Contents
Essays xvii
Preface xviii
A Note to Students xxviii
About the Authors xxxvii
About the Cover xxxviii
Part One Basics of Chemistry 1
1 Chemistry and Measurement 1
An Introduction to Chemistry 2
1.1 Modern Chemistry: A Brief Glimpse 2
1.2 Experiment and Explanation 4
A Chemist Looks at The Birth of the Post-it Note® 5
1.3 Law of Conservation of Mass 6
1.4 Matter: Physical State and Chemical Constitution 8
Physical Measurements 13
1.5 Measurement and Significant Figures 13
Instrumental Methods Separation of Mixtures by Chromatography 14
1.6 SI Units 19
1.7 Derived Units 22
1.8 Units and Dimensional Analysis (Factor-Label Method) 25
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
Questions • Concept Explorations • Conceptual Problems • Practice Problems • General
Problems • Strategy Problems • Cumulative-Skills Problems
2 Atoms, Molecules, and Ions 41
Atomic Theory and Atomic Structure 42
2.1 Atomic Theory of Matter 42
2.2 The Structure of the Atom 44
2.3 Nuclear Structure; Isotopes 47
2.4 Atomic Masses 49
2.5 Periodic Table of the Elements 51
Chemical Substances: Formulas and Names 54
2.6 Chemical Formulas; Molecular and Ionic Substances 54
A Chemist Looks at Thirty Seconds on the Island of Stability 54
2.7 Organic Compounds 59
2.8 Naming Simple Compounds 60
Chemical Reactions: Equations 70
2.9 Writing Chemical Equations 71
2.10 Balancing Chemical Equations 71
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
Questions • Concept Explorations • Conceptual Problems • Practice Problems • General
Problems • Strategy Problems • Cumulative-Skills Problems
3 Calculations with Chemical Formulas and Equations 86
Mass and Moles of Substance 87
3.1 Molecular Mass and Formula Mass 87
3.2 The Mole Concept 89
Determining Chemical Formulas 93
3.3 Mass Percentages from the Formula 93
3.4 Elemental Analysis: Percentages of Carbon, Hydrogen, and Oxygen 95
3.5 Determining Formulas 97
Instrumental Methods Mass Spectrometry and Molecular Formula 98
Stoichiometry: Quantitative Relations in Chemical Reactions 102
3.6 Molar Interpretation of a Chemical Equation 103
3.7 Amounts of Substances in a Chemical Reaction 104
3.8 Limiting Reactant; Theoretical and Percentage Yields 107
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4 Chemical Reactions 124
Ions in Aqueous Solution 125
4.1 Ionic Theory of Solutions and Solubility Rules 125
4.2 Molecular and Ionic Equations 130
Types of Chemical Reactions 133
4.3 Precipitation Reactions 134
4.4 Acid–Base Reactions 136
4.5 Oxidation–Reduction Reactions 144
4.6 Balancing Simple Oxidation–Reduction Equations 151
Working with Solutions 154
4.7 Molar Concentration 154
4.8 Diluting Solutions 156
Quantitative Analysis 158
4.9 Gravimetric Analysis 158
4.10 Volumetric Analysis 160
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
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5 The Gaseous State 175
Gas Laws 176
5.1 Gas Pressure and Its Measurement 177
5.2 Empirical Gas Laws 178
5.3 The Ideal Gas Law 187
A Chemist Looks at Nitrogen Monoxide Gas and Biological Signaling 186
5.4 Stoichiometry Problems Involving Gas Volumes 193
5.5 Gas Mixtures; Law of Partial Pressures 194
Kinetic-Molecular Theory 198
5.6 Kinetic Theory of an Ideal Gas 199
5.7 Molecular Speeds; Diffusion and Effusion 201
5.8 Real Gases 207
A Chemist Looks at Carbon Dioxide Gas and the Greenhouse Effect 210
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
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6 Thermochemistry 223
Understanding Heats of Reaction 224
6.1 Energy and Its Units 225
6.2 Heat of Reaction 227
6.3 Enthalpy and Enthalpy Change 230
6.4 Thermochemical Equations 232
A Chemist Looks at Lucifers and Other Matches 235
6.5 Applying Stoichiometry to Heats of Reaction 235
6.6 Measuring Heats of Reaction 236
Using Heats of Reaction 240
6.7 Hess’s Law 241
6.8 Standard Enthalpies of Formation 244
6.9 Fuels—Foods, Commercial Fuels, and Rocket Fuels 249
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
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Problems • Strategy Problems • Cumulative-Skills Problems
7 Quantum Theory of the Atom 263
Light Waves, Photons, and the Bohr Theory 264
7.1 The Wave Nature of Light 265
7.2 Quantum Effects and Photons 268
A Chemist Looks at Zapping Hamburger with Gamma Rays 270
7.3 The Bohr Theory of the Hydrogen Atom 271
A Chemist Looks at Lasers and Compact Disc Players 274
Quantum Mechanics and Quantum Numbers 277
7.4 Quantum Mechanics 277
Instrumental Methods Scanning Tunneling Microscopy 280
7.5 Quantum Numbers and Atomic Orbitals 281
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
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8 Electron Configurations and Periodicity 293
Electronic Structure of Atoms 294
8.1 Electron Spin and the Pauli Exclusion Principle 294
Instrumental Methods Nuclear Magnetic Resonance (NMR) 296
8.2 Building-Up Principle and the Periodic Table 299
Instrumental Methods X Rays, Atomic Numbers, and Orbital Structure (Photoelectron
Spectroscopy) 304
8.3 Writing Electron Configurations Using the Periodic Table 304
8.4 Orbital Diagrams of Atoms; Hund’s Rule 308
A Chemist Looks at Levitating Frogs and People 310
Periodicity of the Elements 311
8.5 Mendeleev’s Predictions from the Periodic Table 311
8.6 Some Periodic Properties 312
8.7 Periodicity in the Main-Group Elements 318
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9 Ionic and Covalent Bonding 328
Ionic Bonds 329
9.1 Describing Ionic Bonds 329
A Chemist Looks at Ionic Liquids and Green Chemistry 335
9.2 Electron Configurations of Ions 336
9.3 Ionic Radii 339
Covalent Bonds 341
9.4 Describing Covalent Bonds 342
A Chemist Looks at Chemical Bonds in Nitroglycerin 344
9.5 Polar Covalent Bonds; Electronegativity 345
9.6 Writing Lewis Electron-Dot Formulas 347
9.7 Delocalized Bonding: Resonance 350
9.8 Exceptions to the Octet Rule 352
9.9 Formal Charge and Lewis Formulas 355
9.10 Bond Length and Bond Order 358
9.11 Bond Energy 359
Instrumental Methods Infrared Spectroscopy and Vibrations of Chemical Bonds 362
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
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10 Molecular Geometry and Chemical Bonding Theory 373
Molecular Geometry and Directional Bonding 375
10.1 The Valence-Shell Electron-Pair Repulsion (VSEPR) Model 375
10.2 Dipole Moment and Molecular Geometry 383
A Chemist Looks at Left-Handed and Right-Handed Molecules 384
10.3 Valence Bond Theory 389
10.4 Description of Multiple Bonding 395
Molecular Orbital Theory 399
10.5 Principles of Molecular Orbital Theory 400
10.6 Electron Configurations of Diatomic Molecules of the Second-Period Elements 402
10.7 Molecular Orbitals and Delocalized Bonding 405
A Chemist Looks at Human Vision 407
A Chemist Looks at Stratospheric Ozone (An Absorber of Ultraviolet Rays) 408
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
Questions • Concept Explorations • Conceptual Problems • Practice Problems • General
Problems • Strategy Problems • Cumulative-Skills Problems
11 States of Matter; Liquids and Solids 418
11.1 Comparison of Gases, Liquids, and Solids 419
Changes of State 420
11.2 Phase Transitions 420
11.3 Phase Diagrams 430
A Chemist Looks at Removing Caffeine from Coffee 433
Liquid State 434
11.4 Properties of Liquids: Surface Tension and Viscosity 434
11.5 Intermolecular Forces; Explaining Liquid Properties 436
A Chemist Looks at Gecko Toes, Sticky But Not Tacky 443
Solid State 444
11.6 Classification of Solids by Type of Attraction of Units 444
11.7 Crystalline Solids; Crystal Lattices and Unit Cells 448
11.8 Structures of Some Crystalline Solids 451
A Chemist Looks at Liquid-Crystal Displays 452
11.9 Calculations Involving Unit-Cell Dimensions 458
11.10 Determining Crystal Structure by X-Ray Diffraction 460
Instrumental Methods Automated X-Ray Diffractometry 462
A Chemist Looks at Water (A Special Substance for Planet Earth) 463
Questions • Concept Explorations • Conceptual Problems • Practice Problems • General
Problems • Strategy Problems • Cumulative-Skills Problems
12 Solutions 478
Solution Formation 479
12.1 Types of Solutions 479
12.2 Solubility and the Solution Process 481
A Chemist Looks at Hemoglobin Solubility and Sickle-Cell Anemia 486
12.3 Effects of Temperature and Pressure on Solubility 487
Colligative Properties 490
12.4 Ways of Expressing Concentration 490
12.5 Vapor Pressure of a Solution 496
12.6 Boiling-Point Elevation and Freezing-Point Depression 500
12.7 Osmosis 504
12.8 Colligative Properties of Ionic Solutions 507
Colloid Formation 508
12.9 Colloids 509
A Chemist Looks at The World’s Smallest Test Tubes 512
A Checklist for Review • Media Summary • Learning Objectives • Self-Assessment and Review
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13 Rates of Reaction 523
Reaction Rates 524
13.1 Definition of Reaction Rate 525
13.2 Experimental Determination of Rate 529
13.3 Dependence of Rate on Concentration 530
13.4 Change of Concentration with Time 536
13.5 Temperature and Rate; Collision and Transition-State Theories 544
13.6 Arrhenius Equation 548
Reaction Mechanisms 550
13.7 Elementary Reactions 550
13.8 The Rate Law and the Mechanism 554
13.9 Catalysis 560
A Chemist Looks at Seeing Molecules React 564
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14 Chemical Equilibrium 580
Describing Chemical Equilibrium 582
14.1 Chemical Equilibrium—A Dynamic Equilibrium 582
14.2 The Equilibrium Constant 585
14.3 Heterogeneous Equilibria; Solvents in Homogeneous Equilibria 591
A Chemist Looks at Slime Molds and Leopards’ Spots 592
Using the Equilibrium Constant 594
14.4 Qualitatively Interpreting the Equilibrium Constant 594
14.5 Predicting the Direction of Reaction 595
14.6 Calculating Equilibrium Concentrations 597
Changing the Reaction Conditions; Le Châtelier’s Principle 602
14.7 Removing Products or Adding Reactants 602
14.8 Changing the Pressure and Temperature 604
14.9 Effect of a Catalyst 609
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15 Acids and Bases 623
Acid–Base Concepts 624
15.1 Arrhenius Concept of Acids and Bases 625
15.2 Brønsted–Lowry Concept of Acids and Bases 625
15.3 Lewis Concept of Acids and Bases 628
A Chemist Looks at Taking Your Medicine 630
Acid and Base Strengths 631
15.4 Relative Strengths of Acids and Bases 631
15.5 Molecular Structure and Acid Strength 633
Self-Ionization of Water and pH 636
15.6 Self-Ionization of Water 636
15.7 Solutions of a Strong Acid or Base 637
15.8 The pH of a Solution 639
A Chemist Looks at Unclogging the Sink and Other Chores 643
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16 Acid–Base Equilibria 652
Solutions of a Weak Acid or Base 653
16.1 Acid-Ionization Equilibria 653
16.2 Polyprotic Acids 660
A Chemist Looks at Acid Rain 662
16.3 Base-Ionization Equilibria 664
16.4 Acid–Base Properties of Salt Solutions 667
Solutions of a Weak Acid or Base with Another Solute 672
16.5 Common-Ion Effect 672
16.6 Buffers 675
16.7 Acid–Base Titration Curves 682
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17 Solubility and Complex-Ion Equilibria 699
Solubility Equilibria 700
17.1 The Solubility Product Constant 700
17.2 Solubility and the Common-Ion Effect 705
17.3 Precipitation Calculations 707
17.4 Effect of pH on Solubility 712
A Chemist Looks at Limestone Caves 714
Complex-Ion Equilibria 715
17.5 Complex-Ion Formation 715
17.6 Complex Ions and Solubility 718
An Application of Solubility Equilibria 720
17.7 Qualitative Analysis of Metal Ions 720
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18 Thermodynamics and Equilibrium 731
18.1 First Law of Thermodynamics; Enthalpy 732
Spontaneous Processes and Entropy 735
18.2 Entropy and the Second Law of Thermodynamics 736
18.3 Standard Entropies and the Third Law of Thermodynamics 741
Free-Energy Concept 745
18.4 Free Energy and Spontaneity 745
18.5 Interpretation of Free Energy 749
A Chemist Looks at Coupling of Reactions 750
Free Energy and Equilibrium Constants 752
18.6 Relating G to the Equilibrium Constant 753
18.7 Change of Free Energy with Temperature 755
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19 Electrochemistry 770
Half-Reactions 771
19.1 Balancing Oxidation–Reduction Reactions in Acidic and Basic Solutions 771
Voltaic Cells 776
19.2 Construction of Voltaic Cells 776
19.3 Notation for Voltaic Cells 779
19.4 Cell Potential 781
19.5 Standard Cell Potentials and Standard Electrode Potentials 783
19.6 Equilibrium Constants from Cell Potentials 790
19.7 Dependence of Cell Potential on Concentration 793
19.8 Some Commercial Voltaic Cells 797
Electrolytic Cells 800
19.9 Electrolysis of Molten Salts 800
19.10 Aqueous Electrolysis 802
19.11 Stoichiometry of Electrolysis 806
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20 Nuclear Chemistry 820
Radioactivity and Nuclear Bombardment Reactions 821
20.1 Radioactivity 821
A Chemist Looks at Magic Numbers 827
20.2 Nuclear Bombardment Reactions 832
20.3 Radiations and Matter: Detection and Biological Effects 836
20.4 Rate of Radioactive Decay 838
20.5 Applications of Radioactive Isotopes 845
Energy of Nuclear Reactions 848
A Chemist Looks at Positron Emission Tomography (PET) 849
20.6 Mass–Energy Calculations 850
20.7 Nuclear Fission and Nuclear Fusion 854
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Cumulative-Skills Problems
21 Chemistry of the Main-Group Elements 866
21.1 General Observations About the Main-Group Elements 867
Chemistry of the Main-Group Metals 870
21.2 Metals: Characteristics and Production 870
21.3 Bonding in Metals 874
A Chemist Looks at Superconductivity 876
21.4 Group IVA: The Alkali Metals 877
21.5 Group IIA: The Alkaline Earth Metals 883
21.6 Group IIIA and Group IVA Metals 888
Chemistry of the Nonmetals 892
21.7 Hydrogen 893
21.8 Group IVA: The Carbon Family 895
21.9 Group VA: Nitrogen and the Phosphorous Family 900
A Chemist Looks at Buckminsterfullerene—A Third Form of Carbon 901
21.10 Group VIA: Oxygen and the Sulfur Family 908
21.11 Group VIIA: The Halogens 914
21.12 Group VIIIA: The Noble Gases 918
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22 The Transition Elements and Coordination Compounds 930
Properties of the Transition Elements 931
22.1 Periodic Trends in the Transition Elements 931
22.2 The Chemistry of Two Transition Elements 935
Complex Ions and Coordination Compounds 938
22.3 Formation and Structure of Complexes 938
22.4 Naming Coordination Compounds 942
A Chemist Looks at Salad Dressing and Chelate Stability 943
22.5 Structure and Isomerism in Coordination Compounds 946
22.6 Valence Bond Theory of Complexes 953
22.7 Crystal Field Theory 954
A Chemist Looks at The Cooperative Release of Oxygen from Oxyhemoglobin 961
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23 Organic Chemistry 968
23.1 The Bonding of Carbon 969
Hydrocarbons 970
23.2 Alkanes and Cycloalkanes 970
23.3 Alkenes and Alkynes 977
23.4 Aromatic Hydrocarbons 981
23.5 Naming Hydrocarbons 984
Derivatives of Hydrocarbons 991
23.6 Organic Compounds Containing Oxygen 991
23.7 Organic Compounds Containing Nitrogen 995
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24 Polymer Materials: Synthetic and Biological 1004
Synthetic Polymers 1005
24.1 Synthesis of Organic Polymers 1006
A Chemist Looks at The Discovery of Nylon 1008
24.2 Electrically Conducting Polymers 1010
Biological Polymers 1012
24.3 Proteins 1012
24.4 Nucleic Acids 1017
A Chemist Looks at Tobacco Mosaic Virus and Atomic Force Microscopy 1025
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Problems • Strategy
Problems
Appendixes A-1
A. Mathematical Skills A-1
B. Vapor Pressure of Water at Various Temperatures A-7
C. Thermodynamic Quantities for Substances and Ions at 25 C A-8
D. Electron Configurations of Atoms in the Ground State A-12
E. Acid-Ionization Constants at 25 C A-13
F. Base-Ionization Constants at 25 C A-14
G. Solubility Product Constants at 25 C A-15
H. Formation Constants of Complex Ions at 25 C A-16
I. Standard Electrode (Reduction) Potentials in Aqueous Solution at 25 C A-16
