suffix), 40, 44

Joliot, Frederick, 991Jorgensen, Sophus Mads, 953Joule

conversion from L atm,162, 365

defined, 162of electrical work, 475, 482

Juglone, 646Jumper cables, 493Junction potential, 809Junction transistor, 810

K. See Equilibrium constant (K)Ka. See Acid dissociation

constant (Ka)Kb, 251–252

relation to Ka, 264–265salt solutions and,

263–265, 266, 267–268table of values, A25

Ksp. See Solubility product(Ksp)

Kw (ion-product constant),238–239

relation to Ka and Kb,264–265

weak acid solutions and,271–276

Kairomones, 646, 647Kaolinite, 806Kekulé, F. August, 21Kelvin temperature

conversion from Celsius, 146kinetic energy of gas

particles and, 157, 161,366, 368

See also TemperatureKenny, Jonathan, 690Kerogen, 400Kerosene, 390, 391

Ketones, 1032–1033Kidney, artificial, 869Kinetic energy

of electrons in hydrogenmolecule, 595, 596

Hamiltonian operator for,541, 542

heat and, 360, 361of ideal gas, 157, 160–161,

366, 368internal energy and, 362of particle in a box, 542potential energy and,

359–360, 411of reacting molecules, 747temperature and, 157, 161,

366, 368, 821Kinetic molecular theory of

gases, 155–163collision rate and, 167–169effusion and, 164–165ideal gas law and, 157–161postulates of, 157real gases and, 169, 172–175temperature and, 157,

161–163velocity distribution and,

162–163Kinetics, chemical

definition of reaction rate,717, 720

determining form of ratelaw, 722–726

differential rate laws, 721,722–726, 735, 736

equilibrium and, 208first-order, 723, 726–730half-life, 729–730, 731,

733, 734instantaneous rate law, 717integrated rate laws, 721,

722, 726–737introduction to rate laws,

719–722introduction to reaction

rates, 715–717, 719mechanisms and, 715, 718,

737–746model for, 747–751with multiple reactants,

734–735, 736–737noninteger order, 742–743pseudo-first-order, 735rate-determining step, 739,

740, 743second-order, 724,

731–733, 737spontaneity and, 714–715summary, 735–737temperature dependence of,

747–752zero-order, 733–734



Licensed to:

Index A91

Kinetics of radioactive decay,987, 989–990, 995

Kinetic stability, 442, 828,829

of nucleus, 982Koopmans’ theorem, 571Krypton, 35, 564, 923, 924Kuznick, Steven, 156

Lactic acid, 248Lake Nyos tragedy, 859Lanthanide contraction, 939Lanthanide series, 565, 566,

886, 934, 935atomic radii, 939

Lasersin atomic clock, 534for cooling atoms, 147in electronic spectroscopy,

693–694in femtochemistry, 718gallium arsenide, 807nuclear fusion and, 1004in protein mass

determination, 59in X-ray spectroscopy, 738

Lattice, 785, 787Lattice defects, 818–819Lattice energy, 607–611Lauterbur, Paul, 705Lavoisier, Antoine, 10, 17,

506, 522, 536Law of conservation of energy,

359, 361, 362, 411Law of conservation of mass,

9, 17Law of definite proportion, 18Law of mass action, 200–203,

206, 208Law of multiple proportions,

18–19Law of partial pressures,

152–155Laws of nature, 9, 155–156LDPE (low-density

polyethylene), 1040Lead, 899, 900–901

age of rocks and, 994–995colorimetric test for, 339in gasoline, 391, 758, 900in stabilizers for PVC, 13

Leading zeros, A13–A14Lead poisoning, 900, 901, 948Lead storage battery,

492–493, 900Le Châtelier, Henri, 216Le Châtelier’s principle,

216–222concentration and, 216–218for electrochemical cell,

485–486, 487energy and, 221

pressure and, 218–220summary, 222temperature and, 220–221volume and, 218, 219–220

Leclanché, George, 493LE model. See Localized

electron (LE) modelLeptons, 1005Leucippus, 522Levorotatory isomer, 955Lewis, G. N., 614, 620, 947Lewis acid–base concept, 947

complex ions and, 936,946, 947, 958

Group 5A elements and,902

Lewis structures, 620–624of electron-deficient

compounds, 626–627,628

with extra electrons,627–630, 632, 634

formal charge and,630–631, 633–636

hyperconjugation and, 630, 632

with odd number ofelectrons, 630

resonance and, 625–626,632, 634, 635

summary, 622, 628validity of, 636VSEPR model and, 638

Libby, Willard, 993Ligand field model, 968Ligands, 946–948

defined, 341, 936, 947d-orbital splitting and,

960–962, 963–964,967–968

equilibria involving,341–347

nomenclature, 948–951See also Complex ions

Lightcontinuous spectrum of, 530diffraction of, 529dual nature of, 528electronic spectroscopy and,

690, 692–694photocatalysis and, 752photoelectric effect,

526–527polarized, 952–955, 957scattering by particles, 873speed of, 522, 523See also Colors;

Electromagnetic radiationLightning, nitrogen oxides

and, 905–906“Like dissolves like,” 93, 849,

851, 853

Lime. See Calcium oxide (lime)Lime–soda process, 250Limestone

cave formation in, 287, 335for scrubbing, 179See also Calcium carbonate

Limiting reactant, 73–79Linear accelerator, 991Linear complex ions, 947,

958, 959, 964–965, 966Linear equations, A4–A5Linear low-density

polyethylene, 1040Linear molecules

hybrid orbitals for,666–667, 671

with polar bonds, 601–602rotational states, 698–700VSEPR model, 637, 641,

642, 645Line spectrum, 530–531, 535Linkage isomerism, 951–952Liquefaction of air, 890–891,

915Liquid–liquid solutions,

862–864Liquids, 778, 781–785

activity of, 207–208in chemical equations, 67ionic, 857standard state, 384vapor pressure of, 819–826See also Solutions

Liter (L), A16Lithium, 35, 580–582,

891–892atomic radius, 887electron configuration, 561ionization energy, 573molecular orbital model, 677for mood disorders, 582reaction with water,

581–582, 891, 894See also Alkali metals

Lithium fluoridecrystal structure, 609lattice energy, 607–609

Lithium-ion batteries, 495Livesag, Richard, 42Lobes, of orbitals, 553, 554Localized electron (LE)

model, 619–620combined with molecular

orbitals, 685–688of complex ions, 958–959exceptions to octet rule

and, 626, 630hybrid orbitals and, 661,

663, 667, 670–671limitations of, 673, 685resonance and, 626summary, 670–671

Logarithms, A3–A4of exponential equation, A5significant figures for, 240

London dispersion forces,780–781

in ethane, 1029gecko adhesion and, 782in molecular solids, 813in proteins, 1050vapor pressure and, 821

Lone pairs, 620in Lewis structures, 622,

631, 635of ligands, 947in VSEPR model, 639,

640, 650Longbottom, Chris, 474Lowry, Thomas M., 234Low-spin case, 961, 968Lysis, 870

Magic numbers, 983Magnesium, 35, 895–897

band model of crystal,797–798

in chlorophyll, 969electron configuration,

563ionization energy, 575

Magnesium hydroxide, 249,334

Magnesium oxide, latticeenergy, 609–611

Magnetic fieldof electromagnetic

radiation, 522nuclear spin and, 700–702

Magnetic quantum number,548, 549, 550, 552

Magnetic resonance imaging(MRI), 704–705

Magnetism. See Diamagnetism;Paramagnetism

Magnetite, 121Magnetorheological (MR)

fluid, 784Maillard, Louis-Camille, 1052Maillard reaction, 1052Main-group elements. See

Representative elementsMajor species, 241, 276Malleability of metals, 34,

790, 797steels, 799

Manganese, 564, 937,943–944

Manganese nodules, 943Manometer, 142Mansfield, Peter, 705Marble, 180–181Mars Climate Orbiter, 9Masel, Richard, 496



Licensed to:

A92 Index

Massatomic, 19–24, 53–56conservation of, 9, 17of electron, 25, 29equivalence to energy,

527–528, 984–985,997–999, 1005

of reactants and products,70–79

reduced, 695, 698relativistic increase in, 574vs. weight, 19–20See also Molar mass

Mass action, law of,200–203, 206, 208

Mass defect, 997, 999Mass number, 30, 982, 983,

984Mass percent, 60–61

chemical formula and,62–66

in solution, 847Mass spectrometer, 53, 54, 55

for molar massdetermination, 59

for radiocarbon dating, 994Material balance equation,

271Matrix-assisted laser

desorption, 59Maxwell, James C., 163Maxwell–Boltzmann

distribution law,162–163, 169

Mean, A10Mean free path, 162, 171Measurements, 8

uncertainties in, A8–A13units of, A15–A17

Measuring pipet, 100Mechanisms. See Reaction

mechanismsMedian, A10Medicine

artificial kidney in, 869magnetic resonance imaging

in, 704–705nanotechnology in, 833,

835radioactivity in, 995–996See also Cancer

Melting point, 823–824of alkali metals, 580enthalpy change at, 428,

778, 823entropy change at, 428free energy change at,

434–435freezing-point depression,

866–867of noble gases, 781normal, 825, 827

pressure dependence of,830

relativistic effects on,574–575

vapor pressure at, 824, 825

Mendeleev, Dmitri Ivanovich,26, 559, 563

Meniscus, 783Mercury

convex meniscus of, 783electron configuration, 575melting point, 574, 575pressure measurements

and, 142relativistic effects on,

574–575in superconductors, 802,

803Mercury barometer, 142, 820Mercury cell

for calculator, 494for electrolysis of brine,

509–510Mescaline, 253Messenger RNA, 1058, 1060Metallic hydrides, 400,

894–895Metalloids, 580, 886Metallurgy, 16, 890Metals, 34, 579–580,

886–887bonding in, 797–798corrosion of, 451, 497–502,

505, 508crystal structure, 790–797electrorefining of, 507–508hydrides of, 400, 894–895ionic compounds with

nonmetals, 603–605noble, 497, 498, 506,

508, 936ores of, 506, 890photoelectric effect with,

526–527physical properties, 34,

790, 797plating of, 500, 503, 504,

508reactions with nonmetals,

581surface motions in, 793See also Alkali metals;

Alkaline earth metals;Alloys; Transition metals

Metastable substance, 828meta- substituents, 1027Methane

bond energy, 616bond polarities, 603chlorination of, 1021from coal conversion, 395

combustion of, 118, 122,360–361, 380, 385–386,411, 495–496

for fuel cells, 495–496as greenhouse gas, 394in hydrogen preparation,

891, 893in natural gas, 156, 390reaction with water, 73as real gas, 176sp3 orbitals for, 661–663,

689, 1015stability of bonding in,

612–613, 614–615VSEPR model, 637–638,

639–640Methanol, 1029–1030

enthalpy of combustion,389–390

free energy of combustion,443

fuel cells powered by, 496,497

molecular structure,649–650

oxidation states incombustion, 123

state-of-the art detection of, 119

from syngas, 397uses of, 397, 1030

Method of initial rates,723–726, 736

Methylamine, 251, 252Methyl chloride, bonding

in, 613Methylene group, 1016Methyl group, 1018Methyl red, 324Metric system, 9, A15–A16MeV (million electron-volts),

998Meyer, Julius Lothar, 559Microstates, 415–417,

425–427Microwave radiation, 524,

525in atomic clock, 534cooking with, 525, 690rotational spectroscopy

and, 690, 698–700Milk of magnesia, 334Millikan, Robert, 25–26Milliliter (mL), A16Millimeters of mercury, 142Millimole (mmol), 304Mineral acids, 94–95Minor species, 241Minton, Allen, 426Mirror images,

nonsuperimposable,954–957, 1051, 1053

Mixtures. See Solutions;Suspensions

mm Hg, 142Models, 8, 9, 615–616

chemical bond, 612–615of gases, 155–163hybrid orbitals, 663, 667of ions, 33for kinetics, 747–751of molecules, 31orbitals, 688–689

Moderator, of nuclear reactor,1002

Molal boiling-point elevationconstant, 865–866

Molal freezing-pointdepression constant, 867

Molality, 847Molar absorptivity, A18Molar concentration of gas,

204Molar heat capacity

defined, 374of ideal gas, 366–370

Molarity, 97–98, 847in millimoles per mL, 304temperature dependence

of, 847Molar mass, 58–60

from boiling-pointelevation, 865–866

from density of gas,151–152

from freezing-pointdepression, 867

molecular formula from,63–65, 66

from osmotic pressure,868–869

of polymers, 1041–1042of proteins, 59, 868–869from vapor pressure,

861–862Molar volume of gas, 150Mole (mol), 56–58Molecular equation, 106,

107–108Molecular formula, 63–65, 66Molecularity, 737Molecular orbitals (MOs),

673–677combined with localized

electron model, 685–688of complex ions, 966–968of diamond, 799–800of graphite, 801heteronuclear diatomic,

684–685homonuclear diatomic,

677–684of hydrogen, 673–676of metals, 797–798



Licensed to:

Index A93

of nitric oxide, 909paramagnetism and,

680–684resonance and, 685–688of silicon, 808, 809

Molecular orientations, incollision, 749

Molecular sieves, 119, 156Molecular solids, 788,

812–813Molecular spectroscopy. See

Spectroscopy, molecularMolecular structure. See

VSEPR modelMolecular weight, 59–60

of polymer, 1041–1042Molecules, 30–31Mole fraction

defined, 152partial pressure and,

153–154in solution, 847

Mole ratio, 71limiting reactant and,

75–76, 77Molybdenum, 940Moment of inertia, 698, 700Momentum

of gas particles, 158–159of photon, 528uncertainty principle and,

539–541wavelength and, 528–529

Monoclinic sulfur, 917Monodentate ligands, 947Monomers, 1035, 1042Monoprotic acids, Ka values

of, 236–237, A24Monosaccharides, 1051–1054

in nucleic acids, 1057Moore, Jeffrey, 1043Morse potential, 695–696MR (magnetorheological)

fluid, 784MRI (magnetic resonance

imaging), 704–705Multiple bonds. See Double

bonds; Triple bondsMultiple proportions, law of,

18–19Multiplication

in exponential notation,A1, A2

significant figures, A14,A15

Mulvihill, Gene, 704Myoglobin, 970–971, 1049

Names of compounds, 36–45acids, 44–45coordination compounds,

948–951

covalent compounds, 40, 41flowcharts for, 38, 41, 45formulas from, 43–44ionic compounds, 36–39, 41

Nanocrystalline materials, 832Nanotechnology, 22, 831–835

defined, 833safety concerns with, 835surface motions and, 793ultrasound and, 174

Nanotubes, carbon, 833–834,835

Naphthalene, 1028Natta, Giulio, 1040Natural gas, 390

hydrogen derived from,397, 891

separating nitrogen from,156

treatment with ionic liquid, 857

Natural law, 9, 155–156Natural logarithms, A4, A5Neon, 35, 923

electron configuration, 562, 563

freezing point, 781ionization energy, 573, 575Lewis structure, 622molecular orbital theory

and, 683Nernst, Walter Hermann

von, 486Nernst equation, 486–488

for concentration cell,490–492

equilibrium constant from,489–490

Net ionic equation, 107, 108Network solids, 799

carbon as, 799–801phosphorus as, 912silicon as, 801–804

Neutralization reaction, 114Neutral solutions

defined, 239of salts, 263, 267–268

Neutrons, 29–30, 982bombardment with,

991–992, 1000fission and, 1000–1001,

1002, 1003nuclear stability and, 983,

984, 985quark structure of, 1005in stellar nucleosynthesis,

988in thermal neutron analysis,

119Newlands, John, 559Newton, Isaac, 522Nickel, 564, 937, 944–945

Nickel–cadmium battery,494–495

Nicotine, 646Niobium, 940Nitrate ion

ball-and-stick model, 33Lewis structures, 625–626,

686molecular orbital model,

688VSEPR model, 645–647,

649Nitrates

in soil, 905, 906solubility in water, 105

Nitric acid, 94–95, 236,910–911

in acid rain, 180in aqua regia, 346, 485, 942concentrated, 911

Nitric oxide, 686, 908–909biological roles, 686from combustion in

vehicles, 177, 178, 758,759, 905

localized electron modeland, 630

molecular orbital model,684, 909

naming of, 40in nitric acid synthesis,

910, 911nitrogen dioxide and, 686,

715–717, 719–720ozone and, 758–759paramagnetism of, 684, 909reaction with hydrogen,

744–746Nitrite anion

electronic structure, 626as ligand, 952

Nitrite salts, 911Nitrito ligand, 952Nitrogen, 902, 903–911

commercial preparation of,890–891

electron affinity, 576electron configuration,

562, 563explosive compounds, 10,

119, 200, 682, 806, 904, 905

in fertilizers, 10, 905, 906as inert gas, 903ionization energy, 573molecular structure, 667,

681–682, 888, 903new ion discovery, 905oxidation state, 120oxyacids of, 910–911as real gas, 176

Nitrogen cycle, 906

Nitrogen dioxide, 908, 909in acid rain formation, 180air pollution and, 177,

693, 759in automobile engine, 905dimerization equilibrium,

196–197localized electron model

and, 630in nitric acid synthesis,

910–911rate of decomposition,

715–717, 719–721reaction mechanisms with,

737–740Nitrogen fixation, 905–906Nitrogen hydrides, 906–907.

See also AmmoniaNitrogen monoxide. See

Nitric oxideNitrogen oxides, 907–910

air pollution and, 177, 180, 905

lightning-associated,905–906

naming of, 40titanium dioxide and, 752See also specific oxides

Nitroglycerin, 904Nitrosyl ion, 909Nitrous acid, 180, 236, 911Nitrous oxide, 907–908,

909, 910decomposition rate, 734naming of, 40

NMR (nuclear magneticresonance) spectroscopy,700–705

Noble gas electronconfigurations, 603, 605,621, 622, 671

Noble gases (Group 8A), 35, 923

compounds of, 635,643–645, 670, 673,923–925

freezing points, 781ionization energies, 573London dispersion forces

in, 780–781See also specific elements

Noble metals, 497, 498, 506,508, 936

Nodal surfaces, 553Nodes

of hydrogen orbitals, 553of particle-in-a-box wave

function, 546of standing wave, 538

Nonbonding orbitals, 966Nonelectrolytes, 93, 96Nonideal gases. See Real gases



Licensed to:

A94 Index

Nonideal solutions, 862–864Nonmetals, 35, 579, 580,

886, 887binary covalent compounds

of, 40, 41covalent bonding of,

35, 603ionic compounds with

metals, 603–605preparation of, 890–891reactions with metals, 581

Nonpolar molecules,dispersion forces of, 780, 781

Nonpolar side chains, 1045,1046

Nonpolar solvents, 849, 851supercritical carbon

dioxide, 852Nonstoichiometric

compounds, 819interstitial hydrides, 895

Norepinephrine, 253Normal boiling point,

825, 827Normal hydrocarbons,

1015–1016Normal melting point,

825, 827Normal modes, 696Nose, electronic, 648Novocaine, 253n–p–n junction, 810, 811n-type semiconductor, 807,

808, 809, 810, 811Nuclear atom, 28Nuclear charge

effective, 557–558, 577shielding from, 570,

572–573, 577Nuclear fission, 984,

1000–1002Nuclear fusion, 1000,

1003–1004in stars, 988, 1003

Nuclear magnetic resonance(NMR) spectroscopy,700–705

Nuclear physics, 1005Nuclear reactors, 1002–1003,

1007uranium enrichment for,

166–167Nuclear spin, 700Nuclear stability, 982–983,

996–1000Nuclear transformations,

991–992Nuclear waste, 1007Nucleic acids, 4, 1056–1060Nucleosynthesis, stellar, 989,

1003

Nucleotides, 1057, 1058Nucleus, 29–30, 982

density of, 982forces in, 1003–1004, 1005Rutherford experiment,

27–28, 982size of, 982See also Radioactivity

Nuclidesdefined, 982half-lives of, 989–990stability of, 982, 983

Nylon, 1036, 1039, 1041

-oate (suffix), 1034Observations, 8–9, A15Octahedral complexes,

947, 953crystal field model,

960–963, 965geometrical isomerism

in, 952hybrid orbitals for, 958molecular orbital model,

966–968VSEPR model and, 958

Octahedral holes, 813–814,815–816, 817–818

Octahedral structureswith Group 5A elements,

902hybrid orbitals for, 670,

671VSEPR model, 642, 643

Octane ratings, 71Octaves, 559Octet rule, 621, 622, 623

electron-deficient compoundsand, 626–627, 628

exceptions to, 626–636extra electrons and,

627–630, 632, 634, 668formal charge and, 634hyperconjugation and,

630, 632odd-electron molecules

and, 630summary, 628

Odd-electron molecules, 630Odors, 646–647, 648Oelert, Walter, 986-oic (suffix), 1033Oil seeds, 401Oil shale, 400-ol (suffix), 1028-one (suffix), 1032Operator, Hamiltonian, 538,

541, 542Optical isomerism, 952–958

of monosaccharides, 1051,1053–1054

Orbital diagram, 561

Orbitals, 538complex, 549–550, 552, 568exclusion principle and,

556, 562filling of, 561–568, 570as human models, 688–689of hydrogen atom, 538–539,

541, 550–556, 568ionization energy and,

571–572of polyelectronic atoms,

558, 568–570size of, 551, 556See also Hybrid orbitals;

Molecular orbitals (MOs)Orbits, in Bohr model,

531–533, 535, 538Order

of overall reaction, 724of reactant, 720See also Bond order

Oresof metals, 506, 890of sulfur, 916

Organic acids, 236, 1033Organic chemistry, 1014. See

also Biomolecules;Hydrocarbon derivatives;Hydrocarbons

Orthophosphoric acid. SeePhosphoric acid

ortho- substituents, 1027Osmium, 940Osmosis

defined, 867reverse, 870–871

Osmotic pressure, 867–871of electrolyte solutions,

872–873glucose storage and,

1055–1056Ostwald process, 910–911-ous (suffix), 37, 44Overall reaction order, 724Overvoltage, 504, 506, 509Oxalate ligand, 948Oxidation

at anode of galvanic cell, 475

corrosion of metals, 451,497–502, 505, 508

defined, 122of iron in heat pack, 400

Oxidation half-reaction, 126,473

Oxidation numbers. SeeOxidation states

Oxidation–reductionreactions, 101, 117–118,120–122

in acidic solution, 125–127,130–131

balancing equations for,123–130, 479–480

in basic solution, 127–129electrochemical (see

Galvanic cells)equilibrium constants for,

489–490in fireworks, 536–537of metals with nonmetals,

581Oxidation–reduction

titrations, 130–131Oxidation states, 118,

120–121compared to formal charge,

631, 636in coordination compounds,

946, 949–950of nitrogen, 907noninteger, 121of phosphorus, 912rules for, 120of transition metals, 936,

938Oxidation states method,

123–124Oxide ion, 576–577, 604, 888Oxides

of alkaline earth metals, 888of fluorine, 923minerals as, 914of phosphorus, 912–913of sulfur, 917–918

Oxidizing agent, 122, 473, 475Oxyacids, 236

of halogens, 922, 923of nitrogen, 910–911of phosphorus, 913of sulfur, 918

Oxyanionsof halogens, 922names of, 39–40

Oxygen, 914, 915–916abundance, 889in atmosphere, 176,

177, 178biological role, 969–973bonding properties, 888commercial preparation of,

890–891early research on, 16, 17electron affinity, 576–577electron configuration, 562ionization energy, 573liquid, 682, 915molecular orbital model,

681–683oxidation states, 120paramagnetism of,

682–683, 915silicon compounds with,

801–804, 888



Licensed to:

Index A95

Oxygen difluoride, 923Oxytocin, 1047Ozone, 915–916

decomposition rate,740–741

nitric oxide and, 758–759resonance structures, 686in smog formation,

177, 693Ozone layer, 177, 915–916

depletion of, 693, 759, 761, 1022

Ozonolysis, 915

Paintlead-based, 900polymers added to, 426for rust prevention, 501titanium dioxide in,

752, 940Palladium, 940

antitumor compound of,956

economic importance, 933interstitial hydride of,

894–895Paper

acid decomposition of, 3–7titanium dioxide in,

752, 940Paracelsus, 16Paramagnetism, 680–684

complex ions, 961hemoglobin, 971nitric oxide, 684, 909nitrogen dioxide, 909oxygen, 682–683, 915

para- substituents, 1027Partial (fractional) charge, 92,

597, 600. See also Polarcovalent bonds

Partial ionic character, 611–612Partial pressures, 152–155

at equilibrium, 204–206liquid–liquid solutions

and, 863Particle accelerators, 36, 986,

991, 1005Particle in a box, 541–547

conjugated molecules and, 693

Particlesclassical view of, 525modern classification of,

1005wave properties of,

529–530, 537, 538, 540Pascal (unit of pressure), 143Pasteur, Louis, 953Pathway dependence, 360, 425Patina, 498, 499, 945Pauli, Wolfgang, 556

Pauli exclusion principle, 556, 562

Pauling, Linus, 597, 598, 599, 614

Pencils, 596Penetration effect, 570, 573Pentoses, 1051, 1053–1054

in nucleic acids, 1057Peptide linkage, 1045, 1060per- (prefix), 40Percent composition, 60–61Percent dissociation, 247–248

common ion effect and,288–289

Percent ionic character, 611Percent yield, 77Perchlorate ion, 922Perchloric acid, 236, 922Periodic table, 34–35,

886–887atomic radius and,

577–578, 887–889, 939electron affinity and,

576–577, 580filling of orbitals and,

561–568, 570history of, 559–561information contained in,

578–580ionic sizes and, 605–606ionization energy and,

571–575, 579–580, 938new form of, 565transition metals in,

563–564, 565, 566, 934, 935

transuranium elements, 992valence electrons and, 563,

564, 565, 566, 886–887See also Elements; Groups

Periods, 35Permanent waving, 1050Permanganate ion, 130–131,

943–944in galvanic cell, 473,

480–481spectrophotometric analysis,

A19–A21Perovskites, 802–803Peroxides, 120PET (positron emission

tomography), 995–996Petroleum, 390–391

air pollution and, 177desulfurization of, 758residual oil from, 397See also Gasoline

pH, 239–240indicator color change and,

319–324of polyprotic acid solutions,

257–258, 260–262

in polyprotic acid titrations,326–328

of salt solutions, 263–270solubility of ionic solids

and, 334–335, 338of strong acid solutions,

241–242, 275–276of strong base solutions,

250, 276water’s contribution to,

270–276of weak acid solutions,

242–246, 270–275of weak base solutions,

251–252, 254See also Buffered solutions;

pH curve; pH meterPhase diagrams

aqueous solution, 864–865,866

carbon, 828–829carbon dioxide, 831water, 826–831

pH curve, 304, 319acid strength and, 315strong acid–strong base,

306–307weak acid–strong base,

307, 312, 315weak base–strong acid, 318

Phenanthrene, 1028Phenol, 1030Phenolphthalein, 115, 319, 324Phenyl group, 1027Pheromones, 646, 647Phlogiston, 16, 17pH meter, 240, 488–489

equivalence point and, 319Phosphate minerals,

gravimetric analysis of,112–113

Phosphate rock, 112, 913,918

Phosphate salts, solubility,105

Phosphide salts, 912Phosphine, 650, 912Phosphoric acid, 236, 913

equilibria of, 256–260in nucleic acids, 1057titration of, 324, 327

Phosphorous acid, 913Phosphorus, 902, 903,

911–913bonding properties, 888,

911diatomic, 683–684in fertilizers, 913ionization energy, 573–574oxides of, 912–913oxyacids of, 913solid structure, 812, 813

Phosphorus pentachloridehybrid orbitals for, 668–669Lewis structures, 628–629,

630, 632VSEPR model, 642–643

Phosphorus pentoxide, 912Photochemical smog,

177–178, 693, 905. Seealso Air pollution

Photochemistry, 693of titanium dioxide, 752

Photochromic glass, 924Photoelectric effect, 526–527Photons, 526, 527, 528,

530, 1005Bohr model and, 533

Photosynthesisas experimental hydrogen

source, 398fossil fuels and, 390in grasses vs. trees, 54

Physical changes. See Changesof state

Physical states, of reactantsand products, 67

Pi (�) bonds, 665, 666–667,672

delocalized, 686–688of graphite, 801group properties and, 888,

899, 903, 911, 917Pi (�) molecular orbitals,

679–680Piezoelectric detector, 119Pilot-plant test, 11Pipet, 100Pitchblende, 26–27, 914pK, 240pKa, 294, 302Planck, Max, 525, 528Planck’s constant, 525, 526,

539, 542, 698Plane-polarized light,

952–955, 957Plasma, cavitation and, 174Plasticizers, 12–13, 14Plastics

blowing agents for, 907self-healing, 1043titanium dioxide in, 940See also Polymers

Plating of metals, 500, 503,504, 508

Platinum, 940antitumor compounds

of, 956economic importance, 933

Platinum electrode, 476–477,481, 504

Platinum group metals, 940Platinum surface, reaction

on, 734



Licensed to:

A96 Index

Pleated sheet, 1048, 1049Plum pudding model, 25,

27, 28Plunkett, Roy, 1037Plutonium, 1003p–n junction, 809, 812p–n–p junction, 810pOH, 240Point defects, 818Polar coordinates, 548Polar covalent bonds, 597

dipole–dipole forces and,779–780

electronegativity and,597–599

of ethanol, 93molecular orbitals and, 685partial ionic character of,

611–612of water, 91–92, 597, 894See also Dipole moments;

Hydrogen bondingPolarizability, dispersion

forces and, 781, 821Polarized light, 952–955, 957Polar liquids, capillary action

of, 783Polar side chains, 1045, 1046Polar solvents, 92, 93, 849,

851, 852Polonium, 27, 914Polyatomic gas, heat capacity

of, 367–368Polyatomic ions, 33, 39–40,

612. See also Complexions

Polycrystalline materials, 832Polydentate ligands, 948Polyelectronic atoms,

556–558, 568–570Polyester, 1040Polyethylene, 1037–1038,

1040–1042Polymers, 12, 1035–1060

carbohydrates, 1051–1056crosslinked, 1036entropic forces and, 426ethylene-based, 1037–1038,

1040–1042, 1044historical development of,

1035–1036, 1037ion-exchange resins, 896–897nanoscale applications

of, 834nucleic acids, 4, 1056–1060in paint, 501polyvinyl chloride, 12–14self-healing, 1043types of, 1037–1040unsaturated hydrocarbons

and, 1026See also Plastics; Proteins

Polypeptides, 1045Polypropylene, 1042Polyprotic acids, 254–263

common ion effect with,288

table of Ka values, A24titration of, 324–328

Polysaccharides, 1054–1056Polystyrene, 1044Polyvinyl chloride (PVC),

12–14, 1044p orbitals, 552, 553–554

of polyelectronic atoms,568, 570

Porous disk, 474Porphyrin, 969, 970Positional probability,

416–417, 430, 444–445chemical reactions and,

436–438Positron, 985, 986Positron emission tomography

(PET), 995–996Post-it Notes, 11Potassium, 35, 580–582,

891, 892electron configuration,

563, 570See also Alkali metals

Potassium dichromate, 130Potassium hydroxide, 95,

248–249Potassium ions, in human

body, 892Potassium permanganate,

130–131, 1033Potassium salts, soluble,

105Potential difference, 482. See

also Cell potentialPotential energy

chemical reactions and,361–362, 411, 747–748

of diatomic molecule,694–695

Hamiltonian operator and,541, 542

of hydrogen atom, 548of hydrogen molecule,

595, 596internal energy and, 362kinetic energy and,

359–360, 411of particle in a box, 542of polyelectronic atom,

557, 558Potentiometer, 475, 476, 483

of pH meter, 488Powers of a number, A2–A3Precipitate, 101

gravimetric analysis of, 112

Precipitation reactions,101–106, 335–341

equations for, 106–108in qualitative analysis,

109–110, 339–341, 344,346–347

in selective precipitation,108–110, 337–341,346–347

stoichiometry of, 110–112Precipitator, electrostatic, 875Precision, A9–A11, A12Prediction, 8Pre-exponential factor, 749Pressure

altitude and, 176boiling point and, 830Boyle’s law and, 143–145,

146collisions with walls and,

157, 159–160, 167defined, 143enthalpy and, 365–366,

444entropy and, 444–445equilibrium constant in

terms of, 203–206, 207,222–223

equilibrium position and,218–220

force and, 143, 157, 159free energy and, 444–447ideal gas law and, 146–150,

161melting point and, 830partial, 152–155, 204–206,

863psi unit for, 1040of real gas, 172–176solubility and, 855–856units of, 142–143work and, 363–367,

376–378, 418–425, 454, 455

See also Osmotic pressure;Vapor pressure

Priestley, Joseph, 16, 910Primary alcohols, 1028, 1033Primary amines, 1034Primary structure, of protein,

1045, 1047Principal quantum number,

548–549, 552periodic table and, 566

Probabilityentropy and, 413–417,

425–427, 430, 437–438,444–445

of radioactive decay, 982, 987

wave function and,544–545, 550, 674

Probability distributionsof hydrogen atomic

orbitals, 550–551,553–556

of molecular orbitals,674–675

of particle in a box, 546of polyelectronic atoms,

570Problem solving

creativity in, 2–3paper decomposition

and, 3–7Products, 66–68

calculation of masses of,70–79

Propane, 1015, 1026combustion of, 70–72

Propene, 1024, 1026Propyl group, 1018Proteins, 1044–1050

in calcium carbonatecomposite, 789

enzymatic breakdown of, 756

heme complex and, 969,970–971

ice crystal formation and,874

molar mass determination,59, 868–869

NMR spectroscopy of, 704synthesis of, 1058, 1060See also Enzymes

Proton acceptor, 113, 234,235, 248, 250–251

Proton donor, 113, 234, 235Protons, 29–30, 982

fusion of, 1003hydration of, 234, 235, 238nuclear magnetic resonance

with, 700–704nuclear stability and, 983,

984, 985quark structure of, 1005See also Hydrogen ions

Proust, Joseph, 17–18Pseudo-first-order rate law,

735psi (pounds per square inch),

1040p-type semiconductors, 809,

810, 811PVC (polyvinyl chloride),

12–14, 1044PV work, 364–366

in calorimetry, 376–378heat capacity and,

366–367maximum, 424maximum useful work and,

454, 455



Licensed to:

Index A97

Pyramidal structures. SeeTrigonal bipyramidalstructures; Trigonalpyramidal structures

Pyridine, 251Pyroaurite, 501Pyrolytic cracking, 391, 893Pyrophoric substance, 912

Quadratic equations, A5–A8Quadratic formula, A5–A6Qualitative analysis, 109–110,

339–341, 344, 346–347Qualitative observations, 8Quantitative observations,

8, A15Quantum, 526, 528Quantum dots, 835Quantum mechanics, 522

development of waveequation, 536–539

early developments leadingto, 525–530

of particle in a box,541–547, 693

of polyelectronic atoms,556–558, 568–570

probabilistic interpretationof, 544–545, 550, 674

uncertainty principle,539–541, 547, 550, 556

See also Hydrogen atomQuantum numbers

electron spin, 556of hydrogen atom,

548–550, 551–552, 568of particle in a box, 546of polyelectronic atoms, 569rotational, 698–699vibrational, 695

Quarks, 982, 1005Quartet signal, 702, 703Quartz, 802–804, 888, 935

Racemic mixture, 955, 957Rad (radiation dose), 1006Radial probability distribution

of hydrogen 1s orbital, 551in polyelectronic atoms,

569, 570Radiation, electromagnetic. See

Electromagnetic radiationRadiation hazards, 1004,

1006–1007protein denaturation and,

1050Radiation therapy, 996Radicals. See Free radicalsRadii

atomic, 577–578, 781,887–889, 939

ionic, 605–607

Radioactive decay. SeeRadioactivity

Radioactive wastes, 1007Radioactivity

for dating ancient articles,993–995

detection of, 993discovery of, 26–27equations for decay in, 982kinetics of, 987, 989–990medical applications,

995–996stability of nuclides and,

982, 983types of, 26–27, 984–986

Radiocarbon dating, 993–994Radiotracers, 995–996Radium, 27, 35, 568, 896Radon, 35

as biological hazard, 1007compounds of, 925

Random-coil arrangement,1049

Random error, A9, A10Range of measurements,

A10–A11Raoult, François M., 860Raoult’s law, 860–864Rate

defined, 715of radioactive decay, 987,

989Rate constant, 720

calculation of, 724, 730for radioactive decay, 989temperature dependence of,

749–751Rate-determining step, 739,

740, 743Rate laws. See Kinetics,

chemicalRBE (relative biological

effectiveness), 1006, 1007Reactants, 66–68

calculation of masses of,70–79

limiting, 73–79Reaction mechanisms, 715,

737–743defined, 738femtosecond studies of, 718steady-state approximation,

743–746Reaction order, overall, 724Reaction quotient, 208–209,

210, 211, 217cell potential and, 486–488,

489, 490, 491free energy change and,

445–446, 449, 486Reaction rate, 717, 720. See

also Kinetics, chemical

Reactions, chemical, 66–67bond energies and,

361–362, 617–619to completion, 196, 197,

208, 276, 447Dalton’s atomic theory

and, 19enthalpy changes in, 366,

374–378, 380–390,617–619

entropy changes in,436–440

equations for, 66–70,106–108

free energy changes in,440–444, 445–451

types of, 101See also Acid–base reactions;

Oxidation–reductionreactions; Precipitationreactions

Reactor core, 1002–1003Reagent, limiting, 73–79Real gases, 171–176

Boyle’s law and, 145equilibria of, 222–223intermolecular collisions in,

169–171molar volumes, 150

Rectifier, 812Redox reactions. See

Oxidation–reductionreactions

Red phosphorus, 912Reduced mass, 695, 698Reducing agents

alkali metals, 891–892defined, 122of galvanic cell, 473, 475hydride ion, 894in metallurgy, 890transition metals, 938

Reductionat cathode of galvanic

cell, 475defined, 122See also Oxidation–reduction

reactionsReduction half-reaction, 126,

473Reduction potentials

corrosion of metals and,497, 498

standard, 476–482, A26of transition metals, 938

Reference state, 205–206for pure liquid or solid, 207

Refrigeration, acoustic, 175Relative solubilities, 331–332Relativity, 527–528, 574–575

nuclear stability and,997–999

rem (roentgen equivalent forman), 1006

Representative elements, 565,578–579, 886–891

Residual oil, 397Resonance, 625–626

formal charge and, 634,635

hyperconjugation and, 632molecular orbitals and,

685–688VSEPR model and,

645–647, 649, 650Respiratory chain, 969Respiratory inhibitor, 973Reverse bias, 810, 812Reverse osmosis, 870–871Reversible chemical reactions,

719–720Reversible processes

adiabatic expansion–compression, 457–460

changes of state, 428–429defined, 421, 425electrochemical, 483isothermal expansion–

compression, 421–422,423, 424, 425, 460

maximum work and,454–455

summary, 455–457Rhodium, 940Rhombic sulfur, 917Ribonucleic acids (RNA),

1057, 1058, 1060rms (root mean square)

velocity, 161–163Roasting, 218Rocket fuels, 907, 923Rohrer, Heinrich, 22Roman numerals

for complex ions, 949, 950for ions, 37–38, 43

Root mean square velocity(rms), 161–163

Rootsof exponential expression,

A2–A3of quadratic equation,

A5–A8Rose-Petruck, Christopher, 738Rotational motion

entropy and, 439–440heat capacity and, 367–368

Rotational quantum number,698–699

Rotational spectroscopy,690–692, 698–700

Rounding numbers, A15Rubber, 1036, 1041, 1044Rubidium, 35, 564, 580, 581,

817, 891, 892

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Licensed to:

A98 Index

Rust, 497, 499–500, 944equilibrium constant, 451heat packs and, 400paint for prevention of, 501

Ruthenium, 940Rutherford, Ernest, 27–28,

982, 991Rutile, 940

Salt bridge, 474Salts

acidic solutions of, 265–268basic solutions of, 263–265,

267–268common ion effect with,

287–289defined, 33, 263, 612as electrolytes, 94neutral solutions of, 263,

267–268solubility rules for, 104–105See also Ionic compounds;

SolubilitySantoro, Mario, 804Saturated fats, 893–894, 1026Saturated hydrocarbons,

1014–1023Saturated solution, 328SAW (surface acoustic wave)

device, 119Scandium, 563, 936, 937, 940Scanning tunneling

microscopy (STM), 22,540, 543, 742, 793

SCF (self-consistent field)method, 558, 568–570

Schoenbein, Christian, 1035Schottky defects, 818Schrödinger, Erwin, 536–537,

538Schrödinger wave equation,

536–539for hydrogen atom, 548–550orbital model and, 688for particle in a box, 541–547for polyelectronic atoms,

557, 558, 568–569Scientific method, 7–10,

155–156Scintillation counter, 993Scrubbing, 179, 181–182,

249, 916Secondary alcohols,

1028, 1033Secondary amines, 1034Secondary structure, of

protein, 1047–1049Second ionization energy,

571–572, 575Second law of

thermodynamics, 426,429–430, 456–457

Second-order reactiondifferential rate law, 724half-life, 731, 733integrated rate law, 731–733mechanism and, 737

sec- prefix, 1018Seddon, Kenneth R., 857Seed oil, 401See-saw structures, 642Selective precipitation,

108–110, 337–341,346–347

Selenium, 914Self-consistent field (SCF)

method, 558, 568–570Self-healing materials, 1043Seltzer, 16Semiconductors, 808–812

gallium arsenide, 807germanium in, 899selenium, 914tellurium, 914titanium dioxide, 752See also Silicon chips

Semimetals, 580, 886, 888Semiochemicals, 646–647Semipermeable membrane,

867, 868, 869, 870, 871Semon, Waldo, 13Sensors, 119, 648Sheele, Carl, 596Shielding, from nuclear charge,

570, 572–573, 577Sickle cell anemia, 972Side chains, of amino acids,

1045Side reactions, 77Siegel, Dick, 832Sieves, molecular, 119, 156Sigma (�) bonds, 665, 666,

667, 669, 672Sigma (�) molecular orbitals,

675–676Significant figures, A8–A9,

A13–A15for logarithms, 240

Silica, 802–804, 888, 889in glass, 921

Silicates, 506, 804, 805, 806,889

Silicon, 788, 801–804, 886,888, 899

abundance, 889as semiconductor, 808–809,

810–811Silicon chips, 810–811Silver

as conductor, 934corrosion of, 498, 505crystal structure, 794–795plating with, 504, 508

Silver, Spencer F., 11

Silver cell, 494Silver chloride, in

photochromic glass, 924Silver halides, Frenkel defects

in, 818–819Silver sulfide, 498, 505Simple sugars, 1051–1054Single bond, 616SI units, A16–A17Sizing agent, 4Slaked lime, 249–250“Slightly soluble,” 104Slope of line, A4, A5

instantaneous reaction rateand, 717

Slurrycoal, 397in scrubbing process, 181

Smalley, Richard, 833Smog. See Air pollutionSmoke, removal of soot

from, 875Soap, hard water and,

895–896, 897Soda ash, 250Sodium, 35, 580–582, 891, 892

commercial production of,508–509

electron configuration,562–563

ionization energy, 575isotopes of, 30radial distributions of

orbitals, 570See also Alkali metals

Sodium acetate, 263–264Sodium azide, 153Sodium chloride

bonding in, 31–33, 594crystal structure, 609, 788,

790, 817desalination of seawater,

870–871electrolysis of, 508–510formation from elements,

117–118, 581freezing-point depression

with, 866, 871ion pairing in solution, 872isotonic solution of, 870in solar ponds, 848solubility in water, 850–851

Sodium chloride structure, 609Sodium fluoride, lattice

energy, 609–611Sodium hydroxide, 95,

248–249commercial production of,

509–510paper decomposition and, 5reaction with hydrochloric

acid, 113

Sodium ions, in human body, 892

Sodium salts, soluble, 105Softening hard water, 250,

895–897Solar ponds, 848Solids

activity of, 207–208atomic, 790in chemical equations, 67molecular, 788, 812–813polycrystalline, 832properties of, 778standard state, 384types of, 785vapor pressure, 823See also Ionic compounds;

Metals; Network solidsSolubility, 92–93, 94

common ion effect and,332–333

complex ion formation and,334, 344–347

complications incalculations of, 333–334

entropy and, 416–417,850–851, 853

equilibrium calculations,328–334

free energy and, 850–851of gases, 855–856, 857–858like dissolves like, 93, 849,

851, 853pH effects, 334–335, 338practical importance

of, 328pressure effects, 855–856relative, 331–332vs. solubility product, 329strategies for enhancing,

345–346structure effects, 854–855temperature effects, 346,

856–858thermodynamics of, 847,

849–851, 853See also Precipitation

reactionsSolubility product (Ksp),

328–334electrochemical measurement

of, 491–492precipitation and, 335–338vs. solubility, 329table of values, 330, A25

Solubility rules, 104–105Solute, 93, 847Solutions, 846–875

boiling-point elevation,864–866, 872

colligative properties,864–873



Licensed to:

Index A99

composition of, 97–100, 847defined, 93, 846dilution of, 99–100freezing-point depression,

866–867, 871, 872gravimetric analysis of, 112hypertonic, 870hypotonic, 870ideal, 862, 863isotonic, 869, 870liquid–liquid, 862–864nonideal, 862–864osmotic pressure, 867–871,

872–873positional probability and,

416–417reactions in (see Acid–base

reactions; Oxidation–reduction reactions;Precipitation reactions)

sound waves and, 174standard, 98–99standard state in, 384states of, 846thermodynamics of, 847,

849–851, 853vapor pressures of, 859–864See also Aqueous solutions

Solvents, 93, 847nonpolar, 849, 851, 852polar, 92, 93, 849, 851,

852water as, 91–93, 851, 853

Somatic radiation damage,1006

Sonochemistry, 174Soot, electrostatic precipitator

and, 875s orbitals, 550–551, 552, 553

of polyelectronic atoms, 570

Sottos, Nancy, 1043Sound waves

cavitation and, 174refrigeration with, 175

Space-filling model, 31Space vehicles

fuel cells for, 496–497rocket fuels for, 907, 923

Special relativity, 527–528,574–575

Specific heat capacity, 374Spectator ions, 107, 108Spectrochemical series, 961Spectrophotometer, A18Spectroscopy, molecular,

690–692, A17–A21electronic, 690, 691–694nuclear magnetic resonance,

700–705real-world applications

of, 690

rotational, 690–692,698–700

vibrational, 690, 691–692,694–697

Spectroscopy, ultrafast X-ray,738

Spectrumcontinuous, 530electromagnetic, 524–525electron spin and, 556of fireworks, 536–537of hydrogen, 530–531, 532,

533, 535Spherical polar coordinates,

548sp hybridization, 666–667sp2 hybridization, 663–665,

666sp3 hybridization, 661–663,

669, 689Spin

electron, 556, 575, 703nuclear, 700–704

Spinneret, 1036Spin quantum number, 556Spin–spin coupling, 701,

702–704Spontaneous fission, 984Spontaneous processes,

411–417electrochemical, 480, 483,

484, 485, 487entropy increase in,

413–417, 429–433free energy and, 433–436,

444, 447–448, 453–454reaction rates and, 442,

714–715temperature and, 430–433,

435–436work available from, 456See also Irreversible

processesSquare planar structures

complex ions with, 947,952, 958, 964–966

VSEPR model, 644Square roots, A2–A3Stability constants, 341Stahl, Georg, 16Stainless steel, 498, 501Stalactites and stalagmites,

287, 335Standard atmosphere, 142–143Standard deviation, A11

confidence limits and, A13Standard enthalpy of

formation, 384–390bond energies and, 618defined, 384of element, 386, 387table of values, A21–A23

Standard entropy values, 439,440, A21–A23

Standard free energy change,440–444

Standard free energy offormation, 443–444,A21–A23

Standard hydrogen electrode,477

Standard reduction potentials,476–482, A26

corrosion of metals and,497, 498

of transition metals, 938Standard solution, 98–99

for titration, 114, 115Standard states, 384Standard temperature and

pressure (STP), 150, 151Standing waves, 537–538,

546Starch, 1054–1056State function

defined, 360energy as, 360, 373, 425enthalpy as, 365, 373entropy as, 439free energy as, 441

State of a gas, 147States of matter, 777–778

in solutions, 846Statue of Liberty, restoration

of, 498–499Staudinger, Hermann, 1036Steady-state approximation,

743–746Steel

alloy structures, 799chrome-plated, 508, 941chromium in, 941corrosion of, 497, 498–500corrosion prevention,

500–502galvanized, 500, 946stainless, 498, 501tin-coated, 508, 900vanadium in, 941

Stellar nucleosynthesis, 988, 1003

Stereoisomerism, 952–958,1024

of sugars, 1051, 1053–1054Steric factor, 749STM (scanning tunneling

microscope), 22, 540,543, 742, 793

Stock solutions, 99Stoichiometric point, 114,

115, 306of oxidation–reduction, 130See also Equivalence point

Stoichiometric quantities, 73

Stoichiometry, 70–73of acid–base reactions,

113–114defined, 53of gases, 150–152with limiting reactant,

73–79of precipitation reactions,

110–112of reactions in solution, 97,

110–112summary, 77

STP (standard temperatureand pressure), 150, 151

Straight-chain hydrocarbons,1015–1016

Stregay, Heather Ryphemi,413, 414

Strong acids, 94–95, 236–237equilibrium problems with,

241–242, 275–276polyprotic, 260–262

Strong acid–strong basetitrations, 304–307,321–323

indicator for, 321, 323Strong acid–weak base

titrations, 316–318Strong bases, 94, 95, 248–250

cations from, 263very dilute, pH of, 276

Strong electrolytes, 93, 94–95Strong-field ligands, 961,

964, 971Strong nuclear force, 1005Strontium, 35, 564, 895, 896Strontium-90, 989, 1006Structural formula, 30–31Structural isomerism, 951–952

of alkanes, 1016–1021Subcritical nuclear process,

1001, 1002Sublimation, 823, 827–828,

831Subshell, 552Substitutional alloy, 798–799Substitution reactions

of alkanes, 1021of aromatic hydrocarbons,

1026–1027Substrate, 756Subtraction

in exponential notation, A2significant figures,

A14–A15Successive approximations,

213–214, A6–A8Sucrose, 1054

as molecular solid, 788as nonelectrolyte, 96reaction with sulfuric

acid, 918



Licensed to:

A100 Index

Sugar of lead, 900Sugars, 1051–1056

ethanol derived from, 401in nucleic acids, 1057

Sulfate ion, electronicstructure, 630–631,633–634

Sulfate salts, solubility, 105Sulfides

of metals, 506, 914solubility equilibria and,

333, 338, 339–341, 346solubility in water, 105

Sulfites, 918Sulfur, 914, 916–918

bonding properties, 888electron configuration, 567ionization energy, 573–574oxidation state, 120solid structures, 812, 813vulcanization with, 1036

Sulfur dioxide, 917, 918in acid rain formation,

178–179, 180, 755in auto exhaust, 758from coal burning, 178–179molecular structure, 649oxidation of, 755from petroleum

combustion, 758scrubbing of, 179,

181–182, 249, 916vibrational modes, 696

Sulfur hexafluorideclimactic effects of, 394hybrid orbitals for, 670Lewis structures, 627–628,

629, 630, 632Sulfuric acid, 94–95, 236, 918

in acid rain, 179, 180, 755as dehydrating agent,

911, 918dissociation equilibria,

260–262, 263manufacture of, 755, 918

Sulfur monoxide, 917Sulfurous acid, 918Sulfur trioxide, 917–918

in atmosphere, 178–179, 180bond polarities in, 602in sulfuric acid

manufacture, 755Sunflower oil, 401Sunglasses, photochromic, 924Sunscreens, 524Superconductivity, 802–803Supercooling, 825–826

polar fish and, 874Supercritical fluids, 852Supercritical nuclear

processes, 1001, 1002Superfluid water, 852

Superheating, 826Frasch process and, 916

Supernova explosion, 988Superphosphate of lime, 913Surface acoustic wave (SAW)

device, 119Surface alloys, 501Surfaces

architecture of, 543cavitation and, 174of copper crystal, 793reactions on, 753–755, 758

Surface tension, 782–783Surroundings, 360–361

entropy change in,430–433, 456

Suslick, Kenneth, 174Suspensions, 873–875

slurries, 181, 397Swartzentruber, Brian, 793Sykes, Charles, 543Syndiotactic chain, 1042Syngas, 395, 397System, 360–361

entropy change in,430–431, 433

Systematic error, A9–A10

Taggants, 42–43Tanning lotions, 1052Tantalum, 940Tarnish, silver, 498Tastes, 648Technetium-99m, 995Teflon, 1037Tellurium, 914Temperature

absolute zero, 146, 147adiabatic processes and,

457–460of atmosphere, altitude

and, 176blackbody radiation and,

525Celsius to Kelvin

conversion, 146changes of state and,

823–826entropy and, 428, 438equilibrium constant and,

220–221, 452–453gas volume and, 145–146vs. heat, 360heat capacity and, 438kinetic energy and, 157,

161, 366, 368, 821kinetic theory of gases and,

157, 161–163reaction rates and, 747–752real gas behavior and,

172–174, 175solubility and, 346, 856–858

solution composition and,847

spontaneity and, 430–433,435–436

vapor pressure and,821–823, 824–825

See also HeatTermolecular step, 737Tertiary alcohols, 1028Tertiary amines, 1034Tertiary structure, of protein,

1049–1050tert- prefix, 1018Tetraethyl lead, 391, 758, 900Tetrahedral holes, 813,

814–815, 817, 818Tetrahedral structures

of complex ions, 947, 958,963–964

of diamond, 799with Group 5A elements,

902optical isomerism of,

1051, 1053with polar bonds, 602, 603of silica, 888sp3 orbitals for, 661–663,

669, 689VSEPR model, 638, 641,

643, 650Tetraphosphorus decoxide,

912–913Thallium, 897, 898Thallium-201, 995Theoretical yield, 76–77Theory, 8, 9, 10, 156. See

also ModelsThermal conductivity, 790,

797, 798Thermal neutron analysis, 119Thermal pollution, 857Thermodynamics

defined, 362first law, 362, 363, 411, 456vs. kinetics, 412second law, 426, 429–430,

456–457sign convention in, 363standard states in, 384third law, 438See also Energy; Enthalpy;

Entropy; Free energyThermodynamic stability, 442,

828, 829of nuclei, 982, 996–1000

Thermoplastic polymer, 1036,1040, 1041

Thermoset polymer, 1036Thiols, in petroleum, 758Third law of thermodynamics,

438Thomson, J. J., 24–25, 26, 27

Thorium, 984, 986Three-center bonds, 897–898Thundat, Thomas, 806Thymol blue, 324Time measurements, 534Tin, 899–900, 901

in stabilizers for PVC,13–14

stable isotopes of, 983steel plated with, 508, 900

Tin disease, 900Titanium, 563, 936, 937,

940, 942Titanium dioxide, 752,

940–941in polyvinyl chloride, 14in sunscreen, 524

Titanosilicate, 156Titrant, 114–115Titration curve. See pH curveTitrations

acid–base (see Acid–basetitrations)

oxidation–reduction,130–131

TNT (trinitrotoluene), 904Tongue, electronic, 648Tooth decay, 328, 474Torquato, Salvatore, 792torr (unit of pressure), 142Torricelli, Evangelista, 142Trailing zeros, A14Transfer RNA, 1058, 1060trans isomers, 952, 955–956,

1024Transistors, 810–811Transition metals, 35, 886

3d series (first-row),936–939, 940–946

4d series, 939–9405d series, 939–940biological importance,

934, 969economic importance, 889,

933–934electron configurations,

563–564, 579, 936–937forming only one ion, 38in gemstones, 965general properties, 934–936interstitial hydrides of,

894–895ionization energies, 938oxidation states, 936, 938paramagnetic compounds

of, 936periodic table and, 563–564,

565, 566, 934, 935rarity of, 889reduction potentials, 938See also Coordination

compounds; Metals



Licensed to:

Index A101

Transition state, 748Translational kinetic energy,

heat capacity and,367–368

Transmittance, 697, A18Transuranium elements, 992Triads, 559Trial and error, 7Trifluoromethyl sulfur

pentafluoride, 394Trigonal bipyramidal

structures, 641–642with Group 5A elements, 902hybrid orbitals for,

668–669, 671Trigonal holes, 813, 814Trigonal planar structures,

637, 641hybrid orbitals for, 664, 671

Trigonal pyramidal structures,639, 641, 902, 906

phosphine, 650, 912Triiodide ion

hybrid orbitals for, 669Lewis structure, 629VSEPR model, 645

Trimethylamine, 251Trinitrotoluene (TNT), 904Triple bonds

in alkynes, 1024–1026bond energies, 617, 682bond lengths, 617hybrid orbitals for, 667, 672in nitrogen, 903in VSEPR model, 647

Triple phosphate, 913Triple point

of carbon dioxide, 831of water, 828

Triplet, 702, 703Triprotic acids

phosphoric acid, 256–260titration of, 324–328

Troposphere, 176, 177Tsapatsis, Michael, 156Tungsten, 934, 936Tunneling, 22Tyndall effect, 873

Uhlenbeck, George, 556Ultrasound, chemical effects

of, 174Ultraviolet catastrophe, 525Ultraviolet radiation, 524

chlorination of hydrocarbonsand, 1021

electronic spectroscopy and,690, 692

ozone and, 177, 759,915–916

polyvinyl chloride and, 14sunscreens and, 524

Unbranched hydrocarbons,1015–1016

Uncertain digit, A8–A9Uncertainties in measurement,

A8–A13Uncertainty principle, 539–541

wave function and, 550, 556

zero-point energy and, 547Unidentate ligands, 947Unimolecular step, 737Unit cells, 785, 787, 796–797Unit factor method, A17Units of measurement, 8, 9,

A15–A16conversions, A17

Universal gas constant, 147, 161

Unsaturated fats, 754,893–894, 1026

Unsaturated hydrocarbons,1014, 1023–1028

addition reactions, 754,1026

See also EthyleneUranium

age of rocks and, 994–995enrichment of, 166–167fission of, 1000–1001,

1002, 1003, 1007radioactive decay, 26, 27,

984, 985, 986, 992Urea, synthesis of, 1014

Vacuum pump, 142Valence electrons

bonding types and, 603chemical properties and,

578defined, 563periodic table and, 563,

564, 565, 566, 886–887See also Lewis structures

Valence shell electron-pairrepulsion model. SeeVSEPR model

Vanadium, 563, 936, 937, 941Vanadium oxide, 941Vanadium steel, 941van der Waals, Johannes, 172van der Waals equation,

172–175, 176van der Waals forces, 780.

See also Dipole–dipoleforces; London dispersionforces

van Gastel, Raoul, 793Van Helmont, Jan Baptista,

142van’t Hoff, Jacobus H.,

453, 872van’t Hoff equation, 453

van’t Hoff factor, 872–873Vapor, defined, 819Vaporization, 819

entropy change, 429,430–431, 822

free energy change,435–436

Vapor pressure, 819–826at boiling point, 825in gas collection over

water, 154measurement of, 820at melting point, 824, 825of solids, 823of solutions, 859–864temperature and, 821–823,

824–825Vasopressin, 1047Velocity of gas particles,

157–160average, 162, 163,

167–168, 170, 171diffusion and, 165, 166distribution of, 162–163effusion and, 164–165most probable, 163root mean square, 161–163

Vibrational motionentropy and, 439–440heat capacity and, 367–368

Vibrational quantum number,695

Vibrational spectroscopy, 690,691–692, 694–696

Vinegar. See Acetic acidVinyl chloride, 12, 1044Viscosity, 783–785

of polymers, 1041Visible radiation. See LightVitamins, solubilities, 854–855Volatile liquids, 821Volt (unit of electrical

potential), 475, 482Volta, Alessandro, 476Voltaic cells. See Galvanic cellsVoltmeter, 475, 476, 483Volume

equilibrium position and,218, 219–220

PV work and, 364–365,376–378, 424, 454, 455

uncertainty in measurement,A8

units of, A16Volumetric analysis, 114. See

also Acid–base titrations;Oxidation–reductiontitrations

Volumetric flask, 99, 100Volumetric pipet, 100VSEPR model, 620, 636–650

complex ions and, 958

hybrid orbitals and, 661, 670linear structures, 637, 641,

642, 645lone pairs in, 639, 640with multiple bonds,

645–647, 649, 650with no central atom, 649octahedral structures, 642,

643square planar structure, 644success of, 650summary, 638, 650tetrahedral structures, 638,

641, 643trigonal bipyramidal

structures, 641–642, 902trigonal planar structures,

637, 641trigonal pyramidal

structures, 639, 641Vulcanization, 1036

Waage, Peter, 200–201Walsh, William, 901Waste management

radioactive wastes, 1007with superfluid water, 852

Wateras acid, 237–239activity of, 235in atmosphere, 393autoionization of, 237–239,

241–242, 250as base, 234, 236,

237–239, 265biological decomposition

of, 398bond angle of, 91in buffered solutions,

297–300capillary action, 783changes of state, 823–826as coolant, 819, 857, 894density, 778, 830, 894dipole moment, 600–601electrolysis of, 398,

503–504, 893free radicals derived from,

1006gas collection over, 154hard, 250, 895–897heating curve for, 823–824hydrogen bonding in, 779,

780, 813, 819, 821, 822,823, 894

hydrogen ions contributedby, 238–239, 270–276

Lewis structure, 622–623naming of, 40phase diagram, 826–831as polar molecule, 91–92,

597, 894



Licensed to:

A102 Index

Water (continued)purification of, 915reaction with alkali metal,

891, 894reaction with alkaline earth

metal, 895reaction with base, 251,

252, 333as solvent, 91–93, 851, 853states of, 778supercooled, 825–826, 874supercritical, 852thermal decomposition of,

398unusual properties of, 894vaporization of, 429,

430–431, 778, 779, 819,822, 824

vapor pressure andtemperature, 821–822,824

VSEPR model, 639–640See also Aqueous

solutions; IceWaters of hydration, 181Water-soluble vitamins,

854–855Wave function, 538, 541

of hydrogen atom, 541,548–550

molecular orbital, 674of particle in a box,

541–546physical meaning of,

550–551of polyelectronic atom,


550, 674Wavelength, 522, 523

color and, 962–963

of particle, 528–530photon energy and, 526,

533Wave mechanics, 536–538.

See also Quantummechanics

Wave number, 696, 697Waves, 522–523Weak acids, 95–96, 236, 237

common ion effect with,287–289

conjugate base of, 236,237, 263–264

equilibrium problems with,242–248, 270–275

as indicators, 319–324mixtures of, 245–246organic, 236, 1033percent dissociation,

247–248polyprotic, 254–260,

262–263reaction with hydroxide

ion, 113, 117table of Ka values, A24See also Buffered solutions

Weak acid–strong basetitrations, 307–316,323–324

indicator for, 323–324Weak bases, 96, 251–252, 254

in buffered solution, 289,295–297

cyanide ion as, 265table of Kb values, A25

Weak base–strong acidtitrations, 316–318

Weak electrolytes, 93, 95–96Weak-field ligands, 961,

964, 971Weak nuclear force, 1005

Weight, vs. mass, 19–20Weight percent, 60, 847Wentorf, Robert H., Jr., 828Werner, Alfred, 946, 948, 953White, Scott, 1043White dwarf, 988White lead, 13White phosphorus, 888,

911–912White tin, 900Wieman, Carl, 147Williams, Alison, 4Wilson, William W., 905Window shades,

electrochemical, 494–495Wind power, 396Wine, 704Wöhler, Friedrich, 1014Wood alcohol. See MethanolWork

in adiabatic expansion–compression, 457,459–460

defined, 360electrochemical, 475,

482–484energy and, 359, 360free energy and, 453–455internal energy and, 363–365in isothermal expansion–

compression, 417–425maximum, 424, 453–456,

483-484pathway-dependence of, 425PV work, 364–367,

376–378, 424, 454, 455sign convention for, 363,

364Worst-case method, for

estimating uncertainty,A11–A12

Wurtzite, 818Wüstite, 819

Xenon, 35, 923–925freezing point, 781

Xenon difluoride, 673Xenon tetrafluoride, 924, 925

hybrid orbitals for, 670VSEPR model, 643–645

Xenon trioxide, 635X-ray diffraction, 529,

785–788X-ray spectroscopy, 738

Yates, John, 754Yield of reaction, 76–77Yi Lu, 339-yne (suffix), 1025Yttrium, 564

Zeolite, 119, 400Zero-order rate laws, 733–734Zero-point energy, 547Zeros in calculations,

A13–A14Zewail, Ahmed H., 718, 740Ziegler, Karl, 1040Ziegler–Natta catalyst, 1040,

1042Zinc, 564, 937, 938, 945–946

in human body, 889plating with, 500, 504

Zinc blende, 818Zinc oxide, 524Zinc sulfide, crystal

structure, 818Zink, Jeffrey I., 835Zirconium, 939–940Zirconium oxide, 940Zone of stability, nuclear,

983, 984, 985



Licensed to:

Perio

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Tabl

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the

Ele

men

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1 H 3 Li

11 Na

19 K 37 Rb

55 Cs

87 Fr

4 Be

12 Mg

20 Ca

38 Sr 56 Ba

88 Ra

21 Sc 39 Y 57 La* 89 Ac†

22 Ti

40 Zr

72 Hf

104

Rf

23 V 41 Nb

73 Ta 105

Db

24 Cr

42 Mo

74 W 106

Sg

25 Mn

43 Tc

75 Re

107

Bh

26 Fe 44 Ru

76 Os

108

Hs

27 Co

45 Rh

77 Ir 109

Mt

110

Ds

111

Rg

28 Ni

46 Pd 78 Pt

29 Cu

47 Ag

79 Au

34

56

78

910

1112

31 Ga

49 In 81 Tl5 B 13 Al

32 Ge

50 Sn 82 Pb6 C 14 Si

33 As

51 Sb 83 Bi7 N 15 P

34 Se 52 Te 84 Po8 O 16 S

9 F 17 Cl

35 Br

53 I 85 At

10 Ne

18 Ar

36 Kr

54 Xe

86 Rn

118

Uuo2 He

58 Ce

90 Th

59 Pr 91 Pa

60 Nd

92 U

61 Pm 93 Np

62 Sm 94 Pu

63 Eu

95 Am

64 Gd

96 Cm

65 Tb

97 Bk

66 Dy

98 Cf

67 Ho

99 Es

68 Er

100

Fm

69 Tm

101

Md

70 Yb

102

No

71 Lu

103

Lr

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2A

Tra

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dine

I53

126.

9Ir

idiu

mIr

7719

2.2

Iron

Fe26

55.8

5K

rypt

onK

r36

83.8

0L

anth

anum

La

5713

8.9

Law

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Lr

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(260

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Pb82

207.

2L

ithi

umL

i3

6.94

1L

utet

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Lu

7117

5.0

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nesi

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g12

24.3

1M

anga

nese

Mn

2554

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Mei

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Mt

109

(268

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ende

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d10

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58)

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Hg

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4295

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Nd

6014

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Neo

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Np

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Nic

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Nio

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4192

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Nit

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Os

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16.0

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1530

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Pt78

195.

1Pl

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Pu94

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1939

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1122

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3887

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180.

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Licensed to:

Page Numbers of SomeImportant Tables

Bond Energies 617

Electron Configurations of the Elements 566

Ionization Constants of Acids and Bases 238, 252, 256, A24, A25

Reduction Potentials 479, A26

Solubility Products 330, A25

Thermodynamic Data A21–A24

Vapor Pressures of Water 821

Physical ConstantsConstant Symbol Value

Atomic mass unit amu 1.66054 � 10�27 kg

Avogadro’s number N 6.02214 � 1023 mol�1

Bohr radius a0 5.292 � 10�11 m

Boltzmann’s constant k 1.38066 � 10�23 J K�1

Charge of an electron e 1.60218 � 10�19 C

Faraday’s constant F 96,485 C mol�1

Gas constant R 8.31451 J K�1 mol�1

0.08206 L atm K�1 mol�1

Mass of an electron me 9.10939 � 10�31 kg

5.48580 � 10�4 amu

Mass of a neutron mn 1.67493 � 10�27 kg

1.00866 amu

Mass of a proton mp 1.67262 � 10�27 kg

1.00728 amu

Planck’s constant h 6.62608 � 10�34 J s

Speed of light c 2.99792458 � 108 m s�1

1019833_endpaper_002-005 09/06/2007 14:50 Page 4 pinnacle 108:HMQY020:hmzum6_2433T:zum6ep:


Licensed to:

SI Units and Conversion FactorsLength

SI unit: meter (m)

1 meter � 1.0936 yards1 centimeter � 0.39370 inch1 inch � 2.54 centimeters

(exactly)1 kilometer � 0.62137 mile1 mile � 5280 feet

� 1.6093 kilometers1 angstrom � 10�10 meter

� 100 picometers

Mass

SI unit: kilogram (kg)

1 kilogram � 1000 grams� 2.2046 pounds

1 pound � 453.59 grams� 0.45359 kilogram� 16 ounces

1 ton � 2000 pounds� 907.185 kilograms

1 metric ton � 1000 kilograms� 2204.6 pounds

1 atomicmass unit � 1.66054 � 10�27 kilograms

Volume

SI unit: cubic meter (m3)

1 liter � 10�3 m3

� 1 dm3

� 1.0567 quarts1 gallon � 4 quarts

� 8 pints� 3.7854 liters

1 quart � 32 fluid ounces� 0.94633 liter

Temperature

SI unit: kelvin (K)

0 K � �273.15�C� �459.67�F

K � �C � 273.15

�C � (�F � 32)

�F � (�C) � 329�5

5�9

Energy

SI unit: joule (J)

1 joule � 1 kg m2 s�2

� 0.23901 calorie� 9.4781 � 10�4 btu

(British thermal unit)1 calorie � 4.184 joules

� 3.965 � 10�3 btu1 btu � 1055.06 joules

� 252.2 calories

Pressure

SI unit: pascal (Pa)

1 pascal � 1 N m�2

� 1 kg m�1 s �2

1 atmosphere � 101.325 kilopascals� 760 torr (mm Hg)� 14.70 pounds per

square inch1 bar � 105 pascals



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