AP Chemistry Online Textbook

1172 Pages·2015·54.87 MB·English

Chemistry
Seventh Edition
Steven S. Zumdahl
University of Illinois
Susan A. Zumdahl
University of Illinois
Houghton Mifflin Company Boston New York
Executive Editor:Richard Stratton
Developmental Editor:Rebecca Berardy Schwartz
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Cover image:Masaaki Kazama/Photonica
Photo credits:Page A39.
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Library of Congress Catalog Card Number:2005929890
Student edition:
ISBN 13:978-0-618-52844-8
ISBN 10:0-618-52844-X
Instructor’s Annotated Edition:
ISBN 13:978-0-618-52845-5
ISBN 10:0-618-52845-8
Advanced Placement edition:
ISBN 13:978-0-618-71370-7
ISBN 10:0-618-71370-0
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Contents
To the Professor ix 3.3 The Mole 82
To the Student xv ■ CHEMICAL IMPACT Elemental Analysis Catches
Elephant Poachers 84
1 Chemical Foundations 1
3.4 Molar Mass 86
■ CHEMICAL IMPACT Measuring the Masses of Large
1.1 Chemistry:An Overview 2
Molecules, or Making Elephants Fly 87
■ CHEMICAL IMPACT The Chemistry of Art 4
3.5 Percent Composition of Compounds 89
1.2 The Scientific Method 5
3.6 Determining the Formula of a Compound 91
■ CHEMICAL IMPACT A Note-able Achievement 7
3.7 Chemical Equations 96
■ CHEMICAL IMPACT Critical Units! 8
3.8 Balancing Chemical Equations 98
1.3 Units of Measurement 8
3.9 Stoichiometric Calculations:Amounts of Reactants and
1.4 Uncertainty in Measurement 10
Products 102
1.5 Significant Figures and Calculations 13
■ CHEMICAL IMPACT High Mountains—Low
1.6 Dimensional Analysis 16 Octane 103
1.7 Temperature 19 3.10 Calculations Involving a Limiting Reactant 106
■ CHEMICAL IMPACT Faux Snow 22 For Review 113 • Key Terms 113 • Questions and
1.8 Density 24 Exercises 115
1.9 Classification of Matter 25
For Review 29 • Key Terms 29 • Questions and 4 Types of Chemical Reactions and
Exercises 30 Solution Stoichiometry 126
2 Atoms, Molecules, and Ions 38
4.1 Water, the Common Solvent 127
2.1 The Early History of Chemistry 39 4.2 The Nature of Aqueous Solutions: Strong and Weak
■ CHEMICAL IMPACT There’s Gold in Them There Plants! 40 Electrolytes 129
■ CHEMICAL IMPACT Arrhenius: A Man with
2.2 Fundamental Chemical Laws 41
Solutions 132
2.3 Dalton’s Atomic Theory 43
4.3 The Composition of Solutions 133
2.4 Early Experiments to Characterize the Atom 45
■ CHEMICAL IMPACT Tiny Laboratories 138
■ CHEMICAL IMPACT Berzelius, Selenium, and Silicon 46
4.4 Types of Chemical Reactions 140
2.5 The Modern View of Atomic Structure:
4.5 Precipitation Reactions 140
An Introduction 49
4.6 Describing Reactions in Solution 145
■ CHEMICAL IMPACT Reading the History of Bogs 51
4.7 Stoichiometry of Precipitation Reactions 147
2.6 Molecules and Ions 52
4.8 Acid–Base Reactions 149
2.7 An Introduction to the Periodic Table 55
4.9 Oxidation–Reduction Reactions 154
■ CHEMICAL IMPACT Hassium Fits Right in 57
■ CHEMICAL IMPACT Iron Zeroes in on
2.8 Naming Simple Compounds 57
Pollution 156
For Review 67 • Key Terms 67 • Question and
■ CHEMICAL IMPACT Pearly Whites 159
Exercises 69
■ CHEMICAL IMPACT Aging: Does It Involve
3 Stoichiometry 76 Oxidation? 160
4.10 Balancing Oxidation–Reduction
3.1 Counting by Weighing 77 Equations 162
3.2 Atomic Masses 78
For Review 168 • Key Terms 168 • Questions and
■ CHEMICAL IMPACT Buckyballs Teach Some History 80 Exercises 170
iii
7 Atomic Structure and Periodicity 274
7.1 Electromagnetic Radiation 275
■ CHEMICAL IMPACT Flies That Dye 277
7.2 The Nature of Matter 277
■ CHEMICAL IMPACT Chemistry That Doesn’t Leave You in
the Dark 280
■ CHEMICAL IMPACT Thin Is In 282
7.3 The Atomic Spectrum of Hydrogen 284
7.4 The Bohr Model 285
■ CHEMICAL IMPACT Fireworks 288
7.5 The Quantum Mechanical Model of the Atom 290
7.6 Quantum Numbers 293
7.7 Orbital Shapes and Energies 295
7.8 Electron Spin and the Pauli Principle 296
7.9 Polyelectronic Atoms 298
7.10 The History of the Periodic Table 299
5 Gases 178
■ CHEMICAL IMPACT The Growing Periodic Table 302
5.1 Pressure 179 7.11 The Aufbau Principle and the Periodic Table 302
5.2 The Gas Laws of Boyle, Charles, and Avogadro 181 7.12 Periodic Trends in Atomic Properties 309
5.3 The Ideal Gas Law 186 7.13 The Properties of a Group:The Alkali Metals 314
5.4 Gas Stoichiometry 190 ■ CHEMICAL IMPACT Potassium—Too Much of a Good
5.5 Dalton’s Law of Partial Pressures 194 Thing Can Kill You 317
■ CHEMICAL IMPACT Separating Gases 196 For Review 318 • Key Terms 318 • Questions and
Exercises 320
■ CHEMICAL IMPACT The Chemistry of Air Bags 197
5.6 The Kinetic Molecular Theory of Gases 199
5.7 Effusion and Diffusion 206
8 Bonding: General Concepts 328
5.8 Real Gases 208
5.9 Characteristics of Several Real Gases 210 8.1 Types of Chemical Bonds 330
5.10 Chemistry in the Atmosphere 211 ■ CHEMICAL IMPACT No Lead Pencils 332
■ CHEMICAL IMPACT Acid Rain: A Growing Problem 212 8.2 Electronegativity 333
For Review 215 • Key Terms 215 • Questions and 8.3 Bond Polarity and Dipole Moments 335
Exercises 217
8.4 Ions: Electron Configurations and Sizes 338
6 Thermochemistry 228 8.5 Energy Effects in Binary Ionic Compounds 342
8.6 Partial Ionic Character of Covalent Bonds 346
6.1 The Nature of Energy 229 8.7 The Covalent Chemical Bond:A Model 347
6.2 Enthalpy and Calorimetry 235 8.8 Covalent Bond Energies and Chemical Reactions 350
■ CHEMICAL IMPACT Nature Has Hot Plants 238 8.9 The Localized Electron Bonding Model 353
■ CHEMICAL IMPACT Firewalking: Magic or Science? 241 8.10 Lewis Structures 354
6.3 Hess’s Law 242 ■ CHEMICAL IMPACT Nitrogen Under Pressure 358
6.4 Standard Enthalpies of Formation 246 8.11 Exceptions to the Octet Rule 358
6.5 Present Sources of Energy 252 8.12 Resonance 362
6.6 New Energy Sources 256 8.13 Molecular Structure:The VSEPR Model 367
■ CHEMICAL IMPACT Farming the Wind 258 ■ CHEMICAL IMPACT Chemical Structure and
■ CHEMICAL IMPACT Veggie Gasoline? 262 Communication: Semiochemicals 378
For Review 264 • Key Terms 264 • Questions and For Review 380 • Key Terms 380 • Questions and
Exercises 265 Exercises 382
iv
9 Covalent Bonding: Orbitals 390
9.1 Hybridization and the Localized Electron Model 391
9.2 The Molecular Orbital Model 403
9.3 Bonding in Homonuclear Diatomic Molecules 406
9.4 Bonding in Heteronuclear Diatomic Molecules 412
9.5 Combining the Localized Electron and Molecular
Orbital Models 413
■ CHEMICAL IMPACT What’s Hot? 414
For Review 416 • Key Terms 416 • Questions and
Exercises 417
10 Liquids and Solids 424
10.1 Intermolecular Forces 426
10.2 The Liquid State 429
10.3 An Introduction to Structures and Types of
Solids 430
■ CHEMICAL IMPACT Smart Fluids 434
10.4 Structure and Bonding in Metals 436
■ CHEMICAL IMPACT Seething Surfaces 438
11.7 Colligative Properties of Electrolyte Solutions 512
■ CHEMICAL IMPACT Closest Packing of M & Ms 441
■ CHEMICAL IMPACT The Drink of Champions—
■ CHEMICAL IMPACT What Sank the Titanic? 443 Water 514
10.5 Carbon and Silicon: Network Atomic Solids 444 11.8 Colloids 514
■ CHEMICAL IMPACT Golfing with Glass 449 ■ CHEMICAL IMPACT Organisms and Ice Formation 516
■ CHEMICAL IMPACT Transistors and Printed For Review 516 • Key Terms 516 • Questions and
Circuits 452 Exercises 518
10.6 Molecular Solids 454
■ CHEMICAL IMPACT Explosive Sniffer 455 12 Chemical Kinetics 526
10.7 Ionic Solids 456
12.1 Reaction Rates 527
10.8 Vapor Pressure and Changes of State 459
12.2 Rate Laws:An Introduction 532
10.9 Phase Diagrams 467
12.3 Determining the Form of the Rate Law 534
■ CHEMICAL IMPACT Making Diamonds at Low Pressures:
12.4 The Integrated Rate Law 538
Fooling Mother Nature 470
12.5 Rate Laws:A Summary 548
For Review 472 • Key Terms 472 • Questions and
Exercises 474 12.6 Reaction Mechanisms 549
12.7 A Model for Chemical Kinetics 552
11 Properties of Solutions 484
12.8 Catalysis 557
11.1 Solution Composition 485 ■ CHEMICAL IMPACT Automobiles: Air Purifiers? 560
■ CHEMICAL IMPACT Electronic Ink 488 ■ CHEMICAL IMPACT Enzymes: Nature’s Catalysts 562
11.2 The Energies of Solution Formation 488 For Review 564 • Key Terms 564 • Questions and
Exercises 566
11.3 Factors Affecting Solubility 492
■ CHEMICAL IMPACT Ionic Liquids? 494 13 Chemical Equilibrium 578
■ CHEMICAL IMPACT The Lake Nyos Tragedy 497
11.4 The Vapor Pressures of Solutions 497 13.1 The Equilibrium Condition 579
■ CHEMICAL IMPACT Spray Power 500 13.2 The Equilibrium Constant 582
11.5 Boiling-Point Elevation and Freezing-Point 13.3 Equilibrium Expressions Involving Pressures 586
Depression 504 13.4 Heterogeneous Equilibria 588
11.6 Osmotic Pressure 508 13.5 Applications of the Equilibrium Constant 591
v
15 Applications of Aqueous
Equilibria 680
Acid–Base Equilibria 681
15.1 Solutions of Acids or Bases Containing
a Common Ion 681
15.2 Buffered Solutions 684
15.3 Buffering Capacity 693
15.4 Titrations and pH Curves 696
15.5 Acid–Base Indicators 711
Solubility Equilibria 717
15.6 Solubility Equilibria and the Solubility
Product 771
■ CHEMICAL IMPACT The Chemistry of Teeth 720
15.7 Precipitation and Qualitative Analysis 724
Complex Ion Equilibria 731
15.8 Equilibria Involving Complex Ions 731
For Review 736 • Key Terms 736 • Questions and
Exercises 739
13.6 Solving Equilibrium Problems 600
16 Spontaneity, Entropy, and Free
13.7 Le Châtelier’s Principle 604
Energy 748
For Review 610 • Key Terms 610 • Questions and
Exercises 613
16.1 Spontaneous Processes and Entropy 749
14 Acids and Bases 622 16.2 Entropy and the Second Law of
Thermodynamics 755
14.1 The Nature of Acids and Bases 623
■ CHEMICAL IMPACT Entropy: An Organizing Force? 756
14.2 Acid Strength 626
16.3 The Effect of Temperature on Spontaneity 756
14.3 The pH Scale 631
16.4 Free Energy 759
■ CHEMICAL IMPACT Arnold Beckman, Man of
16.5 Entropy Changes in Chemical Reactions 762
Science 632
16.6 Free Energy and Chemical Reactions 766
14.4 Calculating the pH of Strong Acid
16.7 The Dependence of Free Energy on Pressure 770
Solutions 634
16.8 Free Energy and Equilibrium 774
14.5 Calculating the pH of Weak Acid
Solutions 635 16.9 Free Energy and Work 778
■ CHEMICAL IMPACT Household Chemistry 643 For Review 780 • Key Terms 780 • Questions and
Exercises 782
14.6 Bases 644
■ CHEMICAL IMPACT Amines 648 17 Electrochemistry 790
14.7 Polyprotic Acids 650
14.8 Acid–Base Properties of Salts 655 17.1 Galvanic Cells 791
14.9 The Effect of Structure on Acid–Base 17.2 Standard Reduction Potentials 794
Properties 661 17.3 Cell Potential, Electrical Work, and
14.10 Acid–Base Properties of Oxides 662 Free Energy 800
14.11 The Lewis Acid–Base Model 663 17.4 Dependence of Cell Potential on Concentration 803
■ CHEMICAL IMPACT Self-Destructing Paper 666 17.5 Batteries 808
14.12 Strategy for Solving Acid–Base Problems: ■ CHEMICAL IMPACT Printed Batteries 809
A Summary 666 ■ CHEMICAL IMPACT Thermophotovoltaics: Electricity
For Review 668 • Key Terms 668 • Questions and from Heat 810
Exercises 672 ■ CHEMICAL IMPACT Fuel Cells for Cars 812
vi
17.6 Corrosion 813
■ CHEMICAL IMPACT Paint that Stops Rust—
Completely 814
17.7 Electrolysis 816
■ CHEMICAL IMPACT The Chemistry of Sunken
Treasure 820
17.8 Commercial Electrolytic Processes 821
For Review 826 • Key Terms 826 • Questions and
Exercises 829
18 The Nucleus: A Chemist’s View 840
18.1 Nuclear Stability and Radioactive Decay 841
18.2 The Kinetics of Radioactive Decay 846
18.3 Nuclear Transformations 849
■ CHEMICAL IMPACT Stellar Nucleosynthesis 850
18.4 Detection and Uses of Radioactivity 852
18.5 Thermodynamic Stability of the Nucleus 856
18.6 Nuclear Fission and Nuclear Fusion 859
18.7 Effects of Radiation 863
■ CHEMICAL IMPACT Nuclear Physics:
An Introduction 864
For Review 867 • Key Terms 867 • Questions and
Exercises 869
19 The Representative Elements: Groups
20.4 The Group 6A Elements 918
1A Through 4A 874
20.5 The Chemistry of Oxygen 919
20.6 The Chemistry of Sulfur 920
19.1 A Survey of the Representative Elements 875
20.7 The Group 7A Elements 924
19.2 The Group 1A Elements 880
19.3 Hydrogen 883 ■ CHEMICAL IMPACT Photography 926
20.8 The Group 8A Elements 931
19.4 The Group 2A Elements 885
19.5 The Group 3A Elements 888 ■ CHEMICAL IMPACT Automatic Sunglasses 931
■ CHEMICAL IMPACT Boost Your Boron 889 For Review 933 • Key Terms 933 • Questions and
Exercises 936
19.6 The Group 4A Elements 890
■ CHEMICAL IMPACT Concrete Learning 892
21 Transition Metals and Coordination
■ CHEMICAL IMPACT Beethoven: Hair Is the Story 893
Chemistry 942
For Review 894 • Key Terms 894 • Questions and
Exercises 895
21.1 The Transition Metals:A Survey 943
20 The Representative Elements: Groups 21.2 The First-Row Transition Metals 949
5A Through 8A 900 ■ CHEMICAL IMPACT Titanium Dioxide—Miracle
Coating 951
20.1 The Group 5A Elements 901 ■ CHEMICAL IMPACT Titanium Makes Great
20.2 The Chemistry of Nitrogen 903 Bicycles 952
■ CHEMICAL IMPACT Nitrous Oxide: Laughing Gas That 21.3 Coordination Compounds 955
Propels Whipped Cream and Cars 912 ■ CHEMICAL IMPACT Alfred Werner: Coordination
20.3 The Chemistry of Phosphorus 913 Chemist 960
■ CHEMICAL IMPACT Phosphorus: An Illuminating 21.4 Isomerism 960
Element 914 ■ CHEMICAL IMPACT The Importance of Being cis 963
vii
22.5 Polymers 1016
■ CHEMICAL IMPACT Heal Thyself 1018
■ CHEMICAL IMPACT Wallace Hume Carothers 1022
■ CHEMICAL IMPACT Plastic That Talks and Listens 1024
22.6 Natural Polymers 1025
■ CHEMICAL IMPACT Tanning in the Shade 1032
For Review 1040 • Key Terms 1040 • Questions and
Exercises 1044
Appendix 1 Mathematical Procedures A1
A1.1 Exponential Notation A1
A1.2 Logarithms A4
A1.3 Graphing Functions A6
A1.4 Solving Quadratic Equations A7
A1.5 Uncertainties in Measurements A10
Appendix 2 The Quantitative Kinetic Molecular
Model A13
Appendix 3 Spectral Analysis A16
21.5 Bonding in Complex Ions:The Localized Electron
Appendix 4 Selected Thermodynamic Data A19
Model 965
Appendix 5 Equilibrium Constants and Reduction
21.6 The Crystal Field Model 967
Potentials A22
■ CHEMICAL IMPACT Transition Metal Ions Lend Color
to Gems 970 A5.1 Values of K for Some Common Monoprotic
a
21.7 The Biologic Importance of Coordination Acids A22
Complexes 973 A5.2 Stepwise Dissociation Constants for Several Common
■ CHEMICAL IMPACT The Danger of Mercury 975 Polyprotic Acids A23
■ CHEMICAL IMPACT Supercharged Blood 978 A5.3 Values of K for Some Common Weak Bases A23
b
21.8 Metallurgy and Iron and Steel Production 978 A5.4 K Values at 25(cid:1)C for Common Ionic Solids A24
sp
For Review 987 • Key Terms 987 • Questions and A5.5 Standard Reduction Potentials at 25(cid:1)C (298K) for
Exercises 989 Many Common Half-Reactions A25
22 Organic and Biological Molecules 996 Appendix 6 SI Units and Conversion Factors A26
Glossary A27
22.1 Alkanes: Saturated Hydrocarbons 997
Photo Credits A39
22.2 Alkenes and Alkynes 1005
22.3 Aromatic Hydrocarbons 1008 Answers to Selected Exercises A41
22.4 Hydrocarbon Derivatives 1010 Index A70
viii
To the Professor
W
ith this edition of Chemistry, students and instructors doing.”The art program along with animations emphasize
alike will experience a truly integrated learning program. The this goal. Also, we have placed a larger emphasis on the
textbook’s strong emphasis on conceptual learning and prob- qualitative understanding of concepts before quantitative
lem solving is extended through the numerous online media as- problems are considered. Because using an algorithm to
signments and activities. It was our mission to create a media correctly solve a problem often masks misunderstanding—
program that embodies the spirit of the textbook so that,when students assume they understand the material because they
instructors and students look online for either study aids or on- got the right “answer”—it is important to probe their
line homework, that each resource supports the goals of the understanding in other ways. In this vein the text includes
textbook—a strong emphasis on models, real-world applica- a number of Active Learning Questions (previously called
tions, and visual learning. In-Class Discussion Questions) at the end of each chapter
We have gone over every page in the sixth edition thor- that are intended for group discussion. It is our experience
oughly, fine-tuning in some cases and rewriting in others. In that students often learn the most when they teach each
doing so,we have incorporated numerous constructive sugges- other. Students are forced to recognize their own lack of
tions from instructors who used the previous edition. Based on conceptual understanding when they try and fail to explain
this feedback new content has been added, such as the treat- a concept to a colleague.
ment of real gases in Chapter 5, which has been expanded to ● With a strong problem-solving orientation,this text talks to
include a discussion of specific gases,and also coverage of pho- the student about how to approach and solve chemical prob-
toelectric effect has been added to Chapter 7. In addition, the lems. We have made a strong pitch to students for using a
Sample Exercises in Chapter 2 have been revised to cover the thoughtful and logical approach rather than simply memo-
naming of compounds given the formula and the opposite rizing procedures. In particular, an innovative method is
process of writing the formula from the name. To help students given for dealing with acid–base equilibria,the material the
review key concepts, the For Review section of each chapter typical student finds most difficult and frustrating. The key
has been reorganized to provide an easy-to-read bulleted sum- to this approach involves first deciding what species are pre-
mary; this section includes new review questions. The art pro- sent in solution,then thinking about the chemical properties
gram has been enhanced to include electrostatic potential maps of these species. This method provides a general framework
to show a more accurate distribution of charge in molecules. for approaching all types of solution equilibria.
In the media program instructors will find a variety of re- ● The text contains almost 300 sample exercises, with many
sources to assign additional practice, study, and quiz mater- more examples given in the discussions leading to sample
ial.ChemWork interactive assignments,end-of-chapter online exercises or used to illustrate general strategies. When a spe-
homework, HM Testing, and classroom response system ap- cific strategy is presented,it is summarized,and the sample
plications allow you to assess students in multiple ways. The exercise that follows it reinforces the step-by-step attack on
Online Study Center promotes self-study with animations, the problem. In general,in approaching problem solving we
video demonstrations, and practice exercises. emphasize understanding rather than an algorithm-based
approach.
● We have presented a thorough treatment of reactions that
Important Features of Chemistry
occur in solution,including acid–base reactions. This mate-
● Chemistry contains numerous discussions, illustrations, rial appears in Chapter 4,directly after the chapter on chem-
and exercises aimed at overcoming common misconcep- ical stoichiometry, to emphasize the connection between
tions.It has become increasingly clear from our own teach- solution reactions and chemical reactions in general. The
ing experience that students often struggle with chemistry early presentation of this material provides an opportunity
because they misunderstand many of the fundamental con- to cover some interesting descriptive chemistry and also sup-
cepts. In this text, we have gone to great lengths to pro- ports the lab,which typically involves a great deal of aque-
vide illustrations and explanations aimed at giving students ous chemistry. Chapter 4 also includes oxidation–reduction
more accurate pictures of the fundamental ideas of chem- reactions,because a large number of interesting and impor-
istry. In particular, we have attempted to represent the tant chemical reactions involve redox processes. However,
microscopic world of chemistry so that students have a pic- coverage of oxidation–reduction is optional at this point and
ture in their minds of “what the atoms and molecules are depends on the needs of a specific course.
ix