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 Periodic Table of the Elements
Noble
Alkaline gases
1 earth metals Halogens 18
1A 8A
metals nonmetals
1
H 2 13 14 15 16 17 He
1.008 2A 3A 4A 5A 6A 7A 4.003

3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Na Mg Transition metals Al Si P S Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Alkali metals

39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.59 74.92 78.96 79.90 83.80

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac† Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
(223) 226 (227) (261) (262) (263) (264) (265) (268) (271) (272) (285) (289) (293)

58 59 60 61 62 63 64 65 66 67 68 69 70 71

*Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
†
Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 (231) 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)

Group numbers 1–18 represent the system recommended by the International Union
of Pure and Applied Chemistry.
 Table of Atomic Masses*
Atomic Atomic Atomic Atomic Atomic Atomic
Element Symbol Number Mass Element Symbol Number Mass Element Symbol Number Mass
Actinium Ac 89 [227]§ Germanium Ge 32 72.59 Potassium K 19 39.10
Aluminum Al 13 26.98 Gold Au 79 197.0 Praseodymium Pr 59 140.9
Americium Am 95 [243] Hafnium Hf 72 178.5 Promethium Pm 61 [145]
Antimony Sb 51 121.8 Hassium Hs 108 [265] Protactinium Pa 91 [231]
Argon Ar 18 39.95 Helium He 2 4.003 Radium Ra 88 226
Arsenic As 33 74.92 Holmium Ho 67 164.9 Radon Rn 86 [222]
Astatine At 85 [210] Hydrogen H 1 1.008 Rhenium Re 75 186.2
Barium Ba 56 137.3 Indium In 49 114.8 Rhodium Rh 45 102.9
Berkelium Bk 97 [247] Iodine I 53 126.9 Roentgenium Rg 111 [272]
Beryllium Be 4 9.012 Iridium Ir 77 192.2 Rubidium Rb 37 85.47
Bismuth Bi 83 209.0 Iron Fe 26 55.85 Ruthenium Ru 44 101.1
Bohrium Bh 107 [264] Krypton Kr 36 83.80 Rutherfordium Rf 104 [261]
Boron B 5 10.81 Lanthanum La 57 138.9 Samarium Sm 62 150.4
Bromine Br 35 79.90 Lawrencium Lr 103 [260] Scandium Sc 21 44.96
Cadmium Cd 48 112.4 Lead Pb 82 207.2 Seaborgium Sg 106 [263]
Calcium Ca 20 40.08 Livermorium Lv 116 [293] Selenium Se 34 78.96
Californium Cf 98 [251] Lithium Li 3 6.9419 Silicon Si 14 28.09
Carbon C 6 12.01 Lutetium Lu 71 175.0 Silver Ag 47 107.9
Cerium Ce 58 140.1 Magnesium Mg 12 24.31 Sodium Na 11 22.99
Cesium Cs 55 132.90 Manganese Mn 25 54.94 Strontium Sr 38 87.62
Chlorine Cl 17 35.45 Meitnerium Mt 109 [268] Sulfur S 16 32.07
Chromium Cr 24 52.00 Mendelevium Md 101 [258] Tantalum Ta 73 180.9
Cobalt Co 27 58.93 Mercury Hg 80 200.6 Technetium Tc 43 [98]
Copernicium CN 112 [285] Molybdenum Mo 42 95.94 Tellurium Te 52 127.6
Copper Cu 29 63.55 Neodymium Nd 60 144.2 Terbium Tb 65 158.9
Curium Cm 96 [247] Neon Ne 10 20.18 Thallium Tl 81 204.4
Darmstadtium Ds 110 [271] Neptunium Np 93 [237] Thorium Th 90 232.0
Dubnium Db 105 [262] Nickel Ni 28 58.69 Thulium Tm 69 168.9
Dysprosium Dy 66 162.5 Niobium Nb 41 92.91 Tin Sn 50 118.7
Einsteinium Es 99 [252] Nitrogen N 7 14.01 Titanium Ti 22 47.88
Erbium Er 68 167.3 Nobelium No 102 [259] Tungsten W 74 183.9
Europium Eu 63 152.0 Osmium Os 76 190.2 Uranium U 92 238.0
Fermium Fm 100 [257] Oxygen O 8 16.00 Vanadium V 23 50.94
Flerovium Fl 114 [289] Palladium Pd 46 106.4 Xenon Xe 54 131.3
Fluorine F 9 19.00 Phosphorus P 15 30.97 Ytterbium Yb 70 173.0
Francium Fr 87 [223] Platinum Pt 78 195.1 Yttrium Y 39 88.91
Gadolinium Gd 64 157.3 Plutonium Pu 94 [244] Zinc Zn 30 65.38
Gallium Ga 31 69.72 Polonium Po 84 [209] Zirconium Zr 40 91.22

§
*The values given here are to four significant figures where possible. A value given in parentheses denotes the mass of the longest-lived isotope.
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Chemistry

Photo by Dr. Eric Heller

Ninth Edition

StevenS.Zumdahl
University of Illinois

SusanA.Zumdahl
University of Illinois

Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States
 Chemistry, Ninth Edition
Steven S. Zumdahl and Susan A. Zumdahl
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 Contents

TotheProfessor ix Chapter 3 Stoichiometry 81

TotheStudent xiii  3.1 Counting by Weighing 82
 3.2 Atomic Masses 83
Chapter 1 Chemical Foundations 1  3.3 The Mole 85
 1.1 Chemistry: An Overview 3  3.4 Molar Mass 90
 1.2 The Scientific Method 5  3.5 Learning to Solve Problems 93
CHEMICAL CONNECTIONS A Note-able Achievement 7  3.6 Percent Composition of Compounds 94
 1.3 Units of Measurement 8  3.7 Determining the Formula of a Compound 96
CHEMICAL CONNECTIONS Critical Units! 9  3.8 Chemical Equations 103
 1.4 Uncertainty in Measurement 11  3.9 Balancing Chemical Equations 105
 1.5 Significant Figures and Calculations 14  3.10 Stoichiometric Calculations: Amounts of Reactants
 1.6 Learning to Solve Problems Systematically 18 and Products 108
 1.7 Dimensional Analysis 18 CHEMICAL CONNECTIONS High Mountains—Low
Octane 109
 1.8 Temperature 22
 3.11 The Concept of Limiting Reactant 114
 1.9 Density 26
ForReview 124 ∣ KeyTerms 124 ∣ Questionsand
 1.10 Classification of Matter 27 Exercises 126
ForReview 31 ∣ KeyTerms 31 ∣ QuestionsandExercises 33

Chapter 2 Atoms, Molecules, and Ions 42

 2.1 The Early History of Chemistry 43

 2.2 Fundamental Chemical Laws 44
 2.3 Dalton’s Atomic Theory 47
CHEMICAL CONNECTIONS Berzelius, Selenium, and
Silicon 48
 2.4 Early Experiments to Characterize the Atom 50
 2.5 The Modern View of Atomic Structure:
An Introduction 54
 2.6 Molecules and Ions 55
 2.7 An Introduction to the Periodic Table 57 Daff/Dreamstime.com

CHEMICAL CONNECTIONS Hassium Fits Right In 60

 2.8 Naming Simple Compounds 60
ForReview 71 ∣ KeyTerms 71 ∣ QuestionsandExercises 72

Unless otherwise noted, all art on this page is © Cengage Learning 2014.  iii
iv Contents

Chapter 4 Types of Chemical Reactions

and Solution Stoichiometry 138

 4.1 Water, the Common Solvent 139

 4.2 The Nature of Aqueous Solutions: Strong and Weak
Electrolytes 141
CHEMICAL CONNECTIONS Arrhenius: A Man with
Solutions 144

© Caren Brinkema/Science Faction/Corbis

 4.3 The Composition of Solutions 145
CHEMICAL CONNECTIONS Tiny Laboratories 152
 4.4 Types of Chemical Reactions 153
 4.5 Precipitation Reactions 153
 4.6 Describing Reactions in Solution 158
 4.7 Stoichiometry of Precipitation Reactions 160
 4.8 Acid–Base Reactions 163
 4.9 Oxidation–Reduction Reactions 170
 4.10 Balancing Oxidation–Reduction Equations 175
 6.6 New Energy Sources 275
ForReview 177 ∣ KeyTerms 177 ∣ Questionsand
CHEMICAL CONNECTIONS Farming the Wind 277
Exercises 179
CHEMICAL CONNECTIONS Veggie Gasoline? 282
ForReview 283 ∣ KeyTerms 283 ∣ Questionsand
Chapter 5 Gases 189
Exercises 285
 5.1 Pressure 190
 5.2 The Gas Laws of Boyle, Charles, and Chapter 7 Atomic Structure
Avogadro 192
and Periodicity 295
 5.3 The Ideal Gas Law 198
 7.1 Electromagnetic Radiation 296
 5.4 Gas Stoichiometry 203
 7.2 The Nature of Matter 298
 5.5 Dalton’s Law of Partial Pressures 208
CHEMICAL CONNECTIONS Fireworks 300
CHEMICAL CONNECTIONS Separating Gases 210
 7.3 The Atomic Spectrum of Hydrogen 305
CHEMICAL CONNECTIONS The Chemistry of Air
Bags 211  7.4 The Bohr Model 306
 5.6 The Kinetic Molecular Theory of Gases 214 CHEMICAL CONNECTIONS 0.035 Femtometer Is a Big
Deal 309
 5.7 Effusion and Diffusion 222
 7.5 The Quantum Mechanical Model of the Atom 310
 5.8 Real Gases 224
 7.6 Quantum Numbers 313
 5.9 Characteristics of Several Real Gases 226
 7.7 Orbital Shapes and Energies 314
 5.10 Chemistry in the Atmosphere 227
 7.8 Electron Spin and the Pauli Principle 318
ForReview 230 ∣ KeyTerms 230 ∣ Questionsand
Exercises 232  7.9 Polyelectronic Atoms 318
 7.10 The History of the Periodic Table 320
Chapter 6 Thermochemistry 245  7.11 The Aufbau Principle and the Periodic Table 322
CHEMICAL CONNECTIONS The Chemistry of
 6.1 The Nature of Energy 246 Copernicium 323
 6.2 Enthalpy and Calorimetry 252  7.12 Periodic Trends in Atomic Properties 329
CHEMICAL CONNECTIONS Nature Has Hot
Plants 256
 7.13 The Properties of a Group: The Alkali Metals 335
CHEMICAL CONNECTIONS Potassium—Too Much of a
 6.3 Hess’s Law 260 Good Thing Can Kill You 337
 6.4 Standard Enthalpies of Formation 264 ForReview 339 ∣ KeyTerms 339 ∣ Questionsand
 6.5 Present Sources of Energy 271 Exercises 341

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 Contents v

Chapter 8 Bonding: General Concepts 351

 8.1 Types of Chemical Bonds 352

CHEMICAL CONNECTIONS No Lead Pencils 354

Carsten Peter/Speleoresearch Films/National Geographic Stock

 8.2Electronegativity 356
 8.3Bond Polarity and Dipole Moments 358
 8.4Ions: Electron Configurations and Sizes 361
 8.5Energy Effects in Binary Ionic Compounds 365
 8.6Partial Ionic Character of Covalent Bonds 369
 8.7The Covalent Chemical Bond: A Model 370
 8.8Covalent Bond Energies and Chemical
Reactions 373
 8.9 The Localized Electron Bonding Model 376
 8.10 Lewis Structures 376
 8.11 Exceptions to the Octet Rule 380
CHEMICAL CONNECTIONS Nitrogen Under Pressure 381
 8.12 Resonance 384 10.5 Carbon and Silicon: Network Atomic Solids 471
CHEMICAL CONNECTIONS Graphene—Miracle
 8.13 Molecular Structure: The VSEPR Model 389
Substance? 472
CHEMICAL CONNECTIONS Chemical Structure and
Communication: Semiochemicals 398
10.6 Molecular Solids 479
ForReview 402 ∣ KeyTerms 402 ∣ Questionsand 10.7 Ionic Solids 480
Exercises 404 10.8 Vapor Pressure and Changes of State 483
10.9 Phase Diagrams 491
Chapter 9 Covalent Bonding: Orbitals 415 CHEMICAL CONNECTIONS Making Diamonds at Low
Pressures: Fooling Mother Nature 494
 9.1 Hybridization and the Localized Electron
ForReview 496 ∣ KeyTerms 496 ∣ Questionsand
Model 416
Exercises 498
 9.2 The Molecular Orbital Model 428
 9.3 Bonding in Homonuclear Diatomic Molecules 431
Chapter 11 Properties of Solutions 510
 9.4 Bonding in Heteronuclear Diatomic
Molecules 438 11.1 Solution Composition 511
 9.5 Combining the Localized Electron and Molecular 11.2 The Energies of Solution Formation 514
Orbital Models 439 11.3 Factors Affecting Solubility 517
CHEMICAL CONNECTIONS What’s Hot? 440 11.4 The Vapor Pressures of Solutions 521
 9.6 Photoelectron Spectroscopy (PES) 441 CHEMICAL CONNECTIONS The Lake Nyos
ForReview 443 ∣ KeyTerms 443 ∣ Questionsand Tragedy 522
Exercises 444 11.5 Boiling-Point Elevation and Freezing-Point
Depression 527
Chapter 10 Liquids and Solids 453 11.6 Osmotic Pressure 531
11.7 Colligative Properties of Electrolyte Solutions 535
10.1 Intermolecular Forces 455
CHEMICAL CONNECTIONS The Drink of Champions—
10.2 The Liquid State 458 Water 537
10.3 An Introduction to Structures and Types of 11.8 Colloids 538
Solids 459
CHEMICAL CONNECTIONS Organisms and Ice
CHEMICAL CONNECTIONS Smart Fluids 463 Formation 539
10.4 Structure and Bonding in Metals 465 ForReview 540 ∣ KeyTerms 540 ∣ Questionsand
CHEMICAL CONNECTIONS Closest Packing of M & Ms 469 Exercises 542

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vi Contents

13.7 Le Châtelier’s Principle 633

ForReview 640 ∣ KeyTerms 640 ∣ Questionsand
Exercises 642

Chapter 14 Acids and Bases 652

14.1 The Nature of Acids and Bases 653

14.2 Acid Strength 656
14.3 The pH Scale 661
CHEMICAL CONNECTIONS Arnold Beckman, Man of
Science 663
14.4 Calculating the pH of Strong Acid Solutions 665
14.5 Calculating the pH of Weak Acid Solutions 666
14.6 Bases 675
CHEMICAL CONNECTIONS Amines 679

National Cancer Institute/Photo Researchers, Inc.

14.7 Polyprotic Acids 681
14.8 Acid–Base Properties of Salts 686
14.9 The Effect of Structure on Acid–Base
Properties 691
14.10 Acid–Base Properties of Oxides 693
14.11 The Lewis Acid–Base Model 694
14.12 Strategy for Solving Acid–Base Problems:
A Summary 696
ForReview 697 ∣ KeyTerms 697 ∣ Questionsand
Exercises 701

Chapter 12 Chemical Kinetics 552

Chapter 15 Acid–Base Equilibria 711
12.1 Reaction Rates 553
12.2 Rate Laws: An Introduction 557 15.1 Solutions of Acids or Bases Containing a
Common Ion 712
12.3 Determining the Form of the Rate Law 559
15.2 Buffered Solutions 715
12.4 The Integrated Rate Law 563
15.3 Buffering Capacity 724
12.5 Reaction Mechanisms 574
15.4 Titrations and pH Curves 727
12.6 A Model for Chemical Kinetics 577
15.5 Acid–Base Indicators 742
12.7 Catalysis 583
ForReview 748 ∣ KeyTerms 748 ∣ Questionsand
CHEMICAL CONNECTIONS Enzymes: Nature’s
Exercises 749
Catalysts 586
ForReview 590 ∣ KeyTerms 590 ∣ Questionsand
Exercises 592 Chapter 16 Solubility and Complex Ion
Equilibria 758
Chapter 13 Chemical Equilibrium 606 16.1 Solubility Equilibria and the Solubility
13.1 The Equilibrium Condition 607 Product 759
CHEMICAL CONNECTIONS The Chemistry of
13.2 The Equilibrium Constant 610
Teeth 763
13.3 Equilibrium Expressions Involving Pressures 614
16.2 Precipitation and Qualitative Analysis 768
13.4 Heterogeneous Equilibria 617
16.3 Equilibria Involving Complex Ions 774
13.5 Applications of the Equilibrium Constant 618 ForReview 779 ∣ KeyTerms 779 ∣ Questionsand
13.6 Solving Equilibrium Problems 628 Exercises 780

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 Contents vii

Chapter 17 Spontaneity, Entropy, 18.8 Electrolysis 864

and Free Energy 787 CHEMICAL CONNECTIONS The Chemistry of Sunken
Treasure 868
17.1 Spontaneous Processes and Entropy 788
18.9 Commercial Electrolytic Processes 868
CHEMICAL CONNECTIONS Entropy: An Organizing
ForReview 874 ∣ KeyTerms 874 ∣ Questionsand
Force? 794
Exercises 877
17.2 Entropy and the Second Law of
Thermodynamics 794
Chapter 19 The Nucleus: A Chemist’s
17.3 The Effect of Temperature on Spontaneity 795
17.4 Free Energy 798
View 890

17.5 Entropy Changes in Chemical Reactions 801 19.1 Nuclear Stability and Radioactive Decay 891

17.6 Free Energy and Chemical Reactions 805 19.2 The Kinetics of Radioactive Decay 896
17.7 The Dependence of Free Energy on Pressure 810 19.3 Nuclear Transformations 899
CHEMICAL CONNECTIONS Element 117 901
17.8 Free Energy and Equilibrium 813
17.9 Free Energy and Work 817 19.4 Detection and Uses of Radioactivity 902
ForReview 820 ∣ KeyTerms 820 ∣ Questionsand 19.5 Thermodynamic Stability of the Nucleus 906
Exercises 822 19.6 Nuclear Fission and Nuclear Fusion 910
CHEMICAL CONNECTIONS Future Nuclear
Power 912
Chapter 18 Electrochemistry 832
19.7 Effects of Radiation 915
18.1 Balancing Oxidation–Reduction Equations 833
ForReview 917 ∣ KeyTerms 917 ∣ Questionsand
18.2 Galvanic Cells 839 Exercises 919
18.3 Standard Reduction Potentials 842
18.4 Cell Potential, Electrical Work, and Free Chapter 20 The Representative
Energy 849
Elements 926
18.5 Dependence of Cell Potential on
Concentration 852 20.1 A Survey of the Representative Elements 927

18.6 Batteries 858 20.2 The Group 1A Elements 932

CHEMICAL CONNECTIONS Fuel Cells—Portable 20.3 The Chemistry of Hydrogen 933
Energy 861 20.4 The Group 2A Elements 935
18.7 Corrosion 861 20.5 The Group 3A Elements 937
20.6 The Group 4A Elements 939
CHEMICAL CONNECTIONS Beethoven: Hair Is the
Story 940
20.7 The Group 5A Elements 941
20.8 The Chemistry of Nitrogen 942
CHEMICAL CONNECTIONS Nitrous Oxide: Laughing Gas
That Propels Whipped Cream and Cars 948
20.9 The Chemistry of Phosphorus 949
20.10 The Group 6A Elements 952
20.11 The Chemistry of Oxygen 952
20.12 The Chemistry of Sulfur 954
20.13 The Group 7A Elements 956
20.14 The Group 8A Elements 960
NASA/SDO/AIA

ForReview 961 ∣ KeyTerms 961 ∣ Questionsand

Exercises 964

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viii Contents

Chapter 21 Transition Metals 22.4 Hydrocarbon Derivatives 1037

and Coordination Chemistry 972 22.5 Polymers 1044
CHEMICAL CONNECTIONS Wallace Hume
21.1 The Transition Metals: A Survey 973
Carothers 1045
21.2 The First-Row Transition Metals 978 CHEMICAL CONNECTIONS Super-Slippery Slope 1046
CHEMICAL CONNECTIONS Titanium Dioxide—Miracle
22.6 Natural Polymers 1052
Coating 980
CHEMICAL CONNECTIONS Tanning in the
21.3 Coordination Compounds 983
Shade 1059
21.4 Isomerism 987 ForReview 1067 ∣ KeyTerms 1067 ∣ Questionsand
CHEMICAL CONNECTIONS The Importance of Exercises 1070
Being cis 990
21.5 Bonding in Complex Ions: The Localized Electron Appendix 1 Mathematical Procedures A1
Model 992 A1.1 Exponential Notation A1
21.6 The Crystal Field Model 994 A1.2 Logarithms A4
CHEMICAL CONNECTIONS Transition Metal Ions Lend
A1.3 Graphing Functions A6
Color to Gems 997
A1.4 Solving Quadratic Equations A7
21.7 The Biological Importance of Coordination
Complexes 1000 A1.5 Uncertainties in Measurements A10
21.8 Metallurgy and Iron and Steel Production 1004
Appendix 2 The Quantitative Kinetic
ForReview 1012 ∣ KeyTerms 1012 ∣ Questionsand
Exercises 1015 Molecular Model A13

Appendix 3 Spectral Analysis A16

Chapter 22 Organic and Biological
Molecules 1023 Appendix 4 Selected Thermodynamic
22.1 Alkanes: Saturated Hydrocarbons 1024 Data A19

22.2 Alkenes and Alkynes 1032

Appendix 5 Equilibrium Constants and
22.3 Aromatic Hydrocarbons 1035
Reduction Potentials A22

A5.1 Values of Ka for Some Common Monoprotic

Acids A22
A5.2 Stepwise Dissociation Constants for Several
Common Polyprotic Acids A23
A5.3 Values of Kb for Some Common Weak Bases A23
A5.4 Ksp Values at 258C for Common Ionic Solids A24
A5.5 Standard Reduction Potentials at 258C (298 K) for
Many Common Half-Reactions A25

Appendix 6 SI Units and Conversion

Factors
Chip Clark/Smithsonian Institute

A26

Glossary A27

AnswerstoSelectedExercises A39

Index A71

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 To the Professor
Features of Chemistry,
Ninth Edition
Conceptual learning and problem solving are fundamental to
the approach of Chemistry. For the Ninth Edition, we have
extended this emphasis by beginning the problem-solving ap-
proach in Chapter 1 (rather than Chapter 3 as in the Eighth
Edition) to assist students as they learn to use dimensional
analysis for unit conversions. Our philosophy is to help stu-
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process of problem solving to all aspects of their lives. We
give students the tools to become critical thinkers: to ask ques-
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It was also our mission to create a media program that embod-
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What’s New
We have made extensive updates to the Ninth Edition to en-
hance the learning experience for students. Here’s what’s
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❯ A new emphasis has been placed on systematic problem
solving in the applications of dimensional analysis.
❯ Critical Thinking questions have been added throughout the
text to emphasize the importance of conceptual learning.
❯ Interactive Examples have been added throughout the text.
These computer-based examples force students to think
through the example step-by-step rather than simply scan
the written example in the text as many students do.
❯ ChemWork problems have been added to the end-of-
chapter problems throughout the text. These problems
test students’ understanding of core concepts from each
chapter. Students who solve a particular problem with no
assistance can proceed directly to the answer. However,
students who need help can get assistance through a se-
ries of online hints. The online procedure for assisting
students is modeled after the way a teacher would help
with homework problems in his or her office. The hints
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students through the problem-solving process. Students
cannot receive the correct answer from the computer;
rather, it encourages students to continue working though
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the hints to arrive at the answer. ChemWork problems
in the text can be worked using the online system or as
pencil-and-paper problems.
❯ New end-of-chapter questions and problems have been
added throughout the text.
❯ The art program has been modified and updated as needed,
and new macro/micro illustrations have been added.
❯ In Chapter 3 the treatment of stoichiometry has been en-
hanced by the addition of a new section on limiting reac-
tants, which emphasizes calculating the amounts of prod-
ucts that can be obtained from each reactant. Now students
are taught how to select a limiting reactant both by com-
paring the amounts of reactants present and by calculating
the amounts of products that can be formed by complete
consumption of each reactant.
❯ A section on photoelectron spectroscopy was added to
Chapter 9 (Section 9.6).
HallmarksofChemistry
❯ Chemistry contains numerous discussions, illustrations,
and exercises aimed at overcoming misconceptions. It has
become increasingly clear from our own teaching experi-
ence that students often struggle with chemistry because
they misunderstand many of the fundamental concepts. In
this text, we have gone to great lengths to provide illus-
trations and explanations aimed at giving students a more
accurate picture of the fundamental ideas of chemistry. In
particular, we have attempted to represent the microscopic
world of chemistry so that students have a picture in their
minds of “what the atoms and molecules are doing.” The
art program along with the animations emphasize this goal.
We have also placed a larger emphasis on the qualitative
understanding of concepts before quantitative problems are
considered. Because using an algorithm to correctly solve
a problem often masks misunderstanding—when students
assume they understand the material because they got the
right “answer”—it is important to probe their understand-
ing in other ways. In this vein, the text includes many Criti-
cal Thinking questions throughout the text and a number
of Active Learning Questions at the end of each chapter
that are intended for group discussion. It is our experience
that students often learn the most when they teach each
other. Students are forced to recognize their own lack of
understanding when they try and fail to explain a concept
to another student.
 ix
x TotheProfessor
❯ With a strong problem-solving orientation, this text talks
to students about how to approach and solve chemical
problems. We emphasize a thoughtful, logical approach
rather than simply memorizing procedures. In particular,
an innovative method is given for dealing with acid–base
equilibria, the material the typical student finds most diffi-
cult and frustrating. The key to this approach involves first
deciding what species are present in solution, then think-
ing about the chemical properties of these species. This
method provides a general framework for approaching all
types of solution equilibria.
❯ The text contains almost 300 Examples, with more given
in the text discussions, to illustrate general problem-
solving strategies. When a specific strategy is presented, it is
summarized in a Problem-Solving Strategy box, and the Ex-
ample that follows it reinforces the use of the strategy to solve
the problem. In general, we emphasize the use of conceptual
understanding to solve problems rather than an algorithm-
based approach. This approach is strongly reinforced by the
inclusion of many Interactive Examples, which encourage
students to thoughtfully consider the example step-by-step.
❯ We have presented a thorough treatment of reactions that
occur in solution, including acid–base reactions. This mate-
rial appears in Chapter 4, “Types of Chemical Reactions
and Solution Stoichiometry,” directly after the chapter on
chemical stoichiometry, to emphasize the connection be-
tween solution reactions and chemical reactions in general.
The early presentation of this material provides an oppor-
tunity to cover some interesting descriptive chemistry and
also supports the lab, which typically involves a great deal
of aqueous chemistry. Chapter 4 also includes oxidation–
reduction reactions and balancing by oxidation state, be-
cause a large number of interesting and important chemical
reactions involve redox processes. However, coverage of
oxidation–reduction is optional at this point and depends
on the needs of a specific course.
❯ Descriptive chemistry and chemical principles are thor-
oughly integrated in this text. Chemical models may ap-
pear sterile and confusing without the observations that
stimulated their invention. On the other hand, facts without
organizing principles may seem overwhelming. A com-
bination of observation and models can make chemistry
both interesting and understandable. In the chapter on the
chemistry of the elements, we have used tables and charts
to show how properties and models correlate. Descriptive
chemistry is presented in a variety of ways—as applica-
tions of principles in separate sections, in photographs, in
Examples and exercises, in paragraphs, and in Chemical
Connections.
❯ Throughout the book a strong emphasis on models prevails.
Coverage includes how they are constructed, how they are
tested, and what we learn when they inevitably fail. Mod-
els are developed naturally, with pertinent observation al-
ways presented first to show why a particular model was
invented.
❯ Chemical Connections boxes present applications of
chemistry in various fields and in our daily lives. Margin
notes in the Instructor’s Annotated Edition also highlight
many more Chemical Connections available on the student
website.
❯ We offer end-of-chapter exercises for every type of student
and for every kind of homework assignment: questions
that promote group learning, exercises that reinforce stu-
dent understanding, and problems that present the ultimate
challenge with increased rigor and by integrating multiple
concepts. We have added biochemistry problems to make
the connection for students in the course who are not chem-
istry majors.
❯ Judging from the favorable comments of instructors and
students who have used the eighth edition, the text seems to
work very well in a variety of courses. We were especially
pleased that readability was cited as a key strength when
students were asked to assess the text.
Supporting Materials
Please visit www.cengage.com
/chemistry/zumdahl/chemistry9e for
information about student and instruc-
tor resources for this text.
Acknowledgments
This book represents the efforts of many talented and dedi-
cated people. We particularly want to thank Mary Finch, Pub-
lisher, for her vision and oversight of the project, and Lisa
Lockwood, Executive Editor, whose enthusiasm, powers of
organization, and knowledge of the market have contributed
immensely to the success of this revision. We also greatly ap-
preciate the work of Teresa Trego, Content Project Manager,
who did an outstanding job of managing the production of
this complex project.
We especially appreciate the outstanding and untiring
work of Tom Martin, Developmental Editor. Tom is always
upbeat and has great suggestions. He contributed in many im-
portant ways to the successful completion of this edition,
keeping the details in order and managing many different
people with grace and good humor.
We are especially grateful to Tom Hummel, University
of Illinois, Urbana-Champaign, who managed the revision of
the end-of-chapter problems and the solutions manuals.
Tom’s extensive experience teaching general chemistry and
his high standards of accuracy and clarity have resulted in
great improvements in the quality of the problems and solu-
tions in this edition. Don DeCoste and Gretchen Adams sup-
port us in so many ways it is impossible to list all of them.
Don wrote all of the Critical Thinking questions for this edi-
tion. Gretchen constructed all of the online Interactive Exam-
ples, created the PowerPoint slides, and worked on many of
Unless otherwise noted, all art on this page is © Cengage Learning 2014.

the other media aspects of the program. We are very grateful
to Don and Gretchen for their creativity and their incredible
work ethic and for being such wonderful colleagues.
Special thanks to Kathy Thrush Saginaw, who contrib-
uted excellent suggestions for improving the art in the text,
and to Sharon Donahue, who did her usual outstanding job
finding just the right photos for this edition. Also we greatly
appreciate the advice and support of Nicole Hamm, Senior
Marketing Manager.
There are many other people who made important con-
tributions to the success of this edition, including Megan
Greiner at Graphic World; Maria Epes, Art Director; Ellen
Pettengill, Text Designer; Lisa Weber, Senior Media Editor;
and Stephanie VanCamp, Media Editor. Special thanks to
Krista Mastroianni, Assistant Editor, who helped in many dif-
ferent ways.
We are especially thankful to all of the reviewers who
participated in different aspects of the development process,
from reviewing the illustrations and chapters to providing
feedback on the development of new features. We sincerely
appreciate all of these suggestions.
Reviewers
NinthEditionReviewers
Kaveh Azimi, Tarrant County College–South
Ron Briggs, Arizona State University
Maureen Burkart, Georgia Perimeter College
Paula Clark, Muhlenberg College
Russell Franks, Stephen F. Austin State University
Judy George, Grossmont College
Roger LeBlanc, University of Miami
Willem Leenstra, University of Vermont
Gary Mort, Lane Community College
Hitish Nathani, St. Philip’s College
Shawn Phillips, Vanderbilt University
Elizabeth Pulliam, Tallahassee Community College
Michael Sommer, University of Wyoming
Clarissa Sorensen-Unruh, Central New Mexico Community
College
William Sweeney, Hunter College, The City University of
New York
Brooke Taylor, Lane Community College
Hongqiu Zhao, Indiana University-Purdue University
Indianapolis
Lin Zhu, Indiana University-Purdue University Indianapolis
AP Reviewers:
Todd Abronowitz, Parish Episcopal High School
Kristen Jones, College Station ISD
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TotheProfessor xi
Lisa McGaw, Laying the Foundation
Priscilla Tuttle, Eastport-South Manor Junior/Senior High
School
EighthEditionReviewers
Yiyan Bai, Houston Community College
David A. Boyajian, Palomar College San Marcos
Carrie Brennan, Austin Peay State University
Alexander Burin, Tulane University
Jerry Burns, Pellissippi State Technical Community College
Stuart Cohen, Horry-Georgetown Technical College
Philip Davis, University of Tennessee at Martin
William M. Davis, The University of Texas at Brownsville
Stephanie Dillon, Florida State University
David Evans, Coastal Carolina University
Leanna Giancarlo, University of Mary Washington
Tracy A. Halmi, Penn State Erie, The Behrend College
Myung Han, Columbus State Community College
Carl Hoeger, University of California, San Diego
Richard Jarman, College of DuPage
Kirk Kawagoe, Fresno City College
Cathie Keenan, Chaffey College
Donald P. Land, University of California, Davis Department
of Chemistry
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Chavonda Mills, Georgia College & State University
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Edward Walters, University of New Mexico
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AP Reviewers:
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xii TotheProfessor

SeventhEditionReviewers Jim McCormick, Truman State

Richard Orwell, Blue Ridge Community College
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Robert D. Pike, The College of William and Mary
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Raymond Scott, Mary Washington College
Ken Carter, Truman State
Alan Stolzenberg, West Virginia University, Morgantown
Bette Davidowitz, University of Cape Town
Rashmi Venkateswaran, University of Ottawa
Natalie Foster, Lehigh University
Tracy A. Halmi, Penn State Erie, The Behrend College AP Reviewers:
Carl Hoeger, University of California, San Diego Annis Hapkiewicz, Okemos High School
Ahmad Kabbani, Lebanese American University Tina Ohn-Sabatello, Maine Township HS East
Arthur Mar, University of Alberta

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 To the Student
As you jump into the study of chemistry, we hope that you
will find our text helpful and interesting. Our job is to present
the concepts and ideas of chemistry in a way you can under-
stand. We hope to encourage you in your studies and to help
you learn to solve problems in ways you can apply in all areas
of your professional and personal lives.
Our main goal is to help you learn to become a truly
creative problem solver. Our world badly needs people who
can “think outside the box.” Our focus is to help you learn to
think like a chemist. Why would you want to do that? Chem-
ists are great problem solvers. They use logic, trial and error,
and intuition—along with lots of patience—to work through
complex problems. Chemists make mistakes, as we all do in
our lives. The important thing that a chemist does is to learn
from the mistakes and to try again. This “can do” attitude is
useful in all careers.
In this book we develop the concepts in a natural way:
The observations come first and then we develop models to
explain the observed behavior. Models help us to understand
and explain our world. They are central to scientific thinking.
Models are very useful, but they also have limitations, which
we will point out. By understanding the basic concepts in
chemistry we lay the foundation for solving problems.
Our main goal is to help you learn a thoughtful method of
problem solving. True learning is more than memorizing facts.
Truly educated people use their factual knowledge as a starting
point—a basis for creative problem solving. Our strategy for
solving problems is explained first in Section 1.6 and is cov-
ered in more details in Section 3.5. To solve a problem we ask
ourselves questions, which help us think through the problem.
We let the problem guide us to the solution. This process can
be applied to all types of problems in all areas of life.
As you study the text, use the Examples and the problem-
solving strategies to help you. The strategies are boxed to
highlight them for you, and the Examples show how these
strategies are applied. It is especially important for you to
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
do the computer-based Interactive Examples that are found
throughout the text. These examples encourage you to think
through the examples step-by-step to help you thoroughly un-
derstand the concepts involved.
After you have read and studied each chapter of the
text, you’ll need to practice your problem-solving skills. To
do this we have provided plenty of review questions and
end-of-chapter exercises. Your instructor may assign these
on paper or online; in either case, you’ll want to work with
your fellow students. One of the most effective ways to
learn chemistry is through the exchange of ideas that comes
from helping one another. The online homework assign-
ments will give you instant feedback, and in print, we have
provided answers to some of the exercises in the back of
the text. In all cases, your main goal is not just to get the
correct answer but to understand the process for getting the
answer. Memorizing solutions for specific problems is not
a very good way to prepare for an exam (or to solve prob-
lems in the real world!).
To become a great problem solver, you’ll need these
skills:
1. Look within the problem for the solution. (Let the prob-
lem guide you.)
2. Use the concepts you have learned along with a system-
atic, logical approach to find the solution.
3. Solve the problem by asking questions and learn to trust
yourself to think it out.
You will make mistakes, but the important thing is to learn
from these errors. The only way to gain confidence is to prac-
tice, practice, practice and to use your mistakes to find your
weaknesses. Be patient with yourself and work hard to under-
stand rather than simply memorize.
We hope you’ll have an interesting and successful year
learning to think like a chemist!
Steve and Susan Zumdahl
xiii
 Rules Governing Formal Charge
❯ To calculate the formal charge on an atom:
1. Take the sum of the lone pair electrons and one-half the shared electrons. This is
the number of valence electrons assigned to the atom in the molecule.

Chemistry, NINTHEdITIoN
2. Subtract the number of assigned electrons from the number of valence elec-
trons on the free, neutral atom to obtain the formal charge.

AGuIdETo
❯ The sum of the formal charges of all atoms in a given molecule or ion must equal
the overall charge on that species.
❯ If nonequivalent Lewis structures exist for a species, those with formal charges
closest to zero and with any negative formal charges on the most electronegative
atoms are considered to best describe the bonding in the molecule or ion.

Conceptual Understanding Conceptual learning and problem solving are fundamental to

the approach of Chemistry. The text gives students the tools to Formal
Example 8.10
become Charges
critical thinkers: to ask
Give possible Lewis structures for XeO , an explosive compound of xenon. Which 3

questions, to apply rules and models, and to evaluate the outcome.Lewis structure or structures are most appropriate according to the formal charges?

Solution
For XeO3 (26 valence electrons) we can draw the following possible Lewis structures
(formal charges are indicated in parentheses):
(+3) (+2) (+2) (+2)
Xe Xe Xe Xe
O O O O O O O O
(−1) O (−1) (0) O (−1) (−1) O (−1) (−1) O (0)
(−1) (−1) (0) (−1)

“Before students are ready to figure out complex problems, they need to
(+1) (+1) (+1) (0)
Xe Xe Xe Xe
O O O O O O O O
(−1) O (0) (0) O (0) (0) O (−1) (0) O (0)

master simpler problems in various contortions. This approach works, and

(0) (−1) (0) (0)

Based on the ideas of formal charge, we would predict that the Lewis structures with
the lower values of formal charge would be most appropriate for describing the

the authors’ presentation of it should have the students buying in.” bonding in XeO3.

See Exercises 8.101 and 8.102

—JerryBurns,Pellissippi State Technical Community College

As a final note, there are a couple of cautions about formal charge to keep in mind.
First, although formal charges are closer to actual atomic charges in molecules than are
oxidation states, formal charges still provide only estimates of charge—they should
not be taken as actual atomic charges. Second, the evaluation of Lewis structures using
formal charge ideas can lead to erroneous predictions. Tests based on experiments
ter 12 Chemical Kinetics must be used to make the final decisions on the correct description of the bonding in a
molecule or polyatomic ion.
| The decomposition
g) n 2N2(g) 1 O2(g)
a platinum surface.
The authors’ emphasis on modeling (or chemical theories) IBLG: See questions from
“Molecular Structure: The 8.13 Molecular Structure: The VSEPR Model
] is three times as great
the rate of decomposi- throughout the text addresses the problem of rote memorization VSEPR Model” The structures of molecules play a very important role in determining their chemical
properties. As we will see later, this is particularly important for biological molecules;
he same in both cases
tinum surface can by helping students better understand and appreciate the proc- a slight change in the structure of a large biomolecule can completely destroy its use-
fulness to a cell or may even change the cell from a normal one to a cancerous one.
only a certain number
s a result, this reaction ess of scientific thinking. By stressing the limitations and uses of
Unless otherwise noted, all art on this page is © Cengage Learning 2014.

scientific models, the authors show students how chemists think

Pt Pt
and work. NO 2

a b
11097_Ch08_0351-0414.indd 389 9/6/12 8:24 AM
8.13 Molecular Structure: The VSEPR Model 401

cules, such as methanol (CH3OH). This molecule is represented by the following

The text includes a number of open-ended Critical Thinking
H
Critical Thinking Lewis structure:
Consider the simple reaction aA n products. You run this reaction and wish H to deter-
Cmine its order. What if you made a graph of reaction rate versus time? Could you use
questions that emphasize
232 Chapter 5 theGases importance of conceptual learning.
H
this to determine
O the order? Sketch three plots of rate versus timeHfor the
C reaction
O H
it is zero, first, or second order. Sketch these plots on the same graph and compare
if
These questions7. are particularly useful for generating
Consider the following velocity distribution curves A
group
b. If the plots represent the velocity distribution of
H them. Defend your answer. H
a
discussion. and B. 1.0 L of O (g) at temperatures of 273 K versus
1273 K, which plot corresponds to each tempera-
2

The molecular structure can be predicted from the arrangement of pairs around the
Relative number of molecules

carbon and oxygen atoms. Note that there are four pairs of electrons around the car- ture? Explain your reasoning. Under which tem-
Integrated Rate Laws bon, for
whichReactions
requires a tetrahedral arrangement [Fig. 8.22(a)]. The oxygen also has four A perature condition would the O2(g) sample behave
most ideally? Explain.
pairs, which requires a tetrahedral arrangement. However, in this case the tetrahedron
C with More Than One Reactant
will be slightly distorted by the space requirements of the lone pairs [Fig. 8.22(b)]. The 8. Briefly describe two methods one might use to find the
H
SoO far we have considered theoverall geometric
integrated arrangement
rate laws for simplefor the molecule
reactions is shown
with only one in Fig. 8.22(c). molar mass of a newly synthesized gas for which a
reactant. Special techniques are required to deal with more complicated reactions. Let’s B molecular formula was not known.
consider the reaction
Summary
Let’s Review boxes help students organize their thinking about the 9. In the van der Waals equation, why is a term added to
Let’s
BrO32 1aq2 1 5Br2 1aq2 1 Review
6H1 1aq2 h 3Br2 1l2of
1the
3H2VSEPR
O 1l2 Model Velocity (m/s)
the observed pressure and why is a term subtracted

b
The rules for using the VSEPR model to predict molecular structure are as follows:
From experimental evidence we know that the rate law is crucial chemical concepts that they encounter. from the container volume to correct for nonideal gas
behavior?
❯ Determine the Lewis structure(s) for the molecule. a. If the plots represent the velocity distribution of
D3BrO 2 4 1.0 L of He(g) at STP versus 1.0 L of Cl2(g) at 10. Why do real gases not always behave ideally? Under
H Rate 5 2 ❯ For3molecules
5 k3BrOwith2resonance 1structures,
3 4 3Br 4 3H 4
2 2 use any of the structures to predict the
what conditions does a real gas behave most ideally?
Dt
molecular structure. STP, which plot corresponds to each gas? Explain
your reasoning. Why?
Suppose we run this reaction❯under
Sum the electron where
conditions pairs around
[BrO3the
2 central atom. 23
]0 5 1.0 3 10 M,
[Br H
C ]0 5 1.0 M, and [H ]0 5 1.0 M.
2 1 ❯ In As the reaction
counting proceeds,
pairs, count [BrO32]bond
each multiple decreases sig-effective pair.
as a single
H nificantly, but because the Br ion
2
andarrangement
H ion concentrations
1
are so largebyinitially, A discussion of the Active Learning Questions can be found online in the Instructor’s Resource Guide and on PowerLecture. The questions
❯ The of the pairs is determined minimizing electron-pair repulsions.
O allow students to explore their understanding of concepts through discussion and peer teaching. The real value of these questions is the
relatively little of these two reactants is consumed.
These arrangements Thus [Br2] in
are shown and [H18.6.
Table ] remain ap- learning that occurs while students talk to each other about chemical concepts.
Hproximately constant. In other words,
❯ Loneunder the conditions where
thanthe Br2 ion
pairsand
do. H
1
pairs require more space bonding Choose an arrangement that
ion concentrations are much largergives
thanthe
thelone
BrOpairs
3 ion
2
concentration,
as much we canRecognize
room as possible. assume that the lone pairs may Active Learning Questions d. Capillary action of the mercury causes the mercury to go
c up the tube.
that throughout the reaction produce a slight distortion of the structure at angles less than 120 degrees. These questions are designed to be used by groups of students in
e. The vacuum that is formed at the top of the tube holds up
Figure 8.22 | The molecular 3Br2 4 5 3Br2 4 0 and 3H1 4 5 3H1 4 0 class.
the mercury.
structure of methanol. (a) The 1. Consider the following apparatus: a test tube covered with a
arrangement This means that
of electron pairsthe
andrate law can be written nonpermeable elastic membrane inside a container that is Justify your choice, and for the choices you did not pick, ex-
atoms around the carbon atom. The VSEPR Model—How Well Does It Work?
Rate 5 k3Br2 4 0 3H1 4 02 3BrO32 4 5 kr 3BrO32 4
closed with a cork. A syringe goes through the cork. plain what is wrong with them. Pictures help!
(b) The arrangement of bonding and 3. The barometer below shows the level of mercury at a given at-
lone pairs around The VSEPR model is very simple. There are only a few rules to remember, yet the mospheric pressure. Fill all the other barometers with mercury
where,the oxygen
since [Br2atom.
]0 and [H1]0 are constant,
(c) The molecular structure. model correctly predicts the molecular structures of most molecules formed from non- for that same atmospheric pressure. Explain your answer.
metallic Syringe
kr 5 elements.
k3Br2 4 0 3HMolecules
40
1 2 of any size can be treated by applying the VSEPR model
to each appropriate atom (those bonded to at least two other atoms) in the molecule.
Thus we can use this model to predict the structures of molecules with hundreds of
atoms. It does, however, fail in a few instances. For example, phosphine (PH3), which Cork
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
has a Lewis structure analogous to that of ammonia,
Membrane
H P H H N H

H H Hg(l )
2 9/6/12 8:44 AM
would be predicted to have a molecular structure similar to that for NH3, with bond
angles of approximately 107 degrees. However, the bond angles of phosphine are actu-
ally 94 degrees. There are ways of explaining this structure, but more rules have to be a. As you push down on the syringe, how does the mem-
added to the model. brane covering the test tube change? 4. As you increase the temperature of a gas in a sealed, rigid
This again illustrates the point that simple models are bound to have exceptions. In b. You stop pushing the syringe but continue to hold it container, what happens to the density of the gas? Would the
introductory chemistry we want to use simple models that fit the majority of cases; we down. In a few seconds, what happens to the membrane? results be the same if you did the same experiment in a con-
2. Figure 5.2 shows a picture of a barometer. Which of the fol- tainer with a piston at constant pressure? (See Fig. 5.17.)
are willing to accept a few failures rather than complicate the model. The amazing
thing about the VSEPR model is that such a simple model predicts correctly the struc- lowing statements is the best explanation of how this barom- 5. A diagram in a chemistry book shows a magnified view of a
eter works? flask of air as follows:
tures of so many molecules.
a. Air pressure outside the tube causes the mercury to move in
The text includes a number of Active Learning Questions at the tube until the air pressure inside and outside the tube is
equal.
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
the end of each chapter that are intended for group discussion, b. Air pressure inside the tube causes the mercury to move in
the tube until the air pressure inside and outside the tube is

since students often learn the most when they teach each other. equal.
c. Air pressure outside the tube counterbalances the weight
of the mercury in the tube.
11097_Ch08_0351-0414.indd 401 9/6/12 8:24 AM
Unless otherwise noted, all art on this page is © Cengage Learning 2014.

11097_Ch05_0189-0244.indd 232 9/6/12 8:27 AM

xiv Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Problem Solving This text talks to the student about how to approach and solve chemical
problems, since one of the main goals of general chemistry is to help students become crea-
tive problem solvers. The authors emphasize a thoughtful, logical approach rather than simply
memorizing procedures.

“The text gives a meaningful explanation and alternative to memorization. This

approach and the explanation [to the student] of the approach will supply the ‘secret’
of successful problem solving abilities to all students.”
—davidBoyajian,Palomar College
3.5 Learning to Solve Problems 93

3.5 Learning to Solve Problems In Chapter 3, “Stoichiometry,” the authors introduce a new section,
One of the great rewards of studying chemistry is to become a good problem solver.
Being able to solve complex problems is a talent that will serve you well in all walks
of life. It is our purpose in this text to help you learn to solve problems in a flexible,
Learning to Solve Problems, which emphasizes the importance of prob-
creative way based on understanding the fundamental ideas of chemistry. We call this
approach conceptual problem solving. lem solving. This new section helps students understand that thinking their
The ultimate goal is to be able to solve new problems (that is, problems you have
not seen before) on your own. In this text we will provide problems and offer solutions
by explaining how to think about the problems. While the answers to these problems
way through a problem produces more long-term, meaningful learning than
are important, it is perhaps even more important to understand the process—the think-
ing necessary to get the answer. Although at first we will be solving the problem for simply memorizing steps, which are soon forgotten.
you, do not take a passive role. While studying the solution, it is crucial that you inter-
actively think through the problem with us. Do not skip the discussion and jump to the
answer. Usually, the solution will involve asking a series of questions. Make sure that
you understand each step in the process. This active approach should apply to prob- 1.8 Temperature 25
lems outside of chemistry as well. For example, imagine riding with someone in a car
to an unfamiliar destination. If your goal is simply to have the other person get you to
that destination, you will probably not pay much attention to how to get there (pas- Figure 1.10 | Normal body Fahrenheit Celsius Kelvin
sive), and if you have to find this same place in the future on your own, you probably temperature on the Fahrenheit,
will not be able to do it. If, however, your goal is to learn how to get there, you would Celsius, and Kelvin scales.
pay attention to distances, signs, and turns (active). This is how you should read the
solutions in the text (and the text in general). 98.6°F ?°C ?K
While actively studying our solutions to problems is helpful, at some point you will
need to know how to think through these problems on your own. If we help you too
much as you solve a problem, you won’t really learn effectively. If we always “drive,” 5°C
66.6°F 66.6°F × = 37.0°C 37.0 + 273.15 K = 310.2 K
9°F
you won’t interact as meaningfully with the material. Eventually you need to learn to
drive yourself. We will provide more help at the beginning of the text and less as we
proceed to later chapters.
There are two fundamentally different ways you might use to approach a problem. 32°F 0°C 273.15 K
One way emphasizes memorization. We might call this the “pigeonholing method.” In
this approach, the first step is to label the problem—to decide in which pigeonhole it
fits. The pigeonholing method requires that we provide you with a set of steps that you
John Humble/The Image Bank/Getty Images

memorize and store in the appropriate slot for each different problem you encounter.
The difficulty with this method is that it requires a new pigeonhole each time a prob-
lem is changed by even a small amount.
Consider the driving analogy again. Suppose you have memorized how to drive from
your house to the grocery store. Do you know how to drive back from the grocery store
to your house? Not necessarily. If you have only memorized the directions and do not
understand fundamental principles such as “I traveled north to get to the store, so my
house is south of the store,” you may find yourself stranded. In a more complicated Example 1.12 Temperature Conversions II
Pigeonholes can be used for sorting and example, suppose you know how to get from your house to the store (and back) and One interesting feature of the Celsius and Fahrenheit scales is that 40C and 40F
classifying objects like mail. from your house to the library (and back). Can you get from the library to the store represent the same temperature, as shown in Fig. 1.9. Verify that this is true.
without having to go back home? Probably not if you have only memorized directions
and you do not have a “big picture” of where your house, the store, and the library are Solution
relative to one another.
Where are we going?
The second approach is conceptual problem solving, in which we help you get the
To show that 40C  40F
Chapters 1–6 introduce a series of questions into the in- “big picture”—a real understanding of the situation. This approach to problem solving
looks within the problem for a solution. In this method we assume that the problem is What do we know?
a new one, and we let the problem guide us as we solve it. In this approach we ask a
chapter Examples to engage students in the process of prob-
❯ The relationship between the Celsius and Fahrenheit scales
series of questions as we proceed and use our knowledge of fundamental principles to
answer these questions. Learning 3.7 this
Determining the Formula
approach requires someofpatience,
a Compound 99
but the reward How do we get there?

Figure 3.6 | such as Where are we going? and How do we

for learning to solve problems this way is that we become an effective solver of any
lem solving, Examples of substances
new problem that confronts us in daily life or in our work in any field. In summary,
instead of looking outside the problem for a memorized solution, we will look inside
The difference between 32F and 40F is 72F. The difference between 0C and
40C is 40C. The ratio of these is
whose empirical and molecular
get there? This more active approach helps students think
formulas differ. Notice that molecular
formula 5 (empirical
Unless otherwise formula)
noted, all art on this page isn,©where
Cengage Learning 2014.
the problem and let the problem help us as we proceed to a solution. 72°F
40°C
5
8 3 9°F
8 3 5°C
5
9°F
5°C
n is an integer.
their way through the solution to the problem. as required. Thus 40C is equivalent to 40F.

See Exercise 1.61

17.1 Spontaneous Processes and Entropy 793
11097_Ch03_0081-0137.indd 93 9/6/12 8:46 AM
Since, as shown in Example 1.12, 40 on both the Fahrenheit and Celsius scales
C6H6 = (CH)6 S8 = (S)8 C6H12O6 = (CH2O)6 The tendency to mix is due to the Positional
represents theentropy is also verythis
same temperature, important in the
point can formation
be used of solutions.
as a reference pointIn(like
Chapter
0C
increased volume available to the particles 11
andwe sawfor
32F) thata solution formation
relationship betweenis favored
the two by the natural tendency for substances to
scales:
of each component of the mixture. For mix. We can now be more precise. The entropy change associated with the mixing of
example, when two liquids are mixed,
two pure substancesNumber of Fahrenheit
is expected to be positive. F 2 12402
degrees AnTincrease in 9°F is expected be-
entropy
the molecules of each liquid have more 5 5
cause there are many Number
moreofmicrostates
Celsius degrees TC 2
for the mixed 12402 than
condition 5°Cfor the separated
Problem-Solving Strategy boxes focus students’ attention on the very im-
available volume and thus more available
positions. condition. This effect is due principally to the increased volume available to a given
Problem-Solving Strategy T 1 40 9°F
“particle” after mixing occurs. For Fexample, 5 when two liquids are mixed to form (1.3)a
T 1 40 5°C
portant process of problem solving. solution, the molecules of each liquid have more available volume and thus more avail-
C
Determining Molecular Formula from Empirical Formula
❯ Obtain the empirical formula. able
wherepositions.
TF and TCTherefore,
represent thethesame
increase in positional
temperature entropy
(but not associated
the same number).with
Thismixing
equa-
favors thebeformation
tion can of solutions.
used to convert Fahrenheit temperatures to Celsius, and vice versa, and
❯ Compute the mass corresponding to the empirical formula.
may be easier to remember than Equations (1.1) and (1.2).
❯ Calculate the ratio:
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Molar mass
Empirical formula mass
❯ The integer from the previous step represents the number of empirical formula Interactive Positional Entropy
units in one molecule. When the empirical formula subscripts are multiplied by Example 17.1
For each of the following pairs, choose the substance with the higher positional en-
this integer, the molecular formula results. This procedure is summarized by the 11097_Ch01_0001-0041.indd 25
Sign in at http://login.cengagebrain tropy (per mole) at a given temperature.
9/25/12 5:06 PM

equation: .com to try this Interactive Example

a. Solid CO2 and gaseous CO2
molar mass in OWL.
Molecular formula 5 empirical formula 3 b. N2 gas at 1 atm and N2 gas at 1.0 3 1022 atm
empirical formula mass

Solution
a. Since a mole of gaseous CO2 has the greater volume by far, the molecules have
many more available positions than in a mole of solid CO2. Thus gaseous CO2
has the higher positional entropy.
Interactive Determining Empirical and Molecular Formulas I b. A mole of N2 gas at 1 3 1022 atm has a volume 100 times that (at a given
Example 3.10 temperature) of a mole of N2 gas at 1 atm. Thus N2 gas at 1 3 1022 atm has
Determine the empirical and molecular formulas for a compound that gives the follow-
Sign in at http://login.cengagebrain ing percentages on analysis (in mass percents): the higher positional entropy.
.com to try this Interactive Example

Interactive Examples engage students in the problem- 71.65% Cl 24.27% C 4.07% H See Exercise 17.31
in OWL.
The molar mass is known to be 98.96 g/mol.

solving process by requiring

Solution them to think through the ex-
Where are we going?
ample step-by-step rather
To find thethan
empirical andsimply scanning
molecular formulas the written
for the given compound Interactive
Example 17.2
Predicting Entropy Changes
What do we know? Predict the sign of the entropy change for each of the following processes.
example in the text as many Percent students
of each element do. ❯ Sign in at http://login.cengagebrain
.com to try this Interactive Example
a. Solid sugar is added to water to form a solution.
❯ Molar mass of the compound is 98.96 g/mol b. Iodine vapor condenses on a cold surface to form crystals.
in OWL.
What information do we need to find the empirical formula?
❯ Mass of each element in 100.00 g of compound Solution
❯ Moles of each element a. The sugar molecules become randomly dispersed in the water when the solution
forms and thus have access to a larger volume and a larger number of possible
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
positions. The positional disorder is increased, and there will be an increase in
entropy. DS is positive, since the final state has a larger entropy than the initial
state, and DS 5 Sfinal 2 Sinitial.
b. Gaseous iodine is forming a solid. This process involves a change from a
relatively large volume to a much smaller volume, which results in lower
11097_Ch03_0081-0137.indd 99 9/6/12 8:47 AM
positional disorder. For this process DS is negative (the entropy decreases).

See Exercise 17.32

Unless otherwise noted, all art on this page is © Cengage Learning 2014.

Unless otherwise noted, all art on this page is © Cengage Learning 2014. xv
11097_Ch17_0787-0831.indd 793 9/6/12 8:57 AM
 170 Chapter 4 Types of Chemical Reactions and Solution Stoichiometry

been emphasizing this approach in dealing with the reactions between ions in solution.
Make it a habit to write down the components of solutions before trying to decide what
reaction(s) might take place as you attempt the end-of-chapter problems involving
titrations.

4.9 Oxidation–Reduction Reactions

We have seen that many important substances are ionic. Sodium chloride, for example,
can be formed by the reaction of elemental sodium and chlorine:
2Na1s2 1 Cl2 1g2 h 2NaCl1s2
Dynamic Art Program Most of the glassware, orbitals, graphs, flowcharts, and molecules
In this reaction, solid sodium, which contains neutral sodium atoms, reacts with chlo-
rine gas, which contains diatomic Cl2 molecules, to form the ionic solid NaCl, which
have been redrawn to better serve visual learners and enhance the textbook.
contains Na1 and Cl2 ions. This process is represented in Fig. 4.19. Reactions like this
one, in which one or more electrons are transferred, are called oxidation–reduction
reactions or redox reactions.
Many important chemical reactions involve oxidation and reduction. Photosynthe-
Experiment 26: Classification of sis, which stores energy from the sun in plants by converting carbon dioxide and water
Chemical Reactions 4.3 The Composition of Solutions 149
to sugar, is a very important oxidation–reduction reaction. In fact, most reactions used
IBLG: See questions from “Oxidation for energy production are redox reactions. In humans, the oxidation of sugars, fats, and
Reduction” proteins provides the energy necessary for life. Combustion reactions, which provide What information do we need to find volume of blood containing 1.0 mg of NaCl?
❯ Moles of NaCl (in 1.0 mg)

How do we get there?

What are the moles of NaCl (58.44 g/mol)?
1 g NaCl 1 mol NaCl
1.0 mg NaCl 3 3 5 1.7 3 1025 mol NaCl
1000 mg NaCl 58.44 g NaCl
What volume of 0.14 M NaCl contains 1.0 mg (1.7 3 1025 mole) of NaCl?

Photos © Cengage Learning. All rights reserved.

There is some volume, call it V, that when multiplied by the molarity of this solution
will yield 1.7 3 1025 mole of NaCl. That is,
0.14 mol NaCl
The art program emphasizes V 3molecular-level
L solution
5 1.7 3 10interactions
mol NaCl that 25

help students visualize thefor“micro/macro”

We want to solve the volume: connection.
1.7 3 1025 mol NaCl
V5 5 1.2 3 1024 L solution
0.14 mol NaCl
L solution
j Thus 0.12 mL of blood contains 1.7 3 1025 mole of NaCl or 1.0 mg of NaCl.

See Exercises 4.33 and 4.34

Cl− Cl− Na+
Na+
A standard solution is a solution whose concentration is accurately known. Stan-
Na dard solutions, often used in chemical analysis, can be prepared as shown in Fig. 4.10
Na and in Example 4.6.

Cl Cl
CCl
l
Interactive Solutions of Known Concentration
2Na(s) Cl2(g) 2NaCl(s) Example 4.6
Sodium + Chlorine Sodium chloride To analyze the alcohol content of a certain wine, a chemist needs 1.00 L of an aqueous
Sign in at http://login.cengagebrain 0.200-M K2Cr2O7 (potassium dichromate) solution. How much solid K2Cr2O7 must be
Figure 4.19 | The reaction of solid sodium and gaseous chlorine to form solid sodium chloride. .com to try this Interactive Example weighed out to make this solution?
in OWL.
Unless otherwise noted, all art on this page is © Cengage Learning 2014. Solution
Where are we going?
To find the mass of K2Cr2O7 required for the solution

11097_Ch04_0138-0188.indd 170 9/6/12 8:59 AM

Wash
Figure 4.10 | Steps involved in the bottle
preparation of a standard aqueous
solution. (a) Put a weighed amount
of a substance (the solute) into the
Realistic drawings of glassware and instrumentation found in volumetric flask, and add a small Volume marker
quantity of water. (b) Dissolve the (calibration mark)
the lab help students make real connections. solid in the water by gently swirling
the flask (with the stopper in place).
(c) Add more water (with gentle
swirling) until the level of the solution Weighed
amount
just reaches the mark etched on the
of solute
neck of the flask. Then mix the
solution thoroughly by inverting the
flask several times. a b c
Unless otherwise noted, all art on this page is © Cengage Learning 2014.

8.3 Bond Polarity and Dipole Moments 359

11097_Ch04_0138-0188.indd 149 9/6/12 8:59 AM

Figure 8.5 | (a) The charge distribu- − +
tion in the water molecule. (b) The
water molecule in an electric field.
δ+
(c) The electrostatic potential diagram H H
of the water molecule.
O 2δ− Δ+ Δ− O

H H
δ+

a b c

Figure 8.6 | (a) The structure and +

charge distribution of the ammonia
3δ− Δ−
molecule. The polarity of the NOH
bonds occurs because nitrogen has a H
N
H
N Electrostatic potential maps help students visualize the
H H
greater electronegativity than
hydrogen. (b) The dipole moment of
δ+ H
δ+
δ+ Δ+ H distribution of charge in molecules.
the ammonia molecule oriented in an −
electric field. (c) The electrostatic
potential diagram for ammonia. a b c

2δ+
δ− δ−
O C O O C O
Figure 8.7 | (a) The carbon dioxide
molecule. (b) The opposed bond
polarities cancel out, and the carbon
dioxide molecule has no dipole
moment. (c) The electrostatic
potential diagram for carbon dioxide. a b c

than the hydrogen atoms, the molecular charge distribution is that shown in Fig. 8.5(a).
Because of this charge distribution, the water molecule behaves in an electric field as if
it had two centers of charge—one positive and one negative—as shown in Fig. 8.5(b).
The water molecule has a dipole moment. The same type of behavior is observed for the
xvi NH3 molecule (Fig. 8.6). Some molecules have polar bonds but do not have a dipole
moment. This occurs when the individual bond polarities are arranged in such a way
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
that they cancel each other out. An example is the CO2 molecule, which is a linear mol-
ecule that has the charge distribution shown in Fig. 8.7. In this case the opposing bond
polarities cancel out, and the carbon dioxide molecule does not have a dipole moment.
There is no preferential way for this molecule to line up in an electric field. (Try to find
a preferred orientation to make sure you understand this concept.)
 Real-World Applications Interesting applications of modern chemistry show students the
relevance of chemistry to their world.
Each chapter begins
with an engaging intro-
duction that demon-
strates how chemistry is
related to everyday life.
Chemical connections
A Note-able Achievement
Post-it Notes, a product of the 3M
Corporation, revolutionized casual
written communications and personal
reminders. Introduced in the United
States in 1980, these sticky-but-not-
too-sticky notes have now found
countless uses in offices, cars, and
homes throughout the world.
The invention of sticky notes
occurred over a period of about 10
years and involved a great deal of
serendipity. The adhesive for Post-it
Notes was discovered by Dr. Spencer
F. Silver of 3M in 1968. Silver found
that when an acrylate polymer
material was made in a particular way,
it formed cross-linked microspheres.
When suspended in a solvent and
sprayed on a sheet of paper, this
substance formed a “sparse mono-
layer” of adhesive after the solvent
evaporated. Scanning electron
microscope images of the adhesive
show that it has an irregular surface, a
little like the surface of a gravel road.
In contrast, the adhesive on cello-
phane tape looks smooth and uniform,
like a superhighway. The bumpy
surface of Silver’s adhesive caused it
to be sticky but not so sticky to
produce permanent adhesion,
because the number of contact points
between the binding surfaces was
limited.
When he invented this adhesive,
Silver had no specific ideas for its use,
so he spread the word of his discovery
to his fellow employees at 3M to see if
anyone had an application for it. In
addition, over the next several years
development was carried out to
improve the adhesive’s properties. It
was not until 1974 that the idea for
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
11097_Ch01_0001-0041.indd 7
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Post-it Notes popped up. One Sunday
Art Fry, a chemical engineer for 3M,
was singing in his church choir when
he became annoyed that the book-
mark in his hymnal kept falling out. He
thought to himself that it would be
nice if the bookmark were sticky
enough to stay in place but not so
sticky that it couldn’t be moved.
Luckily, he remembered Silver’s
glue—and the Post-it Note was born.
For the next three years, Fry
worked to overcome the manufac-
turing obstacles associated with the
product. By 1977 enough Post-it Notes
were being produced to supply 3M’s
corporate headquarters, where the
employees quickly became addicted to
their many uses. Post-it Notes are now
available in 62 colors and 25 shapes.
In the years since the introduction
of Post-it Notes, 3M has heard some
Chapter 13
Chemical Equilibrium
13.1 The Equilibrium Condition
The Characteristics of Chemical
13.5 Applications of the Equilibrium
Constant
Equilibrium The Extent of a Reaction
13.2 The Equilibrium Constant Reaction Quotient
13.3 Equilibrium Expressions Involving Calculating Equilibrium Pressures and
Concentrations
Pressures
13.4 Heterogeneous Equilibria
The equilibrium in a salt water aquarium must be carefully maintained to keep the sea life healthy.
(Borissos/Dreamstime.com)
606
11097_Ch13_0606-0651.indd 606
1.2 The Scientific Method 7
Chemical Connections describe current applications of chemistry. These special-
interest boxes cover such topics as the invention of Post-it Notes, farming the
wind, and the use of iron metal to clean up contaminated groundwater. Additional
Chemical Connections are available on the student website.
Chemical connections
Photo © Cengage Learning. All rights reserved.
Farming the Wind
In the Midwest the wind blows across
fields of corn, soybeans, wheat, and
wind turbines—wind turbines? It turns
out that the wind that seems to blow
remarkable stories connected to the
almost continuously across the plains is
use of these notes. For example, a
now becoming the latest cash crop. One
Post-it Note was applied to the nose of
of these new-breed wind farmers is
a corporate jet, where it was intended
Daniel Juhl, who recently erected
to be read by the plane’s Las Vegas
17 wind turbines on six acres of land
ground crew. Someone forgot to
near Woodstock, Minnesota. These
remove it, however. The note was still
turbines can generate as much as
on the nose of the plane when it
10 megawatts (MW) of electricity, which
landed in Minneapolis, having survived
Juhl sells to the local electrical utility.
a takeoff, a landing, and speeds of
There is plenty of untapped wind
500 miles per hour at temperatures as
power in the United States. Wind
low as 2568F. Stories on the 3M Web
mappers rate regions on a scale of
site describe how a Post-it Note on the
1 to 6 (with 6 being the best) to
front door of a home survived the
indicate the quality of the wind
140-mile-per-hour winds of Hurricane
resource. Wind farms are now being
Hugo and how a foreign official
developed in areas rated from 4 to 6.
accepted Post-it Notes in lieu of cash
The farmers who own the land
when a small bribe was needed to cut
welcome the increased income derived
through bureaucratic hassles.
from the wind blowing across their
Post-it Notes have definitely
land. Economists estimate that each
changed the way we communicate and
acre devoted to wind turbines can pay
remember things.
royalties to the farmers of as much as
$8000 per year, or many times the
revenue from growing corn on that
same land. Juhl claims that farmers
who construct the turbines themselves
can realize as much as $20,000 per
year per turbine. Globally, wind
generation of electricity has nearly
quadrupled in the last five years and
is expected to increase by about 60%
9/6/12 9:02 AM
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
I n doing stoichiometry calculations we assumed that reactions proceed to comple-
tion, that is, until one of the reactants runs out. Many reactions do proceed essen-
tially to completion. For such reactions it can be assumed that the reactants are quan-
titatively converted to products and that the amount of limiting reactant that remains is
negligible. On the other hand, there are many chemical reactions that stop far short of
completion. An example is the dimerization of nitrogen dioxide:
NO2 1g2 1 NO2 1g2 h N2O4 1g2
The reactant, NO2, is a dark brown gas, and the product, N2O4, is a colorless gas.
When NO2 is placed in an evacuated, sealed glass vessel at 258C, the initial dark
brown color decreases in intensity as it is converted to colorless N2O4. However, even
over a long period of time, the contents of the reaction vessel do not become color-
less. Instead, the intensity of the brown color eventually becomes constant, which
means that the concentration of NO2 is no longer changing. This is illustrated on the
molecular level in Fig. 13.1. This observation is a clear indication that the reaction
has stopped short of completion. In fact, the system has reached chemical equilib-
rium, the state where the concentrations of all reactants and products remain con-
stant with time.
Any chemical reactions carried out in a closed vessel will reach equilibrium. For
some reactions the equilibrium position so favors the products that the reaction ap-
pears to have gone to completion. We say that the equilibrium position for such reac-
tions lies far to the right (in the direction of the products). For example, when gaseous
hydrogen and oxygen are mixed in stoichiometric quantities and react to form water
vapor, the reaction proceeds essentially to completion. The amounts of the reactants
that remain when the system reaches equilibrium are so tiny as to be negligible. By
contrast, some reactions occur only to a slight extent. For example, when solid CaO is
placed in a closed vessel at 258C, the decomposition to solid Ca and gaseous O2 is
virtually undetectable. In cases like this, the equilibrium position is said to lie far to the
left (in the direction of the reactants).
In this chapter we will discuss how and why a chemical system comes to equi-
librium and the characteristics of equilibrium. In particular, we will discuss how to
calculate the concentrations of the reactants and products present for a given system
at equilibrium.
13.6 Solving Equilibrium Problems
Treating Systems That Have Small
13.1 The Equilibrium Condition
Equilibrium Constants IBLG: See questions from Since no changes occur in the concentrations of reactants or products in a reaction
“The Equilibrium Condition and system at equilibrium, it may appear that everything has stopped. However, this is not
13.7 Le Châtelier’s Principle the Equilibrium Constant” the case. On the molecular level, there is frantic activity. Equilibrium is not static but
The Effect of a Change in Concentration
Equilibrium is a dynamic situation. is a highly dynamic situation. The concept of chemical equilibrium is analogous to the
The Effect of a Change in Pressure
flow of cars across a bridge connecting two island cities. Suppose the traffic flow on
The Effect of a Change in Temperature
the bridge is the same in both directions. It is obvious that there is motion, since one
can see the cars traveling back and forth across the bridge, but the number of cars in
each city is not changing because equal numbers of cars are entering and leaving. The
result is no net change in the car population.
To see how this concept applies to chemical reactions, consider the reaction be-
tween steam and carbon monoxide in a closed vessel at a high temperature where the
reaction takes place rapidly:
H2O 1g2 1 CO1g2 m H2 1g2 1 CO2 1g2
Unless otherwise noted, all art on this page is © Cengage Learning 2014. Unless otherwise noted, all art on this page is © Cengage Learning 2014. 607
9/6/12 9:06 AM 11097_Ch13_0606-0651.indd 607 9/6/12 10:57
6.6 New Energy Sources 277
per year in the United
States. The economic
feasibility of wind-
generated electricity
has greatly improved in
the past 30 years as the
wind turbines have
become more efficient.
Courtesy, NextEra Energy Resources
Today’s turbines can
produce electricity that
costs about the same as
that from other sources.
The most impressive
thing about wind power
is the magnitude of the
This State Line Wind Project along the Oregon–Washington border
supply. According to the uses approximately 399 wind turbines to create enough electricity to
American Wind Energy power some 70,000 households.
Association in Wash-
ington, D.C., the wind-power potential power 1 million homes if transmission
in the United States is comparable or problems can be solved.
larger than the energy resources under Another possible scenario for wind
the sands of Saudi Arabia. farms is to use the electrical power
The biggest hurdle that must be generated to decompose water to
overcome before wind power can produce hydrogen gas that could be
become a significant electricity carried to cities by pipelines and used
producer in the United States is as a fuel. One real benefit of hydrogen
construction of the transmission is that it produces water as its only
infrastructure—the power lines combustion product. Thus, it is
needed to move the electricity from essentially pollution-free.
the rural areas to the cities where Within a few years, wind power
most of the power is used. For could be a major source of electricity.
example, the hundreds of turbines There could be a fresh wind blowing
planned in southwest Minnesota in a across the energy landscape of the
development called Buffalo Ridge United States in the near future.
could supply enough electricity to
carbon dioxide. However, even though it appears that hydrogen is a very logical choice
as a major fuel for the future, there are three main problems: the cost of production, stor-
xvii
age, and transport.
First let’s look at the production problem. Although hydrogen is very abundant on
the earth, virtually none of it exists as the free gas. Currently, the main source of hy-
drogen gas is from the treatment of natural gas with steam:
CH4 1g2 1 H2O 1g2 h 3H2 1g2 1 CO 1g2
Comprehensive End-of-Chapter Practice and Review We offer end-of-chapter exer-
cises for every type of student and for every kind of homework assignment.

748 Chapter 15 Acid–Base Equilibria

Each chapter has a For Review section to reinforce key con-

For review
Key terms Buffered solutions
cepts and includes review questions for students to practice
Section 15.1
common ion
❯
❯
Contains a weak acid (HA) and its salt (NaA) or a weak base (B) and its salt (BHCl)
Resists a change in its pH when H1 or OH2 is added
independently.
common ion effect
❯ For a buffered solution containing HA and A2
Section 15.2 ❯ The Henderson–Hasselbalch equation is useful:
buffered solution
Henderson–Hasselbalch 3A2 4
pH 5 pKa 1 log a b
equation 3HA 4
Section 15.3 ❯ The capacity of the buffered solution depends on the amounts of HA and A2 present
buffering capacity 3A2 4
❯ The most efficient buffering occurs when the ratio is close to 1
Section 15.4 3HA 4
pH curve (titration curve) ❯ Buffering works because the amounts of HA (which reacts with added OH2) and A2
millimole (mmol) 3A2 4
equivalence point (which reacts with added H1) are large enough that the ratio does not change
3HA 4
(stoichiometric point)
significantly when strong acids or bases are added
Section 15.5
acid–base indicator Acid–base titrations
phenolphthalein ❯ The progress of a titration is represented by plotting the pH of the solution versus the volume
of added titrant; the resulting graph is called a pH curve or titration curve
❯ Strong acid–strong base titrations show a sharp change in pH near the equivalence point
❯ The shape of the pH curve for a strong base–strong acid titration before the equivalence point
is quite different from the shape of the pH curve for a strong base–weak acid titration
❯ The strong base–weak acid pH curve shows the effects of buffering before the equiva-
lence point
❯ For a strong base–weak acid titration, the pH is greater than 7 at the equivalence point
because of the basic properties of A2
❯ Indicators are sometimes used to mark the equivalence point of an acid–base titration
❯ The end point is where the indicator changes color
❯ The goal is to have the end point and the equivalence point be as close as possible

Review questions Answers to the Review Questions can be found on the Student website.

1. What is meant by the presence of a common ion? How
does the presence of a common ion affect an equilib-
rium such as
HNO2 1aq2 m H1 1aq2 1 NO22 1aq2
What is an acid–base solution called that contains a
common ion?
2. Define a buffer solution. What makes up a buffer
solution? How do buffers absorb added H1 or OH2
with little pH change?
Is it necessary that the concentrations of the weak
acid and the weak base in a buffered solution be equal?
Explain. What is the pH of a buffer when the weak acid
and conjugate base concentrations are equal?
11097_Ch15_0711-0757.indd 748
A buffer generally contains a weak acid and its
weak conjugate base, or a weak base and its weak
conjugate acid, in water. You can solve for the pH by A discussion of the Active Learning Questions can be found online in the Instructor’s Resource Guide and on
setting up the equilibrium problem using the Ka reaction PowerLecture. The questions allow students to explore their understanding of concepts through discussion and
peer teaching. The real value of these questions is the learning that occurs while students talk to each other
of the weak acid or the Kb reaction of the conjugate about chemical concepts.
base. Both reactions give the same answer for the pH of
the solution. Explain. Active Learning Questions
A third method that can be used to solve for the pH These questions are designed to be used by groups of students in
of a buffer solution is the Henderson–Hasselbalch class.
equation. What is the Henderson–Hasselbalch equa- 1. Consider two beakers of pure water at different temperatures.
tion? What assumptions are made when using this How do their pH values compare? Which is more acidic? more
equation? basic? Explain.
3. One of the most challenging parts of solving acid–base 2. Differentiate between the terms strength and concentration as
they apply to acids and bases. When is HCl strong? Weak?
problems is writing out the correct equation. When a
Concentrated? Dilute? Answer the same questions for ammo-
nia. Is the conjugate base of a weak acid a strong base?
3. Sketch two graphs: (a) percent dissociation for weak acid HA
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
versus the initial concentration of HA ([HA]0) and (b) H1 con-
centration versus [HA]0. Explain both.
4. Consider a solution prepared by mixing a weak acid HA and
HCl. What are the major species? Explain what is occurring in
solution. How would you calculate the pH? What if you added
9/6/12 9:08 AM NaA to this solution? Then added NaOH?
5. Explain why salts can be acidic, basic, or neutral, and show
examples. Do this without specific numbers.
6. Consider two separate aqueous solutions: one of a weak acid
HA and one of HCl. Assuming you started with 10 molecules
of each:
a. Draw a picture of what each solution looks like at
equilibrium.
b. What are the major species in each beaker?
c. From your pictures, calculate the Ka values of each acid.
For Review 701
10. A certain sodium compound is dissolved in water to liberate
Na1 ions and a certain negative ion. What evidence would you
look for to determine whether the anion is behaving as an acid
or a base? How could you tell whether the anion is a strong
base? Explain how the anion could behave simultaneously as
an acid and a base.
11. Acids and bases can be thought of as chemical opposites (ac-
ids are proton donors, and bases are proton acceptors). There-
fore, one might think that Ka 5 1yKb. Why isn’t this the case?
What is the relationship between Ka and Kb? Prove it with a
derivation.
12. Consider two solutions of the salts NaX(aq) and NaY(aq) at
equal concentrations. What would you need to know to deter-
mine which solution has the higher pH? Explain how you
would decide (perhaps even provide a sample calculation).
13. What is meant by pH? True or false: A strong acid solution
always has a lower pH than a weak acid solution. Explain.
14. Why is the pH of water at 258C equal to 7.00?
15. Can the pH of a solution be negative? Explain.
16. Is the conjugate base of a weak acid a strong base? Explain.
Explain why Cl2 does not affect the pH of an aqueous solution.
17. Match the following pH values: 1, 2, 5, 6, 6.5, 8, 11, 11, and
13 with the following chemicals (of equal concentration):
HBr, NaOH, NaF, NaCN, NH4F, CH3NH3F, HF, HCN, and
NH3. Answer this question without performing calculations.
18. The salt BX, when dissolved in water, produces an acidic solu-
tion. Which of the following could be true? (There may be

Active Learning Questions are designed to promote dis- d. Order the following from the strongest to the weakest
base: H2O, A2, Cl2. Explain your order.
more than one correct answer.)
a. The acid HX is a weak acid.
7. You are asked to calculate the H1 concentration in a solution b. The acid HX is a strong acid.
cussion among groups of students in class. of NaOH(aq). Because sodium hydroxide is a base, can we
say there is no H1, since having H1 would imply that the solu-
c. The cation B1 is a weak acid.
Explain.
tion is acidic?
8. Consider a solution prepared by mixing a weak acid HA, HCl,
and NaA. Which of the following statements best describes A blue question or exercise number indicates that the answer to
what happens? that question or exercise appears at the back of this book and a
a. The H1 from the HCl reacts completely with the A2 from solution appears in the Solutions Guide, as found on PowerLecture.
the NaA. Then the HA dissociates somewhat.
b. The H1 from the HCl reacts somewhat with the A2 from Questions
the NaA to make HA, while the HA is dissociating. Even-
tually you have equal amounts of everything. 19. Anions containing hydrogen (for example, HCO32 and
H2PO42) usually show amphoteric behavior. Write equations
c. The H1 from the HCl reacts somewhat with the A2 from
illustrating the amphoterism of these two anions.
the NaA to make HA while the HA is dissociating. Even-
tually all the reactions have equal rates. 20. Which of the following conditions indicate an acidic solution
at 258C?
d. The H1 from the HCl reacts completely with the A2 from
the NaA. Then the HA dissociates somewhat until “too a. pH 5 3.04
much” H1 and A2 are formed, so the H1 and A2 react to b. [H1] . 1.0 3 1027 M
form HA, and so on. Eventually equilibrium is reached. c. pOH 5 4.51
Justify your choice, and for choices you did not pick, explain d. [OH2] 5 3.21 3 10212 M
what is wrong with them. 21. Which of the following conditions indicate a basic solution at
9. Consider a solution formed by mixing 100.0 mL of 0.10 M 258C?
HA (Ka 5 1.0 3 1026), 100.00 mL of 0.10 M NaA, and a. pOH 5 11.21
100.0 mL of 0.10 M HCl. In calculating the pH for the final
b. pH 5 9.42
solution, you would make some assumptions about the order
in which various reactions occur to simplify the calculations. c. [OH2] . [H1]
State these assumptions. Does it matter whether the reactions d. [OH2] . 1.0 3 1027 M
actually occur in the assumed order? Explain.

Unless otherwise noted, all art on this page is © Cengage Learning 2014.

11097_Ch14_0652-0710.indd 701 9/6/12 9:07 AM

xviii Unless otherwise noted, all art on this page is © Cengage Learning 2014.
 For Review 919
Comprehensive End-of-Chapter Practice and Review 90
problems associated with nuclear reactors? What are the dangers associated with the decay of Sr are much
breeder reactors? What are some problems associated greater than those linked to 85Kr. Why? Although g rays
with breeder reactors? are far more penetrating than a particles, the latter are
10. The biological effects of a particular source of radiation more likely to cause damage to an organism. Why?
depend on several factors. List some of these factors. Which type of radiation is more effective at promoting
Even though 85Kr and 90Sr are both b-particle emitters, the ionization of biomolecules?

A blue question or exercise number indicates that the answer to decays to 176Hf, was used to estimate this age. The half-life of
176
that question or exercise appears at the back of this book and a Lu is 37 billion years. How are ratios of 176Lu to 176Hf uti-
solution appears in the Solutions Guide, as found on PowerLecture. lized to date very old rocks?
7. Why are the observed energy changes for nuclear processes so
Questions
Questions are homework problems directed at concepts
much larger than the energy changes for chemical and physi-
cal processes?
1. When nuclei undergo nuclear transformations, g rays of charac- within the chapter and in general don’t require calculation.
8. Natural uranium is mostly nonfissionable 238U; it contains
teristic frequencies are observed. How does this fact, along with only about 0.7% of fissionable 235U. For uranium to be useful
other information in the chapter on nuclear stability, suggest as a nuclear fuel, the relative amount of 235U must be increased
that a quantum mechanical model may apply to the nucleus? to about 3%. This is accomplished through a gas diffusion pro-
2. There is a trend in the United States toward using coal-fired cess. In the diffusion process, natural uranium reacts with flu-
power plants to generate electricity rather than building new orine to form a mixture of 238UF6(g) and 235UF6(g). The fluo-
nuclear fission power plants. Is the use of coal-fired power ride mixture is then enriched through a multistage diffusion
plants without risk? Make a list of the risks to society from the process to produce a 3% 235U nuclear fuel. The diffusion pro- For Review 445
use of each type of power plant. cess utilizes Graham’s law of effusion (see Chapter 5, Section
3. Which type of radioactive decay has the net effect of changing 5.7). Explain how Graham’s law of effusion allows natural
a neutron into a proton? Which type of decay has the net effect Exercises
uranium to be enriched by the gaseous diffusion process. 30. For each of the following molecules or ions that contain sul-
fur, write the Lewis structure(s), predict the molecular struc-
of turning a proton into a neutron? 9. Much of the research on controlled fusion
In this focuses
section on the
similar prob- are paired.
exercises ture (including bond angles), and give the expected hybrid
4. Consider the following graph of binding energy per nucleon as lem of how to contain the reacting material. Magnetic fields
orbitals for sulfur.
a function of mass number. appear to be the most promisingThe modeLocalized Electron
of containment. WhyModel
is and Hybrid Orbitals
containment such a problem? Why must one resort to mag- a. SO2
17. Use the localized electron model to describe the bonding in
56 netic fields for containment? b. SO3
16
O Fe 84
Kr 119 H2O.
9 Sn 10. A recent study concluded that any amount of radiation expo- c. 2−
12
C 34 205 235 18. Use the localized electron model to describe the bonding in O
Binding energy per nucleon (MeV)

S Tl U sure can cause biological damage. Explain the differences be-

8 CCl4.
14
N 238 tween the two models of radiation damage, the linear model S2O32− S S O
7 4
He U
and the threshold model. 19. Use the localized electron model to describe the bonding in
6 7 H2CO (carbon is the central atom). O
Li
6
Li 20. Use the localized electron model to describe the bonding in
5 Exercises C2H2 (exists as HCCH). d. 2−
4 O O
In this section similar exercises are paired.
3 21. The space-filling models of ethane and ethanol are shown 2−
3 H Radioactive Decay and Nuclear Transformations S2O8 O S O O S O
3
He below.
2 11. Write an equation describing the radioactive decay of each of
2 O O
H the following nuclides. (The particle produced is shown in pa- C
1
rentheses, except for electron capture, where an electron is a H e. SO322
0 Ethane Ethanol
20 40 60 80 100 120 140 160 180 200 220 240 260 reactant.) O f. SO422
(C2H6) (C2H5OH)
Mass number (A) a. 31H (b) g. SF2
b. 83Li (b followed by a) Use the localized electron model to describe the bonding in h. SF4
a. What does this graph tell us about the relative half-lives
c. 74Be (electron capture) ethane and ethanol.
of the nuclides? Explain your answer. i. SF6
d. 85B (positron) 22. The space-filling models of hydrogen cyanide and phosgene
b. Which nuclide shown is the most thermodynamically sta- j. F3SOSF
ble? Which is the least thermodynamically stable? 12. In each of the following radioactive are shown
decay below. supply
processes, k. SF51
c. What does this graph tell us about which nuclides the missing particle.
C 31. Why must all six atoms in C2H4 lie in the same plane?
60
undergo fusion and which undergo fission to become a. Co S 60Ni 1 ? H
more stable? Support your answer. 97 32. The allene molecule has the following Lewis structure:
b. Tc 1 ? S 97Mo O
5. What are transuranium elements and how are they synthesized? c. 99 99
Tc S Ru 1 ? Hydrogen cyanide Phosgene H H
(HCN) (COCl2) N
6. Scientists have estimated that the earth’s crust was formed 239 C C C
d. Pu S 235U 1 ?
4.3 billion years ago. The radioactive nuclide 176Lu, which Cl
H H
Use the localized electron model to describe the bonding in Must all hydrogen atoms lie the same plane? If not, what is
Unless otherwise noted, all art on this page is © Cengage Learning 2014. hydrogen cyanide and phosgene. their spatial relationship? Explain.
23. Give the expected hybridization of the central atom for the 33. Indigo is the dye used in coloring blue jeans. The term navy
molecules or ions in Exercises 83 and 89 from Chapter 8. blue is derived from the use of indigo to dye British naval
24. Give the expected hybridization of the central atom for the uniforms in the eighteenth century. The structure of the indigo
There are numerous Exercises to reinforce stu- molecules or ions in Exercises 84 and 90 from Chapter 8. molecule is
11097_Ch19_0890-0925.indd 919 9/6/12 9:01 AM

dents’ understanding of each section. These prob- 25. Give the expected hybridization of the central atom for the
molecules or ions in Exercise 87 from Chapter 8.
H
O H
H
H C C H
lems are paired and organized by topic so that 26. Give the expected hybridization of the central atom for the
molecules in Exercise 88 from Chapter 8.
C C
C N
C C
C C
instructors can review them in class and assign 27. Give the expected hybridization of the central atom for the
H
C
C
C
N C
C
C
C
H
molecules in Exercises 113 and 114 from Chapter 8.
them for homework. 28. Give the expected hybridization of the central atom for the H H O H
molecules in Exercises 115 and 116 from Chapter 8.
a. How many s bonds and p bonds exist in the molecule?
29. For each of the following molecules, write the Lewis b. What hybrid orbitals are used by the carbon atoms in the
structure(s), predict the molecular structure (including bond indigo molecule?
angles), give the expected hybrid orbitals on the central atom, 34. Urea, a compound formed in the liver, is one of the ways hu-
and predict the overall polarity. mans excrete nitrogen. The Lewis structure for urea is
a. CF4 e. BeH2 i. KrF4
H O H
b. NFFor3 Review 829 f. TeF4 j. SeF6
c. OF2 g. AsF5 k. IF5 H N C N H
d. BF h. KrF2 l. IF3 Using hybrid orbitals for carbon, nitrogen, and oxygen, deter-
ChemWork Problems e. When DG8 for this reaction is negative,3 then Kp is greater
than 1.00. mine which orbitals overlap to form the various bonds in urea.
These multiconcept problems (and additional ones) are found inter- 102. The equilibrium constant for aUnless
certain reaction increases by isa© Cengage Learning 2014.
otherwise noted, all art on this page
actively online with the same type of assistance a student would get factor of 6.67 when the temperature is increased from 300.0 K
from an instructor. to 350.0 K. Calculate the standard change in enthalpy (DH8)
95. Which of the following reactions (or processes) are expected for this reaction (assuming DH8 is temperature-independent).
to have a negative value for DS8?
a. SiF6 1aq2 1 H2 1g2 h 2HF1g2 1 SiF4 1g2
Challenge Problems
11097_Ch09_0415-0452.indd 445 9/6/12 9:08 AM
b. 4Al1s2 1 3O2 1g2 h 2Al2O3 1s2
c. CO 1g2 1 Cl2 1g2 h COCl2 1g2 103. Consider two perfectly insulated vessels. Vessel 1 initially
d. C2H4 1g2 1 H2O 1l2 h C2H5OH 1l2 New ChemWork end-of-chapter problems are now included, with many addi-
contains an ice cube at 08C and water at 08C. Vessel 2 initially
contains an ice cube at 08C and a saltwater solution at 08C.
e. H2O 1s2 h H2O 1l2
96. For rubidium DH8vap 5 69.0 kJ/mol at 6868C, its boiling point.
tional problems available to assign online for more practice.
Consider the process H2O 1s2 S H2O 1l2 .
a. Determine the sign of DS, DSsurr, and DSuniv for the pro-
Calculate DS8, q, w, and DE for the vaporization of 1.00 mole cess in vessel 1.
of rubidium at 6868C and 1.00 atm pressure. b. Determine the sign of DS, DSsurr, and DSuniv for the pro-
97. Given the thermodynamic data below, calculate DS and DSsurr cess in vessel 2.
for the following reaction at 258C and 1 atm: (Hint: Think about the effect that a salt has on the freezing
XeF6 1g2 h XeF4 1s2 1 F2 1g2 point of a solvent.)
104. Liquid water at 258C is introduced into an evacuated, insulated
DH8f (kJ/mol) S8 (J/K ? mol) vessel. Identify the signs of the following thermodynamic func-
tions for the process that occurs: DH, DS, DTwater, DSsurr, DSuniv.
XeF6(g) 2294 300.
XeF4(s) 2251 146 105. Using data from Appendix 4, calculate DH8, DG8, and K (at
F2(g) 0 203 298 K) for the production of ozone from oxygen:
3O2 1g2 m 2O3 1g2
98. Consider the reaction: At 30 km above the surface of the earth, the temperature
H2S1g2 1 SO2 1g2 h 3S1g2 1 2H2O 1l2 is about 230. K and the partial pressure of oxygen is about
Unless otherwise noted, all art on this page is © Cengage Learning
for which DH is 2233 kJ and DS is 2424 J/K.
2014. 1.0 3 1023 atm. Estimate the partial pressure of ozone in equi- xix
librium with oxygen at 30 km above the earth’s surface. Is it
a. Calculate the free energy change for the reaction (DG) at reasonable to assume that the equilibrium between oxygen
393 K. and ozone is maintained under these conditions? Explain.
b. Assuming DH and DS do not depend on temperature, at 106. Entropy can be calculated by a relationship proposed by
what temperatures is this reaction spontaneous? Ludwig Boltzmann:
99. The following reaction occurs in pure water:
 Wealth of End-of-Chapter Problems The text offers an unparalleled variety of end-of-
chapter content with problems that increase in rigor and integrate multiple concepts.
For Review 785

10 ) and the over-

219
98. The Hg 21
(1.0 3 1013), calcu-
ant for the following
21
1aq2 1 2OH2 1aq2
ant you calculated
mol/L) of Cu(OH)2
ntration of OH2 is
s in each of the fol-
4 say that Ba(OH)2, Challenge Problems
soluble hydroxides.
f each of these mar-
99. The copper(I) ion forms a complex ion with CN2 according to
ormation, we ran the Cu 1aq2 1 3CN 1aq2 m Cu 1CN2 3 1aq2
then let some of the
ibrium. To see why,
Equilibrium
entration (mol/L) 100. Consider a solution made by HClmixing
5 3.75 3 1023 2 y
6.25 3 1022 2 2y
Ag 1aq2 1 NH3 1aq2 m AgNH
AgNH31 1aq2 1 NH3 1aq2 m Agmine
101. a. Calculate the molar solubility of AgBr in pure water. Ksp
nes) are found inter-
a student would get
Ag1 1aq2 1 2NH3 1aq2 h 3.50
)2(s) is 1.3 3 10232
lt. Ignore any poten-
east soluble to most
the ions with water.
102. Calculate the equilibrium concentrations of NH3, Cu ,
ate the solubility of
022-M KIO3 solution
ue for Pb(IO3)2(s).
) is added to 50.0 mL
at equilibrium in the
7 3 1028.]
014.
ion forms complex ions with I as follows:
2
For Review 551
Hg21 1aq2 1 I2 1aq2 m HgI1 1aq2 K1 5 1.0 3 108
HgI1 1aq2 1 I2 1aq2 m HgI2 1aq2 K2 5 1.0 3 105 a. What­fraction­of­the­moles­of­NaCl­in­this­solution­exist­ t­emperature­ of­ the­ solution.­The­ vapor­ at­ equilibrium­ above­
HgI2 1aq2 1 I2 1aq2 m HgI32 1aq2 K3 5 1.0 3 109 as­ion­pairs? the­solution­has­double­the­mole­fraction­of­substance­A­that­
the­solution­does.­What­is­the­mole­fraction­of­liquid­A­in­the­
HgI32 1aq2 1I 2
1aq2 m HgI4 22
1aq2 K4 5 1.0 3 10 8 b. Calculate­the­freezing­point­that­would­be­observed­for­
this­solution. solution?
A solution is prepared by dissolving 0.088 mole of Hg(NO3)2
123. The­ vapor­ in­ equilibrium­ with­ a­ pentane–hexane­ solution­ at­ 129. In­some­regions­of­the­southwest­United­States,­the­water­is­
and 5.00 mole of NaI in enough water to make 1.0 L of
258C­ has­ a­ mole­ fraction­ of­ pentane­ equal­ to­ 0.15­ at­ 258C.­ very­hard.­For­example,­in­Las­Cruces,­New­Mexico,­the­tap­
solution.
What­is­the­mole­fraction­of­pentane­in­the­solution?­(See­Ex- water­contains­about­560­mg­of­dissolved­solids­per­milliliter.­
a. Calculate the equilibrium concentration of [HgI422].
ercise­57­for­the­vapor­pressures­of­the­pure­liquids.) Reverse­ osmosis­ units­ are­ marketed­ in­ this­ area­ to­ soften­­
b. Calculate the equilibrium concentration of [I2]. water.­A­­typical­unit­exerts­a­pressure­of­8.0­atm­and­can­pro-
124. A­forensic­chemist­is­given­a­white­solid­that­is­suspected­of­
c. Calculate the equilibrium concentration of [Hg ]. 21
duce­45­L­­­water­per­day.
being­pure­cocaine­(C17H21NO4,­molar­mass­5­303.35­g/mol).­
a. Assuming­all­of­the­dissolved­solids­are­MgCO3­and­
Challenge Problems take students one step She­ dissolves­ 1.22­ 6­ 0.01­ g­ of­ the­ solid­ in­ 15.60­ 6­ 0.01­ g­
benzene.­The­freezing­point­is­lowered­by­1.32­6­0.048C. assuming­a­temperature­of­278C,­what­total­volume­of­
water­must­be­processed­to­produce­45­L­pure­water?
further and challenge them more rigorously thana. What­is­the­molar­mass­of­the­substance?­Assuming­that­
the­percent­uncertainty­in­the­calculated­molar­mass­is­the­ b. Would­the­same­system­work­for­purifying­seawater?­
the following equation: (Assume­seawater­is­0.60­M­NaCl.)
1 2 22
K 5 1.0 3 10 11 the Additional Exercises. same­as­the­percent­uncertainty­in­the­temperature­
change,­calculate­the­uncertainty­in­the­molar­mass.
a. Calculate the solubility of CuBr(s) (Ksp 5 1.0 3 1025) in b. Could­the­chemist­unequivocally­state­that­the­substance­ Integrative Problems
1.0 L of 1.0 M NaCN. is­cocaine?­For­example,­is­the­uncertainty­small­enough­
to­distinguish­cocaine­from­codeine­(C18H21NO3,­molar­ These­problems­require­the­integration­of­multiple­concepts­to­find­
b. Calculate the concentration
188 of Br2 at equilibrium.
Chapter 4 Types of Chemical Reactions and Solution Stoichiometry
mass­5­299.36­g/mol)? the­solutions.
c. Calculate the concentration of CN2 at equilibrium.
c. Assuming­that­the­absolute­uncertainties­in­the­measure- 130. Creatinine,­C4H7N3O,­is­a­by-product­of­muscle­metabolism,­
for 1 500.0 mL of 4.0
neutralization. M NH3the molarity of the original
Calculate here. If the percent yield of the reaction was 88.0%, what mass and­ creatinine­ levels­ in­ the­ body­ are­ known­ to­ be­ a­ fairly­
ments­of­temperature­and­mass­remain­unchanged,­how­
and 500.0 mL of 0.40 M AgNO sample3. Ag of H reacts with NH3 to form of chromium(III) chromate wascould­the­chemist­improve­the­precision­of­her­results?
isolated?
2SO4. Sulfuric acid has two acidic hydrogens. ­reliable­indicator­of­kidney­function.­The­normal­level­of­cre-
AgNH31 and Ag(NH3)21:
136. A 6.50-g sample of a diprotic acid requires 137.5 mL of a 142. The vanadium in a sample of ore is converted to VO21. The
125. A­1.60-g­sample­of­a­mixture­of­naphthalene­(C 10H8)­and­an-
atinine­ in­ the­ blood­ for­ adults­ is­ approximately­ 1.0­ mg­ per­
1
0.7503 M
1
1aq2NaOH solutionK1 5 2.1 10 3
for3complete neutralization. Deter- VO21 ion is subsequently titrated with 14
thracene­(C MnO 4 in acidic solu-
2
H10)­is­dissolved­in­20.0­g­benzene­(C 6H6).­The­
deciliter­(dL)­of­blood.­If­the­density­of­blood­is­1.025­g/mL,­
1NH3the 2 21molar
1aq2 mass K2 of
5 the
8.2 acid.
3 103 tion to form V(OH)41 and manganese(II) ion. The unbalanced
freezing­point­of­the­solution­is­2.818C.­What­is­the­composi- calculate­the­molality­of­a­normal­creatinine­level­in­a­10.0-mL­
blood­sample.­What­is­the­osmotic­pressure­of­this­solution­at­
137. Citric
Determine the concentration of allacid,
species which
in solution.
molecular formula C6H8O7. A 0.250-g sample of citric acid
Integrative Problems combine concepts from
can be obtained from lemon juice, has the titration reaction is tion­as­mass­percent­of­the­sample­mixture?­The­freezing­point­
MnO42 1aq2 1 VO21 1aq2 1of­benzene­is­5.518C­and­K
H2O 1l2 h f­is­5.128C­?­kg/mol.
25.08C?
for AgBr is 5.0 3 10213.
dissolved in 25.0 mL of water requires 37.2 mL of 0.105 M
NaOH for complete neutralization. What number of acidic hy-
multiple chapters. 126.
V 1OH2 4 1aq2 1 Mn 1aq2 1 H 1aq2
A­solid­mixture­contains­MgCl
1 21 1 ­and­NaCl.­When­0.5000­g­of­
2
this­solid­is­dissolved­in­enough­water­to­form­1.000­L­of­solu-
131. An­ aqueous­ solution­ containing­ 0.250­ mole­ of­ Q,­ a­ strong­
electrolyte,­in­5.00­3­102­g­water­freezes­at­22.798C.­What­is­
b. Calculate the molar solubility of AgBr in 3.0 Mdoes
NH3.citric
The acid have? To titrate the solution, 26.45 mL of 0.02250 M MnO42 was the­van’t­Hoff­factor­for­Q?­The­molal­freezing-point­depres-
drogens per molecule tion,­the­osmotic­pressure­at­25.08C­is­observed­to­be­0.3950­
overall formation constant for Ag(NH3)21 is 1.7 3 107, required. If the mass percent of vanadium in the ore was sion­constant­for­water­is­1.868C­?­kg/mol.­What­is­the­formula­
138. A stream flows at a rate of 5.00 3 104 liters per second (L/s) atm.­What­is­the­mass­percent­of­MgCl2­in­the­solid?­(Assume­
that is, 58.1%, what was the mass of the ore sample? Hint: Balance of­Q­if­it­is­38.68%­chlorine­by­mass­and­there­are­twice­as­
upstream of a manufacturing plant. The plant discharges ideal­­behavior­for­the­solution.)
the titration reaction by the oxidation states method. many­anions­as­cations­in­one­formula­unit­of­Q?
Ag 1NH 3 10 32 2 L/s
31 1aq2
of water 107. 65.0 ppm HCl into the
that3contains
K 5 1.7 127. Formic­acid­(HCO2H)­is­a­monoprotic­acid­that­ionizes­only­
143. The unknown acid H2X can be neutralized completely by 132. Anthraquinone­contains­only­carbon,­hydrogen,­and­oxygen.­
stream. (See Exercise
c. Compare the calculated solubilities from parts a and b. 121 for definitions.) partially­in­aqueous­solutions.­A­0.10-M­formic­acid­solution­
OH2 according to the following (unbalanced) equation: When­ 4.80­ mg­ anthraquinone­ is­ burned,­ 14.2­ mg­ CO2­ and­
Explain any differences.a. Calculate the stream’s total flow rate downstream from is­4.2%­ionized.­Assuming­that­the­molarity­and­molality­of­
this plant. H2X 1aq2 1 OH2 1aq2the­solution­are­the­same,­calculate­the­freezing­point­and­the­
h X22 1aq2 1 H2O 1l2 1.65­mg­H2O­are­produced.­The­freezing­point­of­camphor­is­
d. What mass of AgBr will dissolve in 250.0 mL of 3.0 M lowered­by­22.38C­when­1.32­g­anthraquinone­is­dissolved­in­
b. Calculate the concentration of HCl in ppm downstream The ion formed as a product, boiling­point­of­0.10­M­formic­acid.
X22, was shown to have 36 total
NH3? 11.4­g­camphor.­Determine­the­empirical­and­molecular­for-
fromhave this onplant. 128. You­have­a­solution­of­two­volatile­liquids,­A­and­B­(assume­
electrons. What is element X? Propose a name for H2X. To
e. What effect does adding HNO 3 the solubilities mulas­of­anthraquinone.
completely neutralize a sampleideal­behavior).­Pure­liquid­A­has­a­vapor­pressure­of­350.0­torr­
of H2X, 35.6 mL of 0.175 M
calculated in parts a andc.b? Further downstream, another manufacturing plant diverts
1.80 3 10 4
L/s of water from21the stream for its own use.
OH2 solution was required.and­ Whatpure­ liquid­
was the B­ has­of
mass a­ vapor­
the H2pressure­
X of­ 100.0­ torr­ at­ the­
This) plant must first neutralize sample used?
Cu(NH3)21, Cu(NH3)221, Cu(NH 21
3 3 , and Cu(NH3)4
21
in a the acid and does so by
solution prepared by mixing 500.0 addingmL lime:
of 3.00 M NH with
3
500.0 mL of 2.00 3 1023 M Cu(NO 3)2. 1s2
CaO 2H1 1aq2equilib-
The1stepwise h Ca21 1aq2 1 H2O 1l2 Marathon Problems
ria are What mass of CaO is consumed in an 8.00-h work day by
These problems are designed to incorporate several concepts and
Cu21 1aq2 1 NH3 1aq2 m this CuNH
plant? 21 1aq2
3 techniques into one situation.
d. The original stream water3contained
K1 5 1.86 104 10.2 ppm Ca21.
144. Three students were asked to find the identity of the metal in a
Although no calcium was in the waste water from the first
CuNH3 21
1aq2 1 NH3 1aq2 m Cu 1NH 32 2 1aq2
21
particular sulfate salt. They dissolved a 0.1472-g sample of the
plant, the waste water of the second plant contains Ca21
K2 5 3.88 3 103 salt in water and treated it with excess barium chloride, result-
from the neutralization process. If 90.0% of the water
Cu 1NH32 221 1aq2 1 NH3 1aq2 m ing in the precipitation of barium sulfate. After the precipitate
usedCuby1NH 2 321 1aq2plant is returned to the stream, calcu-
the3second
21 3 had been filtered and dried, it weighed 0.2327 g.
late the concentration
K3 5 1.00 of 3
Ca10 in ppm downstream of the
Each student analyzed the data independently and came to
Cu 1NH32 321 1aq2 1 NH3 1aq2 m second plant.2 21 1aq2
Cu 1NH 3 4 different conclusions. Pat decided that the metal was titanium.
139. It took 25.06 60.05 mL of a
K4 5 1.55 3 10 sodium
2 hydroxide solution to ti- Chris thought it was sodium. Randy reported that it was gal-
trate a 0.4016-g sample of KHP (see Exercise 77). Calculate lium. What formula did each student assign to the sulfate salt?
the concentration and uncertainty in the concentration of the Look for information on the sulfates of gallium, sodium, and
sodium hydroxide solution. (See Appendix 1.5.) Neglect any
uncertainty in the mass.
titanium in this text and reference books such as the CRC
Handbook of Chemistry and Physics. What further tests would
Marathon Problems also combine con-
you suggest to determine Unlesswhich student
otherwise noted, allis
artmost
on thislikely correct?
page is © Cengage Learning 2014. cepts from multiple chapters; they are the
Integrative Problems 145. You have two 500.0-mL aqueous solutions. Solution A is a

These problems require the integration of multiple concepts to find

9/6/12 9:11 AM
the solutions.
140. Tris(pentafluorophenyl)borane, commonly known by its acro-
nym BARF, is frequently used to initiate polymerization of
ethylene or propylene in the presence of a catalytic transition
metal compound. It is composed solely of C, F, and B; it is
42.23% C and 55.66% F by mass.
a. What is the empirical formula of BARF?
b. A 2.251-g sample of BARF dissolved in 347.0 mL of
solution produces a 0.01267-M solution. What is the
molecular formula of BARF?
141. In a 1-L beaker, 203 mL of 0.307 M ammonium chromate was
mixed with 137 mL of 0.269 M chromium(III) nitrite to pro-
duce ammonium nitrite and chromium(III) chromate. Write
the balanced chemical equation for the reaction occurring
solution of a metal nitrate that is 8.246% nitrogen by mass. most challenging problems in the end-of-
The ionic compound in solution B consists of potassium, chro-
mium, and oxygen; chromium has an oxidation state of 16 chapter material.
and there are 2 potassiums and 1 chromium in the formula.
11097_Ch11_0510-0551.indd 551 9/6/12 9:10 AM
The masses of the solutes in each of the solutions are the same.
When the solutions are added together, a blood-red precipitate
forms. After the reaction has gone to completion, you dry the
solid and find that it has a mass of 331.8 g.
a. Identify the ionic compounds in solution A and solution B.
b. Identify the blood-red precipitate.
c. Calculate the concentration (molarity) of all ions in the
original solutions.
d. Calculate the concentration (molarity) of all ions in the
final solution.
Marathon Problems can be used in class by groups of students to
help facilitate problem-solving skills.

Unless otherwise noted, all art on this page is © Cengage Learning 2014.

11097_Ch04_0138-0188.indd 188 9/6/12 9:00 AM

“The end-of-chapter content helps students identify and review the central concepts.
There is an impressive range of problems that are well graded by difficulty.”
—AlanM.Stolzenberg,West Virginia University

xx Unless otherwise noted, all art on this page is © Cengage Learning 2014.
 About the Authors

Steven S. Zumdahl earned a B.S. in Chemistry from

Wheaton College (IL) and a Ph.D. from the University of
Illinois, Urbana-Champaign. He has been a faculty member
at the University of Colorado–Boulder, Parkland College
(IL), and the University of Illinois at Urbana-Champaign
(UIUC), where he is Professor Emeritus. He has received
numerous awards, including the National Catalyst Award for
Excellence in Chemical Education, the University of Illinois
Teaching Award, the UIUC Liberal Arts and Sciences Award
for Excellence in Teaching, UIUC Liberal Arts and Sci-
ences Advising Award, and the School of Chemical Sciences
Teaching award (five times). He is the author of several
chemistry textbooks. In his leisure time he enjoys traveling
and collecting classic cars.

Susan A. Zumdahl earned a B.S. and M.A. in Chemistry at

California State University–Fullerton. She has taught sci-
ence and mathematics at all levels, including middle school,
high school, community college, and university. At the
University of Illinois at Urbana-Champaign, she developed
a program for increasing the retention of minorities and
women in science and engineering. This program focused
on using active learning and peer teaching to encourage
students to excel in the sciences. She has coordinated and
led workshops and programs for science teachers from
elementary through college levels. These programs encour-
age and support active learning and creative techniques for
teaching science. For several years she was director of
an Institute for Chemical Education (ICE) field center in
Southern California, and she has authored several chem-
istry textbooks. Susan spearheaded the development of a
sophisticated web-based electronic homework system for
teaching chemistry. She enjoys traveling, classic cars, and
gardening in her spare time—when she is not playing with
her grandchildren.

Unless otherwise noted, all art on this page is © Cengage Learning 2014. xxi
 Chapter 1

Chemical Foundations
1.1 Chemistry: An Overview 1.4 Uncertainty in Measurement 1.7 Dimensional Analysis
Science: A Process for Understanding Precision and Accuracy 1.8 Temperature
Nature and Its Changes 1.5 Significant Figures and 1.9 Density
1.2 The Scientific Method Calculations
1.10 Classification of Matter
Scientific Models 1.6 Learning to Solve Problems
1.3 Units of Measurement Systematically

A high-performance race car uses chemistry for its structure, tires, and fuel. (© Maria Green/Alamy)

Unless otherwise noted, all art on this page is © Cengage Learning 2014. 1
 W hen you start your car, do you think about chemistry? Probably not, but you
should. The power to start your car is furnished by a lead storage battery.
How does this battery work, and what does it contain? When a battery goes dead, what
does that mean? If you use a friend’s car to “jump-start” your car, did you know that
your battery could explode? How can you avoid such an unpleasant possibility? What
is in the gasoline that you put in your tank, and how does it furnish energy to your car
so that you can drive it to school? What is the vapor that comes out of the exhaust pipe,
and why does it cause air pollution? Your car’s air conditioner might have a substance
in it that is leading to the destruction of the ozone layer in the upper atmosphere. What
are we doing about that? And why is the ozone layer important anyway?
All of these questions can be answered by understanding some chemistry. In fact,
we’ll consider the answers to all of these questions in this text.
Chemistry is around you all the time. You are able to read and understand this sen-
tence because chemical reactions are occurring in your brain. The food you ate for
breakfast or lunch is now furnishing energy through chemical reactions. Trees and
grass grow because of chemical changes.
Chemistry also crops up in some unexpected places. When archaeologist Luis
Alvarez was studying in college, he probably didn’t realize that the chemical elements
iridium and niobium would make him very famous when they helped him solve the
problem of the disappearing dinosaurs. For decades scientists had wrestled with the
mystery of why the dinosaurs, after ruling the earth for millions of years, suddenly
became extinct 65 million years ago. In studying core samples of rocks dating back to
that period, Alvarez and his coworkers recognized unusual levels of iridium and nio-
bium in these samples—levels much more characteristic of extraterrestrial bodies than
of the earth. Based on these observations, Alvarez hypothesized that a large meteor hit
the earth 65 million years ago, changing atmospheric conditions so much that the
dinosaurs’ food couldn’t grow, and they died—almost instantly in the geologic
timeframe.
Chemistry is also important to historians. Did you realize that lead poisoning prob-
ably was a significant contributing factor to the decline of the Roman Empire? The
Romans had high exposure to lead from lead-glazed pottery, lead water pipes, and a
sweetening syrup called sapa that was prepared by boiling down grape juice in lead-
lined vessels. It turns out that one reason for sapa’s sweetness was lead acetate (“sugar
of lead”), which formed as the juice was cooked down. Lead poisoning, with its symp-
toms of lethargy and mental malfunctions, certainly could have contributed to the de-
mise of the Roman society.
Chemistry is also apparently very important in determining a person’s behavior.
Various studies have shown that many personality disorders can be linked directly
to imbalances of trace elements in the body. For example, studies on the inmates at
Stateville Prison in Illinois have linked low cobalt levels with violent behavior. Lith-
ium salts have been shown to be very effective in controlling the effects of manic-
depressive disease, and you’ve probably at some time in your life felt a special “chem-
istry” for another person. Studies suggest there is literally chemistry going on between
two people who are attracted to each other. “Falling in love” apparently causes changes
in the chemistry of the brain; chemicals are produced that give that “high” associated
with a new relationship. Unfortunately, these chemical effects seem to wear off over
time, even if the relationship persists and grows.
The importance of chemistry in the interactions of people should not really surprise
us. We know that insects communicate by emitting and receiving chemical signals
via molecules called pheromones. For example, ants have a very complicated set of
chemical signals to signify food sources, danger, and so forth. Also, various female sex
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 1.1 Chemistry: An Overview 3

attractants have been isolated and used to lure males into traps to control insect popu-
lations. It would not be surprising if humans also emitted chemical signals that we
were not aware of on a conscious level. Thus chemistry is pretty interesting and pretty
important. The main goal of this text is to help you understand the concepts of chem-
istry so that you can better appreciate the world around you and can be more effective
in whatever career you choose.

1.1 Chemistry: An Overview

Since the time of the ancient Greeks, people have wondered about the answer to the
question: What is matter made of? For a long time, humans have believed that matter is
composed of atoms, and in the previous three centuries, we have collected much indi-
rect evidence to support this belief. Very recently, something exciting has happened—
for the first time we can “see” individual atoms. Of course, we cannot see atoms with
the naked eye; we must use a special microscope called a scanning tunneling micro-
scope (STM). Although we will not consider the details of its operation here, the STM
uses an electron current from a tiny needle to probe the surface of a substance. The
STM pictures of several substances are shown in Fig. 1.1. Notice how the atoms are
connected to one another by “bridges,” which, as we will see, represent the electrons
that interconnect atoms.
So, at this point, we are fairly sure that matter consists of individual atoms. The
nature of these atoms is quite complex, and the components of atoms don’t behave
much like the objects we see in the world of our experience. We call this world the
macroscopic world—the world of cars, tables, baseballs, rocks, oceans, and so forth.
One of the main jobs of a scientist is to delve into the macroscopic world and discover
its “parts.” For example, when you view a beach from a distance, it looks like a con-
tinuous solid substance. As you get closer, you see that the beach is really made up of
individual grains of sand. As we examine these grains of sand, we find that they are
composed of silicon and oxygen atoms connected to each other to form intricate shapes
(Fig. 1.2). One of the main challenges of chemistry is to understand the connection
between the macroscopic world that we experience and the microscopic world of
atoms and molecules. To truly understand chemistry, you must learn to think on the
atomic level. We will spend much time in this text helping you learn to do that.

Lawrence Livermore Laboratory/Science Photo Library/Photo

Lawrence Berkeley National Laboratory/MCT

Researchers, Inc.

Figure 1.1 | Scanning tunneling An image showing the individual carbon Scanning tunneling microscope image
microscope images. atoms in a sheet of graphene. of DNA.
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Another random document with
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Westermarck that he had suffered from painful boils through entering
a granary in a state of uncleanness.57.1 The same rule applies in
Morocco to a vegetable garden. Only the sexually clean may enter it,
otherwise both the vegetables and the person entering would be the
worse for it.57.2
The Dinkas of the Upper Nile believe that incest
Incest supposed by angers the ancestral spirits (jok), who punish the
the Dinkas to be
punished with girl by making her barren. Even should she marry,
sterility. she will have no children until she has confessed
her sin, and atonement has been made for it. Her
lover must provide a bullock for sacrifice. His father kills the animal,
and the girl’s father takes some of the contents of the large intestine
and smears it on his daughter’s abdomen and on that of her guilty
partner. Thus the taint of sin is removed, and the woman is rendered
capable of bearing children.57.3 The Maloulekes and Hlengoues, two
tribes of Southern Africa to the north of the Thonga, think that if a
young man gets a girl, who is not his wife, with child, people will die
in the village. Hence, when the girl’s pregnancy is discovered, the
lover has to provide a girl by way of fine.57.4
It is very remarkable, however, that among
Incest enjoined in tribes which strongly disapprove of incestuous
certain cases as a
mode of ensuring relations in general, the act of incest is
good luck. nevertheless positively enjoined in certain
circumstances as a mode of ensuring good luck.
Thus in the Thonga tribe of South-Eastern Africa, round about
Delagoa Bay, there is a class of men who devote themselves to the
business of hunting hippopotamuses on the rivers. In the pursuit of
their trade they observe a number of curious superstitions which
have been handed down among them for generations from father to
son. For example, they inoculate themselves with a certain drug
which is supposed to endow them with such a power over the
hippopotamuses that when the hunter wounds one of them the
animal cannot go far away and the man can track and despatch it.
During the day the hunter fishes in the river, keeping his eye all the
time on the unwieldy monsters disporting themselves in the water or
lumbering through the thickets on the banks. “When he sees that the
propitious season has come and when he is ready to undertake a
 hunting expedition of one month, he first calls his
Incest of Thonga own daughter to his hut and has sexual relations
hippopotamus
hunter with his with her. This incestuous act, which is strongly
daughter. taboo in ordinary life, has made of him a
‘murderer’: he has killed something at home; he
has acquired the courage for doing great deeds on the river.
Henceforth he will have no sexual relations with his wives during the
whole campaign. On the same night, immediately after the act, he
starts with his sons; they close the drift where the beasts leave the
river by putting a canoe across the track.” Meantime the
hippopotamuses are browsing in the forest or trampling down the
crops of the fields in their clumsy fashion. As they come trooping
back to the river they are stopped by the canoe in the path, and
while they are examining the strange obstacle, the hunters, lying in
ambush, dart their spears into the thick hides of the beasts. The
handles of the spears are loosely attached to the blades, but
connected with them by a long string, so that when the wounded
monster, crashing irresistibly in his rage through the thicket, plunges
into the river and sinks out of sight in the water, the handle of the
spear becomes detached from the blade and floats like a buoy on
the surface, shewing the direction taken by the beast. As soon as the
hunter has thrown his spear he runs home to tell his wife. She must
at once shut herself up in the hut and remain perfectly quiet, without
eating or drinking or crushing her mealies; for were she to do any of
these things, the wounded hippopotamus would shew fight and
might kill her husband, whereas if she keeps quiet, the animal will be
quiet too. All the hunters in the village are then called up, and
embarking in a canoe, paddle away after their prey, whose retreat is
marked by the bobbing of the spear-handle on the surface of the
water and the occasional emergence of a great flat snout to breathe.
When the beast has been despatched, and the carcase landed on
the bank, it is turned on its back and the hunter creeps between its
legs from behind and along its belly and chest as far as the mouth.
Then he goes away. By this ceremony the man is supposed to take
upon himself the defilement, possibly the nature, of the animal, so
that in future when he meets hippopotamuses the animals will not
perceive him to be a man but will mistake him for an hippopotamus;
and thus he will be able to slaughter the deluded creatures with
impunity.59.1
So far as we can guess at the meaning of these
Suggested curious rites, their general intention seems to be to
explanation of the
Thonga practice. identify the hunter and his family with the game
which he hunts in order to give him full power over
the animals. This intention is manifested in the behaviour of the
hunter’s wife while the hippopotamus is wounded; she so far
identifies herself with the animal that whatever she does he is
supposed to do. If she goes about her work briskly and refreshes
herself with food and drink, the hippopotamus also will be brisk and
refreshed, and will give warm work to his pursuers; whereas if she
keeps perfectly still, the animal will make no resistance but follow the
hunters like a sheep to the slaughter. Perhaps the same train of
thought partially explains the incest which the hunter has to commit
with his own daughter before he sets out for the chase. Can it be that
by this violence done to his offspring he is supposed to acquire
power over the beast? It may be so, yet it is difficult to see why the
violence should take this particular form, and why, on the principles
of homoeopathic or imitative magic, a pretence of wounding and
killing the girl with a spear would not have served his turn better.
Another tribe of savages who imagine that in
Incest prescribed certain circumstances incest is the road to fortune
among the
Antambahoaka of are the Antambahoaka of South-Eastern
Madagascar. Madagascar. Before setting out for the chase or
the fishing or war or other enterprise, every
Antambahoaka arranges to have sexual relations with his sister or
with his nearest female relation; he thinks in this way to ensure the
success of his expedition.59.2 What the exact train of thought may be
which prompts these exceptional and deliberate aberrations from the
usual rules of morality, it is difficult to understand; I mention the facts
because they apparently contradict the ordinary savage view of
conduct, and so far help us to perceive how little as yet we really
know about the inmost workings of the savage mind.
Leaving out of account these remarkable and as
Similar beliefs as to
the disastrous effect
yet not fully explained exceptions to the rule,60.1
of sexual crimes we may say generally that among many savage
among the civilized races breaches of the marriage laws are believed
peoples of antiquity.
to draw down on the community public calamities
of the most serious character, and that in particular they are thought
to blast the fruits of the earth through excessive rain or excessive
drought. Traces of similar beliefs may perhaps be detected among
the civilized races of antiquity. Thus among the
The Hebrews. Hebrews we read how Job, passionately
protesting his innocence before God, declares that
he is no adulterer; “For that,” says he, “were an heinous crime; yea it
were an iniquity to be punished by the judges: for it is a fire that
consumeth unto Destruction, and would root out all mine
increase.”60.2 In this passage the Hebrew word translated “increase”
commonly means “the produce of the earth”;60.3 and if we give the
word its usual sense here, then Job affirms adultery to be destructive
of the fruits of the ground, which is precisely what many savages still
believe. This interpretation of his words is strongly confirmed by two
narratives in Genesis, where we read how Sarah, Abraham’s wife,
was taken by a king into his harem, and how thereafter God visited
the king and his household with great plagues, especially by closing
up the wombs of the king’s wife and his maid-servants so that they
bare no children. It was not till the king had discovered and
confessed his sin, and Abraham had prayed God to forgive him, that
the king’s women again became fruitful.61.1 These narratives seem
to imply that adultery, even when it is committed in ignorance, is a
cause of plague and especially of sterility among women. Again, in
Leviticus, after a long list of sexual crimes, we read:61.2 “Defile not ye
yourselves in any of these things: for in all these the nations are
defiled which I cast out from before you: and the land is defiled:
therefore I do visit the iniquity thereof upon it, and the land vomiteth
out her inhabitants.” This passage seems to imply that the land itself
was somehow physically affected by sexual transgressions in such a
way that it could no longer support the inhabitants.
The Greeks. Apparently the ancient Greeks entertained a
similar view of the wasting effect of incest; for
according to Sophocles the land of Thebes suffered from blight,
pestilence, and the sterility both of women and cattle under the reign
of Oedipus, who had unwittingly slain his father and married his
mother; the country was emptied of its inhabitants, and the Delphic
oracle declared that the only way to restore prosperity to it was to
banish the sinner.61.3 No doubt the poet and his hearers set down
these public calamities in part to the guilt of parricide which rested on
Oedipus; but probably they also laid much of the evil at the door of
the incest which he had committed with his mother. In the reign of
the emperor Claudius a Roman noble was
The Romans. accused of incest with his sister. He committed
suicide, his sister was banished, and the emperor
ordered that certain ancient ceremonies derived from the laws of
King Servius Tullius should be performed, and that expiation should
be made by the pontiffs at the sacred grove of Diana.61.4 As Diana
appears to have been a goddess of fertility in general and of the
fruitfulness of women in particular,62.1 the expiation for incest offered
at her sanctuary may perhaps be accepted as evidence that the
Romans, like other peoples, attributed to sexual immorality a
tendency to blast the fruits both of the earth and of the womb.
According to an ancient Irish legend Munster
Blighting effect was afflicted in the third century of our era with a
attributed to incest
by the ancient Irish. failure of the crops and other misfortunes. When
the nobles enquired into the matter, they learned
that these calamities were the result of an incest which the king had
committed with his sister. In order to put an end to the evil they
demanded of the king his two sons, the fruit of this unholy union, that
they might consume them with fire and cast their ashes into the
running stream.62.2 Again, Irish legend relates that Cairbre Musc
“had two sons by his sister. Her name was Duben, and theirs were
Corc and Cormac respectively. The children were twins, and the
story of their birth is no less strange than that of Dylan and Llew, for
one of them was found to have nipped off his brother’s ears before
his birth. The crime of their parents caused the crops to fail, which,
according to the idea prevalent in ancient Ireland, was its natural
result, and Cairbre was obliged to confess his guilt to the nobles of
his realm, who, when the children were born, ordered them to be
burnt, that the incest might not remain in the land. ‘Give me,’ said
Cairbre’s druid, ‘that Corc62.3 there, that I may place him outside
Erinn, so that the incest may not be within it.’ Corc was given to the
druid, and the latter, with his wife, whose name was Bói, took him to
an island. They had a white cow with red ears, and an ablution was
performed by them every morning on Corc, placed on the cow’s
back; so in a year’s time to the day the cow sprang away from them
into the sea, and she became a rock in it; to wit, the heathenism of
the boy had entered into her. Bó Búi, or Bói’s Cow, is the name of
the rock, and Inis Búi, or Bói’s Isle, that of the island. The boy was
afterwards brought back into Erinn. Such is the story how Corc was
purged of the virulence of his original sin, and the scene is one of the
three islets called the Bull, the Cow and the Calf, not far from Dursey
Island, in the gulf called Kenmare River.”63.1
Thus it appears that in the opinion of many
Thus sexual peoples sexual irregularities, whether of the
irregularities are
often supposed to married or the unmarried, are not merely moral
endanger the whole offences which affect only the few persons
community. immediately concerned; they are believed to
involve the whole people in danger and disaster
either directly by a sort of magical influence or indirectly by rousing
the wrath of gods to whom these acts are offensive. Nay they are
often supposed to strike a blow at the very existence of the
community by blighting the fruits of the earth and thereby cutting off
the food supply. Wherever these superstitions prevail, it is obvious
that public opinion and public justice will treat sexual offences with
far greater severity than is meted out to them by peoples who, like
most civilized nations, regard such misdemeanours as matters of
private rather than of public concern, as sins rather than crimes,
which may perhaps affect the eternal welfare of the individual sinner
in a life hereafter, but which do not in any way imperil the temporal
welfare of the innocent community as a whole.
Hence the extreme And conversely, wherever we find that incest,
rigour with which
sexual crimes have adultery, and fornication are treated by the
been punished by community with extreme rigour, we may
many races. reasonably infer that the original motive for such
treatment was superstition; in other words, that
wherever a tribe or nation, not content with leaving these
transgressions to be avenged by the injured parties, has itself
punished them with exceptional severity, the reason for doing so has
probably been a belief that the effect of all such delinquencies is to
disturb the course of nature and thereby to endanger the whole
people, who accordingly must protect themselves by effectually
disarming and, if necessary, exterminating the delinquents. This may
explain, for example, why the Indian Laws of Manu
Ancient codes. decreed that an adulteress should be devoured by
dogs in a public place, and that an adulterer
should be roasted to death on a red-hot iron bed;64.1 why the
Babylonian code of Hammurabi sentenced an adulterous couple to
be strangled and cast into the river; and why the same code
punished incest with a mother by burning both the culprits.64.2 On the
same supposition we can understand the severity of the
punishments meted out to certain sexual offences by the Mosaic law.
Thus, for example, under it an adulteress and her paramour were
sentenced to death:64.3 a woman who at marriage was found not to
be a maid was stoned:64.4 the unchaste daughter of a priest was
burned with fire;64.5 and if a man married a woman and her daughter,
he and they were in like manner doomed to the flames.64.6
Many African tribes repress sexual crimes by
Rigorous penalties rigorous penalties, or did so until their moral
inflicted in Africa.
standard was modified by contact with Europeans.
Among the Baganda of Central Africa, “though
The Baganda, their death was usually the punishment inflicted for
punishments for
breaches of sexual adultery, an offender’s life would sometimes be
morality. spared, and he be fined two women, if he were
able to pay them; the culprit was, however,
maimed; he lost a limb, or had an eye gouged out, and showed by
his maimed condition that he had been guilty of a crime. A slave
taken in adultery with one of his master’s wives was invariably put to
death. Women were compelled by torture to name their seducers; if
the accused man denied the charge, the woman was asked to
describe some personal peculiarity of his, or some mark on his body
which could be identified; then if the man was found to have the
peculiarity, he was either fined or put to death. In order to arrive at
the truth, a man who denied a charge made against him was
sometimes stretched out with his arms and feet tied to stakes driven
firmly into the ground, a piece of barkcloth was then fastened about
his private parts, and set smouldering. As soon as the fire reached
his body, the pain became too great to bear, and the man would own
himself guilty in order to be released from torture. He would then be
either killed or fined. An adulterer was called a murderer (musi),
because he was looked upon as a man who deliberately set about to
compass the death of the woman’s husband; either directly, for he
would go armed to visit the woman, and if he was disturbed, he
would not hesitate to strike; or indirectly, by offending the fetiches.
Men knew that, if they were caught in the act of adultery, the penalty
would be death, unless they were related to the person wronged, in
which case the latter might be willing to accept a fine, and might
content himself with mutilating the culprit. The worst consequence to
the injured husband was the anger of his fetiches and gods, whose
custodian was his wife. By her action the wife had involved her
husband in their displeasure; he was thus left exposed to the malice
of any enemy, and his danger was increased in the time of war,
because the gods had withdrawn their protection from him.”65.1 Thus
among the Baganda adultery was regarded not simply as a civil
offence but as a sin, which brought down the anger of the gods, not
as we might expect, on the adulterer, but on the injured husband.
Further, the Baganda were divided into a number of totemic clans,
and members of any one clan were strictly prohibited from marrying
or having sexual relations with each other. “Sexual intercourse with a
member of the same clan (kive), or with a woman of the mother’s
clan, was punished by the death of both parties, because they were
considered to have brought the god’s displeasure on the whole
clan.”65.2
Among the Basoga, who border on the Baganda
Fornication, to the east, when a man got a virgin with child, the
adultery, and incest
severely punished guilty couple used to be dragged off to the River
by other African Ntakwe; there stones were tied to their ankles and
tribes. legs, and, along with a sacrificial sheep, they were
thrown into the water and drowned. However, this
rigorous penalty was abolished and a fine substituted before the
country came under British rule.65.3 Among the Kavirondo, who
border on the Basoga to the east, “until quite recently adultery on the
part of a wife was punished with death, and death equally was meted
out to young men and girls who were found guilty of fornication. It
was thought a shameful thing if a girl was not found to be a virgin on
her wedding day.”66.1 Among the Nandi, who border on the
Kavirondo to the north-east, “incest, intercourse with a step-mother,
step-daughter, cousin or other near relation, is punished by what is
known as injoket. A crowd of people assemble outside the house of
the culprit, who is dragged out, and the punishment is inflicted by the
women, all of whom, both young and old, strip for the occasion. The
man is flogged, his houses and crops destroyed, and some of his
stock confiscated.”66.2 Among the Barea, a tribe on the borders of
Abyssinia, when a single woman, whether maid or widow, is found
with child, she is strangled by her father or brother, and the same
punishment is inflicted on her seducer; the child of their unlawful
union is stabbed. This custom is rigorously carried out, except when
the seducer is a noble and his paramour a vassal; in that case both
are spared, but the infant is killed.66.3 Among the Beni Amer, another
tribe of the same region, an unmarried girl found pregnant is put to
death by her own brother, whatever her rank, and the seducer is
killed by his own brother; the child also is slain. But the law is not so
severe on a widow or divorced wife who is detected in a slip; her
seducer has only to pay a fine; but the child is buried alive. The Beni
Amer will not suffer a bastard to live.66.4 Among the Anyanja of
British Central Africa adultery was punished by drowning and
shooting. If one of the culprits was a chief’s wife, she was tied to her
paramour, and the pair were then thrown into a river to drown or left
in the open space of the village to die of hunger and exposure. A
man who had committed a rape was bound, weighted with stones,
and cast into the lake.66.5 Among the Awemba of Northern Rhodesia,
when a husband detected his wife in the act of adultery, he killed
both her and her partner in guilt. For such execution he might not be
indicted for murder or manslaughter. He would merely return the
blood-stained spear to the woman’s father, who by his words in the
marriage ceremony, “You shall spear the man who lusts after your
wife,” was estopped from taking vengeance for the death of his
daughter. If the husband spared the erring couple and the wife was
again taken in adultery, the villagers themselves decreed the
punishment. The unfaithful wife and her lover were dragged outside
the village and impaled on sharp stakes amid the taunts and jeers of
the bystanders, who only desisted from their mockery when death
had stilled the writhing agony of the sufferers.67.1 “The Hottentots,”
says an old writer, “allow not marriages between first or second
cousins. They have a traditionary law, which ordains, that both man
and woman, so near to each other in blood, who shall be convicted
of joining together either in marriage or fornication, shall be cudgel’d
to death. This law, they say, has prevail’d through all the generations
of ’em; and that they execute it at once, upon a conviction, without
any regard to wealth, power or affinity.”67.2
We have seen that in the East Indies sexual
Incest and adultery crimes, particularly incest, adultery, and
severely punished
in the East Indies. fornication, are often viewed with grave
displeasure because they are believed to draw
down the wrath of the higher powers on the whole community.
Hence it is natural that such offences should be treated as high
treason and the offenders punished with death. A common
punishment is drowning. For example, when incest between a parent
and a child or between a brother and a sister has been detected
among the Kubus, a primitive aboriginal tribe of Sumatra, the culprits
are enclosed in a large fish-trap, made of rattan or bamboo, and
sunk in a deep pool of the river. However, they are not pinioned; nay,
they are even furnished with a tin knife, and if they can cut their way
out of the trap, rise through the bubbling water to the surface, and
swim ashore, they are allowed to live.68.1 In the island of Bali incest
and adultery are punished by drowning; the criminals are sewed up
in a sack half-filled with stones and rice and cast into the sea. A like
doom is incurred by a woman who marries a man of a lower caste;
but sometimes she dies a more dreadful death, being burnt alive.
Both modes of execution may be adopted in order
Modes of execution to avoid shedding the blood of the sinners; for in
adopted which
avoid the shedding Bali, the ordinary way of despatching a criminal is
of blood. to stab him to the heart with a creese (kris) or
crooked Malay sword.68.2 In the island of Celebes,
as we saw, the blood of persons who have been guilty of certain
sexual crimes is believed to blast the ground on which it falls;68.3 so
that it is natural in their case to resort to a bloodless mode of
execution such as drowning or burning. In Mamoedjoe, a district on
the west coast of Celebes, the incest of a father with his daughter or
of a brother with his sister is punished by binding the culprits hand
and foot, weighting them with stones, and flinging them into the
sea.68.4 Among the Bugineese of Southern Celebes persons of
princely rank who have committed this crime are placed on a raft of
bamboos and set floating away out to sea.68.5 In
Persons guilty of
incest buried alive.
Semendo, a district of Sumatra, the punishment
for incest and murder used to be to bury the
criminals alive. Before they were led to their doom, it was customary
for the villagers to feast them, every family killing a fowl for the
purpose. Then the whole population escorted the culprits to their
grave outside the village and saw the earth shovelled in upon them.
In the year 1864, at the village of Tandjong Imam, this doom was
executed on a man and his deceased wife’s sister, with whom he
had been detected in an intrigue. “Great was my emotion and
indignation,” said the humane Dutch governor, “when I stood by the
grave of these poor wretches along with the unworthy chiefs who
had sat on the bench of justice during the enforced absence of
Pangeran Anom and pronounced this sentence. I told them in plain
language that judges who pronounced such a sentence of death on
grounds so trivial (the request of the family concerned) deserved
themselves to undergo the same punishment.” The Dutch
Government has since issued stringent orders that no one
henceforth is to be buried alive, and has threatened with death any
person who shall dare to disregard its orders.69.1 The same
punishment for incest is, or used to be, inflicted by the Pasemhers,
another tribe of Sumatra, but more merciful than the people of
Semendo they gave the culprits at least a chance for their life. The
guilty pair were bound back to back and buried in a deep hole, but
from the mouth of each a hollow bamboo communicated with the
upper air; and if when the grave was opened after seven days the
wretches were found to have survived a prolonged agony far worse
than death, they were granted their life.69.2 Nor was even this
dreadful fate the worst that could befall the sinner who broke the
rules of sexual morality in Sumatra. The Battas or
Adulterers killed Bataks of Central Sumatra condemned an
and eaten.
adulterer to be killed and eaten; strictly speaking
he should be speared to death first and eaten afterwards, but as the
injured husband and his friends were commonly the judges and
executioners, it sometimes happened that, passion proving too
strong for a strict adherence to the letter of the law, they cut the flesh
from his living body, ate it, and drank his blood, before it occurred to
them to terminate his sufferings by a spear-thrust. However, an
adulterer occasionally escaped with his life on the payment of a fine,
always provided that his accomplice was not the wife of a chief; for in
that case there was no help for it but he must be killed and eaten.69.3
Even trivial misdemeanours or acts which we should deem
perfectly innocent may draw condign punishment on the thoughtless,
the imprudent, the light-hearted in the Indian Archipelago. Thus we
read that in the island of Lombok “the men are
Extreme severity of exceedingly jealous and very strict with their
the code of sexual
morality in Lombok. wives. A married woman may not accept a cigar or
a sirih leaf from a stranger under pain of death. I
was informed that some years ago one of the English traders had a
Balinese woman of good family living with him—the connexion being
considered quite honourable by the natives. During some festival this
girl offended against the law by accepting a flower or some such
trifle from another man. This was reported to the Rajah (to some of
whose wives the girl was related), and he immediately sent to the
Englishman’s house ordering him to give the woman up as she must
be ‘krissed.’ In vain he begged and prayed, and offered to pay any
fine the Rajah might impose, and finally refused to give her up
unless he was forced to do so. This the Rajah did not wish to resort
to, as he no doubt thought he was acting as much for the
Englishman’s honour as for his own; so he appeared to let the matter
drop. But some time afterwards he sent one of his followers to the
house, who beckoned the girl to the door, and then saying, ‘The
Rajah sends you this,’ stabbed her to the heart. More serious
infidelity is punished still more cruelly, the woman and her paramour
being tied back to back and thrown into the sea, where some large
crocodiles are always on the watch to devour the bodies. One such
execution took place while I was at Ampanam, but I took a long walk
into the country to be out of the way till it was all over.”70.1
As the Malay peoples of the Indian Archipelago,
The severity of the from whom the foregoing examples are drawn,
code based at
bottom on have reached a fair level of culture, it might
superstition. perhaps be thought that the extreme severity with
which they visit offences against their code of
sexual morality springs from an excessive refinement of feeling
rather than from a crude superstition; and no doubt it may well
happen that extreme sensitiveness on the point of honour, of which
the Malays are susceptible, contributes in many cases to sharpen
the sword of justice and add fresh force to the stroke. Yet under this
delicacy of sentiment there appears to lie a deep foundation of
superstition, as we may see by the extraordinary and disastrous
influence which in the opinion of these people sexual crime exerts,
not so much on the criminals themselves, as on the whole realm of
nature, drawing down deluges of rain from the clouds till the crops
rot in the fields, shaking the solid earth beneath men’s feet, and
blowing up into flames the slumbering fires of the volcano, till the sky
is darkened at noon by a black canopy of falling ashes and illumined
at night by the sullen glow of the molten lava shot forth from the
subterranean furnace.71.1 And however much an
A similar severity in
sexual matters
over-refinement of feeling may be invoked to
observed among explain the more than Puritanical severity of the
the Australian Malay moral code in sexual matters, no such
aborigines, the
lowest of existing explanation can be applied to the like emotion of
savages. horror which similar offences excite among the
savage aborigines of Australia, the lowest and the
least refined probably of all the races of men about whom we
possess accurate information. These rude savages also treated with
rigorous severity all breaches of that widely ramified network of
prohibitions in which throughout the Australian continent, before it fell
under English rule, the two sexes lived immeshed. The whole
community of a tribe or nation was commonly subdivided into a
number of minute bodies, which we are accustomed to call classes
or clans according to the principle on which they were variously
constituted. No man might marry a woman of his own class or clan,
and in most tribes his freedom of choice was still further limited by
complex rules of marriage and descent which excluded him from
seeking a wife in many more subdivisions of the tribe, and
sometimes compelled him to look for her only in one out of them all.
And the ordinary penalty for any violation of these rules was death.
The offender was lucky who escaped with his life and a body more
or less riddled with spear wounds. Thus one who
Severe knew the aborigines of Victoria well in the old
punishments
inflicted for sexual days, before they were first contaminated and then
offences among the destroyed by contact with European civilization,
aborigines of tells us that “no marriage or betrothal is permitted
Victoria.
without the approval of the chiefs of each party,
who first ascertain that no ‘flesh’ relationship exists, and even then
their permission must be rewarded by presents. So strictly are the
laws of marriage carried out, that, should any signs of affection and
courtship be observed between those of ‘one flesh,’ the brothers, or
male relatives of the woman beat her severely; the man is brought
before the chief, and accused of an intention to fall into the same
flesh, and is severely reprimanded by the tribe. If he persists, and
runs away with the object of his affections, they beat and ‘cut his
head all over’; and if the woman was a consenting party she is half
killed. If she dies in consequence of her punishment, her death is
avenged by the man’s receiving an additional beating from her
relatives. No other vengeance is taken, as her punishment is legal. A
child born under such conditions is taken from the parents, and
handed over to the care of its grandmother, who is compelled to rear
it, as no one else will adopt it. It says much for the morality of the
aborigines and their laws that illegitimacy is rare, and is looked upon
with such abhorrence that the mother is always severely beaten by
her relatives, and sometimes put to death and burned. Her child is
occasionally killed and burned with her. The father of the child is also
punished with the greatest severity, and occasionally killed. Should
he survive the chastisement inflicted upon him, he is always
shunned by the woman’s relatives, and any efforts to conciliate them
with gifts are spurned, and his presents are put in the fire and
burned. Since the advent of the Europeans among them, the
aborigines have occasionally disregarded their admirable marriage
laws, and to this disregard they attribute the greater weakness and
unhealthiness of their children.”72.1
Again, in the Wakelbura tribe of eastern
Severe Queensland the law was extremely strict as to
punishments
inflicted for sexual unlawful connexions or elopements between
offences in the persons too nearly related to each other. Such
Wakelbura tribe of persons might be, for example, those whom we
Queensland.
call cousins both on the father’s and the mother’s
side, as well as those who belonged to a forbidden class. If such a
man carried off a woman who had been betrothed to another, he
would be pursued not only by the male relations of the woman and of
her betrothed husband, but also by the men of his own tribal
subdivision, whom he had outraged by his breach of the marriage
law; and wherever they overtook him, he would have to fight them
all. His own brothers would challenge him to fight by throwing
boomerangs or other weapons at him; and if he did not accept the
challenge, they would turn on the woman and cripple or kill her with
their weapons, unless she could escape into the bush. Nay, the
woman’s own mother would cut and perhaps slay her with her own
hands. Sooner or later the ravisher had to engage in single combat
with the man he had injured. Both were fully armed with shield,
spear, boomerang and knife. When they had exhausted their
missiles, they closed on each other with their knives, a dense ring of
blacks generally forming round the combatants to see fair play. In
such a fight the man who had broken the tribal law always came off
worst; for even if he got the better of his adversary, the other men
and even his own brothers would attack him and probably gash him
with their knives. Fatal stabs were sometimes given in these fights,
but more usually, it would seem, the onlookers interfered and
wrested the weapons from the two combatants before they
proceeded to extremities. In any case the woman who had eloped
was terribly mauled with knives, and if she survived the ordeal was
restored to the man whom she had deserted.73.1
Among the tribes in the central parts of North-West Queensland, if
a man eloped with a single woman whom he might lawfully marry,
 but who for any reason was forbidden to him by
Severe punishment the tribal council, he had on returning to camp with
inflicted for sexual
offences among the his wife to run the gauntlet of the outraged
aborigines of other community, who hacked his buttocks and
parts of Australia. shoulders with knives, beat his head and limbs
with sticks and boomerangs, and pricked the
fleshy parts of his thighs with spears, taking care, however, not to
inflict fatal injuries, lest they should incur blood revenge. But if the
woman with whom the man had eloped was of a class into which he
might not marry, both the culprits were put to death, the relations on
both sides tacitly consenting to the execution.74.1 In the Yuin tribe of
New South Wales, if a man eloped with a woman of his own tribal
subdivision, all the men would pursue him; and if he refused to give
the woman up, the sorcerer of the place would probably say to his
men, “This man has done very wrong, you must kill him”; whereupon
somebody would thrust a spear into him, his relatives not interfering
lest the same fate should befall them.74.2 The same punishment was
inflicted for the same offence by the Wotjobaluk tribe of North-
Western Victoria; but their western neighbours, the Mukjarawaint
tribe, not content with killing the guilty man, cut off the flesh off his
thighs and upper arms, roasted and ate it, his own brother partaking
of the cannibal meal. As for the rest of the body, they chopped it up
small and left it lying on a log. The same custom is said to have been
observed by the Jupagalk tribe.74.3 Among many tribes of Western
Australia, as well as of other parts of that continent, persons who
bear the same class-name may not marry. Any such marriage is
regarded as incest and rigorously punished. For example, “the union
of Boorong and Boorong is to the natives the union of brother and
sister, although there may be no real blood relationship between the
pair, and a union of that kind is looked upon with horror, and the
perpetrators very severely punished and separated, and if the crime
is repeated they are both killed.”74.4 On the other side of the
continent the Kamilaroi of New South Wales similarly inflicted
condign punishment on both the culprits who persisted in marrying
each other contrary to the tribal law; the male relations of the man
killed him, and the female relations of the woman killed her. The
Kamilaroi of the Gwydir River went further; they killed any man who
 so much as spoke to or held any communication
Penalty of death
inflicted for the
with his mother-in-law,75.1 for one of the most
crime of speaking tostringent laws of savage etiquette is that which
a mother-in-law. prohibits any direct social intercourse between a
man and his wife’s mother. The law has been
variously explained,75.2 but a large body of evidence points to the
conclusion that this custom of mutual avoidance is simply a
precaution to prevent improper relations between the two. Hence a
brief consideration of it is appropriate in this place; for to all
appearance the custom, though it may be wholesome and beneficial
in practice, has originated purely in superstition. But before giving my
reasons for thinking so it may be well, for the sake of those who are
unfamiliar with savage etiquette, to illustrate the practice itself by a
few examples.75.3
Speaking of the Boloki, a Bantu tribe of the
The custom of Upper Congo, an experienced missionary, the
avoiding a mother-
in-law and other Rev. John H. Weeks, writes as follows: “Perhaps
relations by this will be the best place in which to make a few
marriage among the remarks on the mother-in-law. She and her son-in-
Boloki of the
Congo. law may never look on each other’s face. I have
often heard a man say, ‘So-and-so, your mother-
in-law is coming,’ and the person addressed would run into my
house and hide himself until his wife’s mother had gone by. They can
sit at a little distance from each other, with their backs to one
another, and talk over affairs when necessary. Bokilo means mother-
in-law, daughter-in-law, brother-in-law, father-in-law, sister of mother-
in-law, brother of father-in-law, wife of wife’s brother, and in fact any
relation-in-law. Bokilo, the noun, is derived from kila = to forbid,
prohibit, taboo, and indicates that all bearing the relationship of
bokilo can have no intimate relationship with one another, for it is
regarded as incestuous; and it is according to native ideas just as
wrong for a daughter-in-law to speak or look at her husband’s father,
as for the son-in-law to speak or look at his wife’s mother. Some
have told me that this was to guard against all possibility of
cohabitation, ‘For a person you never look at you never desire.’
Others have said, ‘Well, don’t you see, my wife came from her
womb.’ I am strongly inclined to the opinion that the former is the real
reason.”76.1
From this statement it appears that a man and his wife’s mother
are not the only persons who are bound to avoid each other in
society; the same rule of social avoidance is incumbent on a man
and his son’s wife, and on many other persons of opposite sex who
are connected with each other by marriage; and in regard to all such
persons it is held that any intimate relationship between them would
be incestuous. Hence we see, what is important to bear in mind, that
the rule of social avoidance incumbent on a man and his wife’s
mother is by no means solitary of its kind, and cannot be considered
apart from a large number of similar rules of avoidance observed
between other persons. The same large extension
The custom of of the rule appears in the customs of the Batamba,
avoiding relations
by marriage among a Bantu tribe of Busoga, a country on the north
the Batamba of side of the Lake Victoria Nyanza. A Catholic
Busoga. missionary, who has laboured among the Batamba
for nine years, describes their practice in this
matter as follows:—
“There is a very strange custom which may be considered here. If
a son marries or if a daughter does the same, then if they are grown
up, from the day the son or daughter marries, the mother, father of
both parties, the brothers and sisters of both parties are not allowed
to sleep under the same roof. If a man marries, then he builds a
house for himself, and should his parents live with him, or his
brothers and sisters, then they must have a separate house near by.
They are not forbidden to go in and visit him or her, but are not
allowed to sleep there. The reason is this. They say that otherwise
sickness is caused, and this is called endivade ya buko, the sickness
of relationship, literally taken. The sickness is called bujugumiro,
trembling, from the verb kujugumira, to shiver or tremble. This
cannot be got out of their heads, and no amount of talking or arguing
will convince them of the opposite. I have attended many cases of
this disease and I have not known one to recover.
“Again, the father and mother of the bride and bridegroom, the
aunts and uncles of bride and bridegroom may no more shake hands
or touch in any way the bride and bridegroom, or else the same
disease, bujugumiro, will follow. Of course much less will they
commit themselves between each other for the fear of the same
reason. And it is never heard of that a brother and sister, aunt and
nephew, niece and uncle have ever committed themselves seriously.
They are so afraid of the disease they say will follow, that, as a man
here over seventy years of age tells me, he has never in his whole
life heard of such a misbehaviour. The people say, ‘Jekiyinzika = it is
impossible for such a thing to happen.’ And no doubt one is struck
with the care they take. The disease following does not come as a
punishment from the gods, but they say, ‘Endwada ejja yokka, the
illness comes by itself.’ ”77.1
From the foregoing account it appears that
Avoidance of blood among the Batamba the rules of social avoidance
relations as well as
of connexions by are observed between blood-relations of opposite
marriage. sexes, such as brothers and sisters, uncles and
nieces, aunts and nephews, as well as between
connexions by marriage. This is a further extension of the rule of
social avoidance which it is important to bear in mind. We shall recur
to it presently. For our present purpose it deserves also to be noticed
that breaches of the custom are believed to be punished by a
disease of trembling or shivering, which, though it probably springs
purely from the imagination of the culprits, nevertheless appears to
be always fatal. Further, we learn that the mere apprehension of this
disease acts as a most efficient check upon improper relations
between persons who are connected with each other by blood or
marriage.
Among the Akamba, a Bantu tribe of British East
The custom of Africa, “if a man meets his mother-in-law in the
avoiding mother-in-
law and own road they both hide their faces and pass by in the
daughter among the bush on opposite sides of the path. If a man did
Akamba of British not observe this custom and at any time wanted to
East Africa.
marry another wife, it would prove a serious
stigma, and parents would have nothing to do with him. Moreover, if
a wife heard that her husband had stopped and spoken to her
mother in the road, she would leave him. If a man has business he
wishes to discuss with his mother-in-law, he goes to her hut at night,
and she will talk to him from behind the partition in the hut.… If a girl
of the age of puberty meets her father in the road, she hides as he
passes, nor can she ever go and sit near him in the village until the
day comes when he tells her that it has been arranged for her to
marry a certain man. After marriage she does not avoid her father in
any way.”78.1 Thus among the Akamba a man must avoid his own
marriageable, but unmarried, daughter exactly as he avoids his
wife’s mother; but the custom of avoidance ceases when his
daughter marries. This extension of the rule to a man’s own
daughter, and its limitation to the time during which the girl is nubile
but single, are most significant, and point plainly to a fear of improper
relations between father and daughter. To that point we shall return
shortly.
Among the Bakerewe, a Bantu people inhabiting
The custom of a large and fertile island in Lake Victoria Nyanza,
avoiding parents-in-
law among various “the wife, whether the first (omukuru) or the last
tribes of Central (omwenga), must always belong to a family other
and East Africa. than that of the husband, for marriages are not
contracted between relations. Never in any case
will the new household establish itself in the immediate
neighbourhood of the wife’s parents. The reason is that the son-in-
law (omukwerima) and his mother-in-law (mazara), according to their
customs, may not see each other nor look upon each other; hence in
order not to run the risk of breaking a rule to which everybody
attaches grave importance, they go as far away as possible.”78.2
Among some tribes of Eastern Africa which formerly acknowledged
the suzerainty of the sultan of Zanzibar, before a young couple had
children they might meet neither their father-in-law nor their mother-
in-law. To avoid them they must make a long roundabout. But if they
could not do that, they must throw themselves on the ground and
hide their faces till the father-in-law or mother-in-law had passed
by.79.1
Among the Anyanja, a Bantu people of British
The custom of Central Africa, “a man used never to speak to his
avoiding parents-in-
law among the mother-in-law till after the birth of his first son.
tribes of British Neither a man nor his wife will eat in company of
Central Africa and their mother or father-in-law until after birth of a
Northern Rhodesia.
child. If a man sees his mother-in-law eat, he has