Chemistry

Dr. James Spencer is a professor of chemistry at Franklin and Marshall College. He has received a number of awards and commendations including the Lindback Award for Distinguished Teaching, Bradley R. Dewey Award for Outstanding Scholarship, and the Chemical Manufacturers Association National Award for Teaching. Dr. Spencer was a founding member of the Council on Undergraduate Research, a national organization dedicated to promoting research in all disciplines by undergraduates. He was appointed chair of the ACS Task Force on the General Chemistry Curriculum, served as a member and chair of the Advanced Placement Chemistry Committee and now chairs the Advanced Placement Redesign Panel for Chemistry.

Chapter 1 Elements and Compounds 1

1.1 Chemistry: A Definition, 2

1.2 Elements, Compounds, and Mixtures, 3

1.3 Atomic Symbols, 4

1.4 Chemical Formulas, 5

1.5 Evidence for the Existence of Atoms, 6

1.6 The Role of Measurement in Chemistry, 7

1.7 The Structure of Atoms, 9

1.8 Atomic Number and Mass Number, 11

1.9 Isotopes, 12

1.10 The Difference Between Atoms and Ions, 14

1.11 Polyatomic Ions, 16

1.12 The Periodic Table, 16

1.13 The Macroscopic, Atomic and Symbolic Worlds of Chemistry, 18

1.14 The Mass of an Atom, 19

1.15 Chemical Reactions and the Law of Conservation of Atoms, 21

1.16 Chemical Equations as a Representation of Chemical Reactions, 21

1.17 Balancing Chemical Equations, 22

Chapter 2 The Mole: The Link between the Macroscopic and the Atomic Worlds of Chemistry 31

2.1 The Mole as the Bridge Between the Macroscopic and Atomic Scales, 32

2.2 The Mole as a Collection of Atoms, 33

2.3 Converting Grams into Moles and Number of Atoms, 35

2.4 The Mole as a Collection of Molecules, 37

2.5 Percent by Mass, 40

2.6 Determining the Formula of a Compound, 41

2.7 Two Views of Chemical Equations: Molecules Versus Moles, 45

2.8 Mole Ratios and Chemical Equations, 46

2.9 Stoichiometry, 48

2.10 The Stoichiometry of the Breathalyzer, 49

2.11 The Nuts and Bolts of Limiting Reagents, 50

2.12 Density, 53

2.13 Solute, Solvent, and Solution, 54

2.14 Concentration, 55

2.15 Molarity as a Way to Count Particles in a Solution, 56

2.16 Dilution Calculations, 58

2.17 Solution Stoichiometry, 59

Problems, 63

Chapter 3 The Structure of the Atom 71

3.1 Rutherford’s Model of the Atom, 72

3.2 Particles and Waves, 73

3.3 Light and Other Forms of Electromagnetic Radiation, 74

3.4 Atomic Spectra, 76

3.5 The Wave-Packet Model of Electromagnetic Radiation, 77

3.6 The Bohr Model of the Atom, 79

3.7 The Energy States of the Hydrogen Atom, 80

3.8 Electromagnetic Radiation and Color, 82

3.9 The First Ionization Energy, 83

3.10 The Shell Model, 85

3.11 The Shell Model and the Periodic Table, 87

3.12 Photoelectron Spectroscopy and the Structure of Atoms, 88

3.13 Electron Configurations from Photoelectron Spectroscopy, 89

3.14 Allowed Combinations of Quantum Numbers, 95

3.15 Shells and Subshells of Orbitals, 96

3.16 Orbitals and the Pauli Exclusion Principle, 98

3.17 Predicting Electron Configurations, 100

3.18 Electron Configurations and the Periodic Table, 101

3.19 Electron Configurations and Hund’s Rules, 102

3.20 The Sizes of Atoms: Metallic Radii, 104

3.21 The Sizes of Atoms: Covalent Radii, 104

3.22 The Relative Sizes of Atoms and Their Ions, 105

3.23 Patterns in Ionic Radii, 107

3.24 Second, Third, Fourth, and Higher Ionization Energies, 108

3.25 Average Valence Electron Energy (AVEE), 110

3.26 AVEE and Metallicity, 111

Problems, 113

Chapter 4 The Covalent Bond 123

4.1 Valence Electrons, 124

4.2 The Covalent Bond, 125

4.3 How Does the Sharing of Electrons Bond Atoms?, 126

4.4 Using Lewis Structures to Understand the Formation of Bonds, 127

4.5 Drawing Skeleton Structures, 128

4.6 A Step-by-Step Approach to Writing Lewis Structures, 129

4.7 Molecules That Don’t Seem to Satisfy the Octet Rule, 131

4.8 Bond Lengths, 134

4.9 Resonance Hybrids, 136

4.10 Electronegativity, 139

4.11 Partial Charge, 141

4.12 Formal Charge, 142

4.13 The Shapes of Molecules, 145

4.14 Predicting the Shapes of Molecules (The Electron Domain Model), 148

4.15 The Role of Nonbonding Electrons in the ED Model, 151

4.16 Bond Angles, 154

4.17 The Difference Between Polar Bonds and Polar Molecules, 156

Problems, 158

Special Topics

4A.1 Valence Bond Theory, 165

4A.2 Hybrid Atomic Orbitals, 166

4A.3 Molecules with Double and Triple Bonds, 169

4A.4 Molecular Orbital Theory, 170

Problems, 176

Chapter 5 Ionic and Metallic Bonds 177

5.1 Metals, Nonmetals, and Semimetals, 178

5.2 The Active Metals, 178

5.3 Main-Group Metals and Their Ions, 180

5.4 Main-Group Nonmetals and Their Ions, 181

5.5 Transition Metals and Their Ions, 184

5.6 Chemistry and Color, 184

5.7 Predicting the Formulas of Ionic Compounds, 185

5.8 Predicting the Products of Reactions That Produce Ionic Compounds, 186

5.9 Oxides, Peroxides, and Superoxides, 188

5.10 The Ionic Bond, 189

5.11 Structures of Ionic Compounds, 190

5.12 Metallic Bonds, 191

5.13 The Relationship among Ionic, Covalent, and Metallic Bonds, 192

5.14 Bond-Type Triangles, 197

5.15 Properties of Metallic, Covalent, and Ionic Compounds, 201

5.16 Oxidation Numbers, 201

5.17 Calculating Oxidation Numbers, 204

5.18 Oxidation–Reduction Reactions, 207

5.19 Nomenclature, 209

Problems, 213

Chapter 6 Gases 221

6.1 Temperature, 222

6.2 Temperature as a Property of Matter, 223

6.3 The States of Matter, 224

6.4 Elements or Compounds That Are Gases at Room Temperature, 225

6.5 The Properties of Gases, 226

6.6 Pressure versus Force, 227

6.7 Atmospheric Pressure, 229

6.8 Boyle’s Law, 231

6.9 Amontons’ Law, 232

6.10 Charles’ Law, 233

6.11 Gay-Lussac’s Law, 234

6.12 Avogadro’s Hypothesis, 234

6.13 The Ideal Gas Equation, 236

6.14 Dalton’s Law of Partial Pressures, 237

6.15 Ideal Gas Calculations: Part I, 240

6.16 Ideal Gas Calculations: Part II, 244

6.17 The Kinetic Molecular Theory, 246

6.18 How the Kinetic Molecular Theory Explains the Gas Laws, 247

6.19 Graham’s Laws of Diffusion and Effusion, 250

Problems, 252

Special Topics

6A.1 Deviations from Ideal Gas Law Behavior: The van der Waals Equation, 259

6A.2 Analysis of the van der Waals Constants, 262

Problems, 263

Chapter 7 Making and Breaking of Bonds 264

7.1 Energy, 265

7.2 Heat, 268

7.3 Heat and the Kinetic Molecular Theory, 268

7.4 Specific Heat, 269

7.5 State Functions, 273

7.6 The First Law of Thermodynamics, 274

7.7 Work, 276

7.8 The Enthalpy of a System, 280

7.9 Enthalpies of Reaction, 282

7.10 Enthalpy as a State Function, 285

7.11 Standard-State Enthalpies of Reaction, 287

7.12 Calculating Enthalpies of Reaction, 288

7.13 Enthalpies of Atom Combination, 289

7.14 Using Enthalpies of Atom Combination to Probe Chemical Reactions, 296

7.15 Bond Length and the Enthalpy of Atom Combination, 299

7.16 Hess’s Law, 300

7.17 Enthalpies of Formation, 301

Problems, 305

Chapter 8 Liquids and Solutions 313

8.1 The Structure of Gases, Liquids, and Solids, 314

8.2 Intermolecular Forces, 316

8.3 Relative Strengths of Intermolecular Forces, 320

8.4 The Kinetic Theory of Liquids, 324

8.5 The Vapor Pressure of a Liquid, 325

8.6 Melting Point and Freezing Point, 328

8.7 Boiling Point, 330

8.8 Phase Diagrams, 332

8.9 Hydrogen Bonding and the Anomalous Properties of Water, 333

8.10 Solutions: Like Dissolves Like, 334

8.11 Hydrophilic and Hydrophobic Molecules, 337

8.12 Soaps, Detergents, and Dry-Cleaning Agents, 339

8.13 Why Do Some Solids Dissolve in Water?, 341

8.14 Solubility Equilibria, 344

8.15 Solubility Rules, 346

8.16 Net Ionic Equations, 347

Problems, 349

Special Topics

8A.1 Colligative Properties, 357

8A.2 Depression of the Partial Pressure of a Solvent, 358

8A.3 Boiling Point Elevation, 361

8A.4 Freezing Point Depression, 363

Problems, 365

Chapter 9 Solids 367

9.1 Types of Solids, 368

9.2 Molecular and Network Covalent Solids, 369

9.3 The Physical Properties of Molecular and Network Covalent Solids, 372

9.4 Metallic Solids, 373

9.5 Physical Properties That Result from the Structure of Metals, 374

9.6 The Structure of Metals, 375

9.7 Coordination Numbers and the Structures of Metals, 378

9.8 Unit Cells: The Simplest Repeating Unit in a Crystal, 379

9.9 Solid Solutions and Intermetallic Compounds, 380

9.10 Semimetals, 381

9.11 Ionic Solids, 382

9.12 The Search for New Materials, 385

9.13 Measuring the Distance Between Particles in a Unit Cell, 388

9.14 Determining the Unit Cell of a Crystal, 389

9.15 Calculating the Size of an Atom or Ion, 391

Problems, 392

Special Topics

9A.1 Defects, 397

9A.2 Metals, Semiconductors, and Insulators, 398

9A.3 Thermal Conductivity, 401

9A.4 Thermal Expansion, 402

9A.5 Glass and Other Ceramics, 403

Problems, 407

Chapter 10 The Connection Between Kinetics and Equilibrium 408

10.1 Reactions That Don’t Go to Completion, 409

10.2 Gas-Phase Reactions, 411

10.3 The Rate of a Chemical Reaction, 413

10.4 The Collision Theory Model of Gas-Phase Reactions, 415

10.5 Equilibrium Constant Expressions, 418

10.6 Reaction Quotients: A Way to Decide Whether a Reaction is at Equilibrium, 423

10.7 Changes in Concentration That Occur as a Reaction Comes to Equilibrium, 425

10.8 Hidden Assumptions That Make Equilibrium Calculations Easier, 430

10.9 What Do We Do When the Assumption Fails?, 434

10.10 The Effect of Temperature on an Equilibrium Constant, 436

10.11 Le Châtelier’s Principle, 437

10.12 Le Châtelier’s Principle and the Haber Process, 443

10.13 What Happens When a Solid Dissolves in Water?, 445

10.14 The Solubility Product Expression, 446

10.15 The Relationship Between Ksp and the Solubility of a Salt, 448

10.16 The Role of the Ion Product (Qsp) in Solubility Calculations, 451

10.17 The Common-Ion Effect, 453

Problems, 458

Chapter 11 Acids and Bases 468

11.1 Properties of Acids and Bases, 469

11.2 The Arrhenius Definition of Acids and Bases, 469

11.3 The Brønsted–Lowry Definition of Acids and Bases, 470

11.4 Conjugate Acid–Base Pairs, 472

11.5 The Role of Water in the Brønsted Model, 474

11.6 To What Extent Does Water Dissociate to Form Ions?, 475

11.7 pH as a Measure of the Concentration of the H3O+ Ion, 478

11.8 Relative Strengths of Acids and Bases, 481

11.9 Relative Strengths of Conjugate Acid–Base Pairs, 485

11.10 Relative Strengths of Different Acids and Bases, 486

11.11 Relationship of Structure to Relative Strengths of Acids and Bases, 490

11.12 Strong Acid pH Calculations, 494

11.13 Weak Acid pH Calculations, 494

11.14 Base pH Calculations, 500

11.15 Mixtures of Acids and Bases: Buffers, 504

11.16 Buffers and Buffer Capacity, 506

11.17 Buffers in the Body, 510

11.18 Acid–Base Reactions, 511

11.19 pH Titration Curves, 513

Problems, 520

Special Topics

11A.1 Diprotic Acids, 530

11A.2 Diprotic Bases, 534

11A.3 Compounds That Could Be Either Acids or Bases, 536

Problems, 539

Chapter 12 Oxidation–Reduction Reactions 540

12.1 Common Oxidation–Reduction Reactions, 541

12.2 Determining Oxidation Numbers, 542

12.3 Recognizing Oxidation–Reduction Reactions, 544

12.4 Voltaic Cells, 548

12.5 Standard Cell Potentials, 551

12.6 Oxidizing and Reducing Agents, 553

12.7 Relative Strengths of Oxidizing and Reducing Agents, 554

12.8 Batteries, 559

12.9 Electrochemical Cells at Nonstandard Conditions: The Nernst Equation, 563

12.10 Electrolysis and Faraday’s Law, 567

12.11 Electrolysis of Molten NaCl, 571

12.12 Electrolysis of Aqueous NaCl, 572

12.13 Electrolysis of Water, 574

12.14 The Hydrogen Economy, 575

Problems, 576

Special Topics

12.A1 Balancing Oxidation–Reduction Equations, 585

12.A2 Redox Reactions in Acidic Solutions, 585

12.A3 Redox Reactions in Basic Solutions, 589

12.A4 Molecular Redox Reactions, 590

Problems, 592

Chapter 13 Chemical Thermodynamics 594

13.1 Spontaneous Chemical and Physical Processes, 595

13.2 Entropy and Disorder, 596

13.3 Entropy and the Second Law of Thermodynamics, 597

13.4 Standard-State Entropies of Reaction, 600

13.5 The Third Law of Thermodynamics, 600

13.6 Calculating Entropy Changes for Chemical Reactions, 601

13.7 Gibbs Free Energy, 606

13.8 The Effect of Temperature on the Free Energy of a Reaction, 612

13.9 Beware of Oversimplifications, 613

13.10 Standard-State Free Energies of Reaction, 613

13.11 Equilibria Expressed in Partial Pressures, 615

13.12 Interpreting Standard-State Free Energy of Reaction Data, 619

13.13 The Relationship between Free Energy and Equilibrium Constants, 620

13.14 The Temperature Dependence of Equilibrium Constants, 626

13.15 Gibbs Free Energies of Formation and Absolute Entropies, 630

Problems, 632

Chapter 14 Kinetics 640

14.1 The Forces That Control a Chemical Reaction, 641

14.2 Chemical Kinetics, 642

14.3 Is the Rate of Reaction Constant?, 642

14.4 Instantaneous Rates of Reaction, 644

14.5 Rate Laws and Rate Constants, 645

14.6 The Rate Law Versus the Stoichiometry of a Reaction, 646

14.7 Order and Molecularity, 647

14.8 A Collision Theory Model of Chemical Reactions, 650

14.9 The Mechanisms of Chemical Reactions, 652

14.10 Zero-Order Reactions, 654

14.11 Determining the Order of a Reaction from Rates of Reaction, 655

14.12 The Integrated Form of Zero-, First-, and Second-Order Rate Laws, 658

14.13 Determining the Order of a Reaction with the Integrated Form of Rate Laws 663

14.14 Reactions That Are First-Order in Two Reactants, 666

14.15 The Activation Energy of Chemical Reactions, 667

14.16 Catalysts and the Rates of Chemical Reactions, 669

14.17 Determining the Activation Energy of a Reaction, 671

14.18 The Kinetics of Enzyme-Catalyzed Reactions, 673

Problems, 675

Special Topics

14A.1 Deriving the Integrated Rate Laws, 686

Chapter 15 Nuclear Chemistry 688

15.1 Radioactivity, 689

15.2 The Structure of the Atom, 690

15.3 Modes of Radioactive Decay, 692

15.4 Neutron-Rich Versus Neutron-Poor Nuclides, 694

15.5 Binding Energy Calculations, 697

15.6 The Kinetics of Radioactive Decay, 700

15.7 Dating by Radioactive Decay, 703

15.8 Ionizing Versus Nonionizing Radiation, 705

15.9 Biological Effects of Ionizing Radiation, 706

15.10 Natural Versus Induced Radioactivity, 709

15.11 Nuclear Fission, 713

15.12 Nuclear Fusion, 715

15.13 Nuclear Synthesis, 717

15.14 Nuclear Medicine, 719

Problems, 720

Chapter 16 Organic Chemistry 723

16.1 What Is an Organic Compound?, 724

16.2 The Saturated Hydrocarbons or Alkanes, 726

16.3 Rotation Around C—C Bonds, 729

16.4 The Nomenclature of Alkanes, 730

16.5 The Unsaturated Hydrocarbons: Alkenes and Alkynes, 733

16.6 Aromatic Hydrocarbons and Their Derivatives, 735

16.7 The Chemistry of Petroleum Products, 737

16.8 The Chemistry of Coal, 740

16.9 Functional Groups, 742

16.10 Oxidation-Reduction Reactions, 746

16.11 Alkyl Halides, 750

16.12 Alcohols and Ethers, 752

16.13 Aldehydes and Ketones, 755

16.14 Reactions at the Carbonyl Group, 757

16.15 Carboxylic Acids and Carboxylate Ions, 759

16.16 Esters, 761

16.17 Amines, Alkaloids, and Amides, 763

16.18 Alkene Stereoisomers, 765

16.19 Stereogenic Atoms, 768

16.20 Optical Activity, 771

Problems, 774

Appendix A

A.1 Systems of Units A-2

The English Units of Measurement A-2

SI Units of Measurement A-3

Derived SI Units A-4

Non-SI Units A-4

Conversion Factors A-5

A.2 Uncertainty in Measurement A-6

Systematic and Random Errors A-6

Accuracy and Precision A-7

A.3 Significant figures A-8

Addition and Subtraction with Significant Figures A-9

Multiplication and Division with Significant Figures A-10

Rounding Off A-10

A.4 Scientific Notation A-10

A.5 The Graphical Treatment of Data A-12

A.6 Significant Figures and Unit Conversion Worksheet A-15

Significant Figures A-15

Counting Significant Figures in a Measurement A-15

Measurements versus Definitions A-18

Unit Conversions A-19

Appendix B

Table B.1 Values of Selected Fundamental Constants B-2

Table B.2 Selected Conversion Factors B-2

Table B.3 The Vapor Pressure of Water B-3

Table B.4 Radii of Atoms and Ions B-4

Table B.5 Ionization Energies B-6

Table B.6 Electron Affinities B-8

Table B.7 Electronegativities B-9

Table B.8 Acid-Dissociation Equilibrium Constants B-10

Table B.9 Base-Ionization Equilibrium Constants B-11

Table B.10 Solubility Product Equilibrium Constants B-12

Table B.11 Complex Formation Equilibrium Constants B-13

Table B.12 Standard Reduction Potentials B-14

Table B.13 Standard-State Enthalpies, Free Energies and Entropies of Atom Combination B- 17

Table B.14 Bond-Dissociation Enthalpies B-25

Table B.15 Electron Configuration of the First 86 Elements B-26

Table B.16 Standard-State Enthalpy of Formation, Free Energy of Formation and Absolute Entropy Data B-28

Appendix C

Answers to Selected Problems C-1

Appendix D

Answers to Checkpoints D-1

Photo Credits P-1

Index I-1

Modules (available at www.wiley.com/college/spencer)

Module 1 Chemistry of the Nonmetals

Module 2 Transition Metal Chemistry

Module 3 Complex Ion Equilibria

Module 4 Organic Chemistry: Structure and Nomenclature of Hydrocarbons

Module 5 Organic Chemistry: Functional Groups

Module 6 Organic Chemistry: Reaction Mechanisms

Module 7 Polymer Chemistry

Module 8 Biochemistry

Module 9 Chemical Analysis