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vi Contents
13.11 The Lewis Acid–Base Model 569

13.12 Strategy for Solving Acid–Base Problems:
A Summary 571
Connecting to Atoms Understanding Various Models
of Acids and Bases 572
For Review 573 ∣ Key Terms 573 ∣ Questions and Exercises 577
Chapter 14 Acid–Base Equilibria 578
14.1 Solutions of Acids or Bases Containing

a Common Ion 579
14.2 Buffered Solutions 582
14.3 Buffering Capacity 591
mitzy/Shutterstock.com
14.4 Titrations and pH Curves 594
14.5 Acid–Base Indicators 609
Chapter 15 Solubility and Complex

Chapter 12 Chemical Equilibrium 487 Ion Equilibria 619
12.1 The Equilibrium Condition 489 15.1 Solubility Equilibria and the Solubility
12.2 The Equilibrium Constant 491 Product 620
12.3 Equilibrium Expressions Involving Pressures 495 Chemical connections The Chemistry
of Teeth 628
12.4 Heterogeneous Equilibria 498
15.2 Precipitation and Qualitative Analysis 629
12.5 Applications of the Equilibrium Constant 500
15.3 Equilibria Involving Complex Ions 635
12.6 Solving Equilibrium Problems 509
For Review 640 ∣ Key Terms 640 ∣ Questions and Exercises 641a
12.7 Le Châtelier’s Principle 514
Connecting to Atoms The Difference Between
Equilibrium Constant and Equilibrium Condition 521
Chapter 16 Spontaneity, Entropy,
and Free Energy 642
Chapter 13 Acids and Bases 527
16.1 Spontaneous Processes and Entropy 643
Chemical connections Entropy: An Organizing
13.1 The Nature of Acids and Bases 528 Force? 649
13.2 Acid Strength 531 16.2 Entropy and the Second Law
13.3 The pH Scale 536 of Thermodynamics 649
Chemical connections Arnold Beckman, Man of 16.3 The Effect of Temperature on Spontaneity 650
Science 538
16.4 Free Energy 653
13.4 Calculating the pH of Strong Acid Solutions 540 16.5 Entropy Changes in Chemical Reactions 656
13.5 Calculating the pH of Weak Acid Solutions 541 16.6 Free Energy and Chemical Reactions 660
13.6 Bases 550 Connecting to Atoms Entropy and Positional
Chemical connections Amines 554 Probability 662
13.7 Polyprotic Acids 556 16.7 The Dependence of Free Energy on
13.8 Acid–Base Properties of Salts 561 Pressure 666
13.9 The Effect of Structure on Acid–Base 16.8 Free Energy and Equilibrium 669
Properties 566 16.9 Free Energy and Work 673
13.10 Acid–Base Properties of Oxides 568 For Review 676 ∣ Key Terms 676 ∣ Questions and Exercises 678
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Contents vii
Chapter 17 Electrochemistry 679 19.8 The Chemistry of Nitrogen 773
17.1 Balancing Oxidation–Reduction Equations 680 Chemical connections Nitrous Oxide: Laughing Gas
That Propels Whipped Cream and Cars 779
17.2 Galvanic Cells 686
19.9 The Chemistry of Phosphorus 780
17.3 Standard Reduction Potentials 689
19.10 The Group 6A (16) Elements 782
17.4 Cell Potential, Electrical Work, and Free
Energy 696 19.11 The Chemistry of Oxygen 783
17.5 Dependence of Cell Potential 19.12 The Chemistry of Sulfur 784
on Concentration 699 19.13 The Group 7A (17) Elements 787
17.6 Batteries 705 19.14 The Group 8A (18) Elements 791
Chemical connections Fuel Cells—Portable For Review 792 ∣ Key Terms 792 ∣ Questions and Exercises 795a
Energy 708
17.7 Corrosion 708 Chapter 20 Transition Metals and
17.8 Electrolysis 711 Coordination Chemistry 796
Chemical connections The Chemistry of Sunken
Treasure 714 20.1 The Transition Metals: A Survey 797
17.9 Commercial Electrolytic Processes 716 20.2 The First-Row Transition Metals 802
Chemical connections Titanium Dioxide—Miracle
Coating 804
20.3 Coordination Compounds 807
Chapter 18 The Nucleus: A Chemist’s 20.4 Isomerism 811

Chemical connections The Importance of Being
View 727
cis 814
18.1 Nuclear Stability and Radioactive 20.5 Bonding in Complex Ions: The Localized Electron
Decay 728 Model 816
18.2 The Kinetics of Radioactive Decay 733
20.6 The Crystal Field Model 818
Connecting to Atoms Radioactive Decay
Chemical connections Transition Metal Ions Lend
Processes 734
Color to Gems 821
18.3 Nuclear Transformations 736 20.7 The Biological Importance of Coordination
18.4 Detection and Uses of Radioactivity 739 Complexes 824
18.5 Thermodynamic Stability of the Nucleus 743 20.8 Metallurgy and Iron and Steel Production 828
18.6 Nuclear Fission and Nuclear Fusion 746 For Review 836 ∣ Key Terms 836 ∣ Questions and Exercises 839
Chemical connections Future Nuclear Power 748
18.7 Effects of Radiation 751 Chapter 21 Organic and Biological
For Review 753 ∣ Key Terms 753 ∣ Questions and Exercises 755 Molecules 841
21.1 Alkanes: Saturated Hydrocarbons 842

Connecting to Atoms Structural Representations of
Chapter 19 The Representative Organic Molecules 844
Elements 757
21.2 Alkenes and Alkynes 851
19.1 A Survey of the Representative Elements 758 21.3 Aromatic Hydrocarbons 854
19.2 The Group 1A (1) Elements 763 21.4 Hydrocarbon Derivatives 856
19.3 The Chemistry of Hydrogen 764 21.5 Polymers 863
19.4 The Group 2A (2) Elements 766 Chemical connections Wallace Hume
19.5 The Group 3A (13) Elements 768 Carothers 864
19.6 The Group 4A (14) Elements 769 Chemical connections Super-Slippery Slope 865
Chemical connections Beethoven: Hair Is the 21.6 Natural Polymers 871
Story 771 Chemical connections Tanning in the Shade 885
19.7 The Group 5A (15) Elements 772 For Review 886 ∣ Key Terms 886 ∣ Questions and Exercises 889
viii Contents
Appendix 1 Mathematical Procedures A1 A5.1 Values of Ka for Some Common Monoprotic

Acids A22
A1.1 Exponential Notation A1
A5.2 Stepwise Dissociation Constants for Several
A1.2 Logarithms A4
Common Polyprotic Acids A23
A1.3 Graphing Functions A6
A5.3 Values of Kb for Some Common Weak
A1.4 Solving Quadratic Equations A7 Bases A23
A1.5 Uncertainties in Measurements A10 A5.4 Ksp Values at 25°C for Common Ionic
Solids A24
Appendix 2 The Quantitative Kinetic
A5.5 Standard Reduction Potentials at 25°C (298 K)
Molecular Model A13 for Many Common Half-Reactions A25
Appendix 3 Spectral Analysis A16 Appendix 6 SI Units and Conversion

Factors A26
Appendix 4 Selected Thermodynamic
Glossary A27
Data A19
Answers to Selected Exercises A39
Appendix 5 Equilibrium Constants and Index A71
Reduction Potentials A22
To the Professor
Features of Chemistry: Over the years, thousands of students and instructors

who have used our books have found that these approaches
An Atoms First Approach work. The third edition of Chemistry: An Atoms First Ap-
proach continues this tradition by being a text that effectively
Conceptual learning and problem solving have been funda- explains chemistry to the students and helps them to learn to
mental to our approach in Chemistry through ten successful be creative problem solvers. The most significant difference
editions, and Chemistry: An Atoms First Approach through from our widely used Chemistry textbook is that we present
two successful editions. Our philosophy is to help students atoms, bonding, and molecules at the beginning of the text
learn to think like chemists so they can apply the process of and have made sure that the rest of the topics flow smoothly
problem solving to all aspects of their lives. In the third edi- from this starting point, while moving stoichiometry to a po-
tion of Chemistry: An Atoms First Approach, we have contin- sition earlier in the text.
ued with this philosophy while making some structural To strengthen the atoms first approach we have empha-
changes. Atoms, molecules, and bonding are still discussed sized at every opportunity throughout the text the importance
early in the text, and we have included stoichiometry imme- and advantages of thinking about chemistry from an atomic/
diately following VSEPR and MO theory. This is to allow molecular perspective.
students to be able to perform measurement and stoichiome-
try experiments early in the course. In this edition, we have
extended the discussion of energy in the Review chapter so
that the students will have sufficient background to better un-
What’s New
derstand electron energy states and the importance of distin- Considerable effort went into making the third edition of
guishing between a system and its surroundings. Chemistry: An Atoms First Approach.
We found that users of our texts strongly support our ap- ❯❯ Core Text—All chapters were reviewed for clarity, en-
proach to general chemistry. We have always written with a hanced understanding, and cohesive flow. Many sections
student-first approach. That is, in writing every page we ask were also revised as needed to help enhance the atoms first
ourselves: “How can we explain the material in a way that emphasis throughout the textbook.
will be most clear to the students?” We always develop con-
❯❯ Energy—An increased discussion of energy is included in
cepts in accord with the scientific method. That is, we always
the Review chapter (Chapter R). This includes discussions
consider the observed properties of substances first. We then
of the concepts of endothermic, exothermic, system, sur-
look for common threads among these properties (formulate
roundings, and chemical energy.
laws). Finally we help the students understand why and how
the theories of chemistry developed. In describing theories ❯❯ Chemistry Pioneers—A new boxed feature “Chemistry
we always make clear that models are works in progress. We Pioneers” contains historical background on many early
expect to find areas where the models fail and, in fact, that chemists.
this occurrence often leads to the greatest progress in our un- ❯❯ Bond Energy—We have moved the bond energy discus-
derstanding of how nature operates. sion from the bonding chapter to the energy chapter. In this
One of the main goals of our treatment of chemistry is to way we are able to more coherently discuss different meth-
help students learn to be effective problem solvers. We want ods for determining the enthalpy change for a reaction. We
to go beyond memorized steps to help students think their also provide a direct comparison of using bond energies
way through the problems. To do this we take a “think like a and standard enthalpies of formations for determining the
chemist” approach. In solving problems we ask students sev- enthalpy of a given reaction and discuss the results.
eral questions to guide them through the process: Where are ❯❯ Liquids and Solids—Chapter 9 has been reorganized so that
we going?, What do we know?, and How do we get there? the discussion of vapor pressure and phase diagrams comes
Our goal is to foster creative, concept-based problem solving, immediately after the discussion of liquids. This makes for a
which will serve the students in their lives and careers beyond smoother transition to discussing phase changes.
the general chemistry course.
ix
x To the Professor
❯❯ ChemWork Problems—All of end of chapter problems As we proceed in the text, we gradually shift more re-
were converted into ChemWork problems. These multi- sponsibility to the students to think through the examples so
concept problems (and additional ones) are found inter- that they do not become overly dependent on our help.
actively online with the same type of assistance a student One of the characteristics of this text is an innovative
would get from an instructor. method for dealing with acid–base equilibria, the material the
typical student finds most difficult and frustrating. The key to
this approach involves first deciding what species are present
Hallmarks of Chemistry: in solution, then thinking about the chemical properties of
An Atoms First Approach these species. This method provides a general framework for
approaching all types of solution equilibria.
❯❯ Chemistry: An Atoms First Approach contains numerous
❯❯ The text contains almost 250 Examples, with more given
discussions, illustrations, and exercises aimed at overcom-
in the text discussions, to illustrate general problem-
ing misconceptions. It has become increasingly clear from
solving strategies. When a specific strategy is presented, it
our own teaching experience that students often struggle
is summarized in a Problem-Solving Strategy box and the
with chemistry because they misunderstand many of the
Example that follows it reinforces the use of the strategy
fundamental concepts. In this text, we have gone to great
to solve the problem. In general, we emphasize the use
lengths to provide illustrations and e xplanations aimed at
of conceptual understanding to solve problems rather than
giving students a more accurate picture of the fundamen-
an algorithm-based approach. This approach is strongly
tal ideas of chemistry. In particular, we have attempted to
reinforced by the inclusion of 204 Interactive Examples,
represent the microscopic world of chemistry so that stu-
which encourage students to thoughtfully consider the ex-
dents have a picture in their minds of “what the atoms and
amples step-by-step.
molecules are doing.” The art program along with the ani-
mations emphasize this goal. We have also placed a larger ❯❯ We have presented a thorough treatment of reactions that
emphasis on the qualitative understanding of concepts o ccur in solution, including acid–base reactions. This ma-
before quantitative problems are considered. Because us- terial appears in Chapter 6, “Types of Chemical Reactions
ing an algorithm to correctly solve a problem often masks and Solution Stoichiometry,” directly after the chapter on
misunderstanding—when students assume they under- chemical stoichiometry, to emphasize the connection be-
stand the material because they got the right “answer”—it tween solution reactions and chemical reactions in general.
is important to probe their understanding in other ways. Chapter 6 also includes oxidation–reduction reactions and
In this vein, the text includes a number of Active Learn- balancing by oxidation state, because a large number of
ing Questions at the end of each chapter that are intended interesting and important chemical reactions involve redox
for group discussion. It is our experience that students processes.
often learn the most when they teach each other. Students ❯❯ Descriptive chemistry and chemical principles are thor-
are forced to recognize their own lack of understanding oughly integrated in this text. Chemical models may ap-
when they try and fail to explain a concept to another pear sterile and confusing without the observations that
student. stimulated their invention. On the other hand, facts with-
With a strong problem-solving orientation, this text talks to out organizing principles may seem overwhelming. A
students about how to approach and solve chemical prob- combination of observation and models can make chem-
lems. We emphasize a thoughtful, logical approach rather istry both interesting and understandable. In the chapter
than simply memorizing procedures. This approach is thor- on the chemistry of the elements we have used tables
oughly described in Section 5.3 (Learning to Solve Prob- and charts to show how properties and models correlate.
lems), which promotes the importance of thoughtful, creative Descriptive chemistry is presented in a variety of ways—
problem solving. This section emphasizes to students that as applications of principles in separate sections, in
thinking through a problem produces more long-term, mean- Examples and exercises, in photographs, and in Chemical
ingful learning that can be applied to “real life” than memo- Connections.
rizing steps that apply only to a particular type of problem. To ❯❯ Throughout the book a strong emphasis on models pre-
help students adopt this way of thinking we have organized vails. Coverage includes how they are constructed, how
the problem-solving process in terms of: they are tested, and what we learn when they inevitably
fail. Models are developed naturally, with pertinent ob-
❯❯ Where are we going?
servation always presented first to show why a particular
❯❯ What do we know? model was invented.
❯❯ How do we get there? ❯❯ Chemical Connections boxes present applications of
❯❯ Reality check, which prompts students to check whether chemistry in various fields and in our daily lives. Margin
their answer makes sense notes in the Instructor’s Annotated Edition also highlight
To the Professor xi
many more Chemical Connections available on the stu- Professor Tom McGrath of Baylor University for providing a
dent Web site. great deal of useful insight as we prepared the third edition.
❯❯ We offer end-of-chapter exercises for every type of stu- We followed many of Professor McGrath’s suggestions as we
dent and for every kind of homework assignment: ques- revised the text.
tions that promote group learning, exercises that reinforce Thanks to others who supplied valuable assistance for
student understanding, and problems that present the this text: Nellie Mitchell, Product Assistant; Lizz Anderson,
ultimate challenge with increased rigor and by integrat- Designer; Timothy Cali, Marketing Manager; Nicole Hurst,
ing multiple concepts. To further encourage this approach Senior Market Development Manager; Beth McCracken,
we have included a selection of ChemWork Problems in Digital Delivery Lead; and Ann Hoffman, Intellectual Prop-
the text. These multiconcept problems (and additional erty Analyst.
ones) are found interactively online with the same type of We are especially thankful to all of the reviewers who
assistance a student would get from an instructor. We have participated in different aspects of the development process
also included biochemistry problems to make the con- from reviewing chapters to providing feedback on the devel-
nection for students in the course who are not chemistry opment of new features. We sincerely appreciate all of these
majors. suggestions.
❯❯ Judging from the favorable comments of instructors and
students who have used our books, the text seems to work
very well in a variety of courses. We are especially pleased
that readability is cited as a key strength when students are Reviewers
asked to assess our textbooks.
Third Edition Reviewers
Robin Bond, The Evergreen State College
Supporting Materials Sujata Guha, Tennessee State University

Ryan Hayes, Andrews University
Please visit https://www.cengage.com/c/chemistry-an-atoms
Jeremy Kua, University of San Diego
-first-approach-3e-zumdahl/ for information about student and
instructor resources for this book and about custom versions. Craig P. McClure, Drexel University
Douglas R. Mulford, Emory University
Llanie Nobile, Marquette University
Acknowledgments Van Quach, Seminole State College
Ashely Corrigan Steffey, University of San Diego
The successful completion of the third edition of Chemistry:
An Atoms First Approach is due to the efforts of many tal- Shuai Sun, University of Kansas
ented and dedicated people. We especially want to thank
Maureen McLaughlin, Senior Product Manager, for her sup-
port and oversight of the project. We also want to thank Peter Second Edition Reviewers
McGahey, Learning Designer, and Theresa Dearborn, In-
House Subject Matter Expert for their knowledge of the field David Boatright, University of West Georgia
and helpful input. Special thanks as well go to Vanessa Nancy Breen, Roger Williams University
Desiato, Associate Content Manager, for her ideas and atten- Elzbieta Cook, Louisiana State University
tion to detail. Special thanks also go to Brendan Killion, who
came aboard as Senior Content Manager and was able to see Tracy McGill, Emory University
this edition to its successful completion with his expertise Douglas Mulford, Emory University
and efficiency. Edith Osborne, Angelo State University
We are especially grateful to Tom Hummel, University
Yasmin Patell, Kansas State University
of Illinois at Urbana–Champaign, who managed the end-of
chapter problems and the solutions manuals. We greatly ap- Jerry Poteat, Georgia Perimeter College
preciate the outstanding work of Gretchen Adams, University Michael Sakuta, Georgia Perimeter College
of Illinois at Urbana–Champaign, who created the Interactive Jeff Statler, University of Utah
Examples and who converted many of the end-of-chapter
Shane Street, University of Alabama
problems to ChemWork problems. We are deeply indebted to
these two colleagues who contribute in so many ways to our Dennis Taylor, Clemson University
various projects. We owe a large debt of appreciation to Joshua Wallach, Old Dominion University
xii To the Professor
First Edition Reviewers Jon Hardesty, Collin County Community College

Jennie Mayer, Bellevue College
David Boatright, University of West Georgia
Katherine Parks, Motlow State Community College
Gene Carlisle, West Texas A&M University
Casey Raymond, SUNY Oswego
Tsun-Mei Chang, University of Wisconsin–Parkside
David Smith, New Mexico State University
Charles Cox, Georgia Institute of Technology
Lydia Tien, Monroe Community College
Michelle Driessen, University of Minnesota
Wayne Wesolowski, University of Arizona
Amina El-Ashmawy, Collin College
David Zax, Cornell University
Deborah Exton, University of Oregon
David Geiger, SUNY-College at Geneseo
To the Student
As you jump into the study of chemistry we hope that you After you have read and studied each chapter of the text
will find our text helpful and interesting. Our job is to present you’ll need to practice your problem-solving skills. To do this
the concepts and ideas of chemistry in a way you can under- we have provided plenty of review questions and end-of-
stand. We hope to encourage you in your studies and to help chapter exercises. Your instructor may assign these on p aper
you learn to solve problems in ways you can apply in all areas or online; in either case, you’ll want to work with your fellow
of your professional and personal lives. students. One of the most effective ways to learn chemistry is
Our main goal is to help you learn to become a truly through the exchange of ideas that comes from helping one
creative problem solver. Our world badly needs people who another. The online homework assignments will give you in-
can “think outside the box.” Our focus is to help you learn to stant feedback, and, in print, we have provided a nswers to
think like a chemist. Why would you want to do that? Chem- some of the exercises in the back of the text. In all cases, your
ists are great problem solvers. They use logic, trial and error, main goal is not just to get the correct answer, but to under-
and intuition—along with lots of patience—to work through stand the process for getting the answer. Memorizing solu-
complex problems. Chemists make mistakes, as we all do in tions for specific problems is not a very good way to prepare
our lives. The important thing that a chemist does is to learn for an exam (or to solve problems in the real world!).
from the mistakes and to try again. This “can do” attitude is To become a great problem solver you’ll need these
useful in all careers. skills:
In this book we develop the concepts in a natural way:
1. Look within the problem for the solution. (Let the prob-
The observations come first and then we develop models to
lem guide you.)
explain the observed behavior. Models help us to understand
2. Use the concepts you have learned along with a system-
and explain our world. They are central to scientific thinking.
atic, logical approach to find the solution.
Models are very useful, but they also have limitations, which
3. Solve the problem by asking questions and learn to trust
we will point out. By understanding the basic concepts in
yourself to think it out.
chemistry we lay the foundation for solving problems.
Our main goal is to help you learn a thoughtful method You will make mistakes, but the important thing is to learn
of problem solving. True learning is more than memorizing from these errors. The only way to gain confidence is to prac-
facts. Truly educated people use their factual knowledge as a tice, practice, practice and to use your mistakes to find your
starting point—a basis for creative problem solving. Our weaknesses. Be patient with yourself and work hard to under-
strategy for solving problems is explained in Section 5.3. To stand rather than simply memorize.
solve a problem we ask ourselves questions, which help us We hope you’ll have an interesting and successful year
think through the problem. We let the problem guide us to the learning to think like a chemist!
solution. This process can be applied to all types of problems Steve and Susan Zumdahl and Don DeCoste
in all areas of life.
As you study the text, use the Examples and the problem-
solving strategies to help you. The strategies are boxed to
highlight them for you, and the Examples show how these
strategies are applied.
xiii
A Guide to Chemistry, An Atoms First Approach THIRD Edition
Connecting To Atoms This new boxed feature contains atoms first summaries that cover key atoms first
concepts at point-of-use.
Chemical Connections Interesting applications of modern chemistry show students the relevance of
chemistry to the real world. 48 ChApter 1 Chemical Foundations
connecting to atoms 1.1

Atoms, Ions, and Isotopes: A Pictorial Summary
Connecting To Atoms is a new boxed feature that contains sum- Atomic Number
(number of protons)
Nucleus Nucleus
maries that cover key atoms first concepts at point-of-use. They have 11 protons
12 neutrons Protons
11 protons
13 neutrons
Relative charge = +1
visuals and text to help students understand how an atomic/molecular 11+

Relative mass = 1
11+
approach clarifies chemical concepts. Examples of topics include At- 11 electrons

Mass Number
Total number of
protons and neutrons 11 electrons
oms, Ions, and Isotopes: A Pictorial Summary, Lewis Structures and the
Relative charge = –1 Relative charge = –1
23 Relative mass = 1/1840 Relative mass = 1/1840 24
11 Na Neutrons 11 Na
Relative charge = 0
Periodic Table, Polar Molecules—It’s All About Symmetry, and Entropy

Relative mass = 1
Isotopes
and Positional Probability. Same number protons (same atomic number)

Different number neutrons (different mass number)
11.7 Catalysis 483 Loss of

Sodium ion
(Na+ )
electron
The lost electron
is transferred to
the Cl atom Cation
ConneCting to atoms 11.1

11+ Positive charge
Number of protons > Number of electrons
Zero-, First-, and Second-Order Reactions and the Collision Model 10 electrons
I n Section 11.4 we derived integrated

rate laws for zero-, first-, and second-
order reactions, and in Section 11.5 we
since only the AB molecules on the
surface can react.
collisions between AB molecules only
transfer energy from one AB to another.
If the first and third steps in the above
Chloride ion
(Cl−)
Neutral chlorine
discussed mechanisms for such mechanism occur at a much faster rate atom (Cl)
reactions. Let’s consider what each of than the second step, the decomposi-
these types of reactions would “look” tion of the excited state is the rate-
like at the molecular level. determining step. Thus the second step Gain of electron Anion
17+ 17+ Negative charge
Let’s consider the generic reaction dictates the rate and the rate law 5 Number of electrons > Number of protons
2AB n AB2 1 A, which we can repre- k[AB], which is first order.
sent as + n + . How In all three mechanisms, then, the
could various possible mechanisms molecules must collide for a reaction to 17 electrons
lead to different rate laws for this occur.
reaction? 18 electrons
Collision model
Pt
Possible mechanism that yields In Section 11.6, you learned about the
a second order rate law collision model, which tells us that in
Note the molecules still must collide to order for a reaction to occur, mol-
As we discussed in Section 11.6, the
react, but since the rate does not ecules must collide. We can see that
molecules must collide in order to
change with concentration of AB, then even with this simple model, we can
react. The most obvious rate law, then,
rate 5 k[AB]0, or rate 5 k. develop different mechanisms that
would seem to be second order since
we need two molecules to collide. A Possible mechanism that yields give rise to different rate laws. As we
simple mechanism for a second-order a first-order rate law have discussed, however, while a
63362_ch01_rev03.indd 48 07/10/19 4:49 PM
reaction could be: collision is necessary, it is not the
Because molecules must collide in
only factor required to result in a 3.1 Types of Chemical Bonds 101
order to react, first-order reactions may
1. + (slow) reaction. The molecules must be
seem impossible at first. For example,
oriented correctly (which is one way
2. + (fast) how can the slow step of a mechanism
in which a catalyst works to speed up
be + , if molecules do not
a reaction), and activation energy
The first step is the rate-determining
step, making the rate 5 k[AB]2, or
collide? The key to understanding this
is to realize that for a molecule to react,
must be overcome (which is why
reactions proceed at a higher rate
ChemiCal ConneCtions 3.1
second order. it must have enough energy to
with increased temperature). To
surmount the reaction energy barrier.
better understand how reactions
No Lead Pencils
Possible mechanism that yields a We will represent such an excited state
D
proceed and what factors are id you ever wonder why the part of The ratio of clay to graphite is adjusted atoms bound together in a “chicken-
zero-order rate law molecule with an asterisk in the
important in the rate of a reaction, a pencil that makes the mark is to vary the hardness of the lead—the wire” structure. Although the bonding
Zero-order reactions are often the mechanism below.
we need to take a molecular-level called the “lead”? Pencils have no lead in more clay in the mix, the harder the lead within each layer is very strong, the
result of catalysis. For example, approach to consider how the
1. + *+ (fast) them now—and they never have. and the lighter the line it makes. bonding between layers is weak, giving
suppose the reaction occurs on the molecules are interacting.
2. * + (slow) Apparently the association between Pencils are made from a slat of graphite its slippery, soft nature. In this
surface of a metal catalyst, such as
writing and the element lead arose wood with several grooves cut in it to way, graphite is much different from
platinum (Pt). Once the surface is 3. + (fast)
during the Roman Empire, when lead hold the leads. A similar grooved slat is diamond, the other common elemental
completely covered with AB mol-
rods were used as writing utensils then placed on top and glued to form a form of carbon. In diamond the carbon
ecules, increasing the concentration of Note that the AB molecules must because they leave a gray mark on “sandwich” from which individual atoms are bound tightly in all three
AB would have no effect on the rate collide in order to react. However, the paper. Many centuries later, in 1564, a pencils are cut, sanded smooth, and dimensions, making it extremely
deposit of a black substance found to be painted. Although many types of wood hard—the hardest natural substance.
very useful for writing was discovered in have been used over the years to make Pencils are very useful—especially
Borrowdale, England. This substance, pencils, the current favorite is incense for doing chemistry problems—
originally called “black lead,” was shown cedar from the Sierra Nevada Moun- because we can erase our mistakes.
in 1879 by Swedish chemist Carl Scheele tains of California. Most pencils used in the United States
to be a form of carbon and was Modern pencils are simple but have erasers (first attached to pencils in
subsequently named graphite (after the amazing instruments. The average 1858), although most European pencils
Greek graphein, meaning “to write”). pencil can write approximately 45,000 do not. Laid end to end, the number of
Originally, chunks of graphite from words, which is equivalent to a line 35 pencils made in the United States each
Borrowdale, called marking stones, were miles long. The graphite in a pencil is year would circle the earth about 15
used as writing instruments. Later, sticks easily transferred to paper because times. Pencils illustrate how useful a
of graphite were used. Because graphite graphite contains layers of carbon simple substance like graphite can be.
is brittle, the sticks needed reinforce-
63362_ch11_rev02.indd 483 24/10/19 11:16 AM
ment. At first they were wrapped in
string, which was unwound as the core
wore down. Eventually, graphite rods
were tied between two wooden slats or
480 ChapteR 11 Chemical Kinetics 11.7inserted into hollowed-out
Catalysis 481 wooden
sticks to form the first crude pencils.
Although Borrowdale graphite was
Sezeryadigarl/iStockphoto.com
pure enough to use directly, most
graphite must be mixed with other
ChemiCal ConneCtions 11.1 materials to be useful for writing
instruments. In 1795, the French chemist
Nicolas-Jaques Conté invented a process
Enzymes: Nature’s Catalysts in which graphite is mixed with clay and
T he most impressive examples of water to produce pencil “lead,” a recipe

H H
homogeneous catalysis occur in that is still used today. In modern pencil
O O O O
nature, where the complex reactions manufacture, graphite and clay are
C C
necessary for plant and animal life are mixed and crushed into a fine powder to
H C R'' H C R'' which water is added. After the gray
made possible by enzymes. Enzymes
H N H N sludge is blended for several days, it is
are large molecules specifically tailored
O Amino dried, ground up again, and mixed with
to facilitate a given type of reaction. C O H H
H acid
Usually enzymes are proteins, an more water to give a gray paste. The
Kenneth Eward / BioGrafx / Science Source
Water H C R' paste is extruded through a metal tube

important class of biomolecules molecule H
constructed from a-amino acids that N H O O
to form thin rods, which are then cut
have the general structure C into pencil-length pieces called “leads.”
These leads are heated in an oven to
H C R'
R 10008C until they are smooth and hard. Graphite
H O N H
N
N C C
H H
H OH Protein
H a b
N FIguRe 11.18 (a) The structure of the enzyme carboxypeptidase-A, which
where R represents any one of 20 FIguRe 11.17 The removal of the end amino acid from a
H H contains 307 amino acids. The zinc ion is shown above as a black sphere in the center.
different substituents. These amino protein by reaction with a molecule of water. The products are an 63362_ch03_rev02.indd 101 10/5/19 5:54 PM
New protein
(b) Carboxypeptidase-A with a substrate (pink) in place.
acid molecules can be “hooked amino acid and a new, smaller protein.
together” to form a polymer (a word
meaning “many parts”) called a protein.
The general structure of a protein can
containing one less amino acid.
Without the enzymes found in human
formed amino acid are released by
the enzyme.
Chemical Connections de-
be represented as follows:
R R'
cells, this reaction would be much too
R''
slow to be useful. One
of these enzymes is
The process just described for
carboxypeptidase-A is characteristic of
the behavior of other enzymes. Enzyme
scribe current applications of
H O
H
N N C C N C C N C C
H H O H H O H H
O H
carboxypeptidase-A, a
zinc-containing
catalysis can be represented by the
series of reactions shown below: chemistry. These special-interest
protein (Fig. 11.18).
Many amino Fragment Fragment

acid fragments from an from an
Fragment
from an amino
Carboxypepti-
dase-A captures the
E 1 S ¡ ES
ES ¡ E 1 P boxes cover such topics as the
protein to be acted where E represents the enzyme, S
invention of Post-it Notes, farm-
amino amino acid with sub-
acid acid stituent R'' on (called the represents the substrate, E  S OH
with sub- with sub- substrate) in a special represents the enzyme–substrate
stituent R stituent R'
ing the wind, and the use of iron

groove and positions complex, and P represents the
the substrate so that the end is in the products. The enzyme and substrate
Since specific proteins are needed CH2
active site, where the catalysis occurs form a complex, where the reaction
by the human body, the proteins in
food must be broken into their
constituent amino acids, which are
(Fig. 11.19). Note that the Zn21 ion
bonds to the oxygen of the CPO
occurs. The enzyme then releases the
product and is ready to repeat the
HN
CH CO2– +
NH2 C
NH2
metal to clean up contaminated
(carbonyl) group. This polarizes the process. The most amazing thing HO
groundwater. Additional Chemi-

then used to construct new proteins in Zn2+ O C
electron density in the carbonyl about enzymes is their efficiency.
the body’s cells. The reaction in which a
group, allowing the neighboring Because an enzyme plays its catalytic FIguRe 11.19 Protein– H O CHR
protein is broken down one amino acid substrate interaction. The substrate is
CON bond to be broken much more role over and over and very rapidly,
cal Connections are available on
H NH
at a time is shown in Fig. 11.17. Note that shown in black and red, with the red
easily. When the reaction is com- only a tiny amount of enzyme is –
O
in this reaction a water molecule reacts representing the terminal amino acid. C O
pleted, the remaining portion of the required. This makes the isolation of
with a protein molecule to produce an Blue indicates side chains from the C
the student Web site.

substrate protein and the newly enzymes for study quite difficult.
amino acid and a new protein enzyme that help bind the substrate. O
xiv
63362_ch11_rev02.indd 480 24/10/19 11:16 AM
63362_ch11_rev02.indd 481 24/10/19 11:16 AM
Conceptual Understanding Conceptual learning and problem solving are fundamental to
the approach of Chemistry. The text gives students the tools to become critical thinkers: to ask
questions, to apply rules and models, and to evaluate the outcome.
2.4 The Bohr Model 63
FIguRE 2.6 (a) A continuous Continuous

spectrum containing all wavelengths of spectrum
visible light (indicated by the initial VI B
G Y O
letters of the colors of the rainbow). Slit Prism R
I
(b) The hydrogen line spectrum contains
only a few discrete wavelengths.
“The first principles of the universe are atoms and empty space; everything
+
2.7 Orbital Shapes and Energies 75

Spectrum based on C. W. Keenan, D. C. Kleinfel- n Chapter 2 we considered the structure of the atom. We needed this knowledge to
ter, and J. H. Wood, General College Chemistry, be able to discuss chemical bonds and better understand how and why atoms come
FIguRE 2.17Sixth Representation
Edition (New York: Harper & Row, 1980). z z z
Detector
else is merely thought to exist.” —Democritus

together to form molecules. In Chapter 3 we used a relatively simple model, the local-
of the 4f orbitals in terms of their (photographic plate)
− ized electron model, to draw Lewis structures for molecules.
boundary surfaces. Electric arc As chemists we are interested in the answers to questions like the following: “Why
(white light
source) x x x is water a liquid at room conditions?,” and “Why don’t water and oil mix?” To answer
questions such as these we need to understand the three-dimensional structure of the
a
molecules and how they interact with one another. Lewis structures do not tell us di-
y y y rectly about molecular structure. In this chapter, we will focus on molecular structure
fz3 – fx3 – fy3 – Detector
3 zr2
—
5
3 xr2
—
5
3 yr2
—
5 (photographic plate) and more complex bonding models.
Arc
+
Slit Prism
z z z z
The authors’ emphasis on modeling (or chemical theories) 4.1 Molecular Structure:
throughout the Hightext addresses the problem of rote memorization
voltage
x x x x The VSEPR Model
by helping students better understand and appreciate the pro- The structures of molecules play a very important role in determining their chemi-
cess ofy scientific− thinking. By stressing the ylimitations and uses of cal properties. As we will see later, this is particularly important for biological
New York Public Library / Science Source

y y
f Hydrogen
f gas f f molecules; a slight change in the structure of a large biomolecule can completely
scientific models, the xyz
authors
discharge tube show students how chemists think
y(x 2 – z2) x(z 2 – y 2) z(x 2 – y 2)
destroy its usefulness to a cell or may even change the cell from a normal one to a
cancerous one.
and work.ΔE = 3 Many accurate methods now exist for determining molecular structure, the three-
410 nm 434 nm 486 nm 656 nm
dimensional arrangement of the atoms in a molecule. These methods must be used if
E TheΔEfifth
2= orbital, dz2, has a unique shape with two lobes along the z axis and a belt precise information about structure is required. However, it is often useful to be able
b to predict the approximate molecular structure of a molecule. In this section we con-
centered in the xy plane. The d orbitals for levels n . 3 look like the 3d orbitals but
have
ΔE1larger
= lobes. sider a simple model that allows us to do this. This model, called the valence shell
The f orbitals first occur in level n 5 4, and as might be expected, they have shapes electron-pair repulsion (VSEPR) model, is useful in predicting the geometries of
even more complex than those of the d orbitals. Fig. 2.17 shows representations of the molecules formed from nonmetals. The main postulate of this model is that the struc-
Various energy levels ture around a given atom is determined principally by minimizing electron-pair repul-
in the
4f orbitals ( 5 3) along with their designations. These orbitals are not involved in the
3s 3p 3d hydrogen atom
bonding in any of the compounds we will consider in this text. Their shapes and labels sions. The idea here is that the bonding and nonbonding pairs around a given atom will
FIguRE 2.7 In this diagram the included for completeness.
are simply be positioned as far apart as possible. To see how this model works, we will first con-
CritiCal thinking We now have evidence that electron
E
2s 2p horizontal lines indicate allowed
electron energies in the hydrogen
So far we have energies
talked about in thethe shapes
atoms of the hydrogen
are quantized. Some of atomic orbitals isbut
this evidence not
discussed in this The text includes a number of open-ended Critical Think-
sider the molecule BeCl2, which has the Lewis structure
about atom.
their energies.chapter.
For theWhathydrogen atom,in
if energies the energy
atoms of anot
were particular
quantized? orbital
What is are
deter-
some differ-
1s
Because only certain energies are
mined by its valueences
allowed when electrons release energy,
of n. weThus all orbitals
would notice? with the same value of n have the same ing questions that emphasize the importance of conceptual
energy—they are said to be degenerate. This is shown in Fig. 2.18, where the energies
only certain colors are seen.
for the orbitals in the first three quantum levels for hydrogen are shown. learning. These questions are particularly useful for generating
Hydrogen’s single electron can occupy any of its atomic orbitals. However, in the BeCl2 has only four electrons around Be Note that there are two pairs of electrons immediately around the beryllium atom.
FIguRE 2.18 Orbital energy levels
lowest energy state, the ground state, the electron resides in the 1s orbital. If energy is and is expected to be very reactive with group discussion.
What arrangement of these electron pairs allows them to be as far apart as possible to
for the hydrogen atom.
2.4 the Bohr Model
electron-pair donors. minimize the repulsions? Clearly, the best arrangement places the pairs on opposite
put into the atom, the electron can be transferred to a higher-energy orbital, producing
an excited state. sides of the beryllium atom at 180 degrees from each other:
In 1913, a Danish physicist named Niels Bohr (1885–1962), aware of the experimental
results we have just discussed, developed a quantum model for the hydrogen atom.
let’s review Bohr proposed Athat the electron
Summary of thein aHydrogen
hydrogen Atom atom moves around the nucleus only in
certain allowed circular orbits. He calculated the radii for these allowed orbits by us-
» In the quantuming(wave)
the theories
mechanical of classical
model, thephysics
electronand by making
is viewed some wave.
as a standing new assumptions.
This
representation leads
From to aclassical
series of wave functions
physics Bohr(orbitals)
knew thatthat describe
a particlethe in
possible
motion tends to move in a This is the maximum possible separation for two electron pairs. Once we have deter-
mined the optimal arrangement of the electron pairs around the central atom, we can
energies andstraight
» In agreementthe
spatial distributions
center
with
line and can available
of the circle.
the Heisenberg
be made to the
Thus Bohr
uncertainty
toelectron.
travel in a circle only by application of a force toward
reasoned
principle, thatcannot
the model the tendency
specify of the revolving electron
Let’s Review boxes help students organize their thinking about
specify the molecular structure of BeCl2, that is, the positions of the atoms. Since each
electron pair on beryllium is shared with a chlorine atom, the molecule has a linear
the detailed electron
to fly off
probability distribution
motions.
nucleus. But of the
Instead,
the atom must
electron in
classical
thebesquare
justofbalanced
that orbital.
physics
the wave function
also This allowsthat
decreed
representsfor
by its attraction
us toapicture
charged
the the positively charged
orbitals in under acceleration
particle
358 the crucial chemical concepts that they encounter.
ChAPTer 8 Gases
structure with a 180-degree bond angle:
terms of probability distributions, or electron density maps.
should radiate energy. Since an electron revolving around the nucleus constantly your reasoning. Under which temperature condition 9. In the van der Waals equation, why is a term added to
» The size of an orbital is arbitrarily defined as the surface that contains 90% of the total Cl Be Cl
would the O (g) sample behave most ideally? the observed pressure and why is a term subtracted
2
electron probability. Explain. from the container volume to correct for nonideal gas
180°
» The hydrogen atom has many types of orbitals. In the ground state, the single electron 8. Briefly describe two methods one might use to find the behavior?
resides in the 1s orbital. The electron can be excited to higher-energy orbitals if energy is molar mass of a newly synthesized gas for which a 10. Why do real gases not always behave ideally? Under what
put into the atom. molecular formula was not known. conditions does a real gas behave most ideally? Why?
63362_ch02_rev03.indd 63 07/10/19 5:30 PM 143
Active Learning Questions

63362_ch04_rev02.indd 143 These questions are designed to be used by groups of students 10/5/19 6:09 PM
07/10/19 5:31 PM in class.
1. Consider the following apparatus: a test tube covered with a
nonpermeable elastic membrane inside a container that is
closed with a cork. A syringe goes through the cork.
Hg(l)
Syringe
The text includes a number of Active Learning Questions at Cork

4. As you increase the temperature of a gas in a sealed, rigid
container, what happens to the density of the gas? Would the
the end of each chapter that are intended for group discussion, as results be the same if you did the same experiment in a con-
tainer with a piston at constant pressure? (See Fig. 8.17.)
students often learn the most when they teach each other. Membrane
5. A diagram in a chemistry book shows a magnified view of a
flask of air as follows:
a. As you push down on the syringe, how does the mem-

brane covering the test tube change?
b. You stop pushing the syringe but continue to hold it
down. In a few seconds, what happens to the membrane?
2. Fig. 8.2 shows a picture of a barometer. Which of the follow- What do you suppose is between the dots (the dots represent
ing statements is the best explanation of how this barometer air molecules)?
works?
a. air
a. Air pressure outside the tube causes the mercury to move
b. dust
in the tube until the air pressure inside and outside the tube
is equal. c. pollutants
b. Air pressure inside the tube causes the mercury to move in d. oxygen
the tube until the air pressure inside and outside the tube e. nothing
is equal. 6. If you put a drinking straw in water, place your finger over the
c. Air pressure outside the tube counterbalances the weight opening, and lift the straw out of the water, some water stays
of the mercury in the tube. in the straw. Explain.
7. A chemistry student relates the following story: I noticed my
xv
d. Capillary action of the mercury causes the mercury to go
up the tube. tires were a bit low and went to the gas station. As I was filling
e. The vacuum that is formed at the top of the tube holds up the tires, I thought about the kinetic molecular theory (KMT).
the mercury. I noticed the tires because the volume was low, and I realized
that I was increasing both the pressure and volume of the tires.
Justify your choice, and for the choices you did not pick,
“Hmmm,” I thought, “that goes against what I learned in
explain what is wrong with them. Pictures help!
chemistry, where I was told pressure and volume are inversely
3. The barometer on the right column shows the level of mer- proportional.” What is the fault in the logic of the chemistry
cury at a given atmospheric pressure. Fill all the
Copyright 2021 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 other studentthein eBook and/orExplain
this situation? eChapter(s).
why we think pressure and
barometers with mercury for that same atmospheric pres-
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 volume subsequent to be rights
inversely related (draw
restrictions pictures
require it. and use the
sure. Explain your answer.
Problem Solving This text talks to the student about how to approach and solve chemical
problems, as one of the main goals of general chemistry is to help students become creative
problem solvers. The authors emphasize a thoughtful, logical approach rather than simply
memorizing procedures.
194 ChaPter 5 Stoichiometry
5.3 Learning to Solve Problems In Chapter 5, “Stoichiometry,” the authors dedicate a section, Learning to
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,
Solve Problems, that emphasizes the importance of problem solving. This
creative way based on understanding the fundamental ideas of chemistry. We call this
approach conceptual problem solving. section helps students understand that thinking their way through a prob-
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 lem produces more long-term, meaningful learning than simply memorizing
by explaining how to think about the problems. While the answers to these problems
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
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-
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-
5.2 Atomic Masses 193
sive), and if you have to find this same place in the future on your own, you will prob-
ably not be able to do it. If, however, your goal is to learn how to get there, you would
100 91
pay attention to distances, signs, and turns (active). This is how you should read the
Ion beam intensity at detector
Relative number of atoms

solutions in the text (and the text in general). 80
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 60
Paul Brennan/Shutterstock.com
much as you solve a problem, you won’t really learn effectively. If we always “drive,”
40
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 20
9
proceed to later chapters. .3
There are two fundamentally different ways you might use to approach a problem. 0
18 19 20 21 22 23 24 20 21 22
One way emphasizes memorization. We might call this the “pigeonholing method.” In Mass number Mass number
this approach, the first step is to label the problem—to decide in which pigeonhole it a b c
fits. The pigeonholing method requires that we provide you with a set of steps that you
memorize and store in the appropriate slot for each different problem you encounter. FigURE 5.2 (a) In advertising signs, the red color is due to the emission of red light by neon gas.
The difficulty with this method is that it requires a new pigeonhole each time a prob- The relative intensities of the signals recorded when natural neon is injected into a mass spectrometer are
lem is changed by even a small amount. represented in terms of (b) “peaks” and (c) a bar graph. The relative areas of the peaks are 0.9092 (20Ne),
Consider the driving analogy again. Suppose you have memorized how to drive 0.00257 (21Ne), and 0.0882 (22Ne); natural neon is therefore 90.92% 20Ne, 0.257% 21Ne, and 8.82% 22Ne.
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 compli- ExAMPLE 5.1 the Average Mass of an element
cated example, suppose you know how to get from your house to the store (and back)
When a sample of natural copper is vaporized and injected into a mass spectrometer,
and from your house to the library (and back). Can you get from the library to the store
the results shown in Fig. 5.3 are obtained. Use these data to compute the average mass
without having to go back home? Probably not if you have only memorized directions
of natural copper. (The mass values for 63Cu and 65Cu are 62.93 u and 64.93 u,
and you do not have a “big picture” of where your house, the store, and the library are
respectively.)
relative to one another. 5.4 The Mole 199
John Humble/The Image Bank/Getty Images
The second approach is conceptual problem-solving, in which we help you get the
Solution Where are we going?
Chapters 1–8 introduce a series of questions into the in- “big picture”—a
How real understanding
do we get there? of the situation. This approach to problem-solving
looks within the problem for a solution. In this method we assume that the problem is To calculate the average mass of natural copper
a new one,The and strategy forproblem
we let the doing this problem
guide us asiswe
to solve
convertit. from
In thismilligrams
approach ofwesilicon
ask a to grams
chapter Examples to engage students in the process of of silicon,
series of questions as then to molesand
we proceed of silicon,
use our and finally to
knowledge ofatoms of silicon:
fundamental principles to Arturo Limon/Shutterstock.com What do we know?
answer these questions. Learning this approach requires some patience, but the reward ❯ 63Cu mass 5 62.93 u
problem solving, such as Where are we going? and How for learning to solve problems this way is that
5.68 mg Si 3we
any new problem that confronts us in daily life or in 1000
each 1 gbecome
our work
Si
mg Si
5 5.68 3 10 g Si of
an effective solver
23
in any field. In summary,
❯ 65Cu mass 5 64.93 u
and classifying objects likedo

mail. we get there? This more active approach helps students
▲ Pigeon holes can be used for sorting instead of looking outside the problem for a memorized solution, we will look inside How do we get there?
the problem and let the problem 5.68 help 3us 10
as23weg proceed 1 mol Si
Si 3 to a solution. 5 2.02 3 1024 mol Si 63
28.09 g Si As shown by the graph, of every 100 atoms of natural copper, 69.09 are Cu and
think their way through the6.022
solution
3 10 atoms
to the problem. 23
▲ Copper nugget. 30.91 are 65Cu. Thus the mass of 100 atoms of natural copper is
S D S D
Always check to see if your answer is 2.02 3 1024 mol Si 3 5 1.22 3 1020 atoms 100
1 mol Si u u
s69.09 atomsd 62.93 1 s30.91 atomsd 64.93
Relative number of atoms
sensible. Paying careful attention to units 5 6355 u

and making sure the answer is reasonable 80 atom atom
Reality Check Note that 5.68 mg of silicon is clearly much less than 1 mole of silicon 69.09
can help you detect an inverted conversion
63362_ch05_rev03.indd factor or a number that was incorrectly
194 (which has a mass of 28.09 g), so the final answer of 1.22 3 1020 atoms (compared07/11/19 5:30 PM 60 The average mass of a copper atom is
entered in your calculator. with 6.022 3 1023 atoms) is in the right direction. 40 30.91
6355 u
20 5 63.55 uyatom
See Exercise 5.47
100 atoms
0
63 65 This mass value is used in doing calculations involving the reactions of copper and is
Mass number the value given in the table inside the front cover of this book.
FigURE 5.3 Mass spectrum of
natural copper. Reality Check When you finish a calculation, you should always check whether your
inTERACTivE ExAMPLE 5.5 Calculating the Number of Moles and Mass answer makes sense. In this case our answer of 63.55 u is between the masses of the
Always check to see if your answer is atoms that make up natural copper. This makes sense. The answer could not be smaller
Cobalt (Co) is a metal that is added to steel to improve its resistance to corrosion. Cal- than 62.93 u or larger than 64.93 u.
sensible (Reality Check). Paying careful
culate both the number of moles in a sample of cobalt containing 5.00 3 1020 atoms
and the mass of the sample.
attention to units and making sure the
answer is reasonable can help you detect an 4.1 Molecular Structure: The VSEPR Model 145
inverted conversion factor or a number that See Exercises 5.37 and 5.38
Interactive Examples engage students in the problem-solving process
was incorrectly entered in your calculator.
It can be shown that this is the maximum possible separation of four pairs around a
To calculate the number of moles and the mass of a sample of Co H
What do we know? by requiring them toatom.
given think through
This the
means that example
whenever four step-by-step
pairs of electronsrather than
are present around an
❯ Sample contains 5.00 3 1020 atoms of Co
simply scanningatom,
the they shouldexample
written always be arranged tetrahedrally.
in the text as many students do.
How do we get there? 63362_ch05_rev02.indd 193 Now that we have the electron-pair arrangement that gives the least repulsion, we 22/10/19 10:09 PM
C
Russ Lappa/Science Source
Note that the sample of 5.00 3 1020 atoms of cobalt is less than 1 mole
H
(6.022 3 1023 atoms) of cobalt. What fraction of a mole it represents can be deter-
can determine the positions of the atoms and thus the molecular structure of CH4. In
mined as follows: H methane, each of the four electron pairs is shared between the carbon atom and a hy-
5.00 3 1020 atoms Co 3
1 mol Co
5 8.30 3 1024 mol Co H drogen atom. Thus the hydrogen atoms are placed as in Fig. 4.1, and the molecule has
▲ Fragments of cobalt metal. 6.022 3 1023 atoms Co
a tetrahedral structure with the carbon atom at the center.
be determined as follows: FIguRE 4.1 The molecular
Since the mass of 1 mole of cobalt atoms is 58.93 g, the mass of 5.00 3 1020 atoms can
Recall that the main idea of the VSEPR model is to find the arrangement of electron
58.93 g Co
structure of methane. The tetrahedral pairs around the central atom that minimizes the repulsions. Then we can determine
arrangement of electron pairs produces
24
8.30 3 10 mol Co 3 5 4.89 3 1022 g Co
1 mol Co the molecular structure from knowing how the electron pairs are shared with the pe-
a tetrahedral arrangement of hydrogen
Reality Check In this case the sample contains 5 3 1020 atoms, which is approxi- ripheral atoms. Use the following steps to predict the structure of a molecule using the
mately 1y1000 of a mole. Thus the sample should have a mass of atoms.
(58.93) > 0.06. Our answer of ,0.05 makes sense.
about (1y1000)
VSEPR model.
See Exercise 5.48
PROblEM-SOlVing STRaTEgy
Steps to apply the VSEPR Model
Notice that we need to determine the 1. Draw the Lewis structure for the molecule.
Lewis structure as a first step.
63362_ch05_rev02.indd 199 22/10/19 10:09 PM 2. Count the electron pairs and arrange them in the way that minimizes repulsion (that
is, put the pairs as far apart as possible).
Problem-Solving Strategy boxes focus students’ attention on the very im- 3. Determine the positions of the atoms from the way the electron pairs are
shared.
portant process of problem solving.
4. Determine the name of the molecular structure from the positions of
the atoms.
We will predict the structure of ammonia (NH3) using this stepwise approach.
1. Draw the Lewis structure:
xvi
2. Count the pairs of electrons and arrange them to minimize repulsions. The NH3
Copyright 2021 Cengage Learning. All Rights Reserved. May not be ▲ When
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Dynamic Art Program Most of the glassware, orbitals, graphs, flowcharts, and molecules 6.3 The Composition of Solutions 245
have been redrawn to better serve visual learners and enhance the textbook. How do we get there?
What are the moles of NaCl (58.44 g/mol)? 246
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 mol) NaCl?
There is some volume, call it V, that when multiplied by the molarity of this solution M3V5
1.1 Chemistry: An Atoms-First Approach 35 will yield 1.7 3 1025 moles of NaCl. That is,
0.14 mol NaCl
FiguRE 1.2 Sand on a beach looks V3 5 1.7 3 1025 mol NaCl
L solution
uniform from a distance, but up close What mass of K2Cr2O
the irregular sand grains are visible, and We want to solve for the volume:
each grain is composed of tiny atoms.
1.7 3 1025 mol NaCl
V5 5 1.2 3 1024 L solution
0.14 mol NaCl
L solution
The artThusprogram emphasizes molecular-level interactions that
0.12 mL of blood contains 1.7 3 10 moles of NaCl or 1.0 mg NaCl.
25
O
help students visualize the “micro/macro” connection.
See Exercises 6.35 and 6.36
Si
A standard solution is a solution whose concentration is accurately known. Stan- Dilution
S CI E N
Masterfile Royalty Free

dard solutions, often used in chemical analysis, can be prepared as shown in Fig. 6.10
CE
and in Example 6.6.
PH
OT
LIB
O
RA
RY/
S ci e
nc e S o ur ce
iNTERACTivE ExAMplE 6.6 Solutions of Known Concentration

To analyze the alcohol content of a certain wine, a chemist needs 1.00 L of an aqueous
the most common and important substances on the earth, is composed of two types of 0.200 M K2Cr2O7 (potassium dichromate) solution. How much solid K2Cr2O7 must be
atoms: hydrogen and oxygen. There are two hydrogen atoms and one oxygen atom weighed out to make this solution? Dilution with water does not alter the
number of moles of solute present.
bound together to form the water molecule:
oxygen atom
water molecule To find the mass of K2Cr2O7 required for the solution
from a 17.4 M
What do we know?
hydrogen atom Calibration
❯ 1.00 L of 0.200 M K2Cr2O7 is required mark
When an electric current passes through it, water is decomposed to hydrogen and What information do we need to find the mass of K2Cr2O7?
oxygen. These chemical elements themselves exist naturally as diatomic (two-atom)
❯ Moles of K2Cr2O7 in the required solution
molecules: 500. mL solution 3
oxygen molecule written O2 Wash

FiguRE 6.10 Steps involved in bottle HC2H3O2. That is,
Realistic drawings of glassware and instrumentation
hydrogen molecule written H
the preparation of a standard aqueous
solution. (a) Put a weighed amount 2
V
found in the lab help students makethe real
We can represent connections.
decomposition
of a substance (the solute) into the
of water to its component elements, hydrogen andflask, and add a small
volumetric Volume marker
oxygen, as follows: quantity of water. (b) Dissolve the (calibration mark) Solving for V gives
solid in the water by gently swirling
the flask (with the stopper in place).
one oxygen molecule V5
written O2 (c) Add more water (with gentle
two water Weighed
electric swirling) until the level of the solution
molecules amount a b
current just reaches the mark etched on
written 2H2O two hydrogen molecules of solute
the neck of the flask. Then mix the
written 2H2 FiguRE 6.11 (a) A measuring 17.4 M
solution thoroughly by inverting the
flask several times. a b c pipet is graduated and can be used to
6.3various
measure The Composition of Solutions
volumes of liquid 247
By thinking of the atoms and molecules Notice that it takes two molecules of water to furnish the right number of oxygen and metric flask. A pipet
we can determine the relative numbers of accurately. (b) A volumetric (transfer)
hydrogen atoms to allow for the formation of the two-atom molecules. This reaction
molecules involved in a chemical reaction. FiguRE 6.12 (a) A measuring pipet is designed to measure one
explains why the battery in your car can explode if you jump start it improperly. When volume accurately. When filled to the pipets and
We will consider this idea in more detail in pipet is used to transfer 28.7 mL of 17.4 M
Chapter 5. you hook up the jumper cables, current flows through the dead battery, which contains acetic acid solution to a volumetric flask. mark, it delivers the volume indicated
water (and other things), and causes hydrogen and oxygen to form by decomposition (b) Water is added to the flask to the on the pipet.
of some of the water. A spark can cause this accumulated hydrogen and oxygen
63362_ch06_rev02.indd 245 to calibration mark. (c) The resulting 23/10/19 4:55 PM
explode, forming water again. solution is 1.00 M acetic acid.
O2
spark
2H2O 63362_ch06_rev02.indd 246
2H2
9.1 Intermolecular Forces 367
dipolar charge distribution. Thus we say that large atoms with many electrons exhibit
a higher polarizability than small atoms. This means that the importance of London
dispersion forces increases greatly as the size of the atom increases.
The dispersion forces in molecules with These same ideas also apply to nonpolar molecules such as H2, CH4, CCl4, and
63362_ch01_rev03.indd 35 large atoms are quite significant and CO2 [see Fig. 9.5(b)]. Since none of these molecules has a 07/10/19
permanent dipole mo-
4:48 PM
500 mL
are often actually more important than ment, their principal means of attracting each other is through London dispersion
dipole–dipole forces. forces.
a b c
Summary of Intermolecular Forces

So far in this chapter we have considered various forces that occur among molecules.
These interactions vary considerably in terms of the energies involved. In Table 9.3 we measuring pipet as shown in Fig. 6.12 to deliver 28.7 mL of 17.4 M acetic acid into a
summarize and compare forces that are typically called intermolcular interactions. 500-mL volumetric flask and then add water to the mark to perform the dilution
These interactions usually are weaker than bonding forces but are very important in described above.
determining the properties of substances.
TABLe 9.3 Intermolecular Forces iNTERACTivE ExAMplE 6.7 Concentration and Volume
Range of What volume of 16 M sulfuric acid must be used to prepare 1.5 L of a 0.10 M H2SO4
Type of Energies solution?
Interaction Nature of Attraction Model (kJ/mol) Examples
Ion–dipole Attraction between 35–400

+ H
charge on anion and end Na+ O To find the volume of H2SO4 required to prepare the solution
of dipole with opposite – – +
partial charge
H
Tables containing visuals
What do we help
know? students understand and
– ❯ 1.5 L of 0.10 M H SO is required
compare intramolecular and16 M intermolecular forces be-
2 4
–
❯ We have H SO 2 4
+ +
tween ions, atoms, What
andinformation
molecules.
do we need to find the volume of H SO ? 2 4
Dipole– Attraction between 5–30 δ+ δ+ ❯ Moles of H2SO4 in the required solution

dipole opposite partially charged – + – + O O
ends of polar molecules δ− S δ− S How do we get there?
O O
What are the moles of H2SO4 required?
Hydrogen Attraction between H 10–40 H M 3 V 5 mol
bond partially positively O
where is N, O, or F and is an H
charged H atom 0.10 mol H2SO4
attached to a highly atom with a lone pair of electrons H O 1.5 L solution 3 5 0.15 mol H2SO4
L solution
electronegative atom and H
a lone pair on another What volume of 16 M H2SO4 contains 0.15 mole of H2SO4?
atom
16 mol H2SO4
London Attraction between an ,1–40 V3 5 0.15 mol H2SO4
H H H H
F F F F L solution
dispersion instantaneous dipole
and a dipole induced in
a neighboring atom or
molecule
δ– δ+
H H H H
63362_ch06_rev02.indd 247 23/10/19 4:55 PM
δ– δ+ δ– δ+
H H H H
xvii
63362_ch09_rev02.indd 367 23/10/19 10:57 pm
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.
For review 615
For review
Key Terms Buffered Solutions
Section 14.1 ❯ Contains a weak acid (HA) and its salt (NaA) or a weak base (B) and its salt (BHCl)
common ion ❯ Resists a change in its pH when H1 or OH2 is added
common ion effect ❯ For a buffered solution containing HA and A2
Section 14.2 ❯ The Henderson–Hasselbalch equation is useful:
S D
buffered solution
Henderson–Hasselbalch pH 5 pKa 1 log
fA2g
fHAg
Each chapter has a For Review section to reinforce key con-
equation
Section 14.3 ❯ The capacity of the buffered solution depends on the amounts of HA and A2 present cepts and includes review questions for students to practice
buffering capacity
Section 14.4 ❯ The most efficient buffering occurs when the
fA2g
ratio is close to 1 independently.
fHAg
pH curve (titration curve)
millimole (mmol) ❯ Buffering works because the amounts of HA (which reacts with added OH2) and A2
equivalence point
fA2g
(stoichiometric point) (which reacts with added H1) are large enough that the ratio does not change signifi-
fHAg
Section 14.5
acid–base indicator cantly when strong acids or bases are added
phenolphthalein
Acid–Base Titrations
❯ 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 Web site (accessible from www.cengagebrain.com).
1. What is meant by the presence of a common ion? How Is it necessary that the concentrations of the weak
does the presence of a common ion affect an equilib- acid and the weak base in a buffered solution be equal?
rium such as Explain. What is the pH of a buffer when the weak acid
and conjugate base concentrations are equal?
HNO2saqd m H1saqd 1 NO22saqd
A buffer generally contains a weak acid and its weak
What is an acid–base solution called that contains a conjugate base, or a weak base and its weak conjugate
common ion? acid, in water. You can solve for the pH by setting up
2. Define a buffer solution. What makes up a buffer solu- the equilibrium problem using the Ka reaction of the
tion? How do buffers absorb added H1 or OH2 with weak acid or the Kb reaction of the conjugate base. Both
little pH change? reactions give the same answer for the pH of the solu-
tion. Explain. 140 ChapTer 3 Bonding: general Concepts
the bonding in the substance. Why do we draw reso- octet rule in organic compounds so as to have a formula
nance structures? charge of zero?
7. Define formal charge and explain how to calculate it. 8. The compounds AlCl3, CrCl3, and ICl3 have similar
What is the purpose of the formal charge? Organic formulas, yet each follows a different set of rules to
compounds are composed mostly of carbon and hydro- name it. Name these compounds, and then compare and
gen but also may have oxygen, nitrogen, and/or halo- contrast the nomenclature rules used in each case.
gens in the formula. Formal charge arguments work 9. How would you name HBrO4, KIO3, NaBrO2, and
63362_ch14_rev02.indd 615 10/31/19 5:09 PM
very well for organic compounds when drawing the best HIO? Refer to Table 3.5 and the acid nomenclature
Lewis structure. How do C, H, N, O, and Cl satisfy the discussion in the text.
Active learning Questions 14. The following electrostatic potential diagrams represent H2,
HCl, or NaCl. Label each and explain your choices.
These questions are designed to be used by groups of students in
class.
1. Explain the electronegativity trends across a row and down a
column of the periodic table. Compare these trends with those a.
of ionization energies and atomic radii. How are they related?
2. Using only the periodic table, predict the most stable ion for (a)
Active Learning Questions are designed to promote dis- Na, Mg, Al, S, Cl, K, Ca, and Ga. Arrange these from largest
to smallest radius, and explain why the radius varies as it does.
cussion among groups of students in class. Compare your predictions with Fig. 3.5.
3. Which has the greater bond lengths: NO22 or NO32? Explain. b. + –
4. The following ions are best described with resonance struc-
tures. Draw the resonance structures, and using formal charge (b)
arguments, predict the best Lewis structure for each ion.
a. NCO2
b. CNO2
5. What is meant by a chemical bond? Why do atoms form bonds c.
with each other? Why do some elements exist as molecules in
(c)
nature instead of as free atoms?
6. Why are some bonds ionic and some covalent? 15. Describe the type of bonding that exists in the Cl2(g) mole-
7. How does a bond between Na and Cl differ from a bond cule. How does this type of bonding differ from that found in
between C and O? What about a bond between N and N? the HCl(g) molecule? How is it similar?
8. Does a Lewis structure tell which electrons come from which 16. Some of the important properties of ionic compounds are as
atoms? Explain. follows:
9. Evaluate each of the following as an acceptable name for i. low electrical conductivity as solids and high conductivity
water: in solution or when molten
a. dihydrogen oxide ii. relatively high melting and boiling points
b. hydroxide hydride iii. brittleness
c. hydrogen hydroxide iv. solubility in polar solvents
d. oxygen dihydride How does the concept of ionic bonding discussed in this chap-
10. Why do we call Ba(NO3)2 barium nitrate, but we call Fe(NO3)2 ter account for these properties?
iron(II) nitrate? 17. Label the type of bonding for each of the following.
11. Why is calcium dichloride not the correct systematic name for a. b.
CaCl2?
12. The common name for NH3 is ammonia. What would be the
systematic name for NH3? Support your answer.
A blue question or exercise number indicates that the answer to

that question or exercise appears at the back of this book and a 18. Distinguish between the following terms.
solution appears in the Student Solutions Manual. a. molecule versus ion
b. covalent bonding versus ionic bonding
Questions c. molecule versus compound
13. Compare and contrast the bonding found in the H2(g) and d. anion versus cation
HF(g) molecules with that found in NaF(s).
xviii
63362_ch03_rev02.indd 140 10/5/19 5:55 PM
Comprehensive End-of-Chapter Practice and Review
For Review 233
A blue question or exercise number indicates that the answer to

that question or exercise appears at the back of the book and a
solution appears in the Solutions Guide, as found on PowerLecture.
37
Cl and 35Cl. Which is
Questions
23. Reference Section 5.2 to find the atomic masses of 12C and
13
C, the relative abundance of 12C and 13C in natural carbon,
and the average mass (in u) of a carbon atom. If you had a
sample of natural carbon containing exactly 10,000 atoms, Questions are homework problems directed at concepts
determine the number of 12C and 13C atoms present. What
- would be the average mass (in u) and the total mass (in u) of
within the chapter and in general don’t require calculation.
- the carbon atoms in this 10,000-atom sample? If you had a
sample of natural carbon containing 6.0221 3 1023 atoms,
2A 1 B ¡ A2B. If you mix 1.0 mole determine the number of 12C and 13C atoms present. What
B, what amount (moles) of A2B can be would be the average mass (in u) and the total mass (in u) of this
6.0221 3 1023 atom sample? Given that 1 g 5 6.0221 3 1023 u,
what is the total mass of 1 mole of natural carbon in units
of grams?
24. Avogadro’s number, molar mass, and the chemical formula of
a compound are three useful conversion factors. What unit con-
versions can be accomplished using these conversion factors?
25. If you had a mole of U.S. dollar bills and equally distributed
the money to all of the people of the world, how rich would
2H2, and benzene, C6H6
every person be? Assume a world population of 7 billion.
6, and butane, C4H10
26. Describe 1 mole of CO2 in as many ways as you can.
2, and dinitrogen tetroxide, N2O4 52 ChApter 1 Chemical Foundations
27. Which of the following compounds have the same empirical
12H10O, and phenol, C6H5OH
formulas?
h, 17. The vitamin niacin (nicotinic acid, C6H5NO2) can be isolated 26. Observations of the reaction between nitrogen gas and hydro-
from a variety of natural sources such as liver, yeast, milk, and gen gas show us that 1 volume of nitrogen reacts with 3 vol-
hhD react to form OhD and whole grain. It also can be synthesized from commercially umes of hydrogen to make 2 volumes of gaseous product, as
available materials. From a nutritional point of view, which shown below:
source of nicotinic acid is best for use in a multivitamin tablet?
a. b.
Why?
true regarding the lim- 18. Section 1.4 describes the postulates of Dalton’s atomic theory. N N + HH HH HH
With some modifications, these postulates hold up very well
regarding how we view elements, compounds, and chemical
reactions today. Answer the following questions concerning Determine the formula of the product and justify your answer.
Dalton’s atomic theory and the modifications made today. 27. A sample of chloroform is found to contain 12.0 g of carbon,
c. d. a. The atom can be broken down into smaller parts. What 106.4 g of chlorine, and 1.01 g of hydrogen. If a second sam-
28. What is the difference between the molar mass and the empiri- are the smaller parts? ple of chloroform is found to contain 30.0 g of carbon, what is
cal formula mass of a compound? When are these masses the the total mass of chloroform in the second sample?
b. How are atoms of hydrogen identical to each other and
same, and when are they different? When different, how is the how can they be different from each other? 28. A sample of H2SO4 contains 2.02 g of hydrogen, 32.07 g of
molar mass related to the empirical formula mass? sulfur, and 64.00 g of oxygen. How many grams of sulfur and
c. How are atoms of hydrogen different from atoms of
29. How is the mass percent of elements in a compound different grams of oxygen are present in a second sample of H2SO4 con-
helium? How can H atoms be similar to He atoms?
for a 1.0-g sample versus a 100.-g sample versus a 1-mole taining 7.27 g of hydrogen?
d. How is water different from hydrogen peroxide (H2O2)
3A 1 B S C 1 D. You react 4 moles sample of the compound? 29. In Section 1.1 of the text, the concept of a chemical reaction
even though both compounds are composed of only
30. A balanced chemical equation contains a large amount of was introduced with the example of the decomposition of
hydrogen and oxygen?
information. What information is given in a balanced water, represented as follows:
equation? e. What happens in a chemical reaction and why is mass
conserved in a chemical reaction?
31. The reaction of an element X with element Y is represented in one oxygen molecule
the following diagram. Which of the equations best describes 19. The contributions of J. J. Thomson and Ernest Rutherford led written O2
two water
this reaction? the way to today’s understanding of the structure of the atom. molecules electric
What were their contributions? written 2H2O current
X two hydrogen molecules
20. What is the modern view of the structure of the atom? written 2H2
Y
21. The number of protons in an atom determines the identity of
the atom. What do the number and arrangement of the Use ideas from Dalton’s atomic theory to explain how the above
electrons in an atom determine? What does the number of representation illustrates the law of conservation of mass.
neutrons in an atom determine?
30. In a combustion reaction, 46.0 g of ethanol reacts with 96.0 g
22. If the volume of a proton is similar to the volume of an elec- of oxygen to produce water and carbon dioxide. If 54.0 g of
tron, how will the densities of these two particles compare to water is produced, what mass of carbon dioxide is produced?
each other?
31. Early tables of atomic weights (masses) were generated by
23. For lighter, stable isotopes, the ratio of the mass number to the measuring the mass of a substance that reacts with 1.00 g of
atomic number is close to a certain value. What is the value? oxygen. Given the following data and taking the atomic mass
What happens to the value of the mass number to atomic num- of hydrogen as 1.00, generate a table of relative atomic masses
07/11/19 5:31 PM ber ratio as stable isotopes become heavier? for oxygen, sodium, and magnesium.
24. What refinements had to be made in Dalton’s atomic theory to
account for Gay-Lussac’s results on the combining volumes of Mass That
gases? Combines
with 1.00 g Assumed
Element Oxygen Formula
There are numerous Exercises to reinforce stu- Exercises Hydrogen 0.126 g HO
dents’ understanding of each section. These prob- In this section, similar exercises are paired. Sodium 2.875 g NaO
lems are paired and organized by topic so that Development of the Atomic Theory Magnesium 1.500 g MgO
instructors can review them in class and assign 25. When mixtures of gaseous H2 and gaseous Cl2 react, a product
forms that has the same properties regardless of the relative
32. Indium oxide contains 4.784 g of indium for every 1.000 g of
them for homework. amounts of H2 and Cl2 used.
oxygen. In 1869, when Mendeleev first presented his version
a. How is this result interpreted in terms of the law of defi- of the periodic table, he proposed the formula In2O3 for indium
nite proportion? oxide. Before that time it was thought that the formula was
b. When a volume of H2 reacts with an equal volume of Cl2 InO. What values for the atomic mass of indium are obtained
at the same temperature and pressure, what volume of using these two formulas? Assume that oxygen has an atomic
product having the formula HCl is formed? mass of 16.00.
63362_ch01_rev03.indd 52 07/10/19 4:49 PM
xix
23 28 20 190
89 76 Os
39 Y
50
27Co
35 44 36
15 16 32
51. Four Fe21
48. Complete the following table: are 53Fe21
Wealth of End-of-Chapter Problems The text offers an unparalleled variety of end-of- Number of Number of
Protons in Neutrons in Number of Net
52. Complete the following table.
chapter content with problems that increase in rigor and integrate multipleSymbol
concepts. 53 21
Nucleus Nucleus Electrons Charge
26Fe 120
50Sn
26 33 31 25 21
12 Mg
85 125 86
56 21
26 Fe
13 14 10
79
76 54 22 34Se
35
17Cl
63
29Cu
ChemWork problems
These multiconcept problems (and additional ones) are found in- 53.
For Review 52c teractively online with the same type of assistance a student would statements, correct them.
New ChemWork end-of-chapter multiconcept problems, with many additional get from an instructor. a.
55. The isotope of an unknown element, X, has a mass number of
problems, are found interactively online61.with
79. The most stable ion of this isotope has 36 electrons and has
Each of the following statements is true, but Dalton might
the same type of assistance a stu-
have had trouble explaining some of them with his atomic
49. Complete the following table, including the mass number and
the atomic number with the symbol for the isotope.
b.
in which electrons are embedded.
dent would get from an instructor. These problems
a 22 charge. Which of the following statements is(are) true? are available
theory. Give explanations to assign
for the following statements.online
c.
For the false statements, correct them. a. The space-filling models for ethyl alcohol and dimethyl Number of Number of the mass of the entire atom.
for more
a. This practice.
ion has more electrons than protons in the nucleus. ether are shown below. Protons Neutrons Symbol
d.
b. The isotope of X contains 38 protons. 9 10 the total volume of the atom.
C
c. The isotope of X contains 41 neutrons. 13 14 e.
O number of electrons.
d. The identity of X is strontium, Sr. 53 74
H 54. Which of the following is(are) correct?
56. An element’s most stable ion has a 21 charge. If the ion of 34 45
element X has a mass number of 230 and has 86 electrons, a. 40Ca21
These two compounds have the same composition by 16 16
what is the identity of the element, and how many neutrons b.
mass (52% carbon, 13% hydrogen, and 35% oxygen), yet
does it have?
the two have different melting points, boiling points, and
57. In a reaction, 34.0 g of chromium(III) oxide reacts with 12.1 g solubilities in water. c. An electron is heavier than a proton.
of aluminum to produce chromium and aluminum oxide. If d.
b. Burning wood leaves an ash that is only a small fraction
23.3 g of chromium is produced, what mass of aluminum
of the mass of the original wood.
oxide is produced?
c. Atoms can be broken down into smaller particles.
58. Using the information in Table 1.1, answer the following ques-
tions. In an ion with an unknown charge, the total mass of all the d. One sample of lithium hydride is 87.4% lithium by mass,
electrons was determined to be 2.55 3 10226 g, while the total while another sample of lithium hydride is 74.9% lithium
by mass. However, the two samples have the same chemi-
mass of its protons was 5.34 3 10223 g. What is the identity and
cal properties.
charge of this ion? What is the symbol and mass number of a
neutral atom whose total mass of its electrons is 3.92 3 10226 g, 62. Reaction of 2.0 L of hydrogen gas with 1.0 L of oxygen gas
while its neutrons have a mass of 9.35 3 10223 g? yields 2.0 L of water vapor. All gases are at the same tempera-
ture and pressure. Show how these data support the idea that
59. A single molecule has a mass of 7.31 3 10223 g. Provide an
oxygen gas is a diatomic molecule. Must we consider hydro-
example of a real molecule that can have this mass. Assume
gen to be a diatomic molecule to explain these results?
the elements that make up the molecule are made of light iso-
topes where the number of protons equals the number of neu- 63. A combustion reaction involves the reaction of a substance
trons in the nucleus of each element. with oxygen gas. The complete combustion of any hydrocar-
bon (binary compound of carbon and hydrogen) produces car-
Challenge problems
Challenge Problems take students one step
bon dioxide and water as the only products. Octane is a
hydrocarbon that is found in gasoline. Complete combustion
60. Confronted with the box shown in the diagram, you wish to further and challenge them more rigorously than
of octane produces 8 liters of carbon dioxide for every 9 liters 63362_ch01_rev03.indd 2
discover something about its internal workings. You have no

tools and cannot open the box. You pull on rope B, and it the Additional Exercises.
of water vapor (both measured at the same temperature and
52d ChApter 1 Chemical
pressure). What is the ratio of carbon atoms to hydrogen atoms Foundations
moves rather freely. When you pull on rope A, rope C appears in a molecule of octane?
to be pulled slightly into the box. When you pull on rope C, 65. You have two distinct gaseous compounds made from element
64. A chemistry instructor makes the following claim: “Consider
X and element Y. The mass percents are as follows:
Marathon problem
rope A almost disappears into the box. that if the nucleus were the size of a grape, the electrons would
be about 1 mile away on average.” Is this claim reasonably This problem is designed to incorporate several concepts and
Compound I: 30.43% X, 69.57% Y
accurate? Provide mathematical support. techniques into one situation.
Compound II: 63.64% X, 36.36% Y
C
66. You have gone back in time and are working with Dalton on a
A B In their natural standard states, element X and element Y exist table of relative masses. Following are his data.
as gases. (Monatomic? Diatomic? Triatomic? That is for you
to determine.) When you react “gas X” with “gas Y” to make 0.602 g gas A reacts with 0.295 g gas B
the products, you get the following data (all at the same pres- 0.172 g gas B reacts with 0.401 g gas C
sure and temperature): 0.320 g gas A reacts with 0.374 g gas C
Marathon Problems
1 volume “gas X”also combine
1 2 volumes “gas Y” con- a. Assuming simplest formulas (AB, BC, and AC), construct
a table of relative masses for Dalton.
cepts from multiple chapters; they2 are the
volumes compound I
b. Knowing some history of chemistry, you tell Dalton that
2 volumes “gas X” 1 1 volume “gas Y”
most challenging problems in the2 end-of- volumes compound II
if he determines the volumes of the gases reacted at
a. Based on these observations, construct a model for the constant temperature and pressure, he need not assume
interior mechanism of the box. chapter material.
Assume the simplest possible formulas for reactants and prod- simplest formulas. You collect the following data:
b. What further experiments could you do to refine your ucts in the chemical equations above. Then, determine the 6 volumes gas A 1 1 volume gas B → 4 volumes product
model? relative atomic masses of element X and element Y. 1 volume gas B 1 4 volumes gas C → 4 volumes product
3 volumes gas A 1 2 volumes gas C → 6 volumes product
Write the simplest balanced equations, and find the actual
relative masses of the elements. Explain your reasoning.
63362_ch01_rev03.indd 3 07/10/19 4:49 PM
xx
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 Sci-
ences Award for Excellence in Teaching, UIUC Liberal Arts
and Sciences 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 stu-
dents to excel in the sciences. She has coordinated and led
workshops and programs for science teachers from elemen-
tary through college levels. These programs encourage 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 Cali-
fornia, and she has authored several chemistry 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.
xxi
xxii About the Authors
Donald J. DeCoste is the Associate Director of General

Chemistry at the University of Illinois, Urbana–Champaign
and has been teaching chemistry at the high school and
college levels for 30 years. He earned his B.S. in Chemistry
and Ph.D. from the University of Illinois, Urbana–Champaign.
At Illinois, he teaches courses in general chemistry and the
teaching of chemistry. He has also developed chemistry
courses for non-science majors, preservice secondary
teachers, and preservice elementary/middle school teachers.
He has received the LAS Award for Excellence in Under-
graduate Teaching, the Provost’s Excellence in Undergradu-
ate Teaching Award, and the School of Chemistry Sciences
Teaching Award (five times). Don has led workshops for
secondary teachers and graduate student teaching assistants,
discussing the methods and benefits of getting students more
actively involved in class. When not involved in teaching
and advising, Don enjoys spending time with his wife and
three children.
review
Glassware used to measure volumes of liquids. (Alexander Raths/Shutterstock.com)
Measurement and Calculations

in Chemistry
R.1 Units of Measurement R.4 Learning to Solve Problems R.8 Classification of Matter
R.2 Uncertainty in Measurement Systematically R.9 Energy
Precision and Accuracy R.5 Dimensional Analysis Chemical Energy
R.3 Significant Figures and Calculations R.6 Temperature R.10 The Mole
R.7 Density
Another random document with
no related content on Scribd:
Harpsichord composers. From top left to bottom right:
D. Scarlatti, Couperin, C. P. E. Bach, Clementi.
When a man like Alberti at last endeavored to write purely melodic
music on the harpsichord alone, which by the way was wholly
unfitted to sing, three methods of accompaniment were open to him.
One of these was to give to the left hand, as accompanist, a counter-
melody or counter-melodies, which, interweaving with the upper
melody, would create harmonic progressions. Allowing him to have
had the skill to do this, as Couperin or Bach had been able to do, it
would not have recommended itself to him as the best way to set off
the chief melody. Such a procedure inevitably tangled melody with
accompaniment. Secondly, he could give to the left hand a series of
chords. But owing to the nature of the harpsichord, these would
sound dry and detached, with cold harmonic vacancies between;
unless he chose to repeat the chords rapidly, which process was
decidedly clumsy. Finally he could break up the chords into their
separate notes, combine these in groups easily within the grasp of
the hand, and by playing these groups rapidly over and over again,
produce a constantly moving harmonic current on which his melody
might float along. This is in fact what Alberti did, and this is the
legitimate function of the Alberti bass, one which can no more be
dispensed with from pianoforte music than the tremolo from the
orchestra.
It is hardly possible to believe that he invented the particular formula

which plays such a part in his music. Bach had devised many
methods of breaking chords so that their component parts might be
kept in rapid and constant vibration. Witness alone the first and
second preludes in the first book of the ‘Well-tempered Clavichord.’
In the ninth toccata of the elder Scarlatti there is an eight-measure
passage of chords broken exactly in the Alberti manner. But such
devices were employed by Bach and likewise by A. Scarlatti in
passages of purely harmonic significance. Alberti must be among the
first, if he is not actually the first, to use them to supply a simple
harmonic basis for his melodies.
From the almost universal acceptance of the formula in the last half
of the eighteenth century one may deduce two facts: one, that a
good many composers were too lazy or too lacking in natural
endowment to bother with acquiring a skill in counterpoint; second,
that the whole trend of music was away from the contrapuntal style
towards the purely melodic. Both facts are true; but one should no
more deplore the former than be thankful for the latter, to which is
owing many an imperishable page of Mozart and of Beethoven.
Other formulas of accompaniment in no way superior to Alberti’s

were quick to make their appearance. Among them should be
noticed the arpeggio figures:
and the perhaps even more monotonous ones which one finds even
in such a sublime masterpiece as the sonata in A-flat major (op. 110)
of Beethoven.
Alberti is a convenient figure to whom to trace an early style of

sonata movement which developed through Christian Bach and
Clementi, and Haydn and Mozart. He fits the case pretty well
because he happened to write a number of sonatas for harpsichord
alone. But the great influences which, apart from Pergolesi, affected
the growth of this triplex form not only in the symphony, but in the
sonata as well, emanated from Mannheim in the Upper Palatinate.
The orchestra there under the gifted Johann Stamitz had come to
be, before the middle of the century, the best in Europe. The two
great composers who were associated with it, Franz Xaver Richter
(1709-89) and Stamitz (1717-57) himself, did perhaps more than any
other composers of the time to strengthen the new form and give it
use as a vehicle of lively feeling. Their energy and their success left
an indelible impression upon the symphony, and upon the string-
quartet. And they made themselves felt upon the pianoforte sonata;
in Vienna through the famous pianist-composer, G. C. Wagenseil
(1715-1777); in Paris through the young and popular Jean Schobert
(d. 1767) already mentioned; and even in London through Christian
Bach.
Emanuel Bach, who was frequently publishing sets of sonatas in

Berlin from 1740 to 1786, rather gradually adopted the new form
than contributed to its development. He never quite shook off a
conception of music inherited from his father, which was at the time a
little too serious to submit wholly to the new influences. Hence, for
example, the triplex form is always a little vague in his music. The
themes which he employed, though often beautiful and poetic, were
not of the distinct and melodious type which was characteristic of the
form. The first and second themes were not often clearly
differentiated. In fact he frequently inclined towards constructing his
movements out of one theme, which dominated them as the opening
figure dominated the old binary form. And he very rarely made use of
the stereotyped formulas of the harmonic accompaniment, born of
the universal tendency towards a melodic or homophonic style.
He cannot be closely associated with the developments which took

place within the ‘singing allegro,’ preparing it for use in the great
sonatas of the Viennese period. These took the form of setting the
two themes out of which the movement was constructed distinctly
apart from each other, in strong relief, so to speak; and of similarly
giving the three sections a clear outline, and the movement as a
whole a stable balance.
The processes by which this was accomplished in harpsichord music

may be briefly touched upon. The first theme tended towards
simplicity. Already in sonatas of Christian Bach and Jean Schobert a
dignified and somewhat declamatory type of melody is favored for
the opening. This was usually repeated, that it might be impressed
upon the mind of the listener. Often it came to an end squarely in a
full tonic cadence.
The transitional passage which was then to accomplish the

modulation to the dominant or relative major key in which the second
theme was to be announced, tended to become highly conventional,
a sort of service music with little more than formal significance.
Usually a figure of some technical brilliance carried the music along
in repetitions that could not fail to attract the attention of the listener
and arouse his curiosity as to what was coming next. These figures
might or might not be fragments of the opening theme. The
modulation to the desired key having been accomplished, the
passage came to an end in a flourish or in a pause of a beat or two.
No feature of the triplex form is more distinctive than these
conventional transitional passages which seem to carry on the
double function of porter and herald.
After the claim to attention had been thereby established the second
theme was allowed to sing. The general tendency was to give to this
second theme a gentler and more truly melodious character than the
first. Here was the great domain of the Alberti bass, for instance. And
following the second theme came another busy little passage,
service music again, of which the duty was to bring the first section
of the movement to an orderly close in the key of the dominant.
The treatment of the middle section varied. It remained always the

part in which the composer exercised the most freedom. It might be
long or short, in the manner of a fantasia; it might merely present
fragments of the first or second themes or both in a series of
modulations or sequences. It may be said that the tendency towards
a more or less dramatic development made an appearance before
the end of the century, as if the composer was submitting his will to
the suggestions of the themes themselves. The greater the inherent
vitality of these themes the more likely were they to assert
themselves in this middle section and to reveal, as it were, the
germinating power within them and color the section with their
nature. The end of the section was more and more contrived to lead
up to the last section in an obvious manner, either with a long run, a
series of flourishes reaching a climax, or a pause, or anticipations of
the coming theme.
The last section differed little from the first except that the second
theme now appeared in the tonic key. The transitional passage was
taken, along with the themes themselves, from the first section; but,
relieved of one half its duty—that of bringing to pass a modulation
from tonic to dominant—was likely to be considerably shortened.
The closing measures, however, were usually an exact reduplication
in the tonic key of those which had closed the first section in the
dominant. The first section was always repeated, and so were the
second and third, en bloc.
Such was the sonata form of movement which we have chosen to

call the triplex form; a movement in three clear sections, made up of
two themes appearing variously in each of them. The three sections
are generally known in English as the exposition, the development,
and the recapitulation or restatement; and what distinguishes them is
the conventional figure or passage work which was used to mark
them off, one from the other, and to stand as dividing line between
the first and second themes. In the sonatas of Christian Bach all
these things are clear and en règle; in Emanuel Bach they are
obscure. They are clear in the works of the Mannheim group, and in
those of the Viennese and Parisian composers who responded to
their influence. They are clear in the sonatas and symphonies of
Haydn and Mozart and can still be traced in most of those of
Beethoven. Hence it would seem that in many ways Emanuel Bach,
instead of being the source of the pianoforte sonata, stands very
nearly outside the current of influences to which it really owes its
most distinctive feature.
We may again define the sonata as a piece of music which is a

conventional group of several pieces or movements, usually three,
more rarely four. The movements are not internally related to each
other. The bond which holds them together is only traditional. One of
these movements, most often the first, is written in a form sprung of
the love of Italians and Slavs for melody, known generally as the
sonata form. The presence of a movement in this form in a group of
pieces will give an unchallenged right to call that group a sonata.[24]
III
The pianoforte sonata was a sufficiently clearly defined product of
musical craftsmanship, if not art, before Haydn and Mozart began
seriously to express themselves in it. It is right then to summarize
briefly the musical value of the chief sonatas before their day.
The many writers may be divided according to the countries in which

they practised their art. In London are to be found P. D. Paradies
(1710-1792) and Baldassare Galuppi (1706-1785), both Italians, and
Johann Christian Bach, submitting almost unconditionally to Italian
influence. In the London group too must be reckoned one of the
most important men in the development of pianoforte music, Muzio
Clementi. In Vienna the chief figure is G. C. Wagenseil; in Paris,
Jean Schobert; in Berlin, Emanuel Bach, with whom may be
reckoned Friedrich Wilhelm Rust, who, through his brother Johann
Ludwig Anton, a pupil of Sebastian Bach, was clearly influenced by
the works of the great masters.
Both Galuppi and Paradies rather continue the tradition of Scarlatti

than contribute to the development of the new style. Both, however,
published sets of sonatas, that is sets of pieces in more than one
movement; though the triplex form is practically unfamiliar to them.
Their music has great sprightliness and charm. It should be
mentioned because the work of Paradies especially was admired
and recommended by Clementi.
Christian Bach, on the other hand, is full of the new idea. His life
itself may well claim attention. It is sufficiently remarkable that he
almost alone of the great Bach family which had for generations
played a part in the development of music in Germany, and was to
play such a part there for many years to come, broke the traditions of
his fathers, went to Italy for eight years, even became a Catholic,
and finally decided to pass the last twenty years of his life in London.
Though the many stories of his extravagances and dissipations have
been most unrighteously exaggerated, he was none the less of a
gay, light-hearted and pleasure-loving nature which is in sharp
contrast to the graver and more pious dispositions of his ancestors.
His father died when he was but fifteen years old. He had already
shown marked ability as a player of the harpsichord, and his brother
Emanuel took him to Berlin after the father’s death and trained him
further in the art for four years. Then followed the eight years in Italy
where he was beloved and admired by all with whom he came in
contact, not the least by the great Padre Martini in Bologna, with
whom he studied for many years. In 1762 he went to London, chiefly
to write operas. He was enormously popular and successful. He was
court clavecinist to Queen Anne and in 1780 a Bath paper spoke of
him as the greatest player of his time.
At some time not long after his arrival in England he published a set
of six sonatas for the harpsichord, dedicated to the amusement of
‘His Serene Highness, Monseigneur le duc Ernst, duc de
Mecklenburg.’ Of these the second, in D major, offers a particularly
excellent example of clear, lucid writing in the sonata form. The first
movement is admirable. The first theme is composed of vigorous
chords. It is given twice, then followed by a transitional passage full
of fire; the right hand keeping a continuous flow of broken chord
figures, over the rising and falling powerful motives in the left. The
preparation for the announcement of the second theme is in
remarkably mature classical manner, and the lovely melodious
second theme, with its gentle Albertian accompaniment, is clearly a
promise of Mozart to come. There is a fine free closing passage. The
development section is long and varied, astonishingly modern; and
the return to the first theme, prepared by a long pedal point and a
crescendo, is not a little fiery and dramatic. The second movement,
an andante in G major, and the quick final movement in D again,
round off a work which for clearness of form, for balance in
proportions, and for a certain fine and healthy charm, is wholly
admirable. Above all there is about all his work a real grace which,
superficial as it may be, is a precious and perhaps a rare quality in
pianoforte music, a quality both of elegance and amiability. It is a
reflection of his own amiable nature, so conspicuous in all his
dealings with the little Mozart during the spring of 1765.
Christian Bach is no careless musician. His work is done with a sure

and unfailing hand. No man could have lived fifteen years in the
house of his father, Sebastian, and four more in that of his brother
Emanuel, and yet again eight under the strong personal influence of
Padre Martini, the most learned contrapuntist of his day, without
acquiring a mastery of the science of music. Such Christian Bach
had at his command; such he chose to conceal under a lightness
and gaiety of thought and style.
As regards instrumental music in particular his influence upon

Mozart, though in some ways ineradicable, was largely supplanted
by the influence of Josef and Michael Haydn. What Mozart received
from him in the domain of opera, however, as summarized by
Messrs. de Wyzewa and Saint-Foix in their ‘W. A. Mozart’ (Paris,
1912), was characteristic of all of Bach’s music: ‘A mixture of
discrete elegance and melodic purity, a sweetness sometimes a little
too soft [un peu molle] but always charming, a preference of beauty
above intensity of dramatic expression, or rather a constant
preoccupation to keep expression within the limits of beauty.’
Muzio Clementi was born in Rome in 1752, but when hardly more
than a lad of fourteen was brought to London by an English
gentleman, and London was henceforth his home until he died in
1832. He was a brilliant virtuoso, though he travelled but little to
exhibit his powers; an excellent pedagogue; a very shrewd business
man. Among his many compositions of all kinds, about sixty are
sonatas for pianoforte. The first series of three was published in
1770 and is usually taken to determine the date at which the
pianoforte began really to supplant the harpsichord.
Concerning Clementi’s relation to the development of a new

pianoforte technique we shall speak further on. Here we have to do
with the musical worth of his sonatas. Clementi was born before
Mozart and Beethoven. He outlived them both, not to mention
Haydn, Weber and Schubert. Mozart, after a test of skill with him in
Vienna, had little to say of him save that he had an excellent, clear
technique. He remained primarily a virtuoso in all his composition;
but on the one hand he undoubtedly influenced Mozart and
Beethoven,—and not only in the matter of pianoforte effects,—while
on the other he no less obviously held himself open to influence from
them, particularly from Beethoven.
His pianoforte sonatas show a steady development towards the

curtailing of sheer virtuosity and the supremacy of emotional
seriousness. In the early works, op. 2, op. 7, and op. 12, for
example, he is obviously writing for display. The sonatas in op. 2
have but two movements. After that he generally composes them of
three. The spirit of Scarlatti prevails, though it is almost impossible to
point to any close relationship between the two men. The last
movement of the second sonata in op. 26 perhaps resembles
Scarlatti as definitely as any. But the fundamental difference
between them, which may well obliterate all traces of the
indebtedness of the one to the other, is that Clementi writes in the
new melodic style. That he was a skilled contrapuntist did not
restrain his use of the Alberti bass and other formulas of
accompaniment.
He composed with absolute clearness. The classical triplex form,

with its conventional transitional passages, its clear-cut sections,
and, above all, its well-defined thematic melodies, can nowhere else
be better exemplified. What perhaps mars his music, or at any rate
makes a great part of it tiresome to modern ears, is the employment
of long scale passages in many of his transitional passages. They
cannot but suggest the exercise book and the hours of practice
which are back of them. The concise figures of Schobert, of Haydn
and Mozart may sound thin, but, though they suggest sometimes the
schoolboy, they spare us the school.
On the other hand, Clementi was wonderfully fertile in figures that
sound well on the piano, and many of his sonatas, empty enough of
genuine feeling, are still pleasant and vivacious to the listener. Yet
they seem to have sunk down into the tomb. They are perhaps never
heard in concerts at the present day. Those which are only show
music may willingly be let go. They lack the diamond sparkle of
Scarlatti. But there are others, even among the earlier ones, which
are musically too worthy and still too interesting to be so ruthlessly
consigned to the grave as the modern temper has consigned them.
Have we after all too much pianoforte music as it is? It seems to be
more than a change of fashion that keeps Clementi dead. Perhaps it
is the shade of the admirable but awful Gradus ad Parnassum over
all his other work. Perhaps a man has the right to live immortally by
the virtue of but one of his excellencies. In the case of Clementi
posterity has chosen to remember only the success of a teacher.
The great series of studies or exercises published in 1817 under the
usual pompous title of Gradus ad Parnassum alone of all his work
still retains some general attention.
And this in spite of many beauties in his sonatas. Even among the
early ones there are some distinguished by a fineness of feeling and
a true if not great gift of musical expression. Take, for example, the
sonata in G minor, number three of the seventh opus. The first
movement, allegro con spirito, has more to recommend it than
unusual formal compactness and perfection. The opening theme has
a color not in the power of the mere music-maker. It is true that there
is the almost ever-present scale passage in the transition to the
second theme; but the second theme itself has a grace of movement
and even a certain sinuousness of harmony that cannot but suggest
Mozart. There are sudden accents and rough chords that
foreshadow a mannerism of Beethoven; and the full measure of
silence before the restatement begins is a true romantic touch.
The spirit of the slow movement is perhaps a trifle perfunctory. There

is little hint of Mozart, who, alone of the classical composers, could
somehow always keep the wings of his music gently fluttering
through the leaden tempo adagio. The sharp—one may well say
shocking—sudden fortissimos herald Beethoven again. The
movement is, however, blessedly short; and the final presto is full of
fire and dark, flaring and subsiding by turns.
Of the later sonatas that in B minor, op. 40, No. 2, and that in G
minor, op. 50, No. 3, have been justly admired. Yet excellent as they
are, one can hardly pretend to do more than lay a tribute on their
graves. Only some unforeseen trump can rouse them from what
seems to be their eternal sleep. One feature of the former may be
noted: the return of a part of the slow movement in the midst of the
rapid last movement. Such a process unites at least the last two
movements very firmly together, tends to make of the sonata as a
whole something more than a series of independent movements put
in line according to the rule of convention.
The sonata in G minor also seems to have an organic life as a

whole. Clementi gave it a title, Didone abbandonata, and called the
whole a scena tragica. This is treating the whole sonata as a drama
based upon a single idea; but inasmuch as it was written probably
between 1820 and 1821, this conception of the sonata probably
came to him from Beethoven rather than from his own idealism.[25]
It is hard to turn our thumbs down on Clementi. It may be unjust as

well. He entered the arena of the sonata and in many ways no man
excelled him there. Mozart’s impulsive condemnation has gone hard
with him. We are like sheep, and even the wisest will listen all but
unquestioning to a man who had, if ever man had, the voice of an
angel. And so Clementi is all but forgotten as a sonatorial gladiator
and remembered only as a trainer. That the greatest of the fighters
profited by his teaching cannot be doubted. That they despoiled him
of many ideas and even of his finery before his flesh was cold is also
true. They made better use of them.
A glance over Clementi’s sonatas can hardly astonish more than by

what it reveals of the great commonness of musical idioms during
the Viennese period. Phrase after phrase and endless numbers of
fragments bob up with the features we had thought were only
Haydn’s, or Mozart’s, or Beethoven’s. Mozart quite openly
appropriated a theme from one of Clementi’s sonatas[26] as the
basis of his overture to the ‘Magic Flute.’ Such a fact is, however, far
less suggestive than the intangible similarity between the stuff
Clementi used and that which his greater contemporaries in Vienna
built with. Compare, for instance, the first movement of Clementi’s
sonata in B-flat, op. 34, No. 2, with the first movement of
Beethoven’s symphony in C minor. Likeness of treatment, likeness of
skill, likeness of mood there are not; but the juxtaposition of the two
movements creates a whisper that Clementi passed through music
side by side with some of the greatest of all composers.
IV
Both Schobert in Paris and Wagenseil in Vienna are more than
straws which show the way the wind blew through the classical
sonata. They are streaks in the wind itself. On the one came the
seeds of the new works in Mannheim to the clavecins in Paris; and
on the other such seeds were blown to harpsichords in Vienna. Both
men wrote great quantities of music for the harpsichord, but oftenest
with a part for violin added. This part was, however, usually ad
libitum.
Concerning Schobert we may quote once more from the ‘Life of

Mozart’ by Messrs. de Wyzewa and de Saint-Foix. ‘From 1763 up to
the general upheaval caused by the Revolution, he was the most
played and the most loved of all the composers of French sonatas. *
* * Outside France, moreover, his works were equally highly prized;
we find testimony to it in every sort of German, English and Italian
treatise on the history or on the esthétique of the piano.’
Concerning Wagenseil we may recall the anecdote of little Mozart

who one evening, on the occasion of his first visit to Vienna, refused
to play unless Wagenseil, the greatest of players and composers for
harpsichord in Vienna, were present. Dr. Burney visited him some
years later and heard him play, old and ailing, with great fire and
majesty.
Schobert was, as we have said, of Silesian origin. He came to Paris

as a young man, probably by way of Mannheim, some time between
1755 and 1760; and from then on to the time of his death in 1767
adapted his music more and more to the French taste. Hence we
find in it a simple but strong expression, an elegant clearness and a
touch of that sensibilité larmoyante made fashionable by Rousseau,
showing itself in the frequent use of minor keys, evidently at the root
of the very personal emotional life of his music.[27] Mozart came very
strongly under his influence.
Wagenseil, on the other hand, shows yet more of the Italian

influence, so strong even at that day in Vienna, to which Haydn was
to owe much. His work lacks emotion and poetry, is facile and
brilliant and clear, without much personal color.
In the matter of emotional warmth the sonatas of Emanuel Bach,

however vague they may be in form by contrast with those of
Schobert and his brother Christian, are distinguished above those of
his contemporaries. Emanuel—his full name was Carl Philipp
Emanuel—was born in Weimar in March, 1714. An early intent to
devote himself to the practice of law was given up because of his
marked aptitude for music. In 1740 he entered the service of
Frederick the Great as court cembalist. In 1757 he gave up this post
and went to Hamburg, where he worked as organist, teacher, and
composer until his death there on the fourteenth of December, 1788.
The works by which he is best known are the six sets of sonatas,
with rondos and fantasies too, which he published between 1779
and 1787 in Leipzig under the title of Sonaten für Kenner und
Liebhaber (‘Sonatas for Connoisseurs and Amateurs’). Many of the
sonatas, however, had been composed before 1779.
An earlier set, dedicated to the Princess Amelia of Prussia and

published in 1760, bears the interesting title, Sechs Sonaten fürs
Clavier mit veränderten Reprisen (‘Six Sonatas for Clavier with
Varied Repeats’). This title, together with Bach’s preface to the set,
shows conclusively that in repeating the sections of movements of
sonatas, players added some free ornamentation of their own to the
music as the composer published it. The practice seems to have
been an ancient one, applied to the suite before the sonata came
into being. Thus some of the doubles of Couperin and Sebastian
Bach may be taken as special efforts on the part of the composers to
safeguard their music from the carelessness and lack of knowledge
and taste of dilettanti. To what an extent such variation in repeat
might go and how much it might add to the richness of the music are
shown, for example, by the double of the sarabande in Sebastian
Bach’s sixth English suite.
Emanuel Bach’s sonatas are of very unequal merit. The sonata in F

minor,[28] published in the third set for Kenner und Liebhaber in
1781, but written nearly twenty years earlier, has little either of
extrinsic or intrinsic beauty to recommend it. Not only does the
inchoate nature of the second theme in the first movement fail to
save the movement from monotony; the first theme itself is stark and
devoid of life. There is a lack of smoothness, a constant hitching.
The andante is not spontaneous for all its sentimentality, and the
final movement is fragmentary.
A sonata in A major, on the other hand, written not long after, and
published in 1779, is charming throughout. The first theme in the first
movement is conventional enough, but it has sparkle; and though the
second theme is not very distinctly different from the first, the
movement is full of variety and life. Particularly charming are the
measures constituting an unusually long epilogue to the first section.
The harmonies are richly colored, if not striking; and the use of the
epilogue in the development section is most effective. So is the full
measure pause before the cascade of sound which flows into the
restatement. The andante is over-ornamented, but the harmonic
groundwork is solid and interesting. The last movement suggests
Scarlatti, and has the animated and varied flow which characterizes
the first.
A sonata in A minor, written about 1780 and published in the second
series for Kenner und Liebhaber, is in many ways typical of Emanuel
Bach at his best. There is still in the first movement that vagueness
of structure which may usually be attributed to the lack of
distinctness of his second theme. But the first theme has a fine
declamatory vigor, in the spirit of the theme out of which his father
built the fifth fugue in the first book of the ‘Well-tempered Clavichord’;
and the movement as a whole has the broad sweep of a brilliant
fantasy.
The andante, with its delicate imitations, foreshadowing Schumann,

is full of poetic sentiment. It leads without break into the rapid final
movement. Here the declamatory spirit of the first movement reigns
again, but in lighter mood. There is in fact an unmistakable kinship
between the first and last movements, which must be felt though it
cannot be traced to actual thematic relationship. Here is a sonata,
then, which, though divided into three movements, seems sprung of
one fundamental idea.
Such a conception of the sonata is by no means always so clear in

his work; yet it must be said that he, more than any composer down
to Beethoven, was inclined to make of the sonata a poetic whole. His
aim was rather furthered than hindered by the vagueness of form of
the separate movements. His sonatas are all the more fantasies for
being less clearly sonatas; and they are often rich in that very quality
in which the regular classical sonata was so poor—imagination.
Most of what has been said regarding his creation or establishing of

the sonata, particularly of the triplex form, must be very largely
discounted. Haydn and Mozart learned little from him in the
arrangement of their ideas, which is form; much in the treatment of
them, which is expression. That quality of poetry which we may still
admire in his music today, vague or obscure as its form may be, was
the quality in his playing most admired by those contemporaries who
heard him.
His excellent book on how to play the clavier counsels clearness and
exactness, but it is a heartfelt appeal for beauty and expressiveness
as well. What is the long, detailed analysis of agrémens but the
explanation of practically the only means of subtle expression which
the cembalist could acquire? His love for the clavichord, which, for all
the frailty of its tone, was capable of fine shadings of sound, never
waned. He commended it to all as the best instrument upon which to
practise, for the clumsy hand had no power to call forth the charm
which was its only quality. Indeed, he received the pianoforte coldly.
His keyboard music was probably conceived, the brilliant for the
harpsichord, the more intimate for the clavichord. And towards the
end of his life he gave utterance to his belief that the only function of
music was to stir the emotions and that the player who could not do
that might as well not play.
In turning to the best of his sonatas one turns to profoundly beautiful

music, music that unquestionably has the power to stir the heart. The
great spirit of the father has breathed upon it and given it life. The
turns of his melodies and their ineffably tender cadences, and, above
all, the chromatic richness of his harmonies are the voice of his
father. One may be constantly startled and bewildered. There is
something ghostly abroad in them. We hear and do not hear, we
almost see and do not see, the all-powerful Sebastian. But it is the
voice of the father in a new language, his face in shadow, in the mist
before dawn. One is tempted to cry with Hamlet: ‘Well said, old mole!
Canst work i’ the ground so fast?’ It is easy to understand that
Haydn, worn out with his daily fight against starvation, could come
back to his cracked clavichord and play away half the night with the
sonatas of Emanuel Bach; that Mozart could call him father of them
all. But in spirit, not in flesh. And it is, after all, the spirit of Sebastian
that thus attends the succeeding births and rebirths of music.
The harpsichord works by W. Friedemann Bach, the oldest and,

according to some accounts, the favorite son of Johann Sebastian,
have had probably far less influence upon the development of
pianoforte music. But they contain many measures of great beauty.
Madame Farrenc included twelve polonaises, a sonata (in E-flat
major), several fugues, and four superb fantasias in the Trésor des
pianistes. The sonata is regular in form, and a few of the polonaises
are in the triplex form. Thus Friedemann Bach shows that he, too,
like his brother Emanuel, allied himself to the new movement in
music. His mastery of musical science, however, is evident; and that
he knew the keyboard well is proved by the unusual brilliance of his
fantasias. In the main it may be said that the greatest beauty of his
music whispers of his father.
Something of the spirit shows itself in the pianoforte sonatas of

Friedrich Wilhelm Rust, a composer now little known, whose work
deserves study. He died at Dessau, where most of his life had been
spent, in 1796, just on the eve of Beethoven’s rise to prominence.
Twelve of his sonatas have recently been published in Paris under
the supervision of M. Vincent d’Indy. They show a blending of two
styles: the German style which he acquired from Emanuel Bach in
Berlin, and the Scarlatti style, of which he made a study during two
years spent in Italy. Three sonatas, in E minor, in F-sharp minor, and
in D major, written near the close of his life, are in two movements,
both of which seem welded together in the manner of the later
sonatas of Beethoven. The treatment of the pianoforte or
harpsichord is modern, particularly in the major section of the Rondo
of the sonata in E minor, and in the passage work contrasted with
the beautiful first theme of the sonata in F-sharp minor. In a sonata in
C major, belonging to this period, a fugue is introduced as an
episode in the final rondo. Haydn had already used the fugue as the
last movement of the string quartet, Mozart as the last movement of
a symphony. Rust, in applying it to the pianoforte sonata,
foreshadowed Beethoven.[29]
FOOTNOTES:
[21] Pietro Locatelli, b. Bergamo, 1693; d. Amsterdam, 1764; famous violinist,
pupil of Corelli. His works, Concerti, trio sonatas, etc., are important in the
development of the sonata form.
[22] Antonio Vivaldi, b. Venice, ca. 1680; d. 1743; completed Torelli’s and
Albinoni’s work in the creation of the violin concerto.
[23] Jean Benjamin de Laborde: Essai sur la musique ancienne et moderne, 1780.
[24] It seems hardly worth while to add that there are well-known sonatas in which
no movement is in the triplex form. Cf. the Mozart sonata in A major (K. 331) and
the Beethoven sonata in A-flat major, op. 26.
[25] It is worthy of note that a sonata in G minor for violin by Tartini was at one
time known by the name Didone abbandonata. Cf. Wasielewski: Die Violine und
ihre Meister.
[26] Opus 43, No. 2.
[27] Op. cit., Vol. I, p. 65, et seq.
[28] See Musical Examples (Vol. XIII).
[29] The sonatas of Rust as printed by his grandson showed many extraordinary
modern features which have since been proved forgeries. The fiery discussions to
which they gave rise have been summarized by M. D. Calvocoressi in two articles
in the Musical Times (London) for January and February, 1914.

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Approach 3rd Edition

13.11 The Lewis Acid–Base Model 569

Chapter 14 Acid–Base Equilibria 578

14.1 Solutions of Acids or Bases Containing

Chapter 15 Solubility and Complex

Chapter 17 Electrochemistry 679 19.8 The Chemistry of Nitrogen 773

Chapter 18 The Nucleus: A Chemist’s 20.4 Isomerism 811

21.1 Alkanes: Saturated Hydrocarbons 842

Appendix 1 Mathematical Procedures A1 A5.1 Values of Ka for Some Common Monoprotic

Appendix 3 Spectral Analysis A16 Appendix 6 SI Units and Conversion

Features of Chemistry: Over the years, thousands of students and instructors

Supporting Materials Sujata Guha, Tennessee State University

First Edition Reviewers Jon Hardesty, Collin County Community College

connecting to atoms 1.1

visuals and text to help students understand how an atomic/molecular 11+

approach clarifies chemical concepts. Examples of topics include At- 11 electrons

Periodic Table, Polar Molecules—It’s All About Symmetry, and Entropy

and Positional Probability. Same number protons (same atomic number)

11.7 Catalysis 483 Loss of

ConneCting to atoms 11.1

I n Section 11.4 we derived integrated

T he most impressive examples of water to produce pencil “lead,” a recipe

Water H C R' paste is extruded through a metal tube

Many amino Fragment Fragment

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groundwater. Additional Chemi-

the student Web site.

FIguRE 2.6 (a) A continuous Continuous

2.7 Orbital Shapes and Energies 75

else is merely thought to exist.” —Democritus

New York Public Library / Science Source

Active Learning Questions

The text includes a number of Active Learning Questions at Cork

a. As you push down on the syringe, how does the mem-

194 ChaPter 5 Stoichiometry

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and classifying objects likedo

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See Exercise 5.48

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iNTERACTivE ExAMplE 6.6 Solutions of Known Concentration

oxygen molecule written O2 Wash

explode, forming water again. solution is 1.00 M acetic acid.

9.1 Intermolecular Forces 367

Summary of Intermolecular Forces

Ion–dipole Attraction between 35–400

Dipole– Attraction between 5–30 δ+ δ+ ❯ Moles of H2SO4 in the required solution

For review 615

A blue question or exercise number indicates that the answer to

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For Review 233

A blue question or exercise number indicates that the answer to

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51. Four Fe21

48. Complete the following table: are 53Fe21

discover something about its internal workings. You have no

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

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

else is merely thought to exist.” —Democritus