Etextbook 978 1133611103 Chemistry AP Edition 9th Edition

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(AP Edition) 9th Edition

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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
For Review 177 ∣ Key Terms 177 ∣ Questions and
CHEMICAL CONNECTIONS Farming the Wind 277
Exercises 179
CHEMICAL CONNECTIONS Veggie Gasoline? 282
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
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
7.13 The Properties of a Group: The Alkali Metals 335
Plants 256
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 For Review 339 ∣ Key Terms 339 ∣ Questions and
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

8.2 Electronegativity 356
8.3 Bond Polarity and Dipole Moments 358
8.4 Ions: Electron Configurations and Sizes 361
8.5 Energy Effects in Binary Ionic Compounds 365
8.6 Partial Ionic Character of Covalent Bonds 369
8.7 The Covalent Chemical Bond: A Model 370
8.8 Covalent 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
For Review 402 ∣ Key Terms 402 ∣ Questions and 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
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
For Review 443 ∣ Key Terms 443 ∣ Questions and 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 For Review 540 ∣ Key Terms 540 ∣ Questions and
CHEMICAL CONNECTIONS Closest Packing of M & Ms 469 Exercises 542
vi Contents
13.7 Le Châtelier’s Principle 633

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
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
CHEMICAL CONNECTIONS Enzymes: Nature’s
Exercises 749
Catalysts 586
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 For Review 779 ∣ Key Terms 779 ∣ Questions and
13.6 Solving Equilibrium Problems 628 Exercises 780
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
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
For Review 820 ∣ Key Terms 820 ∣ Questions and 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
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
20.8 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
20.11 The Chemistry of Oxygen 952
20.12 The Chemistry of Sulfur 954
NASA/SDO/AIA

Exercises 964
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 For Review 1067 ∣ Key Terms 1067 ∣ Questions and
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
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
Answers to Selected Exercises A39
Index A71
To the Professor
Features of Chemistry, the hints to arrive at the answer. ChemWork problems

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

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

2. Subtract the number of assigned electrons from the number of valence elec-
trons on the free, neutral atom to obtain the formal charge.
A Guide to
❯ 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
—Jerry Burns, 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
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
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.
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
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.”
—David Boyajian, 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:
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
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. 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
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
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
Copyright 2012 Cengage cancelAll
Learning. out,Rights
and the carbon dioxide
Reserved. molecule
May not doesscanned,
be copied, not haveora duplicated,
dipole moment.
in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
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.
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
Each chapter begins 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
Chapter 13 contrast, some reactions occur only to a slight extent. For example, when solid CaO is
with an engaging intro- 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
duction that demon- left (in the direction of the reactants).

In this chapter we will discuss how and why a chemical system comes to equi-
Chemical Equilibrium
librium and the characteristics of equilibrium. In particular, we will discuss how to
strates how chemistry is calculate the concentrations of the reactants and products present for a given system
at equilibrium.
related to everyday life.

13.1 The Equilibrium Condition
The Characteristics of Chemical
13.5 Applications of the Equilibrium
Constant
13.6 Solving Equilibrium Problems
Treating Systems That Have Small
13.1 The Equilibrium Condition
Equilibrium The Extent of a Reaction 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
13.2 The Equilibrium Constant Reaction Quotient 13.7 Le Châtelier’s Principle the Equilibrium Constant” the case. On the molecular level, there is frantic activity. Equilibrium is not static but
13.3 Equilibrium Expressions Involving Calculating Equilibrium Pressures and The Effect of a Change in Concentration
Concentrations Equilibrium is a dynamic situation. is a highly dynamic situation. The concept of chemical equilibrium is analogous to the
Pressures The Effect of a Change in Pressure
flow of cars across a bridge connecting two island cities. Suppose the traffic flow on
13.4 Heterogeneous Equilibria 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
The equilibrium in a salt water aquarium must be carefully maintained to keep the sea life healthy. reaction takes place rapidly:
(Borissos/Dreamstime.com)
H2O 1g2 1 CO 1g2 m H2 1g2 1 CO2 1g2
606 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
11097_Ch13_0606-0651.indd 606 9/6/12 9:06 AM 11097_Ch13_0606-0651.indd 607 9/6/12 10:57
1.2 The Scientific Method 7
Chemical connections Chemical Connections describe current applications of chemistry. These special-
A Note-able Achievement 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.
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. 6.6 New Energy Sources 277
The invention of sticky notes
occurred over a period of about 10
years and involved a great deal of
Chemical connections
Photo © Cengage Learning. All rights reserved.
serendipity. The adhesive for Post-it

Notes was discovered by Dr. Spencer
F. Silver of 3M in 1968. Silver found Farming the Wind
that when an acrylate polymer
material was made in a particular way,
it formed cross-linked microspheres.
When suspended in a solvent and In the Midwest the wind blows across per year in the United
sprayed on a sheet of paper, this fields of corn, soybeans, wheat, and States. The economic
substance formed a “sparse mono- wind turbines—wind turbines? It turns feasibility of wind-
layer” of adhesive after the solvent out that the wind that seems to blow generated electricity
evaporated. Scanning electron Post-it Notes popped up. One Sunday remarkable stories connected to the
almost continuously across the plains is has greatly improved in
microscope images of the adhesive Art Fry, a chemical engineer for 3M, use of these notes. For example, a
now becoming the latest cash crop. One the past 30 years as the
show that it has an irregular surface, a was singing in his church choir when Post-it Note was applied to the nose of
of these new-breed wind farmers is wind turbines have
little like the surface of a gravel road. he became annoyed that the book- a corporate jet, where it was intended
Daniel Juhl, who recently erected become more efficient.
Courtesy, NextEra Energy Resources
In contrast, the adhesive on cello- mark in his hymnal kept falling out. He to be read by the plane’s Las Vegas
17 wind turbines on six acres of land Today’s turbines can
phane tape looks smooth and uniform, thought to himself that it would be ground crew. Someone forgot to
near Woodstock, Minnesota. These produce electricity that
like a superhighway. The bumpy nice if the bookmark were sticky remove it, however. The note was still
turbines can generate as much as costs about the same as
surface of Silver’s adhesive caused it enough to stay in place but not so on the nose of the plane when it
10 megawatts (MW) of electricity, which that from other sources.
to be sticky but not so sticky to sticky that it couldn’t be moved. landed in Minneapolis, having survived
Juhl sells to the local electrical utility. The most impressive
produce permanent adhesion, Luckily, he remembered Silver’s a takeoff, a landing, and speeds of
There is plenty of untapped wind thing about wind power
because the number of contact points glue—and the Post-it Note was born. 500 miles per hour at temperatures as
power in the United States. Wind is the magnitude of the This State Line Wind Project along the Oregon–Washington border
between the binding surfaces was For the next three years, Fry low as 2568F. Stories on the 3M Web
mappers rate regions on a scale of supply. According to the uses approximately 399 wind turbines to create enough electricity to
limited. worked to overcome the manufac- site describe how a Post-it Note on the
1 to 6 (with 6 being the best) to American Wind Energy power some 70,000 households.
When he invented this adhesive, turing obstacles associated with the front door of a home survived the
indicate the quality of the wind Association in Wash-
Silver had no specific ideas for its use, product. By 1977 enough Post-it Notes 140-mile-per-hour winds of Hurricane
resource. Wind farms are now being ington, D.C., the wind-power potential power 1 million homes if transmission
so he spread the word of his discovery were being produced to supply 3M’s Hugo and how a foreign official
developed in areas rated from 4 to 6. in the United States is comparable or problems can be solved.
to his fellow employees at 3M to see if corporate headquarters, where the accepted Post-it Notes in lieu of cash
The farmers who own the land larger than the energy resources under Another possible scenario for wind
anyone had an application for it. In employees quickly became addicted to when a small bribe was needed to cut
welcome the increased income derived the sands of Saudi Arabia. farms is to use the electrical power
addition, over the next several years their many uses. Post-it Notes are now through bureaucratic hassles.
from the wind blowing across their The biggest hurdle that must be generated to decompose water to
development was carried out to available in 62 colors and 25 shapes. Post-it Notes have definitely
land. Economists estimate that each overcome before wind power can produce hydrogen gas that could be
improve the adhesive’s properties. It In the years since the introduction changed the way we communicate and
acre devoted to wind turbines can pay become a significant electricity carried to cities by pipelines and used
was not until 1974 that the idea for of Post-it Notes, 3M has heard some remember things.
royalties to the farmers of as much as producer in the United States is as a fuel. One real benefit of hydrogen
$8000 per year, or many times the construction of the transmission is that it produces water as its only
revenue from growing corn on that infrastructure—the power lines combustion product. Thus, it is
same land. Juhl claims that farmers needed to move the electricity from essentially pollution-free.
who construct the turbines themselves the rural areas to the cities where Within a few years, wind power
can realize as much as $20,000 per most of the power is used. For could be a major source of electricity.
Unless otherwise noted, all art on this page is © Cengage Learning 2014. year per turbine. Globally, wind example, the hundreds of turbines There could be a fresh wind blowing
generation of electricity has nearly planned in southwest Minnesota in a across the energy landscape of the
quadrupled in the last five years and development called Buffalo Ridge United States in the near future.
is expected to increase by about 60% could supply enough electricity to
11097_Ch01_0001-0041.indd 7 9/6/12 9:02 AM
Unless otherwise noted, all art on this page is © Cengage Learning 2014. 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-
Copyright 2012 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in from the eBook and/or eChapter(s). drogen
part. Duegastois electronic
from the treatment of natural
rights, some gas third
with steam:
party content may be suppressed
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 A buffer generally contains a weak acid and its
does the presence of a common ion affect an equilib- weak conjugate base, or a weak base and its weak
rium such as 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 For Review 701
HNO2 1aq2 m H1 1aq2 1 NO22 1aq2 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.
What is an acid–base solution called that contains a base. Both reactions give the same answer for the pH of
common ion? the solution. Explain. Active Learning Questions 10. A certain sodium compound is dissolved in water to liberate
Na1 ions and a certain negative ion. What evidence would you
2. Define a buffer solution. What makes up a buffer A third method that can be used to solve for the pH These questions are designed to be used by groups of students in look for to determine whether the anion is behaving as an acid
solution? How do buffers absorb added H1 or OH2 of a buffer solution is the Henderson–Hasselbalch class. or a base? How could you tell whether the anion is a strong
with little pH change? equation. What is the Henderson–Hasselbalch equa- 1. Consider two beakers of pure water at different temperatures. base? Explain how the anion could behave simultaneously as
Is it necessary that the concentrations of the weak tion? What assumptions are made when using this How do their pH values compare? Which is more acidic? more an acid and a base.
equation? basic? Explain. 11. Acids and bases can be thought of as chemical opposites (ac-
acid and the weak base in a buffered solution be equal?
Explain. What is the pH of a buffer when the weak acid 3. One of the most challenging parts of solving acid–base 2. Differentiate between the terms strength and concentration as ids are proton donors, and bases are proton acceptors). There-
they apply to acids and bases. When is HCl strong? Weak? fore, one might think that Ka 5 1yKb. Why isn’t this the case?
and conjugate base concentrations are equal? problems is writing out the correct equation. When a
Concentrated? Dilute? Answer the same questions for ammo- What is the relationship between Ka and Kb? Prove it with a
nia. Is the conjugate base of a weak acid a strong base? derivation.
3. Sketch two graphs: (a) percent dissociation for weak acid HA 12. Consider two solutions of the salts NaX(aq) and NaY(aq) at
versus the initial concentration of HA ([HA]0) and (b) H1 con- equal concentrations. What would you need to know to deter-
centration versus [HA]0. Explain both. mine which solution has the higher pH? Explain how you
4. Consider a solution prepared by mixing a weak acid HA and would decide (perhaps even provide a sample calculation).
HCl. What are the major species? Explain what is occurring in 13. What is meant by pH? True or false: A strong acid solution
solution. How would you calculate the pH? What if you added always has a lower pH than a weak acid solution. Explain.
11097_Ch15_0711-0757.indd 748 9/6/12 9:08 AM NaA to this solution? Then added NaOH? 14. Why is the pH of water at 258C equal to 7.00?
5. Explain why salts can be acidic, basic, or neutral, and show 15. Can the pH of a solution be negative? Explain.
examples. Do this without specific numbers. 16. Is the conjugate base of a weak acid a strong base? Explain.
6. Consider two separate aqueous solutions: one of a weak acid Explain why Cl2 does not affect the pH of an aqueous solution.
HA and one of HCl. Assuming you started with 10 molecules 17. Match the following pH values: 1, 2, 5, 6, 6.5, 8, 11, 11, and
of each: 13 with the following chemicals (of equal concentration):
a. Draw a picture of what each solution looks like at HBr, NaOH, NaF, NaCN, NH4F, CH3NH3F, HF, HCN, and
equilibrium. NH3. Answer this question without performing calculations.
b. What are the major species in each beaker? 18. The salt BX, when dissolved in water, produces an acidic solu-
c. From your pictures, calculate the Ka values of each acid. 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.
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.
21. The space-filling models of ethane and ethanol are shown
3 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
is about 230. K and the partial pressure of oxygen is about
H2S1g2 1 SO2 1g2 h 3S1g2 1 2H2O 1l2
Unless otherwise noted, all art on this page is © Cengage Learning 2014. 1.0 3 1023 atm. Estimate the partial pressure of ozone in equi-
for which DH is 2233 kJ and DS is 2424 J/K.
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
Copyright 2012 Cengage DHAll
Learning. andRights
DS do not depend on
Reserved. Maytemperature, at
not be copied, scanned, or duplicated,
106. Entropy can be in whole orbyin apart.
calculated Due to electronic
relationship proposed rights,
by some third party content may be suppressed from the eBook and/or eChapter(s).
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
ion forms complex ions with I as follows:
2
For Review 551
(1.0 3 1013), calcu-
Hg21 1aq2 1 I2 1aq2 m HgI1 1aq2 K1 5 1.0 3 108
ant for the following
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 I 1aq2 m HgI3 1aq2
2 2
K3 5 1.0 3 109 asionpairs? thesolutionhasdoublethemolefractionofsubstanceAthat
21
1aq2 1 2OH2 1aq2 thesolutiondoes.WhatisthemolefractionofliquidAinthe
HgI32 1aq2 1 I2 1aq2 m HgI422 1aq2 K4 5 1.0 3 108 b. Calculatethefreezingpointthatwouldbeobservedfor
ant you calculated thissolution. solution?
A solution is prepared by dissolving 0.088 mole of Hg(NO3)2
mol/L) of Cu(OH)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
ntration of OH2 is 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].
s in each of the fol- 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 [Hg21]. duce45Lwaterperday.
beingpurecocaine(C17H21NO4,molarmass5303.35g/mol).
a. AssumingallofthedissolvedsolidsareMgCO3and
4 say that Ba(OH)2, Challenge Problems 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?
soluble hydroxides.
f each of these mar-
99. The copper(I) ion forms a complex ion with CN2 according to further and challenge them more rigorously thana. Whatisthemolarmassofthesubstance?Assumingthat
thepercentuncertaintyinthecalculatedmolarmassisthe b. Wouldthesamesystemworkforpurifyingseawater?
the following equation: (Assumeseawateris0.60MNaCl.)
ormation, we ran the Cu 1aq2 1 3CN 1aq2 m Cu 1CN2 3 1aq2
1 2 22
K 5 1.0 3 10 11 the Additional Exercises. sameasthepercentuncertaintyinthetemperature
change,calculatetheuncertaintyinthemolarmass.
then let some of the a. Calculate the solubility of CuBr(s) (Ksp 5 1.0 3 1025) in b. Couldthechemistunequivocallystatethatthesubstance Integrative Problems
ibrium. To see why, 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.
Equilibrium c. Assumingthattheabsoluteuncertaintiesinthemeasure- 130. Creatinine,C4H7N3O,isaby-productofmusclemetabolism,
entration (mol/L) 100. Consider a solution made by HClmixing
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-
5 3.75 3 1023 2 y AgNH31 and Ag(NH3)21:
6.25 3 1022 2 2y 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
Ag 1aq2 1 NH3 1aq2 m AgNH
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,
AgNH31 1aq2 1 NH3 1aq2 m Agmine 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?
101. a. Calculate the molar solubility of AgBr in pure water. Ksp
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
nes) are found inter- 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
a student would get 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?
Ag1 1aq2 1 2NH3 1aq2 h 3.50 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
)2(s) is 1.3 3 10232 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
lt. Ignore any poten- 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
east soluble to most 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
the ions with water. 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
102. Calculate the equilibrium concentrations of NH3, Cu ,
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
ate the solubility of 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
022-M KIO3 solution These problems are designed to incorporate several concepts and
Cu21 1aq2 1 NH3 1aq2 m this CuNH
plant? 21 1aq2
ue for Pb(IO3)2(s). 3 techniques into one situation.
d. The original stream water3contained
K1 5 1.86 104 10.2 ppm Ca21.
) is added to 50.0 mL 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
at equilibrium in the 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
7 3 1028.] 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
014.
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

solution of a metal nitrate that is 8.246% nitrogen by mass. most challenging problems in the end-of-
9/6/12 9:11 AM The ionic compound in solution B consists of potassium, chro-
the solutions. mium, and oxygen; chromium has an oxidation state of 16 chapter material.
140. Tris(pentafluorophenyl)borane, commonly known by its acro- and there are 2 potassiums and 1 chromium in the formula.
11097_Ch11_0510-0551.indd 551 9/6/12 9:10 AM
nym BARF, is frequently used to initiate polymerization of The masses of the solutes in each of the solutions are the same.
ethylene or propylene in the presence of a catalytic transition When the solutions are added together, a blood-red precipitate
metal compound. It is composed solely of C, F, and B; it is forms. After the reaction has gone to completion, you dry the
42.23% C and 55.66% F by mass. solid and find that it has a mass of 331.8 g.
a. What is the empirical formula of BARF? a. Identify the ionic compounds in solution A and solution B.
b. A 2.251-g sample of BARF dissolved in 347.0 mL of b. Identify the blood-red precipitate.
solution produces a 0.01267-M solution. What is the c. Calculate the concentration (molarity) of all ions in the
molecular formula of BARF? original solutions.
141. In a 1-L beaker, 203 mL of 0.307 M ammonium chromate was d. Calculate the concentration (molarity) of all ions in the
mixed with 137 mL of 0.269 M chromium(III) nitrite to pro- final solution.
duce ammonium nitrite and chromium(III) chromate. Write
the balanced chemical equation for the reaction occurring Marathon Problems can be used in class by groups of students to
help facilitate problem-solving skills.
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.”
—Alan M. 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 S ignificant 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
2 Unless otherwise noted, all art on this page is © Cengage Learning 2014.
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.
4 Chapter 1 Chemical Foundations
Figure 1.2 | Sand on a beach looks

uniform from a distance, but up close
the irregular sand grains are visible,
and each grain is composed of tiny
atoms.
Chuck Place. Inset: Jeremy Burgess/SPL/Photo Researchers, Inc.

O
Si
Critical Thinking
The scanning tunneling microscope allows us to “see” atoms. What if you were sent
back in time before the invention of the scanning tunneling microscope? What
evidence could you give to support the theory that all matter is made of atoms and
molecules?
One of the amazing things about our universe is that the tremendous variety of
substances we find there results from only about 100 different kinds of atoms. You can
think of these approximately 100 atoms as the letters in an alphabet from which all the
“words” in the universe are made. It is the way the atoms are organized in a given
substance that determines the properties of that substance. For example, water, one of
the most common and important substances on the earth, is composed of two types of
atoms: hydrogen and oxygen. Two hydrogen atoms and one oxygen atom are bound
together to form the water molecule:
oxygen atom
water molecule
hydrogen atom
When an electric current passes through it, water is decomposed to hydrogen and oxy-
gen. These chemical elements themselves exist naturally as diatomic (two-atom)
molecules:
oxygen molecule written O2
hydrogen molecule written H2
We can represent the decomposition of water to its component elements, hydrogen and
oxygen, as follows:
one oxygen molecule

two water written O2
molecules electric
written 2H2O current
two hydrogen molecules
written 2H2
Notice that it takes two molecules of water to furnish the right number of oxygen and
hydrogen atoms to allow for the formation of the two-atom molecules. This reaction
explains why the battery in your car can explode if you jump-start it improperly. When
you hook up the jumper cables, current flows through the dead battery, which contains
water (and other things), and causes hydrogen and oxygen to form by decomposition of
some of the water. A spark can cause this accumulated hydrogen and oxygen to explode,
forming water again.
O2
spark
2H2O
2H2
This example illustrates two of the fundamental concepts of chemistry: (1) Matter is
composed of various types of atoms, and (2) one substance changes to another by re-
organizing the way the atoms are attached to each other.
These are core ideas of chemistry, and we will have much more to say about them.
Science: A Process for Understanding

Nature and Its Changes
How do you tackle the problems that confront you in real life? Think about your trip
to school. If you live in a city, traffic is undoubtedly a problem you confront daily. How
do you decide the best way to drive to school? If you are new in town, you first get a
map and look at the possible ways to make the trip. Then you might collect informa-
tion about the advantages and disadvantages of various routes from people who know
the area. Based on this information, you probably try to predict the best route. How-
ever, you can find the best route only by trying several of them and comparing the re-
sults. After a few experiments with the various possibilities, you probably will be able
to select the best way. What you are doing in solving this everyday problem is applying
the same process that scientists use to study nature. The first thing you did was collect
relevant data. Then you made a prediction, and then you tested it by trying it out. This
process contains the fundamental elements of science.
1. Making observations (collecting data)
2. Suggesting a possible explanation (formulating a hypothesis)
3. Doing experiments to test the possible explanation (testing the hypothesis)
Scientists call this process the scientific method. We will discuss it in more detail in the
next section. One of life’s most important activities is solving problems—not “plug and
chug” exercises, but real problems—problems that have new facets to them, that involve
things you may have never confronted before. The more creative you are at solving these
problems, the more effective you will be in your career and your personal life. Part of the
reason for learning chemistry, therefore, is to become a better problem solver. Chemists
are usually excellent problem solvers because to master chemistry, you have to master
the scientific approach. Chemical problems are frequently very complicated—there is
usually no neat and tidy solution. Often it is difficult to know where to begin.
1.2 The Scientific Method

IBLG: See questions from “Chemistry: Science is a framework for gaining and organizing knowledge. Science is not simply a
An Overview and the Scientific Method” set of facts but also a plan of action—a procedure for processing and understanding
certain types of information. Scientific thinking is useful in all aspects of life, but in
this text we will use it to understand how the chemical world operates. As we said in
our previous discussion, the process that lies at the center of scientific inquiry is called
the scientific method. There are actually many scientific methods, depending on the
nature of the specific problem under study and the particular investigator involved.
Observation
However, it is useful to consider the following general framework for a generic scien-
Hypothesis tific method (Fig. 1.3):
Experiment
Steps in the Scientific Method
1. Making observations. Observations may be qualitative (the sky is blue; water is a
liquid) or quantitative (water boils at 1008C; a certain chemistry book weighs 2 kg).
Theory (model) A qualitative observation does not involve a number. A quantitative observation
(called a measurement) involves both a number and a unit.
Theory 2. Formulating hypotheses. A hypothesis is a possible explanation for an observation.
modified Prediction 3. Performing experiments. An experiment is carried out to test a hypothesis. This in-
as needed volves gathering new information that enables a scientist to decide whether the
hypothesis is valid—that is, whether it is supported by the new information
Experiment learned from the experiment. Experiments always produce new observations, and
this brings the process back to the beginning again.
Figure 1.3 | The fundamental steps
of the scientific method. To understand a given phenomenon, these steps are repeated many times, gradually
accumulating the knowledge necessary to provide a possible explanation of the
phenomenon.
Scientific Models
Once a set of hypotheses that agrees with the various observations is obtained, the hy-
potheses are assembled into a theory. A theory, which is often called a model, is a set
of tested hypotheses that gives an overall explanation of some natural phenomenon.
It is very important to distinguish between observations and theories. An observa-
tion is something that is witnessed and can be recorded. A theory is an interpretation—
a possible explanation of why nature behaves in a particular way. Theories inevitably
change as more information becomes available. For example, the motions of the sun
and stars have remained virtually the same over the thousands of years during which
humans have been observing them, but our explanations—our theories—for these mo-
tions have changed greatly since ancient times.
The point is that scientists do not stop asking questions just because a given theory
seems to account satisfactorily for some aspect of natural behavior. They continue do-
ing experiments to refine or replace the existing theories. This is generally done by us-
ing the currently accepted theory to make a prediction and then performing an experi-
Observation ment (making a new observation) to see whether the results bear out this prediction.
Always remember that theories (models) are human inventions. They represent at-
Hypothesis tempts to explain observed natural behavior in terms of human experiences. A theory
is actually an educated guess. We must continue to do experiments and to refine our
Experiment
theories (making them consistent with new knowledge) if we hope to approach a more
complete understanding of nature.
As scientists observe nature, they often see that the same observation applies to
Theory many different systems. For example, studies of innumerable chemical changes have
Law
(model) shown that the total observed mass of the materials involved is the same before and
after the change. Such generally observed behavior is formulated into a statement
Theory called a natural law. For example, the observation that the total mass of materials is
modified Prediction not affected by a chemical change in those materials is called the law of conservation
as needed of mass.
Note the difference between a natural law and a theory. A natural law is a summary of
Experiment observed (measurable) behavior, whereas a theory is an explanation of behavior. A law
summarizes what happens; a theory (model) is an attempt to explain why it happens.
Figure 1.4 | The various parts of the In this section we have described the scientific method as it might ideally be applied
scientific method. (Fig. 1.4). However, it is important to remember that science does not always progress
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 Post-it Notes popped up. One Sunday remarkable stories connected to the
microscope images of the adhesive Art Fry, a chemical engineer for 3M, use of these notes. For example, a
show that it has an irregular surface, a was singing in his church choir when Post-it Note was applied to the nose of
little like the surface of a gravel road. he became annoyed that the book- a corporate jet, where it was intended
In contrast, the adhesive on cello- mark in his hymnal kept falling out. He to be read by the plane’s Las Vegas
phane tape looks smooth and uniform, thought to himself that it would be ground crew. Someone forgot to
like a superhighway. The bumpy nice if the bookmark were sticky remove it, however. The note was still
surface of Silver’s adhesive caused it enough to stay in place but not so on the nose of the plane when it
to be sticky but not so sticky to sticky that it couldn’t be moved. landed in Minneapolis, having survived
produce permanent adhesion, Luckily, he remembered Silver’s a takeoff, a landing, and speeds of
because the number of contact points glue—and the Post-it Note was born. 500 miles per hour at temperatures as
between the binding surfaces was For the next three years, Fry low as 2568F. Stories on the 3M Web
limited. worked to overcome the manufac- site describe how a Post-it Note on the
When he invented this adhesive, turing obstacles associated with the front door of a home survived the
Silver had no specific ideas for its use, product. By 1977 enough Post-it Notes 140-mile-per-hour winds of Hurricane
so he spread the word of his discovery were being produced to supply 3M’s Hugo and how a foreign official
to his fellow employees at 3M to see if corporate headquarters, where the accepted Post-it Notes in lieu of cash
anyone had an application for it. In employees quickly became addicted to when a small bribe was needed to cut
addition, over the next several years their many uses. Post-it Notes are now through bureaucratic hassles.
development was carried out to available in 62 colors and 25 shapes. Post-it Notes have definitely
improve the adhesive’s properties. It In the years since the introduction changed the way we communicate and
was not until 1974 that the idea for of Post-it Notes, 3M has heard some remember things.
Robert Boyle (1627–1691) was born in Ireland. He became especially interested in experiments
involving air and developed an air pump with which he produced evacuated cylinders. He used
© Devonshire Collection/Reproduced by permission of Chatsworth Settlement Trustees/The Bridgeman

these cylinders to show that a feather and a lump of lead fall at the same rate in the absence of
air resistance and that sound cannot be produced in a vacuum. His most famous experiments
involved careful measurements of the volume of a gas as a function of pressure. In his book Boyle
urged that the ancient view of elements as mystical substances should be abandoned and that an
element should instead be defined as anything that cannot be broken down into simpler
substances. This concept was an important step in the development of m odern chemistry.
smoothly and efficiently. For one thing, hypotheses and observations are not totally
independent of each other, as we have assumed in the description of the idealized sci-
entific method. The coupling of observations and hypotheses occurs because once we
begin to proceed down a given theoretical path, our hypotheses are unavoidably
couched in the language of that theory. In other words, we tend to see what we expect
to see and often fail to notice things that we do not expect. Thus the theory we are test-
ing helps us because it focuses our questions. However, at the same time, this focusing
process may limit our ability to see other possible explanations.
It is also important to keep in mind that scientists are human. They have prejudices;
Art Library
they misinterpret data; they become emotionally attached to their theories and thus
lose objectivity; and they play politics. Science is affected by profit motives, budgets,
fads, wars, and religious beliefs. Galileo, for example, was forced to recant his astro-
nomical observations in the face of strong religious resistance. Lavoisier, the father of
modern chemistry, was beheaded because of his political affiliations. Great progress in
the chemistry of nitrogen fertilizers resulted from the desire to produce explosives to
fight wars. The progress of science is often affected more by the frailties of humans
and their institutions than by the limitations of scientific measuring devices. The sci-
entific methods are only as effective as the humans using them. They do not automati-
cally lead to progress.
Critical Thinking
What if everyone in the government used the scientific method to analyze and solve
society’s problems, and politics were never involved in the solutions? How would this
be different from the present situation, and would it be better or worse?
1.3 Units of Measurement

IBLG: See questions from “Uncertainty, Making observations is fundamental to all science. A quantitative observation, or mea-
Measurement, and Calculations” surement, always consists of two parts: a number and a scale (called a unit). Both parts
must be present for the measurement to be meaningful.
In this textbook we will use measurements of mass, length, time, temperature, electric
current, and the amount of a substance, among others. Scientists recognized long ago
that standard systems of units had to be adopted if measurements were to be useful. If
every scientist had a different set of units, complete chaos would result. Unfortunately,
different standards were adopted in different parts of the world. The two major systems
are the English system used in the United States and the metric system used by most of
the rest of the industrialized world. This duality causes a good deal of trouble; for ex-
ample, parts as simple as bolts are not interchangeable between machines built using the
two systems. As a result, the United States has begun to adopt the metric system.
Most scientists in all countries have used the metric system for many years. In 1960,
an international agreement set up a system of units called the International System (le
Système International in French), or the SI system. This system is based on the metric
system and units derived from the metric system. The fundamental SI units are listed in
Table 1.1. We will discuss how to manipulate these units later in this chapter.
1.3 Units of Measurement 9
Critical Units!
How important are conversions

from one unit to another? If you ask
the National Aeronautics and Space
Administration (NASA), very impor-
tant! In 1999, NASA lost a $125 million
Mars Climate Orbiter because of a
failure to convert from English to
metric units.
The problem arose because two
teams working on the Mars mission
were using different sets of units.
NASA’s scientists at the Jet Propulsion
Laboratory in Pasadena, California,
NASA
assumed that the thrust data for the
rockets on the Orbiter they received Artist’s conception of the lost Mars Climate Orbiter.
from Lockheed Martin Astronautics in
Denver, which built the spacecraft,
were in metric units. In reality, the switch to the metric system. About between life and death on some
units were English. As a result, the 95% of the world now uses the metric occasions. In 1983, for example, a
Orbiter dipped 100 km lower into the system, and the United States is slowly Canadian jetliner almost ran out of
Mars atmosphere than planned, and switching from English to metric. For fuel when someone pumped 22,300 lb
the friction from the atmosphere example, the automobile industry has of fuel into the aircraft instead of
caused the craft to burn up. adopted metric fasteners, and we buy 22,300 kg. Remember to watch your
NASA’s mistake refueled the our soda in 2-L bottles. units!
controversy over whether Congress Units can be very important. In
should require the United States to fact, they can mean the difference
Because the fundamental units are not always convenient (expressing the mass of a
pin in kilograms is awkward), prefixes are used to change the size of the unit. These
are listed in Table 1.2. Some common objects and their measurements in SI units are
listed in Table 1.3.
One physical quantity that is very important in chemistry is volume, which is not a
fundamental SI unit but is derived from length. A cube that measures 1 meter (m) on
Table 1.1 | Fundamental SI Units

Physical Quantity Name of Unit Abbreviation
Mass kilogram kg
Length meter m
Time second s
Temperature kelvin K
Electric current ampere A
Soda is commonly sold in 2-L bottles—
Amount of substance mole mol
an example of the use of SI units in Luminous intensity candela cd
everyday life.
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no related content on Scribd:
DANCE ON STILTS AT THE GIRLS’ UNYAGO, NIUCHI
Newala, too, suffers from the distance of its water-supply—at least

the Newala of to-day does; there was once another Newala in a lovely
valley at the foot of the plateau. I visited it and found scarcely a trace
of houses, only a Christian cemetery, with the graves of several
missionaries and their converts, remaining as a monument of its
former glories. But the surroundings are wonderfully beautiful. A
thick grove of splendid mango-trees closes in the weather-worn
crosses and headstones; behind them, combining the useful and the
agreeable, is a whole plantation of lemon-trees covered with ripe
fruit; not the small African kind, but a much larger and also juicier
imported variety, which drops into the hands of the passing traveller,
without calling for any exertion on his part. Old Newala is now under
the jurisdiction of the native pastor, Daudi, at Chingulungulu, who,
as I am on very friendly terms with him, allows me, as a matter of
course, the use of this lemon-grove during my stay at Newala.
FEET MUTILATED BY THE RAVAGES OF THE “JIGGER”
(Sarcopsylla penetrans)
The water-supply of New Newala is in the bottom of the valley,

some 1,600 feet lower down. The way is not only long and fatiguing,
but the water, when we get it, is thoroughly bad. We are suffering not
only from this, but from the fact that the arrangements at Newala are
nothing short of luxurious. We have a separate kitchen—a hut built
against the boma palisade on the right of the baraza, the interior of
which is not visible from our usual position. Our two cooks were not
long in finding this out, and they consequently do—or rather neglect
to do—what they please. In any case they do not seem to be very
particular about the boiling of our drinking-water—at least I can
attribute to no other cause certain attacks of a dysenteric nature,
from which both Knudsen and I have suffered for some time. If a
man like Omari has to be left unwatched for a moment, he is capable
of anything. Besides this complaint, we are inconvenienced by the
state of our nails, which have become as hard as glass, and crack on
the slightest provocation, and I have the additional infliction of
pimples all over me. As if all this were not enough, we have also, for
the last week been waging war against the jigger, who has found his
Eldorado in the hot sand of the Makonde plateau. Our men are seen
all day long—whenever their chronic colds and the dysentery likewise
raging among them permit—occupied in removing this scourge of
Africa from their feet and trying to prevent the disastrous
consequences of its presence. It is quite common to see natives of
this place with one or two toes missing; many have lost all their toes,
or even the whole front part of the foot, so that a well-formed leg
ends in a shapeless stump. These ravages are caused by the female of
Sarcopsylla penetrans, which bores its way under the skin and there
develops an egg-sac the size of a pea. In all books on the subject, it is
stated that one’s attention is called to the presence of this parasite by
an intolerable itching. This agrees very well with my experience, so
far as the softer parts of the sole, the spaces between and under the
toes, and the side of the foot are concerned, but if the creature
penetrates through the harder parts of the heel or ball of the foot, it
may escape even the most careful search till it has reached maturity.
Then there is no time to be lost, if the horrible ulceration, of which
we see cases by the dozen every day, is to be prevented. It is much
easier, by the way, to discover the insect on the white skin of a
European than on that of a native, on which the dark speck scarcely
shows. The four or five jiggers which, in spite of the fact that I
constantly wore high laced boots, chose my feet to settle in, were
taken out for me by the all-accomplished Knudsen, after which I
thought it advisable to wash out the cavities with corrosive
sublimate. The natives have a different sort of disinfectant—they fill
the hole with scraped roots. In a tiny Makua village on the slope of
the plateau south of Newala, we saw an old woman who had filled all
the spaces under her toe-nails with powdered roots by way of
prophylactic treatment. What will be the result, if any, who can say?
The rest of the many trifling ills which trouble our existence are
really more comic than serious. In the absence of anything else to
smoke, Knudsen and I at last opened a box of cigars procured from
the Indian store-keeper at Lindi, and tried them, with the most
distressing results. Whether they contain opium or some other
narcotic, neither of us can say, but after the tenth puff we were both
“off,” three-quarters stupefied and unspeakably wretched. Slowly we
recovered—and what happened next? Half-an-hour later we were
once more smoking these poisonous concoctions—so insatiable is the
craving for tobacco in the tropics.
Even my present attacks of fever scarcely deserve to be taken
seriously. I have had no less than three here at Newala, all of which
have run their course in an incredibly short time. In the early
afternoon, I am busy with my old natives, asking questions and
making notes. The strong midday coffee has stimulated my spirits to
an extraordinary degree, the brain is active and vigorous, and work
progresses rapidly, while a pleasant warmth pervades the whole
body. Suddenly this gives place to a violent chill, forcing me to put on
my overcoat, though it is only half-past three and the afternoon sun
is at its hottest. Now the brain no longer works with such acuteness
and logical precision; more especially does it fail me in trying to
establish the syntax of the difficult Makua language on which I have
ventured, as if I had not enough to do without it. Under the
circumstances it seems advisable to take my temperature, and I do
so, to save trouble, without leaving my seat, and while going on with
my work. On examination, I find it to be 101·48°. My tutors are
abruptly dismissed and my bed set up in the baraza; a few minutes
later I am in it and treating myself internally with hot water and
lemon-juice.
Three hours later, the thermometer marks nearly 104°, and I make
them carry me back into the tent, bed and all, as I am now perspiring
heavily, and exposure to the cold wind just beginning to blow might
mean a fatal chill. I lie still for a little while, and then find, to my
great relief, that the temperature is not rising, but rather falling. This
is about 7.30 p.m. At 8 p.m. I find, to my unbounded astonishment,
that it has fallen below 98·6°, and I feel perfectly well. I read for an
hour or two, and could very well enjoy a smoke, if I had the
wherewithal—Indian cigars being out of the question.
Having no medical training, I am at a loss to account for this state
of things. It is impossible that these transitory attacks of high fever
should be malarial; it seems more probable that they are due to a
kind of sunstroke. On consulting my note-book, I become more and
more inclined to think this is the case, for these attacks regularly
follow extreme fatigue and long exposure to strong sunshine. They at
least have the advantage of being only short interruptions to my
work, as on the following morning I am always quite fresh and fit.
My treasure of a cook is suffering from an enormous hydrocele which
makes it difficult for him to get up, and Moritz is obliged to keep in
the dark on account of his inflamed eyes. Knudsen’s cook, a raw boy
from somewhere in the bush, knows still less of cooking than Omari;
consequently Nils Knudsen himself has been promoted to the vacant
post. Finding that we had come to the end of our supplies, he began
by sending to Chingulungulu for the four sucking-pigs which we had
bought from Matola and temporarily left in his charge; and when
they came up, neatly packed in a large crate, he callously slaughtered
the biggest of them. The first joint we were thoughtless enough to
entrust for roasting to Knudsen’s mshenzi cook, and it was
consequently uneatable; but we made the rest of the animal into a
jelly which we ate with great relish after weeks of underfeeding,
consuming incredible helpings of it at both midday and evening
meals. The only drawback is a certain want of variety in the tinned
vegetables. Dr. Jäger, to whom the Geographical Commission
entrusted the provisioning of the expeditions—mine as well as his
own—because he had more time on his hands than the rest of us,
seems to have laid in a huge stock of Teltow turnips,[46] an article of
food which is all very well for occasional use, but which quickly palls
when set before one every day; and we seem to have no other tins
left. There is no help for it—we must put up with the turnips; but I
am certain that, once I am home again, I shall not touch them for ten
years to come.
Amid all these minor evils, which, after all, go to make up the
genuine flavour of Africa, there is at least one cheering touch:
Knudsen has, with the dexterity of a skilled mechanic, repaired my 9
× 12 cm. camera, at least so far that I can use it with a little care.
How, in the absence of finger-nails, he was able to accomplish such a
ticklish piece of work, having no tool but a clumsy screw-driver for
taking to pieces and putting together again the complicated
mechanism of the instantaneous shutter, is still a mystery to me; but
he did it successfully. The loss of his finger-nails shows him in a light
contrasting curiously enough with the intelligence evinced by the
above operation; though, after all, it is scarcely surprising after his
ten years’ residence in the bush. One day, at Lindi, he had occasion
to wash a dog, which must have been in need of very thorough
cleansing, for the bottle handed to our friend for the purpose had an
extremely strong smell. Having performed his task in the most
conscientious manner, he perceived with some surprise that the dog
did not appear much the better for it, and was further surprised by
finding his own nails ulcerating away in the course of the next few
days. “How was I to know that carbolic acid has to be diluted?” he
mutters indignantly, from time to time, with a troubled gaze at his
mutilated finger-tips.
Since we came to Newala we have been making excursions in all
directions through the surrounding country, in accordance with old
habit, and also because the akida Sefu did not get together the tribal
elders from whom I wanted information so speedily as he had
promised. There is, however, no harm done, as, even if seen only
from the outside, the country and people are interesting enough.
The Makonde plateau is like a large rectangular table rounded off
at the corners. Measured from the Indian Ocean to Newala, it is
about seventy-five miles long, and between the Rovuma and the
Lukuledi it averages fifty miles in breadth, so that its superficial area
is about two-thirds of that of the kingdom of Saxony. The surface,
however, is not level, but uniformly inclined from its south-western
edge to the ocean. From the upper edge, on which Newala lies, the
eye ranges for many miles east and north-east, without encountering
any obstacle, over the Makonde bush. It is a green sea, from which
here and there thick clouds of smoke rise, to show that it, too, is
inhabited by men who carry on their tillage like so many other
primitive peoples, by cutting down and burning the bush, and
manuring with the ashes. Even in the radiant light of a tropical day
such a fire is a grand sight.
Much less effective is the impression produced just now by the
great western plain as seen from the edge of the plateau. As often as
time permits, I stroll along this edge, sometimes in one direction,
sometimes in another, in the hope of finding the air clear enough to
let me enjoy the view; but I have always been disappointed.
Wherever one looks, clouds of smoke rise from the burning bush,
and the air is full of smoke and vapour. It is a pity, for under more
favourable circumstances the panorama of the whole country up to
the distant Majeje hills must be truly magnificent. It is of little use
taking photographs now, and an outline sketch gives a very poor idea
of the scenery. In one of these excursions I went out of my way to
make a personal attempt on the Makonde bush. The present edge of
the plateau is the result of a far-reaching process of destruction
through erosion and denudation. The Makonde strata are
everywhere cut into by ravines, which, though short, are hundreds of
yards in depth. In consequence of the loose stratification of these
beds, not only are the walls of these ravines nearly vertical, but their
upper end is closed by an equally steep escarpment, so that the
western edge of the Makonde plateau is hemmed in by a series of
deep, basin-like valleys. In order to get from one side of such a ravine
to the other, I cut my way through the bush with a dozen of my men.
It was a very open part, with more grass than scrub, but even so the
short stretch of less than two hundred yards was very hard work; at
the end of it the men’s calicoes were in rags and they themselves
bleeding from hundreds of scratches, while even our strong khaki
suits had not escaped scatheless.
NATIVE PATH THROUGH THE MAKONDE BUSH, NEAR

MAHUTA
I see increasing reason to believe that the view formed some time
back as to the origin of the Makonde bush is the correct one. I have
no doubt that it is not a natural product, but the result of human
occupation. Those parts of the high country where man—as a very
slight amount of practice enables the eye to perceive at once—has not
yet penetrated with axe and hoe, are still occupied by a splendid
timber forest quite able to sustain a comparison with our mixed
forests in Germany. But wherever man has once built his hut or tilled
his field, this horrible bush springs up. Every phase of this process
may be seen in the course of a couple of hours’ walk along the main
road. From the bush to right or left, one hears the sound of the axe—
not from one spot only, but from several directions at once. A few
steps further on, we can see what is taking place. The brush has been
cut down and piled up in heaps to the height of a yard or more,
between which the trunks of the large trees stand up like the last
pillars of a magnificent ruined building. These, too, present a
melancholy spectacle: the destructive Makonde have ringed them—
cut a broad strip of bark all round to ensure their dying off—and also
piled up pyramids of brush round them. Father and son, mother and
son-in-law, are chopping away perseveringly in the background—too
busy, almost, to look round at the white stranger, who usually excites
so much interest. If you pass by the same place a week later, the piles
of brushwood have disappeared and a thick layer of ashes has taken
the place of the green forest. The large trees stretch their
smouldering trunks and branches in dumb accusation to heaven—if
they have not already fallen and been more or less reduced to ashes,
perhaps only showing as a white stripe on the dark ground.
This work of destruction is carried out by the Makonde alike on the
virgin forest and on the bush which has sprung up on sites already
cultivated and deserted. In the second case they are saved the trouble
of burning the large trees, these being entirely absent in the
secondary bush.
After burning this piece of forest ground and loosening it with the
hoe, the native sows his corn and plants his vegetables. All over the
country, he goes in for bed-culture, which requires, and, in fact,
receives, the most careful attention. Weeds are nowhere tolerated in
the south of German East Africa. The crops may fail on the plains,
where droughts are frequent, but never on the plateau with its
abundant rains and heavy dews. Its fortunate inhabitants even have
the satisfaction of seeing the proud Wayao and Wamakua working
for them as labourers, driven by hunger to serve where they were
accustomed to rule.
But the light, sandy soil is soon exhausted, and would yield no
harvest the second year if cultivated twice running. This fact has
been familiar to the native for ages; consequently he provides in
time, and, while his crop is growing, prepares the next plot with axe
and firebrand. Next year he plants this with his various crops and
lets the first piece lie fallow. For a short time it remains waste and
desolate; then nature steps in to repair the destruction wrought by
man; a thousand new growths spring out of the exhausted soil, and
even the old stumps put forth fresh shoots. Next year the new growth
is up to one’s knees, and in a few years more it is that terrible,
impenetrable bush, which maintains its position till the black
occupier of the land has made the round of all the available sites and
come back to his starting point.
The Makonde are, body and soul, so to speak, one with this bush.
According to my Yao informants, indeed, their name means nothing
else but “bush people.” Their own tradition says that they have been
settled up here for a very long time, but to my surprise they laid great
stress on an original immigration. Their old homes were in the
south-east, near Mikindani and the mouth of the Rovuma, whence
their peaceful forefathers were driven by the continual raids of the
Sakalavas from Madagascar and the warlike Shirazis[47] of the coast,
to take refuge on the almost inaccessible plateau. I have studied
African ethnology for twenty years, but the fact that changes of
population in this apparently quiet and peaceable corner of the earth
could have been occasioned by outside enterprises taking place on
the high seas, was completely new to me. It is, no doubt, however,
correct.
The charming tribal legend of the Makonde—besides informing us
of other interesting matters—explains why they have to live in the
thickest of the bush and a long way from the edge of the plateau,
instead of making their permanent homes beside the purling brooks
and springs of the low country.
“The place where the tribe originated is Mahuta, on the southern
side of the plateau towards the Rovuma, where of old time there was
nothing but thick bush. Out of this bush came a man who never
washed himself or shaved his head, and who ate and drank but little.
He went out and made a human figure from the wood of a tree
growing in the open country, which he took home to his abode in the
bush and there set it upright. In the night this image came to life and
was a woman. The man and woman went down together to the
Rovuma to wash themselves. Here the woman gave birth to a still-
born child. They left that place and passed over the high land into the
valley of the Mbemkuru, where the woman had another child, which
was also born dead. Then they returned to the high bush country of
Mahuta, where the third child was born, which lived and grew up. In
course of time, the couple had many more children, and called
themselves Wamatanda. These were the ancestral stock of the
Makonde, also called Wamakonde,[48] i.e., aborigines. Their
forefather, the man from the bush, gave his children the command to
bury their dead upright, in memory of the mother of their race who
was cut out of wood and awoke to life when standing upright. He also
warned them against settling in the valleys and near large streams,
for sickness and death dwelt there. They were to make it a rule to
have their huts at least an hour’s walk from the nearest watering-
place; then their children would thrive and escape illness.”
The explanation of the name Makonde given by my informants is
somewhat different from that contained in the above legend, which I
extract from a little book (small, but packed with information), by
Pater Adams, entitled Lindi und sein Hinterland. Otherwise, my
results agree exactly with the statements of the legend. Washing?
Hapana—there is no such thing. Why should they do so? As it is, the
supply of water scarcely suffices for cooking and drinking; other
people do not wash, so why should the Makonde distinguish himself
by such needless eccentricity? As for shaving the head, the short,
woolly crop scarcely needs it,[49] so the second ancestral precept is
likewise easy enough to follow. Beyond this, however, there is
nothing ridiculous in the ancestor’s advice. I have obtained from
various local artists a fairly large number of figures carved in wood,
ranging from fifteen to twenty-three inches in height, and
representing women belonging to the great group of the Mavia,
Makonde, and Matambwe tribes. The carving is remarkably well
done and renders the female type with great accuracy, especially the
keloid ornamentation, to be described later on. As to the object and
meaning of their works the sculptors either could or (more probably)
would tell me nothing, and I was forced to content myself with the
scanty information vouchsafed by one man, who said that the figures
were merely intended to represent the nembo—the artificial
deformations of pelele, ear-discs, and keloids. The legend recorded
by Pater Adams places these figures in a new light. They must surely
be more than mere dolls; and we may even venture to assume that
they are—though the majority of present-day Makonde are probably
unaware of the fact—representations of the tribal ancestress.
The references in the legend to the descent from Mahuta to the
Rovuma, and to a journey across the highlands into the Mbekuru
valley, undoubtedly indicate the previous history of the tribe, the
travels of the ancestral pair typifying the migrations of their
descendants. The descent to the neighbouring Rovuma valley, with
its extraordinary fertility and great abundance of game, is intelligible
at a glance—but the crossing of the Lukuledi depression, the ascent
to the Rondo Plateau and the descent to the Mbemkuru, also lie
within the bounds of probability, for all these districts have exactly
the same character as the extreme south. Now, however, comes a
point of especial interest for our bacteriological age. The primitive
Makonde did not enjoy their lives in the marshy river-valleys.
Disease raged among them, and many died. It was only after they
had returned to their original home near Mahuta, that the health
conditions of these people improved. We are very apt to think of the
African as a stupid person whose ignorance of nature is only equalled
by his fear of it, and who looks on all mishaps as caused by evil
spirits and malignant natural powers. It is much more correct to
assume in this case that the people very early learnt to distinguish
districts infested with malaria from those where it is absent.
This knowledge is crystallized in the
ancestral warning against settling in the
valleys and near the great waters, the
dwelling-places of disease and death. At the
same time, for security against the hostile
Mavia south of the Rovuma, it was enacted
that every settlement must be not less than a
certain distance from the southern edge of the
plateau. Such in fact is their mode of life at the
present day. It is not such a bad one, and
certainly they are both safer and more
comfortable than the Makua, the recent
intruders from the south, who have made USUAL METHOD OF
good their footing on the western edge of the CLOSING HUT-DOOR
plateau, extending over a fairly wide belt of
country. Neither Makua nor Makonde show in their dwellings
anything of the size and comeliness of the Yao houses in the plain,
especially at Masasi, Chingulungulu and Zuza’s. Jumbe Chauro, a
Makonde hamlet not far from Newala, on the road to Mahuta, is the
most important settlement of the tribe I have yet seen, and has fairly
spacious huts. But how slovenly is their construction compared with
the palatial residences of the elephant-hunters living in the plain.
The roofs are still more untidy than in the general run of huts during
the dry season, the walls show here and there the scanty beginnings
or the lamentable remains of the mud plastering, and the interior is a
veritable dog-kennel; dirt, dust and disorder everywhere. A few huts
only show any attempt at division into rooms, and this consists
merely of very roughly-made bamboo partitions. In one point alone
have I noticed any indication of progress—in the method of fastening
the door. Houses all over the south are secured in a simple but
ingenious manner. The door consists of a set of stout pieces of wood
or bamboo, tied with bark-string to two cross-pieces, and moving in
two grooves round one of the door-posts, so as to open inwards. If
the owner wishes to leave home, he takes two logs as thick as a man’s
upper arm and about a yard long. One of these is placed obliquely
against the middle of the door from the inside, so as to form an angle
of from 60° to 75° with the ground. He then places the second piece
horizontally across the first, pressing it downward with all his might.
It is kept in place by two strong posts planted in the ground a few
inches inside the door. This fastening is absolutely safe, but of course
cannot be applied to both doors at once, otherwise how could the
owner leave or enter his house? I have not yet succeeded in finding
out how the back door is fastened.
MAKONDE LOCK AND KEY AT JUMBE CHAURO

This is the general way of closing a house. The Makonde at Jumbe
Chauro, however, have a much more complicated, solid and original
one. Here, too, the door is as already described, except that there is
only one post on the inside, standing by itself about six inches from
one side of the doorway. Opposite this post is a hole in the wall just
large enough to admit a man’s arm. The door is closed inside by a
large wooden bolt passing through a hole in this post and pressing
with its free end against the door. The other end has three holes into
which fit three pegs running in vertical grooves inside the post. The
door is opened with a wooden key about a foot long, somewhat
curved and sloped off at the butt; the other end has three pegs
corresponding to the holes, in the bolt, so that, when it is thrust
through the hole in the wall and inserted into the rectangular
opening in the post, the pegs can be lifted and the bolt drawn out.[50]
MODE OF INSERTING THE KEY
With no small pride first one householder and then a second

showed me on the spot the action of this greatest invention of the
Makonde Highlands. To both with an admiring exclamation of
“Vizuri sana!” (“Very fine!”). I expressed the wish to take back these
marvels with me to Ulaya, to show the Wazungu what clever fellows
the Makonde are. Scarcely five minutes after my return to camp at
Newala, the two men came up sweating under the weight of two
heavy logs which they laid down at my feet, handing over at the same
time the keys of the fallen fortress. Arguing, logically enough, that if
the key was wanted, the lock would be wanted with it, they had taken
their axes and chopped down the posts—as it never occurred to them
to dig them out of the ground and so bring them intact. Thus I have
two badly damaged specimens, and the owners, instead of praise,
come in for a blowing-up.
The Makua huts in the environs of Newala are especially
miserable; their more than slovenly construction reminds one of the
temporary erections of the Makua at Hatia’s, though the people here
have not been concerned in a war. It must therefore be due to
congenital idleness, or else to the absence of a powerful chief. Even
the baraza at Mlipa’s, a short hour’s walk south-east of Newala,
shares in this general neglect. While public buildings in this country
are usually looked after more or less carefully, this is in evident
danger of being blown over by the first strong easterly gale. The only
attractive object in this whole district is the grave of the late chief
Mlipa. I visited it in the morning, while the sun was still trying with
partial success to break through the rolling mists, and the circular
grove of tall euphorbias, which, with a broken pot, is all that marks
the old king’s resting-place, impressed one with a touch of pathos.
Even my very materially-minded carriers seemed to feel something
of the sort, for instead of their usual ribald songs, they chanted
solemnly, as we marched on through the dense green of the Makonde
bush:—
“We shall arrive with the great master; we stand in a row and have
no fear about getting our food and our money from the Serkali (the
Government). We are not afraid; we are going along with the great
master, the lion; we are going down to the coast and back.”
With regard to the characteristic features of the various tribes here
on the western edge of the plateau, I can arrive at no other
conclusion than the one already come to in the plain, viz., that it is
impossible for anyone but a trained anthropologist to assign any
given individual at once to his proper tribe. In fact, I think that even
an anthropological specialist, after the most careful examination,
might find it a difficult task to decide. The whole congeries of peoples
collected in the region bounded on the west by the great Central
African rift, Tanganyika and Nyasa, and on the east by the Indian
Ocean, are closely related to each other—some of their languages are
only distinguished from one another as dialects of the same speech,
and no doubt all the tribes present the same shape of skull and
structure of skeleton. Thus, surely, there can be no very striking
differences in outward appearance.
Even did such exist, I should have no time
to concern myself with them, for day after day,
I have to see or hear, as the case may be—in
any case to grasp and record—an
extraordinary number of ethnographic
phenomena. I am almost disposed to think it
fortunate that some departments of inquiry, at
least, are barred by external circumstances.
Chief among these is the subject of iron-
working. We are apt to think of Africa as a
country where iron ore is everywhere, so to
speak, to be picked up by the roadside, and
where it would be quite surprising if the
inhabitants had not learnt to smelt the
material ready to their hand. In fact, the
knowledge of this art ranges all over the
continent, from the Kabyles in the north to the
Kafirs in the south. Here between the Rovuma
and the Lukuledi the conditions are not so
favourable. According to the statements of the
Makonde, neither ironstone nor any other
form of iron ore is known to them. They have
not therefore advanced to the art of smelting
the metal, but have hitherto bought all their
THE ANCESTRESS OF
THE MAKONDE
iron implements from neighbouring tribes.
Even in the plain the inhabitants are not much
better off. Only one man now living is said to
understand the art of smelting iron. This old fundi lives close to
Huwe, that isolated, steep-sided block of granite which rises out of
the green solitude between Masasi and Chingulungulu, and whose
jagged and splintered top meets the traveller’s eye everywhere. While
still at Masasi I wished to see this man at work, but was told that,
frightened by the rising, he had retired across the Rovuma, though
he would soon return. All subsequent inquiries as to whether the
fundi had come back met with the genuine African answer, “Bado”
(“Not yet”).
BRAZIER
Some consolation was afforded me by a brassfounder, whom I

came across in the bush near Akundonde’s. This man is the favourite
of women, and therefore no doubt of the gods; he welds the glittering
brass rods purchased at the coast into those massive, heavy rings
which, on the wrists and ankles of the local fair ones, continually give
me fresh food for admiration. Like every decent master-craftsman he
had all his tools with him, consisting of a pair of bellows, three
crucibles and a hammer—nothing more, apparently. He was quite
willing to show his skill, and in a twinkling had fixed his bellows on
the ground. They are simply two goat-skins, taken off whole, the four
legs being closed by knots, while the upper opening, intended to
admit the air, is kept stretched by two pieces of wood. At the lower
end of the skin a smaller opening is left into which a wooden tube is
stuck. The fundi has quickly borrowed a heap of wood-embers from
the nearest hut; he then fixes the free ends of the two tubes into an
earthen pipe, and clamps them to the ground by means of a bent
piece of wood. Now he fills one of his small clay crucibles, the dross
on which shows that they have been long in use, with the yellow
material, places it in the midst of the embers, which, at present are
only faintly glimmering, and begins his work. In quick alternation
the smith’s two hands move up and down with the open ends of the
bellows; as he raises his hand he holds the slit wide open, so as to let
the air enter the skin bag unhindered. In pressing it down he closes
the bag, and the air puffs through the bamboo tube and clay pipe into
the fire, which quickly burns up. The smith, however, does not keep
on with this work, but beckons to another man, who relieves him at
the bellows, while he takes some more tools out of a large skin pouch
carried on his back. I look on in wonder as, with a smooth round
stick about the thickness of a finger, he bores a few vertical holes into
the clean sand of the soil. This should not be difficult, yet the man
seems to be taking great pains over it. Then he fastens down to the
ground, with a couple of wooden clamps, a neat little trough made by
splitting a joint of bamboo in half, so that the ends are closed by the
two knots. At last the yellow metal has attained the right consistency,
and the fundi lifts the crucible from the fire by means of two sticks
split at the end to serve as tongs. A short swift turn to the left—a
tilting of the crucible—and the molten brass, hissing and giving forth
clouds of smoke, flows first into the bamboo mould and then into the
holes in the ground.
The technique of this backwoods craftsman may not be very far
advanced, but it cannot be denied that he knows how to obtain an
adequate result by the simplest means. The ladies of highest rank in
this country—that is to say, those who can afford it, wear two kinds
of these massive brass rings, one cylindrical, the other semicircular
in section. The latter are cast in the most ingenious way in the
bamboo mould, the former in the circular hole in the sand. It is quite
a simple matter for the fundi to fit these bars to the limbs of his fair
customers; with a few light strokes of his hammer he bends the
pliable brass round arm or ankle without further inconvenience to
the wearer.
SHAPING THE POT
SMOOTHING WITH MAIZE-COB
CUTTING THE EDGE

FINISHING THE BOTTOM
LAST SMOOTHING BEFORE

BURNING
FIRING THE BRUSH-PILE

LIGHTING THE FARTHER SIDE OF
THE PILE
TURNING THE RED-HOT VESSEL
NYASA WOMAN MAKING POTS AT MASASI

Pottery is an art which must always and everywhere excite the
interest of the student, just because it is so intimately connected with
the development of human culture, and because its relics are one of
the principal factors in the reconstruction of our own condition in
prehistoric times. I shall always remember with pleasure the two or
three afternoons at Masasi when Salim Matola’s mother, a slightly-
built, graceful, pleasant-looking woman, explained to me with
touching patience, by means of concrete illustrations, the ceramic art
of her people. The only implements for this primitive process were a
lump of clay in her left hand, and in the right a calabash containing
the following valuables: the fragment of a maize-cob stripped of all
its grains, a smooth, oval pebble, about the size of a pigeon’s egg, a
few chips of gourd-shell, a bamboo splinter about the length of one’s
hand, a small shell, and a bunch of some herb resembling spinach.
Nothing more. The woman scraped with the
shell a round, shallow hole in the soft, fine
sand of the soil, and, when an active young
girl had filled the calabash with water for her,
she began to knead the clay. As if by magic it
gradually assumed the shape of a rough but
already well-shaped vessel, which only wanted
a little touching up with the instruments
before mentioned. I looked out with the
MAKUA WOMAN closest attention for any indication of the use
MAKING A POT. of the potter’s wheel, in however rudimentary
SHOWS THE a form, but no—hapana (there is none). The
BEGINNINGS OF THE embryo pot stood firmly in its little
POTTER’S WHEEL
depression, and the woman walked round it in
a stooping posture, whether she was removing
small stones or similar foreign bodies with the maize-cob, smoothing
the inner or outer surface with the splinter of bamboo, or later, after
letting it dry for a day, pricking in the ornamentation with a pointed
bit of gourd-shell, or working out the bottom, or cutting the edge
with a sharp bamboo knife, or giving the last touches to the finished
vessel. This occupation of the women is infinitely toilsome, but it is
without doubt an accurate reproduction of the process in use among
our ancestors of the Neolithic and Bronze ages.
There is no doubt that the invention of pottery, an item in human
progress whose importance cannot be over-estimated, is due to
women. Rough, coarse and unfeeling, the men of the horde range
over the countryside. When the united cunning of the hunters has
succeeded in killing the game; not one of them thinks of carrying
home the spoil. A bright fire, kindled by a vigorous wielding of the
drill, is crackling beside them; the animal has been cleaned and cut
up secundum artem, and, after a slight singeing, will soon disappear
under their sharp teeth; no one all this time giving a single thought
to wife or child.
To what shifts, on the other hand, the primitive wife, and still more
the primitive mother, was put! Not even prehistoric stomachs could
endure an unvarying diet of raw food. Something or other suggested
the beneficial effect of hot water on the majority of approved but
indigestible dishes. Perhaps a neighbour had tried holding the hard
roots or tubers over the fire in a calabash filled with water—or maybe
an ostrich-egg-shell, or a hastily improvised vessel of bark. They
became much softer and more palatable than they had previously
been; but, unfortunately, the vessel could not stand the fire and got
charred on the outside. That can be remedied, thought our
ancestress, and plastered a layer of wet clay round a similar vessel.
This is an improvement; the cooking utensil remains uninjured, but
the heat of the fire has shrunk it, so that it is loose in its shell. The
next step is to detach it, so, with a firm grip and a jerk, shell and
kernel are separated, and pottery is invented. Perhaps, however, the
discovery which led to an intelligent use of the burnt-clay shell, was
made in a slightly different way. Ostrich-eggs and calabashes are not
to be found in every part of the world, but everywhere mankind has
arrived at the art of making baskets out of pliant materials, such as
bark, bast, strips of palm-leaf, supple twigs, etc. Our inventor has no
water-tight vessel provided by nature. “Never mind, let us line the
basket with clay.” This answers the purpose, but alas! the basket gets
burnt over the blazing fire, the woman watches the process of
cooking with increasing uneasiness, fearing a leak, but no leak
appears. The food, done to a turn, is eaten with peculiar relish; and
the cooking-vessel is examined, half in curiosity, half in satisfaction
at the result. The plastic clay is now hard as stone, and at the same
time looks exceedingly well, for the neat plaiting of the burnt basket
is traced all over it in a pretty pattern. Thus, simultaneously with
pottery, its ornamentation was invented.
Primitive woman has another claim to respect. It was the man,
roving abroad, who invented the art of producing fire at will, but the
woman, unable to imitate him in this, has been a Vestal from the
earliest times. Nothing gives so much trouble as the keeping alight of
the smouldering brand, and, above all, when all the men are absent
from the camp. Heavy rain-clouds gather, already the first large
drops are falling, the first gusts of the storm rage over the plain. The
little flame, a greater anxiety to the woman than her own children,
flickers unsteadily in the blast. What is to be done? A sudden thought
occurs to her, and in an instant she has constructed a primitive hut
out of strips of bark, to protect the flame against rain and wind.
This, or something very like it, was the way in which the principle
of the house was discovered; and even the most hardened misogynist
cannot fairly refuse a woman the credit of it. The protection of the
hearth-fire from the weather is the germ from which the human
dwelling was evolved. Men had little, if any share, in this forward
step, and that only at a late stage. Even at the present day, the
plastering of the housewall with clay and the manufacture of pottery
are exclusively the women’s business. These are two very significant
survivals. Our European kitchen-garden, too, is originally a woman’s
invention, and the hoe, the primitive instrument of agriculture, is,
characteristically enough, still used in this department. But the
noblest achievement which we owe to the other sex is unquestionably
the art of cookery. Roasting alone—the oldest process—is one for
which men took the hint (a very obvious one) from nature. It must
have been suggested by the scorched carcase of some animal
overtaken by the destructive forest-fires. But boiling—the process of
improving organic substances by the help of water heated to boiling-
point—is a much later discovery. It is so recent that it has not even
yet penetrated to all parts of the world. The Polynesians understand
how to steam food, that is, to cook it, neatly wrapped in leaves, in a
hole in the earth between hot stones, the air being excluded, and
(sometimes) a few drops of water sprinkled on the stones; but they
do not understand boiling.
To come back from this digression, we find that the slender Nyasa
woman has, after once more carefully examining the finished pot,
put it aside in the shade to dry. On the following day she sends me
word by her son, Salim Matola, who is always on hand, that she is
going to do the burning, and, on coming out of my house, I find her
already hard at work. She has spread on the ground a layer of very
dry sticks, about as thick as one’s thumb, has laid the pot (now of a
yellowish-grey colour) on them, and is piling brushwood round it.
My faithful Pesa mbili, the mnyampara, who has been standing by,
most obligingly, with a lighted stick, now hands it to her. Both of
them, blowing steadily, light the pile on the lee side, and, when the
flame begins to catch, on the weather side also. Soon the whole is in a
blaze, but the dry fuel is quickly consumed and the fire dies down, so
that we see the red-hot vessel rising from the ashes. The woman
turns it continually with a long stick, sometimes one way and
sometimes another, so that it may be evenly heated all over. In
twenty minutes she rolls it out of the ash-heap, takes up the bundle
of spinach, which has been lying for two days in a jar of water, and
sprinkles the red-hot clay with it. The places where the drops fall are
marked by black spots on the uniform reddish-brown surface. With a
sigh of relief, and with visible satisfaction, the woman rises to an
erect position; she is standing just in a line between me and the fire,
from which a cloud of smoke is just rising: I press the ball of my
camera, the shutter clicks—the apotheosis is achieved! Like a
priestess, representative of her inventive sex, the graceful woman
stands: at her feet the hearth-fire she has given us beside her the
invention she has devised for us, in the background the home she has
built for us.
At Newala, also, I have had the manufacture of pottery carried on
in my presence. Technically the process is better than that already
described, for here we find the beginnings of the potter’s wheel,
which does not seem to exist in the plains; at least I have seen
nothing of the sort. The artist, a frightfully stupid Makua woman, did
not make a depression in the ground to receive the pot she was about
to shape, but used instead a large potsherd. Otherwise, she went to
work in much the same way as Salim’s mother, except that she saved
herself the trouble of walking round and round her work by squatting
at her ease and letting the pot and potsherd rotate round her; this is
surely the first step towards a machine. But it does not follow that
the pot was improved by the process. It is true that it was beautifully
rounded and presented a very creditable appearance when finished,
but the numerous large and small vessels which I have seen, and, in
part, collected, in the “less advanced” districts, are no less so. We
moderns imagine that instruments of precision are necessary to
produce excellent results. Go to the prehistoric collections of our
museums and look at the pots, urns and bowls of our ancestors in the
dim ages of the past, and you will at once perceive your error.
MAKING LONGITUDINAL CUT IN
BARK
DRAWING THE BARK OFF THE LOG
REMOVING THE OUTER BARK

BEATING THE BARK
WORKING THE BARK-CLOTH AFTER BEATING, TO MAKE IT

SOFT
MANUFACTURE OF BARK-CLOTH AT NEWALA

To-day, nearly the whole population of German East Africa is
clothed in imported calico. This was not always the case; even now in
some parts of the north dressed skins are still the prevailing wear,
and in the north-western districts—east and north of Lake
Tanganyika—lies a zone where bark-cloth has not yet been
superseded. Probably not many generations have passed since such
bark fabrics and kilts of skins were the only clothing even in the
south. Even to-day, large quantities of this bright-red or drab
material are still to be found; but if we wish to see it, we must look in
the granaries and on the drying stages inside the native huts, where
it serves less ambitious uses as wrappings for those seeds and fruits
which require to be packed with special care. The salt produced at
Masasi, too, is packed for transport to a distance in large sheets of
bark-cloth. Wherever I found it in any degree possible, I studied the
process of making this cloth. The native requisitioned for the
purpose arrived, carrying a log between two and three yards long and
as thick as his thigh, and nothing else except a curiously-shaped
mallet and the usual long, sharp and pointed knife which all men and
boys wear in a belt at their backs without a sheath—horribile dictu!
[51]
Silently he squats down before me, and with two rapid cuts has
drawn a couple of circles round the log some two yards apart, and
slits the bark lengthwise between them with the point of his knife.
With evident care, he then scrapes off the outer rind all round the
log, so that in a quarter of an hour the inner red layer of the bark
shows up brightly-coloured between the two untouched ends. With
some trouble and much caution, he now loosens the bark at one end,
and opens the cylinder. He then stands up, takes hold of the free
edge with both hands, and turning it inside out, slowly but steadily
pulls it off in one piece. Now comes the troublesome work of
scraping all superfluous particles of outer bark from the outside of
the long, narrow piece of material, while the inner side is carefully
scrutinised for defective spots. At last it is ready for beating. Having
signalled to a friend, who immediately places a bowl of water beside
him, the artificer damps his sheet of bark all over, seizes his mallet,
lays one end of the stuff on the smoothest spot of the log, and
hammers away slowly but continuously. “Very simple!” I think to
myself. “Why, I could do that, too!”—but I am forced to change my
opinions a little later on; for the beating is quite an art, if the fabric is
not to be beaten to pieces. To prevent the breaking of the fibres, the
stuff is several times folded across, so as to interpose several
thicknesses between the mallet and the block. At last the required
state is reached, and the fundi seizes the sheet, still folded, by both
ends, and wrings it out, or calls an assistant to take one end while he
holds the other. The cloth produced in this way is not nearly so fine
and uniform in texture as the famous Uganda bark-cloth, but it is
quite soft, and, above all, cheap.
Now, too, I examine the mallet. My craftsman has been using the
simpler but better form of this implement, a conical block of some
hard wood, its base—the striking surface—being scored across and
across with more or less deeply-cut grooves, and the handle stuck
into a hole in the middle. The other and earlier form of mallet is
shaped in the same way, but the head is fastened by an ingenious
network of bark strips into the split bamboo serving as a handle. The
observation so often made, that ancient customs persist longest in
connection with religious ceremonies and in the life of children, here
finds confirmation. As we shall soon see, bark-cloth is still worn
during the unyago,[52] having been prepared with special solemn
ceremonies; and many a mother, if she has no other garment handy,
will still put her little one into a kilt of bark-cloth, which, after all,
looks better, besides being more in keeping with its African
surroundings, than the ridiculous bit of print from Ulaya.
MAKUA WOMEN

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eTextbook 978-1133611103 Chemistry

(AP Edition) 9th Edition

Chapter 4 Types of Chemical Reactions

4.1 Water, the Common Solvent 139

© Caren Brinkema/Science Faction/Corbis

Chapter 8 Bonding: General Concepts 351

8.1 Types of Chemical Bonds 352

Carsten Peter/Speleoresearch Films/National Geographic Stock

13.7 Le Châtelier’s Principle 633

Chapter 14 Acids and Bases 652

14.1 The Nature of Acids and Bases 653

National Cancer Institute/Photo Researchers, Inc.

Chapter 12 Chemical Kinetics 552

Chapter 17 Spontaneity, Entropy, 18.8 Electrolysis 864

For Review 961 ∣ Key Terms 961 ∣ Questions and

Chapter 21 Transition Metals 22.4 Hydrocarbon Derivatives 1037

Appendix 3 Spectral Analysis A16

22.2 Alkenes and Alkynes 1032

A5.1 Values of Ka for Some Common Monoprotic

Appendix 6 SI Units and Conversion

Answers to Selected Exercises A39

Features of Chemistry, the hints to arrive at the answer. ChemWork problems

Seventh Edition Reviewers Jim McCormick, Truman State

Chemistry, Ninth Edition

Conceptual Understanding Conceptual learning and problem solving are fundamental to

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

See Exercises 8.101 and 8.102

—Jerry Burns, Pellissippi State Technical Community College

scientific models, the authors show students how chemists think

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

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

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

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

See Exercise 1.61

equation: .com to try this Interactive Example

solving process by requiring

See Exercise 17.32

4.9 Oxidation–Reduction Reactions

How do we get there?

Photos © Cengage Learning. All rights reserved.

help students visualize thefor“micro/macro”

See Exercises 4.33 and 4.34

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

8.3 Bond Polarity and Dipole Moments 359

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

Figure 8.6 | (a) The structure and +

I n doing stoichiometry calculations we assumed that reactions proceed to comple-

duction that demon- left (in the direction of the reactants).

related to everyday life.

11097_Ch13_0606-0651.indd 606 9/6/12 9:06 AM 11097_Ch13_0606-0651.indd 607 9/6/12 10:57

1.2 The Scientific Method 7

serendipity. The adhesive for Post-it

11097_Ch01_0001-0041.indd 7 9/6/12 9:02 AM

748 Chapter 15 Acid–Base Equilibria

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

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

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

10 ) and the over-

These problems require the integration of multiple concepts to find

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

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

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

1.1 Chemistry: An Overview