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Textbook Chemistry 9Th Edition Steven S Zumdahl Ebook All Chapter PDF
Textbook Chemistry 9Th Edition Steven S Zumdahl Ebook All Chapter PDF
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Periodic Table of the Elements
Noble
Alkaline gases
1 earth metals Halogens 18
1A 8A
metals nonmetals
1
H 2 13 14 15 16 17 He
1.008 2A 3A 4A 5A 6A 7A 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Na Mg Transition metals Al Si P S Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Alkali metals
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac† Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
(223) 226 (227) (261) (262) (263) (264) (265) (268) (271) (272) (285) (289) (293)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
*Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
† Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Actinides
232.0 (231) 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
Group numbers 1–18 represent the system recommended by the International Union
of Pure and Applied Chemistry.
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Table of Atomic Masses*
Atomic Atomic Atomic Atomic Atomic Atomic
Element Symbol Number Mass Element Symbol Number Mass Element Symbol Number Mass
Actinium Ac 89 [227]§ Germanium Ge 32 72.59 Potassium K 19 39.10
Aluminum Al 13 26.98 Gold Au 79 197.0 Praseodymium Pr 59 140.9
Americium Am 95 [243] Hafnium Hf 72 178.5 Promethium Pm 61 [145]
Antimony Sb 51 121.8 Hassium Hs 108 [265] Protactinium Pa 91 [231]
Argon Ar 18 39.95 Helium He 2 4.003 Radium Ra 88 226
Arsenic As 33 74.92 Holmium Ho 67 164.9 Radon Rn 86 [222]
Astatine At 85 [210] Hydrogen H 1 1.008 Rhenium Re 75 186.2
Barium Ba 56 137.3 Indium In 49 114.8 Rhodium Rh 45 102.9
Berkelium Bk 97 [247] Iodine I 53 126.9 Roentgenium Rg 111 [272]
Beryllium Be 4 9.012 Iridium Ir 77 192.2 Rubidium Rb 37 85.47
Bismuth Bi 83 209.0 Iron Fe 26 55.85 Ruthenium Ru 44 101.1
Bohrium Bh 107 [264] Krypton Kr 36 83.80 Rutherfordium Rf 104 [261]
Boron B 5 10.81 Lanthanum La 57 138.9 Samarium Sm 62 150.4
Bromine Br 35 79.90 Lawrencium Lr 103 [260] Scandium Sc 21 44.96
Cadmium Cd 48 112.4 Lead Pb 82 207.2 Seaborgium Sg 106 [263]
Calcium Ca 20 40.08 Livermorium Lv 116 [293] Selenium Se 34 78.96
Californium Cf 98 [251] Lithium Li 3 6.9419 Silicon Si 14 28.09
Carbon C 6 12.01 Lutetium Lu 71 175.0 Silver Ag 47 107.9
Cerium Ce 58 140.1 Magnesium Mg 12 24.31 Sodium Na 11 22.99
Cesium Cs 55 132.90 Manganese Mn 25 54.94 Strontium Sr 38 87.62
Chlorine Cl 17 35.45 Meitnerium Mt 109 [268] Sulfur S 16 32.07
Chromium Cr 24 52.00 Mendelevium Md 101 [258] Tantalum Ta 73 180.9
Cobalt Co 27 58.93 Mercury Hg 80 200.6 Technetium Tc 43 [98]
Copernicium CN 112 [285] Molybdenum Mo 42 95.94 Tellurium Te 52 127.6
Copper Cu 29 63.55 Neodymium Nd 60 144.2 Terbium Tb 65 158.9
Curium Cm 96 [247] Neon Ne 10 20.18 Thallium Tl 81 204.4
Darmstadtium Ds 110 [271] Neptunium Np 93 [237] Thorium Th 90 232.0
Dubnium Db 105 [262] Nickel Ni 28 58.69 Thulium Tm 69 168.9
Dysprosium Dy 66 162.5 Niobium Nb 41 92.91 Tin Sn 50 118.7
Einsteinium Es 99 [252] Nitrogen N 7 14.01 Titanium Ti 22 47.88
Erbium Er 68 167.3 Nobelium No 102 [259] Tungsten W 74 183.9
Europium Eu 63 152.0 Osmium Os 76 190.2 Uranium U 92 238.0
Fermium Fm 100 [257] Oxygen O 8 16.00 Vanadium V 23 50.94
Flerovium Fl 114 [289] Palladium Pd 46 106.4 Xenon Xe 54 131.3
Fluorine F 9 19.00 Phosphorus P 15 30.97 Ytterbium Yb 70 173.0
Francium Fr 87 [223] Platinum Pt 78 195.1 Yttrium Y 39 88.91
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Gadolinium Gd 64 157.3 Plutonium Pu 94 [244] Zinc Zn 30 65.38
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Gallium Ga 31 69.72 Polonium Po 84 [209] Zirconium Zr 40 91.22
*The values given here are to four significant figures where possible. §A value given in parentheses denotes the mass of the longest-lived isotope.
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Chemistry
Steven S. Zumdahl
University of Illinois
Susan A. Zumdahl
University of Illinois
Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States
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Chemistry, Ninth Edition © 2014, 2010 Brooks Cole, a part of Cengage Learning
Steven S. Zumdahl and Susan A. Zumdahl
ALL RIGHTS RESERVED. No part of this work covered by the copyright herein
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Contents
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iv Contents
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Contents v
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vi Contents
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Contents vii
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
For Review 917 ∣ Key Terms 917 ∣ Questions and
18.2 Galvanic Cells 839 Exercises 919
18.3 Standard Reduction Potentials 842
18.4 Cell Potential, Electrical Work, and Free Chapter 20 The Representative
Energy 849
Elements 926
18.5 Dependence of Cell Potential on
Concentration 852 20.1 A Survey of the Representative Elements 927
18.6 Batteries 858 20.2 The Group 1A Elements 932
CHEMICAL CONNECTIONS Fuel Cells—Portable 20.3 The Chemistry of Hydrogen 933
Energy 861 20.4 The Group 2A Elements 935
18.7 Corrosion 861 20.5 The Group 3A Elements 937
20.6 The Group 4A Elements 939
CHEMICAL CONNECTIONS Beethoven: Hair Is the
Story 940
20.7 The Group 5A Elements 941
20.8 The Chemistry of Nitrogen 942
CHEMICAL CONNECTIONS Nitrous Oxide: Laughing Gas
That Propels Whipped Cream and Cars 948
20.9 The Chemistry of Phosphorus 949
20.10 The Group 6A Elements 952
20.11 The Chemistry of Oxygen 952
20.12 The Chemistry of Sulfur 954
20.13 The Group 7A Elements 956
20.14 The Group 8A Elements 960
NASA/SDO/AIA
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viii Contents
A26
Glossary A27
Index A71
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To the Professor
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
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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
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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
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xii To the Professor
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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
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Copyright 2012 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
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.
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.
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)
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.
a b
11097_Ch08_0351-0414.indd 389 9/6/12 8:24 AM
8.13 Molecular Structure: The VSEPR Model 401
The molecular structure can be predicted from the arrangement of pairs around the
Relative number of molecules
carbon and oxygen atoms. Note that there are four pairs of electrons around the car- ture? Explain your reasoning. Under which tem-
Integrated Rate Laws bon, for
whichReactions
requires a tetrahedral arrangement [Fig. 8.22(a)]. The oxygen also has four A perature condition would the O2(g) sample behave
most ideally? Explain.
pairs, which requires a tetrahedral arrangement. However, in this case the tetrahedron
C with More Than One Reactant
will be slightly distorted by the space requirements of the lone pairs [Fig. 8.22(b)]. The 8. Briefly describe two methods one might use to find the
H
SoO far we have considered theoverall geometric
integrated arrangement
rate laws for simplefor the molecule
reactions is shown
with only one in Fig. 8.22(c). molar mass of a newly synthesized gas for which a
reactant. Special techniques are required to deal with more complicated reactions. Let’s B molecular formula was not known.
consider the reaction
Summary
Let’s Review boxes help students organize their thinking about the 9. In the van der Waals equation, why is a term added to
Let’s
BrO32 1aq2 1 5Br2 1aq2 1 Review
6H1 1aq2 h 3Br2 1l2of
1the
3H2VSEPR
O 1l2 Model Velocity (m/s)
the observed pressure and why is a term subtracted
b
The rules for using the VSEPR model to predict molecular structure are as follows:
From experimental evidence we know that the rate law is crucial chemical concepts that they encounter. from the container volume to correct for nonideal gas
behavior?
❯ Determine the Lewis structure(s) for the molecule. a. If the plots represent the velocity distribution of
D3BrO 2 4 1.0 L of He(g) at STP versus 1.0 L of Cl2(g) at 10. Why do real gases not always behave ideally? Under
H Rate 5 2 ❯ For3molecules
5 k3BrOwith2resonance 1structures,
3 4 3Br 4 3H 4
2 2 use any of the structures to predict the
what conditions does a real gas behave most ideally?
Dt
molecular structure. STP, which plot corresponds to each gas? Explain
your reasoning. Why?
Suppose we run this reaction❯under
Sum the electron where
conditions pairs around
[BrO3the
2 central atom. 23
]0 5 1.0 3 10 M,
[Br H
C ]0 5 1.0 M, and [H ]0 5 1.0 M.
2 1 ❯ In As the reaction
counting proceeds,
pairs, count [BrO32]bond
each multiple decreases sig-effective pair.
as a single
H nificantly, but because the Br ion
2
andarrangement
H ion concentrations
1
are so largebyinitially, A discussion of the Active Learning Questions can be found online in the Instructor’s Resource Guide and on PowerLecture. The questions
❯ The of the pairs is determined minimizing electron-pair repulsions.
O allow students to explore their understanding of concepts through discussion and peer teaching. The real value of these questions is the
relatively little of these two reactants is consumed.
These arrangements Thus [Br2] in
are shown and [H18.6.
Table ] remain ap- learning that occurs while students talk to each other about chemical concepts.
Hproximately constant. In other words,
❯ Loneunder the conditions where
thanthe Br2 ion
pairsand
do. H
1
pairs require more space bonding Choose an arrangement that
ion concentrations are much largergives
thanthe
thelone
BrOpairs
3 ion
2
concentration,
as much we canRecognize
room as possible. assume that the lone pairs may Active Learning Questions d. Capillary action of the mercury causes the mercury to go
c up the tube.
that throughout the reaction produce a slight distortion of the structure at angles less than 120 degrees. These questions are designed to be used by groups of students in
e. The vacuum that is formed at the top of the tube holds up
Figure 8.22 | The molecular 3Br2 4 5 3Br2 4 0 and 3H1 4 5 3H1 4 0 class.
the mercury.
structure of methanol. (a) The 1. Consider the following apparatus: a test tube covered with a
arrangement This means that
of electron pairsthe
andrate law can be written nonpermeable elastic membrane inside a container that is Justify your choice, and for the choices you did not pick, ex-
atoms around the carbon atom. The VSEPR Model—How Well Does It Work?
Rate 5 k3Br2 4 0 3H1 4 02 3BrO32 4 5 kr 3BrO32 4
closed with a cork. A syringe goes through the cork. plain what is wrong with them. Pictures help!
(b) The arrangement of bonding and 3. The barometer below shows the level of mercury at a given at-
lone pairs around The VSEPR model is very simple. There are only a few rules to remember, yet the mospheric pressure. Fill all the other barometers with mercury
where,the oxygen
since [Br2atom.
]0 and [H1]0 are constant,
(c) The molecular structure. model correctly predicts the molecular structures of most molecules formed from non- for that same atmospheric pressure. Explain your answer.
metallic Syringe
kr 5 elements.
k3Br2 4 0 3HMolecules
40
1 2 of any size can be treated by applying the VSEPR model
to each appropriate atom (those bonded to at least two other atoms) in the molecule.
Thus we can use this model to predict the structures of molecules with hundreds of
atoms. It does, however, fail in a few instances. For example, phosphine (PH3), which Cork
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
has a Lewis structure analogous to that of ammonia,
Membrane
H P H H N H
H H Hg(l )
2 9/6/12 8:44 AM
would be predicted to have a molecular structure similar to that for NH3, with bond
angles of approximately 107 degrees. However, the bond angles of phosphine are actu-
ally 94 degrees. There are ways of explaining this structure, but more rules have to be a. As you push down on the syringe, how does the mem-
added to the model. brane covering the test tube change? 4. As you increase the temperature of a gas in a sealed, rigid
This again illustrates the point that simple models are bound to have exceptions. In b. You stop pushing the syringe but continue to hold it container, what happens to the density of the gas? Would the
introductory chemistry we want to use simple models that fit the majority of cases; we down. In a few seconds, what happens to the membrane? results be the same if you did the same experiment in a con-
2. Figure 5.2 shows a picture of a barometer. Which of the fol- tainer with a piston at constant pressure? (See Fig. 5.17.)
are willing to accept a few failures rather than complicate the model. The amazing
thing about the VSEPR model is that such a simple model predicts correctly the struc- lowing statements is the best explanation of how this barom- 5. A diagram in a chemistry book shows a magnified view of a
eter works? flask of air as follows:
tures of so many molecules.
a. Air pressure outside the tube causes the mercury to move in
The text includes a number of Active Learning Questions at the tube until the air pressure inside and outside the tube is
equal.
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
the end of each chapter that are intended for group discussion, b. Air pressure inside the tube causes the mercury to move in
the tube until the air pressure inside and outside the tube is
since students often learn the most when they teach each other. equal.
c. Air pressure outside the tube counterbalances the weight
of the mercury in the tube.
11097_Ch08_0351-0414.indd 401 9/6/12 8:24 AM
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
xiv Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Copyright 2012 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
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.
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?
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.
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Unless otherwise noted, all art on this page is © Cengage Learning 2014. xv
11097_Ch17_0787-0831.indd 793 9/6/12 8:57 AM
Copyright 2012 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
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.
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
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
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H H
δ+
a b c
2δ+
δ− δ−
O C O O C O
Figure 8.7 | (a) The carbon dioxide
molecule. (b) The opposed bond
polarities cancel out, and the carbon
dioxide molecule has no dipole
moment. (c) The electrostatic
potential diagram for carbon dioxide. a b c
than the hydrogen atoms, the molecular charge distribution is that shown in Fig. 8.5(a).
Because of this charge distribution, the water molecule behaves in an electric field as if
it had two centers of charge—one positive and one negative—as shown in Fig. 8.5(b).
The water molecule has a dipole moment. The same type of behavior is observed for the
xvi NH3 molecule (Fig. 8.6). Some molecules have polar bonds but do not have a dipole
moment. This occurs when the individual bond polarities are arranged in such a way
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
that they cancel each other out. An example is the CO2 molecule, which is a linear mol-
ecule that has the charge distribution shown in Fig. 8.7. In this case the opposing bond
polarities
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
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
a preferred orientation to make sure you understand this concept.)
Real-World Applications Interesting applications of modern chemistry show students the
relevance of chemistry to their world.
Each chapter begins 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
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.
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.
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
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
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
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.
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
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
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.
Unless otherwise noted, all art on this page is © Cengage Learning 2014.
xviii Unless otherwise noted, all art on this page is © Cengage Learning 2014.
Copyright 2012 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
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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)
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
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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:
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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
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“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
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About the Authors
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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)
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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.
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1.1 Chemistry: An Overview 3
attractants have been isolated and used to lure males into traps to control insect popu-
lations. It would not be surprising if humans also emitted chemical signals that we
were not aware of on a conscious level. Thus chemistry is pretty interesting and pretty
important. The main goal of this text is to help you understand the concepts of chem-
istry so that you can better appreciate the world around you and can be more effective
in whatever career you choose.
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.
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rack and umbrella-stand combined, as red as rhubarb, and as acrid
in suggestion to one’s feelings; more oilcloth in the parlour; more
mahogany, also, with a pert disposition in its doors and drawers to
resent being shut up; glass bead mats and charity bazaar
photograph frames on the whatnots, all so clean and pungent with
sharp furniture stain that the rudder—Gardener by name—felt, as
usual, the necessity of a humble apology for bringing his five feet
four of shabbiness into the midst of so much splendour and
selectness.
Mr. Plumley rumbled condescendingly in reply—
“You’d get used to it, Robert, you’d get used to it, if you’d lived
familiar with it all your life, as I have.”
“Ah!” said Gardener, “but I wasn’t born like you, sir, to shine.”
If he meant that the other was a light in his way—a little tallowy,
perhaps—his own dry, hungry cheeks certainly justified him in the
self-depreciation. They justified him, moreover—or he fancied they
did, which was all the same as to the moral—in continuing to act
jackal to this social lion, who had once been his employer in the
cheap furniture-removal line. He lived—hung, it would seem more
apposite to say—on his traditions of the great man’s business
capacities, capacities whose fruits were here to witness, for evidence
of the competence upon which his principal had retired. He got, in
fact, little else than his traditions out of his former master at this date;
yet it was strange how they served to delude him into a belief in his
continued profit at the hands of the old patronage. The moral benefit
he acquired from stealing into the local chapel to hear Mr. Plumley
take a Sunday-school class, was at least worth as much to him as
the occasional pipe of tobacco, or glass of whisky and water, which
his idol vouchsafed him. For Mr. Gardener, as a true ‘poor relation’ of
the gods, was humbly thankful for their cheapest condescensions.
“You stuck to your principles, sir,” he said, standing on one leg and
the toe of the other, in humble deprecation of his right to any but the
smallest possible allowance of oilcloth. Perhaps he would have
brought his foot down, even he, could he have guessed the true
significance of his own remark.
“I did, Robert,” said Mr. Plumley, placidly sleeking his hair. “I
always do. Have a pipe, Robert?”
“Thank you kindly, sir,” said the man. “That was a mistake you
made, sir.”
“Mistakes,” said Mr. Plumley, “will occur. Have some whisky,
Robert?”
“You’re very good, sir.”
“You don’t like it too strong, I think, Robert? And how’s the world
treating you, my friend?”
“Much as usual, sir. From hand to mouth’s my motto.”
“Sad, sad to be sure. They’ll distrain upon me, I suppose.”
“I’m afraid so, sir.”
“The inhumanity of the world, Robert! You do pretty reg’lar porter’s
work for Bull and Hacker, the auctioneers, don’t you, Robert?”
“That’s so, Mr. Plumley,” said the man, wondering. “But the work’s
heavier than the wages.”
“They’ll be commissioned to seize the necessary goods. I wish
you’d manage to give ’em a hint, Robert—over the left, you know,
without any reference to me—that there’s a picture I prize (and that
I’ve reason to believe a dealer is after), what would more than pay
the two pun odd of the distraint if put up first. O’ course, I can’t
appear to favour the matter myself, being a con——”
“Passive resister, sir.”
“Thank you, Robert; being the one most concerned in disputin’ the
justice of the law. But a hint from you might settle the question at
once. We aren’t very good friends, Bull and me; and, if he thought I
prized the article, he’d be moral sure to seize it, slap away, to spite
me.”
“The picter?”
“The picture, Robert. There it is.”
It hung in an obscure corner, a dingy enough article, in an old
damaged frame.
“It don’t look the price,” said Gardener doubtfully.
“It cost me more in a bad debt,” said the ex-remover, busying
himself with the whisky in his heavy, observant way.
“Very like, sir,” answered the other, and coughed behind his hand.
“I know what you mean,” said his patron; “that I was took in. Well,
I’ve reason to think not, my man. I’ve reason to think that picture’s
worth a deal—say, fifty pun. Anyhow, I mean to try.”
“A dealer’s after it, you say?”
“Yes, I do say.”
“Then why—with deference, sir—don’t you sell direct to him?”
“Why don’t I? Am I a man of business, Robert? Look about you.
Have I learned, do you think, to take a hexpert’s word as to the
precise vally of a article that I see his heye’s on, or to argy by
induction that a good private offer means a better public one? When
it comes to overreaching—hem!—a connoyser’s a man like myself;
so we’ll just, by your leave, put the picture up to auction.”
He carried the decanter back to its place in one of the shiny
cupboards.
“Besides, my friend,” said he, talking over his shoulder, “don’t you
see as how my conscience demands this seizure?”
“Not quite, sir, with humility, if so be as——”
“You’re dense, Robert. Look here, I’m a conscientious resister,
ain’t I? Law ain’t necessarily equity because the devil and Mr.
Chamberlain frames it. There’s some lawgivers that are Vicars of
Jehovah, and some of——but perhaps you’ve never heard of
Abaddon?”
“Haven’t I?” said Mr. Gardener ruefully. “I was near run in once for
tendering one as had been passed on me.”
“He was king of the bottomless pit,” said Mr. Plumley patiently. “He
framed this here law what’s made a passive objector of me. Well, if,
in resigning myself to his unjust processes, I force the picture-
dealer’s hand, thereby making a profit elsewise denied me, don’t you
see how I round on the law—triumph over it—kill two birds with one
stone, as it might be?”
“Yes, sir; I see that,” said Mr. Gardener, though still doubtfully.
“You do, do you?” responded the other. “Well, then, the only thing
is to make the law pay as heavy as possible by getting the picture
run up to the dealer’s figure.”
“But the law wouldn’t go for more’n its two pun odd,” protested the
jackal.
“O, you fool!” snarled the lion. “It’s the moral profit’s the game,
don’t you see? I gain by the very hact what starts of itself to ruin me.
It’s as plain as two pins.”
Mr. Gardener scratched his head, and broke into a short laugh.
“Bless you sir,” said he, “it’s clear enough; if on’y you’ll tell me who
in all this here place is a-going to run up the dealer, since you can’t
yourself.”
Mr. Plumley, bending at the cupboard, did not answer for a
moment. When at last he did, rising and facing round, there was a
curious pallor on his lips, and he had to clear his throat before he
could articulate—
“You, Robert.”
“Me, sir! You’re joking.”
“Never less so, Robert.”
“I ain’t worth a sixpence in the world, sir.”
The ex-remover walked shakily across, and put a flabby,
insinuative hand on the other’s shoulder.
“I think I may say I’ve been a good friend to you, Robert?”
Gardener muttered an uneasy affirmative.
“To justify a great principle, Robert? It’s a mere matter of form; it's
——humph! A moment, if you please. Think of it while I’m gone.”
A rap at the front door had obtruded itself. Mr. Plumley tiptoed
elephantinely out, was heard murmuring a few minutes in the hall,
and returned shortly in a state of suavely perspiring mystery.
“It’s the dealer himself, Robert,” he whispered, his little eyes
twinkling. “He’s come to make another attempt. I’ll humour him—
humour him, never fear. Now, you must be quick. Will you do this
little thing to oblige me?”
“Supposing I were let in, sir?”
Mr. Plumley coughed.
“I guarantee you, of course. It’s just a confidence between us. Go
to fifty pound—not a penny less nor more—and let him take it at any
figure he likes, beyond. He won’t fail you. You’ll do it, Robert?”
“I don’t favour the job, sir.”
“But you’ll do it?”
“Well, yes, then.”
Mr. Plumley showed him out, returned to the parlour, finished his
whisky and water, and called in the dealer from some hidden corner
of the hall where he had lain concealed. He had braced his nerves in
the interval. His attitude all at once was scowling and truculent—
meet for the reception of the shabby loafer who now presented
himself.
“What are you grinning at, sir?” he roared. “This ain’t the face to
bring to business.”
“O! isn’t it?” said the man. “Then I’ll change it——” which he did,
so suddenly and terrifically that the other cowered. The stranger
snorted, and relaxed.
“What now, minion?” said he.
“Bah!” snarled Mr. Plumley: “it comes easy to a barnstormer.”
“Roscius, ye fat old Philistine,” cried the actor, striking his breast
with a ragged-gloved hand: “Roscius, thou ‘villainous, obscene,
greasy tallow-ketch!’ ”
“Well,” said Mr. Plumley, wiping his brow, “I meant no offence,
anyhow. Have a drink?”
The stranger breathed heavily, and assumed a Napoleonic pose.
“I will have a drink,” he said; and, in fact, before he would
condescend to utter another word, he had two.
“Ha!” he said then, ejaculating a little spirituous cloud, and his
lean, pantomimic face was all at once benign. “Richard’s himself
again, and eager for the fray! To the charge, my passive resister, my
heavy lead! Ye need Theophilus Bolton! Ye must pay!”
“As to that there,” began Mr. Plumley, stuttering and glowering; but
the other took him up coolly——
“As to that, dear boy, there’s no question. You’ve withheld me from
a profitable engagement——”
“O, blow profitable!” interposed Mr. Plumley. “And you didn’t jump
at the chanst neither!”
“To play a part for you,” went on the actor unruffled “Well, am I to
be Agnew, or Christie, or Sotheby, or who? My commission’s five per
cent.”
“Well, I don’t object to that,” said Plumley, relieved. “On the vally of
the picture to Gardener, that’s to say. Call it done, and call yourself
what you like.”
“One man in his time plays many parts,” murmured Mr. Bolton.
“Put it on paper, dear boy. I have a weakness for testaments.”
Mr. Plumley protested; the actor whistled. In the end, the latter
pocketed a document to the effect that Joshua Plumley agreed to
pay Theophilus Bolton a sum to be calculated at the rate of five per
cent on the ultimate selling price at auction (on a date hereafter to be
filled in) of a picture known as the “The Wood Shop.”
“You’ll be close?” said Mr. Plumley uneasily. “It might—it might
injure me, you know, if it got about. Short o’ fifty pound’s the figger—
you understand? Let Gardener secure it at that. I’ve my reasons.
You come to me quick and quiet after the sale, and you shall have
your two pound ten on the nail, and slip off with it as private as you
wish.”
Now, what was Plumley’s little game? And wasn’t he anyhow a
good man of business?
That great financial strategist, Mr. Plumley, sat drinking whisky and
water by lamplight. His pipe lay at his side. He had tried to smoke it;
but tobacco flurried him.
“It should be about settled by now,” he muttered. “Where’s that
Bolton?”
“Rap!” came the answer, upon such an acute nervous centre, that
he started as if he had been stung.
He rose, made an effort to compose himself, and went to the door.
A spare tall figure detached itself from the dark, and entered.
“What the devil’s been keeping you?” growled the ex-remover.
“Ah! you’re short-sighted, my friend,” said Mr. Bittern, and walked
coolly into the parlour.
Mr. Plumley stared, felt suddenly wet, shook himself, and followed.
When it came to creeping flesh, he felt the full aggravation of his
size. The slow march of apprehensions, taking time from a sluggish
but persistent brain, seemed minutes encompassing him.
“So,” said the lawyer, dry and wintry, the moment he was in, “you
coveted your neighbour's one ewe lamb?”
Mr. Plumley took up his pipe, blew through it, put it down again,
and said nothing.
“You’d heard of Gardener’s aunt’s little bequest to him of fifty
pounds, duty free, eh?” asked the lawyer.
“No,” said Mr. Plumley.
“O!” said the lawyer. “He bid fifty pounds for that picture of yours
this afternoon, and got it. On whose instructions?”
“Ask him, sir. He acts for many.”
“It wasn’t on yours, then?”
“Is that reasonable, Mr. Bittern, when to my knowledge the man
wasn’t worth a brass farden?”
“What do you say about holding him to his bargain?”
“I say, if he’s bought the picture, he must pay for it.”
“And who bid against him? You don’t know that either, I suppose?”
“Nat’rally. Was I there?”
“Well, I’ve settled for him with Bull and Hacker, and brought you
their cheque, less commission and distraint. Give me a receipt for it.”
The great creature, elated with his own strategy as he was, could
hardly draw it out, his hands shook so. But he managed the business
somehow. The lawyer examined the paper, and buttoning it into his
pocket, took up his hat.
“O, by the way!” he said, as if on an afterthought, “I was forgetting
to mention that Gardener, after securing the picture, put it up to
auction again, at the particular request of some late arrivals, and was
bid a thousand pounds for it. It turned out to be a very good work.”
Mr. Plumley took up his pipe again quite softly, looked at it a
moment, and suddenly dashed it to smithereens on the floor.
“It was a plant!” he cried in a fat, hoarse scream. “I’ll be even with
him—I’ll have the money—the picture was mine—I’ll—by God, I say,
it was a conspiracy!”
The lawyer at the door lashed round on him like whipcord.
“And that’s what I think,” he shouted. “The meanest, dirtiest trick
that was ever played by a canting scoundrel on a poor brother. But I
may get to the bottom of it yet, from the opening scheme to enlist
Gardener’s sympathies for a poor martyr to conscience, to the last
wicked design upon him in the saleroom. I may get to the bottom of
it, cunning as it was planned; and, when I do, let some look out!”
As he flung away, he let in a new-comer, Mr. Bolton, by the
opened door. Mr. Plumley, choking in the backwater of his own fury,
had sunk into a chair, gasping betwixt bitterness and panic. He could
not, for the moment, remember how far he had committed himself.
He looked up to meet the insolent, ironic smile of his confederate.
“Come along, dear boy,” said Mr. Bolton. “Curtain’s down. Cash up!”
He presented a claim for fifty pounds, and stood, his hat cocked
on his head, picking his teeth.
“What’s this curst gammon?” sneered Mr. Plumley, rousing
himself.
“Commission,” said the actor airily. “Five per cent. on the ultimate
selling price of a picture.”
“It went at fifty.”
“Pardon me, sir. Ultimate—ultimate, see agreement” (he smacked
his chest). “One thou’ was the figure, and dirt cheap. Fine example.
I’ll trouble you for a cheque.”
“Two pound ten. I’ll give it you in cash.”
Mr. Bolton whistled a stave, and turned round, his hands deep in
his breeches’ pockets.
“I can sell to the other party. Good day to you, and look out.”
[The End]
TRANSCRIBER’S NOTES
Minor spelling inconsistencies (e.g. cash-box/cash box,
frockcoat/frock-coat, etc.) have been preserved.
Alterations to the text:
[A gallows-bird]
Change “convolutions of war, the merry, the dance-maccabre” to
danse-macabre.
[Our lady of refuge]
“fort of San Fernando. and the cursed French garrison,” change
period to comma.
[The five insides]
(“ ‘Eh, says the old man, ’usky-like, and starting) add right single
quotation mark after Eh.
“a bit forward—‘No, no, no no, no, no, no—’ ” add comma after
third no.
[The jade button]
“The property was recovered—but for the heir…” add period to
sentence.
[End of text]
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