University chemistry, 3rd edition

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University Chemistry

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University Chemistry

Brian B. Laird
University of Kansas

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With significant contributions by

Raymond Chang
Williams College


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UNIVERSITY CHEMISTRY
Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the
Americas, New York, NY 10020. Copyright © 2009 by The McGraw-Hill Companies, Inc. All rights
reserved. No part of this publication may be reproduced or distributed in any form or by any means, or
stored in a database or retrieval system, without the prior written consent of The McGraw-Hill Companies,
Inc., including, but not limited to, in any network or other electronic storage or transmission, or broadcast
for distance learning.
Some ancillaries, including electronic and print components, may not be available to customers outside the
United States.
This book is printed on acid-free paper.
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ISBN 978–0–07–296904–7
MHID 0–07–296904–0
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The credits section for this book begins on page C-1 and is considered an extension of the copyright page.
Library of Congress Cataloging-in-Publication Data
Laird, Brian B., 1960University chemistry / Brian B. Laird.
p. cm.
Includes index.
ISBN 978–0–07–296904–7 — ISBN 0–07–296904–0 (hard copy : alk. paper) 1. Chemistry—Study and
teaching (Higher) 2. Chemistry—Textbooks. I. Title.
QD40.L275 2009
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2007052540

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About the Author

Brian B. Laird,

a native of Port Arthur, Texas, is
currently a Professor of Chemistry at the University of
Kansas in Lawrence, Kansas. He received Bachelor of
Science degrees in Chemistry and Mathematics from the
University of Texas, Austin, in 1982, and a Ph.D. in
Theoretical Chemistry from the University of California,
Berkeley, in 1987. Prior to his current position, he held
postdoctoral and lecturer appointments at Columbia University, Forschungszentrum Jülich, Germany (NATO Fellowship), University of Utah, University of Sydney, and the
University of Wisconsin. His research interests involve the application of statistical mechanics and computer simulation to the determination of properties of liquid and solids. In addition to honors general chemistry, he regularly teaches
undergraduate physical chemistry and graduate courses in quantum and statistical
mechanics. In his spare time, he enjoys golfing, bicycling, playing the piano, and
traveling.

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I dedicate this work to my wife, Uschi, and to the memory of my parents, Don and Nanci Laird.

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Brief Contents
0

The Language of Chemistry ...............................................................

1

The Quantum Theory of the Submicroscopic World ........................ 71

2

Many-Electron Atoms and the Periodic Table ................................... 126

3

The Chemical Bond ............................................................................ 170

4

Molecular Structure and Interaction ................................................... 222

5

The States of Matter I: Phase Diagrams and Gases ......................... 281

6

The States of Matter II: Liquids and Solids ...................................... 333

7

Thermochemistry: Energy in Chemical Reactions ............................ 364

8

Entropy, Free Energy, and the Second Law of Thermodynamics .... 423

9

Physical Equilibrium ........................................................................... 466

1

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10 Chemical Equilibrium ......................................................................... 511
11 Acids and Bases .................................................................................. 556
12 Acid-Base Equilibria and Solubility .................................................. 611
13 Electrochemistry .................................................................................. 663
14 Chemical Kinetics ............................................................................... 712
15 The Chemistry of Transition Metals .................................................. 772
16 Organic and Polymer Chemistry ........................................................ 800
17 Nuclear Chemistry .............................................................................. 855
Appendix 1 Measurement and Mathematical Background ................... A-1
Appendix 2 Thermodynamic Data at 1 Bar and 258C ......................... A-14
Appendix 3 Derivation of the Names of Elements ............................... A-20
Appendix 4 Isotopes of the First Ten Elements .................................... A-26

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Expanded Contents
List of Applications xiv
Preface xv

0 The Language of Chemistry

..........................................................

1

0.1

Chemistry Is the Study of Matter and Change ............................................... 2

0.2

Matter Consists of Atoms and Molecules ..................................................... 11

0.3

Compounds Are Represented by Chemical Formulas .................................. 20

0.4

Reactions Are Represented by Balanced Chemical Equations ..................... 31

0.5

Quantities of Atoms or Molecules Can Be Described
by Mass or Number ....................................................................................... 34

0.6

Stoichiometry Is the Quantitative Study of Mass and

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Mole Relationships
in Chemical Reactions .................................................. 52
1 The Quantum Theory of the Submicroscopic
World ................................................................................................................... 71
1.1

Classical Physics Does Not Adequately Describe the Interaction of Light
with Matter ..................................................................................................... 72

1.2

The Bohr Model Was an Early Attempt to Formulate a Quantum Theory
of Matter ......................................................................................................... 83

1.3

Matter Has Wavelike Properties .................................................................... 94

1.4

The Hydrogen Atom Is an Exactly Solvable
Quantum-Mechanical System ...................................................................... 109

2 Many-Electron Atoms and the Periodic Table

viii

.................... 126

2.1

The Wavefunctions of Many-Electron Atoms Can Be Described to
a Good Approximation Using Atomic Orbitals ........................................... 127

2.2

Electron Configurations of Many-Electron Atoms Are Constructed
Using the Aufbau (or “Building-up”) Principle ........................................... 134

2.3

The Periodic Table Predates Quantum Mechanics ...................................... 143

2.4

Elements Can Be Classified by Their Position in the
Periodic Table ................................................................................................ 146

2.5

The Properties of the Elements Vary Periodically Across
the Periodic Table .......................................................................................... 149


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3 The Chemical Bond

.................................................................................. 170

3.1

Atoms in a Molecule Are Held Together by Chemical Bonds .................. 171

3.2

A Covalent Bond Involves the Sharing of Electrons Between
Atoms in a Molecule .................................................................................... 173

3.3

Electronegativity Differences Determine the Polarity of
Chemical Bonds ............................................................................................ 182

3.4

Drawing Correct Lewis Structures Is an Invaluable Skill for a
Chemist ......................................................................................................... 189

3.5

Molecular Orbital Theory Provides a Detailed Description of
Chemical Bonding ........................................................................................ 202

4 Molecular Structure and Interaction

.........................................

222

4.1

The Basic Three-Dimensional Structure of a Molecule Can Be Predicted
Using the VSEPR Model ............................................................................. 223

4.2

The Polarity of a Molecule Can Be Described Quantitatively by
Its Dipole Moment ....................................................................................... 234

4.3

Valence Bond Theory for Polyatomic Molecules Requires the

Use of Hybrid Orbitals ................................................................................. 240

4.4

Isomers Are Compounds That Have the Same Molecular Formula but
Different Atomic Arrangements ................................................................... 252

4.5

Bonding in Polyatomic Molecules Can Be Explained Using
Molecular Orbitals ........................................................................................ 257

4.6

The Interactions Between Molecules Greatly Affect the Bulk
Properties of Materials ................................................................................. 262

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5 The States of Matter I: Phase Diagrams
and Gases ....................................................................................................... 281
5.1

Pressure and Temperature Are Two Important Macroscopic Properties of
Chemical Systems ........................................................................................ 282

5.2

Substances and Mixtures Can Exist as Solid, Liquid, or Gas, Depending
upon the External Conditions ...................................................................... 286

5.3

The Ideal-Gas Equation Describes the Behavior of All Gases in the
Limit of Low Pressure ................................................................................. 292

5.4

The Kinetic Theory of Gases Provides a Molecular Explanation for the
Behavior of Gases ........................................................................................ 308

5.5

Real Gases Exhibit Deviations from Ideal Behavior at High Pressures .... 317

6 The States of Matter II: Liquids and Solids

........................ 333

6.1

The Structure and Properties of Liquids Are Governed by Intermolecular
Interactions .................................................................................................... 334

6.2

Crystalline Solids Can Be Classified in Terms of Their Structure and
Intermolecular Interactions ........................................................................... 341

6.3

The Properties of Crystalline Solids Are Determined Largely by
Intermolecular Interactions ........................................................................... 351

6.4

Band Theory Accurately Explains the Conductivity of Metals,
Semiconductors, and Insulators ................................................................... 356
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7 Thermochemistry: Energy in Chemical Reactions

........... 364

7.1

Thermodynamics Is the Study of Energy and Its Transformations in
Macroscopic Systems ................................................................................... 365

7.2

The Energy Absorbed by a System as Heat in a Constant-Pressure
Process Is Equal to the Change in Enthalpy ............................................... 375

7.3

The Temperature Change of a System upon Heating Is Governed by
Its Heat Capacity .......................................................................................... 381

7.4

The Enthalpy Changes for any Reaction Can Be Calculated Using
Standard Enthalpies of Formation ................................................................ 395

7.5

The Reaction Enthalpies Can Be Estimated from Bond Enthalpies .......... 401

7.6

Enthalpy Changes Also Accompany Physical Transformations ................. 405

7.7

The Temperature Dependence of Reaction Enthalpies Can
Be Determined from Heat Capacity Data ................................................... 412

8 Entropy, Free Energy, and the Second Law of
Thermodynamics ........................................................................................ 423
8.1

The Entropy of an Isolated System Always Increases in Any
Spontaneous Process .................................................................................... 424

8.2

The Entropy Change for a Process Can Be Calculated Using the
Thermodynamic Definition of Entropy ....................................................... 432

8.3

The Third Law of Thermodynamics Allows Us to Determine
Absolute Entropies ....................................................................................... 440

8.4

The Spontaneity of a Process at Constant Temperature and Pressure Is
Governed by the Gibbs Free Energy ........................................................... 446

8.5 The Mixing of Pure Substances Leads to an Increase in the Entropy
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and a Decrease in the Gibbs Free Energy .................................................. 456
8.6

In Living Systems, Spontaneous Reactions Are Used to Drive Other
Nonspontaneous, but Essential, Biochemical Processes ............................. 459

9 Physical Equilibrium
9.1

The Phase Boundaries in Pure Substances Can Be Predicted Using
Thermodynamics .......................................................................................... 467

9.2

The Solubility of a Substance Is Determined by Temperature, Pressure,
and Intermolecular Forces ............................................................................ 473

9.3

The Liquid-Vapor Phase Equilibrium of a Solution Can Be
Understood in Terms of the Entropy of Mixing and the
Intermolecular Forces ................................................................................... 483

9.4

Colligative Properties Are Properties of Solution Phase Equilibria That
Depend Only upon the Number of Solute Molecules, Not Their Type ........ 491

10 Chemical Equilibrium

x

............................................................................... 466

............................................................................. 511

10.1

The Equilibrium Constant Governs the Concentration of Reactants
and Products at Equilibrium ........................................................................ 512

10.2

The Equilibrium Constant Can Be Used to Predict the Direction and
Equilibrium Concentrations of a Chemical Reaction ................................. 524

10.3

The Equilibrium Constant for a Reaction Can Be Determined from the
Standard Gibbs Energy Change ................................................................... 531

10.4

The Response of an Equilibrium System to a Change in Conditions Can
Be Determined Using Le Châtelier’s Principle ........................................... 536


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11 Acids and Bases

........................................................................................ 556

11.1

Many Processes in Chemistry Are Acid-Base Reactions ........................... 557

11.2

The Acid-Base Properties of Aqueous Solutions Are Governed by the
Autoionization Equilibrium of Water .......................................................... 564

11.3

The Strengths of Acids and Bases Are Measured by Their Ionization
Constants ....................................................................................................... 570

11.4

The pH of an Acid or Base Can Be Calculated If Its Ionization Constant
Is Known ....................................................................................................... 579

11.5

The Strength of an Acid Is Determined in Part by
Molecular Structure ...................................................................................... 590

11.6

Many Salts Have Acid-Base Properties in Aqueous Solution .................... 594

11.7

Oxide and Hydroxide Compounds Can Be Acidic or Basic in Aqueous
Solution Depending on Their Composition ................................................. 600

12 Acid-Base Equilibria and Solubility

............................................ 611

12.1

Ionization of Weak Acids and Bases Is Suppressed by the Addition of a
Common Ion ................................................................................................. 612

12.2

The pH of a Buffer Solution Is Resistant to Large
Changes in pH .............................................................................................. 615

12.3

The Concentration of an Unknown Acid or Base Can Be Determined
by Titration ................................................................................................... 622

12.4

An Acid-Base Indicator Is a Substance That Changes Color at a
Specific pH ................................................................................................... 631

12.5 APDF
Precipitation
Reaction Occurs when a Reaction in Solution Leads to an
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Insoluble Product .......................................................................................... 633
12.6

The Solubility Product Is the Equilibrium Constant for the
Dissolution Process ...................................................................................... 635

12.7

The Solubility of a Substance Is Affected by a Number of Factors ......... 644

12.8

The Solubility Product Principle Can Be Applied to
Qualitative Analysis ...................................................................................... 653

13 Electrochemistry

......................................................................................... 663

13.1

Oxidation-Reduction (Redox) Reactions Involve a Transfer of Electrons
from One Species to Another ...................................................................... 664

13.2

Redox Reactions Can Be Used to Generate Electric Current in a
Galvanic Cell ................................................................................................ 671

13.3

The Standard Emf of Any Electrochemical Cell Can Be Determined
If the Standard Reduction Potentials for the Half-Reactions
Are Known ................................................................................................... 674

13.4

The Emf of an Electrochemical Cell Is Directly Related to the
Gibbs Free-Energy Change of the Redox Reaction ................................... 681

13.5

The Concentration Dependence of the Emf Can Be Determined Using
the Nernst Equation ...................................................................................... 686

13.6

Batteries Use Electrochemical Reactions to Produce a Ready Supply
of Electric Current ........................................................................................ 692

13.7

In Electrolysis, an Electric Current Is Used to Drive a Nonspontaneous
Reaction ........................................................................................................ 697
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14 Chemical Kinetics

..................................................................................... 712

14.1

Chemical Kinetics Is the Study of the Rates at Which Chemical
Reactions Occur ............................................................................................ 713

14.2

The Rate Law Gives the Dependence of the Reaction Rate on the
Reactant Concentration ................................................................................ 720

14.3

Integrated Rate Laws Specify the Relationship Between Reactant
Concentration and Time ............................................................................... 723

14.4

The Arrhenius Equation Gives the Temperature Dependence of Rate
Constants ....................................................................................................... 736

14.5

The Reaction Mechanism Is the Sequence of Elementary Steps
That Lead to Product Formation ................................................................. 744

14.6

Reaction Rates Can Often Be Increased by the Addition
of a Catalyst ................................................................................................. 754

15 The Chemistry of Transition Metals

............................................ 772

15.1

Transition Metals Have Electron Configurations with Incomplete
d or f Shells .................................................................................................. 773

15.2

Transition Metals Can Form a Variety of Coordination Compounds ........ 777

15.3

Bonding in Coordination Compounds Can Be Described by
Crystal Field Theory .................................................................................... 786

15.4

The Reactions of Coordination Compounds Have a Wide Number of
Useful Applications ...................................................................................... 793

16 Organic and Polymer Chemistry

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16.1

Hydrocarbons Are Organic Compounds Containing Only Hydrogen
and Carbon .................................................................................................... 801

16.2

Hydrocarbons Undergo a Number of Important Chemical Reactions ....... 811

16.3

The Structure and Properties of Organic Compounds Are Greatly
Influenced by the Presence of Functional Groups ...................................... 815

16.4

Polymers Are Large Molecular Weight Compounds Formed from the
Joining Together of Many Subunits Called Monomers .............................. 826

16.5

Proteins Are Polymer Chains Composed of Amino Acid Monomers ....... 833

16.6

DNA and RNA Are Polymers Composed of Nucleic Acids ...................... 841

17 Nuclear Chemistry

xii

.................................................................................... 855

17.1

Nuclear Chemistry Is the Study of Changes Involving Atomic Nuclei ..... 856

17.2

The Stability of a Nucleus Is Determined Primarily by
Its Neutron-to-Proton Ratio ......................................................................... 860

17.3

Radioactive Decay Is a First-Order Kinetic Process .................................. 867

17.4

New Isotopes Can Be Produced Through the Process of Nuclear
Transmutation ............................................................................................... 873

17.5

In Nuclear Fission, a Large Nucleus Is Split into Smaller Nuclei ............ 876

17.6

In Nuclear Fusion, Energy Is Produced When Light Nuclei Combine to
Form Heavier Ones ...................................................................................... 882

17.7

Radioactive and Stable Isotopes Alike Have Many Applications
in Science and Medicine .............................................................................. 884

17.8

The Biological Effects of Radiation Can Be Quite Dramatic .................... 886


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Appendix 1 Measurement and Mathematical Background .......................... A-1
A1.1

Measurement ................................................................................................. A-1

A1.2

Mathematical Background ............................................................................ A-7

Appendix 2 Thermodynamic Data at 1 Bar and 258C ......................... A-14
Appendix 3 Derivation of the Names of the Elements ........................ A-20
Appendix 4 Isotopes of the First Ten Elements ...................................... A-26
Glossary ............................................................................................................................... G-1
Answers to Even-Numbered Problems .......................................................................... AP-1
Credits .................................................................................................................................. C-1
Index ..................................................................................................................................... I-1

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List of Applications
Distribution of Elements on Earth and in Living Systems .............................. 18
Important Experimental Technique: The Mass Spectrometer ......................... 46
Laser—The Splendid Light ............................................................................. 92
Important Experimental Technique: Electron Microscopy ........................... 109
The Third Liquid Element? ........................................................................... 156
Discovery of the Noble Gases ....................................................................... 163
Major Experimental Technique: Microwave Spectroscopy .......................... 186
Just Say NO ................................................................................................... 198
Major Experimental Technique: Infrared Spectroscopy ............................... 238
cis-trans Isomerization in the Vision Process ................................................ 254
Buckyball, Anyone? ...................................................................................... 262
Super-Cold Atoms ......................................................................................... 316
Why Do Lakes Freeze from the Top Down? ................................................. 340
High-Temperature Superconductors ............................................................. 358
Fuel Values of Foods and Other Substances ................................................. 390
The Efficiency of Heat Engines: The Carnot Cycle ...................................... 438
The Thermodynamics of a Rubber Band ...................................................... 456
The Killer Lake ............................................................................................. 483
Life at High Altitudes and Hemoglobin Production ...................................... 545
Antacids and the pH Balance in Your Stomach ............................................. 602
Maintaining the pH of Blood ........................................................................ 620
Dental Filling Discomfort ............................................................................. 680
Femtochemistry ............................................................................................. 753
Coordination Compounds in Living Systems ................................................ 784

Cisplatin—an Anticancer Drug ..................................................................... 795
Important Experimental Technique: Nuclear Magnetic
Resonance Spectroscopy ............................................................................... 824
Sickle Cell Anemia: A Molecule Disease ..................................................... 840
DNA Fingerprinting ...................................................................................... 843
Nature’s Own Fission Reactor ....................................................................... 881
Food Irradiation ............................................................................................. 888

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Preface
The concept of University Chemistry grew from my experiences in teaching Honors General Chemistry at the
University of Kansas for a number of semesters. It is my
attempt to inform and challenge the well-prepared student
to discover and learn the diverse, but related, topics within
general chemistry. This text includes the core topics that
are necessary for a solid foundation of chemistry.

The Basic Features
᭤ Organization. In this text, I adopt a “Molecular to
Macroscopic” approach, in which the quantum
theory of atomic and molecular structure and interaction is outlined in Chapters 1– 4. Building on
this molecular foundation, the presentation moves

to the macroscopic concepts, such as states of
matter, thermodynamics, physical and chemical
equilibrium, and chemical kinetics. This organization is based on “natural prerequisites”; that is,
each topic is positioned relative to what other topics are required to understand it. For example,
knowledge of thermodynamics or equilibrium
chemistry is not needed to understand the structure and interaction of atoms and molecules;
whereas, to understand deeply the application of
thermodynamics to chemical systems or the material properties of liquids and solids, knowing how
energy is stored in chemical bonds and how molecular structure and bonding affect intermolecular forces is desirable.
᭤ Mathmematical Level. The presentation in this text
assumes that the student has a good working
knowledge of algebra, trigonometry and coordinate
geometry at the high school level. Knowledge of
calculus, while advantageous, is not strictly
required for full understanding. Integral and differential calculus is used, where appropriate, in intermediate steps of concept development in quantum
theory, thermodynamics, and kinetics. However,

the final primary concepts and most major equations
(denoted by a blue box) do not depend on an understanding of calculus, nor do the overwhelming
majority of end-of-chapter problems. For the interested and advanced student, I have included a small
number of calculus-based end-of-chapter problems
in the relevant chapters.
The level of calculus used in University Chemistry
is similar to that used in other general chemistry texts
at this level; however, it is not relegated to secondary
boxed text, as is often done, but integrated into the
primary discussion, so as not to disrupt the linear flow
of the presentation. For the interested student, I have
included in Appendix 1 a brief review/tutorial of the
basic concepts in integral and differential calculus.

᭤ Problem-Solving Model. Worked Examples are
included in every chapter for students to use as
a base for applying their problem-solving skills to
the concept discussed. The examples present the
problem, a strategy, a solution, a check, and a
practice problem. Every problem is designed to
challenge the student to think logically through
the problem. This problem-solving approach is
used throughout the text.

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Organization and Presentation
᭤ Review. Students with a strong background in high
school chemistry have already been exposed to the
concepts of the structure and classification of matter, chemical nomenclature, and stoichiometry.
Because of this assumed background, I have
condensed the standard introductory chapters of a
typical general chemistry text into a single chapter
(Chapter 0). Chapter 0 is intended to serve as a
refresher of the subject matter students covered
in their high school chemistry courses.
᭤ Early Coverage of Quantum Theory. To provide a
molecular-level foundation for the later chapters on
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states Lai69040_ch01_071-125.indd
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and 8:56:35
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the quantum theory of atoms and molecules is
presented early in the text. In Chapters 1 and 2,
elementary quantum theory is used to discuss the
electronic structure of atoms and the construction of
the periodic table. Chapters 3 and 4 cover molecular
bonding, structure, and interaction, including molecular-orbital theory. Contrary to the organization
of most general chemistry texts, intermolecular
forces are discussed at the end of Chapter 4 on
molecular structure instead of in a later chapter on
liquids and solids. This is a more natural position,
which allows for a molecular-level discussion of the
forces that influence real gas behavior in Chapter 5.
᭤ States of Matter. Phase diagrams, equations of
state, and states of matter (gases, liquids and solids)
are treated in a unified manner in Chapters 5 and 6,
with an emphasis on the role of molecular interaction in the determination of material properties.

allows for a more sophisticated /Volumes/108/MHIA037/mhLai1/Lai1ch01%0
discussion of physical and chemical equilibrium from a thermodynamic
perspective. In particular, the central role of the entropy and free energy of mixing in colligative properties and chemical equilibrium is explored in detail.
᭤ Physical and Chemical Equilibrium. The principles
of physical equilibrium (phase boundary prediction
and solubility) are discussed in Chapter 9, followed

by a discussion of chemical equilibrium in Chapter
10. Chapters 11, 12, and 13 present applications of
chemical equilibrium to acid-base chemistry, aqueous
equilibria, and electrochemistry, respectively.
᭤ Chemical Kinetics. Unlike many general chemistry
texts, discussion of chemical kinetics (Chapter 14)
follows the presentation of chemical equilibrium, allowing for full discussion of transition-state theory
and detailed balance.
᭤ Final chapters. Chapter 15, “The Chemistry of Transition Metals,” Chapter 16, “Organic and Polymer
Chemistry,” and Chapter 17 “Nuclear Chemistry”
are each an entity in itself. Every instructor and
student can choose to assign and study the chapters
according to time and preference.

᭤ Thermochemistry, Entropy, and Free Energy.
The basic principles of thermodynamics are treated
together in Chapters 7 “Thermochemistry: Energy in
Chemical Reactions,” and 8, “Entropy, Free Energy,
and the Second Law of Thermodynamics.” This

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Pedagogy
Problem Solving
The development of problem-solving
skills is a major objective of this text.
Each problem is broken down into
learning steps to help students increase
their logical critical thinking skills.

Example 1.2

Chlorophyll-a is green because it absorbs blue light at about 435 nm and red light at
about 680 nm, so that mostly green light is transmitted. Calculate the energy per mole
of photons at these wavelengths.

Strategy Planck’s equation (Equation 1.3) gives the relationship between energy and
frequency (n). Because we are given wavelength (l), we must use Equation 1.2, in
which u is replaced with c (the speed of light), to convert wavelength to frequency.
Finally, the problem asks for the energy per mole, so we must multiply the result we
get from Equation 1.3 by Avogadro’s number.
Solution The energy of one photon with a wavelength of 435 nm is
3.00 3 108 m s21
c
E 5 hn 5 h a b 5 (6.626 3 10234 J s)
l
435 nm (1 3 1029 m nm21 )
5 4.57 3 10219 J
 

 

For one mole of photons, we have
E 5 (4.57 3 10219 J) (6.022 3 1023 mol21 )
5 2.75 3 105 J mol21
5 275 kJ mol21
Using an identical approach for the photons at 680 nm, we get E 5 176 kJ mol−1.

Practice Exercise X-rays are convenient to study the structure of crystals because
their wavelengths are comparable to the distances between near neighbor atoms (on
the order of a few Ångstroms, where 1Å 5 1 3 10210 m). Calculate the energy of a
photon of X-ray radiation with a wavelength of 2.00 Å.

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There are numerous end-of-chapter problems
to continue skill building and then practice solving
problems. Many of these same problems appear in
the electronic homework program ARIS, providing
a seamless homework solution for the student and
the instructor.

1.58 Certain sunglasses have small crystals of silver
chloride (AgCl) incorporated in the lenses. When
the lenses are exposed to light of the appropriate
wavelength, the following reaction occurs:
AgCl ¡ Ag 1 Cl

The Ag atoms formed produce a uniform gray color
that reduces the glare. If the energy required for the
preceding reaction is 248 kJ mol21, calculate the
maximum wavelength of light that can induce this
process.

Text

ARIS

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End-of-Chapter Material
At the end of every chapter, you will find a summary of
all the material that was presented in the chapter to use as
a study tool. The summary highlights each section within
the chapter. Key words are also listed and include the
page number where the term was introduced.

Summary of Facts and Concepts
Section 1.1
c At the end of the nineteenth century, scientists began to
realize that the laws of classical physics were incompatible with a number of new experiments that probed the
nature of atoms and molecules and their interaction
with light. Through the work of a number of scientists
over the first three decades of the twentieth century, a
new theory—quantum mechanics—was developed that
was able to explain the behavior of objects on the atomic
and molecular scale.
c The quantum theory developed by Planck successfully
explains the emission of radiation by heated solids. The
quantum theory states that radiant energy is emitted by
atoms and molecules in small discrete amounts (quanta),
rather than over a continuous range. This behavior is

a moving particle of mass m and velocity u is given by
the de Broglie equation l 5 h/mu (Equation 1.20).
c The realization that matter at the atomic and subatomic
scale possesses wavelike properties lead to the development of the Heisenberg uncertainty principle, which
states that it is impossible to know simultaneously both
the position (x) and the momentum (p) of a particle with
certainty (see Equation 1.22).
c The Schrödinger equation (Equation 1.24) describes the
motions and energies of submicroscopic particles. This
equation, in which the state of a quantum particle is
described by its wavefunction, launched modern quantum mechanics and a new era in physics. The wavefunction contains information about the probability of
finding a particle in a given region of space.

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Applications
Throughout the text, applications are
included to reinforce students’ grasp of
concepts and principles and to provide
grounding to real-world experiences.
The applications focus on key industrial

chemicals, drugs, and technological
advances in chemistry.

Important Experimental Technique: Electron Microscopy
he electron microscope is an extremely valuable application of the wavelike properties of electrons because it produces images of objects that cannot be seen with the naked
eye or with light microscopes. According to the laws of optics, it is impossible to form an image of an object that is
smaller than half the wavelength of the light used for the observation. Because the range of visible light wavelengths
starts at around 400 nm, or 4 3 1027 m, we cannot see anything smaller than 2 3 1027 m. In principle, we can see objects on the atomic and molecular scale by using X-rays,
whose wavelengths range from about 0.01 nm to 10 nm. Xrays cannot be focused easily, however, so they do not produce crisp images. Electrons, on the other hand, are charged
particles, which can be focused in the same way the image on
a TV screen is focused (that is, by applying an electric field or
a magnetic field). According to Equation 1.20, the wavelength
of an electron is inversely proportional to its velocity. By accelerating electrons to very high velocities, we can obtain
wavelengths as short as 0.004 nm.
A different type of electron microscope, called the scanning tunneling microscope (STM), uses quantum mechanical

T

tunneling to produce an image of the atoms on the surface of
a sample. Because of its extremely small mass, an electron is
able to move or “tunnel” through an energy barrier (instead of
going over it). The STM consists of a metal needle with a very
fine point (the source of the tunneling electrons). A voltage is
maintained between the needle and the surface of the sample
to induce electrons to tunnel through space to the sample. As
the needle moves over the sample at a distance of a few atomic
diameters from the surface, the tunneling current is measured.
This current decreases with increasing distance from the sample. By using a feedback loop, the vertical position of the tip
can be adjusted to a constant distance from the surface. The
extent of these adjustments, which profile the sample, is recorded and displayed as a three-dimensional false-colored

image. Both the electron microscope and the STM are among
the most powerful tools in chemical and biological research.

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An electron micrograph showing a normal red blood cell
and a sickled red blood cell from the same person.

STM image of iron atoms arranged to display the
Chinese characters for atom on a copper surface.

3608 Development Process
A key factor in developing any chemistry text is the ability to adapt
to teaching specifications in a universal way. The only way to do so
is by contacting those universal voices—and learning from their
suggestions.
We are confident that our book has the most current content the industry has to offer, thus pushing our desire for accuracy and up-to-date
information to the highest standard possible. To accomplish this, we
have moved along an arduous road to production. Extensive and openminded advice is critical in the production of a superior text.
Following is a brief overview of the initiatives included in
the 360Њ Development Process of this first edition of University
Chemistry, by Brian B. Laird.

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Symposia Every year McGraw-Hill conducts a

general chemistry symposium, which is attended by
instructors from across the country. These events
provide an opportunity for the McGraw-Hill editors to
gather information about the needs and challenges of
instructors teaching these courses. The information
gleaned from these events helped to create the book
plan for University Chemistry. In addition, these
symposia offer a forum for the attendees to exchange
ideas and experiences with colleagues whom they
might not have otherwise met.

ARIS

Manuscript Review Panels Over 50 teachers and
academics from across the country and internationally
reviewed the various drafts of the manuscript to give
feedback on content, pedagogy, and organization. This
feedback was summarized by the book team and used
to guide the direction of the text.

Build Assignments
᭤ Choose from prebuilt assignments or create your
own custom content by importing your own content
or editing an existing assignment from the prebuilt
assignment.
᭤ Assignments can include quiz questions, animations, and videos—anything found on the website.
᭤ Create announcements and utilize full course or
individual student communication tools.
᭤ Assign questions that were developed using the
same problem-solving strategy as in the textual

material, thus allowing students to continue the
learning process from the text into their homework
assignments.
᭤ Assign algorithmic questions that give students
multiple chances to practice and gain skill at
problem-solving the same concept.

Developmental Editing In addition to being
influenced by a distinguished chemistry author, the
development of this manuscript was impacted by three
freelance developmental editors. The first edit in early
draft stage was completed by an editor who holds a
PhD in chemistry, John Murdzek. Katie Aiken and
Lucy Mullins went through the manuscript line-by-line
offering suggestions on writing style and pedagogy.

Assessment, Review, and Instruction System, also known
as ARIS, is an electronic
homework and course management system designed for
greater flexibility, power, and ease of use than any other
system. Whether you are looking for a preplanned course
or one you can customize to fit your course needs, ARIS
is your solution.
In addition to having access to all student digital learning objects, ARIS allows instructors to do the following.

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Accuracy Check and Class Test Cindy Berrie at the
University of Kansas worked closely with the author,
checking his work and providing detailed feedback as

she and her students did a two-semester class test of
the manuscript. The students also provided the author
with comments on how to improve the manuscript so
that the presentation of content was compatible with
their variety of learning styles.
Shawn Phillips at Vanderbilt University reviewed
the entire manuscript after the final developmental edit
was completed, checked all the content for accuracy,
and provided suggestions for further improvement to
the author.
A select group reviewed text and art manuscript in
draft and final form, reviewed page proofs in first and
revised rounds, and oversaw the writing and accuracy
check of the instructor’s solutions manuals, test bank,
and other ancillary materials.

Enhanced Support for the Instructor
McGraw-Hill offers instructors various tools and technology products in support of University Chemistry.

Track Student Progress
᭤ Assignments are automatically graded.
᭤ Gradebook functionality allows full-course management including:
—Dropping the lowest grades
—Weighting grades and manually adjusting grades
—Exporting your grade book to Excel®, WebCT® or
BlackBoard®
—Manipulating data so that you can track student
progress through multiple reports
Offer More Flexibility
᭤ Sharing Course Materials with Colleagues. Instructors can create and share course materials and

assignments with colleagues with a few clicks of the
mouse, allowing for multiple section courses with
many instructors and teaching assistants to continually be in synch, if desired.
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᭤ Integration with BlackBoard or WebCT. Once a
student is registered in the course, all student activity within McGraw-Hill’s ARIS is automatically
recorded and available to the instructor through a
fully integrated grade book that can be downloaded to Excel, WebCT, or Blackboard.

Presentation Center
The Presentation Center is a complete set of electronic book
images and assets for instructors. You can build instructional
materials wherever, whenever, and however you want!
Accessed from your textbook’s ARIS website, the Presentation Center is an online digital library containing selected
photos, artwork, animations, and other media types that can
be used to create customized lectures, visually enhanced
tests and quizzes, compelling course websites, or attractive
printed support materials. All assets are copyrighted

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by McGraw-Hill Higher Education, but can be used by
instructors for classroom purposes. The visual resources in
this collection include:
᭤ Art Full-color digital files of all illustrations in the
book can be readily incorporated into lecture presentations, exams, or custom-made classroom materials. In addition, all files are preinserted into

PowerPoint® slides for ease of lecture preparation.
᭤ Animations Numerous full-color animations
illustrating important processes are also provided.
Harness the visual impact of concepts in motion
by importing these files into classroom presentations
or online course materials.
᭤ PowerPoint Slides For instructors who prefer to
create their lectures from scratch, all illustrations,
selected photos, and tables are preinserted by chapter into blank PowerPoint slides.

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Animations and Media
Player Content
Topics in chemistry are available in Media
Player format and can be viewed on the text
ARIS site. For the instructor, all McGraw-Hill
chemistry animations are also available on the Presentation
Center for use in lecture.
Access to your book, access to all books! The Presentation Center library includes thousands of assets from
many McGraw-Hill titles. This ever-growing resource
gives instructors the power to utilize assets specific to an
adopted textbook as well as content from all other books
in the library.
Nothing could be easier! Accessed from the instructor side of your textbook’s ARIS website, Presentation

Center’s dynamic search engine allows you to explore by
discipline, course, textbook chapter, asset type, or keyword. Simply browse, select, and download the files you
need to build engaging course materials. All assets are
copyright by McGraw-Hill Higher Education but can be
used by instructors for classroom purposes. Instructors: To
access ARIS, request registration information from your
McGraw-Hill sales representative.

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᭤ Create tests that are compatible with EZ Test
Desktop tests you’ve already created.
᭤ Share tests easily with colleagues, adjuncts, and TAs.

Online Test Management
᭤ Set availability dates and time limits for your quiz
or test.
᭤ Control how your test will be presented.
᭤ Assign points by question or question type with the
drop-down menu.
᭤ Provide immediate feedback to students or delay
until all finish the test.
᭤ Create practice tests online to enable student mastery.
᭤ Upload your roster to enable student self-registration.
Online Scoring and Reporting
᭤ Provides automated scoring for most of EZ Test’s
numerous question types.
᭤ Allows manual scoring for essay and other open
response questions.
᭤ Allows manual rescoring and feedback.

᭤ Is designed so that EZ Test’s grade book will easily
export to your grade book.
᭤ Displays basic statistical reports.

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Computerized Test Bank Online

A comprehensive bank of test questions, created
by Thomas Seery from University of Connecticut, is
provided within a computerized test bank powered by
McGraw-Hill’s flexible electronic testing program EZ
Test Online (www.eztestonline.com). EZ Test Online allows you to create paper and online tests or quizzes in this
easy to use program!
Imagine being able to create and access your test or
quiz anywhere, at any time without installing the testing
software. Now, with EZ Test Online, instructors can select
questions from multiple McGraw-Hill test banks or author
their own, and then either print the test for paper distribution or give it online.

Test Creation
᭤ Author or edit questions online using the 14 different
question-type templates.
᭤ Create printed tests or deliver online to get instant
scoring and feedback.
᭤ Create question pools to offer multiple versions
online—great for practice.
᭤ Export your tests for use in WebCT, Blackboard,
PageOut and Apple’s iQuiz.

Support and Help
The following provide support and help:
᭤ User’s Guide and built-in page-specific help
᭤ Flash tutorials for getting started on the
support site
᭤ Support Website at www.mhhe.com/eztest

Student Response System
Wireless technology brings interactivity into the classroom or lecture hall. Instructors and students receive
immediate feedback through wireless response pads that
are easy to use and engage students. This system can be
used by instructors to:
᭤
᭤
᭤
᭤

Take attendance.
Administer quizzes and tests.
Create a lecture with intermittent questions.
Manage lectures and student comprehension
through the use of the grade book.

᭤ Integrate interactivity into their PowerPoint
presentations.
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Content Delivery Flexibility

Acknowledgments

University Chemistry by Brian B. Laird is available in
many formats in addition to the traditional textbook so
that instructors and students have more choices when deciding on the format of their chemistry text. Choices include the following.

I would like to thank the following instructors, symposium participants, and students, whose comments were
very helpful to me in preparing my first edition text.

Color Custom by Chapter
For greater flexibility, we offer University Chemistry in a
full-color custom version that allows instructors to pick
the chapters they want included. Students pay for only
what the instructor chooses.
Cooperative Chemistry Laboratory Manual
This innovative guide by Melanie Cooper (Clemson
University) features open-ended problems designed to
simulate experience in a research lab. Working in
groups, students investigate one problem over a period
of several weeks. Thus, they might complete three or
four projects during the semester, rather than one preprogrammed experiment per class. The emphasis here
is on experimental design, analysis problem solving,
and communication.

Colin D. Abernethy Western Kentucky University
Joseph J. BelBruno Dartmouth College

Philip C. Bevilacqua The Pennsylvania State University
Toby F. Block Georgia Institute of Technology
Robert Bohn University of Connecticut
B. Edward Cain Rochester Institute of Technology
Michelle Chatellier University of Delaware
Charles R. Cornett University of Wisconsin–
Platteville
Charles T. Cox Georgia Institute of Technology
Darwin B. Dahl Western Kentucky University
Stephen Drucker University of Wisconsin–Eau Claire
Darcy J. Gentleman University of Toronto
David O. Harris University of California–
Santa Barbara
J. Joseph Jesudason Acadia University
Kirk T. Kawagoe Fresno City College
Paul Kiprof University of Minnesota–Duluth
Craig Martens University of California–Irvine
Stephen Mezyk California State University
at Long Beach
Matthew L. Miller South Dakota State University
Michael Mombourquette Queens University
Shawn T. Phillips Vanderbilt University
Rozana Abdul Razak MARA University of Technology
Thomas Schleich University of California–Santa Cruz
Thomas A. P. Seery University of Connecticut
Jay S. Shore South Dakota University
Michael S. Sommer University of Wyoming
Larry Spreer University of the Pacific
Marcus L. Steele Delta State University
Mark Sulkes Tulane University

Paul S. Szalay Muskingum College
Michael Topp University of Pennsylvania
Robert B. Towery Houston Baptist University
Thomas R. Webb Auburn University
Stephen H. Wentland Houston Baptist University

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Enhanced Support for Students
Designed to help students maximize their learning
experience in chemistry, we offer the following options
to students.

ARIS
Assessment, Review, and Instruction System, known as
ARIS, is an electronic study system that offers students a
digital portal of knowledge.
Students can readily access a variety of digital learning objects which include:
᭤
᭤
᭤
᭤

Chapter level quizzing.
Animations.
Interactives.
MP3 and MP4 downloads of selected content.

Student Solutions Manual
In this manual by Jay Shore (South Dakota State
University), the student will find detailed solutions and

explanations for the even-numbered problems in
University Chemistry.
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John S. Winn Dartmouth College
Paulos Yohannes Georgia Perimeter College
Timothy Zauche University of Wisconsin–Platteville
Lois Anne Zook-Gerdau Muskingum College

Student Class Test, University of Kansas
I would like to thank the following students for using my
manuscript for their course throughout the year and providing me insight on student use.
Mirza Nayyar Ahmad
Elizabeth Beech
Amelia Bray
Thomas Chantz
Jason Christian
Connor Dennis
Andrew Dick
Ryan Edward Dowell
Hollie Farrahi
Lindsey Fisher
Stephen Folmsbee
Megan Fowler
Megan Fracol
Jessie Garrett
Casey Gee

Andy Haverkamp
Erica Henderson
Armand Heyns
Allison Ho
Kalin Holthaus
Michael Holtz
Jake S. Hopkins
Josh Istas
Ladini Jayaratne
Libby Johnson
Sophia Kaska
Jim LaRocca
Jenn Logue

Lizzy Mahoney
Amber Markey
Allison Martin
Ian Mayhugh
Nicole E. McClure
Sara McElhaney
Justin Moyes
Chelsea Montgomery
Ryan Murphy
Thomas Northup
Matthew Oliva
Jace Parkhurst
Sweta Patel
Megan L. Razak
Kate Remley
Thomas Reynolds

Richard Robinson
Lauren N. Schimming
Alan Schurle
Amy Soules
Jen Strande
Sharayah Stitt
Jessica Stogsdill
Joanna Marie Wakeman
Andre W. Wendorff
Thomas K. Whitson
Daniel Zehr
Simon Zhang

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I wish to acknowledge my colleagues at the University of Kansas for their help and support in preparing this
text, with a special thanks to Professor Cindy Berrie, who
has been using drafts of the text in her Honors General
Chemistry course. The feedback from her and her students
was invaluable. Thanks also to Craig Lunte and Robert
Dunn who helped me keep my sanity during this project
by enticing me to the golf course on many a sunny day.
This text would have not become a reality without the
extremely dedicated and competent team at McGraw-Hill
Higher Education. For their generous support, I wish to
acknowledge Thomas Timp (Publisher), Tami Hodge
(Senior Sponsoring Editor), Gloria Schiesl (Senior Project
Manager), John Leland (Senior Photo Research Coordinator) and especially my patiently persistent taskmaster
Shirley Oberbroeckling (Senior Developmental Editor)
for her continual advice, pep talks, and general support at

all stages of the project. I would also like to thank former
publisher Kent Peterson (VP—Director of Marketing) for
talking me into pursuing this project on a balmy (if somewhat blurry) evening in Key West.
Finally, I would like to acknowledge the significant
contributions and sage advice of Professor Raymond
Chang of Williams College, without which this book
would not have been possible.

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Brian B. Laird
Lawrence, Kansas
February 2008

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