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This page intentionally left blank
 Sixth Edition

Chemistry
The Molecular Nature of Matter

jespe_fm-hr.indd 1 11/30/10 1:05 PM

This page intentionally left blank
 Sixth Edition

Chemistry
The Molecular Nature of Matter

Neil D. Jespersen
St. John’s University, New York

James E. Brady
St. John’s University, New York

In collaboration with Alison Hyslop

St. John’s University, New York

John Wiley and Sons, Inc.

jespe_fm-hr.indd 3 11/30/10 1:05 PM

 VICE PRESIDENT, EXECUTIVE PUBLISHER Kaye Pace
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COVER PHOTO Ken Lucas/Visuals Unlimited

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Library of Congress Cataloging-in-Publication Data

Jespersen, Neil D.
Chemistry: the molecular nature of matter/Neil D. Jespersen, James E. Brady; In collaboration with
Alison Hyslop. – 6th ed.
p. cm.
Previous edition: Chemistry/James E. Brady, Fred Senese; in collaboration with Neil D. Jespersen.
Includes index.

ISBN 978-0-470-57771-4 (cloth)

Binder-Ready Version ISBN 978-0-470-91770-1

1. Chemistry. I. Jespersen, Neil D. II. Brady, James E. III. Hyslop, Alison

IV. Title.
QD33.2.B73 2012
540–dc22 2010043302

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

jespe_fm-hr.indd 4 11/30/10 1:05 PM

 About the Authors

Neil D. Jespersen is a Professor of Chemistry at St. John’s University in New York. He

earned a B.S. with Special Attainments in Chemistry at Washington and Lee University
(VA) and his Ph.D. in Analytical Chemistry with Joseph Jordan at The Pennsylvania State
University. He has received awards for excellence in teaching and research from St. John’s
University and the E. Emmit Reid Award in college teaching from the American Chemical
Society’s Middle Atlantic Region. He chaired the Department of Chemistry for 6 years
and has mentored the St. John’s student ACS club for over 30 years while continuing
to enjoy teaching Quantitative and Instrumental Analysis courses, along with General
Chemistry. He has been an active contributor to the Eastern Analytical Symposium, chair-
ing it in 1991. Neil has authored the Barrons AP Chemistry Study Guide; has edited
2 books on Instrumental Analysis and Thermal Analysis; and has 4 chapters in research
monographs, 50 refereed publications, and 150 abstracts and presentations.
He is active at the local, regional and national levels of the American Chemical Society,
and was recently elected to the ACS Board of Directors. When there is free time you can
find him playing tennis, baseball with four grandchildren, or traveling with his wife Marilyn.

James E. Brady received his BA degree from Hofstra College in 1959 and his Ph.D.
from Penn State University under the direction of C. David Schmulbach in 1963. He
is Professor Emeritus at St. John’s University, New York, where he taught graduate and
undergraduate courses for 35 years. His first textbook, General Chemistry: Principles and
Structure, coauthored with Gerard Humiston, was published in 1975. An innovative fea-
ture of the text was 3D illustrations of molecules and crystal structures that could be
studied with a stereo viewer that came tucked into a pocket inside the rear cover of the
book. The popularity of his approach to teaching general chemistry is evident in the way
his books have shaped the evolution of textbooks over the last 35 years. His useful chemical
tools approach toward teaching problem solving was introduced by him at the 12th Bien-
nial Conference on Chemical Education at UC Davis in 1992 and continues to evolve. He
has been the principal coauthor of various versions of this text, along with John Holum,
Joel Russell, Fred Senese, and Neil Jespersen. He is particularly pleased to be a member of
the current author team.
In 1999, Jim retired from St. John’s University to devote more time to writing, and
since then he has coauthored three editions of this text. He and his wife, June, enjoy their
current home in Jacksonville, Florida. Jim is an avid photographer and many of his photos
of surfers have been published in the local newspaper.

Alison Hyslop received her BA degree from Macalester College in 1986 and her Ph.D.
from the University of Pennsylvania under the direction of Michael J. Therien in 1998.
She is an Associate Professor at St. John’s University, New York, where she has been teach-
ing graduate and undergraduate courses since 2000. She was a visiting Assistant Professor
at Trinity College (CT) from 1998 to 1999. She was a visiting scholar at Columbia Uni-
versity (NY) in 2005 and in 2007 and at Brooklyn College in 2009, where she worked on
research projects in the laboratory of Brian Gibney. Her research focuses on the synthesis
and study of porphyrin-based light harvesting compounds.
When not in the laboratory, she likes to hike in upstate New York, and practice tae
kwon do.

|v

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This page intentionally left blank
 Brief Contents

1 | Chemistry and the Atomic/Molecular View of Matter 1

2 | Scientific Measurements 29

3 | Elements, Compounds, and the Periodic Table 63

4 | The Mole and Stoichiometry 106

5 | Molecular View of Reactions in Aqueous Solutions 155

6 | Oxidation–Reduction Reactions 213

7 | Energy and Chemical Change 253

8 | The Quantum Mechanical Atom 305

9 | The Basics of Chemical Bonding 357

10 | Theories of Bonding and Structure 408

11 | Properties of Gases 472

12 | Intermolecular Attractions and the Properties of Liquids and Solids 527

13 | Mixtures at the Molecular Level: Properties of Solutions 585

14 | Chemical Kinetics 636

15 | Chemical Equilibrium 695

16 | Acids and Bases, A Molecular Look 740

17 | Acid–Base Equilibria in Aqueous Solutions 773

18 | Solubility and Simultaneous Equilibria 830

19 | Thermodynamics 869

20 | Electrochemistry 918

21 | Nuclear Reactions and Their Role in Chemistry 976

22 | Metal Complexes 1016

23 | Organic Compounds, Polymers, and Biochemicals 1047

Appendix A: Review of Mathematics A-1
Appendix B: Answers to Practice Exercises and Selected Review Problems A-15
Appendix C: Tables of Selected Data A-39
Glossary G-1
Index I-1

| vii

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This page intentionally left blank
 Table of Contents

1 | Chemistry and the Atomic/Molecular

View of Matter 1

1.1 Chemistry and Its Place among the Sciences 2

1.2 Laws and Theories: The Scientific Method 3
1.3 Matter and Its Classifications 5
1.4 Dalton and the Atomic Theory 9
1.5 Atoms and Molecules and Chemical Formulas 10
1.6 Chemical Reactions and Chemical Equations 19
Tools for Problem Solving 24
Review Questions and Problems 24

2 | Scientific Measurements 29

2.1 Physical and Chemical Properties 30

2.2 Measurement of Physical and Chemical Properties 32
2.3 The Uncertainty of Measurements 41
2.4 Dimensional Analysis 45
2.5 Density and Specific Gravity 51
Tools for Problem Solving 56
Review Questions and Problems 58

3 | Elements, Compounds, and the

Periodic Table 63

3.1 Internal Structure of the Atom 64

3.2 The Periodic Table 72
3.3 Metals, Nonmetals, and Metalloids 75
3.4 Ionic Compounds 78
3.5 Nomenclature of Ionic Compounds 85
3.6 Molecular Compounds 90
3.7 Nomenclature of Molecular Compounds 94
Tools for Problem Solving 98
Review Questions and Problems 100

4 | The Mole and Stoichiometry 106

4.1 The Molecular Scale versus the Laboratory Scale 107

4.2 Chemical Formulas and Stoichiometry 113
| ix

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 x | Contents

4.3 Determining Empirical and Molecular Formulas 119

4.4 The Mole and Chemical Reactions 128
4.5 Limiting Reactants 135
4.6 Theoretical Yield and Percentage Yield 139
Tools for Problem Solving 143
Review Questions and Problems 144

Bringing It Together: Chapters 1–4 153

5 | Molecular View of Reactions in Aqueous

Solutions 155

5.1 Describing Solutions 156

5.2 Electrolytes, Weak Electrolytes, and Nonelectrolytes 157
5.3 Acids and Bases 164
5.4 Acid-Base Nomenclature 173
5.5 Double-Replacement (Metathesis) Reactions 175
5.6 Molarity 185
5.7 Solution Stoichiometry 190
5.8 Titrations and Chemical Analysis 196
Tools for Problem Solving 204
Review Questions and Problems 206

6 | Oxidation–Reduction Reactions 213

6.1 Oxidation–Reduction Reactions 214

6.2 Balancing Redox Equations 222
6.3 Acids as Oxidizing Agents 227
6.4 Redox Reactions of Metals 231
6.5 Molecular Oxygen as an Oxidizing Agent 235
6.6 Stoichiometry of Redox Reactions 239
Tools for Problem Solving 243
Review Questions and Problems 244

7 | Energy and Chemical Change 253

7.1 Energy: The Ability to Do Work 254

7.2 Internal Energy 257
7.3 Measuring Heat 259

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 Contents | xi

7.4 Energy of Chemical Reactions 265

7.5 Heat, Work, and the First Law of Thermodynamics 267
7.6 Heats of Reaction 270
7.7 Thermochemical Equations 275
7.8 Hess’s Law 277
7.9 Standard Heats of Reaction 283
Tools for Problem Solving 293
Review Questions and Problems 295

Bringing It Together: Chapters 5–7 303

8 | The Quantum Mechanical Atom 305

8.1 Electromagnetic Radiation 306

8.2 Line Spectra and the Rydberg Equation 314
8.3 The Bohr Theory 316
8.4 The Wave Mechanical Model 318
8.5 Quantum Numbers of Electrons in Atoms 324
8.6 Electron Spin 326
8.7 Energy Levels and Ground State Electron Configurations 328
8.8 Periodic Table and Ground State Electron Configurations 330
8.9 Atomic Orbitals: Shapes and Orientations 337
8.10 Periodic Table and Properties of the Elements 340
Tools for Problem Solving 351
Review Questions and Problems 351

9 | The Basics of Chemical Bonding 357

9.1 Energy Requirements for Bond Formation 358

9.2 Ionic Bonding 358
9.3 Electron Configurations of Ions 362
9.4 Lewis Symbols: Keeping Track of Valence Electrons 366
9.5 Covalent Bonds 368
9.6 Covalent Compounds of Carbon 373
9.7 Bond Polarity and Electronegativity 377
9.8 Lewis Structures 382
9.9 Resonance Structures 394
Tools for Problem Solving 400
Review Questions and Problems 401

jespe_fm-hr.indd 11 11/30/10 1:05 PM

 xii | Contents

10 | Theories of Bonding and Structure 408

10.1 Five Basic Molecular Geometries 409

10.2 Molecular Shapes and the VSEPR Model 411
10.3 Molecular Structure and Dipole Moments 420
10.4 Valence Bond Theory 424
10.5 Hybrid Orbitals and Molecular Geometry 427
10.6 Hybrid Orbitals and Multiple Bonds 439
10.7 Molecular Orbital Theory Basics 445
10.8 Delocalized Molecular Orbitals 452
10.9 Bonding in Solids 453
10.10Atomic Size and the Tendency toward Multiple Bond
Formation 456
Tools for Problem Solving 462
Review Questions and Problems 464

Bringing It Together: Chapters 8–10 470

11 | Properties of Gases 472

11.1 A Molecular Look at Gases 473

11.2 Measurement of Pressure 474
11.3 Gas Laws 480
11.4 Stoichiometry Using Gas Volumes 486
11.5 Ideal Gas Law 490
11.6 Dalton’s Law of Partial Pressures 499
11.7 Kinetic Molecular Theory 509
11.8 Real Gases 513
11.9 Chemistry of the Atmosphere 515
Tools for Problem Solving 519
Review Questions and Problems 521

12 | Intermolecular Attractions and the

Properties of Liquids and Solids 527

12.1 Gases, Liquids, and Solids and Intermolecular Distances 528

12.2 Types of Intermolecular Forces 529
12.3 Intermolecular Forces and Properties of Liquids and Solids 537
12.4 Changes of State and Dynamic Equilibria 542

jespe_fm-hr.indd 12 11/30/10 1:05 PM

 Contents | xiii

12.5 Vapor Pressures of Liquids and Solids 544

12.6 Boiling Points of Liquids 546
12.7 Energy and Changes of State 548
12.8 Determining Heats of Vaporization 552
12.9 Le Châtelier’s Principle and State Changes 555
12.10 Phase Diagrams 556
12.11 Structures of Crystalline Solids 560
12.12 X-Ray Diffraction of Solids 568
12.13 Crystal Types and Physical Properties 671
Tools for Problem Solving 576
Review Questions and Problems 577

13 | Mixtures at the Molecular Level:

Properties of Solutions 585

13.1 Intermolecular Forces and the Formation of Solutions 586

13.2 Heats of Solution 589
13.3 Solubility as a Function of Temperature 593
13.4 Henry’s Law 595
13.5 Temperature-Independent Concentration Units 597
13.6 Temperature-Dependent Concentration Units 602
13.7 Colligative Properties 603
13.8 Heterogeneous Mixtures 623
Tools for Problem Solving 627
Review Questions and Problems 628

Bringing It Together: Chapters 11–13 634

14 | Chemical Kinetics 636

14.1 Factors that Affect Reaction Rates 637

14.2 Measuring Reaction Rates 639
14.3 Rate Laws 645
14.4 Integrated Rate Laws 654
14.5 Molecular Basis of Collision Theory 664
14.6 Molecular Basis of Transition State Theory 667
14.7 Activation Energies 669
14.8 Mechanisms of Reactions 675
14.9 Catalysts 680

jespe_fm-hr.indd 13 11/30/10 1:05 PM

 xiv | Contents

Tools for Problem Solving 684

Review Questions and Problems 686

15 | Chemical Equilibrium 695

15.1 Dynamic Equilibrium in Chemical Systems 696

15.2 Equilibrium Laws 698
15.3 Equilibrium Laws Based on Pressures or Concentrations 703
15.4 Equilibrium Laws for Heterogeneous Reactions 706
15.5 Position of Equilibrium and the Equilibrium Constant 708
15.6 Equilibrium and Le Châtelier’s Principle 710
15.7 Calculating Equilibrium Constants 715
15.8 Using Equilibrium Constants to Calculate Concentrations 719
Tools for Problem Solving 731
Review Questions and Problems 733

16 | Acids and Bases, A Molecular Look 740

16.1 Brønsted–Lowry Definition of Acids and Bases 741

16.2 Strengths of Brønsted–Lowry Acids and Bases 746
16.3 Periodic Trends in the Strengths of Acids 750
16.4 Lewis Definition of Acids and Bases 755
16.5 Acid–Base Properties of Elements and Their Oxides 759
16.6 Advanced Ceramics and Acid–Base Chemistry 762
Tools for Problem Solving 766
Review Questions and Problems 767

Bringing It Together: Chapters 14–16 771

17 | Acid–Base Equilibria in Aqueous

Solutions 773

17.1 Water, pH and “p” notation 774

17.2 pH of Strong Acid and Base Solutions 778
17.3 Ionization Constants, Ka and Kb 780
17.4 Determining Ka and Kb Values 784
17.5 pH of Weak Acid and Weak Base Solutions 788
17.6 pH of Salt Solutions 793
17.7 Buffer Solutions 798

jespe_fm-hr.indd 14 11/30/10 1:05 PM

 Contents | xv

17.8 Polyprotic Acids 805

17.9 Acid–Base Titrations 811
Tools for Problem Solving 821
Review Questions and Problems 822

18 | Solubility and Simultaneous

Equilibria 830

18.1 Equilibria in Solutions of Slightly Soluble Neutral Salts 831

18.2 Equilibria in Solutions of Metal Oxides and Sulfides 845
18.3 Selective Precipitation 847
18.4 Equilibria Involving Complex Ions 855
18.5 Complexation and Solubility 858
Tools for Problem Solving 861
Review Questions and Problems 862

19 | Thermodynamics 869

19.1 First Law of Thermodynamics 870

19.2 Spontaneous Change 874
19.3 Entropy 876
19.4 Second Law of Thermodynamics 880
19.5 Third Law of Thermodynamics 884
19.6 Standard Free Energy Change, DG° 887
19.7 Maximum Work and DG 890
19.8 Free Energy and Equilibrium 893
19.9 Equilibrium Constants and DG° 900
19.10 Bond Energies 904
Tools for Problem Solving 909
Review Questions and Problems 910

20 | Electrochemistry 918

20.1 Galvanic (Voltaic) Cells 919

20.2 Cell Potentials 924
20.3 Standard Reduction Potentials 931
20.4 E°cell and DG° 936
20.5 Cell Potentials and Concentrations 939
20.6 Electricity 945
20.7 Electrolytic Cells 952

jespe_fm-hr.indd 15 11/30/10 1:05 PM

 xvi | Contents

20.8 Electrolysis Stoichiometry 959

20.9 Practical Applications of Electrolysis 962
Tools for Problem Solving 967
Review Questions and Problems 968

Bringing It Together: Chapters 17–20 974

21 | Nuclear Reactions and

Their Role in Chemistry 976

21.1 Conservation of Mass and Energy 977

21.2 Nuclear Binding Energy 978
21.3 Radioactivity 980
21.4 Band of Stability 988
21.5 Transmutation 991
21.6 Measuring Radioactivity 994
21.7 Medical and Analytical Applications of Radionuclides 998
21.8 Nuclear Fission and Fusion 1000
Tools for Problem Solving 1009
Review Questions and Problems 1010

22 | Metal Complexes 1016

22.1 Complex Ions 1017

22.2 Metal Complex Nomenclature 1022
22.3 Coordination Number and Structure 1025
22.4 Isomers of Metal Complex 1027
22.5 Bonding in Metal Complexes 1031
22.6 Biological Functions of Metal Ions 1038
Tools for Problem Solving 1041
Review Questions and Problems 1042

23 | Organic Compounds, Polymers, and

Biochemicals 1047

23.1 The Nature of Organic Chemistry 1048

23.2 Hydrocarbons 1053
23.3 Organic Compounds Containing Oxygen 1060
23.4 Organic Derivatives of Ammonia 1068

jespe_fm-hr.indd 16 11/30/10 1:05 PM

 Contents | xvii

23.5 Organic Polymers 1070

23.6 Biochemical Compounds 1077
23.7 Nucleic Acids 1085
Tools for Problem Solving 1090
Review Exercises 1092

Bringing It Together: Chapters 21–23 1101

Appendices | A-1
Appendix A: Review of Mathematics A-1
Appendix B: Answers to Practice Exercises and
Selected Review Problems A-15
Appendix C: Tables of Selected Data A-39
Glossary G-1
Index I-1

jespe_fm-hr.indd 17 11/30/10 1:05 PM

 Special Topics
On the Cutting edge 1.1 | Nanotechnology: Controlling Structure at the
Molecular Level 18
Chemistry Outside the ClassrOOm 2.1 | Density and Wine 54
On the Cutting edge 3.1 | The Mass Spectrometer and the Experimental
Measurement of Atomic Masses 66
On the Cutting edge 4.1 | Combustion Analysis 124
Chemistry Outside the ClassrOOm 5.1 | Painful Precipitates–Kidney Stones 160
Chemistry Outside the ClassrOOm 5.2 | Hard Water and Its Problems 181
Chemistry Outside the ClassrOOm 6.1 | Polishing Silver—The Easy Way 234
Chemistry Outside the ClassrOOm 7.1 | Water, Climate, and the Body’s
“Thermal Cushion” 262
Chemistry and Current affairs 7.2 | Runaway Reactions: The Importance of
Thermodynamics 288
Chemistry and Current affairs 8.1 | The Electron Microscope 320
On the Cutting edge 8.2 | Photoelectron Spectroscopy 344
Chemistry and Current affairs 9.1 | Sunlight and Skin Cancer 370
On the Cutting edge 10.1 | Graphene and the Future of Electronics 458
Chemistry Outside the ClassrOOm 11.1 | Whipped Cream 483
Chemistry and Current affairs 11.2 | Effusion and Nuclear Energy 505
On the Cutting edge 11.3 | Super Greenhouse Gases 517
Chemistry Outside the ClassrOOm 12.1 | Decaffeinated Coffee and Supercritical
Carbon Dioxide 559
Chemistry Outside the ClassrOOm 12.2 | Giant Crystals 574
Chemistry and Current affairs 13.1 | Pure Water by Reverse Osmosis 615
Chemistry Outside the ClassrOOm 14.1 | Free Radicals, Explosions, Octane
Ratings, and Aging 677
Chemistry Outside the ClassrOOm 15.1 | The Haber Process: Feeding Earth’s
Population 712
Chemistry Outside the ClassrOOm 16.1 | Applications of Advanced Ceramic
Materials 763
Chemistry Outside the ClassrOOm 18.1 | No More Soap Scum—Complex Ions
and Solubility 858
Chemistry Outside the ClassrOOm 19.1 | Carved in Stone 886
On the Cutting edge 19.2 | Thermodynamic Efficiency and Sustainability 892
Chemistry Outside the ClassrOOm 20.1 | Corrosion of Iron and Cathodic
Protection 929
On the Cutting edge 21.1 | Positron Emission Tomography (PET) 990

xviii |

jespe_fm-hr.indd 18 11/30/10 1:05 PM

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