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 MAIN–GROUP MAIN–GROUP

siL40215_fm_i-xxxv.indd 1
ELEMENTS Periodic Table of the Elements ELEMENTS

1A 8A
(1) (18)
1 2
Metals (main-group)
1 H 4 Atomic number He
2A Metals (transition) 3A 4A 5A 6A 7A
1.008 (2) (13) (14) (15) (16) (17) 4.003
Be Atomic symbol Metals (inner transition)
3 4 Metalloids 5 6 7 8 9 10
9.012 Atomic mass (amu)
2 Li Be Nonmetals B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 TRANSITION ELEMENTS 13 14 15 16 17 18
3 Na Mg 3B 4B 5B 6B 7B 8B 1B 2B Al Si P S Cl Ar
22.99 24.31 (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) 26.98 28.09 30.97 32.06 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Period
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.63 74.92 78.97 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.96 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
(223) (226) (227) (265) (268) (271) (270) (277) (276) (281) (280) (285) (284) (289) (288) (293) (294) (294)

INNER TRANSITION ELEMENTS

58 59 60 61 62 63 64 65 66 67 68 69 70 71
6 Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.1 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
7 Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 (231) 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)

10/11/19 1:04 PM
 The Elements
Atomic Atomic Atomic Atomic
Name Symbol Number Mass* Name Symbol Number Mass*
Actinium Ac 89 (227) Mendelevium Md 101 (256)
Aluminum Al 13 26.98 Mercury Hg 80 200.6
Americium Am 95 (243) Molybdenum Mo 42 95.94
Antimony Sb 51 121.8 Moscovium Mc 115 (288)
Argon Ar 18 39.95 Neodymium Nd 60 144.2
Arsenic As 33 74.92 Neon Ne 10 20.18
Astatine At 85 (210) Neptunium Np 93 (244)
Barium Ba 56 137.3 Nickel Ni 28 58.70
Berkelium Bk 97 (247) Nihonium Nh 113 (284)
Beryllium Be 4 9.012 Niobium Nb 41 92.91
Bismuth Bi 83 209.0 Nitrogen N 7 14.01
Bohrium Bh 107 (267) Nobelium No 102 (253)
Boron B 5 10.81 Oganesson Og 118 (294)
Bromine Br 35 79.90 Osmium Os 76 190.2
Cadmium Cd 48 112.4 Oxygen O 8 16.00
Calcium Ca 20 40.08 Palladium Pd 46 106.4
Californium Cf 98 (249) Phosphorus P 15 30.97
Carbon C 6 12.01 Platinum Pt 78 195.1
Cerium Ce 58 140.1 Plutonium Pu 94 (242)
Cesium Cs 55 132.9 Polonium Po 84 (209)
Chlorine Cl 17 35.45 Potassium K 19 39.10
Chromium Cr 24 52.00 Praseodymium Pr 59 140.9
Cobalt Co 27 58.93 Promethium Pm 61 (145)
Copernicium Cn 112 (285) Protactinium Pa 91 (231)
Copper Cu 29 63.55 Radium Ra 88 (226)
Curium Cm 96 (247) Radon Rn 86 (222)
Darmstadtium Ds 110 (281) Rhenium Re 75 186.2
Dubnium Db 105 (262) Rhodium Rh 45 102.9
Dysprosium Dy 66 162.5 Roentgenium Rg 111 (272)
Einsteinium Es 99 (254) Rubidium Rb 37 85.47
Erbium Er 68 167.3 Ruthenium Ru 44 101.1
Europium Eu 63 152.0 Rutherfordium Rf 104 (263)
Fermium Fm 100 (253) Samarium Sm 62 150.4
Flevorium Fl 114 (289) Scandium Sc 21 44.96
Fluorine F 9 19.00 Seaborgium Sg 106 (266)
Francium Fr 87 (223) Selenium Se 34 78.97
Gadolinium Gd 64 157.3 Silicon Si 14 28.09
Gallium Ga 31 69.72 Silver Ag 47 107.9
Germanium Ge 32 72.61 Sodium Na 11 22.99
Gold Au 79 197.0 Strontium Sr 38 87.62
Hafnium Hf 72 178.5 Sulfur S 16 32.07
Hassium Hs 108 (277) Tantalum Ta 73 180.9
Helium He 2 4.003 Technetium Tc 43 (98)
Holmium Ho 67 164.9 Tellurium Te 52 127.6
Hydrogen H 1 1.008 Tennessine Ts 117 (294)
Indium In 49 114.8 Terbium Tb 65 158.9
Iodine I 53 126.9 Thallium Tl 81 204.4
Iridium Ir 77 192.2 Thorium Th 90 232.0
Iron Fe 26 55.85 Thulium Tm 69 168.9
Krypton Kr 36 83.80 Tin Sn 50 118.7
Lanthanum La 57 138.9 Titanium Ti 22 47.88
Lawrencium Lr 103 (257) Tungsten W 74 183.9
Lead Pb 82 207.2 Uranium U 92 238.0
Lithium Li 3 6.941 Vanadium V 23 50.94
Livermorium Lv 116 (293) Xenon Xe 54 131.3
Lutetium Lu 71 175.0 Ytterbium Yb 70 173.0
Magnesium Mg 12 24.31 Yttrium Y 39 88.91
Manganese Mn 25 54.94 Zinc Zn 30 65.41
Meitnerium Mt 109 (268) Zirconium Zr 40 91.22
*All atomic masses are given to four significant figures. Values in parentheses represent the mass number of the most stable isotope.

siL40215_fm_i-xxxv.indd 2 10/11/19 1:04 PM

siL40215_fm_i-xxxv.indd 3 10/11/19 1:04 PM
 CHEMISTRY: THE MOLECULAR NATURE OF MATTER AND CHANGE, NINTH EDITION
Published by McGraw-Hill Education, 2 Penn Plaza, New York, NY 10121. Copyright © 2021 by
McGraw-Hill Education. All rights reserved. Printed in the United States of America. Previous editions
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Library of Congress Cataloging-in-Publication Data

Names: Silberberg, Martin S. (Martin Stuart), 1945- author. | Amateis,
Patricia, author.
Title: Chemistry : the molecular nature of matter and change / [Martin S.]
Silberberg, [Patricia G.] Amateis.
Description: [Ninth edition]. | Dubuque : McGraw-Hill Education, [2021] |
Includes index.
Identifiers: LCCN 2019033353 (print) | LCCN 2019033354 (ebook) | ISBN
9781260240214 (hardcover) | ISBN 9781260477405 (spiral bound) | ISBN
9781260477375 (ebook)
Subjects: LCSH: Chemistry—Textbooks.
Classification: LCC QD33.2 .S55 2021 (print) | LCC QD33.2 (ebook) | DDC
540—dc23
LC record available at https://lccn.loc.gov/2019033353
LC ebook record available at https://lccn.loc.gov/2019033354

The Internet addresses listed in the text were accurate at the time of publication. The inclusion
of a website does not indicate an endorsement by the authors or McGraw-Hill Education, and
McGraw-Hill Education does not guarantee the accuracy of the information presented at these sites.

mheducation.com/highered

siL40215_fm_i-xxxiv_1.indd 4 15/10/19 7:51 AM

 To Ruth and Daniel, with all my love and gratitude.
MSS

To Ralph, Eric, Samantha, and Lindsay:

you bring me much joy.
PGA

siL40215_fm_i-xxxv.indd 5 10/11/19 1:04 PM

 BRIEF CONTENTS
Preface xxii
Acknowledgments 1

1 Keys to Studying Chemistry: Definitions, Units, and Problem Solving 2

2 The Components of Matter 40
3 Stoichiometry of Formulas and Equations 92
4 Three Major Classes of Chemical Reactions 142
5 Gases and the Kinetic-Molecular Theory 202
6 Thermochemistry: Energy Flow and Chemical Change 254
7 Quantum Theory and Atomic Structure 294
8 Electron Configuration and Chemical Periodicity 330
9 Models of Chemical Bonding 368
10 The Shapes of Molecules 404
11 Theories of Covalent Bonding 442
12 Intermolecular Forces: Liquids, Solids, and Phase Changes 470
13 The Properties of Mixtures: Solutions and Colloids 534
14 Periodic Patterns in the Main-Group Elements 588
15 Organic Compounds and the Atomic Properties of Carbon 636
16 Kinetics: Rates and Mechanisms of Chemical Reactions 694
17 Equilibrium: The Extent of Chemical Reactions 752
18 Acid-Base Equilibria 802
19 Ionic Equilibria in Aqueous Systems 852
20 Thermodynamics: Entropy, Free Energy, and Reaction Direction 906
21 Electrochemistry: Chemical Change and Electrical Work 950
22 The Elements in Nature and Industry 1008
23 Transition Elements and Their Coordination Compounds 1048
24 Nuclear Reactions and Their Applications 1086

Appendix A Common Mathematical Operations in Chemistry A-1

Appendix B Standard Thermodynamic Values for Selected Substances A-5
Appendix C Equilibrium Constants for Selected Substances A-8
Appendix D Standard Electrode (Half-Cell) Potentials A-14
Appendix E Answers to Selected Problems A-15
Glossary G-1
Index I-1

vi

siL40215_fm_i-xxxiv_1.indd 6 10/14/19 3:53 PM

 DETAILED CONTENTS

Photodisc/Getty Images

Chapter 1 Keys to Studying Chemistry: Definitions, Units,

and Problem Solving 2

1.1 Some Fundamental Definitions 3
The States of Matter 4
The Properties of Matter and Its
Changes 4
The Central Theme in Chemistry 8
The Importance of Energy in the Study
of Matter 8
1.2 The Scientific Approach: Developing
a Model 10
1.3 Measurement and Chemical Problem
Solving 12
General Features of SI Units 12
Some Important SI Units in Chemistry 13 Significant Figures: Calculations and
Units and Conversion Factors in Rounding Off 28
Calculations 15 Precision, Accuracy, and Instrument
A Systematic Approach to Solving Calibration 30
Chemistry Problems 18 CHAPTER REVIEW GUIDE 31
Temperature Scales 23
PROBLEMS 35
Extensive and Intensive Properties 25
1.4 Uncertainty in Measurement:
Significant Figures 26
Determining Which Digits Are
Significant 27

Chapter 2 The Components of Matter 40

2.1 Elements, Compounds, and Mixtures:
An Atomic Overview 42
2.2 The Observations That Led to an
Atomic View of Matter 44
Mass Conservation 44
Definite Composition 45
Multiple Proportions 47
2.3 Dalton’s Atomic Theory 48
Postulates of the Atomic Theory 48
How the Theory Explains the
Mass Laws 48
2.4 The Observations That Led to the
Nuclear Atom Model 50
Discovery of the Electron and Its
Properties 50
Discovery of the Atomic Nucleus 52
2.5 The Atomic Theory Today 53
Structure of the Atom 53
Atomic Number, Mass Number, and
Atomic Symbol 54
Isotopes 55
Atomic Masses of the Elements 55
2.6 Elements: A First Look at the
Periodic Table 59
2.7 Compounds: Introduction
to Bonding 62
The Formation of Ionic Compounds 62
The Formation of Covalent
Substances 64
2.8 Compounds: Formulas, Names,
and Masses 65
Binary Ionic Compounds 65
Compounds That Contain
Polyatomic Ions 69
Acid Names from Anion Names 71
Binary Covalent Compounds 72
The Simplest Organic Compounds:
Straight-Chain Alkanes 73
Molecular Masses from Chemical
Formulas 74
Representing Molecules with Formulas
and Models 76
2.9 Mixtures: Classification
and Separation 78
An Overview of the Components
of Matter 79
CHAPTER REVIEW GUIDE 81
PROBLEMS 83

vii

siL40215_fm_i-xxxv.indd 7 10/11/19 1:04 PM

 viii   Detailed Contents
Chapter 3 Stoichiometry of Formulas and Equations 92
3.1 The Mole 93
Defining the Mole 93
Determining Molar Mass 94
Converting Between Amount, Mass, and
Number of Chemical Entities 95
The Importance of Mass Percent 99
3.2 Determining the Formula of
an Unknown Compound 102
Empirical Formulas 102
Molecular Formulas 103
Chapter 4 Three Major Classes of Chemical Reactions 142
4.1 Solution Concentration and the Role
of Water as a Solvent 143
The Polar Nature of Water 144
Ionic Compounds in Water 144
Covalent Compounds in Water 148
Expressing Concentration in Terms
of Molarity 148
Amount-Mass-Number Conversions
Involving Solutions 149
Preparing and Diluting Molar
Solutions 150
4.2 Precipitation Reactions 154
The Key Event: Formation of a Solid
from Dissolved Ions 154
Predicting Whether a Precipitate
Will Form 156
Chapter 5 Gases and the Kinetic-Molecular Theory 202
5.1  n Overview of the Physical States
A The Ideal Gas Law 214
of Matter 203
5.2 Gas Pressure and Its Measurement 205
Measuring Gas Pressure: Barometers and
Manometers 205
Units of Pressure 207
5.3 The Gas Laws and Their Experimental
Foundations 208
The Relationship Between Volume and
Pressure: Boyle’s Law 209
The Relationship Between Volume and
Temperature: Charles’s Law 210
The Relationship Between Volume and
Amount: Avogadro’s Law 212
Gas Behavior at Standard Conditions 213
siL40215_fm_i-xxxv.indd 8
Alessandro Bonora/Shutterstock
Chemical Formulas and Molecular
Structures; Isomers 107
3.3 Writing and Balancing Chemical
Equations 108
3.4 Calculating Quantities of Reactant
and Product 113
Stoichiometrically Equivalent Molar
Ratios from the Balanced
Equation 113
Stoichiometry of Precipitation
Reactions 159
4.3 Acid-Base Reactions 162
The Key Event: Formation of H2O from
H+ and OH− 165
Proton Transfer in Acid-Base
Reactions 165
Stoichiometry of Acid-Base Reactions:
Acid-Base Titrations 169
4.4 Oxidation-Reduction (Redox)
Reactions 172
The Key Event: Movement of Electrons
Between Reactants 172
Some Essential Redox Terminology 173
Solving Gas Law Problems 215
5.4 Rearrangements of the Ideal
Gas Law 220
The Density of a Gas 220
The Molar Mass of a Gas 222
The Partial Pressure of Each Gas in
a Mixture of Gases 223
The Ideal Gas Law and Reaction
Stoichiometry 226
5.5 The Kinetic-Molecular Theory: A Model
for Gas Behavior 229
How the Kinetic-Molecular Theory
Explains the Gas Laws 229
Effusion and Diffusion 234
Reactions That Occur in a Sequence 117
Reactions That Involve a Limiting
Reactant 118
Theoretical, Actual, and Percent
Reaction Yields 124
CHAPTER REVIEW GUIDE 127
PROBLEMS 132
Using Oxidation Numbers to Monitor
Electron Charge 173
Stoichiometry of Redox Reactions:
Redox Titrations 177
4.5 Elements in Redox Reactions 179
Combination Redox Reactions 179
Decomposition Redox Reactions 180
Displacement Redox Reactions and
Activity Series 182
Combustion Reactions 184
4.6 The Reversibility of Reactions
and the Equilibrium State 186
CHAPTER REVIEW GUIDE 188
PROBLEMS 194
The Chaotic World of Gases: Mean Free
Path and Collision Frequency 236
CHEMICAL CONNECTIONS TO
ATMOSPHERIC SCIENCE:
HOW THE GAS LAWS APPLY TO EARTH’S
ATMOSPHERE 237
5.6 Real Gases: Deviations from Ideal
Behavior 239
Effects of Extreme Conditions
on Gas Behavior 239
The van der Waals Equation: Adjusting
the Ideal Gas Law 241
CHAPTER REVIEW GUIDE 242
PROBLEMS 245
10/11/19 1:04 PM

Chapter 6 Thermochemistry: Energy Flow and Chemical Change 254
6.1 Forms of Energy and Their
Interconversion 255
Defining the System and Its
Surroundings 256
Energy Change (ΔE): Energy Transfer to
or from a System 256
Heat and Work: Two Forms of Energy
Transfer 257
The Law of Energy Conservation 259
Units of Energy 260
State Functions and the Path
Independence of the Energy
Change 261
Calculating Pressure-Volume Work
(PV Work) 262
Chapter 7 Quantum Theory and Atomic Structure 294
7.1 The Nature of Light 295
The Wave Nature of Light 296
The Particle Nature of Light 299
7.2 Atomic Spectra 302
Line Spectra and the Rydberg
Equation 302
The Bohr Model of the Hydrogen
Atom 303
The Energy Levels of the Hydrogen
Atom 305
Chapter 8 Electron Configuration and Chemical Periodicity 330
8.1 Characteristics of Many-Electron
Atoms 332
The Electron-Spin Quantum Number 332
The Exclusion Principle 333
Electrostatic Effects and Energy-Level
Splitting 333
8.2 The Quantum-Mechanical Model and
the Periodic Table 335
Building Up Period 1 336
Building Up Period 2 336
Building Up Period 3 338
siL40215_fm_i-xxxiv_1.indd 9
Philip Coblentz/Brand X Pictures/
age fotostock
6.2 Enthalpy: Changes at Constant
Pressure 263
The Meaning of Enthalpy 263
Comparing ΔE and ΔH 264
Exothermic and Endothermic
Processes 264
6.3 Calorimetry: Measuring the Heat
of a Chemical or Physical Change 266
Specific Heat Capacity 266
The Two Major Types of
Calorimetry 268
6.4 Stoichiometry of Thermochemical
Equations 272
TOOLS OF THE LABORATORY:
SPECTROMETRY IN CHEMICAL
ANALYSIS 308
7.3 The Wave-Particle Duality of Matter
and Energy 310
The Wave Nature of Electrons and the
Particle Nature of Photons 310
Heisenberg’s Uncertainty Principle 313
7.4 The Quantum-Mechanical Model
of the Atom 314
The Atomic Orbital and the Probable
Location of the Electron 314
Building Up Period 4: The First Transition
Series 338
General Principles of Electron
Configurations 340
Intervening Series: Transition and Inner
Transition Elements 341
Similar Electron Configurations Within
Groups 342
8.3 Trends in Three Atomic
Properties 344
Trends in Atomic Size 345
   ix
6.5 Hess’s Law: Finding ΔH
of Any Reaction 274
6.6 Standard Enthalpies of
Reaction (ΔH°rxn) 276
Formation Equations and Their Standard
Enthalpy Changes 277
Determining ΔH°rxn from ΔH°f Values for
Reactants and Products 278
CHEMICAL CONNECTIONS TO
ATMOSPHERIC SCIENCE:
THE FUTURE OF ENERGY USE 280
CHAPTER REVIEW GUIDE 284
PROBLEMS 287
Quantum Numbers of an Atomic
Orbital 316
Quantum Numbers and Energy
Levels 317
Shapes of Atomic Orbitals 319
The Special Case of Energy Levels in
the Hydrogen Atom 322
CHAPTER REVIEW GUIDE 323
PROBLEMS 325
Trends in Ionization Energy 347
Trends in Electron Affinity 351
8.4 Atomic Properties and Chemical
Reactivity 352
Trends in Metallic Behavior 352
Properties of Monatomic Ions 354
CHAPTER REVIEW GUIDE 361
PROBLEMS 362
10/14/19 11:11 AM
 x   Detailed Contents
Chapter 9 Models of Chemical Bonding 368
9.1  tomic Properties and Chemical
A How the Model Explains the Properties
Bonds 369
The Three Ways Elements Combine 369
Lewis Symbols and the Octet Rule 371
9.2 The Ionic Bonding Model 372
Why Ionic Compounds Form:
The Importance of Lattice
Energy 373
Periodic Trends in Lattice Energy 376
How the Model Explains the Properties
of Ionic Compounds 378
9.3 The Covalent Bonding Model 379
The Formation of a Covalent Bond 379
Bonding Pairs and Lone Pairs 380
Properties of a Covalent Bond:
Order, Energy, and Length 380
Chapter 10 The Shapes of Molecules 404
10.1 Depicting Molecules and Ions with
Lewis Structures 405
Applying the Octet Rule to Write
Lewis Structures 405
Resonance: Delocalized Electron-Pair
Bonding 410
Formal Charge: Selecting the More
Important Resonance Structure 411
Lewis Structures for Exceptions to
the Octet Rule 414
10.2 Valence-Shell Electron-Pair Repulsion
(VSEPR) Theory 418
Electron-Group Arrangements and
Molecular Shapes 418
The Molecular Shape with Two Electron
Groups (Linear Arrangement) 419
siL40215_fm_i-xxxv.indd 10
Stephen Frisch/McGraw-Hill Education
of Covalent Substances 383
TOOLS OF THE LABORATORY:
INFRARED SPECTROSCOPY 384
9.4 Bond Energy and Chemical
Change 385
Changes in Bond Energy: Where Does
ΔH°rxn Come From? 385
Using Bond Energies to Calculate
ΔH°rxn 386
Bond Strengths and the Heat Released
from Fuels and Foods 389
9.5 Between the Extremes:
Electronegativity and Bond
Polarity 390
Electronegativity 390
Molecular Shapes with Three Electron
Groups (Trigonal Planar
Arrangement) 420
Molecular Shapes with Four Electron
Groups (Tetrahedral
Arrangement) 421
Molecular Shapes with Five Electron
Groups (Trigonal Bipyramidal
Arrangement) 422
Molecular Shapes with Six Electron
Groups (Octahedral
Arrangement) 423
Using VSEPR Theory to Determine
Molecular Shape 424
Molecular Shapes with More Than One
Central Atom 427
Bond Polarity and Partial Ionic
Character 392
The Gradation in Bonding Across
a Period 394
9.6 An Introduction to Metallic
Bonding 395
The Electron-Sea Model 395
How the Model Explains the Properties
of Metals 396
CHAPTER REVIEW GUIDE 397
PROBLEMS 399
10.3 Molecular Shape and Molecular
Polarity 429
Bond Polarity, Bond Angle, and Dipole
Moment 429
The Effect of Molecular Polarity on
Behavior 431
CHEMICAL CONNECTIONS TO
SENSORY PHYSIOLOGY: MOLECULAR
SHAPE, BIOLOGICAL RECEPTORS, AND
THE SENSE OF SMELL 432
CHAPTER REVIEW GUIDE 433
PROBLEMS 437
10/11/19 1:04 PM
    xi

Jer Barber/iStockphoto/Getty Images

Chapter 11 Theories of Covalent Bonding 442

11.1 Valence Bond (VB) Theory and
Orbital Hybridization 443
The Central Themes of VB Theory 443
Types of Hybrid Orbitals 444
11.2 Modes of Orbital Overlap and the
Types of Covalent Bonds 452
Orbital Overlap in Single and Multiple
Bonds 452
Orbital Overlap and Rotation Within
a Molecule 455
11.3 Molecular Orbital (MO) Theory and CHAPTER REVIEW GUIDE 464
Electron Delocalization 455 PROBLEMS 466
The Central Themes of MO Theory 456
Homonuclear Diatomic Molecules of
Period 2 Elements 458
Two Heteronuclear Diatomic Molecules:
HF and NO 462
Two Polyatomic Molecules: Benzene and
Ozone 463

Chapter 12 Intermolecular Forces: Liquids, Solids, and Phase Changes 470

12.1 An Overview of Physical States
and Phase Changes 471
A Kinetic-Molecular View of the Three
States 472
Types of Phase Changes and Their
Enthalpies 473
12.2 Quantitative Aspects of Phase
Changes 475
Heat Involved in Phase Changes 475
The Equilibrium Nature of Phase
Changes 479
Phase Diagrams: Effect of Pressure and
Temperature on Physical State 483
12.3 Types of Intermolecular Forces 485
How Close Can Molecules Approach
Each Other? 485
Ion-Dipole Forces 486
Dipole-Dipole Forces 487
The Hydrogen Bond 487
Polarizability and Induced Dipole
Forces 489
Dispersion (London) Forces 490
12.4 Properties of the Liquid State 492
Surface Tension 492
Capillarity 493
Viscosity 494
12.5 The Uniqueness of Water 495
Solvent Properties of Water 495
Thermal Properties of Water 495
Surface Properties of Water 496
The Unusual Density of Solid Water 496
12.6 The Solid State: Structure, Properties,
and Bonding 497
Structural Features of Solids 497
TOOLS OF THE LABORATORY: X-RAY
DIFFRACTION ANALYSIS AND SCANNING
TUNNELING MICROSCOPY 504
Types and Properties of Crystalline
Solids 505
Amorphous Solids 508
Bonding in Solids: Molecular Orbital
Band Theory 509
12.7 Advanced Materials 511
Electronic Materials 511
Liquid Crystals 513
Ceramic Materials 515
Polymeric Materials 517
Nanotechnology: Designing Materials
Atom by Atom 522
CHAPTER REVIEW GUIDE 524
PROBLEMS 527

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 xii   Detailed Contents
Chapter 13 The Properties of Mixtures: Solutions and Colloids 534
13.1 Types of Solutions: Intermolecular
Forces and Solubility 535
Intermolecular Forces in Solution 536
Liquid Solutions and the Role of
Molecular Polarity 537
Gas Solutions and Solid Solutions 539
13.2 Intermolecular Forces and Biological
Macromolecules 541
The Structures of Proteins 541
Dual Polarity in Soaps, Membranes,
and Antibiotics 543
The Structure of DNA 544
13.3 Why Substances Dissolve: Breaking
Down the Solution Process 546
The Heat of Solution and Its
Components 546
Chapter 14 Periodic Patterns in the Main-Group Elements 588
14.1 Hydrogen, the Simplest Atom 589
Where Hydrogen Fits in the Periodic
Table 589
Highlights of Hydrogen Chemistry 590
14.2 Trends Across the Periodic Table:
The Period 2 Elements 591
14.3 Group 1A(1): The Alkali Metals 594
Why the Alkali Metals Are Unusual
Physically 594
Why the Alkali Metals Are
So Reactive 596
14.4 Group 2A(2): The Alkaline Earth
Metals 597
How the Alkaline Earth and Alkali Metals
Compare Physically 597
How the Alkaline Earth and Alkali Metals
Compare Chemically 597
Diagonal Relationships: Lithium and
Magnesium 599
14.5 Group 3A(13): The Boron Family 599
How the Transition Elements Influence
This Group’s Properties 599
Features That First Appear in This
Group’s Chemical Properties 601
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The Heat of Hydration: Dissolving Ionic
Solids in Water 547
The Solution Process and the Change in
Entropy 550
13.4 Solubility as an Equilibrium
Process 552
Effect of Temperature on Solubility 552
Effect of Pressure on Solubility 553
13.5 Concentration Terms 555
Molarity and Molality 555
Parts of Solute by Parts of Solution 557
Interconverting Concentration
Terms 559
13.6 Colligative Properties of Solutions 560
Nonvolatile Nonelectrolyte
Solutions 561
Highlights of Boron Chemistry 601
Diagonal Relationships: Beryllium
and Aluminum 602
14.6 Group 4A(14): The Carbon
Family 602
How Type of Bonding Affects Physical
Properties 604
How Bonding Changes in This Group’s
Compounds 605
Highlights of Carbon Chemistry 606
Highlights of Silicon Chemistry 607
Diagonal Relationships: Boron
and Silicon 608
14.7 Group 5A(15): The Nitrogen
Family 608
The Wide Range of Physical
Behavior 610
Patterns in Chemical Behavior 610
Highlights of Nitrogen Chemistry 612
Highlights of Phosphorus Chemistry 614
14.8 Group 6A(16): The Oxygen
Family 616
How the Oxygen and Nitrogen Families
Compare Physically 616
Using Colligative Properties to Find
Solute Molar Mass 566
Volatile Nonelectrolyte Solutions 567
Strong Electrolyte Solutions 567
Applications of Colligative
Properties 570
13.7 The Structure and Properties
of Colloids 571
CHEMICAL CONNECTIONS TO
ENVIRONMENTAL ENGINEERING:
SOLUTIONS AND COLLOIDS IN WATER
PURIFICATION 573
CHAPTER REVIEW GUIDE 575
PROBLEMS 579
How the Oxygen and Nitrogen Families
Compare Chemically 618
Highlights of Oxygen Chemistry:
Range of Oxide Properties 619
Highlights of Sulfur Chemistry 619
14.9 Group 7A(17): The Halogens 621
Physical Behavior of the Halogens 621
Why the Halogens Are
So Reactive 621
Highlights of Halogen Chemistry 623
14.10 Group 8A(18): The Noble
Gases 626
How the Noble Gases and Alkali
Metals Contrast Physically 626
How Noble Gases Can Form
Compounds 626
CHAPTER REVIEW GUIDE 628
PROBLEMS 629
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Chapter 15 Organic Compounds and the Atomic Properties of Carbon 636
15.1 The Special Nature of Carbon and
the Characteristics of Organic
Molecules 637
The Structural Complexity of Organic
Molecules 638
The Chemical Diversity of Organic
Molecules 638
15.2 The Structures and Classes of
Hydrocarbons 640
Carbon Skeletons and Hydrogen
Skins 640
Alkanes: Hydrocarbons with Only
Single Bonds 643
Dispersion Forces and the Physical
Properties of Alkanes 645
Constitutional Isomerism 645
Chiral Molecules and Optical
Isomerism 646
Alkenes: Hydrocarbons with Double
Bonds 648
Chapter 16 Kinetics: Rates and Mechanisms of Chemical Reactions 694
16.1 Focusing on Reaction Rate 695
16.2 Expressing the Reaction Rate 698
Average, Instantaneous, and Initial
Reaction Rates 698
Expressing Rate in Terms of Reactant
and Product Concentrations 700
16.3 The Rate Law and Its
Components 702
Some Laboratory Methods for
Determining the Initial Rate 703
Determining Reaction Orders 703
Determining the Rate Constant 708
16.4 Integrated Rate Laws: Concentration
Changes over Time 712
Integrated Rate Laws and Reaction
Half-Life for First-Order
Reactions 712
Integrated Rate Law and Reaction
Half-Life for Second-Order
Reactions 716
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Restricted Rotation and Geometric
(cis-trans) Isomerism 649
Alkynes: Hydrocarbons with Triple
Bonds 650
Aromatic Hydrocarbons: Cyclic
Molecules with Delocalized π
Electrons 651
Variations on a Theme: Catenated
Inorganic Hydrides 652
TOOLS OF THE LABORATORY:
NUCLEAR MAGNETIC RESONANCE
(NMR) SPECTROSCOPY 653
15.3 Some Important Classes of Organic
Reactions 655
Types of Organic Reactions 655
The Redox Process in Organic
Reactions 657
15.4 Properties and Reactivities of
Common Functional Groups 658
Functional Groups with Only Single
Bonds 658
Integrated Rate Law and Reaction
Half-Life for Zero-Order
Reactions 718
Determining Reaction Orders from an
Integrated Rate Law 718
16.5 Theories of Chemical Kinetics 720
Collision Theory: Basis of the
Rate Law 720
Transition State Theory: What the
Activation Energy Is Used For 722
The Effect of Temperature on Rate 724
16.6 Reaction Mechanisms: The Steps
from Reactant to Product 727
Elementary Reactions and
Molecularity 727
The Rate-Determining Step of a Reaction
Mechanism 728
Correlating the Mechanism with
the Rate Law 729
Functional Groups with Double
Bonds 663
Functional Groups with Both Single
and Double Bonds 666
Functional Groups with Triple Bonds 670
15.5 The Monomer-Polymer Theme I:
Synthetic Macromolecules 672
Addition Polymers 672
Condensation Polymers 673
15.6 The Monomer-Polymer Theme II:
Biological Macromolecules 674
Sugars and Polysaccharides 674
Amino Acids and Proteins 676
Nucleotides and Nucleic Acids 678
CHEMICAL CONNECTIONS TO
GENETICS AND FORENSICS:
DNA SEQUENCING AND
FINGERPRINTING 683
CHAPTER REVIEW GUIDE 685
PROBLEMS 687
16.7 Catalysis: Speeding Up a Reaction 733
The Basis of Catalytic Action 733
Homogeneous Catalysis 734
Heterogeneous Catalysis 735
Kinetics and Function of Biological
Catalysts 736
CHEMICAL CONNECTIONS TO
ATMOSPHERIC SCIENCE: DEPLETION
OF EARTH’S OZONE LAYER 738
CHAPTER REVIEW GUIDE 739
PROBLEMS 743
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 xiv   Detailed Contents
Chapter 17 Equilibrium: The Extent of Chemical Reactions 752
17.1 The Equilibrium State and
the Equilibrium Constant 753
17.2 The Reaction Quotient and
the Equilibrium Constant 756
The Changing Value of the Reaction
Quotient 756
Writing the Reaction Quotient in Its
Various Forms 757
17.3 Expressing Equilibria with Pressure
Terms: Relation Between Kc
and Kp 763
17.4 Comparing Q and K to Determine
Reaction Direction 764
Chapter 18 Acid-Base Equilibria 802
18.1 Release of H+ or OH− and the
Arrhenius Acid-Base Definition 804
18.2 Proton Transfer and the Brønsted-
Lowry Acid-Base Definition 805
Conjugate Acid-Base Pairs 806
Relative Acid-Base Strength and the
Net Direction of Reaction 807
18.3 Autoionization of Water and
the pH Scale 809
The Equilibrium Nature of Autoionization:
The Ion-Product Constant for
Water (Kw) 810
Expressing the Hydronium Ion
Concentration: The pH Scale 811
18.4 Strong Acids and Bases and
pH Calculations 813
Strong Acids 813
Strong Bases 814
Calculating pH for Strong Acids
and Bases 814
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17.5 How to Solve Equilibrium
Problems 767
Using Quantities to Find the Equilibrium
Constant 767
Using the Equilibrium Constant to Find
Quantities 770
Problems Involving Mixtures of Reactants
and Products 775
17.6 Reaction Conditions and Equilibrium:
Le Châtelier’s Principle 777
The Effect of a Change in
Concentration 777
The Effect of a Change in Pressure
(Volume) 780
18.5 Weak Acids and Their Equilibria
Calculations 815
The Acid Dissociation Constant (Ka) 815
Finding Ka, Given Concentrations 818
Finding Concentrations, Given Ka 819
The Effect of Concentration on the Extent
of Acid Dissociation 821
The Behavior of Polyprotic Acids 822
18.6 Molecular Properties and Acid
Strength 825
Acid Strength of Nonmetal Hydrides 825
Acid Strength of Oxoacids 825
Acidity of Hydrated Metal Ions 826
18.7 Weak Bases and Their Relation to
Weak Acids 827
Molecules as Weak Bases: Ammonia
and the Amines 828
Anions of Weak Acids as
Weak Bases 830
The Relation Between Ka and Kb of a
Conjugate Acid-Base Pair 830
The Effect of a Change in
Temperature 782
The Lack of Effect of a Catalyst 785
Applying Le Châtelier’s Principle to
the Synthesis of Ammonia 787
CHEMICAL CONNECTIONS TO
CELLULAR METABOLISM: DESIGN
AND CONTROL OF A METABOLIC
PATHWAY 788
CHAPTER REVIEW GUIDE 790
PROBLEMS 793
18.8 Acid-Base Properties of Salt
Solutions 833
Salts That Yield Neutral Solutions 833
Salts That Yield Acidic Solutions 833
Salts That Yield Basic Solutions 834
Salts of Weakly Acidic Cations and
Weakly Basic Anions 835
Salts of Amphiprotic Anions 835
18.9 Generalizing the Brønsted-Lowry
Concept: The Leveling Effect 837
18.10 Electron-Pair Donation and the
Lewis Acid-Base Definition 838
Molecules as Lewis Acids 838
Metal Cations as Lewis Acids 839
An Overview of Acid-Base
Definitions 840
CHAPTER REVIEW GUIDE 841
PROBLEMS 844
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Chapter 19 Ionic Equilibria in Aqueous Systems 852
19.1 Equilibria of Acid-Base Buffers 853
What a Buffer Is and How It Works: The
Common-Ion Effect 853
The Henderson-Hasselbalch
Equation 858
Buffer Capacity and Buffer Range 859
Preparing a Buffer 861
19.2 Acid-Base Titration Curves 863
Strong Acid–Strong Base Titration
Curves 863
Weak Acid–Strong Base
Titration Curves 866
Weak Base–Strong Acid Titration
Curves 870
Monitoring pH with Acid-Base
Indicators 872
Chapter 20 Thermodynamics: Entropy, Free Energy, and
Reaction Direction 906
20.1 The Second Law of Thermodynamics:
Predicting Spontaneous Change 907
The First Law of Thermodynamics
Does Not Predict Spontaneous
Change 908
The Sign of ΔH Does Not Predict
Spontaneous Change 908
Freedom of Particle Motion and
Dispersal of Kinetic Energy 909
Entropy and the Number of
Microstates 910
Entropy and the Second Law of
Thermodynamics 913
Standard Molar Entropies and the
Third Law 913
Predicting Relative S ° of a System 914
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Titration Curves for Polyprotic Acids 874
Amino Acids as Biological Polyprotic
Acids 875
19.3 Equilibria of Slightly Soluble Ionic
Compounds 876
The Ion-Product Expression (Qsp) and the
Solubility-Product Constant (Ksp) 876
Calculations Involving the Solubility-
Product Constant 877
Effect of a Common Ion on Solubility 880
Effect of pH on Solubility 882
Applying Ionic Equilibria to the Formation
of a Limestone Cave 883
Predicting the Formation of a
Precipitate: Qsp vs. Ksp 884
20.2 Calculating the Change in Entropy of
a Reaction 918
Entropy Changes in the System: Standard
Entropy of Reaction (ΔS°rxn) 918
Entropy Changes in the Surroundings:
The Other Part of the Total 920
The Entropy Change and the Equilibrium
State 922
Spontaneous Exothermic and
Endothermic Changes 923
20.3 Entropy, Free Energy, and Work 924
Free Energy Change and Reaction
Spontaneity 924
Calculating Standard Free Energy
Changes 925
Separating Ions by Selective
Precipitation and Simultaneous
Equilibria 886
CHEMICAL CONNECTIONS TO
ENVIRONMENTAL SCIENCE:
THE ACID-RAIN PROBLEM 888
19.4 Equilibria Involving Complex Ions 890
Formation of Complex Ions 890
Complex Ions and the Solubility
of Precipitates 891
Complex Ions of Amphoteric
Hydroxides 893
CHAPTER REVIEW GUIDE 895
PROBLEMS 899
The Free Energy Change and the Work a
System Can Do 927
The Effect of Temperature on Reaction
Spontaneity 928
Coupling of Reactions to Drive a
Nonspontaneous Change 932
CHEMICAL CONNECTIONS TO
BIOLOGICAL ENERGETICS:
THE UNIVERSAL ROLE OF ATP 933
20.4 Free Energy, Equilibrium, and
Reaction Direction 934
CHAPTER REVIEW GUIDE 940
PROBLEMS 943
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 xvi   Detailed Contents
Chapter 21 Electrochemistry: Chemical Change and Electrical Work 950
21.1 Redox Reactions and Electrochemical
Cells 951
A Quick Review of Oxidation-Reduction
Concepts 951
Half-Reaction Method for Balancing
Redox Reactions 952
An Overview of Electrochemical
Cells 955
21.2 Voltaic Cells: Using Spontaneous
Reactions to Generate Electrical
Energy 957
Construction and Operation of a
Voltaic Cell 957
Notation for a Voltaic Cell 960
Why Does a Voltaic Cell Work? 961
21.3 Cell Potential: Output of a Voltaic
Cell 962
Standard Cell Potential (E°cell) 962
Relative Strengths of Oxidizing and
Reducing Agents 965
Chapter 22 The Elements in Nature and Industry 1008
22.1 How the Elements Occur in
Nature 1009
Earth’s Structure and the Abundance of
the Elements 1009
Sources of the Elements 1013
22.2 The Cycling of Elements Through
the Environment 1014
The Carbon Cycle 1014
The Nitrogen Cycle 1016
The Phosphorus Cycle 1017
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Using E°half-cell Values to Write
Spontaneous Redox Reactions 967
Explaining the Activity Series of
the Metals 970
21.4 Free Energy and Electrical Work 971
Standard Cell Potential and the
Equilibrium Constant 971
The Effect of Concentration on Cell
Potential 974
Following Changes in Potential During
Cell Operation 975
Concentration Cells 976
21.5 Electrochemical Processes
in Batteries 980
Primary (Nonrechargeable) Batteries 980
Secondary (Rechargeable) Batteries 981
Fuel Cells 982
21.6 Corrosion: An Environmental
Voltaic Cell 984
The Corrosion of Iron 984
Protecting Against the Corrosion
of Iron 985
22.3 Metallurgy: Extracting a Metal
from Its Ore 1020
Pretreating the Ore 1021
Converting Mineral to Element 1022
Refining and Alloying the Element 1024
22.4 Tapping the Crust: Isolation and Uses
of Selected Elements 1026
Producing the Alkali Metals: Sodium
and Potassium 1026
The Indispensable Three: Iron, Copper,
and Aluminum 1027
21.7 Electrolytic Cells: Using Electrical
Energy to Drive Nonspontaneous
Reactions 986
Construction and Operation of an
Electrolytic Cell 986
Predicting the Products of
Electrolysis 988
Stoichiometry of Electrolysis: The
Relation Between Amounts of
Charge and Products 992
CHEMICAL CONNECTIONS TO
BIOLOGICAL ENERGETICS: CELLULAR
ELECTROCHEMISTRY AND THE
PRODUCTION OF ATP 994
CHAPTER REVIEW GUIDE 996
PROBLEMS 999
Mining the Sea for Magnesium 1033
The Sources and Uses of
Hydrogen 1034
22.5 Chemical Manufacturing: Two Case
Studies 1037
Sulfuric Acid, the Most Important
Chemical 1037
The Chlor-Alkali Process 1040
CHAPTER REVIEW GUIDE 1041
PROBLEMS 1042
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Chapter 23 Transition Elements and Their Coordination Compounds 1048
23.1 Properties of the Transition
Elements 1049
Electron Configurations of the Transition
Metals and Their Ions 1050
Atomic and Physical Properties of
the Transition Elements 1052
Chemical Properties of the Transition
Elements 1054
23.2 The Inner Transition Elements 1056
The Lanthanides 1056
The Actinides 1057
Chapter 24 Nuclear Reactions and Their Applications 1086
24.1 Radioactive Decay and Nuclear
Stability 1087
Comparing Chemical and Nuclear
Change 1088
The Components of the Nucleus:
Terms and Notation 1088
The Discovery of Radioactivity and
the Types of Emissions 1089
Modes of Radioactive Decay; Balancing
Nuclear Equations 1089
Nuclear Stability and the Mode
of Decay 1093
24.2 The Kinetics of Radioactive
Decay 1097
Detection and Measurement of
Radioactivity 1097
The Rate of Radioactive Decay 1098
Radioisotopic Dating 1102
Appendix A Common Mathematical
Operations in Chemistry A-1
Appendix B Standard Thermodynamic Values
for Selected Substances A-5
Appendix C Equilibrium Constants for
Selected Substances A-8
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1.5 • Measurement in Scientific Study    xvii
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23.3 Coordination Compounds 1058
Complex Ions: Coordination Numbers,
Geometries, and Ligands 1058
Formulas and Names of Coordination
Compounds 1060
Isomerism in Coordination
Compounds 1064
23.4 Theoretical Basis for the Bonding and
Properties of Complex Ions 1067
Applying Valence Bond Theory to
Complex Ions 1067
Crystal Field Theory 1069
24.3 Nuclear Transmutation: Induced
Changes in Nuclei 1104
Early Transmutation Experiments;
Nuclear Shorthand Notation 1104
Particle Accelerators and the
Transuranium Elements 1105
24.4 Ionization: Effects of Nuclear
Radiation on Matter 1107
Effects of Ionizing Radiation on Living
Tissue 1108
Background Sources of Ionizing
Radiation 1110
Assessing the Risk from Ionizing
Radiation 1111
24.5 Applications of Radioisotopes 1112
Radioactive Tracers 1112
Additional Applications of Ionizing
Radiation 1114
Appendix D Standard Electrode
(Half-Cell) Potentials A-14
Appendix E Answers to Selected
Problems A-15
CHEMICAL CONNECTIONS TO
NUTRITIONAL SCIENCE: TRANSITION
METALS AS ESSENTIAL DIETARY TRACE
ELEMENTS 1076
CHAPTER REVIEW GUIDE 1078
PROBLEMS 1080
24.6 The Interconversion of Mass and
Energy 1115
The Mass Difference Between a Nucleus
and Its Nucleons 1116
Nuclear Binding Energy and Binding
Energy per Nucleon 1117
24.7 Applications of Fission
and Fusion 1119
The Process of Nuclear Fission 1119
The Promise of Nuclear Fusion 1123
CHEMICAL CONNECTIONS TO
COSMOLOGY: ORIGIN OF THE
ELEMENTS IN THE STARS 1124
CHAPTER REVIEW GUIDE 1126
PROBLEMS 1129
Glossary G-1
Index I-1
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 xviii    List of Sample Problems
LIST OF SAMPLE PROBLEMS (Molecular-scene problems are shown in color.)
Chapter 1
1.1 Visualizing Change on the Atomic Scale 6
1.2 Distinguishing Between Physical and Chemical Change 7
1.3 Converting Units of Length 18
1.4 Converting Units of Volume 19
1.5 Converting Units of Mass 20
1.6 Converting Units Raised to a Power 21
1.7 Calculating Density from Mass and Volume 22
1.8 Converting Units of Temperature 25
1.9 Determining the Number of Significant Figures 27
1.10 Significant Figures and Rounding 30
Chapter 2
2.1 Distinguishing Elements, Compounds, and Mixtures
at the Atomic Scale 43
2.2 Calculating the Mass of an Element in a Compound 46
2.3 Visualizing the Mass Laws 49
2.4 Determining the Numbers of Subatomic Particles in the
Isotopes of an Element 55
2.5 Calculating the Atomic Mass of an Element 57
2.6 Identifying an Element from Its Z Value 61
2.7 Predicting the Ion an Element Forms 63
2.8 Naming Binary Ionic Compounds 67
2.9 Determining Formulas of Binary Ionic Compounds 67
2.10 Determining Names and Formulas of Ionic Compounds of
Metals That Form More Than One Ion 69
2.11 Determining Names and Formulas of Ionic Compounds
Containing Polyatomic Ions (Including Hydrates) 70
2.12 Recognizing Incorrect Names and Formulas of Ionic
Compounds 71
2.13 Determining Names and Formulas of Anions and Acids 72
2.14 Determining Names and Formulas of Binary Covalent
Compounds 72
2.15 Recognizing Incorrect Names and Formulas of Binary
Covalent Compounds 73
2.16 Calculating the Molecular Mass of a Compound 75
2.17 Using Molecular Depictions to Determine Formula, Name,
and Mass 75
Chapter 3
3.1 Converting Between Mass and Amount of an Element 96
3.2 Converting Between Number of Entities and Amount
of an Element 97
3.3 Converting Between Number of Entities and Mass
of an Element 97
3.4 Converting Between Number of Entities and Mass
of a Compound 98
3.5 Calculating the Mass Percent of Each Element in a
Compound from the Formula 100
3.6 Calculating the Mass of an Element in a Compound 101
3.7 Determining an Empirical Formula from Masses of
Elements 102
3.8 Determining a Molecular Formula from Elemental Analysis
and Molar Mass 104
3.9 Determining a Molecular Formula from Combustion
Analysis 105
3.10 Balancing a Chemical Equation 111
3.11 Writing a Balanced Equation from a Molecular
Scene 112
3.12 Calculating Quantities of Reactants and Products: Amount
(mol) to Amount (mol) and to Mass (g) 115
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3.13 Calculating Quantities of Reactants and Products:
Mass to Mass 116
3.14 Writing an Overall Equation for a Reaction Sequence 117
3.15 Using Molecular Depictions in a Limiting-Reactant
Problem 120
3.16 Calculating Quantities in a Limiting-Reactant Problem:
Amount to Amount 121
3.17 Calculating Quantities in a Limiting-Reactant Problem:
Mass to Mass 122
3.18 Calculating Percent Yield 125
Chapter 4
4.1 Using Molecular Scenes to Depict an Ionic Compound
in Aqueous Solution 146
4.2 Determining Amount (mol) of Ions in Solution 147
4.3 Calculating the Molarity of a Solution 148
4.4 Calculating Mass of Solute in a Given Volume of Solution 149
4.5 Determining Amount (mol) of Ions in a Solution 150
4.6 Preparing a Dilute Solution from a Concentrated Solution 151
4.7 Visualizing Changes in Concentration 152
4.8 Predicting Whether a Precipitation Reaction Occurs;
Writing Ionic Equations 157
4.9 Using Molecular Depictions in Precipitation Reactions 158
4.10 Calculating Amounts of Reactants and Products in a
Precipitation Reaction 160
4.11 Solving a Limiting-Reactant Problem for a Precipitation
Reaction 161
4.12 Determining the Number of H+ (or OH−) Ions in Solution 164
4.13 Writing Ionic Equations and Proton-Transfer Equations
for Acid-Base Reactions 168
4.14 Calculating the Amounts of Reactants and Products in an
Acid-Base Reaction 169
4.15 Finding the Concentration of an Acid from a Titration 171
4.16 Determining the Oxidation Number of Each Element
in a Compound (or Ion) 174
4.17 Identifying Redox Reactions and Oxidizing and Reducing
Agents 175
4.18 Finding the Amount of Reducing Agent by Titration 177
4.19 Identifying the Type of Redox Reaction 185
Chapter 5
5.1 Converting Units of Pressure 208
5.2 Applying the Volume-Pressure Relationship 215
5.3 Applying the Volume-Temperature and Pressure-
Temperature Relationships 216
5.4 Applying the Volume-Amount and Pressure-Amount
Relationships 216
5.5 Applying the Volume-Pressure-Temperature
Relationship 217
5.6 Solving for an Unknown Gas Variable at Fixed
Conditions 218
5.7 Using Gas Laws to Determine a Balanced Equation 219
5.8 Calculating Gas Density 221
5.9 Finding the Molar Mass of a Volatile Liquid 223
5.10 Applying Dalton’s Law of Partial Pressures 224
5.11 Calculating the Amount of Gas Collected over Water 226
5.12 Using Gas Variables to Find Amounts of Reactants
or Products I 227
5.13 Using Gas Variables to Find Amounts of Reactants
or Products II 228
5.14 Applying Graham’s Law of Effusion 234
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Chapter 6
6.1 Determining the Change in Internal Energy of a System 260
6.2 Calculating Pressure-Volume Work Done by or on a
System 262
6.3 Drawing Enthalpy Diagrams and Determining the Sign
of ΔH 265
6.4 Relating Quantity of Heat and Temperature Change 267
6.5 Determining the Specific Heat Capacity of a Solid 268
6.6 Determining the Enthalpy Change of an Aqueous
Reaction 269
6.7 Calculating the Heat of a Combustion Reaction 271
6.8 Using the Enthalpy Change of a Reaction (ΔH ) to Find the
Amount of a Substance 273
6.9 Using Hess’s Law to Calculate an Unknown ΔH 275
6.10 Writing Formation Equations 277
6.11 Calculating ΔH°rxn from ΔH°f Values 279
Chapter 7
7.1 Interconverting Wavelength and Frequency 297
7.2 Interconverting Energy, Wavelength, and Frequency 301
7.3 Determining ΔE and λ of an Electron Transition 307
7.4 Calculating the de Broglie Wavelength of an Electron 311
7.5 Applying the Uncertainty Principle 313
7.6 Determining Quantum Numbers for an Energy Level 317
7.7 Determining Sublevel Names and Orbital Quantum
Numbers 318
7.8 Identifying Incorrect Quantum Numbers 318
Chapter 8
8.1 Determining Electron Configurations 343
8.2 Ranking Elements by Atomic Size 346
8.3 Ranking Elements by First Ionization Energy 349
8.4 Identifying an Element from Its Ionization Energies 351
8.5 Writing Electron Configurations of Main-Group Ions 355
8.6 Writing Electron Configurations and Predicting Magnetic
Behavior of Transition Metal Ions 358
8.7 Ranking Ions by Size 360
Chapter 9
9.1 Depicting Ion Formation 373
9.2 Predicting Relative Lattice Energy from Ionic Properties 377
9.3 Comparing Bond Length and Bond Strength 382
9.4 Using Bond Energies to Calculate ΔH°rxn 388
9.5 Determining Bond Polarity from EN Values 393
Chapter 10
10.1 Writing Lewis Structures for Species with Single Bonds and
One Central Atom 407
10.2 Writing Lewis Structures for Molecules with Single Bonds and
More Than One Central Atom 408
10.3 Writing Lewis Structures for Molecules with Multiple
Bonds 409
10.4 Writing Resonance Structures and Assigning Formal
Charges 413
10.5 Writing Lewis Structures for Octet-Rule Exceptions 417
10.6 Examining Shapes with Two, Three, or Four Electron
Groups 426
10.7 Examining Shapes with Five or Six Electron Groups 427
10.8 Predicting Molecular Shapes with More Than One Central
Atom 428
10.9 Predicting the Polarity of Molecules 430
Chapter 11
11.1 Postulating Hybrid Orbitals in a Molecule 450
11.2 Describing the Types of Orbitals and Bonds in Molecules 454
siL40215_fm_i-xxxv.indd 19
List of Sample Problems    xix
11.3 Predicting Stability of Species Using MO Diagrams 458
11.4 Using MO Theory to Explain Bond Properties 461
Chapter 12
12.1 Finding the Heat of a Phase Change Depicted
by Molecular Scenes 477
12.2 Applying the Clausius-Clapeyron Equation 481
12.3 Using a Phase Diagram to Predict Phase Changes 484
12.4 Drawing Hydrogen Bonds Between Molecules
of a Substance 488
12.5 Identifying the Types of Intermolecular Forces 491
12.6 Determining the Number of Particles per Unit Cell and the
Coordination Number 499
12.7 Determining Atomic Radius 502
12.8 Determining Atomic Radius from the Unit Cell 503
Chapter 13
13.1 Predicting Relative Solubilities 539
13.2 Calculating an Aqueous Ionic Heat of Solution 549
13.3 Using Henry’s Law to Calculate Gas Solubility 554
13.4 Calculating Molality 556
13.5 Expressing Concentrations in Parts by Mass, Parts by
Volume, and Mole Fraction 558
13.6 Interconverting Concentration Terms 559
13.7 Using Raoult’s Law to Find ΔP 561
13.8 Determining Boiling and Freezing Points of
a Solution 564
13.9 Determining Molar Mass from Colligative Properties 566
13.10 Depicting Strong Electrolyte Solutions 568
Chapter 15
15.1 Drawing Hydrocarbons 641
15.2 Naming Hydrocarbons and Understanding Chirality and
Geometric Isomerism 650
15.3 Recognizing the Type of Organic Reaction 656
15.4 Predicting the Reactions of Alcohols, Alkyl Halides, and
Amines 662
15.5 Predicting the Steps in a Reaction Sequence 665
15.6 Predicting Reactions of the Carboxylic Acid Family 669
15.7 Recognizing Functional Groups 671
Chapter 16
16.1 Expressing Rate in Terms of Changes in Concentration
with Time 701
16.2 Determining Reaction Orders from Rate Laws 705
16.3 Determining Reaction Orders and Rate Constants from
Rate Data 709
16.4 Determining Reaction Orders from Molecular Scenes 710
16.5 Determining the Reactant Concentration After a Given Time
in a First-Order Reaction 712
16.6 Using Molecular Scenes to Find Quantities at Various
Times 714
16.7 Determining the Half-Life of a First-Order Reaction 715
16.8 Determining Reactant Concentration and Half-Life for
Second-Order Reactions 717
16.9 Drawing Reaction Energy Diagrams and Transition States 724
16.10 Determining the Energy of Activation 726
16.11 Determining Molecularities and Rate Laws for Elementary
Steps 728
16.12 Identifying Intermediates and Correlating Rate Laws and
Reaction Mechanisms 731
Chapter 17
17.1 Writing the Reaction Quotient from the Balanced
Equation 759
10/11/19 1:04 PM
 xx    List of Sample Problems
17.2 Finding K for Reactions Multiplied by a Common Factor,
Reversed, or Written as an Overall Process 761
17.3 Converting Between Kc and Kp 764
17.4 Using Molecular Scenes to Determine Reaction
Direction 765
17.5 Using Concentrations to Determine Reaction Direction 766
17.6 Calculating Kc from Concentration Data 769
17.7 Determining Equilibrium Concentrations from Kc 770
17.8 Determining Equilibrium Concentrations from Initial
Concentrations and Kc 770
17.9 Making a Simplifying Assumption to Calculate Equilibrium
Concentrations 773
17.10 Predicting Reaction Direction and Calculating Equilibrium
Concentrations 775
17.11 Predicting the Effect of a Change in Concentration
on the Equilibrium Position 779
17.12 Predicting the Effect of a Change in Volume (Pressure)
on the Equilibrium Position 781
17.13 Predicting the Effect of a Change in Temperature
on the Equilibrium Position 783
17.14 Calculating the Change in Kc with a Change in
Temperature 784
17.15 Determining Equilibrium Parameters from Molecular
Scenes 785
Chapter 18
18.1 Identifying Conjugate Acid-Base Pairs 806
18.2 Predicting the Net Direction of an Acid-Base Reaction 807
18.3 Using Molecular Scenes to Predict the Net Direction
of an Acid-Base Reaction 809
18.4 Calculating [H3O+] or [OH−] in Aqueous Solution 811
18.5 Calculating [H3O+], pH, [OH−], and pOH for Strong Acids
and Bases 814
18.6 Finding Ka of a Weak Acid from the Solution pH 818
18.7 Determining Concentration and pH from Ka and
Initial [HA] 820
18.8 Finding the Percent Dissociation of a Weak Acid 821
18.9 Calculating Equilibrium Concentrations for a
Polyprotic Acid 823
18.10 Determining pH from Kb and Initial [B] 829
18.11 Determining the pH of a Solution of A− 831
18.12 Predicting Relative Acidity of Salt Solutions from Reactions
of the Ions with Water 834
18.13 Predicting the Relative Acidity of a Salt Solution from
Ka and Kb of the Ions 835
18.14 Identifying Lewis Acids and Bases 840
Chapter 19
19.1 Calculating the Effect of Added H3O+ or OH− on
Buffer pH 856
19.2 Using Molecular Scenes to Examine Buffers 860
19.3 Preparing a Buffer 862
19.4 Finding the pH During a Weak Acid–Strong Base
Titration 868
19.5 Writing Ion-Product Expressions 877
19.6 Determining Ksp from Solubility 878
19.7 Determining Solubility from Ksp 879
19.8 Calculating the Effect of a Common Ion on Solubility 881
19.9 Predicting the Effect on Solubility of Adding Strong Acid 883
19.10 Predicting Whether a Precipitate Will Form 884
19.11 Using Molecular Scenes to Predict Whether a Precipitate
Will Form 885
siL40215_fm_i-xxxv.indd 20
19.12 Separating Ions by Selective Precipitation 887
19.13 Calculating the Concentration of a Complex Ion 891
19.14 Calculating the Effect of Complex-Ion Formation
on Solubility 892
Chapter 20
20.1 Predicting Relative Entropy Values 917
20.2 Calculating the Standard Entropy of Reaction,
ΔS°rxn 919
20.3 Determining Reaction Spontaneity 921
20.4 Calculating ΔG°rxn from Enthalpy and Entropy Values 925
20.5 Calculating ΔG°rxn from ΔG°f Values 926
20.6 Using Molecular Scenes to Determine the Signs of ΔH, ΔS,
and ΔG 929
20.7 Determining the Effect of Temperature on ΔG 930
20.8 Finding the Temperature at Which a Reaction Becomes
Spontaneous 931
20.9 Exploring the Relationship Between ΔG° and K 935
20.10 Using Molecular Scenes to Find ΔG for a Reaction
at Nonstandard Conditions 936
20.11 Calculating ΔG at Nonstandard Conditions 938
Chapter 21
21.1 Balancing a Redox Reaction in Basic Solution 954
21.2 Describing a Voltaic Cell with a Diagram and
Notation 960
21.3 Using E°half-cell Values to Find E°cell 963
21.4 Calculating an Unknown E°half-cell from E°cell 965
21.5 Writing Spontaneous Redox Reactions and Ranking
Oxidizing and Reducing Agents by Strength 968
21.6 Calculating K and ΔG° from E°cell 973
21.7 Using the Nernst Equation to Calculate Ecell 974
21.8 Calculating the Potential of a Concentration Cell 978
21.9 Predicting the Electrolysis Products of a Molten Salt
Mixture 989
21.10 Predicting the Electrolysis Products of Aqueous Salt
Solutions 991
21.11 Applying the Relationship Among Current, Time,
and Amount of Substance 993
Chapter 23
23.1 Writing Electron Configurations of Transition Metal
Atoms and Ions 1052
23.2 Finding the Number of Unpaired Electrons 1057
23.3 Finding the Coordination Number and Charge of the Central
Metal Ion in a Coordination Compound 1061
23.4 Writing Names and Formulas of Coordination
Compounds 1063
23.5 Determining the Type of Stereoisomerism 1067
23.6 Ranking Crystal Field Splitting Energies (Δ) for Complex Ions
of a Metal 1073
23.7 Identifying High-Spin and Low-Spin Complex Ions 1074
Chapter 24
24.1 Writing Equations for Nuclear Reactions 1092
24.2 Predicting Nuclear Stability 1094
24.3 Predicting the Mode of Nuclear Decay 1096
24.4 Calculating the Specific Activity and the Decay Constant of a
Radioactive Nuclide 1099
24.5 Finding the Number of Radioactive Nuclei 1101
24.6 Applying Radiocarbon Dating 1103
24.7 Writing Equations for Transmutation Reactions 1107
24.8 Calculating the Binding Energy per Nucleon 1117
10/11/19 1:04 PM

Courtesy of Ruth Melnick
Courtesy of Ralph L. Amateis
siL40215_fm_i-xxxv.indd 21
ABOUT THE AUTHORS
Martin S. Silberberg received a B.S. in Chemistry from the City University of
New York and a Ph.D. in Chemistry from the University of Oklahoma. He then accepted
a position as research associate in analytical biochemistry at the Albert Einstein College
of Medicine in New York City, where he developed methods to study neurotransmitter
metabolism in Parkinson’s disease and other neurological disorders. Following six years
in neurochemical research, Dr. Silberberg joined the faculty of Bard College at Simon’s
Rock, a liberal arts college known for its excellence in teaching small classes of highly
motivated students. As head of the Natural Sciences Major and Director of Premedical
Studies, he taught courses in general chemistry, organic chemistry, biochemistry, and
liberal-arts chemistry. The small class size and close student contact afforded him
insights into how students learn chemistry, where they have difficulties, and what
strategies can help them succeed. Dr. Silberberg decided to apply these insights in a
broader context and established a textbook writing, editing, and consulting company.
Before writing his own texts, he worked as a consulting and development editor on
chemistry, biochemistry, and physics texts for several major college publishers. He
resides with his wife, Ruth, in the Pioneer Valley near Amherst, Massachusetts, where
he enjoys the rich cultural and academic life of the area and relaxes by traveling,
­gardening, and singing.
Patricia G. Amateis graduated with a B.S. in Chemistry Education from Concord
University in West Virginia and a Ph.D. in Analytical Chemistry from Virginia Tech.
She has been on the faculty of the Chemistry Department at Virginia Tech for 34 years,
teaching General Chemistry and Analytical Chemistry and serving as the Director of
General Chemistry and as the Director of Undergraduate Programs. She has taught
thousands of students during her career and has been awarded the University Sporn
Award for Introductory Teaching, the Alumni Teaching Award, the Jimmy W. Viers
Teaching Award, and the William E. Wine Award for a history of university teaching
excellence. She and her husband live in Blacksburg, Virginia, and are the parents of
three adult children. In her free time, she enjoys biking, hiking, competing in the occa-
sional sprint triathlon, and playing the double second in Panjammers, Blacksburg’s steel
drum band.
xxi
10/11/19 1:04 PM
 PREFACE
C hemistry is so crucial to an understanding of medicine and biology, environmental science,
and many areas of engineering and industrial processing that it has become a requirement
for an increasing number of academic majors. Furthermore, chemical principles lie at the core of
some of the key societal issues we face in the 21st century—dealing with climate change, finding
new energy options, and supplying nutrition and curing disease on an ever more populated planet.

SETTING THE STANDARD FOR A CHEMISTRY TEXT

The ninth edition of Chemistry: The Molecular Nature of Matter and Change maintains its
standard-setting position among general chemistry textbooks by evolving further to meet the
needs of professor and student. The text still contains the most accurate molecular illustrations,
consistent step-by-step worked problems, and an extensive collection of end-of-chapter problems.
And changes throughout this edition make the text more readable and succinct, the artwork more
teachable and modern, and the design more focused and inviting. The three hallmarks that have
made this text a market leader are now demonstrated in its pages more clearly than ever.

Visualizing Chemical Models—Macroscopic to Molecular

Chemistry deals with observable changes caused by unobservable atomic-scale events,
requiring an appreciation of a size gap of mind-boggling proportions. One of the text’s
goals coincides with that of so many instructors: to help students visualize chemical events
on the molecular scale. Thus, concepts are explained first at the macroscopic level and then
from a molecular point of view, with pedagogic illustrations always placed next to the
discussions to bring the point home for today’s visually oriented students.

MACROSCOPIC
VIEW

ATOMIC-SCALE
VIEW

Mg2+ 2–
O
Mg Mg O2–
Mg2+
O2

BALANCED
EQUATION
2Mg(s) + O2(g) 2MgO(s)

Charles D. Winters/McGraw-Hill Education

xxii

siL40215_fm_i-xxxv.indd 22 10/11/19 1:04 PM

 216 Chapter 5 • Gases and the Kinetic-Molecular Theory

as long as the same unit is used for both V1 and V2. We used L, but we could have used
cm3 instead; however, both L and cm3 cannot be used. Preface    xxiii
FOLLOW-UP PROBLEMS
5.2A A tank contains 651 L of compressed oxygen gas at a pressure of 122 atm. Assuming
the temperature remains constant, what is the volume of the oxygen (in L) at 745 mmHg?
5.2B A sample of argon gas occupies 105 mL at 0.871 atm. If the volume of the gas is
increased to 352 mL at constant temperature, what is the final pressure of the gas (in kPa)?
SOME SIMILAR PROBLEMS 5.24 and 5.25

Thinking Logically SAMPLE PROBLEM 5.3

Applying the Volume-Temperature and Pressure-

to Solve Problems Temperature Relationships

Problem A balloon is filled with 1.95 L of air at 25°C and then placed in a car sitting in

The problem-solving approach, based on the Road Map

the sun. What is the volume of the balloon when the temperature in the car reaches 90°C?
Plan We know the initial volume (V1) and the initial (T1) and final (T2) temperatures of
four-step method widely accepted by experts in T1 and T2 (°C)
the gas; we must find the final volume (V2). The pressure of the gas is fixed, since the
balloon is subjected to atmospheric pressure, and n is fixed, since air cannot escape or
chemical education, is introduced in Chapter 1 °C + 273.15 = K
enter the balloon. We convert both T values to kelvins, rearrange the ideal gas law, and
solve for V2 (see the road map).
and employed consistently throughout the text. It Solution Summarizing the gas variables:
V1 = 1.95 L V2 = unknown
encourages students to plan a logical approach V1 (L) T1 and T2 (K)
T1 = 25°C (convert to K) T2 = 90°C (convert to K)
P and n remain constant
to a problem, and only then proceed to solve it. multiply by
T2 /T1 Converting T from °C to K:
Each sample problem includes a check, which V2 (L)
T1 (K) = 25°C + 273.15 = 298 K T2 (K) = 90°C + 273.15 = 363 K

fosters the habit of “thinking through” both the Rearranging the ideal gas law and solving for V2: at fixed n and P, we have
P 1 V 1 P 2V 2 V1 V2
chemical and the quantitative reasonableness n1T1
=
n2T2
or =
T1 T2

of the answer. Finally, for practice and 2.3 • Dalton’s Atomic Theory V = V49× T2 = 1.95 L × 363 K = 2.38 L
2 1
T1 298 K
reinforcement, each sample
The simplest arrangement problem
consistent with theismassfollowed
data for carbon oxides I and Check Let’s predict the change to check the math: because T2 > T1, we expect V2 > V1.
Thus, the temperature ratio should be greater than 1 (T2 in the numerator). The T ratio
immediately
II in our earlier by twoissimilar
example follow-up
that one atom problems.
of oxygen combines with one atom of carbon is about 1.2 (363/298), so the V ratio should also be about 1.2 (2.4/2.0 ≈ 1.2).
in compound I (carbon monoxide) and that two atoms of oxygen combine with one
And Chemistry marries problem solving to
FOLLOW-UP PROBLEMS
atom of carbon in compound II (carbon dioxide): 5.3A A steel tank used for fuel delivery is fitted with a safety valve that opens if the
visualizing models with molecular-scene internal pressure exceeds 1.00×103 torr. The tank is filled with methane at 23°C and
0.991 atm and placed in boiling water at 100.°C. What is the pressure in the heated
problems, which appearC notOonly in O
homework
C O
tank? Will the safety valve open?
5.3B A sample of nitrogen occupies a volume of 32.5 L at 40°C. Assuming that the
sets, as in other texts, but also in the running pressure remains constant, what temperature (in °C) will result in a decrease in the
sample’s volume to 28.6 L?
text, where they are (carbon worked out stepwise.
Carbon oxide I
monoxide)
Carbon oxide II
(carbon dioxide)
SOME SIMILAR PROBLEMS 5.26–5.29

Let’s work through a sample problem that reviews the mass laws.
SAMPLE PROBLEM 5.4
Applying the Volume-Amount and Pressure-
Amount Relationships
SAMPLE PROBLEM 2.3 Visualizing the Mass Laws Problem A scale model of a blimp rises when it is filled with helium to a volume of
55.0 dm3. When 1.10 mol of He is added to the blimp, the volume is 26.2 dm3. How
many more grams of He must be added to make it rise? Assume constant T and P.
Problem The scenes below represent an atomic-scale view of a chemical reaction: Plan We are given the initial amount of helium (n1), the initial volume of the blimp
(V1), and the volume needed for it to rise (V2), and we need the additional mass of
helium to make it rise. So, we first need to find n2. We rearrange the ideal gas law to
the appropriate form, solve for n2, subtract n1 to find the additional amount (nadd’l), and
then convert moles to grams (see the road map).

siL40215_ch05_202-253.indd 216 7/19/19 9:12 PM

Which of the mass laws—mass conservation, definite composition, and/or multiple

proportions—is (are) illustrated?
Plan From the depictions, we note the numbers, colors, and combinations of atoms
(spheres) to see which mass laws pertain. If the numbers of each atom are the same before
and after the reaction, the total mass did not change (mass conservation). If a compound
forms that always has the same atom ratio, the elements are present in fixed parts by mass
(definite composition). If the same elements form different compounds and the ratio of the
atoms of one element that combine with one atom of the other element is a small whole
number, the ratio of their masses is a small whole number as well (multiple proportions).
Solution There are seven purple and nine green atoms in each circle, so mass is conserved.
The compound formed has one purple and two green atoms, so it has definite composition.
Only one compound forms, so the law of multiple proportions does not pertain.
FOLLOW-UP PROBLEMS
2.3A The following scenes represent a chemical change. Which of the mass laws is
(are) illustrated?

2.3B Which sample(s) best display(s) the fact that compounds of bromine (orange) and
fluorine (yellow) exhibit the law of multiple proportions? Explain.

A B C

SOME SIMILAR PROBLEMS 2.14 and 2.15

siL40215_ch02_040-091.indd 49 4/16/19 6:43 PM

siL40215_fm_i-xxxv.indd 23 10/11/19 1:04 PM

 xxiv   Preface

Applying Ideas to the Real World

As the most practical science, chemistry should have a textbook that highlights its countless
applications. Moreover, today’s students may enter emerging chemistry-related hybrid fields,
like biomaterials science or planetary geochemistry, and the text they use should point out
the relevance of chemical concepts to such related sciences. The Chemical Connections and
Tools of the Laboratory boxed essays (which include problems for added relevance), the
more pedagogic margin notes, and the many applications woven into the chapter content are
up-to-date, student-friendly features that are directly related to the neighboring content.

CHEMICAL CONNECTIONS TO Solutions and Colloids in

ENVIRONMENTAL ENGINEERING Water Purification

M ost water destined for human use comes from lakes, rivers,
reservoirs, or groundwater. Present in this essential resource
may be soluble toxic organic compounds and high concentrations
of NO3− and Fe3+, colloidal clay and microbes, and suspended de-
bris. Let’s see how water is treated to remove these dissolved,
dispersed, and suspended particles.
Water Treatment Plants
Treating water involves several steps (Figure B13.1):
Step 1. Screening and settling. As water enters the facility,
screens remove debris, and settling removes sand and other
particles.
Step 2. Coagulating. This step and the next two remove col-
loids. These particles have negative surfaces that repel each other.
Added aluminum sulfate [cake alum; Al2(SO4)3] or iron(III) chlo-
ride (FeCl3), which supply Al3+ or Fe3+ ions that neutralize the
charges, coagulates the particles through intermolecular forces.
Step 3. Flocculating and sedimenting. Mixing water and floc-
culating agents in large basins causes a fluffy floc to form. Added
cationic polymers form long-chain bridges between floc particles,
which grow bigger and flow into other basins, where they form a
sediment and are removed. Some plants use dissolved air flotation
(DAF) instead: bubbles forced through the water attach to the floc,
and the floating mass is skimmed.
Step 4. Filtering. Various filters remove remaining particles.
In slow sand filters, the water passes through sand and/or gravel of
increasing particle size. In rapid sand filters, the sand is back-
washed with water, and the colloidal mass is removed. Membrane
filters (not shown) with pore sizes of 0.1–10 μm are thin tubes
bundled together inside a vessel. The water is forced into these
tubes, and the colloid-free filtrate is collected from a large, central
tube. Filtration is very effective at removing microorganisms re-
sistant to disinfectants.
TOOLS OF THE
LABORATORY
Figure B13.1 The typical steps in municipal water treatment.
I n addition to mass spectrometry (Chapter 2) and infrared (IR)
spectroscopy (Chapter 9), one of the most useful tools for ana-
Step 5. Disinfecting. Water sources often contain harmful mi-
croorganisms that are killed by one of three agents:
∙ Chlorine, as aqueous bleach (ClO−) or Cl2, is most common, Ca2+ Na+
+ Ca2+
– Na+
Ca2+
–
– Ca2+
–
Na+
but carcinogenic chlorinated organic compounds can form. Ca2+ –
Na+ – – –
∙ UV light emitted by high-intensity fluorescent tubes disinfects Na+
Na+ Na+ – Na+
by disrupting microorganisms’ DNA. Na+ Ca2+ Ca2+
– –
∙ Ozone (O3) gas is a powerful oxidizing agent. Na +
–
Sodium fluoride (NaF) to prevent tooth decay and phosphate salts Resin bead
to prevent leaching of lead from pipes may then be added. with negative groups
Step 6 (not shown). Adsorbing onto granular activated car- Figure B13.2 Ion exchange to remove hard-water cations.
bon (GAC). Petroleum and other organic contaminants are re-
moved by adsorption. GAC is a highly porous agent formed by
anionic groups, such as SO3− or COO−, and Na+ ions for
“activating” wood, coal, or coconut shells with steam: 1 kg of
charge balance (Figure B13.2). The hard-water cations displace
GAC has a surface area of 275 acres!
the Na+ ions and bind to the anionic groups. When all resin sites
are occupied, the resin is regenerated with concentrated Na+ solu-
Water Softening via Ion Exchange tion that exchanges Na+ ions for bound Ca2+ and Mg2+.
Water with large amounts of 2+ ions, such as Ca2+ and Mg2+, is
called hard water. Combined with fatty-acid anions in soap, these Membrane Processes and Reverse Osmosis
cations form solid deposits on clothes, washing machines, and Membranes with 0.0001–0.01 μm pores can remove unwanted
sinks: ions from water. Recall that solutions of different concentrations
Ca2+ (aq) + 2C17H35COONa(aq) ⟶ separated by a semipermeable membrane create osmotic pressure.
soap In reverse osmosis, a pressure greater than the osmotic pressure
(C17H35COO) 2Ca(s) + 2Na+ (aq) is applied to the more concentrated solution to force water back
insoluble deposit through the membrane and filter out ions. In homes, toxic heavy-
metal ions, such as Pb2+, Cd2+, and Hg2+, are removed this way.
When a large amount of HCO3− is present, the cations form scale,
On a large scale, reverse osmosis is used for desalination, which
a carbonate deposit in boilers and hot-water pipes that interferes
can convert seawater (40,000 ppm of ions) to drinking water
with the transfer of heat:
(400 ppm) (Figure B13.3). There are over 18,000 desalination
Ca2+ (aq) + 2HCO−3 (aq) ⟶ CaCO3 (s) + CO2 (g) + H2O(l) plants worldwide, providing water for 300 million people.
Removing hard-water cations, called water softening, is done by
exchanging Na+ ions for Ca2+ and Mg2+ ions. A home system
for ion exchange contains an insoluble polymer resin with bonded
Nuclear Magnetic Resonance (continued)
(NMR) Spectroscopy
(antiparallel)
Wastewater Treatment
Wastewater, used domestic or industrial water, is treated in
several ways before being returned to a natural source:
∙ In primary treatment, the water enters a settling basin to re-
move particles.
∙ In biological treatment, bacteria metabolize organic com-
pounds and are then removed by settling.
∙ In advanced treatment, a process is tailored to remove a spe-
cific pollutant. For example, ammonia, which causes excessive
growth of plants and algae, is removed in two steps:
1. Nitrification. Certain bacteria oxidize ammonia (electron
donor) with O2 (electron acceptor) to form nitrate ion:
NH 4+ + 2O2 ⟶ NO −3 + 2H + + H2O
410 Other bacteria
Chapter 10 an
• The Shapes of Molecules
2. Denitrification. oxidize added compound,
like methanol (CH3OH), using the NO3−:
5CH3OH + 6NO 3− ⟶ 3N2 + 5CO2 + 7H2O + 6OH − FOLLOW-UP PROBLEMS
Thus, the process converts NH3 in wastewater to N2, which is 10.3A Write Lewis structures for (a) CO (the only comm
released to the atmosphere.
three bonds); (b) HCN; (c) CO2.
Problems 10.3B Write Lewis structures for (a) NO+; (b) H2CO; (c
B13.1 Briefly answer each of the following: SOME SIMILAR PROBLEMS 10.5(c), 10.6(b), 10.7(b), and
(a) Why is cake alum [Al2(SO4)3] added during water purification?
(b) Why is water that contains large amounts of Ca2+ and Mg2+
difficult to use for cleaning?
(c) What is the meaning of reverse in reverse osmosis?
(d) Why might a water treatment plant use ozone as a disinfectant
instead of chlorine?
(e) How does passing a saturated NaCl solution through a “spent” Resonance: Delocalized Electron-Pair B
ion-exchange resin regenerate the resin?
B13.2 Wastewater discharged into a stream by a sugar refinery We often find that, for a molecule or polyatomic ion w
contains 3.55 g of sucrose (C12H22O11) per liter. A government- bonds, we can write more than one Lewis structure. W
sponsored study is testing the feasibility of removing the sugar
by reverse osmosis. What pressure must be applied to the The Need for Resonance Structures To understand
wastewater solution at 20.°C to produce pure water?
an air pollutant at ground level but an absorber of harm
in the stratosphere. Since oxygen is in Group 6A(16)

Storage
valence e− in the molecule. Four electrons are used i
lyzing organic and biochemical structures is nuclear magnetic Magnetic
5 Disinfecting tank
A bonds, leaving 18e− − 4e− = 14e −, enough electrons to
resonance (NMR) spectroscopy, which measures the molecular
2 Coagulating
environments of certain nuclei in a molecule.Al2(SO4)3
3 Flocculating/
sedimenting
field added
Chlorine (B 0)
ΔE
Radiation (h ν) (designated A and C for clarity) an octet of electrons, b
13 19 To users
31
Like electrons, several types of nuclei,
1
such as C, F,
and polymers Cl2 Er f = ΔE Permeator octet of the central O atom (designated B). Applying Ste
P, and H, act as if they spin in either added
of two directions, each Random nuclear spins Water molecules Solute particles Pure water to collector
of which creates a tiny magnetic field. In this discussion, we are of equal energy. O O O
Valve Hollow fibers of High P B B B
focus primarily on 1H-NMR spectroscopy, which measures Aligned spins A spin “flip” results O O O O O
from absorption of a semipermeable
1 changes in the nuclei of the most common isotope of hydrogen. (parallel) A C A C A C
Screening/ photon with energy membrane
1
settling randomly, the magnetic fields of all the H nuclei in a
Oriented I II
equal to ΔE (radio-
sample of compound, when placed in a strong external mag-
Settling tanks frequency region). High P
netic field (B0), become aligned either with the external field 4 Filtering
1
B C In structure I, a lone pair on oxygen A is changed to
(parallel) or against it (antiparallel). Most nuclei adopt the par- Figure B15.1 The basis of H spin resonance.
Figure B13.3 Reverse osmosis to remove ions. A, Part of a reverse-osmosis permeator. B, Each permeator contains a bundle of hollow fibers oxygen B has a double bond to oxygen A and a single bo
allel orientation, which is slightly lower in energy. The energy
difference (ΔE) between Water intake
the two energy states (spin states) lies
of semipermeable membrane. C, Pumping seawater at high pressure removes ions, and purer water enters the fibers and is collected. the single and double bonds are reversed as a lone pai
Source: (A) Robert Essel NYC/Corbis/Getty Images
in the radio-frequency (rf) region of the electromagnetic spec- bonding pair. You can rotate I to get II, so these are
trum (Figure B15.1).
1
When an H (blue arrow) in the lower energy (parallel) spin 573 574 molecules but different Lewis structures for the same
state absorbs a photon in the radio-frequency region with an en- Comparing the bond properties in Lewis structure
ergy equal to ΔE, it “flips,” in a process called resonance, to the 500 400 300 200 100 0 Hz A Purple Mule, Not a Blue Horse
higher energy (antiparallel) spin state. The system then re-emits
of the actual bonds in the molecule results in an intere
and a Red Donkey
that energy, which is detected by the rf receiver of the 1H-NMR Absorption by Lewis structures I and II: one OO double bond w
573spectrometer. The ΔE between the two states depends on the ac-
six 1H nuclei
A mule is a genetic mix, a hybrid, of a
siL40215_ch13_534-587.indd
tual magnetic field acting on each 1H nucleus, which is affected by
6/4/19 10:37 AM
in the two
siL40215_ch13_534-587.indd 574 6/4/19 10:38 AM
one OO single bond w
horse and a donkey; it is not a horse
the tiny magnetic fields of the electrons of atoms adjacent to that O
CH3 groups
O3 molecule: two oxygen-oxygen bon
nucleus. Thus, the ΔE required for resonance of each 1H nucleus one instant and a donkey the next.
CH 3 C CH3 (128 pm) and energy
depends on its specific molecular environment—the C atoms, Similarly, the color purple is a mix of red
electronegative atoms, multiple bonds, and aromatic rings around TMS and blue, not red one instant and blue We explain this discrepancy as follows:
it. 1H nuclei in different molecular environments produce different
peaks in the 1H-NMR spectrum. the next. In the same sense, a reso- ∙ Each bond in O3 has properties between those of
1
An H-NMR spectrum, which is unique for each compound, nance hybrid is one molecular species,
is a series of peaks that represents the resonance as a function of
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0δ bond, making it something like a “one-and-a-half”
(ppm) not one resonance form this instant and
the changing magnetic field. The chemical shift of the 1H nuclei B0
another resonance form the next. The ∙ The molecule is shown more correctly as two Lew
in a given environment is where a peak appears. Chemical shifts 1 structures (or resonance forms), with a two-he
Figure B15.2 The H-NMR spectrum of acetone. problem is that we cannot depict the
are shown relative to that of an added standard, tetramethylsi-
lane [(CH3)4Si, or TMS]. TMS has 12 1H nuclei bonded to four actual species, the hybrid, accurately between them.
C atoms that are bonded to one Si atom in a tetrahedral arrange- with a single Lewis structure. ∙ Resonance structures have the same relative placem
ment, so all 12 are in identical environments and produce only
one peak. tions of bonding and lone electron pairs. You can
1
Figure B15.2 shows the 1H-NMR spectrum of acetone. The six another by moving lone pairs to bonding positions,
H nuclei of acetone have identical environments: all six are bonded
to two C atoms that are each bonded to the C atom involved in the 500 400 300 200 100 0 Hz
O O
CO bond. So one peak is produced, but at a different position from O B O O B
the TMS peak. The spectrum of dimethoxymethane in Figure B15.3 A C A
shows two peaks in addition to the TMS peak, since the H nuclei1 Absorption by six I II
1H nuclei in the
have two different evironments. The taller peak is due to the six 1H
nuclei in the two CH3 groups, and the shorter peak is due to the two CH 3 O CH 2 O CH 3
two CH3 groups ∙ Resonance structures are not real bonding depictio
(20.3 spaces)
1
H nuclei in the CH2 group. The area under each peak (given as
Absorption by two TMS Blue horse Red donkey and forth quickly from structure I to structure II. The
a number of chart-paper grid spaces) is proportional to the number
of 1H nuclei in a given environment. Note that the area ratio is
1H nuclei in the CH
2 hybrid, an average of the resonance structures. ‹
group (6.8 spaces)
20.3/6.8 ≈ 3/1, the same as the ratio of six nuclei in the CH3 groups
to two in the CH2 group. Thus, by analyzing the chemical shifts and Electron Delocalization Our need for more than one
peak areas, the chemist learns the type and number of hydrogen
atoms in the compound.
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 δ (ppm)
due to electron-pair delocalization. In a single, doubl
B0
pair is localized between the bonded atoms. In a resona
(continued) Figure B15.3 The 1H-NMR spectrum of dimethoxymethane. pairs (one bonding and one lone pair) are delocalized:
Purple mule
few adjacent atoms. (This delocalization involves just a
653
extensive than the electron delocalization in metals that

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siL40215_ch10_404-441.indd 410

siL40215_fm_i-xxxv.indd 24 10/11/19 1:05 PM

 ∙ For a metal, the total number of dots is the number of electrons an atom loses to
form a cation; for example, Mg loses two to form Mg2+.
∙ For a nonmetal, the number of unpaired dots equals either the number of electrons
an atom gains to form an anion (F gains one to form F−) or the number it shares
to form covalent bonds.
The Lewis symbol for carbon illustrates the last point. Rather than one pair of dots
and two unpaired dots, as its electron configuration seems to call for ([He] 2s22p2),
carbon has four unpaired dots because it forms four bonds. Larger nonmetals can form
as many bonds as the number of dots in their Lewis symbol (Chapter 10).
Preface    xxv
In his pioneering studies, Lewis generalized much of bonding behavior into a
relatively simple rule:
∙ Octet rule: when atoms bond, they lose, gain, or share electrons to attain a filled-
outer level of eight electrons (or two, for H and Li).
The octet rule holds for nearly all of the compounds of Period 2 elements and a large
number of others as well.

› Summary of Section 9.1

Reinforcing through Review and Practice › Nearly all naturally occurring substances consist of atoms or ions bonded to others. Chemical
bonding allows atoms to lower their energy.

A favorite feature, the section summaries that conclude › Ionic bonding occurs when metal atoms transfer electrons to nonmetal atoms, and the
resulting ions attract each other and form an ionic solid.
every section restate the major ideas concisely and › Covalent bonding is most common between nonmetal atoms and usually results in individual

immediately (rather than postponing such review until the molecules. Bonded atoms share one or more pairs of electrons that are localized between them.
› Metallic bonding occurs when many metal atoms pool their valence electrons into a
end of the chapter). delocalized electron “sea” that holds all the atoms in the sample together.
A rich catalog of study aids ends each chapter to › The Lewis electron-dot symbol of a main-group atom shows valence electrons as dots
surrounding the element symbol.
help students review the content: › The octet rule says that, when bonding, many atoms lose, gain, or share electrons to attain a
filled outer level of eight (or two) electrons.
∙ Learning Objectives, with section and/or sample prob-
lem numbers, focus on the concepts to understand and 9.2 THE IONIC BONDING MODEL
the skills to master. The central idea of the ionic bonding model is the transfer of electrons from metal atoms
∙ Key Terms, boldfaced and defined within the chapter, are listed tohere byatoms to form ions that attract each other and form a solid compound. In
nonmetal
most cases, for the main groups, the ion that forms has a filled outer level of either two
section (with page numbers), as well as being defined in the Glossary. or eight electrons (octet rule), the number in the nearest noble gas. In other words, a metal
∙ Key Equations and Relationships are highlighted and numberedwill within the of electrons needed to achieve the configuration of the noble gas
lose the number
that precedes it in the periodic table, whereas a nonmetal will gain the number of electrons
chapter and listed here with page numbers. Figure 9.5 Three ways to depict elec- needed to achieve the configuration of the noble gas at the end of its period.
The transfer of an electron from a lithium atom to a fluorine atom is depicted
∙ Brief Solutions to Follow-up Problems triple
tron transfer
–
the
in the number
formation of
of Li and
F . The electron being transferred is
worked prob-
+

in three ways in Figure 9.5. In each, Li loses its single outer electron and is left with a
lems by providing multistep calculations shownat the end of the chapter, rather
in red. 575
Chapter 13 • Chapter Review Guide

›than
Summary just numerical
of Section 13.7 answers at the back ofElectron theconfigurations
book.
› Particles in a colloid are smaller than those in a suspension and larger than those in a solution.
› Colloids are classified by the physical states of the dispersed and dispersing substances and
involve many combinations of gas, liquid, and/or solid. Li 1s22s 1 + F 1s 22s 22p5 Li + 1s 2 + F – 1s 22s 22p6
› Colloids have extremely large surface areas, scatter incoming light (Tyndall effect), and exhibit
random (Brownian) motion. Orbital diagrams
› Colloidal particles in water are stabilized by charged surfaces that keep them dispersed, but
they can be coagulated by heating or by the addition of ions.
› Solution behavior and colloid chemistry are applied to water treatment and purification. Li + F 576 Li +
Chapter 13 • The Properties of Mixtures: Solutions and Colloids
+ F–
1s 2s 2p 1s 2s 2p 1s 2s 2p 1s 2s 2p
molality (m) (556) protein (541) solute (535) unsaturated solution (552)
CHAPTER REVIEW GUIDE mole fraction (X) (557) Raoult’s law (561) solvation (547) vapor pressure lowering
mononucleotide (545) reverse osmosis (574) –solvent (535) (ΔP) (561)
Lewis electron-dot symbols Li(560)+ F + +
Li(552) F strong electrolyte (560)
nonelectrolyte saturated solution volume percent [% (v/v)] (557)
Learning Objectives Relevant section (§) and/or sample problem (SP) numbers appear in parentheses. nucleic acid (544) semipermeable membrane (565) supersaturated solution (552) wastewater (574)
osmosis (565) soap (543) suspension (571) water softening (573)
Understand These Concepts 16. The four colligative properties and their dependence on osmotic pressure (Π) (565) solubility (S) (536) Tyndall effect (572) weak electrolyte (560)
1. The quantitative meaning of solubility (§13.1) number of dissolved particles (§13.6)
2. The major types of intermolecular forces in solution and 17. Ideal solutions and the importance of Raoult’s law (§13.6) Key Equations and Relationships Page numbers appear in parentheses.
their relative strengths (§13.1) 18. How the phase diagram of a solution differs from that of the
3. How the like-dissolves-like rule depends on intermolecular pure solvent (§13.6) 13.1 Dividing the general heat of solution into component 13.8 Defining concentration in terms of mole fraction (557):
forces (§13.1) 19. Why the vapor over a solution of a volatile nonelectrolyte is enthalpies (546): Mole fraction (X)
4. Why gases have relatively low solubilities in water (§13.1) richer in the more volatile component (§13.6) ΔHsoln = ΔHsolute + ΔHsolvent + ΔHmix amount (mol) of solute
20. Why strong electrolyte solutions are not ideal and the mean- =
5. General characteristics of solutions formed by various com- 13.2 Dividing the heat of solution of an ionic compound in water amount (mol) of solute + amount (mol) of solvent
binations of gases, liquids, and solids (§13.1) ings of the van’t Hoff factor and ionic atmosphere (§13.6)
into component enthalpies (548): 13.9 Expressing the relationship between the vapor pressure of
6. How intermolecular forces stabilize the structures of pro- 21. How particle size distinguishes suspensions, colloids, and
teins, the cell membrane, and DNA (§13.2) solutionssiL40215_ch09_368-403.indd
(§13.7) 372 ΔHsoln = ΔHlattice + ΔHhydr of the ions solvent above a solution and its mole fraction in the solution 27/05/19 2:54 PM
7. The enthalpy components of a solution cycle and their effect 22. How colloidal behavior is demonstrated by the Tyndall 13.3 Relating gas solubility to its partial pressure (Henry’s (Raoult’s law) (561):
on ΔHsoln (§13.3) effect and Brownian motion (§13.7) law) (554): Psolvent = Xsolvent × P°solvent
8. The dependence of ΔHhydr on ionic charge density and the Master These Skills Sgas = kH × Pgas
13.10 Calculating the vapor pressure lowering due to solute (561):
factors that determine whether ionic solution processes are 1. Predicting relative solubilities from intermolecular forces 13.4 Defining concentration in terms of molarity (555):
exothermic or endothermic (§13.3) ΔP = Xsolute × P°solvent
(SP 13.1)
9. The meaning of entropy and how the balance between the amount (mol) of solute 13.11 Calculating the boiling point elevation of a solution (562):
2. Calculating the heat of solution for an ionic compound Molarity (M) =
change in enthalpy and the change in entropy governs the (SP 13.2) volume (L) of solution ΔTb = Kb m
solution process (§13.3) 3. Using Henry’s law to calculate the solubility of a gas (SP 13.3) 13.5 Defining concentration in terms of molality (556): 13.12 Calculating the freezing point depression of a solution (564):
10. The distinctions among saturated, unsaturated, and supersat- 4. Expressing concentration in terms of molality, parts by
urated solutions, and the equilibrium nature of a saturated amount (mol) of solute ΔTf = Kf m
mass, parts by volume, and mole fraction (SPs 13.4, 13.5) Molality (m) =
solution (§13.4) 5. Interconverting among the various terms for expressing con- mass (kg) of solvent
13.13 Calculating the osmotic pressure of a solution (565):
11. The relation between temperature and the solubility of solids centration (SP 13.6) 13.6 Defining concentration in terms of mass percent (557): nsolute
(§13.4) 6. Using Raoult’s law to calculate the vapor pressure lowering Π= RT = MRT
12. Why the solubility of gases in water decreases with a rise in of a solution (SP 13.7) mass of solute V soln
Mass percent [% (w/w)] = × 100
temperature (§13.4) 7. Determining boiling and freezing points of a solution (SP 13.8) mass of solution
13. The effect of gas pressure on solubility and its quantitative 8. Using a colligative property to calculate the molar mass of
expression as Henry’s law (§13.4) 13.7 Defining concentration in terms of volume percent (557):
a solute (SP 13.9)
14. The meaning of molarity, molality, mole fraction, and parts 9. Calculating the composition of vapor over a solution of volume of solute
Volume percent [% (v/v)] = × 100
by mass or by volume of a solution, and how to convert volatile nonelectrolyte (§13.6) volume of solution
among them (§13.5) 10. Calculating the van’t Hoff factor (i) from the magnitude of
15. The distinction between electrolytes and nonelectrolytes in a colligative property (§13.6)
solution (§13.6)
BRIEF SOLUTIONS TO FOLLOW-UP PROBLEMS
11. Using a depiction to determine colligative properties (SP 13.10)
13.1A (a) 1-Butanol has one OH group/molecule, whereas 13.2B Due to its smaller size, Na+ should have a greater charge
Key Terms Page numbers appear in parentheses. 1,4-butanediol has two OH groups/molecule. 1,4-Butanediol density and thus a larger ΔHhydr than CN–. From Equation 13.2,
is more soluble in water because it can form more H bonds. we have
alloy (540) dipole–induced dipole heat (enthalpy) of hydration immiscible (536) (b) Chloroform is more soluble in water because of dipole-
amino acid (541) force (537) (ΔHhydr) (547) ion exchange (573) ΔHsoln of NaCN = ΔHlattice of NaCN
dipole forces between the polar CHCl3 molecules and water. + (ΔHhydr of Na+ + ΔHhydr of CN−)
boiling point elevation double helix (545) heat (enthalpy) of solution ionic atmosphere (568) The forces between nonpolar CCl4 molecules and water are
(ΔTb) (562) entropy (S) (550) (ΔHsoln) (546) ion–induced dipole force (536) weaker dipole–induced dipole forces, which do not effectively 1.21 kJ/mol = 766 kJ/mol + (−410. kJ/mol + ΔHhydr of CN−)
charge density (547) fractional distillation (567) Henry’s law (554) like-dissolves-like rule (536) replace H bonds between water molecules.
−
ΔHhydr of CN = 1.21 kJ/mol − 766 kJ/mol + 410. kJ/mol
colligative property (560) freezing point depression hydration (547) lipid bilayer (544) = −355 kJ/mol
colloid (571) (ΔTf) (563) hydration shell (536) mass percent [% (w/w)] (557) 13.1B (a) Chloroform dissolves more chloromethane due to 13.3A The partial pressure of N2 in air is the volume percent
desalination (574) hard water (573) ideal solution (561) miscible (536) similar dipole-dipole forces between the polar molecules of divided by 100 times the total pressure (Dalton’s law, Section 5.4):
these two substances. CH3Cl molecules do not exhibit H PN2 = 0.78 × 1 atm = 0.78 atm.
bonding and, so, do not effectively replace H bonds between
methanol molecules. Sgas = kH × Pgas
(b) Hexane dissolves more pentanol due to dispersion forces SN2 = (7×10−4 mol/L · atm)(0.78 atm)
between the hydrocarbon chains in each molecule. = 5×10−4 mol/L
13.2A From Equation 13.2, we have 13.3B In a mixture of gases, the volume percent of a gas divided
siL40215_ch13_534-587.indd 575 6/4/19 10:38 AM
ΔHsoln of KNO3 = ΔHlattice of KNO3 by 100 times the total pressure equals the gas’s partial pressure
+ (ΔHhydr of K+ + ΔHhydr of NO3−) (Dalton’s law, Section 5.4):
34.89 kJ/mol = 685 kJ/mol + (ΔHhydr of K+ + ΔHhydr of NO3−) Pgas = 0.40 × 1.2 atm = 0.48 atm.
ΔHhydr of K+ + ΔHhydr of NO3− = 34.89 kJ/mol − 685 kJ/mol Sgas 1.2×10−2 mol/L
kH = = = 2.5×10−2 mol/L·atm
= −650. kJ/mol Pgas 0.48 atm

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siL40215_fm_i-xxxv.indd 25 10/11/19 1:05 PM

mide. (h) Dry ice, CO2 Cl F
C Cl
luoride. (i) Baking soda, NaHCO3 H
F
xide. (j) Lye, NaOH H Chapter 10 • Problems 437

(b) Four of
ofthe
theIF (c) The two axial SF bonds balance each other, but the two
(b) C: three electron groups;2.112
ula of each compound, and determine
trigonalEach
its ClCCl angle
planarcircle
shape;contains
the double a representation
(c) Four
IF
ofpolar IFbalance
bonds
abalanced
binary bonds balance each
each other,
compound. butother, butIF
the fifth the fifth
bond
equatorial SF bonds (ΔEN = 1.5) are not balanced by the dou-
bond compresses each to <120°. is notbond is notThe
balanced. by the
molecular polarpoints
polarity OItoward
bond. the
Since the
F atom.
mass: (a) ammonium sulfate; (b) sodium Determine its name, formula, and molecular (formula) mass.
IF bond is more polar (ΔEN = 1.5) than the OI bond ble bond between S and O (ΔEN = 1.0). Since the SF bonds are
Cl Cl
(ΔEN = 1.0), the molecular
F more polar, the molecular polarity points toward the F atoms.
(c) potassium bicarbonate. F polarityFpoints toward the F atom.
C C I F
Cl(a) (b) F O F F
ula of each compound,xxviand  Preface
determine its Cl
F F S O
ass: (a) sodium dichromate;(c)(b)
Cl:ammonium
four electron groups; tetrahedral shape; bond angles I F
~109.5°. O (central): four electron groups, two of which are lone 10.9B (a) The four polarFXeF bonds
F balance each other: 438 Chapter 10 • The Shapes
F of Molecules
sium nitrite trihydrate. oxygen
nonpolar molecule. F
pairs; bent (V-shaped); ClOCl bond angle <109.5°.
nitrogen 10.12 Draw Lewis structures of all the important resonance forms Valence-Shell Electron-Pair Repulsion (VSE
molecular (formula) mass of each com- chlorine F F of (a) HCO2− (H is attached to C); (b) HBrO4 (HOBrO3). (Sample Problems 10.6 to 10.8)
O Xe
pentoxide; (b) lead(II) nitrate; (c) calcium O
Cl Cl
O
F F
Concept Review Questions
10.13 Draw the Lewis structure with lowest formal charges,
O O O O and determine the charge of each atom in (a) IF5; (b) AlH4−. 10.27 If you know the formula of a molecule or
(b) Two of the ClF bonds balance each other, but the third first step in predicting its shape?
olecular (formula) mass of each
10.9Acompound:
(a) The CH and CCl polar bonds reinforce each PROBLEMS
ClF bond is not balanced. The molecular polarity points toward 10.14 Draw the Lewis structure with lowest formal charges, and
determine the charge of each atom in (a) OCS; (b) NO. 10.28 In what situation is the name of the m
ahydrate; (b) sulfur tetrachloride; (c)thepotas-
other, with molecular polarity pointing between the Cl atoms. the F atom.
Finally, an exceptionally Mixtures:
Cl large
Classification and Separation F
Problems with colored numbers are answered in Appendix E and 10.15 Drawisthe
10.4 What Lewisfor
required structure
an atomwith lowest its
to expand formal charges,
valence shell?
same as the name of the electron-group arrange
10.29 Which of the following numbers of el
number of qualitative,
er of atoms of the specified element in a H
C quantitative,
Concept Cl Review Questions worked in detail in the Student Cl F Manual. Problem sections
Solutions
match those in the text and give the numbers of relevant sample
and determine
Which the chargeatoms
of the following of each atom
can in (a)itsCN
expand
−
; (b) ClO
valence
−
shell:. F, S, give rise to a bent (V-shaped) molecule: two, th
H, Al, Se, Cl?
and molecular-scene Hproblems end
Draw an example for each case, showing the s
F 10.16 Draw the Lewis structure with lowest formal charges, and
of the following compounds, and calculate 2.113 In what main way is separating the
problems. components
Most offer Concept of a
Review mix-
Questions, Skill-Building Exer-
determine the charge of each atom in (a) ClF2+; (b) ClNO. (AXmEn) and the ideal bond angle.
ture different from separating the cises (grouped in pairs covering the same concept), and Problems in
components of a compound?
a) mass: each (b)chapter. Four
Four of the polar types
IF bonds ofeach
balance problems
other, but the fifth (c) The
Context.two
The
equatorial
axial
sectionSF
SF bonds
Comprehensive
bonds (ΔEN
balance
Problems each
are other,
based but
on the two from
material
= 1.5) are not balanced by the dou-
Skill-Building Exercises (grouped in similar pairs)
Draw aa Lewis
Lewis structure
structure for
for (a)
a resonance 10.30 Name all the molecular shapes that
m sulfate, Al2(SO4)3 IF bond is not balanced by the polar
2.114 WhatOIisbond.
the Since the
difference any
between a or previous
homogeneous chapter.
and a het-
10.17
10.5 Draw SiF4; (b) form
SeClof each ion
2; (c) COF2
are presented—three
nium hydrogen phosphate, IF
(NHbond is more polar (ΔENby
4)2HPO4
= 1.5)chapter
than the OI bond ble bond between S and O (ΔEN = 1.0). Since the SF bonds are with
(C is the
the lowest
central possible
atom). formal charges, show the charges, and
electron-group arrangement.
(ΔEN = 1.0), the molecularerogeneous
polarity pointsmixture?
Depicting
more polar,Molecules andpolarity
the molecular Ions with Lewis
points Structures
toward the F atoms. give oxidation numbers of the atoms: (a) BrO3−; (b) SO32−. 10.31 Consider the following molecular shap
eral azurite, Cu3(OH)section, with comprehensive toward the F atom.
2(CO3)2 (Sample Problems 10.1 to 10.5) F 10.6 Draw a Lewis structure for (a) PH4+; (b) C2F4; (c) SbH3. the most electron pairs (both bonding and l
2.115 Is a solution a homogeneous or a heterogeneous mixture? 10.18 Draw a Lewis structure for a resonance form of each ion
problems following:
O F the central atom? (b) Which has the most lon
er of atoms of the specified element in a F Give anF example of an aqueous solution. Concept Review Questions with
10.7 the
Drawlowest possible
a Lewis formal
structure charges,
for (a) show
PF3; (b) H2CO the charges, and
S O 3 (both H atoms central atom? (c) Do any have only bonding
of the following compounds, and calculate F I F 10.1 Which of these atomsF cannot serve as a central atom in a give oxidationtonumbers
are attached O atoms); of(c)
theCS
atoms:
2.
(a) AsO43−; (b) ClO2−.
central atom?
Lewis structure: (a) O; (b) He; (c)F F; (d) H; (e) P? Explain.
a) mass: ∙ Concept Review Skill-Building Questions
F test
Exercises (grouped 10.2inWhen
similar pairs) hybrid needed to adequately depict the
is a resonance 10.8 Draw
10.19 Thesea species
Lewis structure for (a)the
do not obey CHoctet
4S; (b) S2ClDraw
rule. 2; (c) CHCl 3.
a Lewis
nium benzoate, C6H5COONHqualitative
4 understanding of key bonding in a molecule? Using NO2 as an example, explain how a structure for each, and state the type of octet-rule exception:
nium sulfate, N2H6SO4 BHDraw
10.9
(a) Lewis structures
(b) AsF −
(c)of all 4the important resonance forms
SeCl
2.116 Classify each of the following as a compound,
resonance hybrid a homoge-
is consistent with the actual bond length, bond 3 4
of (a) NO2+; (b) NO2F (N is central).
ideas.
eral leadhillite, Pb4SO4(CO3)2(OH)2 neous mixture, or a heterogeneous strength, and bond order.
mixture: (a) distilled water; 10.20 These species do not obey the octet rule. Draw a Lewis
10.3 In which of these structures does X obey the octet rule? 10.10 Draw Lewisand
structures
state theoftype
all the
of important resonance
exception: forms
A B C
∙ Skill-Building Exercises (b) gasoline;are (c) beach sand; (d) wine; (e) air.
(a) (b) (c) (d) (e) (f) (g) (h)
structure
of (a)
(a)
for each,
PF6−HNO3(b)(HONO
ClO3 2); (b)
(c)HAsO
2−
octet-rule
(HOAsO
H3PO43 (one PH
2−
).
3 bond)
a, name, and molecular mass of the follow-
grouped
PROBLEMS in similar2.117 pairs, witheach
Classify oneof the followingX as aXcompound, aX homoge-
X X
2−
Draw Lewis
10.11 These
10.21 speciesstructures of all the
do not obey the important
octet rule.resonance forms
Draw a Lewis
10.32 Use wedge-bond perspective drawings
X X X sketch the atom positions in a general molecu
of each pair answered in the back
neous mixture, or a heterogeneous mixture: (a) orange juice; of (a) N3−for
structure NO2−and
; (b)each, . state the type of octet-rule exception:
−
shape class) AXn that has each of the following
(b) vegetable
Problems with colored numbers are answeredsoup; (c) cement;
in Appendix E and (d) calcium
10.4 What issulfate;
required (e) tea.
for an atom to expand its valence shell? (a) BrF3 (b) ICl2 (c) BeF2 (a) V-shaped (b) trigonal planar (c) tri
(b ) ofworked
the inbook. A Student
detail in the group of similar
Solutions Manual. Problem sections Which of the following atoms can expand its valence shell: F, S, 10.22 These species do not obey the octet rule. Draw a Lewis (d) T-shaped (e) trigonal pyramidal (f) squ
match those in the text and give the numbers of relevant sample
exercises
problems. Most may begin
offer Concept with
Problems
Review inexplicit
Context
Questions, Skill-Building Exer-
H, Al, Se, Cl? structure for each, and state the type of octet-rule exception: 10.33 What would you expect to be the electr
cisesC(grouped in pairs covering the same concept), and Problems in (a) O3− (b) XeF2 (c) SbF4− ment around atom A in each of the following c
steps
Context.and increase2.118
The Comprehensive
H
in difficulty,
Problems
the technique(s) andSkill-Building
are based on material from
Name Exercises (grouped in similar pairs)
briefly describe the procedure rangement, give the ideal bond angle and th
gradually weaningforthe
any section or previous chapter.
student
separating eachfrom
10.5 Draw a Lewis structure for (a) SiF ; (b) SeCl ; (c) COF
of the following(Cmixtures into pure components:
siL40215_ch10_404-441.indd 437
is the central atom).
4 2 2
Problems in Context
expected deviation:
5/27/19 1:50 PM

theDepicting
need
(Sample
Molecules and (a)
for 10.1
Problems multistep Ionstable
to 10.5)
with Lewis
salt Structures
directions.
and pepper; (b) drinking water contaminated with
10.6 Draw a Lewis structure for (a) PH ; (b) C F ; (c) SbH . +
10.23 Molten beryllium chloride reacts with chloride ion
from molten NaCl to form the BeCl42− ion, in which the Be
(a) X (b) X A X (c) X

soot; (c) crushed ice and crushed glass; (d) table sugar dissolved 4 2 4 3
X A
∙ apply the
X A X
Problems
a, name, and molecular mass
in
of the follow-
Context
Concept Review Questions in ethanol; (e) two pigments (chlorophyll 10.7 Draw a Lewis and chlorophyll
a structure for (a) PF ; (b) H CO (both H atoms
atom attains an octet. Show the net ionic reaction with Lewis
X
X
3 2 3 structures. X
skills learned
10.1 Which of these in the
atoms skill-building
b)cannot
from serve as a central atom in a
spinach leaves.
Lewis structure: (a) O; (b) He; (c) F; (d) H; (e) P? Explain.
are attached to O atoms); (c) CS . 2
10.24 Despite many attempts, the perbromate ion ( BrO4−) was not
(e) X A X (f) A
X
exercises
10.2 When isto interesting
a resonance hybrid
2.119needed scenarios,
Which to adequately
separation depict the is10.8
method
Draw a Lewis structure for (a) CH S; (b) S Cl ; (c) CHCl .
operating in each of the follow-
4 2 2 3 prepared in the laboratory until about 1970. (In fact, articles were
X

(b ) H including
bonding in a molecule? Using NO as an example, explain how a published explaining theoretically why it could never be pre-
realistic ingexamples
procedures? 2
dealing
resonance hybrid is consistent with the actual bond length, bond
10.9 Draw Lewis structures of all the important resonance forms
+
pared!) Draw a Lewis structure for BrO4− in which all atoms have Skill-Building Exercises (grouped in similar
of (a) NO ; (b) NO F (N is central). 10.34 Determine the electron-group arrang
strength, and bond order. (a) Pouring a mixture of cooked pasta and boiling water into a lowest formal charges.
C with industry, medicine, and the
2 2
O shape, and ideal bond angle(s) for each of the f
colander
10.3 In which of these structures does X obey the octet rule? 10.10 Draw Lewis structures of all the important resonance forms 10.25 Cryolite (Na3AlF6) is an indispensable component in the (a) O3 (b) H3O+ (c) NF3
environment.
(a) (b) (c) (b) Removing
(d) (e) (f)colored (g) impurities
(h)
of (a) HNO (HONO ); (b) HAsO (HOAsO ).
from raw sugar to make refined 3 2
2−
4
2−
3 electrochemical production of aluminum. Draw a Lewis structure
for the AlF63− ion. 10.35 Determine the electron-group arrangemen
∙ Comprehensive
X X X Problems,
sugar
X X X mostly X X 10.11 Draw
438
2−
Lewis structures of all the important resonance forms
Chapter 10 • The Shapes of Molecules
− −
and ideal bond angle(s) for each of the followin
of (a) N ; (b) NO . 10.26 Phosgene is a colorless, highly toxic gas that was employed (a) SO42− (b) NO2− (c) PH3
based on realistic2.120 applications,
A quality-control are laboratory 3
analyzes a product mixture
2

10.12 Draw Lewis structures of all the important resonance forms

against troops in World War I and is used today as a key reactant
Valence-Shell Electron-Pair Repulsion (VSEPR) Theory
more challenging using
and gas-liquid
rely on chromatography.
mate- ofThe separation
(a) HCO of components
(H is attached −
to C); (b) HBrO (HOBrO ).
in organic syntheses. From the following resonance structures,
(Sample Problems 10.6 to 10.8) 10.36 Determine the electron-group arrang
of systematic names, many compounds had is more than adequate, but the process takes too long. Suggest two
2 4 3
select the one with the lowest formal charges: shape, and ideal bond angle(s) for each of the f
rialof the
he systematic name for each from any section
following: of the current
ways, other than changing the stationary phase, to shortenwith
10.13 Draw the Lewis structure thelowest formal charges,
Concept Review Questions (a) CO32− (b) SO2 (c) CF4
4·5H2O
− 10.27 If you know O the formula of Oan ion, what is the
O a molecule or
and determine the charge of each atom in (a) IF ; (b) AlH .
chapter or any previous analysis time.chapter. 5 4
first step in predicting
C its shape?C C
10.37 Determine the electron-group arrang
shape, and ideal bond angle(s) for each of the f
H)2 10.14 Draw the Lewis structure with lowest formal charges, and Cl Cl Cl Cl Cl Cl
siL40215_ch10_404-441.indd 437 determine the charge of each atom in (a) OCS; (b) NO. 10.28 In what situation
5/27/19 1:50 PM is the B
name of the molecular shape the (a) SO3 (b) N2O (N is central) (c) CH2C
O4 A C
same as the name of the electron-group arrangement?
CO3 Comprehensive Problems
10.15 Draw the Lewis structure with lowest formal charges,
10.29 Which of the following numbers of electron groups can
2.121 Helium is the lightest nobleandgas and the
determine thesecond
charge ofmost abun-
each atom in (a) CN−; (b) ClO−. Chapter 2 • Problems 89
give rise to a bent (V-shaped) molecule: two, three, four, five, six?
4·7H2O dant element (after hydrogen) in the universe.
10.16 Draw the Lewis structure with lowest formal charges, and Draw an example for each case, showing the shape classification
(a) The radius of a helium atom is 3.1×10the−11charge
determine m; the radius
of each atom of itsClF2+; (b)
in (a) (d)ClNO.
A homogeneous (AXmixture
mEn) and the ideal bond angle.

nucleus is 2.5×10−15 m. What fraction of the spherical for

10.17 Draw a Lewis structure
atomic (e) An element that
a resonance form of each ion 10.30conforms
Name all the to molecular
the wallsshapes
of itsthatcontainer and
have a tetrahedral
volume is occupied by the nucleuswith (Vthe
of lowest
a sphere = 43 πr
possible
3
formal)? charges, showdisplays anand
the charges, upperelectron-group
surface arrangement.
−24 siL40215_ch10_404-441.indd 438
(b) The mass of a helium-4 atom give oxidation numbersg,
is 6.64648×10 of and each(a)
the atoms: ofBrO3−; (f) A 32−
(b) SO gas
. consisting 10.31of Consider
diatomictheparticles
following molecular shapes. (a) Which has
−28
its two electrons has a mass of 9.10939×10
10.18 Draw a Lewisg. What fraction
structure of
for a resonance (g)
formAofgas ion canthe
eachthat bemost
brokenelectron
down pairs (both
into bonding
simpler and lone pairs) around
substances
the central atom? (b) Which has the most lone pairs around the
this atom’s mass is contributed bywith
its the
nucleus?
lowest possible formal charges, show(h) the A substance
charges, and with a 2/1 ratio of its component atoms
give oxidation numbers of the atoms: (a) AsO43−(i) ClO2−. that cancentral
; (b)Matter atom? (c) Do any have only bonding pairs around the
be separated into its component substances by
central atom?
2.122 From the following ions (with their radii in pm), choose the 4/16/19 6:44 PM
physical
Draw a means
bondThese
pair that forms the strongest ionic10.19 species do not obey the octet rule.
and the pair that forms the Lewis
structure for each, and state the type of octet-rule (j)exception:
A heterogeneous mixture
weakest: (a) BH3 (b) AsF4−
(c) SeCl4 (k) Matter that obeys the law of definite composition
Ion: Mg2+ K+ Rb+ 10.20
Ba2+ TheseClspecies
−
Odo2−
not obeyI− the octet rule. Draw a Lewis
A B C D
Radius: 72 138 152 135 − 181 140
structure for each, and state the 220
type of octet-rule exception:
(a) PF6 (b) ClO3 (c) H3PO3 (one PH bond)
2.123 Give the molecular mass of each compound depicted below, 10.32 Use wedge-bond perspective drawings (if necessary) to
10.21 These species do not obey the octet rule. Draw a Lewis
and provide a correct name for anystructure
that are named incorrectly.
for each, and state the type of octet-rule exception:
sketch the atom positions in a general molecule of formula (not
shape class) AXn that has each of the following shapes:
(a) BrF3 (b) ICl2− (c) BeF2 (a) V-shaped (b) trigonal planar (c) trigonal bipyramidal
(a) boron (b)
10.22 These species do not monosulfur
obey the octet rule. Draw a Lewis (d) T-shaped (e) trigonal pyramidal (f) square pyramidal
fluoride S dichloride
structure for each, and state the type of octet-rule exception: 10.33 What would you expect to be the electron-group arrange-
−
(a) O3 (b) XeF2 (c) SbF4− ment around atom A in each of the following cases? For each ar-
Cl A B C
Br F rangement, give the ideal bond angle and the direction of any
expected deviation:
Problems in Context
10.23 Molten beryllium chloride reacts with chloride ion (a) X (b) X A X (c) X (d) X A X
(c) phosphorus (d)
from molten NaClO to form
dinitride
BeCl42− ion, in which the Be
P trichloride N the
pentoxide X A X A X
atom attains an octet. Show the net ionic reaction with Lewis X
X
structures. X
Cl (e) X A X (f) A
10.24 Despite many attempts, the perbromate ion ( BrO4−) was not X
X
prepared in the laboratory until about 1970. (In fact, articles were
2.124 Polyatomic ions are namedpublished
by patterns thattheoretically
explaining apply to why ele- it could never be pre-
Skill-Building Exercises (grouped in
pared!) Draw a table
Lewis structure for BrO − D E F similar pairs)
ments in a given group. Using the periodic and Table 4 in which all atoms have
2.5,
lowest formal charges. 2− 10.34 Determine the electron-group arrangement, molecular
3−
give the name of each of the following: (a) SeO4 ; (b) AsO 4 ; shape, and ideal bond angle(s) for each of the following:
10.25 Cryolite (Na3AlF6) is an indispensable component in the
(c) BrO−2; (d) HSeO−4; (e) TeO2−
3 . electrochemical production of aluminum. Draw a Lewis structure
(a) O3 (b) H3O+ (c) NF3

ion.
for the AlF6 formed 3− 10.35 Determine the electron-group arrangement, molecular shape,
2.125 Ammonium dihydrogen phosphate, from the reac- and ideal bond angle(s) for each of the following:
tion of phosphoric acid with ammonia, is usedisas
10.26 Phosgene a crop fertilizer
a colorless, highly toxic gas that was employed (a) SO42− (b) NO2− (c) PH3
as well as a component of some fire extinguishers. War
against troops in World (a) IWhat
and is used
are today as a key reactant
in organic syntheses. From the following resonance structures, 10.36 Determine the electron-group arrangement, molecular
the mass percentages of N and P in the compound? (b) How much
select the one with the lowest formal charges: shape, and ideal bond angle(s) for each of the following:
ammonia is incorporated into 100. g of the compound? G (a) CO32−H (b) SO2 (c) CF4 I
O O O
siL40215_fm_i-xxxv.indd 26 10/11/19 1:05 PM
2.126 Nitrogen forms more oxides than any other element. The 10.37 Determine the electron-group arrangement, molecular
 Preface   xxvii

OPTIMIZING THE TEXT

The modern chemistry student’s learning experience is changing dramatically. To address the changes that students face,
a modern text partnered with a suite of robust digital tools must continue to evolve. With each edition, students and
instructors alike have been involved in refining this text. From one-on-one interviews, focus groups, and symposia, as
well as extensive chapter reviews and class tests, we learned that everyone praises the pioneering molecular art; the
stepwise problem-solving approach; the abundant mix of qualitative, quantitative, and applied end-of-chapter problems;
and the rigorous and student-friendly coverage of mainstream topics.

Global Changes to Every Chapter

Our revision for the ninth edition focused on continued optimization of the text. To aid us in this process, we were able
to use data from literally thousands of student responses to questions in SmartBook probes, the adaptive learning system
that assesses student knowledge of course content. The data, such as average time spent answering each question and
the percentage of students who correctly answered the question on the first attempt, revealed the learning objectives that
students found particularly difficult. We utilized several approaches to present these difficult concepts in a clear, straight-
forward way in the ninth edition of Chemistry: The Molecular Nature of Matter and Change. 47 2.2 • The Observations That Led to an Atomic View of Matter

Solution Finding the mass (kg) of uranium in 102 kg of pitchblende:

Making the concepts clearer through digital learn- Mass (kg) of uranium = mass (kg) of pitchblende ×
mass (kg) of uranium in pitchblende

ing resources. Students will be able to access digital mass (kg) of pitchblende
71.4 kg uranium
= 102 kg pitchblende × = 86.5 kg uranium
learning resources throughout this text’s SmartBook. Converting the mass of uranium from kg to g:
84.2 kg pitchblende

These learning resources present summaries of concepts 1000 g

Mass (g) of uranium = 86.5 kg uranium × = 8.65×104 g uranium
1 kg
and worked examples, including videos of chemistry Finding the mass (in kg) of oxygen in 102 kg of pitchblende:

instructors solving problems or modeling concepts that Mass (kg) of oxygen = mass (kg) of pitchblende − mass (kg) of uranium
= 102 kg − 86.5 kg = 15.5 kg oxygen

students can view over and over again. Thus, students Converting the mass of oxygen from kg to g:
1000 g
can have an “office hour” moment at any time. Mass (g) of oxygen = 15.5 kg oxygen ×
1 kg
= 1.55×104 g oxygen

Check The analysis showed that most of the mass of pitchblende is due to uranium, so
the large mass of uranium makes sense. Rounding off to check the math gives
70
Student Hot Spots FOLLOW-UP PROBLEMS
∼100 kg pitchblende ×
85
= 82 kg uranium

We are very pleased to incorporate real student data 2.2A The mineral “fool’s gold” does not contain any gold; instead, it is a compound
composed only of the elements iron and sulfur. A 110.0-g sample of fool’s gold

points and input, derived from thousands of our Smart- contains 51.2 g of iron. What mass of sulfur is in a sample of fool’s gold that
contains 86.2 g of iron?
Student Hot Spot

Book users, to help guide our revision. SmartBook Heat
2.2B Silver bromide is the light-sensitive compound coated onto black-and-white film.
A 26.8-g sample contains 15.4 g of silver, with bromine as the only other element. How
Student data indicate that you may struggle with
using mass fraction to calculate the mass of an
element in a compound. Access the eBook to

Maps provided a quick visual snapshot of usage of por- many grams of each element are on a roll of film that contains 3.57 g of silver bromide?
SOME SIMILAR PROBLEMS 2.22–2.25
view an additional Learning Resource video
on this topic.

tions of the text and the relative difficulty students expe-

rienced in mastering the content. With these data, we Multiple Proportions
were able to both hone our text content when needed and, forIt’sparticularly challenging concepts, point students to the learning
quite common for the same two elements to form more than one compound—sulfur
and fluorine do this, as do phosphorus and chlorine and many other pairs of elements.
resource videos that can elucidate and reinforce those concepts. You’ll see these marginal features throughout the text. Students
The third mass law we consider applies in these cases:
∙ Law of multiple proportions: if elements A and B react to form two compounds,
should log into Connect and view the resources through our SmartBook.
the different masses of B that combine with a fixed mass of A can be expressed as
a ratio of small whole numbers.

Applying ideas with enhanced problems throughout the chapters. The much admired four-part problem-solving
Consider two compounds of carbon and oxygen; let’s call them carbon oxides I and
II. These compounds have very different properties: the density of carbon oxide I is

format (plan, solution, check, follow-up) is retained in the ninth edition, in both data-based and molecular-scene Sample
1.25 g/L, whereas that of II is 1.98 g/L; I is poisonous and flammable, but II is not.
Mass analysis shows that

Problems. Two Follow-up Problems are included with each sample problem, as well as a list of Similar Problems within
Carbon oxide I is 57.1 mass % oxygen and 42.9 mass % carbon
Carbon oxide II is 72.7 mass % oxygen and 27.3 mass % carbon

the end-of-chapter problem set. Brief Solutions for all of theof oxygen
follow-up
To demonstrate problems
the phenomenon appear
of multiple atusethe
proportions, we end
the mass of each chapter (rather
percents
and of carbon to find their masses in a given mass, say 100 g, of each com-
than providing just a numerical answer in a distant end-of-book
pound. Then appendix,
we divide the mass as
of is
oxygen bytypical).
the mass of The
carbon in
to obtain the mass of oxygen that combines with a fixed mass of carbon:
each ninth
compound edition has over 250
sample problems and over 500 follow-up problems. In many chapters, severalCarbon sample
Oxide I and follow-up
Carbon Oxide II problems (and their
brief solutions) were revised in this edition with two goals gg in mind.
oxygen/100 We
g compound
carbon/100 g compound
sought57.1
42.9
to provide 72.7
27.3
students with a variety of
problems that would clearly elucidate concepts and demonstrate g oxygen/g problem-solving
carbon
57.1
42.9
= 1.33techniques,
72.7
27.3
= 2.66 while giving students the

opportunity to be challenged and gain competence. We also included more intermediate steps in the solutions to both
sample and follow-up problems so that students could more easily follow the solutions.
Re-learning ideas with annotated illustrations. The innovative three-level figures and other art that raised the bar for
siL40215_ch02_040-091.indd 47 4/16/19 6:43 PM

molecular visualization in chemistry textbooks is still present. Several existing figures have been revised and several new
ones added to create an even better teaching tool. We continue to streamline figure legends by placing their content into
clarifying annotations with the figures themselves.

siL40215_fm_i-xxxv.indd 27 10/11/19 1:05 PM

 xxviii   Preface
Mastering the content with abundant end-of-chapter
problem sets. New problems were added to several chapter
problem sets, providing students and teachers with abundant
choices in a wide range of difficulty and real-life scenarios.
The problem sets are more extensive than in most other texts.
Content Changes to Individual Chapters
In addition to the general optimization of concept explana-
tions and problem solutions throughout the text, specific
improvements were made to most chapters:
∙ Chapter 1 has a revised discussion of significant figures to
make this important topic clearer, two revised sample prob-
lems on significant figures and rounding in calculations, and
a new follow-up problem on using density in calculations.
∙ Chapter 2 includes an improved discussion on mass spec-
trometry, isotopic composition, and atomic mass; five new
figures to aid in nomenclature of compounds, including a
summary nomenclature decision tree; and two new end-of-
chapter problems on naming compounds.
∙ Chapter 3 now features two new problem-solving Student
Hot Spot resources on mass/moles/molecules conversions
and on determination of a molecular formula; and revisions
to four sample problems on stoichiometry.
∙ Chapter 4 has been reorganized for better flow and clarity;
there is a new table on the types of electrolytes, a revised
sample problem on the stoichiometry of ions in solution, and
a revised sample problem on writing acid-base reactions.
∙ Chapter 5 now has three improved sample problems and
two revised figures on gas laws.
∙ Chapter 6 includes heavily revised sample problems on
heat, temperature change, and specific heat capacity; Hess’s
Law; and calculations with heat of formation values. The
Chemical Connections on energy has been updated.
∙ Chapter 7 includes a new video to help students under-
stand line spectra, three revised figures, and a revised
sample problem on quantum numbers.
∙ Chapter 8 incorporates a new figure to illustrate penetra-
tion and shielding of 4s vs. 3d orbitals, four revised figures
(on electron spin, orbital filling, element reactivity, and
acid-base behavior of oxides), a heavily revised discussion
on using the periodic table to write electron configura-
tions, and a new treatment of the concept of assigning
quantum numbers to electrons.
∙ Chapter 9 has a revised treatment of the Born-Haber cycle
and a clearer discussion of the three types of bonding.
∙ Chapter 10 includes two new videos: one video demon-
strates the process of drawing Lewis structures and one
explains the process of determining molecular geometry.
There are also improvements in the text explanation about
drawing Lewis structures, on assigning and using formal
charges, and on determining molecular polarity.
∙ Chapter 11 has a revised sample problem and a new
­follow-up problem on types of orbitals, a revised follow-up
problem on hybrid orbitals, and an improved discussion on
hybridization and bond angles in molecules.
siL40215_fm_i-xxxv.indd 28
∙ Chapter 12 includes a rewritten section on phase changes,
a new discussion on intermolecular forces and boiling
points, a revision to a figure that helps students determine
the type of intermolecular forces in a sample, and updated
discussions in the advanced material section on LEDs,
plastic recycling, 3-D printing, and nanomedicine.
∙ Chapter 13 incorporates a new video on freezing point
depression calculations, a new graphical figure that depicts
Henry’s law for several gases and connects gas solubility
with molar mass and the strength of dispersion forces, a
revised figure on the types of intermolecular forces in
solution, and revised sample and follow-up problems on
predicting charge density.
∙ Chapter 14 has two revised figures, one showing silicates
and the other showing crystals of a noble gas compound, and
an updated discussion, with new figures, on carbon allotropes.
∙ Chapter 15 includes a new example and new art to aid in
naming organic compounds and new videos on naming
alkanes, understanding optical isomers, and recognizing
functional groups.
∙ Chapter 16 has a newly organized section on rate laws
and half-lives for first-, second-, and zero-order reactions,
an addition to a sample problem that requires the calcula-
tion of rate from rate constant and concentration data, a
new follow-up problem on first-order integrated rate law
calculations, and several new or revised end-of-chapter
problems. The section on collision theory, activation
energy, and transition state theory was heavily revised for
better flow and clarity. There is a new Student Hot Spot
resource on solving first-order integrated rate law problems.
∙ Chapter 17 has several revised and new sample problems
and follow-up problems, including a new sample problem on
the van’t Hoff equation for calculating the change in equilib-
rium constant with a change in temperature, several new end-
of-chapter problems, and three new Student Hot Spot
resources explaining equilibrium and Le Châtelier’s princi-
ple. There are two revised figures on equilibrium position.
∙ Chapter 18 has a significant rearrangement of topics,
introducing conjugate acid-base pairs and the pH scale
before the introduction of Ka; two new figures, one describ-
ing the relationship between [H+] and [OH–] and the other
summarizing Ka and Kb calculations; three revised sample
and follow-up problems; and two new videos to help stu-
dents understand acidic metal cations and how to predict
the pH of salts with amphiprotic anions.
∙ Chapter 19 includes three new tables, one summarizing
buffer pH relative to buffer concentration ratio and the other
two summarizing pH calculations for titrations of weak
acids and weak bases. There are new Student Hot Spot
resources on the calculation of buffer pH, the preparation of
a buffer of a specific pH, and the calculation of pH during
acid-base titrations.
∙ Chapter 20 includes new tables with values of entropy and
Gibbs free energy for selected substances, a revised sample
problem on the calculation of the standard entropy of reac-
tion, and a new video on spontaneity and temperature.
10/11/19 1:05 PM

∙ Chapter 21 incorporates a more useful example of balanc-
ing a redox reaction in acidic solution and a new Student
Hot Spot resource that illustrates the balancing method,
new art to explain the function of a salt bridge, a new
follow-problem on the relationship between cell potential
and equilibrium constant, and an updated discussion on
batteries.
∙ Chapter 23 has a revised section on nomenclature of coor-
dination compounds, including a revised sample problem
on nomenclature; new art on the color of complex ions;
and new videos on coordination number, optical isomers,
and low-spin vs. high-spin complex ions.
∙ Chapter 24 includes a new table on stability of isotopes, a
new sample problem on writing transmutation reactions, an
updated table on radiation exposure, and updated discussions
on PET scans and on fusion.
Innovative Topic and Chapter Presentation
Although the topic sequence coincides with that used in
most mainstream courses, built-in flexibility allows a wide
range of differing course structures:
For courses that follow their own topic sequence, the
general presentation, with its many section and subsection
breaks and bulleted lists, allows topics to be rearranged,
or even deleted, with minimal loss of continuity.
For courses that present several chapters, or topics
within chapters, in different orders:
∙ Redox balancing by the half-reaction method is covered
with electrochemistry in Chapter 21, but it can easily
be taught with Chapter 4.
∙ Gases (Chapter 5) can be covered in sequence to explore
the mathematical modeling of physical behavior or, with
no loss of continuity, just before liquids and solids (Chap-
ter 12) to show the effects of intermolecular forces on the
three states of matter.
For courses that use an atoms-first approach for some
of the material, Chapters 7 through 13 move smoothly
from quantum theory (7) through electron configuration
(8), bonding models (9), molecular shape (10), VB and
MO bonding theories (11), intermolecular forces in liquids
and solids (12), and solutions (13). Immediate applications
of these concepts appear in the discussions of periodic
patterns in main-group chemistry (Chapter 14) and in the
survey of organic chemistry (Chapter 15). Some instruc-
tors have also brought forward the coverage of transition
elements and coordination compounds (23) as further
applications of bonding concepts. (Of course, Chapters 14,
15, and 23 can just as easily remain in their more tradi-
tional placement later in the course.)
For courses that emphasize biological/medical applica-
tions, many chapters highlight these topics, including the
siL40215_fm_i-xxxv.indd 29
Preface   xxix
role of intermolecular forces in biomolecular structure
(12), the chemistry of polysaccharides, proteins, and
nucleic acids (including protein synthesis, DNA replica-
tion, and DNA sequencing) (15), as well as introductions
to enzyme catalysis (16), biochemical pathways (17), and
trace elements in protein function (23).
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physical chemistry topics, Chapters 16 through 21 cover
kinetics (16), equilibrium in gases (17), acids and bases
(18), and aqueous ionic systems (19) and entropy and free
energy (20) as they apply to electrochemical systems (21),
all in preparation for coverage of the elements in geochem-
ical cycles, metallurgy, and industry in Chapter 22.
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 Your Class Your Way!
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 ®

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 FOR STUDENTS

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siL40215_fm_i-xxxv.indd 33 10/11/19 1:05 PM

 xxxiv   Preface

ADDITIONAL INSTRUCTOR AND STUDENT RESOURCES FOR YOUR COURSE!

Instructors have access to the following instructor resources through Connect.
∙ Art Full-color digital files of all illustrations, photos, and tables in the book can be readily incorporated into lecture pre-
sentations, exams, or custom-made classroom materials. In addition, all files have been inserted 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 Lecture Outlines Ready-made presentations that combine art and lecture notes are provided for each
chapter of the text updated for the ninth edition by Patricia Amateis.
∙ Test Builder in Connect Available within Connect, Test Builder is a cloud-based tool that enables instructors to format
tests that can be printed or administered within a LMS. Test Builder offers a modern, streamlined interface for easy con-
tent configuration that matches course needs, without requiring a download. Test Builder allows you to:
∙ access all test bank content from a particular title.
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∙ 
Instructor’s Solutions Manual This supplement, prepared by John Murdzek, contains complete, worked-out solutions for
all the end-of-chapter problems in the text.

COOPERATIVE CHEMISTRY LABORATORY MANUAL

Prepared by Melanie Cooper of Michigan State University, this innovative manual 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, so they might complete three or four projects during the semester, rather than one preprogrammed experiment
per class. The emphasis is on experimental design, analytical problem solving, and communication.

STUDENT SOLUTIONS MANUAL

This supplement, prepared by John Murdzek, contains detailed solutions and explanations for all problems in the main
text that have colored numbers.

siL40215_fm_i-xxxv.indd 34 10/11/19 1:05 PM

 ACKNOWLEDGMENTS
I t would be nearly impossible to put together a more profes-
sional, talented, and supportive publishing team than our col-
leagues at McGraw-Hill Education: Managing Director
Kathleen McMahon, Executive Portfolio Manager Michelle
Hentz, Product Developer Marisa Dobbeleare, Program Man-
ager Jolynn Kilburg, Content Project Manager Laura Bies,
Designer Jessica Cuevas, Executive Marketing Manager Tami
Hodge, and Director of Digital Content Shirley Hino, Ph.D. It
is a pleasure to work with them; their leadership, knowledge,
and encouragement have helped to make this latest edition a
reality.
siL40215_fm_i-xxxiv_1.indd 1
John Murdzek provided a thorough accuracy check of all
the new sample problems, follow-up problems, and end-of-
chapter problems as part of his superb preparation of both the
Student and Instructor’s Solutions Manuals.
The following individuals helped write and review
­learning goal-oriented content for LearnSmart for General
Chemistry: Barbara Pappas and David Jones.
Several expert freelancers contributed as well. Deb
DeBord did an excellent job in copyediting the text, and Louis
Poncz, Ph.D. and Lauren Timmer followed with meticulous
proofreading.
15/10/19 7:53 AM
 Keys to Studying

1 Chemistry: Definitions,
Units, and Problem
Solving
1.1 Some Fundamental Definitions 1.3 Measurement and Chemical 1.4 Uncertainty in Measurement:
States of Matter Problem Solving Significant Figures
Properties of Matter and Its Changes Features of SI Units Determining Significant Digits
Central Theme in Chemistry SI Units in Chemistry Calculations and Rounding Off
Importance of Energy Units and Conversion Factors Precision, Accuracy, and Instrument
1.2 The Scientific Approach: Systematic Problem-Solving Approach Calibration
Developing a Model Temperature Scales
Extensive and Intensive Properties

Source: Clockwise: Cosmetics: ©Photodisc/

Getty Images; Stream: ©Ingram Publishing/
SuperStock; Solar panels: ©Gencho Petkov/
Shutterstock; Woman with prosthetic leg:
©MichaelSvoboda/E+/Getty Images;
Medicine: ©Ingram Publishing/Alamy Stock
Photo; Red car: ©Vladimiroquai/iStock/Getty
Images; Computer/cell phone: ©Y Photo
Studio/Shutterstock; Cereal: ©Robert
Santos/BlueMoon Stock/Getty Images;
Boots: ©Ingram Publishing

siL40215_ch01_002-039.indd 2 9/17/19 6:06 PM

 Concepts and Skills to Review Before You Study This Chapter

› exponential (scientific) notation (Appendix A)

Y ou are embarking on the study of chemistry, a fascinating

science that is fundamental to understanding other natural
sciences, and one that has a tremendous impact on all of society—and your every-
day life. For example, your morning routine probably includes using shampoo, soap,
toothpaste, and/or cosmetics to get you ready to face your day. You adorn yourself in
clothing composed of dyed polymeric fibers, perhaps lace up your waterproof boots,
and eat a bowl of nutrient-enriched cereal made of grain grown in fertilized soil.
Grabbing your cell phone and laptop, both of which contain semiconductors and bat-
teries, you hop into your hydrocarbon-fueled, metal-vinyl-ceramic vehicle and ignite
a synchronized series of controlled gaseous explosions to start your car and take off
for class!
Scientists use chemistry not only to manufacture these commercial products of
daily life, but also to create new life-saving medicines, fabricate advanced materials
for mobility-enhancing synthetic hip joints and prosthetic limbs, develop innovative
methods of energy production, and build new chemical models to study climate
change and environmental concerns. There are transformative discoveries to be made
in chemistry every day!
A basic understanding of chemistry is crucial for anyone who wants to study
biochemistry, geochemistry, food chemistry, agricultural chemistry, forensic chemistry,
environmental chemistry, engineering, medicine, or nanotechnology, just to name a
few of the many fields that intersect with chemistry. You’re going to learn some
amazing things in your chemistry course as you begin to view a hidden reality, one
filled with incredibly minute particles moving at fantastic speeds and interacting in
ways that determine how all matter behaves. This chapter holds the keys to unlock
and enter this new world, so let’s get started!

IN THIS CHAPTER . . . We discuss some central ideas about matter and energy, the process
of science, units of measurement, and how scientists handle data.
› We begin with fundamental concepts about matter and energy and their changes.
› We take a look at how scientists build models to study nature.
› We examine modern units for mass, length, volume, density, and temperature and apply
systematic chemical problem solving to unit conversions.
› We see that data collection always includes some uncertainty and examine the distinction
between accuracy and precision.

1.1 SOME FUNDAMENTAL DEFINITIONS

A good place to begin our exploration of chemistry is by defining it and a few central
concepts. Chemistry is the scientific study of matter and its properties, the changes
that matter undergoes, and the energy associated with those changes. Matter is the
“stuff” of the universe: air, glass, planets, students—anything that has mass and volume.
(In Section 1.4, we discuss the meanings of mass and volume in terms of how they
are measured.) Chemists want to know the composition of matter, the types and
amounts of simpler substances that make it up. A substance is a type of matter that
has a defined, fixed composition.

siL40215_ch01_002-039.indd 3 9/17/19 6:06 PM

 4   Chapter 1 • Keys to Studying Chemistry: Definitions, Units, and Problem Solving

The States of Matter

Matter occurs commonly in three physical forms called states: solid, liquid, and gas.
On the macroscopic scale, each state of matter is defined by the way the sample fills
a container (Figure 1.1, flasks at top):
∙ A solid has a fixed shape that does not conform to the container shape. Solids are
not defined by rigidity or hardness: solid iron is rigid and hard, but solid lead is
flexible, and solid wax is soft.
∙ A liquid has a varying shape that conforms to the container shape, but only to the
extent of the liquid’s volume; that is, a liquid has an upper surface.
∙ A gas also has a varying shape that conforms to the container shape, but it fills
the entire container and, thus, does not have a surface.
On the atomic scale, each state is defined by the relative positions of its particles
(Figure 1.1, circles at bottom):
∙ In a solid, the particles lie next to each other in a regular, three-dimensional pattern,
or array.
∙ In a liquid, the particles also lie close together but move randomly around each other.
∙ In a gas, the particles have large distances between them and move randomly
throughout the container.

The Properties of Matter and Its Changes

We learn about matter by observing its properties, the characteristics that give
each substance its unique identity. To identify a person, we might observe height,
weight, hair and eye color, fingerprints, and, now, even DNA pattern, until we
arrive at a unique identification. To identify a substance, we observe two types of
properties, physical and chemical, which are closely related to two types of change
that matter undergoes.

Solid Liquid Gas

Particles are close Particles are close Particles are far apart
together and organized. together but disorganized. and disorganized.

Figure 1.1 The physical states of matter.

siL40215_ch01_002-039.indd 4 4/16/19 6:43 PM

 1.1 • Some Fundamental Definitions    5

Physical Change: No Change in Composition Physical properties are character-

istics a substance shows by itself, without changing into or interacting with another
substance. These properties include color, melting point, electrical conductivity, and
density. A physical change occurs when a substance alters its physical properties,
not its composition. For example, when ice melts, several physical properties change,
such as hardness, density, and ability to flow. But the composition of the sample does
not change: it is still water. The photograph in Figure 1.2A shows what this change
looks like in everyday life. The “blow-up” circles depict a magnified view of the
particles making up the sample. In the icicle, the particles lie in the repeating pattern
characteristic of a solid, whereas they are jumbled in the liquid droplet; however, the
particles are the same in both states of water.
Physical change (same substance before and after):

Water (solid state) ⟶ water (liquid state)

All changes of state of matter are physical changes.

Chemical Change: A Change in Composition Chemical properties are charac-

teristics a substance shows as it changes into or interacts with another substance (or
substances). Chemical properties include flammability, corrosiveness, and reactivity
with acids. A chemical change, also called a chemical reaction, occurs when one or
more substances are converted into one or more substances with different composition
and properties. Figure 1.2B shows the chemical change (reaction) that occurs when
you pass an electric current through water: the water decomposes (breaks down) into
two other substances, hydrogen and oxygen, that bubble into the tubes. The composi-
tion has changed: the final sample is no longer water.
Chemical change (different substances before and after):
electric current
Water hydrogen + oxygen

Let’s work through a sample problem that uses atomic-scale scenes to distinguish
between physical and chemical change.

Oxygen gas
Solid water

Liquid water Hydrogen gas

A Physical change: B Chemical change:

Solid state of water becomes liquid state. Electric current decomposes water into different substances
Particles before and after remain the same, (hydrogen and oxygen). Particles before and after are different,
which means composition did not change. which means composition did change.

Figure 1.2 The distinction between physical and chemical change.

Source: (A) ©Paul Morrell/The Image Bank/Getty Images; (B) ©McGraw-Hill Education/Stephen Frisch, photographer

siL40215_ch01_002-039.indd 5 4/16/19 6:43 PM

 6   Chapter 1 • Keys to Studying Chemistry: Definitions, Units, and Problem Solving

SAMPLE PROBLEM 1.1 Visualizing Change on the Atomic Scale

Problem The scenes below represent an atomic-scale view of a sample of matter, A,

undergoing two different changes, left to B and right to C:

B A C

Decide whether each depiction shows a physical or a chemical change.

Plan Given depictions of two changes, we have to determine whether each represents a
physical or a chemical change. The number and colors of the little spheres that make up
each particle tell its “composition.” Samples with particles of the same composition but
in a different arrangement depict a physical change, whereas samples with particles of a
different composition depict a chemical change.
Solution In A, each particle consists of one blue and two red spheres. The particles in
A change into two types in B, one made of red and blue spheres and the other made of
two red spheres; therefore, they have undergone a chemical change to form different
particles. The particles in C are the same as those in A, but they are closer together and
arranged in a regular pattern; therefore, they have undergone a physical change.
FOLLOW-UP PROBLEMS
Brief Solutions for all Follow-up Problems appear at the end of the chapter.
1.1A Is the following change chemical or physical?

1.1B Is the following change chemical or physical?

SOME SIMILAR PROBLEMS 1.1 and 1.80

Table 1.1 illustrates some of the unique physical and chemical properties of the
common substance copper.

Temperature and Changes in Matter Depending on the temperature and pressure

of the surroundings, many substances can exist in each of the three physical states
and undergo changes in state as well. For example, as the temperature increases, solid
water melts to liquid water, which boils to gaseous water (also called water vapor).

siL40215_ch01_002-039.indd 6 4/16/19 6:43 PM

 1.1 • Some Fundamental Definitions    7

Table 1.1 Some Characteristic Properties of Copper

Physical Properties Chemical Properties

Slowly forms a
Easily hammered blue-green carbonate
into sheets in moist air
(malleable) and
drawn into wires
(ductile)

Reacts with nitric or

sulfuric acid

Can be melted
and mixed with
zinc to form brass

Slowly forms deep-blue

solution in aqueous
Density = 8.95 g/cm3 ammonia
Melting point = 1083°C
Boiling point = 2570°C

Source: (copper) ©Dgstudiodg/iStock/Getty Images, ©McGraw-Hill Education/Stephen Frisch,

photographer; (candlestick) ©Willard/iStock/Getty Images; (copper carbonate, copper reacting with
acid, copper and ammonia) ©McGraw-Hill Education/Stephen Frisch, photographer

Similarly, as the temperature drops, water vapor condenses to liquid water, and with
further cooling, the liquid freezes to ice:
heating heating
Ice liquid water water vapor
cooling cooling

In a steel plant, solid iron melts to liquid (molten) iron and then cools to the solid
again. And, far beyond the confines of a laboratory or steel plant, lakes of molten
sulfur (a solid on Earth at room temperature) lie on Jupiter’s moon Io (see photo),
which is capped by poles of frozen hydrogen sulfide, a gas on Earth.
The main point is that a physical change caused by heating can generally be
reversed by cooling. This is not generally true for a chemical change. For example,
heating iron in moist air causes a chemical reaction that yields the brown, crumbly
substance known as rust. Cooling does not reverse this change; rather, another chemi-
cal change (or series of them) is required.
The following sample problem provides practice in distinguishing some familiar Many substances that are common on
examples of physical and chemical change. Earth occur in unusual states on other
worlds.
Source: NASA-JPL
Distinguishing Between Physical
SAMPLE PROBLEM 1.2
and Chemical Change
Problem Decide whether each of the following processes is primarily a physical or a
chemical change, and explain briefly:
(a) Frost forms as the temperature drops on a humid winter night.
(b) A cornstalk grows from a seed that is watered and fertilized.
(c) A match ignites to form ash and a mixture of gases.
(d) Perspiration evaporates when you relax after jogging.
(e) A silver fork tarnishes slowly in air.
Plan The basic question we ask to decide whether a change is chemical or physical is,
“Does the substance change composition or just change form?”

siL40215_ch01_002-039.indd 7 4/16/19 6:43 PM

 8   Chapter 1 • Keys to Studying Chemistry: Definitions, Units, and Problem Solving
Methane and oxygen form carbon dioxide
and water in the flame of a lab burner.
(Carbon is black, oxygen red, and
hydrogen blue.)
siL40215_ch01_002-039.indd 8
Solution (a) Frost forming is a physical change: the drop in temperature changes
water vapor (gaseous water) in humid air to ice crystals (solid water).
(b) A seed growing involves chemical change: the seed uses water, substances from air,
fertilizer, soil, and energy from sunlight to make complex changes in composition.
(c) The match burning is a chemical change: the combustible substances in the match
head are converted into other substances.
(d) Perspiration evaporating is a physical change: the water in sweat changes its state,
from liquid to gas, but not its composition.
(e) Tarnishing is a chemical change: silver changes to silver sulfide by reacting with
sulfur-containing substances in the air.
FOLLOW-UP PROBLEMS
1.2A Decide whether each of the following processes is primarily a physical or a
chemical change, and explain briefly:
(a) Purple iodine vapor appears when solid iodine is warmed.
(b) Gasoline fumes are ignited by a spark in an automobile engine’s cylinder.
(c) A scab forms over an open cut.
1.2B Decide whether each of the following processes is primarily a physical or a
chemical change, and explain briefly:
(a) Clouds form in the sky.
(b) Old milk turns sour.
(c) Butter is melted to use on popcorn.
SOME SIMILAR PROBLEMS 1.6 and 1.7
The Central Theme in Chemistry
Understanding the properties of a substance and the changes it undergoes
leads to the central theme in chemistry: macroscopic-scale properties
and behavior, those we can see, are the results of atomic-scale proper-
ties and behavior that we cannot see. The distinction between chemi-
cal and physical change is defined by composition, which we study
macroscopically. But composition ultimately depends on the makeup
of substances at the atomic scale. Similarly, macroscopic properties
of substances in any of the three states arise from atomic-scale
behavior of their particles. Picturing a chemical event on the
molecular scale, even one as common as the flame of a laboratory
burner, helps clarify what is taking place. What is happening when
water boils or copper melts? What events occur in the invisible
world of minute particles that cause a seed to grow, a neon light
to glow, or a nail to rust? Throughout the text, we return to this
central idea:
We study observable changes in matter to understand their unobserv-
able causes.
The Importance of Energy in the Study of Matter
Physical and chemical changes are accompanied by energy changes. Energy is often
defined as the ability to do work. Essentially, all work involves moving something.
Work is done when your arm lifts a book, when a car’s engine moves the wheels, or
when a falling rock moves the ground as it lands. The object doing the work (arm,
engine, rock) transfers some of the energy it possesses to the object on which the
work is done (book, wheels, ground).
The total energy an object possesses is the sum of its potential energy and its
kinetic energy.
∙ Potential energy is the energy due to the position of the object relative to other
objects.
∙ Kinetic energy is the energy due to the motion of the object.
4/16/19 6:44 PM
 1.1 • Some Fundamental Definitions    9

Let’s examine four systems that illustrate the relationship between these two forms of
energy: a weight raised above the ground, two balls attached by a spring, two electri-
cally charged particles, and a fuel and its waste products. Two concepts central to all
these cases are
1. When energy is converted from one form to the other, it is conserved, not destroyed.
2. Situations of lower energy are more stable and are favored over situations of higher
energy, which are less stable.
The four cases are
∙ A weight raised above the ground (Figure 1.3A). The energy you exert to lift a
weight against gravity increases the weight’s potential energy (energy due to its
position). When you drop the weight, that additional potential energy is converted
to kinetic energy (energy due to motion). The situation with the weight elevated
and higher in potential energy is less stable, so the weight will fall when released,
resulting in a situation that is lower in potential energy and more stable.
∙ Two balls attached by a spring (Figure 1.3B). When you pull the balls apart, the
energy you exert to stretch the relaxed spring increases the system’s potential
energy. This change in potential energy is converted to kinetic energy when you
release the balls. The system of balls and spring is less stable (has more potential
energy) when the spring is stretched than when it is relaxed.
∙ Two electrically charged particles (Figure 1.3C). Due to interactions known as
electrostatic forces, opposite charges attract each other, and like charges repel each
other. When energy is exerted to move a positive particle away from a negative

Less stable

Stretched
Potential Energy

Potential Energy

Less stable
Change in
potential energy
Change in
equals
potential energy
kinetic energy.
equals
Relaxed kinetic energy.

More stable More stable

A A gravitational system. Potential energy is gained when a weight B A system of two balls attached by a spring. Potential energy is gained
is lifted. It is converted to kinetic energy as the weight falls. when the spring is stretched. It is converted to the kinetic energy of the
moving balls as the spring relaxes.
Potential Energy

Potential Energy

Less stable Less stable

Change in Change in
potential energy potential energy
equals equals
kinetic energy. kinetic energy.
exhaust
More stable More stable

C A system of oppositely charged particles. Potential energy D A system of fuel and exhaust. A fuel is higher in chemical potential
is gained when the charges are separated. It is converted to energy than the exhaust. As the fuel burns, some of its potential
kinetic energy as the attraction pulls the charges together. energy is converted to the kinetic energy of the moving car.

Figure 1.3 Potential energy is converted to kinetic energy. The dashed horizontal lines indicate
the potential energy of each system before and after the change.

siL40215_ch01_002-039.indd 9 4/16/19 6:44 PM

 10   Chapter 1 • Keys to Studying Chemistry: Definitions, Units, and Problem Solving

one, the potential energy of the system increases, and that increase is converted to
kinetic energy when the particles are pulled together by the electrostatic attraction.
Similarly, when energy is used to move two positive (or two negative) particles
together, their potential energy increases and changes to kinetic energy when they
are pushed apart by the electrostatic repulsion. Charged particles move naturally
to a more stable situation (lower energy).
∙ A fuel and its waste products (Figure 1.3D). Matter is composed of positively and
negatively charged particles. The chemical potential energy of a substance results
from the relative positions of its particles and the attractions and repulsions among
them. Some substances are higher in potential energy than others. For example,
gasoline and oxygen have more chemical potential energy than the exhaust gases
they form. This difference is converted into kinetic energy, which moves the car,
heats the interior, makes the lights shine, and so on. Similarly, the difference in
potential energy between the food and air we take in and the wastes we excrete
enables us to move, grow, keep warm, study chemistry, and so on.

› Summary of Section 1.1

› Chemists study the composition and properties of matter and how they change.
› Matter exists in three physical states—solid, liquid, and gas. The behavior of each state is
due to the arrangement of the particles.
› Each substance has a unique set of physical properties (attributes of the substance itself)
and chemical properties (attributes of the substance as it interacts with or changes to other
substances). Changes in matter can be physical (different form of the same substance) or
chemical (different substance).
› A physical change caused by heating may be reversed by cooling. But a chemical change
caused by heating can be reversed only by other chemical changes.
› Macroscopic changes result from submicroscopic changes.
› Changes in matter are accompanied by changes in energy.
› An object’s potential energy is due to its position; an object’s kinetic energy is due to its
motion. Energy used to lift a weight, stretch a spring, or separate opposite charges increases
the system’s potential energy, which is converted to kinetic energy as the system returns to
its original condition. Energy changes form but is conserved.
› Chemical potential energy arises from the positions and interactions of a substance’s
particles. When a higher energy (less stable) substance is converted into a more stable (lower
energy) substance, some potential energy is converted into kinetic energy.

1.2 THE SCIENTIFIC APPROACH:

DEVELOPING A MODEL
Our prehistoric ancestors survived through trial and error, gradually learning which
types of stone were hard enough to use for shaping other types, which plants were
edible and which poisonous, and so forth. Unlike them, we employ the quantitative
theories of chemistry to understand materials, make better use of them, and create
new ones.
To understand nature, scientists use an approach called the scientific method. It
is not a stepwise checklist, but rather a process involving creative proposals and tests
aimed at objective, verifiable discoveries. There is no single procedure, and luck often
plays a key role in discovery. In general terms, the scientific approach includes the
following parts (Figure 1.4):
∙ Observations. These are the facts our ideas must explain. The most useful observa-
tions are quantitative because they can be analyzed to reveal trends. Pieces of quantita-
tive information are data. When the same observation is made by many investigators
in many situations with no clear exceptions, it is summarized, often in mathematical

siL40215_ch01_002-039.indd 10 4/16/19 6:44 PM

 1.2 • The Scientific Approach: Developing a Model    11

Hypothesis is revised if Model is altered if

experimental results predicted events
do not support it. do not support it.

Observations Experiment Model (Theory) Further

Hypothesis
Natural phenomena Procedure to test Set of conceptual Experiment
Tentative proposal that
and measured events; hypothesis; measures assumptions that Tests predictions
explains observations
can be stated as a one variable at a time explains data from based on model
natural law if accumulated experi-
universally consistent ments; predicts
related phenomena

Figure 1.4 The scientific approach to understanding nature. Hypotheses and models are mental
pictures that are revised to match observations and experimental results, not the other way around.

terms, as a natural law. For example, the observation that mass remains constant
during chemical change is known as the law of mass conservation (Chapter 2).
∙ Hypothesis. Whether derived from observation or from a “spark of intuition,” a
hypothesis is a proposal made to explain an observation. A sound hypothesis need
not be correct, but it must be testable by experiment. Indeed, a hypothesis is often
the reason for performing an experiment: if the results do not support it, the hypoth-
esis must be revised or discarded. Hypotheses can be altered, but experimental
results cannot.
∙ Experiment. A set of procedural steps that tests a hypothesis, an experiment often
leads to a revised hypothesis and new experiments to test it. An experiment
typically contains at least two variables, quantities that can have more than one
value. A well-designed experiment is controlled in that it measures the effect of
one variable on another while keeping all other variables constant. Experimental
results must be reproducible by others. Both skill and creativity play a part in
experimental design.
∙ Model. Formulating conceptual models, or theories, based on experiments that test
hypotheses about observations distinguishes scientific thinking from speculation.
As hypotheses are revised according to experimental results, a model emerges to
explain how a phenomenon occurs. A model is a simplified, not an exact, repre-
sentation of some aspect of nature that we use to predict related phenomena. Ongo-
ing experimentation refines the model to account for new facts.
The explanation of combustion, the process of burning a material in air, by the
young French chemist Antoine Lavoisier (1743–1794) demonstrates the scientific
method of thinking. In the late 17th century, observations of burning led to the hypoth-
esis by many scientists that a loss of an undetectable substance called phlogiston
occurred during combustion. Experiments showing that air is required for burning and
that a metal gains mass during combustion led Lavoisier to propose a new hypothesis,
which he tested repeatedly with quantitative experiments. Accumulating evidence sup-
ported his developing model (theory) that combustion involves combination with a
component of air (oxygen). Innumerable predictions based on this theory have sup-
ported its validity, and Lavoisier himself extended the theory to account for animal
respiration and metabolism.

› Summary of Section 1.2

› The scientific method is a process designed to explain and predict phenomena.
› Observations lead to hypotheses about how a phenomenon occurs. When repeated with no
exceptions, observations may be expressed as a natural law.
› Hypotheses are tested by controlled experiments and revised when necessary.
› If reproducible data support a hypothesis, a model (theory) can be developed to explain the
observed phenomenon. A good model predicts related phenomena but must be refined
whenever conflicting data appear.

siL40215_ch01_002-039.indd 11 4/16/19 6:44 PM

Another random document with
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 print, and yet we had to send to England for paper to do the
job. Also all the pronunciation marks for Webster’s dictionary
were to be put in, and we did not have the type or the
matrices. I had to have the letters cut on wood, and matrices
made; this was a world of trouble. Some of the letters were
cut over half-a-dozen times or more, and after all they were
far from perfect. I also had a set of shaped music types cut,
and this took a deal of time and pains to get them all properly
cut, as also to get the matrices made. I finally succeeded
quite well in both respects.... I also experimented not a little in
stereotyping, and succeeded in doing fair work. I trained one
boy who stereotyped Matthew before I left. In order to carry it
on effectually and rapidly I had a furnace and press made and
fitted up, which after sundry changes worked very well.... I
also had a new style of case for Chinese type made, which I
think will be an improvement on the old. I also had a complete
and thorough overhauling of the matrices, reassorted them
all, and had new cases made. This was a serious job, but it
will I am sure prove a very great help to the efficient working
of the establishment.

He consented to manage the press only until a competent man

could be secured to take it off his hands. When casting about for
such a person, his mind had been directed to his brother John,
nearly a year before he was himself forced into this position. John
had hoped to go to college, and to prepare for the ministry, and to go
out as a missionary, but, on account of certain tendencies developed
as to his health, he was compelled to abandon his purpose. As to his
mechanical gifts and his ability to turn them into use in a great
variety of ways, he resembled Calvin; and the latter was so confident
that John could soon fit himself to be a competent superintendent of
the press at Shanghai that he advised the Board of Missions to make
inquiry in regard to him. The result was that eventually he was
selected for the place, and he arrived in China early in August, 1871.
Before he could satisfactorily enter on his duties it was necessary for
him to acquire some knowledge of the language and to acquaint
himself with the business committed to his charge. This detained
Calvin until late in that year; and after a period of some three months
spent at Tengchow, he returned to Shanghai to assist John in moving
the press to new and much better premises that had been
purchased. The moving proper was a heavy job, requiring a week of
hard, dirty labor. The distance was about a mile, mostly by water, but
by land a hundred or more yards at either end. While thus engaged,
although he was no longer officially at the head of the business, he
took the main charge, so as to allow his brother to give his time
chiefly to the acquisition of the language and to other things that he
needed to learn.
The new place is the same now occupied by the press in Peking
Road. Under the superintendency of Rev. G. F. Fitch, it has become
the center not only of the Presbyterian missions, but of the general
missionary activity all over China. In writing to his brother as early as
November, 1869, he said of this plant: “It is a very important place,
and would give you an extensive field for doing good. The
establishment is not very large, it is true, as compared with similar
establishments in such cities as New York or Philadelphia; yet it is
the largest and best of the kind in China. It not only does all the
printing for all our missionaries, but a great deal of job work for
others; besides making and selling a large amount of type.” After he
had completed his term of the management, and while helping John
to get into the traces, he wrote to one of the secretaries of the Board:

I am not in favor of enlargement, but I would be very sorry

to see the present efficiency of the press curtailed. It is doing
a great and a good work not only for our missions, but for all
China. It has exerted a prodigious collateral influence both in
China and in Japan, affording facilities for the production of all
kinds of scientific books, dictionaries, and so forth. Aside from
any general interest in the missionary work, having at no
small sacrifice left my proper work and given more than a
year to the press, and also having a brother here in charge of
it, I feel a lively interest in its future.
 The last record that has come down to us concerning his work
there is: “We have just sold to the Chinese government a large font
of Chinese type. They are going to use movable metal type. This is a
large step for them to take, and it will do good. China yields slowly,
but she is bound to yield to Christianity and Christian civilization.”
At no subsequent period of his life had he any part in the
management of a printing establishment, but indirectly he continued
to have much to do with the press. He was a member of a joint
committee of the Shantung and the Peking mission, in charge of
publications, and as such he had to acquaint himself with what was
needed, and with what was offered, so as to pass intelligent
judgment. Unofficially and as a friend whose aid was solicited, he
revised one or more of the books which his associates submitted to
him for criticism. At the General Conference of Missionaries, held at
Shanghai in 1877, a committee, of which he was a member, was
appointed to take steps to secure the preparation of a series of
schoolbooks for use in mission schools. Not long afterward he
published an elaborate paper on the subject, discussing in it the
character which such publications should have, and especially
calling attention to the need of peculiar care as to the Chinese words
which ought to be employed in the treatises on the sciences. That
committee diligently set itself to work, and initiated measures for a
rather comprehensive set of books by various missionaries to meet
the want recognized in this general field. He was himself called upon
to prepare several books, some of which he was willing to undertake;
others he put aside as not properly falling to him. In one or two
instances he claimed for himself precedence as to treatises
suggested for others to write. Some friction occurred, and when the
Conference met again in 1890 that committee was discharged, and
an Educational Association, composed of missionaries familiar with
the needs of schools, and confining its functions more exclusively to
the publication of books for teaching—largely under his leadership—
was formed. He was its first chairman. This change he had warmly
favored, and he was an active member of the Association. In it he
was chairman of a committee on scientific terms in Chinese, a
subject of great difficulty, and of prime importance in the preparation
of text-books. In the subsequent years he was so much occupied
with the revision of the Mandarin Bible, and with other duties, that he
could give to the technical terms only a secondary place in his
activities. Still, six years after he accepted this chairmanship he
says: “I have collected a large number of lists of subjects for terms in
chemistry, physics, mathematics, astronomy, geology, metallurgy,
photography, watch-making, machinery, printing, music, mental and
moral philosophy, political economy, theology, and so forth.”
Subsequently he continued this work.
The first literary production of his own pen in Chinese was a tract
on infant baptism; this was called forth by local conditions at
Tengchow. A small sheet tract, entitled “A Prayer in Mandarin,” also
followed early. As chairman of the committee appointed by the
Educational Association, he made a report on chemical terms, and
recommended a new and distinctively Chinese method for the
symbols in that science. This was printed.
In a preliminary report of the Shanghai press, made in September,
1871, he, in a list of books in course of preparation, mentions under
his own name as author the following: “1. Catechism on Genesis,
with answers to the more difficult questions,—finished, needing only
a slight revision. 2. An explanation of the moral law as contained in
the ten commandments,—half-finished. 3. Scripture Text-Book and
Treasury, being Scripture references by subjects, supplying in great
part the place of a concordance,—one-third finished.” All of these
had been under way for several years, but had been frequently
shunted off the track by other imperative work. Very soon after that
date the catechism was published. He had a good deal to do with
Julia’s “Music Book,” especially in coining appropriate terminology,
though he never claimed joint authorship in it. Along with Dr. Nevius,
he published a hymn book for use in Chinese services; and down to
the close of his life, especially on a Sabbath when he did not preach,
he now and then made an additional Chinese version of a hymn. In
fact, whenever he heard a new hymn that especially moved him he
wished to enrich the native collection by a translation of it into their
speech. One which the Chinese came greatly to like was his
rendering of the Huguenot song, “My Lord and I.” A subject that was
always dominant in his mind and heart was the call to the ministry,
and it was significant that one of the last things on which he worked
was a translation of the hymn which has the refrain, “Here am I, send
me.” It was not quite finished when his illness compelled him to lay
down his pen; but recently at a meeting of the Chinese student
volunteers, constituting a company rising well toward one hundred
and fifty, that hymn was printed on cards, and a copy was given to
each of these candidates for the ministry. In 1907 he had carried a
theological class through the Westminster Shorter Catechism, and
as an outcome his translation was published. This is the last
religious book he made in Chinese. During his long service as a
missionary he taught a number of theological classes in various
studies, and his lectures were regarded as very superior, but he
published none of them.
His schoolbooks all originated in the necessities of his own work
as a teacher. The first thus to force itself upon his attention was an
arithmetic. He was already at work on it in 1868, and it went to press
while his brother John was superintending the plant at Shanghai.
The preparation of such a book, to one unacquainted with the
conditions under which this one was made, may seem to have been
a rather easy undertaking, and to have required little more than a
sufficient mastery of the Chinese language and of English; yet there
were some perplexing questions that arose in connection with it. For
instance, the method of writing numbers horizontally was wholly
unknown to the Chinese. Should the new arithmetic use the western,
or should it retain the Chinese method? To retain the Chinese would
be to train the pupils in a usage that would be confusing in
subsequent reading of western mathematics; to abandon it would be
equally confusing in printing the text of the book, which, according to
Chinese usage, must be arranged perpendicularly. The difficulty was
gotten over by duplicating each pattern example, giving it once
horizontally and once perpendicularly. Pupils using the book were
permitted to take their choice in performing their work, but in the text
proper all numbers appeared vertically. Such lines as those dividing
the numerator and denominator of a fraction stood perpendicularly,
with the figures to the right and the left. Until he published his
arithmetic, the Chinese numerals had been employed; he introduced
the Arabic. At the dawn of the new era subsequent to the Boxer
outbreak, almost the first book in demand by Chinese teachers and
pupils outside the mission schools was a western arithmetic; and
among others put upon the market were many “pirated” editions of
Mateer’s book, printed on cheap paper and with wooden blocks. The
publishers had not yet learned the significance of “copyright.” The
circulation of the book, however brought about, had at least the
effect of immediately increasing the reputation of its author among
the scholarly classes outside the church. Of the editions issued by
the press at Shanghai tens of thousands of copies have been sold.
Dr. Fitch writes that “it is impossible to state the total number,” and
that “the book has gone into all parts of the empire.”
In October, 1884, he submitted to the schoolbook committee of the
Educational Association the manuscript of his geometry, and in doing
so he said of it:

It is the result of much pains and labor.... The book is

written in plain Wen-li, and much pains has been taken to
make it smooth in style and accurate in meaning. In the few
equations used I have introduced the mathematical signs
employed in the West, of which I have given a full explanation
in the beginning of the book.... Mathematical signs and
symbols are a species of universal language, used alike by all
civilized nations, and it is unwise to change them until it is
absolutely necessary. The young men who have given most
effective assistance in the preparation of this geometry are
decided in their opinion that we should not change or garble
the mathematical symbolism of the West, but give it to them in
its integrity. The only change made is in writing equations
perpendicularly instead of horizontally,—a change which is
necessitated by the form of Chinese writing.

The book was published the following year. To the same

committee he reports in March, 1882, that his algebra was then all in
manuscript, and only needing revision and some rearrangement
before printing. The geometry was followed by his algebra, first part.
These have had a large sale, though, because fewer studied this
branch, not the equal of the arithmetic.
On January 14, 1908, he sent to the manager of the press the
preface to the second volume of his algebra, which covers the same
ground as the “University” edition in the United States. Of this Dr.
Hayes says: “Over twenty years ago he began the preparation of
Part II of his algebra, and the draft then made was used in
manuscript for many years. Other duties pressed upon him, and he
was compelled to lay it away unfinished. Yet he had not forgotten it,
but from time to time he would make a step in advance. It was only a
few months before his death that the work was completed and
published.”
There were a number of other books which he planned, on some
of which he did considerable work, but none of which he completed.
One of these was so colossal in its projected scope and scholarship
that it deserves special notice because indicative of the large things
to which early in his missionary career he was already eager to give
his time and abilities. This was a Mandarin dictionary. In its
preparation he sought to associate with himself Rev. Chauncey
Goodrich, of Peking; and in writing to him under date of June 6,
1874, he thus stated his conception of the work:

My idea of the book is a dictionary of the spoken language

of north China, in all its length and breadth, including on the
one hand all the colloquialisms that the people use in
everyday life,—all they use in Chi-li and in Shantung, and in
all the Mandarin-speaking provinces, so far as we can get it,
noting, of course, as such, the words and phrases we know to
be local. Further, let it include as a prominent feature all sorts
of ready-made idiomatic phrases, and in general all
combinations of two or more characters in which the meaning
coalesces, or varies from the simple rendering of the separate
characters.

Considerable preliminary work had already been done, when the

death of Mrs. Goodrich compelled her husband to withdraw from the
partnership; and the project was abandoned by Mateer, though with
a hope that it might be resumed. In 1900, however, as the fruit of this
and kindred studies he published an analysis of two thousand one
hundred and eighteen Chinese characters. This little book was
designed to help children in dictation exercises to write characters,
and is still largely used for this purpose by mission schools. The
huge dictionary, though never completed, had three direct
descendants. With Dr. Goodrich it produced first a Chinese phrase
book, and then a pocket Chinese-English dictionary, which for brevity
and comprehensiveness is a marvel, and which is regarded by
almost every student of Chinese as a necessity. In marked contrast
with these two volumes is an immense dictionary left behind in
manuscript by Dr. Mateer. It is wholly in Chinese; and as it lies
unfinished it occupies more than a cubic foot of space, and consists
of a set of volumes. No comprehensive dictionary of the Chinese
language has been published for two hundred and fifty years, and
the last issued had been mainly classical. The object of this was to
supply the evident need of a great new work of that sort. One
insurmountable difficulty encountered was a phonetic arrangement
commanding common usage. None had the requisite approval.
Fortunately, on this undertaking Dr. Mateer did not spend his own
time, except so far as that was necessary to direct the preparation of
it by his scribes when they were not otherwise employed.
In his letter to his college classmates in 1897 he says that he has
“well in hand a work on electricity, and one on homiletics prepared
when teaching theology.” Neither of these was finished and
published. To his college classmate, S. C. T. Dodd, Esq., he wrote in
1898 that he was trying also to finish a work on moral philosophy. In
March, 1878, he wrote to Dr. W. A. P. Martin, of Peking: “You will
remember probably that when you were here I spoke of my intention
to make a natural philosophy by and by. You said, ‘Go ahead,’ and
that you would retire in my favor by the time mine was ready, say, ten
years hence. If I am spared I hope to have the book ready within the
time, if not sooner. As you know, natural philosophy is my hobby, and
I have taught it more thoroughly probably than has been done in any
other school in China. I intend when I visit America to prepare myself
with the material and the facilities for such work.” He was not able to
find time for this work; and when later Dr. Martin invited him to write
for the revised edition of his treatise the chapter on electricity, this
privilege had for the same reason to be put aside. He had also
advanced far toward the completion of a translation of “Pilgrim’s
Progress” into Mandarin.
His “Mandarin Lessons” was published early in 1892, and
immediately commanded a success even larger than its author may
have anticipated. Ever since, it has gone on toward a more general
use by foreigners wishing to master the language, and has now far
outstripped every other work of its kind. He was a quarter of a
century in making the book. June 28, 1873, he made the following
entry in his Journal concerning it:

Most of last week and this I have spent in making lessons

and planning a much larger number than I have made. Mr.
Mills urged me to work at them for Dr. ⸺’s benefit, as he did
not seem to take hold of Wade. I did not think of what a job I
was sliding into when I made three lessons for Maggie a few
years ago. I have now laid out quite an extensive plan, and if I
am spared I trust I shall be able to finish it, though it will take
a deal of work. I believe that I can produce a far better book
than any that has yet been brought forth. I was not intending
to do this work now, and cannot work much more at it, as
other matters imperatively demand attention.

Guided by the hint in this quotation, we are able to trace the book
still farther back to its very beginning. June 20, 1867, he said in his
Journal: “Maggie Brown [Julia’s sister] has been pushing on pretty
lively with the Chinese. I made her lessons for a good while, which
she studies, and now she is reading ‘The Peep of Day.’ I tried to
make her lessons with a view to bringing out the peculiarities of
Chinese idiom. It led me to a good deal of thinking and investigating.
I have a mind to review and complete the work, and may some day
give it to the world. My great difficulty is in classifying the results
attained.”
 As the years went by his ideas of the plan for the work took
definite shape. In one of his letters concerning it he wrote:

Each lesson illustrates an idiom, the word idiom being

taken with some latitude. The sentences, as you will see, are
gathered from all quarters, and introduce every variety of
subjects. I have also introduced every variety of style that can
be called Mandarin, the higher style being found chiefly in the
second hundred lessons. The prevailing object, however, is to
help people to learn Mandarin as it is spoken. I have tried to
avoid distinct localisms, but not colloquialisms. A large
acquaintance with these is important, not to say essential, to
every really good speaker of Mandarin. It is, of course,
possible to avoid the most of them, and to learn to use a
narrow range of general Mandarin which never leaves the
dead level of commonplace expressions, except to introduce
some stilted book phrase. This, however, is not what the
Chinese themselves do, nor is it what foreigners should seek
to acquire. Many colloquialisms are very widely used, and
they serve to give force and variety to the language,
expressing in many instances what cannot be expressed in
any other way. I have tried to represent all quarters, and in
order to do so I have in many cases given two or more forms.

In the pursuit of his plan he sought the aid of competent scholars

in the north and in central China, so as to learn the colloquialisms
and the usage of words; also in the preparation of a syllabary of the
sounds of characters as heard in each of the large centers where
foreigners are resident. To accomplish this he also traveled widely.
Late in 1889, after a summer spent in studying the dialects of China,
he, in company with Julia, made a three months’ trip to the region of
the Yangtse, going down on the Grand Canal, spending a month on
the great river, and remaining a month at Nanking; always with the
main purpose of informing himself as to the current Mandarin, so as
to perfect his book. This tour enabled him to give it the final revision;
and in his opinion it “more than doubled the value” of the “Lessons.”
As finished, they were a huge quarto of six hundred pages, which
with the help of Mrs. Julia Mateer he saw through the press down at
Shanghai. In 1901, assisted by Mrs. Ada Mateer, he issued a more
elementary work of the same general nature.
The protracted study and care which he put upon the “Lessons”
were characteristic of him in all his literary productions. Upon this
subject no one is better qualified to bear testimony than is Dr.
George F. Fitch, Superintendent of the Presbyterian Mission Press,
at Shanghai, who speaks from direct personal observation. He says:

One very marked characteristic of Dr. Mateer was the

almost extreme painstaking with which he went over any work
which he was getting ready for publication; revising and re-
revising, seeking the judgment of others, and then waiting to
see if possibly new light might dawn upon the subject. I
remember reading shortly after I came to China the
manuscript of a paper which he had prepared with great labor,
upon the much-mooted “term question”; and in which he had
collected, with infinite pains, seemingly a great number of
quotations from the Chinese classics and other native works,
bearing on the use of Shen as the proper word for God in
Chinese. I urged him to publish at once, as I thought it might
be useful in helping settle that question. But he stoutly
refused, saying that it was not yet complete. Nor did it finally
see the light, in print, until nearly twenty years afterward.

None of his books at all reveal the protracted and toilsome

process of the preparation. We see only the result of years of
research. For instance, in his library there was a long row of Chinese
books each one of which showed a large number of little white slips
at the top. Each one of this multitude of marks had been placed
there by some student whom he had employed respectively to read
works in Chinese likely to use the word Shen, in order to indicate the
passages at which he needed to look. All these were canvassed,
and the different shades of meaning were classified.
 From the “Mandarin Lessons,” and recently from the arithmetic, he
received substantial pecuniary returns, though not at all sufficient to
entitle him to be regarded as wealthy. In his manner of living he
would have been untrue to his training and impulses if he had not
practiced frugality, economy, and simplicity. As the means came into
his possession he used them generously both for personal friends
and for the promotion of the cause to which he had consecrated his
life. Of his outlays for the school and college we shall presently need
to speak. The expenses of the Yangtse trip came out of his own
pocket. March 9, 1895, he wrote to one of the secretaries of the
Board:

The mission minutes spoke, if you remember, of my

intention to erect a building for a museum and public lecture
room, and present it to the Board. This I intend to do at once.
It will cost about twelve hundred dollars, possibly more. I may
say in the same connection also that my “Mandarin Lessons”
has fully paid all the cost of printing, and so forth, and I expect
during the next year to pay into the treasury of the Board one
thousand dollars, Mexican. This I do in view of the liberality of
the Board in giving me my time while editing and printing the
book. When the second edition is printed I expect to pay over
a larger amount. I need not say that I feel very much gratified
that the book has proved such a success: especially do I feel
that it has been, and is going to be, very widely useful in
assisting missionaries to acquire the Chinese language. My
scientific books are also paying for themselves, but as yet
have left no margin of profits.

May 20, 1905, he wrote to a secretary: “I may say, however, that in

view of the great importance of the school both to the Tengchow
station and as a feeder to the college at Wei Hsien, I have set apart
from the profit of my ‘Mandarin Lessons’ enough to support the
school for the present year.” December 13, 1906, he wrote to a
friend in the United States: “My brother is now holding a large
meeting of elders and leading men from all the stations in this field.
There are about three hundred of them. It is no small expense to
board and lodge so many for ten days. I am paying the bill.” In one of
his latest letters to me he mentions this ability pecuniarily to help as
affording him satisfaction.
 X
THE CARE OF THE NATIVE CHRISTIANS

“The need of the hour in China is not more new stations with expensive
buildings and wide itinerating. It is rather teaching and training what
we have, and giving it a proper development. Most of all we should
raise up and prepare pastors and preachers and teachers, who are
well grounded in the truth, so that the Chinese Church may have wise
and safe leaders.... There are already enough mission stations, or
centers, in the province, if they were properly worked. The need of the
hour is to consolidate and develop what we have, and by all means in
our power develop native agency, and teach and locate native
pastors,—men who are well grounded in the faith.”—letter to
secretary fox, of the American Bible Society, January 6, 1906.

Dr. Mateer believed that sooner than most missionaries

anticipated the Chinese Christians will join together and set up an
independent church. He meant by this not merely a union of the
ministers and churches of the various Presbyterian denominations at
work in the country, such as has already been effected, but an
organization that would include in its membership all the Protestant
Christians, and that would leave little or no place for the service of
foreign missionaries. He regarded this as inevitable; and for that
reason he considered it to be of prime importance that such an
effective preliminary work should promptly be done, that this coming
ecclesiastical independence might not be attended by unsoundness
as to creed or laxity in life. At the same time, in holding up the care
and the training of the native Christians as so important a part of the
work of the foreign missionary in China, in anticipation of what is
ahead, he was only for an additional reason urging what he had in all
his long career recognized as second to no other in importance. Of
course, at the beginning of the effort to give the gospel to a people it
is indispensable to do “the work of an evangelist”; that is, to seek by
the spoken word and by the printed book to acquaint them with
elementary Christian truth, and to endeavor to win them to Christ;
and we have already seen how diligent Dr. Mateer was in this
service, especially in his earlier missionary years. But he was just as
diligent in caring for the converts when gained; and in the school and
college it was the preparation of men for pastors and teachers and
evangelists that was constantly his chief aim.
The first body of native Christians with whose oversight he had
anything to do was that very small band that had been gathered into
the church at Tengchow. Mills was the senior missionary, and as
such he presided over that little flock until his death. In 1867 he was
installed as the pastor, and he continued in this office nearly twenty
years. During this long period Dr. Mateer at times supplied the pulpit
and cared for the church in Mills’s absence or illness, but for most of
the time it was only as a sort of adviser that he could render help in
that field. We have no reason to think specially unfavorably of
Chinese converts because some of those with whom he then had to
do at Tengchow, or elsewhere, proved themselves, to him, to be a
discouraging set of professing Christians. Were not a good many of
Paul’s converts very much of the same grade when he traveled
among the churches, and wrote his letters? Did it not take much
patience, and fidelity, and persistence on the part of Christ to make
anything worth while out of his select disciples? Yet these constituted
the membership of the primitive church from which even the
missionaries of our day have originated. At any rate some of the
earliest experiences of Dr. Mateer with the native Christians were of
a very depressing sort. In his Journal, under date of March 17, 1864,
he made this record:

Since coming to Tengchow there have been great

difficulties in the native church. Several of the members were
accused by common fame of various immoral practices,—one
of smoking opium, another of lying and conforming to
idolatrous practices, and another of breaking the Sabbath.
The second of these confessed his fault, and was publicly
reproved; the third also confessed, and on his profession of
penitence was restored to the confidence of the church. But
 though the first confessed to the use of the ashes of opium,
he gave no certain assurance of amendment; and he was
suspended, and so remains. These matters gave us all a
great deal of anxiety and sorrow of heart. It is sad thus to find
that even those who profess the name of Christ are so much
under the power of sin. It is one of the great discouragements
of the missionary work. Yet God is able to keep even such
weak ones as these unto eternal life.

Under date of September 15, 1866, he told of a worse case of

discipline:

We had a hearing with the accused, and gave him notice

that he would be tried, and of the charges and witnesses. We
wrote to Mr. Corbett at Chefoo, to get depositions for us. He
did so, and we met, and tried him. The evidence was
sufficient to convict him of lying, and of forging an account,
and of adultery; notwithstanding, he denied it all, endeavoring
to explain away such evidence as he was forced to admit. We
decided to excommunicate him, and it was done two weeks
ago.

It must not be supposed that there was a great deal of such

discouraging work; as a rule, the native Christians tried to live correct
lives; and the worst that could be said of most of them at those early
dates was that they were “babes” in Christ. But we cannot appreciate
what the missionary needs to do as to the professed converts unless
we look at this depressing phase. Besides, incidentally we are thus
shown one of the methods by which the native Christians were
trained in the conduct of their own churches. Each case is dealt with
just as is required by the regulations of the denomination with which
the church is associated. The same formalities and processes are
employed as if in the United States; the same fairness and fullness
of investigation, with witnesses and hearing of the accused; and the
same effort neither to fall below nor to exceed what justice and
charity combined demand for the good of the individual and of the
organization as a whole. As to this, in these particular cases no
exceptional credit can be claimed for Dr. Mateer; but we can be
perfectly sure that it commanded his hearty approbation. This was a
practical school also in which was called into exercise a quality of
which a young missionary, and especially a man of his type, seldom
has enough,—that of mingling a firm adherence to truth and
righteousness with a forbearing kindness that will not break a
bruised reed or quench the smoking flax. Gradually this became so
characteristic of him that the boys in his school and the Christians in
the churches were accustomed to come to him and unburden
themselves not only of sorrows, but of faults, with no expectation that
he would condone wrong or shield them from its just consequences,
but confident that he would feel for them, and help them if he could.
Nor was it to these classes alone that his heart and hands opened.
As they came to know him better, the professor in the imperial
university sought his advice and the coolie turned to him in his need;
and never in vain.
But there was a brighter side to the experience of those early
days. Several of the boys in the school were converted. What joy this
afforded, we who live in Christian lands cannot appreciate. The little
church at Tengchow also steadily moved forward in those early days
of its history. In 1869 it had risen to about fifty members, and the
attendance was such that a building solely for its services became
indispensable; and in due time an appropriation was made by the
Board of Missions, first for a lot, and soon after for a house of
worship. Pastor Mills was then absent, and by appointment of
presbytery Dr. Mateer acted as stated supply. As such, having first
bought the lot, he made an appeal to the Board for the new edifice,
saying:

We hold our services in the boys’ schoolroom, which has

been kept inconveniently large, for this very purpose. It is the
only room that will seat all, and it will not do it sometimes. The
desks have to be carried out every Sabbath; and all the
benches, chairs, and so forth, about the establishment carried
in, making a decidedly nondescript collection. Aside from the
 inconvenience, two serious drawbacks are felt. One is the
want of sacred associations about the place. All heathen are
wanting in reverence, and no small part of what they need is
to have this idea instilled into their minds. We greatly need in
this work a house especially devoted to the worship of God.
The other drawback is the disorganizing effect the Sabbath
and week-day services have on the school. The room being in
the midst of the premises, it is impossible to prevent a large
amount of lounging, gossiping, and so forth, in the boys’ room
before the service begins. The superintendent feels that it is a
very serious drawback to the school, as well as an injury to
the native Christians.

Any American who is familiar with students and their habits will
perceive that in this matter Chinese young men and boys are very
much like those of our own land.
In that appeal there is another paragraph that deserves
transcription here:

It has been said that the Christians in heathen lands ought

to build their own churches, but this is impossible in the early
stages of the work, especially at the center of operations,
where the foreigner preaches and teaches in person, and
where a large part of his hearers are often from a distance.
The church at this place gives character to the whole work in
the eyes of the people at large, and must of necessity differ in
many respects from churches in small places presided over
by native pastors. Concerning these last we have already
taken a decided stand, requiring the natives to help
themselves to a great extent.

Dr. Mateer was appointed by the presbytery to serve a second

year as stated supply of the Tengchow church; and had it not been
that he was called in 1870 to Shanghai to take charge of the mission
press, he no doubt would have given his personal supervision to the
erection of the new house of worship. It was built during his absence,
and when he came back he rejoiced in its completion. At the death of
Mills in 1895, Dr. Mateer was chosen pastor, and was installed as
such,—a position he was able to assume because he had found in
Mr. Hayes a substitute for himself in the presidency of the college.
He remained pastor until he went with the college to Wei Hsien. Dr.
Hayes had already for years worked quietly and efficiently in the
school, under the presidency of Dr. Mateer, and had shown himself
to be a man of exceptional ability and energy—a man after Dr.
Mateer’s own heart. After he assumed the presidency Dr. Mateer
was still to assist in the college, but he was so often absent or
otherwise engaged that both the college and the preaching were
largely in the hands of Dr. Hayes.
According to the “Form of Government” of the Presbyterian
Church in the United States of America, when a “call” is made out for
a pastor it must be certified to have been voted by a majority of the
people entitled to exercise this right; and it must fill the blank in the
following clause: “And that you may be free from worldly cares and
avocations, we hereby promise and oblige ourselves to pay to you
the sum of ... in regular quarterly (or half-yearly, or yearly) payments
during the time of your being and continuing the regular pastor of this
church.” In the settling of native pastors over the Chinese churches
scattered through the country, the filling of that blank, and the actual
subscription of the funds needed for this and other expenses of the
organization, usually require the presence of a missionary and of his
earnest stimulation and guidance. Sometimes the pledges are very
liberal, if estimated by ability of the members; and sometimes it is
with great difficulty that they are brought up to the measure of their
duty. The salaries, however, are almost incredibly small, and even
according to Chinese standards are scarcely sufficient for a
livelihood. We need to keep this state of things in mind in order to
appreciate the amount that was inserted in the blank in Dr. Mateer’s
call to the pastorate of the Tengchow church. In reporting the entire
procedure to the Board of Missions, he said: “The church in
Tengchow in calling me for their pastor promised a salary of cash
amounting to fifty dollars, which is to be used to employ an
evangelist whom I am to select and direct.” Of course, he continued
to receive his own pay as a missionary from the funds of the Board.
The fifty dollars was probably a creditable amount, as contributed by
the native members out of their narrow means; and as a salary for a
native evangelist it was at least a fair average.
When reporting this pastorate to the Board of Missions, Dr. Mateer
said, “This is work that I love to do, especially the preaching.” When
doing the work of an evangelist among the people at large,
sermonizing could have no place. Even formal addresses of any sort
were rarely practicable. The best that the missionary can do when
itinerating is to get attention by any legitimate means, and then to
talk, and hear and answer questions, and bear with all sorts of
irrelevancies and interruptions. But when a church is organized, a
sermon, consisting of a passage of Scripture and a discourse built
upon it, is just as much in place as it is in one of our home houses of
worship on the Sabbath. It was to the opportunity for that form of
service that he refers when he expressed his pleasure in the
pastorate. In this also he greatly excelled. Some who knew him most
intimately, and who appreciated fully his great worth and efficiency,
did not regard him as a very eloquent preacher in an English pulpit.
He commanded the attention of his audience by his strong, clear,
earnest presentation of the great religious truths which he believed
with all his soul. The personality and consecration of the man were a
tremendous force when he stood in a pulpit in his own land; what he
lacked was the ability which some speakers possess of carrying his
audience with him, almost irrespective of the thoughts to which they
give utterance. But in preaching to the Chinese he took on an
extraordinary effectiveness. There was in the man, in the movement
of his thought, in his mastery of the language, in the intense
earnestness of his delivery, in the substance of his sermons and
addresses, much that captivated the native Christians, and made
others bow before his power. Mr. Baller, who had heard him
frequently, says: “His sermons were logical, direct, a unit in thought
and enriched with a copious vocabulary and illustrations. His points
were usually put from the Chinese point of view, so that a foreign air
was conspicuously absent.” To this day some of his addresses are
recalled as triumphs of real eloquence of speech; perhaps the most
notable of these being an address which he delivered at the opening
of the English Baptist Institution at Tsinan fu, in 1907. It was an