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Petersons

MASTER AP
CHEMISTRY
2nd Edition
Brett Barker
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Previous edition 2005
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ISBN-13: 978-0-7689-2472-5
ISBN-10: 0-7689-2472-3
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1 09 08 07
Second Edition
Petersons.com/publishing
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any revisions or corrections to the content of this book. Weve made sure the information in this book is accurate and
up-to-date; however, the test format or content may have changed since the time of publication.
OTHER RECOMMENDED TITLES
Petersons Master AP Calculus
Petersons Master AP U.S. Government & Politics
Petersons Master AP English Language& Composition
Petersons Master AP English Literature& Composition
Petersons Master AP U.S. History
Contents
Before You Begin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
How This Book Is Organized. . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Special Study Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xii
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xii
Youre Well on Your Way to Success . . . . . . . . . . . . . . . . . . . xii
Give Us Your Feedback . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii
Top 10 Strategies to Raise Your Score. . . . . . . . . . . . . . . . . . . xiv
PART I AP CHEMISTRY BASICS
1 All About the AP Chemistry Test. . . . . . . . . . . . . . . . . . . 3
Getting Started. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Preparing for the AP Chemistry Test . . . . . . . . . . . . . . . . . . . . 3
Making a Study Plan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
What the Test Covers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Getting to Know the Format of the Test . . . . . . . . . . . . . . . . . 9
How the AP Chemistry Test Is Scored. . . . . . . . . . . . . . . . . . . 10
Review of the AP Question Types . . . . . . . . . . . . . . . . . . . . . . 11
The Answer Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
PART II DIAGNOSING STRENGTHS AND
WEAKNESSES
2 Practice Test 1: Diagnostic. . . . . . . . . . . . . . . . . . . . . . . . . 29
Directions for Taking the Diagnostic Test . . . . . . . . . . . . . . . . 29
Answer Key . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
PART III AP CHEMISTRY REVIEW
3 Problem Solving and Measurement . . . . . . . . . . . . . . . 43
Defining Accuracy and Precision . . . . . . . . . . . . . . . . . . . . . . . 44
Using Significant Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Reviewing Scientific Notation . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Using Dimensional Analysis to Organize Your Work . . . . . . . 47
Laboratory Component. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4 Atomic Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
The Historical Development of Modern Atomic Theory . . . . . . . . . . . . . . . . 53
Modern Atomic Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
The Periodic Table of the Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
The Quantum Model of the Atom. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Quantum Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Electron Configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Periodic Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Exercises: Atomic Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5 Nuclear Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
The Discovery of Radioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Rutherford Discovers Different Types of Radiation . . . . . . . . . . . . . . . . . . . . 90
Different Types of Radioactive Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Radioactive Decay. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Half-Life. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Nuclear Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Exercises: Nuclear Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6 Chemical Bonding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Lewis Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Octet Rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Ionic Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Covalent Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Using Lewis Structures to Determine Molecular Bonding . . . . . . . . . . . . . . . 117
Resonance Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Intermolecular Forces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Exercises: Chemical Bonding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
7 Molecular Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
VSEPR Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Molecular Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Dipole Moments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
Valence Bond Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Sigma and Pi Bonds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Molecular Orbital Theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
Exercises: Molecular Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
vi Contents
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8 States of MatterGases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Units of Measure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
The Gas Laws. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
The Ideal Gas Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
Gas Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Daltons Law of Partial Pressures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Kinetic-Molecular Theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Grahams Law of Effusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Deviations from the Ideal Gas Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
Exercises: States of MatterGases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9 States of MatterLiquids and Solids . . . . . . . . . . . . . . . . . . . . . . . . . . 177
General Characteristics of Gases, Liquids, and Solids. . . . . . . . . . . . . . . . . . . 177
Energy and Phase Changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
Heating Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Vapor Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
The Solid State. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Exercises: States of MatterLiquids and Solids . . . . . . . . . . . . . . . . . . . . . . . 191
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
10 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Measuring Concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
Solvation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Colligative Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Exercises: Solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
11 Reaction Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Molecular Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
Chemical Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Major Reaction Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Ionic Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
Oxidation-Reduction Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Summary of the Main Reaction Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
Exercises: Reaction Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Answers and Explanations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
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Contents vii
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12 Stoichiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
The Mole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
Determining Chemical Formulas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Calculations in Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Limiting Reactants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
Exercises: Stoichiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
13 Equilibrium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
The Equilibrium Constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
The Equilibrium Constant, K
c
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
The Equilibrium Constant, K
p
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
The Relationship Between K
c
and K
p
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
The Reaction Quotient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
Solving Problems When Not All Equilibrium Concentrations Are Known . . 297
Le Chteliers Principle. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
Exercises: Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
14 Acids and Bases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Definitions of Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
The pH Concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
Weak Acids and Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Salt Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
The Relationship Between K
a
and K
b
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
The Common-Ion Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
Buffers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Acid-Base Titrations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Exercises: Acids and Bases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
15 Additional Equilibrium Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
The Solubility-Product Constant, K
sp
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
The Ion Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Factors That Affect Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
The Common-Ion Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
The Effect of pH on Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Complex Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
Miscellaneous Topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
Coordination Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Nomenclature of Coordination Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
viii Contents
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www.petersons.com
Exercises: Additional Equilibrium Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . 367
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
16 Kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
Reaction Rate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
Using Concentrations to Describe Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
Units and Rate Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
Determining Rate Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
Reaction Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
Half-Life. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
The Relationship Between Temperature and Rate . . . . . . . . . . . . . . . . . . . . . 392
Reaction Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Rate-Determining Steps and Rate Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
The Effect of Catalysts on Reaction Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Exercises: Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
17 Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
The First Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
Thermochemical Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
Hesss Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
Spontaneity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
Entropy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
The Second Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Gibbs Free Energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
Exercises: Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
18 Electrochemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
Oxidation and Reduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
Voltaic Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
The Relationship Between emf and Free Energy . . . . . . . . . . . . . . . . . . . . . . 439
The Nernst Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
Faradays Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
Exercises: Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Contents ix
www.petersons.com
19 Organic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
Unsaturated Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
Functional Groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
PART IV TWO PRACTICE TESTS
Practice Test 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
Section I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
Section II Reference Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Section II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
Practice Test 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Section I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Section II Reference Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
Section II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
Answer Key and Explanations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542
APPENDIX
College-by-College Guide to AP Credit and Placement . . . . . . . . . . . . 567
x Contents
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www.petersons.com
Before You Begin
HOW THIS BOOK IS ORGANIZED
Whether you have fi ve months, ni ne weeks, or just four short weeks to
prepare for the test, Petersons Master AP Chemistry wi l l hel p you devel op a
study pl an that caters to your i ndi vi dual needs and ti metabl es. These
step-by-step pl ans are easy to fol l ow and are remarkabl y effecti ve.
Top 10 Strategies to Raise Your Score gi ves you tri ed and true
test-taki ng strategi es.
Part I i ncl udes the basi c i nformati on about the AP Chemi stry Test
that you need to know.
Part II provi des a di agnosti c test to determi ne your strengths and
weaknesses. Use the di agnosti c test as a tool to i mprove your
objecti ve test-taki ng ski l l s.
Part III provi des revi ews and strategi es for answeri ng the di fferent
ki nds of mul ti pl e-choi ce and free-response questi ons you wi l l
encounter on the test. You wi l l have numerous opportuni ti es to
practi ce what you are l earni ng i n the Try I t Out! qui zzes and
exerci ses that fol l ow the revi ews. I t i s a good i dea to read the answer
expl anati ons to al l of the questi ons, because you may fi nd i deas or
ti ps that wi l l hel p you better anal yze the answers i n the
practi ce tests.
Part IV i ncl udes two addi ti onal practi ce tests. Remember to appl y
the test-taki ng system careful l y, work the system to get more correct
responses, be careful of your ti me, and stri ve to answer more
questi ons i n the ti me peri od.
The Appendix provi des you wi th the new Petersons Col l ege-by-
Col l ege Gui de to AP Credi t and Pl acement (for more than 400
sel ecti ve col l eges and uni versi ti es).
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
xi
SPECIAL STUDY FEATURES
Petersons Master AP Chemistry was desi gned to be as user-fri endl y as i t i s compl ete. I t
i ncl udes several features to make your preparati on easi er.
Overview
Each chapter begi ns wi th a bul l eted overvi ew l i sti ng the topi cs that wi l l be covered i n the
chapter. You know i mmedi atel y where to l ook for a topi c that you need to work on.
Summing It Up
Each strategy chapter ends wi th a poi nt-by-poi nt summary that captures the most i mportant
poi nts. The summari es are a conveni ent way to revi ew the content of these strategy chapters.
Bonus Information
I n addi ti on, be sure too l ook i n the page margi ns of your book for the fol l owi ng test-prep tool s:
NOTE
Notes hi ghl i ght cri ti cal i nformati on about the test.
TIP
Tips draw your attenti on to val uabl e concepts, advi ce, and shortcuts for tackl i ng the test. By
readi ng the ti ps, you wi l l l earn how to approach di fferent questi on types, pace yoursel f, and
remember what was di scussed previ ousl y i n the book.
ALERT!
Whenever you need to be careful of a common pi tfal l , youl l fi nd an Alert! Thi s i nformati on
reveal s and el i mi nates the mi spercepti ons and wrong turns many peopl e take on the test. By
taki ng ful l advantage of al l features presented i n Petersons Master AP Chemistry, you wi l l
become much more comfortabl e wi th the test and consi derabl y more confi dent about getti ng a
hi gh score.
APPENDIX
Petersons Col l ege-by-Col l ege Gui de to AP Credi t and Pl acement gi ves you the equi val ent
cl asses, scores, and credi t awarded at more than 400 col l eges and uni versi ti es. Use thi s gui de
to fi nd your possi bl e pl acement status, credi t, and/or exempti on based on your AP Chemi stry
score.
YOURE WELL ON YOUR WAY TO SUCCESS
Remember that knowl edge i s power. You wi l l be studyi ng the most comprehensi ve gui de
avai l abl e, and you wi l l become extremel y knowl edgeabl e about the test. We l ook forward to
hel pi ng you rai se your score.
xii Before You Begin
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
GIVE US YOUR FEEDBACK
Petersons, a Nel net company, publ i shes a ful l l i ne of resources to hel p gui de you through the
col l ege admi ssi on process. Petersons publ i cati ons can be found at your l ocal bookstore,
l i brary, and hi gh school gui dance offi ce, and you can access us onl i ne at www.petersons.com.
We wel come any comments or suggesti ons you may have about thi s publ i cati on and i nvi te you
to compl ete our onl i ne survey at www.petersons.com/booksurvey. Or you can fi l l out the
survey at the back of thi s book, tear i t out, and mai l i t to us at:
Publ i shi ng Department
Petersons
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Your feedback wi l l hel p us to provi de personal i zed sol uti ons for your educati onal
advancement.
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Before You Begin xiii
www.petersons.com
TOP 10 STRATEGIES TO RAISE YOUR SCORE
When i t comes to taki ng an AP test, some test-taki ng ski l l s wi l l do you more good than
others. Heres our pi ck for the top 10 strategi es to rai se your score:
1. Pace yourself. Questi ons usual l y go from easi est to most di ffi cul t. Work as
qui ckl y as you can through the begi nni ng of the test. Dont get l ul l ed i nto a
fal se sense of securi ty because you appear to be mai ntai ni ng a good pace i n the
fi rst part.
2. Educated guessingwill boost your score. Al though random guessi ng wont
hel p you, anythi ng better than random guessi ng wi l l . You shoul d be abl e to
make better-than-random guesses by usi ng common sense and the process of
el i mi nati on techni ques that are devel oped throughout thi s book.
3. The easy answer isnt always the best answer. Qui te frequentl y, test
makers wi l l put an attracti ve, but i ncorrect, answer as an (A) or (B) choi ce.
Readi ng al l of the choi ces decreases your chance of bei ng mi sl ed, parti cul arl y i n
questi ons where no cal cul ati ons are i nvol ved.
4. Use common sense. On mul ti pl e-choi ce questi ons, i t mi ght be readi l y
apparent that youve made an error (e.g., none of the choi ces match your
answer). However, on the free response, there i s no i mmedi ate feedback about
the accuracy of your answer. I t i s i mportant to i nspect your work to make sure
i t makes sense.
5. Put down your calculator. On the porti ons of the test where cal cul ators are
prohi bi ted, you shoul d expect to deal wi th numbers that are fai rl y easy to work
wi th. However, you want to sharpen your ski l l s for sol vi ng probl ems wi thout a
cal cul ator.
6. Become familiar with a few properties of logarithms. There are several
formul as that requi re the use of l ogari thms. Because l ogari thms are easy to
work wi th on a cal cul ator, you may never have l earned much about them.
Becomi ng fami l i ar wi th a few properti es of l ogari thms can hel p you work more
qui ckl y on some probl ems, especi al l y pH probl ems.
7. Makesureyou fill in thebubblesheet neatly. Otherwi se, the machi ne that
scores your answers wont gi ve you credi t.
8. Show all of your work on the free-response questions. I f you onl y show
your answer, and i t happens to be i ncorrect, the grader has no choi ce but to gi ve
you no credi t for the enti re questi on. Wri ti ng down al l of your steps makes sense.
9. Know your stuff. You may not know every bi t of i nformati on on the test, but
i t i s i mportant that you remember the i nformati on you have l earned.
10. Be neat on the free-response questions. Let the grader focus on content,
rather than the form. The answers are not l engthy, so do your best to be neat
and organi zed.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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xiv Before You Begin
www.petersons.com
P
ART I
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
AP CHEMISTRY BASICS
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CHAPTER 1 All About the
AP Chemistry Test
All About the AP
Chemistry Test
OVERVIEW
Getting started
Preparing for the AP Chemistry Test
Making a study plan
What the test covers
Getting to know the format of the test
How the AP Chemistry Test is scored
Review of the AP question types
The answer sheets
Summing it up
GETTING STARTED
There i s no questi on that the AP Chemi stry Test i s one of the most ri gorous
tests offered by the Col l ege Board. Chances are, however, that i f you are
pl anni ng to take the AP Chemi stry Test, you are the type of student who i s
ready to take on anythi ng thi s test can di sh out. You di dnt take AP Chem by
acci dentyou wanted to take i t, and thats because you are the type of
student who can handl e chal l enges. So, al though the test i s di ffi cul t, dont be
i nti mi dated by i t. You can beat thi s test!
PREPARING FOR THE AP CHEMISTRY TEST
Your fi rst step i s to understand that thi s test i s not somethi ng to be taken
l i ghtl y. Top athl etes spend a great deal of ti me prepari ng thei r bodi es for bi g
competi ti ons, and you, too, must prepare your mi nd for thi s test. But most
athl etes dont trai n by themsel ves. They work out wi th an experi enced coach
who knows the keys to bei ng successful . I n preparati on for the AP chal l enge,
you wi l l need a coach to hel p you l earn the best strategi es for the test. Your
teacher should be your first coach. Due to the ti me constrai nts that
teachers face and the extensi ve amount of materi al covered i n thi s course, you
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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wi l l al so need an assi stant coach to hel p you prepare. Thi s book can be that assi stant coach,
but i t i s not desi gned to repl ace your teacher. He or she knows the course, the materi al , and
you, but unl ess your teacher can move i n wi th you whi l e you are prepari ng for the test, he or
she cant provi de you wi th al l of the tool s you wi l l need to succeed. There arent enough hours
i n the school day to teach you everythi ng you need to know for the test. Thi s book can be your
personal tutor. The materi al between i ts covers wi l l hel p to fami l i ari ze you wi th al l of the
materi al covered on the test, the structure of the test, and strategi es to prepare for and to take
the test and i t can provi de you wi th i nstant feedback about your performance. Thi s book i s
al so desi gned wi th the understandi ng that your ti me i s val uabl e! You most l i kel y have a very
busy schedul e before and after school , and the l ast thi ng you need i s to add another
ti me-consumi ng acti vi ty. Some of the i nformati on that you may have l earned or that i s i n your
textbook may go beyond the l evel of the AP test. On other subjects, you may have l earned l ess
i nformati on than you need. Thi s book attempts to get ri ght to the poi nt and to onl y revi ew the
materi al that you wi l l need to know for the test.
MAKING A STUDY PLAN
The fact that you bought thi s book i s a step i n the ri ght di recti on for your success on the AP
Chemi stry Test. And there are some strategi es that wi l l hel p you get the most out of i t. The
fol l owi ng are two key questi ons you need to answer before you proceed:
How much ti me do I have before the AP test?
How much ti me can I real i sti cal l y devote to test preparati on?
Your answers to these questi ons wi l l hel p you to set a pace for your revi ew. I f you have a l ong
ti me before the test (two or three months), you can set a fai rl y rel axed pace. I f you have a short
ti me (one month or l ess), your pace wi l l be more ri gorous. Ei ther way, the book i s desi gned to
be fl exi bl e and to accommodate a vari ety of si tuati ons. What fol l ows i s a bri ef descri pti on of the
remai nder of the book and how you can use i t under di fferent ci rcumstances.
Read thi s secti on, and then go on to Chapter 3. These chapters contai n vi tal i nformati on
about the AP test that wi l l hel p you to devel op sound test-taki ng strategi es. Once fi ni shed,
take the di agnosti c test. Before you take i t, however, you need to understand that the
di agnosti c test i s not a practi ce AP test! Thi s book has two ful l -l ength practi ce AP tests, but
they do not appear unti l Part I V of the book. The di agnosti c test i s desi gned to resembl e the
approxi mate di ffi cul ty l evel of the AP test and to refl ect the content on the test, but there are
some si gni fi cant di fferences i n the structures of the two. The purpose of the test i s to hel p you
i denti fy strengths and potenti al weaknesses, whi ch youl l need to know to desi gn your
personal study pl an. Once you fi ni sh the di agnosti c test, use these suggested gui del i nes to
compl ete your test preparati ons.
The Complete Course
I f you have pl enty of ti me before the test (two or three months), i t i s recommended that you
compl ete the enti re course. There are ni neteen chapters, so i f you di vi de these up over a
two-month peri od, you woul d need to compl ete about two chapters a week. I f you have a
three-month peri od, thi s drops down to about one chapter every fi ve or si x days. You wi l l
4 PART 1: AP Chemistry Basics
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recei ve the maxi mum benefi t i f you can compl ete the enti re book. Even i f you are pl anni ng to
compl ete the enti re book, i t i s recommended that you pi ck the most di ffi cul t areas fi rst,
especi al l y those that you may not have covered much (or at al l ) i n cl ass. Thi s way, i f
somethi ng happens and you dont have as much ti me as you thought, youve at l east gone
through the secti ons that wi l l benefi t you the most.
The Accelerated Course
I f you are runni ng out of ti me, youl l need to desi gn an ambush approach to your studi es. Dont
attempt to compl ete the enti re book. From the di agnosti c test, sel ect your weakest areas and
pl an to go through those fi rst. Make a l i st of the topi cs you feel you can reasonabl y work
through before the test. Be very careful duri ng thi s process. Do not ski p secti ons you know very
l i ttl e about, fi guri ng, Oh, that probabl y wont be on the test. I f i t i s on the content outl i ne, i t
wi l l be on the test! And, i f you are especi al l y unfortunate, the secti on you ski p coul d end up as
one of the mandatory essay questi ons. Even i f you dont have ti me for al l of the practi ce
probl ems i n a secti on, get through what you can. I f you know certai n topi cs very wel l , ski p
them. I ts not i deal , but i f you are readi ng thi s secti on (for the accel erated course) i t i s probabl y
because you dont have ti me to do everythi ng. Just remember, though, that every chapter you
can work through i s a bonus for you. Rather than be di scouraged about not havi ng enough ti me
to fi ni sh everythi ng, be encouraged about the secti ons you wi l l fi ni sh. These are areas you
woul dnt have known or woul d have done poorl y on wi thout your extra effort. Be posi ti ve!
WHAT THE TEST COVERS
Each year, the Col l ege Board provi des a content outl i ne for the AP Chemi stry course as wel l
as a breakdown of the approxi mate percentage of the AP test that wi l l deal wi th certai n
topi cs. What fol l ows i s an outl i ne of the content of the most recent test.
Structure of Matter (20 percent)
Atomi c theory and atomi c structure
Evi dence for the atomi c theory
Atomi c masses; determi nati on by chemi cal and physi cal means
Atomi c number and mass number; i sotopes
El ectron energy l evel s: atomi c spectra, quantum numbers, atomi c orbi tal s
Peri odi c rel ati onshi ps, such as atomi c radi i , i oni zati on energi es, el ectron affi ni ti es,
and oxi dati on states
Chemi cal bondi ng
Bi ndi ng forces
Types: i oni c, coval ent, metal l i c, hydrogen bondi ng, van der Waal s theory
(i ncl udi ng London di spersi on forces)
Rel ati onshi ps to states, structure, and properti es of matter
Pol ari ty of bonds, el ectronegati vi ti es
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Chapter 1: All About the AP Chemistry Test 5
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Mol ecul ar model s
Lewi s structures
Val ence bond: hybri di zati on of orbi tal s, resonance, and si gma and pi bonds
VSEPR
Geometry of mol ecul es and i ons, structural i someri sm of si mpl e organi c mol ecul es
and coordi nati on compl exes; di pol e moments of mol ecul es; rel ati on of properti es to
structure
Nucl ear chemi stry: nucl ear equati ons, hal f-l i ves, and radi oacti vi ty; chemi cal appl i cati ons
States of Matter (20 percent)
Gases
Laws of i deal gases
Equati on of state for an i deal gas
Parti al pressures
Ki neti c-mol ecul ar theory
I nterpretati on of i deal gas l aws on the basi s of thi s theory
Avogadros hypothesi s and the mol e concept
Dependence of ki neti c energy of mol ecul es on temperature
Devi ati ons from i deal gas l aws
Li qui ds and sol i ds
Li qui ds and sol i ds from the ki neti c-mol ecul ar vi ewpoi nt
Phase di agrams of one-component systems
Changes of state, i ncl udi ng cri ti cal poi nts and tri pl e poi nts
Structure of sol i ds; l atti ce energi es
Sol uti ons
Types of sol uti ons and factors affecti ng sol ubi l i ty
Methods of expressi ng concentrati on (The use of normal i ti es i s not tested.)
Raoul ts l aw and col l i gati ve properti es (nonvol ati l e sol utes); osmosi s
Noni deal behavi or (qual i tati ve aspects)
Reactions (3540 percent)
Reacti on types
Aci d-base reacti ons; concepts of Arrheni us, Brnsted-Lowry, and Lewi s; coordi na-
ti on compl exes; amphoteri sm
Preci pi tati on reacti ons
6 PART 1: AP Chemistry Basics
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Oxi dati on-reducti on reacti ons
Oxi dati on number
The rol e of the el ectron i n oxi dati on-reducti on
El ectrochemi stry: el ectrol yti c and gal vani c cel l s; Faradays l aws; standard hal f-
cel l potenti al s; Nernst equati on; predi cti on of the di recti on of redox reacti ons
Stoi chi ometry
I oni c and mol ecul ar speci es present i n chemi cal systems: net i oni c equati ons
Bal anci ng of equati ons, i ncl udi ng those for redox reacti ons
Mass and vol ume rel ati ons wi th emphasi s on the mol e concept, i ncl udi ng empi ri cal
formul as and l i mi ti ng reactants
Equi l i bri um
Concept of dynami c equi l i bri um, physi cal and chemi cal ; Le Chtel i ers Pri nci pl e;
equi l i bri um constants
Quanti tati ve treatment
Equi l i bri um constants for gaseous reacti ons: KP, K
Equi l i bri um constants for reacti ons i n sol uti on
Constants for aci ds and bases: pK; pH
Sol ubi l i ty product constants and thei r appl i cati on to preci pi tati on and the
di ssol uti on of sl i ghtl y sol ubl e compounds
Common i on effect; buffers; hydrol ysi s
Ki neti cs
Concept of rate of reacti on
Use of experi mental data and graphi cal anal ysi s to determi ne reactant order, rate
constants, and reacti on rate l aws
Effect of temperature change on rates
Energy of acti vati on; the rol e of catal ysts
The rel ati onshi p between the rate-determi ni ng step and a mechani sm
Thermodynami cs
State functi ons
Fi rst l aw: change i n enthal py; heat of formati on; heat of reacti on; Hesss l aw; heats
of vapori zati on and fusi on; cal ori metry
Second l aw: entropy; free energy of formati on; free energy of reacti on; dependence
of change i n free energy on enthal py and entropy changes
Rel ati onshi p of change i n free energy to equi l i bri um constants and el ectrode potenti al s
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Chapter 1: All About the AP Chemistry Test 7
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Descriptive Chemistry (1015 percent)
Chemi cal reacti vi ty and products of chemi cal reacti ons
Rel ati onshi ps i n the peri odi c tabl e: hori zontal , verti cal , and di agonal wi th exampl es from
al kal i metal s, al kal i ne earth metal s, hal ogens, and the fi rst seri es of transi ti on el ements
I ntroducti on to organi c chemi stry: hydrocarbons and functi onal groups (structure,
nomencl ature, chemi cal properti es). Physi cal and chemi cal properti es of si mpl e organi c
compounds shoul d al so be i ncl uded as exempl ary materi al for the study of other areas
such as bondi ng, equi l i bri a i nvol vi ng weak aci ds, ki neti cs, col l i gati ve properti es, and
stoi chi ometri c determi nati ons of empi ri cal and mol ecul ar formul as.
Laboratory (510 percent)
These questi ons are based on common l aboratory procedures that shoul d have been l earned
as part of the course, such as:
maki ng observati ons of chemi cal reacti ons and substances
recordi ng data
cal cul ati ng and i nterpreti ng resul ts based on the quanti tati ve data obtai ned
effecti vel y communi cati ng the resul ts of experi mental work
Students shoul d be abl e to sol ve speci fi c types of chemi cal cal cul ati ons. The types of probl ems
that mi ght possi bl y be i ncl uded on the test i ncl ude:
Percentage composi ti on
Empi ri cal and mol ecul ar formul as from experi mental data
Mol ar masses from gas densi ty, freezi ng-poi nt, and boi l i ng-poi nt measurements
Gas l aws, i ncl udi ng the i deal gas l aw, Dal tons l aw, and Grahams l aw
Stoi chi ometri c rel ati ons usi ng the concept of the mol e; ti trati on cal cul ati ons
Mol e fracti ons; mol ar and mol al sol uti ons
Faradays l aws of el ectrol ysi s
Equi l i bri um constants and thei r appl i cati ons, i ncl udi ng thei r use for si mul taneous
equi l i bri a
Standard el ectrode potenti al s and thei r use; Nernst equati on
Thermodynami c and thermochemi cal cal cul ati ons
Ki neti cs cal cul ati ons
Thi s may feel l i ke too much i nformati on for you to ever master, and i t i s very rare that any
teacher coul d make i t through al l of the recommended topi cs and acti vi ti es wi thi n an
academi c year. I n the next secti on, we wi l l l ook at some detai l s about how youl l be asked to
appl y your knowl edge of the topi cs above, whi ch shoul d hel p to ease some of your fears.
8 PART 1: AP Chemistry Basics
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GETTING TO KNOW THE FORMAT OF THE TEST
The Col l ege Board reserves the ri ght to make changes to the test as i t chooses; however, the
structure of the test has undergone onl y very sl i ght changes i n the years i ts been offered. To
keep abreast of the speci fi c detai l s about the AP Chemi stry Test, refer to the Col l ege Board
Web si te at http://www.col l egeboard.com/ap.
The test i s 185 mi nutes l ong and i s di vi ded i nto two secti ons. The fi rst part, Secti on I , consi sts
of 75 mul ti pl e-choi ce questi ons. There i s a 90-mi nute ti me l i mi t on Secti on I , and the resul ts
make up 50 percent of the total grade. The second part, Secti on I I , i s the Free-Response
secti on. I t i s 95 mi nutes l ong, makes up 50 percent of the total grade, and i s broken i nto two
secti ons. The fi rst secti on, Part A, i s 55 mi nutes l ong; you may use cal cul ators duri ng thi s
porti on, but thi s i s the onl y part of the test on whi ch you can use a cal cul ator! I t consi sts of
three probl emsthe fri st questi on wi l l be based on equi l i bri um, but the other two questi ons
may be based on any topi c. These probl ems are cal cul ati on-based and are mul ti part probl ems.
After 55 mi nutes, you wi l l be i nstructed to put your cal cul ator away and proceed to the second
porti on of Secti on I I , Part B.
Part B i s di vi ded i nto three mandatory subsecti ons. The fi rst i s a l i st of three chemi cal
equati ons. I n thi s subsecti on, you are provi ded wi th a wri tten descri pti on of the reactants and
condi ti ons of a reacti on, from whi ch you must determi ne the product(s). Each reacti on must
have a bal anced net i oni c equati on, wi th the l owest whol e numbers for the rati os, and you
must answer a questi on about the reacti on (e.g.whi ch reactant i s oxi di zi ng). You must al so
convert the enti re equati on i nto symbol i c form (substi tuti ng symbol s for wri tten descri pti ons).
The second subsecti on i n Part B consi sts of two mul ti part questi ons, one of whi ch may be a
l aboratory-based questi on. The content of these questi ons vari es (l ater i n thi s chapter you
wi l l see a l i st of previ ous topi cs). Al l of these parts of the AP test are summari zed i n the
tabl e bel ow:
Secti on I : Mul ti pl e Choi ce. 75 questi ons. 90 mi nutes. 50 percent of total grade
Secti on I I : Free Response. 6 questi ons. 95 mi nutes. 50 percent of total grade.
Breakdown of the Free-Response Section
Part A
55 Minutes
(with calculatoronly calculators without
alphabetic keyboards)
60 percent of Section II Score
(30 percent of entire test)
Equi l i bri um probl em 20 percent (10 percent overal l )
Other probl em* 20 percent (10 percent overal l )
Other probl em* 20 percent (10 percent overal l )
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Chapter 1: All About the AP Chemistry Test 9
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Breakdown of the Free-Response Section
Part B
40 Minutes
(no calculator)
40 percent of
Section II Score
(20 percent of entire test)
Reacti ons questi on (3 requi red) 10 percent (5 percent overal l )
Essay questi on* 15 percent (7.5 percent overal l )
Essay questi on* 15 percent (7.5 percent overal l )
* One of the other probl ems or essays wi l l be based on l aboratory topi cs.
HOW THE AP CHEMISTRY TEST IS SCORED
Multiple Choice
On the mul ti pl e-choi ce porti on of the test, there are 75 questi ons. Scores are determi ned
accordi ng to the fol l owi ng formul a:
Score5 Correct Score2 0.25(I ncorrect Score)
The reason for the strange equati on i s to prevent wi l d guessi ng. Take, for exampl e, a student
who bubbl ed i n the same l etter for every questi on. To be safe, she chooses C because i t i s i n
the mi ddl e of the fi ve choi ces. On a test of 75 questi ons, wi th fi ve possi bl e responses (A2E) for
each questi on, chances are that 15 of them wi l l actual l y be C (15 wi l l al so be A, 15 wi l l be B,
etc.). That means that the student wi l l have gotten 15 probl ems correct and 60 i ncorrect.
Pl uggi ng these numbers i nto the equati on wi l l gi ve you:
Score5 Correct Score2 0.25(I ncorrect Score) 5 15 2 0.25(60) 5 15 2 15 5 0
As you can see, thi s i ndi vi dual coul d have l eft al l of the answers bl ank and sti l l gotten the
same score. There i s no benefi t to wi l d guessi ng. I n Chapter 2, you wi l l l earn some techni ques
to take the wi l d out of guessi ng.
Free Response
The free-response questi ons are graded by a group of more than 100 AP Chemi stry teachers
and col l ege chemi stry professors who gather at the begi nni ng of the summer to grade al l of
the tests. Scori ng rubri cs are careful l y desi gned for each questi on, and the graders spend the
week gradi ng the tests i n a very thorough, unbi ased manner. The key to your success on the
free-response questi ons i s your abi l i ty to wri te to these rubri cs. Whi l e there i s no way to
predi ct i n advance what topi cs wi l l be covered i n the free-response secti on (even though many
peopl e try), there are some strategi es that wi l l i mprove your chances. Hopeful l y, your teacher
has had you practi ce wri ti ng AP-styl e essays, but even i f he has not, you wi l l sti l l have an
opportuni ty to try some i n thi s book. You wi l l al so be abl e to eval uate your own performance
usi ng scori ng rubri cs that are si mi l ar to those used by the AP graders. Thi s exerci se wi l l hel p
you sharpen your wri ti ng ski l l s and maxi mi ze your chances for a hi gh score.
10 PART 1: AP Chemistry Basics
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YOUR COMPOSITE SCORE
Once your mul ti pl e-choi ce and free-response scores have been cal cul ated, each score wi l l be
used to cal cul ate your composi te score. Thi s score ranges from 0 to 5, accordi ng to the scal e
shown bel ow. Note the percentage of students recei vi ng each score:
AP Grade Qual i fi cati on
Percent of students earni ng
thi s score (from 1999 test)
5 Extremel y wel l qual i fi ed 17.2
4 Wel l qual i fi ed 14.7
3 Qual i fi ed 25.3
2 Possi bl y qual i fi ed 22.0
1 No recommendati on 20.8
One thi ng these numbers dont tel l you i s what i t takes to get a 5 or a 4. The number of poi nts
to achi eve these grades wi l l di ffer sl i ghtl y from year to year, but they remai n rel ati vel y
consi stent over ti me. The Chemi stry test i s i ntenti onal l y made so that a score of 100 percent
i s extremel y unl i kel y. I n most admi ni strati ons, scores of 50260 percent usual l y recei ve scores
of 5.
REVIEW OF THE AP QUESTION TYPES
Now that youve had a chance to get a general feel for the test, l ets begi n to take a cl oser l ook
at the tests desi gn. There are certai n types of questi ons that appear on the AP Chemi stry
Test. Becomi ng aware of these types of questi ons, as wel l as l earni ng some strategi es to
answer them, can hel p you become more confi dent when you take the test.
The mai n advantage of the mul ti pl e-choi ce secti on i s that there are fi ve answers to choose
from, and the correct answer i s al ways gi ven to you! Properl y wri tten mul ti pl e-choi ce
questi ons shoul d not be easy to answer, however. Despi te the fact that the correct answers are
found somewhere i n the fi ve choi ces, the correct answer wi l l be i mbedded among what are
known as di stracters. Di stracters are choi ces that are cl ose to bei ng correct but that are not
the correct answer. The mai n di ffi cul ty comes from the amount of ti me youre gi ven on thi s
secti on. There are 75 questi ons to compl ete i n 90 mi nutes. Thats an average of 1 mi nute and
12 seconds per questi onand wi thout the benefi t of a cal cul ator! For those of you who spent
l ong eveni ngs worki ng on probl em sets that onl y had a handful of probl ems i n them, thi s may
have you concerned. Take heart, though, because there are some tri cks you can l earn to save
you ti me, especi al l y si nce you have the correct answers i n front of you. So, one porti on of thi s
chapter i s devoted to l earni ng typi cal formats for mul ti pl e-choi ce questi ons on the chemi stry
test and how best to approach each to save ti me and i mprove your performance.
The mai n di ffi cul ty of the free-response secti on i s that the answers are not provi ded for you.
You have the benefi t of more ti me (and on part A, you can use a cal cul ator), but youre on your
own for comi ng up wi th a sol uti on. For the free-response questi ons, i t i s i mportant to become
fami l i ar wi th the scori ng rubri cs. Knowi ng how your answers wi l l be graded can hel p you
answer questi ons more effi ci entl y and wi th a hi gher probabi l i ty of earni ng poi nts. Later i n
thi s chapter we wi l l l ook at some strategi es for wri ti ng effecti ve free-response answers.
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Chapter 1: All About the AP Chemistry Test 11
www.petersons.com
Multiple Choice
THE TYPICAL MULTIPLE-CHOICE QUESTION
The typi cal desi gn of a questi on wi th fi ve correct choi ces i s to have one di stracter that i s very
cl ose to the correct answer, two that are sti l l si mi l ar, and one that can usual l y be rul ed out
al most i mmedi atel y. The structure of the di stracters wi l l vary accordi ng to the type of
questi on that i s bei ng asked. For exampl e, i f a cal cul ati on i s i nvol ved, the test-makers wi l l
often use vari ous i ncorrect forms of the formul as to obtai n the di stracters. For exampl e, take
a probl em that i s a cal cul ati on usi ng Charl ess l aw, whi ch states that the rati o of vol ume to
absol ute temperature wi l l remai n constant for a gas at constant pressure:
What vol ume wi l l an amount of ni trogen gas occupy at 77 i f the gas occupi es a
vol ume of 400 ml at a temperature of 27?
To sol ve thi s probl em, you woul d fi rst need to convert each temperature to
kel vi n. I n doi ng so, you woul d have the fol l owi ng i nformati on:
T
1
5 27C 5 300 K
T
2
5 77C 5 350 K
V
1
5 400 ml
V
2
5 ?
Si nce
V
T
5 k (constant), then
V
1
T
1
5
V
2
T
2
; rearrangi ng the equati on, we get
V
2
5
V
1
T
2
T
1
.
At thi s poi nt, l ets l ook at the possi bl e answers. The di stracters are encl osed i n
parentheses.
(A)
1141 ml (uses
~400!~77!
27
; note temperatures are i n C)
(B)
343 ml (uses
~400!~300!
350
; note T i s i n kel vi n but i nverted)
(C)
140 ml (uses
~400!~27!
77
; combi nati on of choi ces [A] and [B])
(D)
467 ml (uses
~400!~350!
300
; correct answer)
(E)
1.33 ml (uses
400
300
; mi ssi ng T
2
)
An i mportant consi derati on: I f you make any of the errors shown above, you wi l l get one of the
answers above, whi ch can make you bel i eve you have gotten the probl em ri ght! I ts very
i mportant to know how you are goi ng to proceed before you attempt to sol ve a probl em.
THE USE OF MULTIPLE ANSWERS
Another versi on of mul ti pl e-choi ce questi ons that you wi l l encounter on the test i s the use of
mul ti pl e answers. Thi s techni que, used to vari ous degrees i n the chemi stry test, provi des
12 PART 1: AP Chemistry Basics
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www.petersons.com
three di fferent choi ces. The fi ve possi bl e answers i nvol ve di fferent combi nati ons of the three
choi ces. Look at thi s sampl e questi on about peri odi ci ty:
As you move from l eft to ri ght between el ements 11 and 17,
I . atomi c radi us decreases.
I I . i oni zati on energy decreases.
I I I . el ectronegati vi ty i ncreases.
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I I
(E) I , I I , and I I I
The probl em wi th these questi ons i s that i f you are uncertai n about one of the
choi ces, they become i ncreasi ngl y more di ffi cul t to answer. For exampl e, i f you are
not sure whether I I i s a correct answer, you may not know how to deal wi th
choi ces (D) and (E). However, a second l ook mi ght provi de you wi th some cl ues
about how to guess. For exampl e, i f you are onl y uncertai n about number I I but
you are sure that I and I I I are correct, you can at l east rul e out (A), (B), and (C)
as possi bl e choi ces. Thi s l eaves you wi th a 50 percent chance of guessi ng correctl y.
REVERSE MULTIPLE CHOICE
The AP test usual l y starts out wi th yet a thi rd type of questi on: somethi ng cal l ed a reverse
mul ti pl e choi ce. That i s, fi ve choi ces are l i sted, and then several questi ons fol l ow. You are
supposed to answer each questi on wi th one of the choi ces from the l i st. For exampl e, say you
are gi ven a probl em about el ectron confi gurati ons. I t mi ght read somethi ng l i ke thi s:
QUESTIONS 14
(A) 1s
2
2s
2
2p
1
(B) 1s
2
2p
1
(C) 1s
2
2s
2
2p
6
3s
2
(D) 1s
2
2s
2
2p
7
3s
1
(E) 1s
2
2s
2
2p
6
1. Corresponds to a nobl e gas
2. Represents an i mpossi bl e confi gurati on
3. Ground state confi gurati on for Mg
4. Represents an atom i n an exci ted state
I n case you were tryi ng to answer these, the answers are:
1. (E)
2. (D)
3. (C)
4. (B)
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Chapter 1: All About the AP Chemistry Test 13
www.petersons.com
A few thi ngs to remember about these probl ems: there are usual l y more choi ces than
questi ons (thats to keep you from getti ng any ri ght by process of el i mi nati on), and you may be
abl e use answers more than once.
The Free-Response Questions
I f you recal l from the I ntroducti on, the free-response porti on of the test has two secti ons. I n
Part A, you are permi tted to use a cal cul ator, but i n Part B, you are not. I n Part A, there are
three probl ems, the fi rst of whi ch i s an equi l i bri um probl em; questi on 4 (reactal s); and two
essay questi ons. Because you are al l owed to use your cal cul ator, anythi ng goes. That i s, the
numbers wont be as conveni ent to work wi th as they are i n the mul ti pl e choi ce. Al so, because
the correct answers are not somewhere i n front of you, you wi l l have to be much more al ert
about carel ess errors. I n addi ti on, you wi l l need to attend to si gni fi cant fi gures (see Chapter 3)
when wri ti ng your answers. I n Part B, you can count on one questi on gi vi ng you wri tten
descri pti ons of three chemi cal reacti ons. You are provi ded wi th a descri pti on of the reactants
and any speci al treatments (i .e., heati ng or el ectrol ysi s) and are asked to wri te out bal anced
chemi cal equati ons for three di fferent sets of reactants. You wi l l answer a short questi on
about each of the three reacti ons. These questi ons i n Part B of the test are much more
conceptual i n nature and wi l l resembl e the format of the mul ti pl e-choi ce test. Any questi ons
requi ri ng cal cul ati ons wi l l use numbers that are easy to work wi th. Thi s i s not to say that the
questi ons are easy! They are very chal l engi ng. I t just means that the cal cul ati ons wi l l not be
the chal l engi ng part of the questi on.
Before we take a detai l ed l ook at free-response questi ons, you may be i nterested i n knowi ng
what topi cs appear most frequentl y i n thi s secti on. I n the tabl e that fol l ows, you wi l l see the
topi cs that have appeared i n the free-response porti on of the AP Chemi stry Test i n the past.
Fol l owi ng the tabl e i s a graphi cal summary of the tabl e. An important note: Dont rel y too
heavi l y on thi s i nformati on. That i s, dont ski p your study of a secti on si mpl y because i t hasnt
appeared very often. The questi ons are changed every year, and you never know when the
Col l ege Board wi l l deci de to throw that one topi c i n there. However, you can use the
i nformati on to hel p you create a personal study pl an for the test. You shoul d see that some
topi cs are al most al ways on the test. I f youre goi ng to ski p any secti ons or go l i ghtl y over
them duri ng your revi ew, these woul d not be the best topi cs to ski p. The other reason for
gi vi ng you thi s i nformati on i s to reduce anxi ety. The more fami l i ar you become wi th the test,
the l ess i nti mi dated you wi l l be by i t. Mi ni mi zi ng your fear wi l l hel p to maxi mi ze your
confi dence and, hopeful l y, your success!
FREE-RESPONSE TOPICS OVER THE YEARS
I n the tabl e that fol l ows, keep i n mi nd that onl y the general topi cs are l i sted. There are some
questi ons i n the free-response secti on that requi re you to i ntegrate topi c areas (e.g., free
energy and equi l i bri um). I n such i nstances, the pri mary topi c of the questi on i s l i sted. Al so,
there i s no di sti ncti on of whether the questi on was a Part A (cal cul ator) or a Part B
(non-cal cul ator) questi on. Fi nal l y, because the questi on wi th the three reacti ons appears
every year, these have been omi tted i n the i nterest of space.
14 PART 1: AP Chemistry Basics
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www.petersons.com
Overview of the Free-Response Problems
PART A
C a lc ula tor Q ue stions
Remember, i n thi s secti on there are three questi onal l are requi red. The fi rst probl em deal s
wi th some aspect of equi l i bri um and wi l l consi st of several parts, usual l y from fi ve to seven.
Each part i s worth 1 or 2 poi nts, for a total of 910 poi nts. Average scores on thi s probl em tend
to be somewhere around 4. The two opti onal probl ems al so contai n mul ti pl e parts, wi th each
worth 810 poi nts. Scores on thi s questi on range from 4 to 5.
How to Im p rove Your C ha nc e s of G e tting Points
There are some i mportant factors to consi der here. Fi rst, the graders are gradi ng l ots of
papershundreds of them. Try putti ng yoursel f i n thei r pl ace. Pi cture yoursel f, after a l ong
day of scori ng chemi stry papers, tryi ng to grade a paper that i s a mess, that i s mi ssi ng work,
and that has some mi stakes. Now pi cture yoursel f, after a l ong day of gradi ng, scori ng a paper
that i s neat and organi zed and that fol l ows a l ogi cal progressi on. Can you pi cture i t? Surel y
the second paper i s l i kel y to recei ve a warmer recepti on than the fi rst. Thats not to say that
you can be compl etel y i ncorrect and sti l l get poi nts for havi ng attracti ve answers. However,
there are opportuni ti es for parti al credi t, that you want to take ful l advantage of. Graders
dont take pl easure i n deducti ng poi nts from a paper, parti cul arl y when they thi nk you mi ght
have known what you were doi ng.
The second poi nt to remember i s that the grader does not know you. Whi l e thi s may be a
rather obvi ous statement, there i s a reason for menti oni ng i t. Your teacher, despi te hi s or her
best attempts to be objecti ve, may gi ve you a l i ttl e l eeway on gradi ng because he or she knows
you and knows what you probabl y meant to say i n your essays. The graders for the AP test
dont know you. They wont know what you probabl y meantunl ess you wri te i t down. You
may know exactl y how to answer every questi on, but i f you dont wri te anythi ng down, no one
wi l l ever know.
Main Topic Details
1997 Aci d-Base K
a
, K
b
, concentrati on
El ectrochemi stry Hal f-reacti ons, cel l potenti al
Ki neti cs Order, rate l aw, mechani sm
Bondi ng Lewi s structures, pol ari ty
Atomi c theory/bondi ng I oni zati on energy, i oni c radi us
Thermodynami cs DS, DG, K
p
Nucl ear Decay, mass defect
Laboratory procedures Mass percent of an unknown sol ubl e sal t
1998 Equi l i bri um K
sp
Stoi chi ometry Empi ri cal formul a, mol ar mass (freezi ng-poi nt
depressi on), mol ar mass (vapor densi ty)
Thermodynami cs DH, DG
Laboratory procedures Aci d-base ti trati on
Ki neti cs Essays: graph i nterpretati on (acti vati on energy, rate,
rate l aw)
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Chapter 1: All About the AP Chemistry Test 15
www.petersons.com
Main Topic Details
Equi l i bri um Le Chtel i ers
El ectrochemi stry Essays: el ectrochemi cal cel l concepts
Vari ous topi cs Essays: bondi ng, sol ubi l i ty, organi c (i somers),
oxi di zi ng/reduci ng agents
Equi l i bri um K
sp
1999 Aci d-base K, pH, K
b
, ti trati on
Atomi c structure E, l, n, emi ssi on spectra
Ki neti cs Rate l aw, reacti on mechani sm
Laboratory procedures Determi nati on of the mol ar mass by vapor densi ty
Thermodynami cs Essay: DH, DS, DG
States of matter: sol i ds, l i qui ds
Bondi ng Lewi s structures, bond l engths, mol ecul ar geometry
Aci d-base K, pH, K
b
, ti trati on
2000 Equi l i bri um K
c
, K
p
, stoi chi ometry
El ectrochemi stry E, DG, hal f-reacti ons, el ectrol yti c cel l
Stoi chi ometry Mass percent, water of hydrati on, redox ti trati on
Laboratory procedures Mol ar mass determi nati on by freezi ng-poi nt
depressi on
Thermodynami cs Hesss l aw, predi cti on of si gns of entropy, free energy
Ki neti cs Rate l aw expressi on from data, reacti on mechani sm
Atomi c structure Vari ous questi ons about atomi c structure
Aci d-base Vari ous questi ons about strong aci d/weak base
ti trati on
PART B
C he m ic a l Eq ua tions
I n thi s secti on, you wi l l begi n wi th the reacti on questi ons. Recal l , you are gi ven three parti al
equati ons. I n each questi on, you are provi ded the reactants and any condi ti ons of the reacti on.
You are then to wri te a bal anced equati on for the reacti on and answer a questi on about
reacti on. The di recti ons for thi s secti on tel l you to assume that al l sol uti ons are aqueous
unl ess otherwi se i ndi cated. You are al so i nstructed to represent substances i n sol uti on as i ons
i f the materi al i s extensi vel y i oni zed, and you shoul d omi t the formul as for any i ons or
mol ecul es that are unchanged by the reacti on (spectators, for i nstance). I t i s necessary to
bal ance the equati ons i n thi s secti on. Here i s a sampl e probl em that i l l ustrates thi s porti on of
the test:
Sample: A sampl e of zi nc powder i s added to a sol uti on of si l ver ni trate.
Question: What speci es i s reduced?
Zn 1 2Ag
1
Zn
21
1 2Ag i s the equati on.
Answer: Ag
+
That i s al l that i s necessary here. Note that, as di rected, the sol uti on i s assumed to be
aqueous, the si l ver ni trate i n sol uti on i s shown as i ons, and the ni trate i on i s omi tted because
16 PART 1: AP Chemistry Basics
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i t remai ns unchanged i n the reacti on. I f you have ti me at the end of the testbut onl y i f you
have ti mego back and add detai l s to the equati ons, such as (aq), (g), or (l). These detai l s are
not requi red, but they hel p to establ i sh you as a more knowl edgeabl e and thorough student.
Agai n, dont add anythi ng youre not sure of. There are other factors to consi der i n thi s
secti on, but these wi l l be addressed i n more detai l i n Chapter 11.
The Essays
These are not l i ke the essays you wri te i n Engl i sh cl ass. Most of the answers i n thi s secti on
are onl y a few sentences l ong. You dont get any extra poi nts for wri ti ng l ong responses, so
dont do i t! Here are some other thi ngs to remember as you answer the essays.
BE LOGICAL
Each questi on has several parts. Make sure you have read through each of these. I n some
questi ons, there i s a l ogi cal progressi on from one questi on to the next. I n your answers, be
sure to refl ect thi s overal l structure. I t hel ps the grader know that you are abl e to grasp the
bi g pi cture i n the probl em. Before you attack the i ndi vi dual parts of the questi on, i t hel ps to
jot down an outl i ne i n your green packet (the one you arent wri ti ng your answers on). Thi s
wi l l hel p you to frame the questi on and devel op a strategy to answer i t.
ANSWER ALL PARTS SEPARATELY
Do not wri te a gi ant paragraph that i ncl udes al l of your answers. Address each subpart i n a
separate, l ettered secti on.
BE THOROUGH
Dont assume that the grader knows anythi ng (even though he probabl y knows everythi ng
about the topi c). Maki ng thi s type of assumpti on can cause you to omi t i mportant i nformati on
from an answer. For exampl e, i f you were asked to i denti fy the oxi di zi ng agent for a reacti on
(for whi ch an equati on has been gi ven), show the grader that you know what an oxi di zi ng
agent i s. I n your answer, you mi ght wri te, The oxi di zi ng agent, or substance that causes
another to l ose el ectrons i n a chemi cal reacti on, i s . . . By wri ti ng your answer thi s way, you
l et the grader know that you understand the topi c. There are ti mes when parti al credi t can be
awarded for correct descri pti ons of porti ons of the questi on. Dont l ose these poi nts just
because you have assumed the grader al ready knows the i nformati on. Of course he knows i t.
You are tryi ng to make sure he knows that you know i t.
DONT OVERDO IT
Over the years, many students devel op the shotgun approach to answeri ng essay questi ons.
A shotgun sprays a l arge amount of smal l l ead shot around wi th the i dea that some of i t wi l l
hi t the target. Li kewi se, these students wi l l wri te down everythi ng they know i n hopes that
some of i t wi l l answer the questi on. The AP graders are on to that game. I t doesnt work. They
do not want to wade through endl ess amounts of wri ti ng to try to fi nd the pearl s that are
buri ed wi thi n. Be cl ear. Be conci se. Say what you need toand nothi ng el se.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 1: All About the AP Chemistry Test 17
www.petersons.com
THE ANSWER SHEETS
For Secti on I of the test (the mul ti pl e-choi ce questi ons), you wi l l be provi ded a test bookl et
and an answer sheet. The answer sheet i s a bubbl e sheet, and the test bookl et contai ns al l of
the mul ti pl e-choi ce questi ons. You are not al l owed to use scratch paper on the test, and you
wi l l have to put your cal cul ator away. Any extra wri ti ng you need to do (e.g., cal cul ati ons) can
be done i n the margi ns of the test bookl etnot on the answer sheet! As far as the bubbl e sheet
goes, fi rst make sure youre usi ng a #2 penci l that way, the marks you make wi l l be dark
enough for the scori ng machi ne to read. I n addi ti on, you must make sure that your answers
are neatl y bubbl ed i nto the oval s.
For the free-response questi ons, you wi l l be gi ven a separate packet. The fi rst part of the
packet consi sts of your answer bookl et. Al l answers are to be wri tten here. You wi l l al so be
gi ven a green packet that contai ns the questi ons and a great deal of reference materi al a
peri odi c tabl e, a tabl e of standard reducti on potenti al s, and several pages of formul as and
constants (shown i n the fol l owi ng Tabl es 1.1 through 1.7).
18 PART 1: AP Chemistry Basics
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TABLE 1.1 STANDARD REDUCTION POTENTIALS IN AQUEOUS SOLUTION AT 25C
Half-reaction E(V)
Li
1
1 e
2
Li (s) 23.05
Cs
1
1 e
2
Cs(s) 22.92
K
1
1 e
2
K(s) 22.92
Rb
1
1 e
2
Rb(s) 22.92
Ba
21
1 2e Ba(s) 22.90
Sr
21
1 2e
2
Sr(s) 22.89
Ca
21
1 2e
2
Ca(s) 22.87
Na
1
1 e
2
Na(s) 22.71
Mg
21
2e
2
Mg(s) 22.37
Be
21
1 2e
2
Be(s) 21.70
Al
31
1 3e
2
Al (s) 21.66
Mn
21
1 2e
2
Mn(s) 21.18
Zn
21
1 2e
2
Zn(s) 20.76
Cr
31
1 3e
2
Cr(s) 20.74
Fe
21
1 2e
2
Fe(s) 20.44
Cr
31
1 e
2
Cr
21
20.41
Cd
21
1 2e
2
Cd(s) 20.40
Tl
1
1 e
2
Tl (s) 20.34
Co
21
1 2e
2
Co(s) 20.28
Ni
21
1 2e
2
Ni (s) 20.25
Sn
21
1 2e
2
Sn(s) 20.14
Pb
21
1 2e
2
Pb(s) 20.13
2H
1
1 2e
2
H
2
(g) 0.00
S(s) 1 2H1 1 2e
2
H
2
S(g) 0.14
Sn
41
1 2e
2
Sn
21
0.15
Cu
21
1 e
2
Cu
1
0.15
Cu
21
1 2e
2
Cu(s) 0.34
Cu
1
1 e
2
Cu(s) 0.52
I
2
(s) 1 2e
2
2I
2
0.53
Fe
31
1 e
2
Fe
21
0.77
Hg
2
21
1 2e
2
2Hg(l) 0.79
Ag
1
1 e
2
Ag(s) 0.80
Hg
21
1 2e
2
Hg(l) 0.85
2Hg
21
1 2e
2
Hg
2
21
0.92
Br
2
(l) 1 2e
2
2Br
2
1.07
O
2
(g) 1 4H
1
1 4e
2
2H
2
O(l) 1.23
Cl
2
(g) 1 2e
2
2Cl
2
1.36
Au
31
1 3e
2
Au(s) 1.50
Co
31
1 e
2
Co
21
1.82
F
2
(g) 1 2e
2
2F
2
2.87
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Chapter 1: All About the AP Chemistry Test 19
www.petersons.com
TABLE 1.2 ATOMIC STRUCTURE
DE 5 hn
c 5 ln
l 5
h
mv
p 5 mv
E
n
5
2.18 3 10
218
n
2
joul e
TABLE 1.3 EQUILIBRIUM
K
a
5
@H
1
# @A
2
#
@HA#
K
b
5
@OH
2
# @HB
1
#
@B#
K
w
5 @OH
2
# @H
1
# 5 1.0 3 10
214
at 25C
5 K
a
3 K
b
pH 5 2l og @H
1
#, pOH 5 2l og @OH
2
#
14 5 pH 1 pOH
pH 5 pK
a
1 l og
@A
2
#
@HA#
pOH 5 pK
b
1 l og
@HB
1
#
@B#
pK
a
5 2l og K
a
, pK
b
5 2l og K
b
K
p
5 K
c
~RT!
Dn
Where Dn 5 mol es product gas 2 mol es reactant gas
20 PART 1: AP Chemistry Basics
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TABLE 1.4 THERMOCHEMISTRY/KINETICS
DS 5 SS products 2 SS reactants
DH 5 SH
f
products 2 SH
f
reactants
DG 5 SDG
f
products 2 SG
f
reactants
DG 5 DH 2 TDS
5 2RT l n K 5 22.303RT l og K
5 2n7E
DG 5 DG 1 RT l n Q 5 DG 1 2.303RT l og Q
q 5 mcDT
C
p
5
DH
DT
E 5 energy
n 5 frequency
l 5 wavel ength
p 5 momentum
v 5 vel oci ty
n 5 pri nci pal quantum number
m5 mass
Speed of l i ght, c 5 3.0 3 10
8
m s
21
Pl ancks constant, h 5 6.63 3 10
234
J s
Bol tzmanns constant, k 5 1.38 3 10
223
J K
21
Avogadros number 5 6.022 3 10
23
parti cl es mol
21
El ectron charge, e5 21.602 3 10
219
coul omb
1 el ectron vol t per atom 5 96.5 kJ mol
21
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Chapter 1: All About the AP Chemistry Test 21
www.petersons.com
TABLE 1.5 CONSTANTS
K
a
(weak aci d)
K
b
(weak base)
K
w
(water)
K
p
(gas pressure)
K
c
(mol ar concentrati ons)
S 5 standard entropy
H 5 standard enthal py
G 5 standard free energy
E 5 standard reducti on potenti al
T 5 temperature
n 5 mol es
m5 mass
q 5 heat
c 5 speci fi c heat capaci ty
C
p
5 mol ar heat capaci ty at constant pressure
1 faraday, 7 5 96,500 coul ombs per mol e of el ectrons
P 5 pressure
V 5 vol ume
T 5 temperature
n 5 number of mol es
D 5 densi ty
m5 mass
v 5 vel oci ty
u
rms
5 root-mean-square speed
KE 5 ki neti c energy
r 5 rate of effusi on
M 5 mol ar mass
p 5 osmoti c pressure
i 5 vant Hoff factor
K
f
5 mol al freezi ng-poi nt depressi on constant
K
b
5 mol al boi l i ng-poi nt el evati on constant
Q 5 reacti on quoti ent
I 5 current (amperes)
q 5 charge (coul ombs)
t 5 ti me (seconds)
E5 standard reducti on potenti al
K 5 equi l i bri um constant
Gas constant, R 5 8.31 J mol
21
K
21
5 0.0821 L atm mol
21
K
21
5 8.31 vol t coul omb mol
21
K
21
Bol tzmanns constant, k 5 1.38 3 10
223
J K
21
K
f
for H
2
O 5 1.86 K kg mol
21
K
b
for H
2
O 5 0.512 K kg mol
21
STP 5 0.000 C and 1.000 atm
Faradays constant, 7 5 96,500 coul ombs per mol e of el ectrons
22 PART 1: AP Chemistry Basics
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TABLE 1.6 GASES, LIQUIDS, AND SOLUTIONS
PV 5 nRT
S
P 1
n
2
a
V
2 D
~V 2 nb! 5 nRT
P
A
5 P
total
3 X
A
, where X
A
5
mol es A
total mol es
P
total
5 P
A
1 P
B
1 P
C
1 . . .
n 5
m
M
K 5 C 1 273
P
1
V
1
T
1
5
P
2
V
2
T
2
D 5
m
V
u
rms
5
3kT
m
5
3RT
M
KE per mol ecul e 5
1
2
mv
2
KE per mol e 5
3
2
RTn
r
1
r
2
5
M
2
M
1
mol ari ty, M 5 mol es sol ute per l i ter sol uti on
mol al i ty, m5 mol es sol ute per ki l ogram sol vent
DT
f
5 iK
f
3 mol al i ty
DT
b
5 iK
b
3 mol al i ty
p 5
nRT
V
i
TABLE 1.7 OXIDATION-REDUCTION/ELECTROCHEMISTRY
Q 5
@C#
c
@D#
d
@A#
a
@B#
b
, where aA 1 bB cC 1 dD
I 5
q
t
E
cell
5 E
cell
2
RT
n7
l n Q
5 E
cell
2
0.0592
n
l og Q at 25C
l og K 5
nE
0.0592
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Chapter 1: All About the AP Chemistry Test 23
www.petersons.com
SUMMING IT UP
Fami l i ari ze yoursel f wi th the structure of the AP Chemi stry Test. Knowi ng the test
format wi l l rel i eve test anxi ety because you wi l l know exactl y what to expect on test day.
Learn the gi ven i nformati on. Your test bookl et wi l l provi de you wi th i mportant data and
formul as. Dont waste ti me memori zi ng that i nformati on. Learn how to use i t and know
where you can fi nd i t duri ng the test.
Make sure you fi l l i n the bubbl e sheet neatl y. Otherwi se, the scori ng machi ne wont gi ve
you credi t for your answers.
Pace yoursel f. You must work qui ckl y and careful l y throughout the test. You can sti l l get
a very hi gh score wi thout answeri ng al l of the questi ons. Answer as many as you can as
qui ckl y as you can, and then go back and try to fi l l i n the others.
Remember that random guessi ng wi l l have no effect on your score, but educated guessi ng
wi l l boost your score. So, i f youve had ti me to read through a questi on and el i mi nate at
l east one choi ce, take a guess!
I n the free-response secti ons, be neat, thorough, and very cl ear. You do not want the
graders havi ng to guess what you wrote or what you meant.
Rememberi f youre worki ng through thi s book, youre gi vi ng yoursel f the best
preparati on avai l abl e for succeedi ng on the AP test. Let your preparati on gi ve you the
confi dence you need to be cal m and focused.
24 PART 1: AP Chemistry Basics
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P
ART II
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
DIAGNOSING STRENGTHS
AND WEAKNESSES
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CHAPTER 2 Practice Test 1: Diagnostic
ANSWER SHEET PRACTICE TEST 1: DIAGNOSTIC
1.
jA jB jC jD jE
2.
jA jB jC jD jE
3.
jA jB jC jD jE
4.
jA jB jC jD jE
5.
jA jB jC jD jE
6.
jA jB jC jD jE
7.
jA jB jC jD jE
8.
jA jB jC jD jE
9.
jA jB jC jD jE
10.
jA jB jC jD jE
11.
jA jB jC jD jE
12.
jA jB jC jD jE
13.
jA jB jC jD jE
14.
jA jB jC jD jE
15.
jA jB jC jD jE
16.
jA jB jC jD jE
17.
jA jB jC jD jE
18.
jA jB jC jD jE
19.
jA jB jC jD jE
20.
jA jB jC jD jE
21.
jA jB jC jD jE
22.
jA jB jC jD jE
23.
jA jB jC jD jE
24.
jA jB jC jD jE
25.
jA jB jC jD jE
26.
jA jB jC jD jE
27.
jA jB jC jD jE
28.
jA jB jC jD jE
29.
jA jB jC jD jE
30.
jA jB jC jD jE
31.
jA jB jC jD jE
32.
jA jB jC jD jE
33.
jA jB jC jD jE
34.
jA jB jC jD jE
35.
jA jB jC jD jE
36.
jA jB jC jD jE
37.
jA jB jC jD jE
38.
jA jB jC jD jE
39.
jA jB jC jD jE
40.
jA jB jC jD jE
41.
jA jB jC jD jE
42.
jA jB jC jD jE
43.
jA jB jC jD jE
44.
jA jB jC jD jE
45.
jA jB jC jD jE
46.
jA jB jC jD jE
47.
jA jB jC jD jE
48.
jA jB jC jD jE
49.
jA jB jC jD jE
50.
jA jB jC jD jE
51.
jA jB jC jD jE
52.
jA jB jC jD jE
53.
jA jB jC jD jE
54.
jA jB jC jD jE
55.
jA jB jC jD jE
56.
jA jB jC jD jE
57.
jA jB jC jD jE
58.
jA jB jC jD jE
59.
jA jB jC jD jE
60.
jA jB jC jD jE
61.
jA jB jC jD jE
62.
jA jB jC jD jE
63.
jA jB jC jD jE
64.
jA jB jC jD jE
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a
n
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w
e
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Chapter 2: Practice Test 1: Diagnostic 27
www.petersons.com
Practice Test 1:
Diagnostic
DIRECTIONS FOR TAKING THE DIAGNOSTIC TEST
The di agnosti c test wi l l hel p you i denti fy your weak spots i n the course, gi ve
you the opportuni ty to test your knowl edge i n a number of areas, and, based
on the resul ts of thi s test, to pl an your study ti me for the AP test accordi ngl y.
The questi ons from each major topi c area do not cover al l of the subject areas
i n a chapter, so thi s test shoul d i n no way be vi ewed as a substi tute for revi ew.
I n addi ti on, the answers on thi s test, unl i ke the other chapters, do not contai n
expl anati ons. Each topi c wi l l be addressed and revi ewed wi thi n speci fi c,
i ndi vi dual chapters. The answer key for the di agnosti c test poi nts out where
i n the chapter you can fi nd the i nformati on. Thi s shoul d hel p you to i denti fy
weak poi nts and customi ze your use of thi s book.
Note: For al l questi ons, assume that the temperature i s 298 K, the
pressure i s 1.00 atmospheres, and sol uti ons are aqueous unl ess
otherwi se speci fi ed.
Throughout the test, the fol l owi ng symbol s have the defi ni ti ons speci fi ed
unl ess otherwi se noted.
T 5 temperature M 5 mol ar
P 5 pressure m 5 mol al
V 5 vol ume L, mL 5 l i ter(s), mi l l i l i ter(s)
S 5 entropy g 5 gram(s)
H 5 enthal py nm 5 nanometer(s)
G 5 free energy atm 5 atmosphere(s)
R 5 mol ar gas constant J, kJ 5 joul e(s), ki l ojoul e(s)
n 5 number of mol es V 5 vol t(s)
mol 5 mol e(s)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
p
r
a
c
t
i
c
e
t
e
s
t
1
29
Directions: Each set of l ettered choi ces bel ow refers to the numbered statements
i mmedi atel y fol l owi ng i t. Sel ect the one l ettered choi ce that best fi ts each.
1. A certai n col or of l i ght has a wave-
l ength of 550 nm. What i s the energy
possessed by a photon of such l i ght?
(A) 2.42 3 10
219
J
(B) 5.45 3 10
14
J
(C) 3.61 3 10
214
J
(D) 3.61 3 10
219
J
(E) 5.37 3 10
219
J
2. How wi l l the ti me i t takes to hard-
boi l an egg compare at hi gher
al ti tudes?
(A) I t wi l l take l onger because of
the l ower boi l i ng temperature of
the water.
(B) I t wi l l take l onger because of
the hi gher vapor pressure of the
water.
(C) I t wi l l take l ess ti me because of
the hi gher boi l i ng temperature
of the water.
(D) I t wi l l take l ess ti me because of
the l ower vapor pressure of the
water.
(E) I t wi l l take the same amount of
ti me, regardl ess of the al ti tude.
3. Cal cul ate the mol ar sol ubi l i ty of
bari um sul fate, BaSO
4
, i n 0.020 M
sodi um sul fate, Na
2
SO
4
. K
sp
for
BaSO
4
i s 1.08 3 10
210
.
(A) 1.04 3 10
25
(B) 5.4 3 10
25
(C) 7.87 3 10
28
(D) 5.4 3 10
29
(E) 1.08 3 10
210
4.
29
59
Cu
+1
0
e 1 ___________I f cop-
per229 undergoes a posi tron emi s-
si on, what i s the resul ti ng product
nucl i de?
(A)
29
59
Cu
(B)
28
59
Ni
(C)
30
58
Zn
(D)
29
57
Cu
(E)
29
60
Cu
5. Cal cul ate the pH of a 0.10 M sol uti on
of HOCl , K
a
5 3.5 3 10
28
.
(A) 4.23
(B) 8.46
(C) 3.73
(D) 1.00
(E) 3.23
6. Determi ne the standard enthal py of
reacti on for the combusti on of
hydrogen sul fi de gas, whi ch proceeds
accordi ng to the reacti on shown
bel ow:
2H
2
S(g) 1 3O
2
(g) 2H
2
O(l) 1
2SO
2
(g)
The standard enthal pi es for the
consti tuents are as fol l ows:
Formul a DH
f
(kJ mol
21
)
H
2
S(g) 220
H
2
O(l) 2285.8
SO
2
(g) 2296.8
(A) 2575 kJ
(B) 2726 kJ
(C) 2963 kJ
(D) 21125 kJ
(E) 21320 kJ
7. I denti fy the type of organi c com-
pound shown:
CH
3
DD C HH O
|
CH
3
(A) Al dehyde
(B) Ester
(C) Carbonyl
(D) Ketone
(E) Carboxyl i c aci d
30 PART II: Diagnosing Strengths and Weaknesses
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www.petersons.com
8. Whi ch one of the fol l owi ng wi l l NOT
react?
(A) Ag 1 Au(NO
3
)
3

(B) Cu 1 AgNO
3

(C) Pb 1 Cu(NO
3
)
2

(D) Cd 1 Pb(NO
3
)
2

(E) Ni 1 Cd(NO
3
)
2

9. For the reacti on 2A 1 B C,
experi mental data was col l ected for
three tri al s:
Experi -
ment [A] M [B] M
I ni ti al Rate
M s
21
1 0.40 0.20 5.5 3 10
23
2 0.80 0.20 5.5 3 10
23
3 0.40 0.40 2.2 3 10
22
What i s the rate l aw of the reacti on?
(A) Rate 5 k[A][B]
(B) Rate 5 k[A]
0
[B]
2
(C) Rate 5 k[A]
2
[B]
2
(D) Rate 5 k[A]
2
[B]
0
(E) Rate 5 k[A][B]
2
10. 4NH
3
(g) 15O
2
(g) 4NO(g) 16H
2
O(g)
I n the above reacti on, 3.10 g of NH
3
reacts wi th 2.50 g of O
2
. What i s the
theoreti cal yi el d of NO?
(A) 1.88 g
(B) 5.46 g
(C) 8.20 g
(D) 24.0 g
(E) 120 g
11. H
2
O(g) 1 Cl
2
O(g) 2HOCl (g)
The reacti on above i s al l owed to
come to equi l i bri um at room tem-
perature. At equi l i bri um, the parti al
pressure of H
2
O i s 296 mm Hg, Cl
2
O
i s 15 mm Hg, and HOCl i s 20 mm
Hg. What i s the val ue of K
p
at thi s
temperature?
(A) 222
(B) 11
(C) 0.017
(D) 0.090
(E) 0.0045
12. A sol uti on i s made by di ssol vi ng
250.0 g of potassi um chromate
crystal s (K
2
CrO
4
, mol ar mass 194.2
g) i n 1.00 kg of water. What wi l l the
freezi ng poi nt of the new sol uti on be?
K
f
for water i s 1.86C m
21
.
(A) 28.87C
(B) 27.18C
(C) 25.73C
(D) 23.2C
(E) 21.86C
13. Copper i s el ectropl ated from a CuSO
4
sol uti on. A constant current of
2.00 amps i s appl i ed by an external
power suppl y. How l ong wi l l i t take
to deposi t 1.00 3 10
2
g of Cu?
(A) 21.1 hours
(B) 10.0 mi n
(C) 42.2 hours
(D) 11.2 sec
(E) 2.91 hours
14. Whi ch mol ecul e has a Lewi s
structure that does NOT obey the
octet rul e?
(A) NO
(B) CS
2
(C) PF
3
(D) HCN
(E) CCl
4
15. Whi ch of the fol l owi ng mol ecul es has
a tri gonal pyrami dal shape?
(A) PCl
5
(B) N
2
O
(C) NH
3
(D) CCl
4
(E) H
2
O
2
d
i
a
g
n
o
s
t
i
c
t
e
s
t
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Chapter 2: Practice Test 1: Diagnostic 31
www.petersons.com
16. Hydrogen gas, l i berated from a
reacti on between hydrochl ori c aci d
and zi nc, i s bubbl ed through water
and col l ected i n an i nverted gradu-
ated cyl i nder at 22C. The pressure
of the gas mi xture i s 765 mm Hg.
The vapor pressure of water at 22C
i s 20 mm Hg. What i s the parti al
pressure of the hydrogen gas?
(A) 22 mm Hg
(B) 743 mm Hg
(C) 745 mm Hg
(D) 765 mm Hg
(E) 785 mm Hg
17. Whi ch set of quantum numbers (n, l,
m
l
, m
s
) i s NOT possi bl e?
(A) 1, 0, 0,
1
2
(B) 1, 1, 0,
1
2
(C) 1, 0, 0, 2
1
2
(D) 2, 1, 21,
1
2
(E) 3, 2, 1,
1
2
18. Whi ch of the fol l owi ng expl ai ns why
CH
3
2O2CH
3
has a l ower boi l i ng
temperature than CH
3
CH
2
OH?
(A) Hydrogen bondi ng
(B) Hybri di zati on
(C) I oni c bondi ng
(D) Resonance
(E) London di spersi on forces
19. I f 87.5 percent of a sampl e of pure
99
Rh decays i n 48 days, what i s the
hal f-l i fe of
99
Rh?
(A) 6 days
(B) 8 days
(C) 12 days
(D) 16 days
(E) 24 days
20. Whi ch of the fol l owi ng expl ai ns why,
at room temperature, I
2
i s a sol i d,
Br
2
i s a l i qui d, and Cl
2
i s a gas?
(A) Hydrogen bondi ng
(B) Hybri di zati on
(C) I oni c bondi ng
(D) Resonance
(E) London di spersi on forces
21. Whi ch of the fol l owi ng reacti ons
i nvol ves the l argest i ncrease i n
entropy?
(A) AgNO
3
(aq) 1 HCl (aq)
AgCl (s) 1 HNO
3
(aq)
(B) N
2
(g) 1 O
2
(g) 2NO(g)
(C) 2NO(g) 1 O
2
(g) 2NO
2
(g)
(D) 2KCl O
3
(s) 2KCl (s) 1 3O
2
(g)
(E) 2SO
2
(g) 1 O
2
(g) 2SO
3
(g)
22. Determi ne the name of
[Cu(NH
3
)
4
]SO
4.
(A) Tetraammi necuprate (I I ) sul fate
(B) Tetracupraammi ne (I V) sul fate
(C) Tetrasul fonoammi ne (I V)
cuprate
(D) Ammi necuprate (I V) sul fate
(E) Cupri c ammoni um sul fate
23. You are supposed to prepare 250 ml
of a 0.1 M sol uti on of Pb(NO
3
)
2
sol uti on (mol ar mass 5 331.2 g). You
woul d need to mi x _____of Pb(NO
3
)
2
wi th enough water to make 250 ml
sol uti on.
(A) 331.2 g
(B) 33.12 g
(C) 8.28 g
(D) 3.312 g
(E) 0.828 g
24. What i s the hybri di zati on around the
central atom i n the mol ecul e Si Cl
4
?
(A) sp
3
(B) sp
2
(C) sp
(D) sp
3
d
(E) sp
3
d
2
32 PART II: Diagnosing Strengths and Weaknesses
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www.petersons.com
Step 1 NO(g) 1
Cl
2
(g) NOCl
2
(g)
(fast
equi l i b-
ri um)
Step 2 NO(g) 1
NOCl
2
(g) 2NOCl (g)
(sl ow)
25. Whi ch of the fol l owi ng rate l aws i s
consi stent wi th the reacti on mecha-
ni sm shown above?
(A) Rate 5 k[NO][Cl
2
]
(B) Rate 5 k[NO]
2
(C) Rate 5 k[NO][NOCl
2
]
(D) Rate 5 k[NO]
2
[Cl ]
(E) Rate 5 k[NO]
2
[Cl ][NOCl
2
]
...C
6
H
5
OH 1 ...O
2
...CO
2
1 ...H
2
O
26. When the equati on above i s bal -
anced, how many water mol ecul es
wi l l be produced?
(A) 1
(B) 2
(C) 3
(D) 4
(E) 6
27. What type of emi ssi on i s the i sotope
6
14
C l i kel y to undergo?
(A) Al pha decay
(B) Beta decay
(C) Posi tron emi ssi on
(D) El ectron capture
(E) Nucl ear fi ssi on
28. Whi ch of the fol l owi ng i s most l i kel y
to be a sol i d at room temperature?
(A) HF
(B) NH
3
(C) K
2
S
(D) N
2
(E) H
2
O
29. What i s the percentage composi ti on
of Mg i n the compound Mg
3
(PO
4
)
2
?
(A) 21.92%
(B) 23.57%
(C) 27.74%
(D) 32.32%
(E) 48.70%
30. Fi ve bal l oons are fi l l ed up wi th one
mol e each of hydrogen (H
2
), hel i um
(He), Ni trogen (N
2
), Oxygen (O
2
), and
Argon (Ar) mol ecul es. After some
ti me has el apsed, whi ch bal l oon wi l l
be the smal l est?
(A) H
2
(B) He
(C) N
2
(D) O
2
(E) Ar
31. Whi ch of these expl ai ns that the
CC bonds i n benzene are al l the
same l ength?
(A) Hydrogen bondi ng
(B) Hybri di zati on
(C) I oni c bondi ng
(D) Resonance
(E) London di spersi on forces
32. What i s the standard free energy
change (DG) for the reacti on shown
bel ow?
Fe
31
(aq) 1Ag(s) Fe
21
(aq) 1Ag
1
(aq)
(A) 22.5 kJ
(B) 2.9 kJ
(C) 8.7 kJ
(D) 10.0 kJ
(E) 29 kJ
33. The vapor pressure of water at 50C
i s 92.5 mm Hg. I f 400.0 g of sucrose
(C
12
H
22
O
11
mol ar mass 342.3 g) i s
added to 900.0 g of H
2
O at 50C,
what wi l l the vapor pressure of the
sol uti on be?
(A) 94.6 mm Hg
(B) 92.3 mm Hg
(C) 90.4 mm Hg
(D) 88.3 mm Hg
(E) 27.4 mm Hg
34. Whi ch mol ecul e l i sted bel ow has two
si gma (s) and two pi (p) bonds?
(A) N
2
(B) C
2
H
4
(C) N
2
F
2
(D) HCN
(E) C
2
H
2
Cl
2
d
i
a
g
n
o
s
t
i
c
t
e
s
t
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Chapter 2: Practice Test 1: Diagnostic 33
www.petersons.com
35. For the reacti on A 1 B C 1 D,
DH 5 140 kJ and DS 5 150 J K
21
.
Therefore, the reacti on under stan-
dard condi ti ons i s
(A) spontaneous at temperatures
l ess than 10 K.
(B) spontaneous at temperatures
greater than 800 K.
(C) spontaneous onl y at tempera-
tures between 10 K and 800 K.
(D) spontaneous at al l temperatures.
(E) nonspontaneous at al l
temperatures.
36. I n whi ch of the fol l owi ng systems
woul d the number of mol es of the
substances present at equi l i bri um
NOT be shi fted by a change i n the
vol ume of the system at constant
temperature?
(A) SO
2
(g) 1 O
2
(g) 2SO
3
(B) N
2
(g) 1 3H
2
(g) 2NH
3
(g)
(C) NO
2
(g) 1 SO
2
(g) SO
3
(g) 1
NO(g)
(D) N
2
O
4
(g) 2NO
2
(g)
(E) CO(g) 1 3H
2
(g) CH
4
(g) 1
H
2
O(g)
37. Whi ch one of the fol l owi ng el ectron
confi gurati ons for the speci es i n thei r
ground state i s NOT correct?
(A) Ca: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
(B) Bi : [Xe]6s
2
4f
14
5d
10
6p
3
(C) As: [Ar] 4s
2
3d
10
4p
3
(D) Br: [Ar] 4s
2
3d
10
4p
5
(E) P: 1s
2
2s
2
2p
6
3p
5
38. What i s the oxi dati on state of Cr i n
the compound K
2
Cr
2
O
7
?
(A) 12
(B) 13
(C) 15
(D) 16
(E) 17
39. A 0.4647 g sampl e of a compound
contai ni ng onl y carbon, hydrogen,
and oxygen was burned i n an excess
of pure oxygen to yi el d 0.8635 g of
CO
2
and 0.1767 g of H
2
O. What i s
the empi ri cal formul a of the com-
pound?
(A) CHO
(B) C
2
H
2
O
(C) C
3
H
3
O
2
(D) C
6
H
3
O
2
(E) C
3
H
6
O
2
40. Whi ch of the fol l owi ng i s a conjugate
aci d/base pai r?
(A) HCl /OCl
2
(B) H
2
SO
4
/SO
4
22
(C) NH
4
1
/NH
3
(D) H
3
O
1
/OH
2
(E) H
3
PO
4
/PO
4
32
Step 1 NO(g) 1
Cl
2
(g) NOCl
2
(g)
(fast
equi l i b-
ri um)
Step 2 NO(g) 1
NOCl
2
(g) 2NOCl (g)
(sl ow)
41. Whi ch of the fol l owi ng rate l aws i s
consi stent wi th the reacti on mecha-
ni sm shown above?
(A) Rate 5 k[NO][Cl
2
]
(B) Rate 5 k[NO]
2
(C) Rate 5 k[NO][NOCl
2
]
(D) Rate 5 k[NO]
2
[Cl ]
(E) Rate 5 k[NO]
2
[Cl ][NOCl
2
]
42. When 0.200 L of 0.015 M Pb(NO
3
)
2
i s
mi xed wi th 0.300 L of 0.050 M KI ,
the val ue of Q wi l l be ___________
and the bri ght yel l ow preci pi tate,
PbI
2
, __________. (K
sp
for PbI
2
i s
9.8 3 10
29
).
(A) l ess than K
sp
; wi l l form
(B) greater than K
sp
; wi l l form
(C) l ess than K
sp
; wi l l not form
(D) greater than K
sp
; wi l l not form
(E) equal to K
sp
; wi l l form
34 PART II: Diagnosing Strengths and Weaknesses
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43. A crystal of NaCl i s
(A) soft, has a l ow mel ti ng tempera-
ture, and i s a good el ectri cal
conductor.
(B) hard, has a hi gh mel ti ng
temperature, and i s a good
el ectri cal conductor.
(C) soft, has a l ow mel ti ng tempera-
ture, and i s a poor el ectri cal
conductor.
(D) hard, has a hi gh mel ti ng
temperature, and i s a poor
el ectri cal conductor.
(E) soft, has a hi gh mel ti ng tem-
perature, and i s a poor el ectri -
cal conductor.
44. What effect wi l l an i ncrease i n
temperature have on the reacti on
bel ow?
2SO
3
(g) 2SO
2
(g) 1 O
2
(g)
DH 5 198.3 kJ per mol e SO
3
(A) Shi ft the equi l i bri um to the ri ght
(B) Shi ft the equi l i bri um to the l eft
(C) Wi l l have no effect on the
equi l i bri um
45. A 1.0 l i ter sol uti on contai ns 0.25 M
HF and 0.60 M NaF (K
a
for HF i s
7.2 3 10
24
). What i s the pH of thi s
sol uti on?
(A) 1.4
(B) 3.5
(C) 4.6
(D) 2.8
(E) 0.94
46. I f a tree di es and the trunk remai ns
undi sturbed for 15,580 years, what
percentage of ori gi nal
6
14
C i s sti l l
present?(hal f-l i fe of
6
14
C 55730 years)
(A) 5.20%
(B) 19.0%
(C) 2.20%
(D) 45.0%
(E) 15.2%
47. What geometry does the mol ecul e
SOCl
2
exhi bi t?
(A) Pyrami dal
(B) Tri gonal bi pyrami dal
(C) Octahedral
(D) Tri gonal pl anar
(E) Bent
48. I n the rate l aw, Rate 5 k[NO]
2
[O
2
],
the reacti on i s ________order for NO,
________order for O
2
, and ________
order overal l .
(A) second; fi rst; thi rd
(B) second; zero; thi rd
(C) fi rst; second; thi rd
(D) fi rst; thi rd; fi rst
(E) thi rd; thi rd; thi rd
49. A 6.00 L sampl e of an aqueous 0.108
M MgCl
2
sol uti on at 30.0C wi l l have
an osmoti c pressure of
(A) 8.05 3 10
2
mm Hg.
(B) 6.12 3 10
3
mm Hg.
(C) 2.04 3 10
3
mm Hg.
(D) 3.68 3 10
4
mm Hg.
(E) 1.02 3 10
3
mm Hg.
50. Whi ch of the fol l owi ng i s most l i kel y
to devi ate from i deal gas behavi or?
(A) Cl
2
(B) He
(C) Ar
(D) O
2
(E) CCl
2
F
2
51. Whi ch of the fol l owi ng shows the
correct ranki ng of the hi ghest to
l owest fi rst i oni zati on energi es for
Na, P, Cl , K, Rb?
(A) Na . P . Cl . K . Rb
(B) Na . Cl . P . Rb . K
(C) Cl . P . Na . K . Rb
(D) Cl . P . Rb . K . Na
(E) Rb . K . Na . P . Cl
d
i
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Chapter 2: Practice Test 1: Diagnostic 35
www.petersons.com
52. How many grams of si l ver ni trate
(AgNO
3
) are requi red to produce
44.0 g of al umi num ni trate
(Al (NO
3
)
3
)?
6AgNO
3
1 Al
2
(SO
4
)
3
3Ag
2
SO
4
1
2Al (NO
3
)
3
(A) 105.3 g
(B) 132.0 g
(C) 169.9 g
(D) 213.0 g
(E) 264.0 g
53. A vol tai c cel l contai ns one hal f-cel l
wi th a zi nc el ectrode i n a Zn
21
(aq)
sol uti on and a copper el ectrode i n a
Cu
21
(aq) sol uti on. At standard
condi ti on, E 5 1.10 V. Whi ch
condi ti on bel ow woul d cause the cel l
potenti al to be greater than 1.10 V?
(A) 1.0 M Zn
21
(aq), 1.0 M Cu
21
(aq)
(B) 5.0 M Zn
21
(aq), 5.0 M Cu
21
(aq)
(C) 5.0 M Zn
21
(aq), 1.0 M Cu
21
(aq)
(D) 0.5 M Zn
21
(aq), 0.5 M Cu
21
(aq)
(E) 0.1 M Zn
21
(aq), 1.0 M Cu
21
(aq)
54. A 2.50 kg pi ece of copper metal i s
heated from 25C to 225C. How
much heat, i n kJ, i s absorbed by the
copper? The speci fi c heat of copper i s
0.384 J/gC.
(A) 124 kJ
(B) 156 kJ
(C) 192 kJ
(D) 212 kJ
(E) 256 kJ
55. I f 25 mL of 0.75 M HCl are added to
100 mL of 0.25 NaOH, what i s the
fi nal pH?
(A) 12.70
(B) 12.80
(C) 1.30
(D) 1.20
(E) 7.00
56. 2HF(g) H
2
(g) 1 F
2
(g) K
eq
5
1.00 3 10
22
1.00 mol HF, 0.500 mol H
2
, and 0.750
mol F
2
are mi xed i n an evacuated
5.00 L fl ask. Whi ch di recti on wi l l the
equi l i bri um shi ft to establ i sh equi l i b-
ri um?
(A) The equi l i bri um shi fts to the
ri ght.
(B) The equi l i bri um shi fts to the
l eft.
(C) The system i s at equi l i bri um.
57. Consi der the fol l owi ng bal anced
equati on:
3Ba(NO
3
)
2
(aq) 1 Fe
2
(SO
4
)
3
(aq)
3BaSO
4
(s) 1 2Fe(NO
3
)
3
(aq)
The net i oni c equati on to descri be
thi s bal anced equati on i s
(A) 3Ba
21
(aq) 1 3SO
4
22
(aq)
3BaSO
4
(s).
(B) 6NO
3
2
(aq) 1 2Fe
21
(aq)
2Fe(NO
3
)
3
(aq).
(C) 3Ba
21
(aq) 1 2NO
3
2
(aq) 1
2Fe
31
(aq) 1 3SO
4
22
(aq)
3BaSO
4
(s) 1 2Fe
31
(aq) 1
6NO
3
2
(aq).
(D) 3Ba
1
(aq) 1 SO
4
32
(aq)
3BaSO
4
(s).
(E) 2Fe
31
(aq) 1 3NO
32
(aq)
2Fe(NO
3
)
3
(aq).
58. Whi ch of the fol l owi ng i oni c com-
pound has the l argest l atti ce energy,
i .e., the l atti ce energy most favorabl e
to a stabl e l atti ce?
(A) CsI
(B) Li I
(C) Li F
(D) CsF
(E) MgO
36 PART II: Diagnosing Strengths and Weaknesses
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www.petersons.com
59. I n a vol tai c cel l , a zi nc el ectrode i s
pl aced i n a sol uti on that i s 1.0 M for
Zn
21
, whi l e a copper el ectrode i s
pl aced i n a 1.0 M Cu
21
sol uti on.
Cal cul ate the cel l potenti al for the
vol tai c cel l . (Assume a sal t bri dge i s
i n pl ace.)
(A) 1.00 V
(B) 1.05 V
(C) 1.10 V
(D) 2.00 V
(E) 11.0 V
60. The K
sp
of PbSO
4
(s) i s 1.3 3 10
28
.
Cal cul ate the sol ubi l i ty (i n mol /L) of
PbSO
4
(s) i n a 0.0010 M sol uti on of
Na
2
SO
4
.
(A) 1.3 3 10
210
M
(B) 4.5 3 10
26
M
(C) 1.3 3 10
25
M
(D) 1.3 3 10
27
M
(E) 1.3 3 10
23
M
61. A 6.50 L sampl e of carbon monoxi de
i s col l ected at 55C and 0.875 atm.
What vol ume wi l l the gas occupy at
1.10 atm and 20C?
(A) 1.96 L
(B) 5.46 L
(C) 4.62 L
(D) 6.10 L
(E) 9.64 L
62. Name the fol l owi ng:
CH
3
CH
2
CCH
3

CH
3
CH
2
CH
3
(A) n-hexane
(B) 2-methyl -2-ethyl butane
(C) 3,3-di methyl pentane
(D) 2,2-di ethyl propane
(E) 3-ethyl -3,3-di methyl propane
Time
l
n

[
A
]
63. The graph shown above i s consi stent
wi th what type of reacti on?
(A) Zero order
(B) Fi rst order
(C) Second order
(D) Thi rd order
(E) Exothermi c
64. When pl aced i n a hot fl ame, copper
ni trate crystal s wi l l turn
(A) yel l ow.
(B) vi ol et.
(C) bl ue-green.
(D) orange.
(E) red.
d
i
a
g
n
o
s
t
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c
t
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Chapter 2: Practice Test 1: Diagnostic 37
www.petersons.com
ANSWER KEY
Number Answer Chapter/Topic
1. D Chapter 4, Atomi c Structure
2. A Chapter 9, States of MatterLi qui ds and Sol i ds
3. D Chapter 15, Addi ti onal Equi l i bri um Concepts
4. B Chapter 5, Nucl ear Chemi stry
5. A Chapter 14, Aci ds and Bases
6. D Chapter 17, Thermodynami cs
7. D Chapter 19, Organi c Chemi stry
8. E Chapter 11, Reacti on Types
9. B Chapter 16, Ki neti cs
10. A Chapter 12, Stoi chi ometry
11. D Chapter 13, Equi l i bri um
12. B Chapter 10, Sol uti ons
13. C Chapter 18, El ectrochemi stry
14. A Chapter 6, Chemi cal Bondi ng
15. C Chapter 7, Mol ecul ar Geometry
16. C Chapter 8, States of MatterGases
17. B Chapter 4, Atomi c Structure
18. A Chapter 6, Chemi cal Bondi ng
19. D Chapter 5, Nucl ear Chemi stry
20. E Chapter 9, States of MatterLi qui ds and Sol i ds
21. D Chapter 17, Thermodynami cs
22. A Chapter 15, Addi ti onal Equi l i bri um Concepts
23. C Chapter 10, Sol uti ons
24. A Chapter 7, Mol ecul ar Geometry
25. D Chapter 16, Ki neti cs
26. C Chapter 11, Reacti on Types
27. B Chapter 5, Nucl ear Chemi stry
28. C Chapter 9, States of MatterLi qui ds and Sol i ds
29. C Chapter 12, Stoi chi ometry
30. A Chapter 8, States of MatterGases
31. D Chapter 6, Chemi cal Bondi ng
32. B Chapter 18, El ectrochemi stry
33. C Chapter 10, Sol uti ons
34. D Chapter 7, Mol ecul ar Geometry
35. B Chapter 17, Thermodynami cs
36. C Chapter 13, Equi l i bri um
37. E Chapter 4, Atomi c Structure
38. D Chapter 11, Reacti on Types
38 PART II: Diagnosing Strengths and Weaknesses
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www.petersons.com
Number Answer Chapter/Topic
39. C Chapter 12, Stoi chi ometry
40. C Chapter 14, Aci ds and Bases
41. D Chapter 16, Ki neti cs
42. B Chapter 15, Addi ti onal Equi l i bri um Concepts
43. D Chapter 9, States of MatterLi qui ds and Sol i ds
44. A Chapter 13, Equi l i bri um
45. B Chapter 14, Aci ds and Bases
46. E Chapter 5, Nucl ear Chemi stry
47. A Chapter 7, Mol ecul ar Geometry
48. A Chapter 16, Ki neti cs
49. B Chapter 10, Sol uti ons
50. E Chapter 8, States of MatterGases
51. C Chapter 4, Atomi c Structure
52. A Chapter 12, Stoi chi ometry
53. E Chapter 18, El ectrochemi stry
54. C Chapter 17, Thermodynami cs
55. A Chapter 14, Aci ds and Bases
56. B Chapter 13, Equi l i bri um
57. A Chapter 11, Reacti on Types
58. E Chapter 6, Chemi cal Bondi ng
59. C Chapter 18, El ectrochemi stry
60. C Chapter 15, Addi ti onal Equi l i bri um Concepts
61. C Chapter 8, States of MatterGases
62. C Chapter 19, Organi c Chemi stry
63. B Chapter 16, Ki neti cs
64. C Chapter 15 Addi ti onal Equi l i bri um Concepts
a
n
s
w
e
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s
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Chapter 2: Practice Test 1: Diagnostic 39
www.petersons.com
P
ART III
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
AP CHEMISTRY REVIEW
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CHAPTER 3 Problem Solving and
Measurement
CHAPTER 4 Atomic Structure
CHAPTER 5 Nuclear Chemistry
CHAPTER 6 Chemical Bonding
CHAPTER 7 Molecular Geometry
CHAPTER 8 States of MatterGases
CHAPTER 9 States of MatterLiquids
and Solids
CHAPTER 10 Solutions
CHAPTER 11 Reaction Types
CHAPTER 12 Stoichiometry
CHAPTER 13 Equilibrium
CHAPTER 14 Acids and Bases
CHAPTER 15 Additional Equilibrium Concepts
CHAPTER 16 Kinetics
CHAPTER 17 Thermodynamics
CHAPTER 18 Electrochemistry
CHAPTER 19 Organic Chemistry
Problem Solving and
Measurement
OVERVIEW
Defining accuracy and precision
Using significant figures
Reviewing scientific notation
Using dimensional analysis to organize your work
Laboratory component
Summing it up
A good porti on of the AP Chemi stry Test deal s wi th cal cul ati ons, ei ther wi th or
wi thout the ai d of a cal cul ator. For al l of these probl ems, there are two
di fferent componentsthe chemi stry component and the math component.
Most of thi s book i s devoted to a revi ew of the chemi stry component of the
probl ems, but thi s chapter i s desi gned to revi ew a few i mportant
mathemati cal ski l l s that you wi l l need to know as you work through the
probl ems. Three ski l l s that are cri ti cal to success on the AP Chemi stry Test
use si gni fi cant fi gures, sci enti fi c notati on, and di mensi onal anal ysi s.
I n the second porti on of thi s chapter, we wi l l revi ew l aboratory equi pment. I n
addi ti on to an occasi onal questi on about l aboratory procedure, the AP test
now contai ns an essay or probl em questi on that i s enti rel y devoted to
l aboratory procedure. The Col l ege Board has a recommended seri es of l abs,
many of whi ch you shoul d have compl eted pri or to taki ng the test, and the test
wi l l contai n a descri pti on of one of these l abs for you to anal yze. I n thi s book,
you wi l l fi nd i nformati on about these l abs i n the chapters that correspond to
thei r subject. The Col l ege Board al so recommends that you shoul d be fami l i ar
wi th a vari ety of l aboratory equi pment. So, i n the l ast part of thi s chapter, you
wi l l fi nd a l i st (Tabl e 3.1) of the recommended l abs as wel l as di agrams of the
l ab equi pment. Make yoursel f fami l i ar wi th the equi pment by name and
functi on.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
3
43
DEFINING ACCURACY AND PRECISION
Students frequentl y have mi sconcepti ons about the defi ni ti ons of accuracy and preci si on
based on popul ar uses of the words. The term accuracy refers to how cl ose a measured val ue
i s to the true val ue of a quanti ty. I n other words, i t descri bes how cl ose you got. Preci si on
descri bes how cl ose your measurements are to each other, not how cl ose they are to the actual
val ue. That i s, i f your val ues are cl ose together, they are consi dered preci se, even i f they are
nowhere near the true val ue (accurate). The di sti ncti on between accuracy and preci si on
becomes extremel y i mportant when you consi der real -worl d measurements. For exampl e, i f
you try to measure the di stance between two objects usi ng a meter sti ck, the accuracy of your
answer i s l i mi ted. The smal l est marki ngs on the meter sti ck are mi l l i meters. Therefore, you
can defi ni tel y know the exact number of mi l l i meters, and you can even esti mate one more
pl ace after the deci mal . However, your val ue can be no more accurate than that as l ong as you
are usi ng a meter sti ck. I t i s possi bl e that you may obtai n a more sophi sti cated devi ce, l i ke a
soni c range-fi nder, that can provi de you wi th a more accurate measurement. The i mportant
thi ng to remember i s that your data can be no more accurate than the devi ce wi th whi ch you
are measuri ng. Thi s concept i s the foundati on for the use of si gni fi cant fi gures i n cal cul ati ons.
USING SIGNIFICANT FIGURES
I n mathemati cs, most of the numbers you work wi th are pure numbers. They do not represent
a real object or amount of any physi cal materi al . Wi th numbers i n chemi stry, you are typi cal l y
deal i ng wi th a quanti ty of somethi ng. Even when you obtai n a rati o, the rati o i s obtai ned from
the di vi si on of two measurements. The poi nt i s that you are deal i ng wi th physi cal quanti ti es.
One of the dangers when sol vi ng a probl em usi ng real measurements i s that you may come up
wi th answers that suggest more accuracy than coul d possi bl y be obtai ned from the measuri ng
devi ces used. However, there are some si mpl e gui del i nes that wi l l hel p you deci de whi ch
di gi ts are si gni fi cant and whi ch shoul d be i gnored. Keep i n mi nd that readers wi l l sti l l award
poi nts i f your answer i s off by one si gni fi cant fi gure, assumi ng the answer needs two, three, or
four si gni fi cant fi gures. The general rul e i s that al l answers expressed i n three si gni fi cant
fi gures wi l l be correct most of the ti me.
5 Rules for Significant Figures:
Al l nonzero numbers are si gni fi cant. (Exampl e: 1, 2, 3, 4, 5, . . . etc.)
Zeros between si gni fi cant numbers are si gni fi cant. (Exampl e: 1002both zeros are
si gni fi cant.)
Zeros at the end after the deci mal are si gni fi cant. (Exampl e: 95.000al l zeros are
si gni fi cant. These represent measured amounts.)
Leadi ng zeros (before si gni fi cant numbers) are not si gni fi cant (before or after the
deci mal ). (Exampl es: 0.51 and 0.000007none of these zeros are si gni fi cant.)
Zeros at the end beforethe deci mal are not si gni fi cant. (Exampl e: 1,875,000,000
none of these zeros are si gni fi cant.)
For numbers that are wri tten i n sci enti fi c notati on, onl y the root porti on of the number i s
consi dered. (Exampl e: 1.605 3 10
7
woul d have 4 si gni fi cant di gi ts.)
44 PART III: AP Chemistry Review
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NOTE
The lab
information
presented in this
book is certainly
no substitute for
the actual lab
work, but it can
serve to refresh
your memory of
those labs you
have done and
give you a basic
idea of any labs
you may not
have had time to
complete.
www.petersons.com
You Try It!
How many si gni fi cant di gi ts are present i n each of the fol l owi ng?
________1. 6.908 g
________2. 81801000 g
________3. 893.760 g
________4. 56890 cm
________5. 8970000 cm
________6. 0.000136 cm
________7. 345000 cm
________8. 0.008710 L
________9. 7890.0 L
Answers:
1. 4 (rul e 2)
2. 5 (rul e 5zeros at the end are pl ace hol ders)
3. 6 (rul e 3)
4. 4 (rul e 5)
5. 3 (rul e 5)
6. 3 (rul e 4zeros are pl ace hol ders)
7. 3 (rul e 5)
8. 4 (rul e 4fi rst zeros are not si gni fi cant; rul e 3l ast zero i s si gni fi cant)
9. 5 (rul e 3 l ast zero i s si gni fi cant; rul e 2mi ddl e zero i s si gni fi cant because i t i s
between two si gni fi cant numbers)
Wi th a basi c understandi ng of si gni fi cant numbers, you can now understand how to
determi ne si gni fi cant numbers i n cal cul ati ons. Assume that you measure the densi ty of an
unknown substance. Remember the equati on for densi ty: D 5
m
v
. The object had a mass of
25.35 g and a vol ume of 4.2 cm
3
. Each of these measurements was taken by some measuri ng
devi ce and was measured as accuratel y as possi bl e. I f you substi tute these numbers i nto the
densi ty equati on, you get an answer of 6.03571429 g/cm
3
. But just because the cal cul ator
gi ves al l of those di gi ts doesnt mean that your measurements are accurate. So, where do you
draw the l i ne i n roundi ng those l ong numbers? When measurements are used i n cal cul ati ons,
i t i s i mportant to keep track of the number of si gni fi cant fi gures throughout the probl em. Thi s
assures you that your answer wi l l be no more accurate than the l east accurate measurement.
One i mportant consi derati on for al l probl ems i s that the cal cul ati ons shoul d be compl eted
before you round. Wai t unti l you have an answer, and then round i t to the proper pl ace or
number of si gni fi cant fi gures.
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NOTE
The rules for
significant figures
are slightly
different for
addition,
subtraction,
multiplication,
and division.
Chapter 3: Problem Solving and Measurement 45
www.petersons.com
Addition and Subtraction
The answer can onl y be as si gni fi cant as the l east accurate number (l east pl ace val ue).
Examples: 3.245 m 1 3.98765 m 1 5.98 m 1 9 m 5 22 m
6.234 g 2 4.0 g 5 2.2 g
You Try It!
1. 14.2 1 23.89 1 37.891 5
2. 345.178 2 4.58 5
3. 892.5 1 234 1 27.88 5
4. 94.234 2 2.7 5
Answers:
1. 76.0
2. 340.60
3. 1154
4. 91.5
Multiplication and Division
The answer can be onl y as si gni fi cant as the l east si gni fi cant number i nvol ved (number of
si gni fi cant fi gures).
Samples: 78.35 m 3 3400 m 5 270 000 m
2
56.78 g 4 6.7 ml 5 8.5 g/ml
Numbers that are wri tten usi ng sci enti fi c notati on are treated the same way. The root porti on
of each number i s what i s counted.
Sample: 6.02 3 10
23
atoms/mol 3 1.4 mol 5 8.4 3 10
23
atoms
You Try It!
1. 3.08 J 3 5.2 s 5
2. 0.075 kg 4 0.030 m 5
3. 4.50 3 10
27
m 3 6.67 3 10
14
s
21
5
4. 3.00 3 10
8
m s
21
4 6.8 3 10
27
m 5
Answers:
1. 16 J s
2. 0.0023 kg m, or 2.3 3 10
23
kg m
3. 3.00 3 10
8
m s
21
4. 4.4 3 10
14
s
21
46 PART III: AP Chemistry Review
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www.petersons.com
REVIEWING SCIENTIFIC NOTATION
Many of the numbers you wi l l deal wi th wi l l ei ther be very l arge (e.g., Avogadros number
6.02 3 10
23
) or very smal l (e.g., Pl ancks constant6.63 3 10
234
J s). Rather than wri te these
numbers wi th al l of the zeros, i t i s much easi er to use sci enti fi c (or exponenti al ) notati on:
M 3 10
n
Where M i s a number equal to or greater than 1 and l ess than 10, M must have one si gni fi cant
di gi t to the l eft of the deci mal poi nt. n i s any posi ti ve or negati ve i nteger.
To change a number i nto sci enti fi c notati on you must do two thi ngs:
Determi ne M by movi ng the deci mal poi nt so that you l eave onl y one nonzero di gi t
to the l eft of the deci mal .
Determi ne n by counti ng the number of pl aces that you moved the deci mal poi nt. I f
you move i t to the l eft, the val ue of n i s posi ti ve. I f you move the deci mal to the
ri ght, the val ue of n i s negati ve.
Sample: Wri te the fol l owi ng numbers i n sci enti fi c notati on:
105,000,000,000 5 1.05 3 10
11
0.00000587 5 5.87 3 10
26
You Try It!
Wri te the fol l owi ng numbers i n sci enti fi c notati on:
1. 400,780,000,000 5
2. 0.00052 5
Answers:
1. 4.0078 3 10
11
2. 5.2 3 10
24
USING DIMENSIONAL ANALYSIS TO ORGANIZE YOUR WORK
There are a vari ety of probl em-sol vi ng strategi es that you wi l l use as you prepare for and take
the AP test. Di mensi onal anal ysi s, someti mes known as the factor l abel method, i s one of
the most i mportant of the techni ques for you to master. Di mensi onal anal ysi s i s a
probl em-sol vi ng techni que that rel i es on the use of conversi on factors to change
measurements from one uni t to another. I t i s a very powerful techni que but requi res careful
attenti on duri ng setup. The conversi on factors that are used are equal i ti es between one uni t
and an equi val ent amount of some other uni t. I n fi nanci al terms, we can say that 100 penni es
i s equal to 1 dol l ar. Whi l e the uni ts of measure are di fferent (penni es and dol l ars) and the
numbers are di fferent (100 and 1), each represents the same amount of money. Therefore, the
two are equal . Lets use an exampl e that i s more al i gned wi th sci ence. We al so know that 100
centi meters are equal to 1 meter. I f we express thi s as an equati on, we woul d wri te:
100 cm 5 1 m
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TIP
You only need to
worry about these
on the free-
response portion
of the test. On
the multiple-
choice portion,
they do not try to
trick you by
having two
answers that
differ only by the
number of
significant digits.
ALERT!
Whileyouare
completingthe
calculation,
check tomake
surethat all units
arecanceling. If
theydonot
cancel, it is a
warningthat you
haveprobably
madeanerror in
thesetupor the
solutionof the
problem.
Chapter 3: Problem Solving and Measurement 47
www.petersons.com
Si nce these represent the same di stance, the val ues can be thought of as equi val ent.
Therefore, we can say that:
100 cm
1 m
5 1
And, because each of these val ues i s equal to the same thi ng, we can al so say that:
1 m
100 cm
5 1
Si nce these two val ues are i nterchangeabl e, we now have a conversi on factor that can be used
to convert between meters and centi meters.
Sample: Convert 455 centi meters to meters.
Answer: Fi rst, set up the conversi on factor to el i mi nate the centi meters uni t and change i t
to meters. When you set up a probl em l i ke thi s, al ways begi n by wri ti ng down your
gi ven (or starti ng) i nformati on. The next step i s to set up the conversi on factor so
that the uni ts i n the denomi nator wi l l cancel the uni ts of the gi ven. Thi s can be
accompl i shed by
455 cm 3
1 m
100 cm
, whi ch al l ows you to cancel uni ts and sol ve the fol l owi ng probl em:
455 cm 3
1 m
100 cm
=
455 m
100
= 4.55 m
Someti mes, students prefer to use a sl i ghtl y di fferent setup, whi ch can be especi al l y hel pful
for l onger stoi chi ometri c conversi ons. Some cal l thi s techni que the egg carton approach
because the probl em i s set up i n a gri d that has sl ots to fi l l i n quanti ti es, much l i ke the sl ots
that hol d eggs i n an egg carton. The same probl em above, wri tten i n the egg carton format,
woul d l ook l i ke thi s:
455 cm 1 m
5 4.55 m
100 cm
Not al l probl ems l end themsel ves to such a l i near method, but you can sti l l use the most
i mportant el ements of thi s techni que i f you i ncl ude uni ts of measure wi th every quanti ty and
careful l y check to be sure that the uni ts are cancel i ng appropri atel y. To see a more compl ex
exampl e, l ets l ook at a gas l aw probl em.
Sample: What i s the pressure of 2.0 mol es of ni trogen gas (N
2
) that occupi es a vol ume of
1.5 L and i s at 298 K?
48 PART III: AP Chemistry Review
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www.petersons.com
Answer: Usi ng the i deal gas equati on, we know that PV 5 nRT. We al so know that when we
sol ve for P, our answer shoul d come out to be i n uni ts of atmospheres (atm). When
we set up and sol ve the probl em, al l uni ts shoul d cancel to gi ve us atm.
PV 5 nRT, rearrange the equati on to sol ve for P
P =
nRT
V
=
~2.0 mol !
S
0.0821
L atm
mol K
D
~298 K!
1.5 L
; cancel i ng uni ts, we see
~2.0 mol !
S
0.0821
L atm
mol K
D
~298 K!
1.5 L
=
48.9316 L atm
1.5 L
= 33 atm
LABORATORY COMPONENT
Tabl e 3.1 provi des you wi th a summary of the l aboratory experi ences and equi pment the
Col l ege Board recommends that you be fami l i ar wi th. Further di scussi ons of many of the l abs
wi l l take pl ace wi thi n the appropri ate chapters. Emphasi s wi l l be pl aced on those l abs that
are most frequentl y referred to on the AP test. Tabl e 3.2 provi des you wi th a l i st of the
recommended equi pment to hel p you remember the speci fi c names for each pi ece. Words
l i ke thi ngy and whatchamacal l i t are not hi ghl y l ooked upon by the AP graders and earn
no credi t.
TABLE 3.1 LABORATORY EXERCISES THAT ARE RECOMMENDED BY THE COLLEGE BOARD
Lab Equipment Used
Determi nati on of the
formul a of a compound
cruci bl e and cover, tongs, anal yti cal bal ance, support stand,
tri angl e cruci bl e support, burner
Determi nati on of the
percentage of water i n a
hydrate
cruci bl e and cover, tongs, test tube, anal yti cal bal ance,
support stand, tri angl e cruci bl e support, wi re gauze, burner
Determi nati on of mol ar
mass by vapor densi ty
barometer, beaker, Erl enmeyer fl ask, graduated cyl i nder,
cl amp, anal yti cal bal ance, support stand
Determi nati on of mol ar
mass by freezi ng-poi nt
depressi on
test tube, thermometer, pi pet, beaker, sti rrer, stopwatch, i ce
Determi nati on of the
mol ar vol ume of a gas
barometer, beaker, Erl enmeyer fl ask, test tubes, graduated
cyl i nder, cl amp, anal yti cal bal ance, thermometer, rubber
tubi ng
Standardi zati on of a
sol uti on usi ng a pri mary
standard
pi pet, buret, Erl enmeyer fl asks, vol umetri c fl ask, wash
bottl e, anal yti cal bal ance, dryi ng oven, desi ccator, support
stand, pH meter
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Chapter 3: Problem Solving and Measurement 49
www.petersons.com
TABLE 3.1 ( c ontinue d )
Lab Equipment Used
Determi nati on of
concentrati on by aci d-
base ti trati on, i ncl udi ng a
weak aci d or weak base
pi pet, buret, Erl enmeyer fl asks, wash bottl e, anal yti cal
bal ance, dryi ng oven, desi ccator, support stand and cl amp,
pH meter
Determi nati on of concen-
trati on by oxi dati on-
reducti on ti trati on
pi pet, buret, Erl enmeyer fl asks, wash bottl e, anal yti cal
bal ance, dryi ng oven, desi ccator, support stand and cl amp, pH
meter as mi l l i vol tmeter
Determi nati on of mass
and mol e rel ati onshi p i n
a chemi cal reacti on
beaker, Erl enmeyer fl ask, graduated cyl i nder, hot pl ate,
desi ccator, anal yti cal bal ance
Determi nati on of the
equi l i bri um constant for a
chemi cal reacti on
pi pet, test tubes and/or cuvettes, vol umetri c fl ask, anal yti cal
bal ance, spectrophotometer (Spec 20 or 21)
Determi nati on of appro-
pri ate i ndi cators for vari -
ous aci d-base ti trati ons;
pH determi nati on
pi pet, Erl enmeyer fl asks, graduated cyl i nder, vol umetri c fl ask,
anal yti cal bal ance, pH meter
Determi nati on of the rate
of a reacti on and i ts order
pi pet, buret, Erl enmeyer fl asks, graduated cyl i nder or gas
measuri ng tubes, stopwatch, thermometer, anal yti cal
bal ance, support stand and cl amp
Determi nati on of enthal py
change associ ated wi th a
reacti on
cal ori meter (can be pol ystyrene cup), graduated cyl i nder,
thermometer, anal yti cal bal ance
Separati on and qual i tati ve
anal ysi s of cati ons and
ani ons
test tubes, beaker, evaporati ng di sh, funnel , watch gl ass,
mortar and pestl e, centri fuge, Pt or Ni test wi re
Synthesi s of a coordi nati on
compound and i ts chemi cal
anal ysi s
beaker, Erl enmeyer fl ask, evaporati ng di sh, vol umetri cfl ask,
pi pet, anal yti cal bal ance, test tubes/cuvettes,
spectrophotometer
Anal yti cal gravi metri c
determi nati on
beakers, cruci bl e and cover, funnel , desi ccator, dryi ng oven,
Meker burner, anal yti cal bal ance, support stand and cruci bl e
support tri angl e
Col ori metri c or
spectrophotometri c
anal ysi s
pi pet, buret, test tubes and/or cuvettes, spectrophotometer,
buret support stand
Separati on by
chromatography
test tubes, pi pet, beaker, capi l l ary tubes or open tubes or
burets, i on exchange resi n or si l i ca gel (or fi l ter paper stri ps,
wi th heat l amp or bl ow dryer)
Preparati on and
properti es of buffer
sol uti ons
pi pet, beaker, vol umetri c fl ask, pH meter
50 PART III: AP Chemistry Review
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TABLE 3.1 ( c ontinue d )
Lab Equipment Used
Determi nati on of
el ectrochemi cal seri es
test tubes and hol der rack, beakers, graduated cyl i nder,
forceps
Measurements usi ng
el ectrochemi cal cel l s and
el ectropl ati ng
test tubes, beaker, fi l ter fl asks, fi l ter cruci bl es and
adapters, el ectrodes, vol tmeter, power suppl y (battery)
Synthesi s, puri fi cati on,
and anal ysi s of an
organi c compound
Erl enmeyer fl ask, water bath, thermometer, burner, fi l ter
fl asks, evaporati ng di sh (dryi ng oven), anal yti cal bal ance,
burets, support stand, capi l l ary tubes
TABLE 3.2 LIST OF EQUIPMENT THE COLLEGE BOARD RECOMMENDS YOU KNOW
Anal yti cal Bal ance
Barometer
Beaker
Buret
Burner
Cal ori meter
Capi l l ary Tubes
Centri fuge
Cl amp
Cruci bl e
Cuvettes
Desi ccator
Dryi ng Oven
El ectrodes
Erl enmeyer Fl ask
Evaporati ng Di sh
Fi l ter Cruci bl es and Adapters
Fi l ter Fl ask
Forceps
Funnel
Gas Measuri ng Tubes
Graduated Cyl i nder
Hot Pl ate
I on Exchange Resi n
Meker Burner
Mortar and Pestl e
pH Meter
Pi pet
Power Suppl y/Battery
Spectrophotometer
Sti rrer
Support Stand
Test Tube
Thermometer
Tongs
Tri angl e Cruci bl e Support
Vol tmeter
Vol umetri c Fl ask
Wash Bottl e
Watch Gl ass
Water Bath
Wi re Gauze
Wi re Loops
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Chapter 3: Problem Solving and Measurement 51
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SUMMING IT UP
Accuracy i s about how cl ose your measurements are to the actual , or true, val ue.
Preci si on means that you are consi stent i n your measurements.
There are fi ve basi c rul es for determi ni ng whether or not di gi ts are si gni fi cant. These
rul es are i mportant to know to earn al l possi bl e poi nts duri ng the free-response secti on of
the test. Si gni fi cant fi gures do not appear i n the mul ti pl e-choi ce porti on.
Sci enti fi c notati on provi des a conveni ent way to wri te very l arge or very smal l numbers
usi ng powers of 10. You shoul d be abl e to wri te, i nterpret, and perform cal cul ati ons wi th
numbers wri tten usi ng sci enti fi c notati on.
Di mensi onal anal ysi s i s a useful techni que for organi zi ng i nformati on i n computati ons.
By usi ng thi s techni que of cancel i ng uni ts and uni t conversi on, you can decrease your
chances of maki ng carel ess errors and can i mprove your score.
Laboratory-based questi ons are becomi ng more common on the AP test. You shoul d
revi ew your ol d l abs and l ook over the exampl es of the l abs i n thi s book. You shoul d al so
know the names and uses for the equi pment l i sted i n thi s chapter.
Whi l e these are some of the tool s you wi l l need to conti nue wi th the book, they are by no
means a comprehensi ve l i st. The more techni ques you can l earn and probl em-sol vi ng
strategi es you can use, the more l i kel y you are to experi ence success on the test probl ems.
52 PART III: AP Chemistry Review
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Atomic Structure
OVERVIEW
The historical development of modern atomic theory
Modern atomic theory
The Periodic Table of the Elements
The quantum model of the atom
Quantum numbers
Electron configurations
Periodic trends
Summing it up
Just as the atom i s the bui l di ng bl ock from whi ch al l materi al s are made, thi s
chapter must be the bui l di ng bl ock upon whi ch the rest of the book i s made.
The remai ni ng chapters of thi s book are devoted to topi cs di rectl y rel ated to
the behavi or that can onl y be understood by fi rst l earni ng atomi c structure.
The i nformati on i n thi s chapter wi l l provi de you wi th a sol i d foundati on of
knowl edge upon whi ch to bui l d the remai nder of your revi ew. The AP test has
a few mul ti pl e-choi ce questi ons on the topi cs covered i n thi s chapter and wi l l
peri odi cal l y have one essay questi on as wel l . You wi l l have a much easi er ti me
on the other secti ons of thi s book and the AP test i f you can devel op a fi rm
understandi ng of atomi c structure and i ts i mpact.
THE HISTORICAL DEVELOPMENT OF MODERN
ATOMIC THEORY
The earl i est known descri pti ons of atoms date back to between 460 and 370
B.C.E., when the Greek phi l osopher Democri tus fi rst proposed the i dea that
matter was composed of i ndi vi si bl e parti cl es. He used the term atomos
(i ndi vi si bl e) to descri be these. Other phi l osophers, i ncl udi ng Pl ato and
Ari stotl e, opposed Democri tuss i deas, bel i evi ng that matter was i nfi ni tel y
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c
h
a
p
t
e
r
4
53
di vi si bl evi ews that were wi del y hel d unti l the ni neteenth century. Tabl e 4.1 summari zes the
major contri buti ons to modern atomi c theory.
Daltons Solid Sphere Model of the Atom
Duri ng the peri od between 1803 and 1807, John Dal ton proposed a theory of the atomi c
nature of matter. Dal tons four basi c postul ates stated the fol l owi ng:
Al l matter i s composed of extremel y smal l parti cl es cal l ed atoms.
Atoms of l i ke el ements are i denti cal , whi l e el ements of di fferent el ements are
di fferent.
Atoms are nei ther created nor destroyed i n chemi cal reacti ons, nor do they
change forms.
Compounds are formed when atoms of di fferent el ements combi ne. Atoms wi l l
combi ne i n certai n fi xed rati os wi th other atoms.
Thomsons Plum Pudding Model of Atomic Structure
These i deas remai ned rel ati vel y unchal l enged unti l l ate i n the ni neteenth century when work
wi th el ectri ci ty uncovered addi ti onal aspects of atomi c structure. The fi rst di scovery was that
the atom, rather than bei ng i ndi vi si bl e, actual l y consi sted of smal l subatomi c parti cl es. The
study of cathode rays uncovered the fi rst subatomi c parti cl e, the negati vel y charged el ectron.
Whi l e studyi ng cathode rays, sci enti sts al so observed a second type of ray, the canal ray,
whi ch l ed to the di scovery of a posi ti vel y charged parti cl e (l ater shown to be a proton). J. J.
Thomson, a l eadi ng researcher i n thi s area, proposed the second major model of atomi c
structure, the pl um puddi ng model of the atom (named for a popul ar Engl i sh dessert). The
atom, he proposed, consi sted of a posi ti vel y charged, spheri cal mass (the puddi ng) wi th
negati vel y charged el ectrons (rai si ns) scattered throughout. Another of Thomsons si gni fi cant
contri buti ons was the determi nati on of the charge-to-mass rati o of the el ectron. Thi s bi t of
evi dence ai ded physi ci st Robert Mi l l i kan, i n 1909, to determi ne the mass of the el ectron i n hi s
famous oi l -drop experi ment.
Whi l e Thomson and others were busy studyi ng el ectri cal phenomena, Henri Becquerel
di scovered a new phenomenonradi ati on. (We wi l l di scuss radi ati on i n more detai l i n
Chapter 5.) The study of thi s new type of hi gh-energy emi ssi on from materi al s was the
pri nci pal focus of Ernest Rutherford. Rutherfords i ni ti al work di scovered two new types of
parti cl es associ ated wi th the hi gh-energy emi ssi ons, the al pha (a) parti cl e and the beta (b).
These are now known to be a hel i um nucl eus and an el ectron, respecti vel y (more on thi s i n
Chapter 5).
Rutherfords Discovery of the Nucleus
I n 1910, Rutherford performed hi s famous gol d-foi l experi ment, the resul ts of whi ch ended the
bri ef rei gn of Thomsons pl um puddi ng model . I n the experi ment, he devi sed an i ngeni ous
apparatus to confi rm current i deas about atomi c structure. Hi s desi gn i nvol ved shooti ng a
beam of al pha parti cl es at a very thi n sheet of gol d foi l . Hi s hypothesi s suggested that the
di stri buti on of charge and mass throughout a pl um puddi ng atom shoul d al l ow the posi ti vel y
54 PART III: AP Chemistry Review
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charged al pha parti cl e to bl ast ri ght through the foi l wi th l i ttl e or no consequence. To hi s
amazement, there were a si gni fi cant number of parti cl es that di d not pass di rectl y through
the foi l , but i nstead were defl ected at vari ous angl essome even strai ght backward! He
ul ti matel y concl uded that the atoms i n the foi l must contai n an extremel y dense, posi ti vel y
charged core, suffi ci ent to defl ect the posi ti vel y charged al pha parti cl es. Rutherfords model ,
the thi rd major atomi c model , consi sted of a dense posi ti vel y charged nucl eus, surrounded by
ti ny, negati vel y charged el ectrons i n a l arge amount of empty space (see Fi gure 4.1).
Several years l ater, i n 1919, the posi ti vel y charged parti cl e, the proton, was di scovered that
makes up the dense nucl eus of an atom. I t woul d be another thi rteen years before James
Chadwi ck di scovered the neutral l y charged neutron, the second component of the nucl eus.
At thi s poi nt, sci enti sts knew of three fundamental components of atoms (and hence matter):
the el ectron, the neutron, and the proton. They knew that protons were l ocated i n a dense
regi on i n the center of the atom and that they were posi ti vel y charged. They al so knew that
protons had a mass nearl y 2,000 ti mes greater than that of an el ectron. I n addi ti on, they
knew that the charge on an el ectron was equal i n magni tude, but opposi te i n si gn, to a proton
(despi te i ts much smal l er si ze). The regi on outsi de the dense nucl eus was mostl y empty space;
however, the el ectrons were bel i eved to be scattered throughout the empty space. The exact
posi ti ons and behavi or of the el ectron were sti l l uncertai n.
Figure4.1 Schematic diagramof thesetup in Rutherfords gold-foil experiment
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Chapter 4: Atomic Structure 55
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MODERN ATOMIC THEORY
Plancks Quantized Energies and Einsteins Photoelectric Effect
I n order to better understand how our exi sti ng model of the atom evol ved, we must step back
to about 1900, when physi ci st Max Pl anck di scovered an unusual property of atoms. Whi l e
studyi ng the spectra emi tted from gl owi ng objects, Pl anck concl uded that energy coul d be
emi tted or absorbed from atoms onl y i n fi xed amounts, or quanta. He proposed that thi s
amount of energy (E) was di rectl y proporti onal to the frequency (n) of the el ectromagneti c
wave. Mathemati cal l y, thi s i s expressed i n the formul a:
E 5 hn, where h, known as Pl ancks constant, i s 6.63 3 10
234
Js
Pl ancks work provi ded Al bert Ei nstei n wi th val uabl e i nformati on that hel ped hi m propose
the photoel ectri c effect i n 1905. Ei nstei n provi ded the expl anati on that when l i ght wi th
certai n frequenci es struck a metal pl ate, i t coul d emi t el ectrons from the metal . He expl ai ned
thi s by descri bi ng radi ant energy (such as l i ght) as a stream of ti ny packets of energy. These
ti ny packets of energy behave l i ke a ti ny parti cl e contai ni ng a fi xed amount of energy. These
parti cl es of l i ght became known as photons. Thi s di scovery created new probl ems for
physi ci sts whose exi sti ng model s vi ewed l i ght as a wave. Ei nstei ns work suggested that thi s
wave al so behaved l i ke a parti cl e. Thi s dual nature of l i ght has yet to be compl etel y
understood.
Bohrs Planetary Model of Atomic Structure
The next major modi fi cati on to Rutherfords nucl ear model of the atom came from Dani sh
physi ci st Ni el s Bohr. Bohr was attempti ng to expl ai n the emi ssi on spectrum of hydrogen gas.
At thi s ti me, the spectral l i nes research, coupl ed wi th Rutherfords work, l ed sci enti sts to
bel i eve that el ectrons may orbi t the nucl eus much l i ke pl anets i n the sol ar system orbi t the
sun. But physi ci sts coul d not expl ai n how the el ectrons stayed i n an orbi t. Movi ng charged
parti cl es emi t el ectromagneti c radi ati on that woul d resul t i n an overal l energy l oss from the
el ectron. Therefore, the el ectron shoul d spi ral i nto the nucl eus of the atom. So Bohr suggested
that there are di sti nct energy l evel s wi thi n an atom. El ectrons wi l l onl y be found i n these
al l owed energy l evel s, and whi l e i n these regi ons they wi l l not radi ate. These l evel s
correspond to speci fi c di stances from the nucl eus. Accordi ng to Bohr, el ectrons can jump to
hi gher energy l evel s after absorbi ng speci fi c amounts of energy. Li kewi se, el ectrons droppi ng
from hi gher to l ower energy l evel s wi l l rel ease certai n amounts of energy i n the form of
photons. El ectrons can onl y jump to an exact energy l evel (they may not stop hal fway
between). Addi ti onal data col l ected subsequent to Bohrs proposal di d not support hi s model .
Subsequentl y, much of the Bohr model has been di scarded.
Shortl y after Bohrs proposal , Loui s de Brogl i e made an i mportant proposal . He sai d that i f
waves have matter-l i ke properti es, then matter shoul d have wave-l i ke properti es. I t i s not
necessary for you to know the de Brogl i e equati on, but you shoul d understand that i t
predi cted that matter of normal mass woul d create i nfi ni tesi mal l y smal l waves. I t i s onl y
matter wi th an extremel y smal l mass, l i ke an el ectron, and travel i ng at hi gh speed that wi l l
emi t appreci abl e wavel engths.
56 PART III: AP Chemistry Review
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The Quantum Model of the Atom
THE HEISENBERG UNCERTAINTY PRINCIPLE
Usi ng de Brogl i es i dea that matter has wave-l i ke properti es, Werner Hei senberg made an
i mportant proposal that bri dged the gap between Bohrs model and the current quantum
model . I n Bohrs model , the el ectron was a parti cl e i n a fi xed orbi t around the nucl eus.
Hei senberg extended de Brogl i es i deas to the el ectron, stati ng that onl y l i mi ted i nformati on
about the el ectrons l ocati on and momentum coul d be gai ned. Hi s asserti on, known as the
Hei senberg uncertai nty pri nci pl e, states that i t i s not possi bl e to know, si mul taneousl y,
i nformati on about the momentum and l ocati on of an el ectron. Therefore, i t i s i mpossi bl e to
concl ude that el ectrons are found i n wel l -defi ned ci rcul ar orbi ts.
TABLE 4.1 SUMMARY OF THE MAJOR CONTRIBUTORS TO MODERN ATOMIC THEORY
Name
Major
Contribution(s) Summary
John Dal ton Dal tons atomi c theory Fi rst quanti tati ve evi dence for di screte
parti cl es (atoms)
J. J. Thomson Pl um puddi ng model ;
charge-to-mass rati o of
el ectron
Work wi th cathode rays di scovered the
posi ti ve and negati ve nature of the
atom; al so determi ned the charge-to-
mass rati o for el ectrons
Max Pl anck Quanti zed energy Energy i s rel eased from atoms i n
di screte packets, or quanta
Al bert Ei nstei n Photoel ectri c effect Dual i ty of l i ght; establ i shed
rel ati onshi ps between energy and
frequenci es of l i ght waves
Robert Mi l l i kan Mass of an el ectron Hi s famous oi l -drop experi ment
establ i shed the charge on an el ectron.
Ernest Rutherford a, b, and g emi ssi ons;
gol d-foi l experi ment;
nucl ear model of
the atom
Determi ned the nature of radi oacti ve
parti cl es. Hi s gol d-foi l experi ment
establ i shed the presence of a posi ti vel y
charged nucl eus and that the atom i s
mostl y empty space.
Nei l s Bohr Pl anetary model of
el ectrons
Devel oped the i dea of di sti nct energy
l evel s where el ectrons coul d be found
si mi l ar to pl anets i n the sol ar system
Werner Hei senberg Hei senberg
uncertai nty pri nci pl e
I t i s not possi bl e to si mul taneousl y know
i nformati on about the l ocati on and
momentum of an el ectron.
Erwi n Schrdi nger Schrdi nger equati on Establ i shed the fi el d of wave mechani cs
that was the basi s for the devel opment
of the quantum model of the atom
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Chapter 4: Atomic Structure 57
www.petersons.com
THE SCHRDINGER EQUATION
At thi s poi nt, the proposed model of atomi c structure began to move i n a di fferent di recti on.
Si nce i t i s not possi bl e to pi npoi nt the exact l ocati on of an el ectron, the task turned to
determi ni ng i ts probabl e l ocati on. I n 1926, Erwi n Schrdi nger proposed an equati on that now
forms the basi s for modern atomi c theory. Whi l e the equati on i s too compl ex to study i n detai l ,
the suggesti ons made by i t can be studi ed. The underl yi ng premi se i s that we can use
mathemati cal probabi l i ty to determi ne the l i kel i hood of fi ndi ng el ectrons i n a parti cul ar
regi on. From thi s, we can begi n to create a map of an atom based on these probabi l i ti es. Thi s
wi l l be di scussed l ater i n the chapter.
Si nce thi s ti me, a number of di scoveri es have been made regardi ng addi ti onal subatomi c
parti cl es; however, these are rel ated to the domai n of nucl ear physi cs. The basi c components
of the atom that rel ate to i ts chemi cal behavi or are the proton, neutron, and el ectron. I t i s to
these that we now turn our attenti on.
THE PERIODIC TABLE OF THE ELEMENTS
I n 1869, Dmi tri Mendel eev was one of the fi rst sci enti sts to create a coherent arrangement of
the el ements. He di d so by arrangi ng el ements i n order of i ncreasi ng atomi c mass. He al so
created rows of el ements that were arranged so that the verti cal col umns represented
el ements that shared si mi l ar characteri sti cs. Much l ater, i n 1913, Henry Mosel y revi sed
Mendel eevs chart so that el ements were arranged by i ncreasi ng atomi c number rather than
i ncreasi ng atomi c mass. Thi s i s the peri odi c tabl e that you are fami l i ar wi th today. Lets
revi ew the components and vocabul ary associ ated wi th the modern Peri odi c Tabl e of the
El ements.
Subatomic Particles
Whi l e there are numerous subatomi c parti cl es, we wi l l onl y l ook at those most rel evant to
chemi stry: the proton, neutron, and el ectron.
Protona posi ti vel y charged parti cl e l ocated i n the atoms nucl eus. The el ectri cal charge has
a magni tude of 11.6 3 10
219
coul ombs (C); however, for si mpl i ci ty, i t i s often referred to by i ts
rel ati ve charge of 11.0 (charge rel ati ve to an el ectron). The mass of a proton i s about
1.67 3 10
224
g. The gram i s not a practi cal uni t to descri be the mass of subatomi c parti cl es,
so i nstead we use the atomi c mass uni t, or amu. An amu i s defi ned as
1
12
the mass of a carbon
atom contai ni ng 6 protons and 6 neutrons. The mass of a proton i s 1.0073 amu.
Neutrona neutral parti cl e l ocated i n the atoms nucl eus. The mass of a neutron i s 1.0087
amu, whi ch i s, for al l practi cal purposes, the same as a proton.
El ectrona negati vel y charged parti cl e* l ocated outsi de of the atoms nucl eus (we wi l l l ook
at thi s more cl osel y l ater i n thi s chapter). The el ectri cal charge of an el ectron i s
21.6 3 10
219
C, or a rel ati ve charge of 21.0 (charge rel ati ve to the proton). The mass of an
el ectron i s 5.486 3 10
24
amu, about 1,836 ti mes l ess than a proton.
* The el ectron i s actual l y bel i eved to have wave-l i ke and parti cl e-l i ke properti es, but, for conveni ence,
we wi l l refer to i t as a parti cl e.
58 PART III: AP Chemistry Review
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Atomi c Number i s the term used to descri be the number of protons i n the nucl eus of an
atom. I n a neutral atom, thi s wi l l al so descri be the number of el ectrons.
Mass Number represents the total number of protons and neutrons i n the atom.
El ements are descri bed as atoms possessi ng the same number of protons. However, not al l
atoms of an el ement possess the same number of neutrons. These di fferent vari eti es of an
el ement that contai n the same number of protons but di fferent numbers of neutrons are
known as i sotopes. I sotopes wi l l possess the same chemi cal properti es, si nce they are
determi ned by the number of el ectrons and protons, but they wi l l have a di fferent mass. I n
Chapter 5, we wi l l l ook at how the number of neutrons affects the stabi l i ty of the nucl eus. Al l
atoms of a speci fi c i sotope are known as nucl i des. I sotopes are represented usi ng a vari ety of
symbol s. Three of these are shown i n Tabl e 4.2.
The atomi c mass i s a number that i s used to descri be the average mass of an el ement. I t
represents the wei ghted average of the mass of al l i sotopes of an el ement. Cal cul ati ng the
atomi c mass requi res knowl edge of the mass numbers of each i sotope for an el ement as wel l
as each i sotopes rel ati ve abundance. Thi s l atter quanti ty i s determi ned experi mental l y wi th
the hel p of a speci al pi ece of equi pment known as a mass spectrometer. Thi s i s not a requi red
cal cul ati on on the AP test, but, for cl ari ty, a sampl e cal cul ati on i s shown bel ow.
Sample: Neon has three i sotopes, Neon-20, Neon-21, and Neon-22. The masses of each
i sotope and the rel ati ve abundances are shown i n the tabl e bel ow:
Isotope Mass (amu) Relative abundance (percent)
Neon-20 19.992 90.51
Neon-21 20.994 0.27
Neon-22 21.991 9.22
Answer: What thi s tel l s you i s that i f you scooped up a 100 g sampl e of Neon, 90.51 g of i t
woul d be Neon-20, 0.27 g woul d be Neon-21, and 9.22 g woul d be Neon-22.
Usi ng a si mpl e mean to cal cul ate the atomi c mass wi l l not work si nce the i sotopes are not
present i n equal amounts. Therefore, we must take i nto account the percentage of the total
sampl e accounted for by each i sotope. To compl ete the cal cul ati on, si mpl y mul ti pl y the mass of
the i sotope by the rel ati ve abundance (expressed as a deci mal ) and add the total val ues:
TABLE 4.2
Style Sample Interpretation
El ement name Neon-20 El ement name i s fol l owed by the mass number of
the i sotope.
El ement symbol
21
Ne El ement symbol wi th the mass number superscri pt
and to the l eft.
El ement symbol 2
10
22
Ne
El ement symbol wi th the mass number superscri pt
and to the l eft, and the atomi c number subscri pt
and to the l eft.
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Chapter 4: Atomic Structure 59
www.petersons.com
Isotope Calculation Relative Mass (amu)
Neon-20 19.992 3 0.9051 18.0947592
Neon-21 20.994 3 0.0027 0.0566838
Neon-22 21.991 3 0.0922 2.0275702
Total 20.179
The modern Peri odi c Tabl e of the El ements can be wri tten to di spl ay di fferent amounts of
i nformati on about the el ements. The one you wi l l be seei ng i n the book i s desi gned to l ook l i ke
the one you wi l l be abl e to use on the AP test. Thi s i s the most basi c peri odi c tabl e, contai ni ng
onl y the atomi c number, the symbol , and the atomi c wei ght of each el ement.
I n each box of the peri odi c tabl e, you wi l l fi nd the fol l owi ng i nformati on:
11
Na
22.99
Atomic number
Symbol
Atomic weight
Different Sections of the Periodic Table
Now that you are fami l i ar wi th the di fferent parts of the tabl e, l ets begi n l ooki ng at more
speci fi c i nformati on that can be gai ned by the tabl e. A peri od i s defi ned as a hori zontal row
on the tabl e. A group or fami l y i s defi ned as a verti cal col umn on the tabl e. El ements i n the
same group are chemi cal l y si mi l arthat i s, they behave the same i n chemi cal reacti ons. I n
Fi gure 4.2, you wi l l see some numbers wri tten at the top of each col umn on the chart. The top
56
Ba
137.33
57
La
138.91
72
Hf
178.49
73
Ta
180.95
74
W
183.85
75
Re
186.21
76
Os
190.2
77
Ir
192.2
78
Pt
195.08
79
Au
196.97
80
Hg
200.59
81
Tl
204.38
82
Pb
207.2
83
Bi
208.98
84
Po
(209)
85
At
(210)
86
Rn
(222)
109
Une
(266)
108
Uno
(265)
107
Uns
(264)
106
Unh
(263)
105
Unp
(262)
104
Unq
(261)
89
Ac
227.03
88
Ra
226.02
87
Fr
(223)
55
Cs
132.91
38
Sr
87.62
39
Y
88.91
40
Zr
91.22
41
Nb
92.91
42
Mo
95.94
43
Tc
(98)
44
Ru
101.1
45
Rh
102.91
46
Pd
106.42
47
Ag
107.87
48
Cd
112.41
49
In
114.82
50
Sn
118.71
51
Sb
121.75
52
Te
127.60
53
I
126.91
54
Xe
131.29
37
Rb
85.47
90
Th
232.04
91
Pa
231.04
92
U
238.03
93
Np
237.05
94
Pu
(244)
95
Am
(243)
96
Cm
(247)
97
Bk
(247)
98
Cf
(251)
99
Es
(252)
100
Fm
(257)
101
Md
(258)
102
No
(259)
58
Ce
140.12
59
Pr
140.91
60
Nd
144.24
61
Pm
(145)
62
Sm
150.4
63
Eu
151.97
64
Gd
157.25
65
Tb
158.93
66
Dy
162.50
67
Ho
164.93
68
Er
167.26
69
Tm
168.93
70
Yb
173.04
103
Lr
(260)
71
Lu
174.97
20
Ca
40.08
21
Sc
44.96
22
Ti
47.90
23
V
50.94
24
Cr
52.00
25
Mn
54.938
26
Fe
55.85
27
Co
58.93
28
Ni
58.69
29
Cu
63.55
30
Zn
65.39
31
Ga
69.72
32
Ge
72.59
33
As
74.92
34
Se
78.96
35
Br
79.90
36
Kr
83.80
13
Al
26.98
14
Si
28.09
15
P
30.974
16
S
32.06
17
Cl
35.453
18
Ar
39.948
19
K
39.10
2A
2
3B
3
4B
4
5B
5
Lanthanide series
Actinide series
6B
6
7B
7 8
8B
9 10
1B
11
2B
12
3A
13
4A
14
5A
15
6A
16
7A
17
8A
18
1A
1
12
Mg
24.30
11
Na
22.99
5
B
10.811
6
C
12.011
7
N
14.007
8
O
16.00
9
F
19.00
10
Ne
20.179
4
Be
9.012
3
Li
6.941
2
He
4.0026
1
H
1.0079
110
Uun
(269)
111
Uuu
(272)
112
Uub
(277)
Figure4.2 Thelayout of thePeriodic Tableof theElements.
60 PART III: AP Chemistry Review
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set of numbers (wi th the A and B desi gnati ons) i s most commonl y used i n North Ameri ca;
however, the I nternati onal Uni on of Pure and Appl i ed Chemi stry (I UPAC) devel oped a
di fferent numberi ng system usi ng 1 through 18 (wi th a bottom set of numbers). The el ements
i n groups 1A through 8A are known as the representati ve el ements, whi l e the el ements i n
groups 1B through 8B represent the transi ti on el ements. El ements 1 through 92 are
natural l y occurri ng el ements.
Most of the el ements on the chart are metal s. I n Fi gure 4.3, al l non-shaded el ements are
metal s. The shaded el ements are nonmetal s. The el ements that are on ei ther si de of the dark
l i ne separati ng the metal s from the nonmetal s have characteri sti cs of both metal s and
nonmetal s and are known as semi metal s, or metal l oi ds.
Looki ng at Fi gure 4.4, you wi l l note that some of the groups on the chart have speci fi c names.
Group 1A el ements are known as the al kal i earth metal s. These materi al s are al l soft,
hi ghl y reacti ve metal s that react readi l y wi th oxygen and water. Group 2A el ements are
known as the al kal i ne earth metal s. These metal s are harder and more dense and have
hi gher mel ti ng temperatures. They are al so l ess reacti ve than the al kal i metal s. Group 7A,
the hal ogens, are hi ghl y reacti ve nonmetal s. These tend to form sal ts wi th reacti ve metal s
(the name hal ogen i s formed from Greek words meani ng sal t formers). Fl uori ne, chl ori ne,
bromi ne, and i odi ne are di atomi c el ements. Group 8A, the nobl egases, are nonreacti ve gases
wi th a very stabl e el ectron structure (more i n the next secti on). The l anthani des and acti ni des
are not real l y separate groups of el ements at al l . They fi t i nto the peri odi c tabl e at the pl ace
i n the si xth and seventh peri od represented wi th the dark l i ne. They are l eft out of the tabl e
si mpl y because pl aci ng them i n creates a very wi de tabl e. Most of the l anthani des were not
known unti l recentl y, si nce they tend to occur together i n nature and are very di ffi cul t to
56
Ba
137.33
57
La
138.91
72
Hf
178.49
73
Ta
180.95
74
W
183.85
75
Re
186.21
76
Os
190.2
77
Ir
192.2
78
Pt
195.08
79
Au
196.97
80
Hg
200.59
81
Tl
204.38
82
Pb
207.2
83
Bi
208.98
84
Po
(209)
85
At
(210)
86
Rn
(222)
109
Une
(266)
108
Uno
(265)
107
Uns
(264)
106
Unh
(263)
105
Unp
(262)
104
Unq
(261)
89
Ac
227.03
88
Ra
226.02
87
Fr
(223)
55
Cs
132.91
38
Sr
87.62
39
Y
88.91
40
Zr
91.22
41
Nb
92.91
42
Mo
95.94
43
Tc
(98)
44
Ru
101.1
45
Rh
102.91
46
Pd
106.42
47
Ag
107.87
48
Cd
112.41
49
In
114.82
50
Sn
118.71
51
Sb
121.75
52
Te
127.60
53
I
126.91
54
Xe
131.29
37
Rb
85.47
90
Th
232.04
91
Pa
231.04
92
U
238.03
93
Np
237.05
94
Pu
(244)
95
Am
(243)
96
Cm
(247)
97
Bk
(247)
98
Cf
(251)
99
Es
(252)
100
Fm
(257)
101
Md
(258)
102
No
(259)
58
Ce
140.12
59
Pr
140.91
60
Nd
144.24
61
Pm
(145)
62
Sm
150.4
63
Eu
151.97
64
Gd
157.25
65
Tb
158.93
66
Dy
162.50
67
Ho
164.93
68
Er
167.26
69
Tm
168.93
70
Yb
173.04
103
Lr
(260)
20
Ca
40.08
71
Lu
174.97
21
Sc
44.96
22
Ti
47.90
23
V
50.94
24
Cr
52.00
25
Mn
54.938
26
Fe
55.85
27
Co
58.93
28
Ni
58.69
29
Cu
63.55
30
Zn
65.39
31
Ga
69.72
32
Ge
72.59
33
As
74.92
34
Se
78.96
35
Br
79.90
36
Kr
83.80
13
Al
26.98
14
Si
28.09
15
P
30.974
16
S
32.06
17
Cl
35.453
18
Ar
39.948
19
K
39.10
2A
2
3B
3
4B
4
5B
5
Lanthanide series
Actinide series
6B
6
7B
7 8
8B
9 10
1B
11
2B
12
3A
13
4A
14
5A
15
6A
16
7A
17
8A
18
1A
1
12
Mg
24.30
11
Na
22.99
5
B
10.811
6
C
12.011
7
N
14.007
8
O
16.00
9
F
19.00
10
Ne
20.179
4
Be
9.012
3
Li
6.941
2
He
4.0026
1
H
1.0079
Figure4.3 Classification of materials on thePeriodic Tableof theElements
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Chapter 4: Atomic Structure 61
www.petersons.com
separate i nto i ndi vi dual el ements. The acti ni des are qui te radi oacti ve, and for that reason
most are not general l y found i n nature.
The Peri odi c Tabl e of the El ements i s an extremel y i mportant tool for both chemi sts and
students of chemi stry. Much of the work you do i n thi s book and on the AP test wi l l need to
begi n wi th some i nformati on found on thi s chart. I n the next two secti ons of thi s chapter, you
wi l l l ook at how the el ectron structures of atoms can be determi ned i ndi rectl y from the
peri odi c tabl e.
THE QUANTUM MODEL OF THE ATOM
I f you recal l from the begi nni ng of thi s chapter, some of the work that l ed to the devel opment
of the modern atomi c theory was done by sci enti sts Max Pl anck, Al bert Ei nstei n, Loui s de
Brogl i e, Werner Hei senberg, Ni el s Bohr, and Erwi n Shrdi nger. The fi rst work centered
around l i ght (el ectromagneti c radi ati on), whi l e the l ater work focused on the wave-l i ke nature
of matter. The AP test does not probe too deepl y i nto the theoreti cal consi derati ons of any of
these sci enti sts, but some cal cul ati ons have popped up on previ ous tests. Therefore, l ets turn
our attenti on to some of the equati ons associ ated wi th these sci enti sts work.
2A
2
3B
3
4B
4
5B
5
Lanthanide series
Actinide series
6B
6
7B
7
Transition metals
A
l
k
a
l
i

e
a
r
t
h

m
e
t
a
l
s
A
l
k
a
l
i
n
e

e
a
r
t
h

m
e
t
a
l
s
H
a
l
o
g
e
n
s
N
o
b
l
e
/
i
n
e
r
t

g
a
s
e
s
8
8B
9 10
1B
11
2B
12
3A
13
4A
14
5A
15
6A
16
7A
17
8A
18
1A
1
Figure4.4 Special groups of elements on thePeriodic Tableof theElements
62 PART III: AP Chemistry Review
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www.petersons.com
Relationships between Wavelength, Frequency, and Energy
Li ght i s a form of el ectromagneti c radi ati on. Other forms of el ectromagneti c radi ati on i ncl ude
radi o waves, mi crowaves, i nfrared rays, ul travi ol et rays, X-rays, and gamma rays. Al l of these
forms of radi ati on travel at the speed of l i ght, but the i ndi vi dual properti es of each type of
radi ati on di ffer. Some of these properti es are the wavel engths (l), or di stance between each
wave (see Fi gure 4.5); the frequency (n), or the frequency of waves that pass by a certai n poi nt
i n a parti cul ar ti me i nterval ; and energy (E).
Wavelength,
Figure4.5 Depiction of a wavelength
The most basi c cal cul ati on i nvol vi ng el ectromagneti c radi ati on descri bes the rel ati onshi p
between the frequency and wavel engths of each wave. Al l el ectromagneti c radi ati on travel s at
the speed of l i ght (c), whi ch i s 3.00 3 10
8
m s
21
. I f you thi nk of frequency as the number of
waves that pass by a poi nt duri ng any gi ven ti me i nterval , you shoul d be abl e to see that i f the
waves are farther apart (i .e., have a l onger wavel ength), fewer waves wi l l pass by duri ng that
ti me i nterval . Conversel y, i f the waves are very cl ose together (have a smal l er wavel ength),
more waves wi l l pass by a poi nt i n a gi ven ti me i nterval . Therefore, frequency and wavel ength
are i nversel y rel ated to one another. Mathemati cal l y speaki ng, thi s can be shown i n the
fol l owi ng equati on:
c 5 ln
Thi s i s one of the equati ons you were provi ded wi th on the AP formul a sheet. The uni ts for c
are m s
21
. Wavel engths are usual l y expressed i n nanometers (nm) or angstroms (). The AP
test has used nanometers i n the past. Frequenci es are expressed i n reci procal seconds (s
21
).
Probl ems typi cal l y provi de one of the vari abl es and ask for the other.
Sample: Cal cul ate the frequency, i n s
21
, of l i ght wi th a wavel ength of 540 nm.
Answer: Fi rst, the equati on must be rearranged to sol ve for n:
n 5
c
l
You al so need to remember that the di stance uni ts for c are i n meters, whereas l i s gi ven i n
nm. Si nce those wont cancel di rectl y, a conversi on i s necessary. Substi tuti ng i nto the
equati on, you get:
n 5
3.00 3 10
8
m s
21
540 nm 3
10
29
m
1 nm
5 5.6 3 10
14
s
21
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Chapter 4: Atomic Structure 63
www.petersons.com
You Try It!
What i s the frequency, i n s
21
, for l i ght wi th a wavel ength of 650 nm?
Answer: 4.6 3 10
14
s
21
PLANCK AND THE QUANTUM
Pl ancks work showed that energy i s emi tted from atoms i n di screte amounts, or quanta. We
al so know that energy i s absorbed i n these same amounts. The di fference between absorbance
and emi ttance i s that when energy i s added to an atom (i .e., absorbed by the atom), el ectrons
are forced to hi gher energy l evel s. When these el ectrons fal l back down to l ower energy l evel s,
energy i s emi tted i n the form of photons. Pl anck found that these energi es coul d be
summari zed i n equati on
E 5 hn
where h i s known as Pl ancks constant and has a val ue of 6.63 3 10
234
J s. Thi s equati on i s
al so one of the equati ons provi ded on the AP test. Energy i s al ways emi tted or absorbed i n
mul ti pl es of hn, whi ch suggests that el ectrons move about between energy l evel s i n an
al l -or-none fashi on. That i s, they ei ther have enough energy to travel to a hi gher energy l evel
or not. They do not travel hal fway between i nterval s. Thi s phenomenon i s si mi l ar to the rungs
on a l adder. You can onl y go up or down a l adder on the rungs. You cannot stop hal fway
between the rungs!
Sample: Cal cul ate the amount of energy associ ated wi th a photon of l i ght wi th a frequency
of 6.23 3 10
14
s
21
.
Answer: The equati on i s al ready set up to sol ve for E, so you just need to substi tute the
numbers. Pl ancks constant has a uni t of J s, whi ch wi l l cancel the reci procal
seconds i n the frequency, gi vi ng us uni ts of Joul es i n our answer:
E 5 hn 5 (6.63 3 10
234
J s)(6.23 3 10
14
s
21
) 5 4.13 3 10
219
J
You Try It!
Cal cul ate the amount of energy, i n J, of a photon of l i ght wi th a frequency of 4.6 310
14
s
21
.
Answer: 3.0 3 10
19
J
The Relationship between Energy and the Principal Quantum Number
Bohr was abl e to show that there i s a cl ear rel ati onshi p between the energy absorbed by
(or rel eased from) atoms. To do thi s he used the equati on (provi ded for you on the AP test)
E
n
5 2R
HS
1
n
2D
where R
H
, known as the Rydberg constant, has a val ue of 2.18 3 10
218
J. The vari abl e n
represents the pri nci pal quantum number (di scussed l ater i n the chapter). I f you l ook at thi s
equati on, you can see that as n approaches `, E approaches 0.
64 PART III: AP Chemistry Review
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www.petersons.com
THE RYDBERG EQUATION
Because the amount of energy rel eased (or absorbed) al ways i s an i nterval of hn, i t i s possi bl e
to probe further i nto the energi es emi tted or absorbed by atoms as el ectrons move between
di fferent energy l evel s. The equati on that al l ows us to determi ne thi s energy i s known as the
Rydberg equati on, whi ch can be wri tten as
DE 5 R
HS
1
n
i
2
2
1
n
f
2D
where R
H
i s the Rydberg constant, 2.18 3 10
218
J, n represents the pri nci pal quantum
number, and the subscri pts i and f, represent the i ni ti al and fi nal states. When the n
i
i s
greater than n
f
, that means that the el ectron i s movi ng from a hi gher to a l ower energy l evel
and energy i s bei ng emi tted. I f you cal cul ate DE under these condi ti ons, you wi l l see that the
val ue you obtai n i s negati ve, whi ch i ndi cates energy i s bei ng l ost. Conversel y when n
i
, n
f
,
the val ue of DE wi l l be posi ti ve, i ndi cati ng energy bei ng absorbed. A very i mportant note here:
The Rydberg equati on i s not provi ded for you on the AP test, but i t i s occasi onal l y needed. On
the 1999 test, one of the free-response questi ons requi red the use of the equati on. The
Rydberg equati on was deri ved from Bohrs equati on, and i t i s possi bl e to use Bohrs equati on
enti rel y. The way you do thi s, shoul d you have to, i s:
DE 5 E
f
2 E
i
(the change i n energy from i ni ti al to fi nal state)
I f you know the energy l evel s that are associ ated wi th the i ni ti al and fi nal states, you si mpl y
substi tute for the E
f
and E
i
val ues:
E
f
5 2R
H S
1
n
f
2D
and E
i
5 2R
HS
1
n
i
2D
Each equati on can be sol ved separatel y. So i f you havent memori zed the Rydberg equati on,
you can al ways use thi s one.
Sample: How much energy i s rel eased from a hydrogen atom when an el ectron moves from
n
i
5 4 to n
f
5 2?
Answer: Lets use the Rydberg equati on fi rst. We know the val ues of n
f
and n
i
, so we just
need to pl ug and chug:
DE 5 R
HS
1
n
i
2
2
1
n
f
2D
5 2.18 3 10
218
J
S
1
4
2
2
1
2
2D
5 2 4.10 3 10
219
J
Because thi s equati on i s not gi ven to you on the test, l ets take a l ook at the same probl em
usi ng the equati on that i s provi ded:
DE 5 E
f
2 E
i
5 E
2
2 E
4
E
2
5 2R
HS
1
n
2
2D
5 22.18 3 10
218
J
S
1
2
2D
5 25.45 3 10
219
J
E
4
5 2R
HS
1
n
4
2D
5 22.18 3 10
218
J
S
1
4
2D
5 21.36 3 10
219
J
DE 5 E
2
2 E
4
5 25.45 3 10
219
J 2 ~21.36 3 10
219
J! 5 2 4.09 3 10
219
J
(Whi ch, consi deri ng roundi ng, i s the same as the previ ous answer.)
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Chapter 4: Atomic Structure 65
www.petersons.com
The fi nal equati on that we wi l l consi der i s de Brogl i es wave equati on. Thi s i s the equati on
that descri bes the wave-l i ke properti es of matter. An extremel y i mportant consi derati on of
thi s equati on i s that l arge movi ng objects produce wavel engths that are so smal l that they are
negl i gi bl e. However, smal l objects, l i ke el ectrons, can produce si gni fi cant wavel engths. The
equati on, whi ch i s gi ven to you on the AP test, i s
l 5
h
mv
where h i s Pl ancks constant, mi s the mass of the object, and v i s the vel oci ty (note thi s i s a
v wri tten i n i tal i cs, not the Greek symbol nu (n) that i s used to descri be frequency). To
i l l ustrate the asserti on about l arge and smal l objects, l ets compl ete a sampl e probl em that
compares the wavel engths of each.
Sample: Fi nd the wavel ength of a 5 oz basebal l (0.14 kg) movi ng at 100 mi l es per hour
(about 45 m s
21
).
Answer: Usi ng the de Brogl i e equati on, we can substi tute our gi ven i nformati on to fi nd the
wavel ength of the basebal l :
l 5
h
mv
5
6.63 3 20
214
J s
0.14 kg 3 45 m
21
5 1.1 3 10
234
m
I ts far too smal l to be detected by anythi ng!
Now, compare that wavel ength to an el ectron travel i ng at the same speed. The mass of an
el ectron i s about 9.11 3 10
231
kg, whi ch i s i n the i nfrared regi on of the el ectromagneti c
spectrum:
l 5
h
mv
5
6.63 3 20
214
J s
9.11 3 10
231
kg 3 45 m s
21
5 1.6 3 10
25
m
You Try It!
Cal cul ate the wavel ength of an el ectron (mass 9.11 3 10
231
kg) travel i ng at a speed of
3.65 3 10
6
m s
21
.
Answer: 1.99 3 10
10
m 5 1.99 3 10
21
nm
Al though these cal cul ati ons can be used to further i nvesti gate the work of Ni el s Bohr, these
quanti tati ve aspects of Bohrs work are rarel y tested on the AP test. Therefore, l ets ski p
ahead to the devel opment of the quantum model of the atom, parts of whi ch are tested on
the test.
66 PART III: AP Chemistry Review
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NOTE
Joule is a
derived unit
that originates
from a Newton
meter, which
equals 1 kg m
2
/s
2
)
www.petersons.com
QUANTUM NUMBERS
I n order to begi n to understand the behavi or of atoms, we must fi rst l ook at some of the detai l s
of the quantum mechani cal model of the atom. Schrdi ngers equati on predi cts the presence of
certai n regi ons i n the atom where el ectrons are l i kel y to be found. These regi ons, known as
orbi tal s, are l ocated at vari ous di stances from the nucl eus, are ori ented i n certai n di recti ons,
and have certai n characteri sti c shapes. Lets l ook at some of the basi c components of the atom
as predi cted by the equati on, and at the same ti me we wi l l revi ew quantum numbers.
I f you have four pi eces of i nformati on about a house, you can fi nd i t just about anywhere i n
the Uni ted States. These four pi eces are the Street Number, the Street Name, the Ci ty, and
the State. So i t i s wi th atoms. There are four pi eces of i nformati on from whi ch you can
i denti fy a speci fi c el ectron wi thi n any atom. These are known as quantum numbers, a l i st of
whi ch i s shown bel ow.
Pri nci pal quantum number (n)Thi s number descri bes the energy l evel i n whi ch the
el ectron can be found. I n our house anal ogy, thi s i s equi val ent to the State, whi ch i s the most
general i nformati on about where the house i s l ocated. These correspond to regi ons that are
found at speci fi c di stances from the nucl eus of the atom. The pri nci pal quantum number, n,
has a whol e number, posi ti ve val ue, from 1 to 7 (n 5 1, 2, 37). Lower val ues of n correspond to
orbi tal s cl ose to the nucl eus and l ower energy l evel s.
Azi muthal quantum number (l)Thi s number descri bes the shape of the orbi tal . The
azi muthal quantum number can have val ues, from 0 to n-1, and these val ues correspond to
certai n orbi tal shapes. Whi l e the val ue can theoreti cal l y have a val ue as hi gh as 6, we wi l l see
l ater that no val ues hi gher than 3 are found. The val ues that do exi st, 0, 1, 2, and 3,
correspond to parti cul ar shapes and are commonl y desi gnated as s, p, d, and f orbi tal s,
respecti vel y. I n our house anal ogy, thi s quantum number woul d correspond roughl y to the
Ci ty. That i s, i t i s a bi t more speci fi c than the State, but i t sti l l doesnt tel l us exactl y where
the house i s.
Magneti c quantumnumber (mor m
1
)Thi s number descri bes the ori entati on of the orbi tal
i n space. The val ue of m i s a range from 21 to 11, i ncl udi ng 0. I n the house anal ogy, thi s
quantum number i s si mi l ar to the Street Name of the house. You can tel l about where the
house i s from thi s i nformati on, but not exactl y. I n much the same way, you can determi ne
whi ch orbi tal an el ectron shoul d be i n from the magneti c quantum number, but you cant
i denti fy the speci fi c el ectron.
Spi n quantum number (s or m
s
)Thi s number descri bes the apparent spi n of the el ectron.
The term apparent spi n i s used si nce the atom behaves magneti cal l y as though i t were a
spi nni ng object, but the wave-l i ke nature of the el ectron makes such spi nni ng di ffi cul t to
comprehend. Onl y two val ues for s are possi bl e: 1
1
2
and 2
1
2
(correspondi ng to cl ockwi se or
countercl ockwi se spi ns). Fi ni shi ng the house anal ogy, we can see that i n an atom, no two
el ectrons can have the same four quantum numbers. I n much the same way, no two houses
can occupy the exact same address at once.
Tabl e 4.4 shows the possi bl e quantum numbers for energy l evel s 1 through 4. We wi l l use thi s
as the basi s for our consi derati on of other components of the model .
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Chapter 4: Atomic Structure 67
www.petersons.com
Before descri bi ng the patterns that occur i n thi s arrangement, l ets revi ew a few terms.
Wi thi n an atom, el ectrons are arranged i n speci fi c regi ons of space based on the amount of
energy they possess. These regi ons are known as energy l evel s, (or, i n some pl aces, shel l s).
Each energy l evel i s composed of one or more subl evel . A subl evel , (someti mes known as a
subshel l ) i s one or more orbi tal s of a parti cul ar shape. Orbi tal s are regi ons of space where
there i s approxi matel y a 90 percent probabi l i ty of l ocati ng an el ectron (based on the
Schrdi nger equati on).
We can see the rel ati onshi p between these terms and quantum numbers by l ooki ng careful l y
at Tabl e 4.3. Fi rst, each uni que val ue of n represents an energy l evel . Each l val ue represents
a speci fi c subl evel wi thi n an energy l evel . Recal l from the previ ous secti on that these
subl evel s are typi cal l y referred to usi ng thei r common names s, p, d, and f. Each uni que
combi nati on of n and l val ues corresponds to a di fferent subl evel . For exampl e, for n 5 3 and
l 5 2, thi s corresponds to the 3d subl evel of the atom. The mval ues tel l us how many orbi tal s
are found i n a gi ven subl evel . For i nstance, i n the 3d subl evel there are 5 orbi tal s possi bl e (for
3d, m5 22, 21, 0, 1, 2). The spi n quantum number tel l s us that there can be no more than
2 el ectrons i n any orbi tal , whi ch you wi l l l earn more about l ater i n thi s chapter. Lets
summari ze what we know i n a new chart.
I n Tabl e 4.4, noti ce some patterns that are now apparent:
The number of subl evel s i n the exampl es above i s equal to the pri nci pal quantum
number (thi s i s onl y apparent for the fi rst four energy l evel s).
The number of orbi tal s i n an energy l evel i s equal to n
2
.
Si nce there are two el ectrons per orbi tal , the number of el ectrons possi bl e i n any
energy l evel i s 2n
2
.
TABLE 4.3 QUANTUM STATES FOR THE FIRST FOUR PERIODS ON THE PERIODIC TABLE OF
THE ELEMENTS
n l m s
1 0 0 6
1
2
2 0 0 6
1
2
1 21, 0, 1 3 3 6
1
2
3 0 0 6
1
2
1 21, 0, 1 3 3 6
1
2
2 22, 21, 0, 1, 2 5 3 6
1
2
4 0 0 6
1
2
1 21, 0, 1 3 3 6
1
2
2 22, 21, 0, 1, 2 5 3 6
1
2
3 23, 22, 21, 0, 1, 2, 3 7 3 6
1
2
68 PART III: AP Chemistry Review
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Sample: Whi ch el ement(s) has an outermost el ectron that coul d be descri bed by the
fol l owi ng quantum numbers (3, 1, 21, 1
1
2
)?
Answer: Begi n wi th the 3. Thi s represents the 3
rd
energy l evel , so the el ements are surel y i n
row 3. Now, l ook at the azi muthal quantum number, 1, whi ch i s 1. Thi s represents
the 3p subl evel . So you know the el ectron i s somewhere i n the 3p subl evel . For
our purposes, the other two numbers (21, and 1
1
2
) dont tel l us anythi ng more. So
the most we can say i s that the el ement i s somewhere between atomi c numbers 13
and 18.
You Try It!
Whi ch el ement(s) has an outermost el ectron that coul d be descri bed by the fol l owi ng
quantum numbers, (4, 0, 0, 1
1
2
)?
Answer: K or Ca
At thi s poi nt we are ready to exami ne the shapes of the orbi tal s. Later you wi l l l earn more
about the arrangement of el ectrons wi thi n atoms, but before you do that, l ets l ook at the basi c
orbi tal confi gurati ons wi thi n an atom. The azi muthal quantum number determi nes the shape
of the orbi tal s. Looki ng at Tabl e 4.3, you wi l l note that the subl evel s are l abel ed s, p, d, and f.
Whi l e each of these subl evel s can be found i n more than one energy l evel , the basi c shapes for
each type are the same. I n hi gher energy l evel s (hi gher n val ues), the shapes woul d just be
l arger. Fi gures 4.64.8 show the basi c shapes for s, p, and d orbi tal s. Note that wi thi n a
TABLE 4.4 QUANTUM NUMBERS AND ORBITAL CONFIGURATIONS FOR THE FIRST 4 PERIODS
OF THE PERIODIC TABLE OF THE ELEMENTS.
n l Sublevel m
Number
of Orbitals s
Electrons
in Sublevel
Electrons in
Energy Level
1 0 1s 0 1 6
1
2
2 2
2 0 2s 0 1 6
1
2
2 8
1 2p 21, 0, 1 3 3 3 6
1
2
6
3 0 3s 0 1 6
1
2
2
1 3p 21, 0, 1 3 3 3 6
1
2
6 18
2 3d 22, 21, 0, 1, 2 5 5 3 6
1
2
10
4 0 4s 0 1 6
1
2
2
1 4p 21, 0, 1 3 3 3 6
1
2
6
2 4d 22, 21, 0, 1, 2 5 5 3 6
1
2
10 32
3 4f 23, 22, 21, 0, 1, 2, 3 7 7 3 6
1
2
14
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Chapter 4: Atomic Structure 69
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subl evel , what makes one orbi tal di fferent from another i s i ts ori entati on, determi ned by the
magneti c quantum number (m
1
):
Figure4.6
Figure4.7
Figure4.8
ELECTRON CONFIGURATIONS
At thi s poi nt, you now have some background about the l ocati ons where el ectrons can be
found i n an atom, so l ets move on to the task of descri bi ng the regi ons where they can be
found i n al most any atom. The speci fi c arrangement of el ectrons wi thi n an atom i s known as
the el ectron confi gurati on of an atom. There are three mai n rul es that are used to gui de the
process of determi ni ng an atoms el ectron confi gurati on.
70 PART III: AP Chemistry Review
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Fi rst i s the Aufbau (bui l dup) pri nci pl e, whi ch states that el ectrons wi l l fi l l orbi tal s of
l owest energy fi rst. Unfortunatel y, thi s order i s not a l i near sequence from 1 to 7. I n our i ni ti al
di scussi on of the Aufbau pri nci pl e, we wi l l l ook at a graphi cal representati on of the energy
l evel s wi thi n an atom. After that, wel l l ook at a si mpl i fi ed chart that i s easy to remember.
Second i s the Paul i excl usi on pri nci pl e(named after Wol fgang Paul i ), whi ch states that no
two el ectrons i n the same atom can have the same set of four quantum numbers. El ectrons
are negati vel y charged parti cl es. I f you recal l , l i ke charges repel one another. The
el ectron-el ectron repul si on becomes too great when more than two el ectrons occupy a si ngl e
orbi tal . The onl y way that two el ectrons can overcome thi s el ectrostati c repul si on i s by a
sl i ght magneti c attracti on. Thi s i s the reason why el ectrons i n the same orbi tal wi l l have
opposi te spi ns.
Cl osel y rel ated to the Paul i excl usi on pri nci pl e i s the thi rd rul e, Hunds rul e, whi ch states
that when el ectrons occupy orbi tal s of equal energy (e.g., the fi ve 3d orbi tal s), one el ectron
enters each orbi tal unti l al l the orbi tal s contai n one el ectron. I n thi s confi gurati on, al l
el ectrons wi l l have paral l el spi n (same di recti on). Second el ectrons then add to each orbi tal so
that thei r spi ns are opposi te to the fi rst el ectrons i n the orbi tal . Atoms wi th al l outer orbi tal s
hal f-fi l l ed are very stabl e.
Diamagnetism and Paramagnetism
Paramagneti sm i s a term used to descri be an attracti on to magnets. Paramagneti c el ements
are attracted to magnets. Di amagneti sm means repel l ed by magnets. Di amagneti c el ements
are weakl y repel l ed by magnets. What di sti ngui shes the two are the spi ns of the el ectrons i n
the orbi tal s. Paramagneti sm occurs i n el ements wi th one or more unpai red el ectrons, whi ch
means that there i s at l east one orbi tal that contai ns a si ngl e el ectron. Most el ements are
paramagneti c. Di amagneti sm occurs i n el ements where al l el ectrons are pai red. There are
fewer atoms wi th thi s confi gurati on (e.g., group 2A el ements, or nobl e gases).
Usi ng these three rul es, l ets l ook at a few exampl es of stabl e el ectron confi gurati ons for the
fi rst three peri ods of el ements i n Tabl e 4.5:
TABLE 4.5 ELECTRON CONFIGURATIONS FOR ELEMENTS 1 TO 20
2nd Period 3rd Period 4th Period
Li 5 1s
2
2s
1
Na 5 1s
2
2s
2
2p
6
3s
1
K 5 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
Be 5 1s
2
2s
2
Mg 5 1s
2
2s
2
2p
6
3s
2
Ca 5 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
B 5 1s
2
2s
2
2p
1
Al 5 1s
2
2s
2
2p
6
3s
2
3p
1
Sc 5 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
1
C 5 1s
2
2s
2
2p
2
Si 5 1s
2
2s
2
2p
6
3s
2
3p
2
Ti 5 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
2
N 5 1s
2
2s
2
2p
3
P 5 1s
2
2s
2
2p
6
3s
2
3p
3
Etc.
O 5 1s
2
2s
2
2p
4
S 5 1s
2
2s
2
2p
6
3s
2
3p
4
F 5 1s
2
2s
2
2p
5
Cl 5 1s
2
2s
2
2p
6
3s
2
3p
5
Ne 5 1s
2
2s
2
2p
6
Ar 5 1s
2
2s
2
2p
6
3s
2
3p
6
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Chapter 4: Atomic Structure 71
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1st Period
H 5 1s
1
where the fi rst 1 i s equal to the energy l evel (or quantum number), the s i s equal to
the subl evel and the second 1 i s equal to the number of el ectrons i n the subl evel :
He 5 1s
2
Orbital Diagrams
You may have noti ced that i n the secti on on quantum numbers, each subl evel (e.g., 2p) i s
composed of a certai n number of orbi tal s. Orbi tal s can onl y hol d up to two el ectrons, so the 2p
subl evel i s actual l y composed of 3 orbi tal s. However, i f you l ook at the el ectron confi gurati ons
of the 2p, for exampl e, al l of the 2p orbi tal s are summari zed i n one numberthe total number
of el ectrons i n al l 2p orbi tal s. Therefore, i n ni trogen you have 2p
3
, but there i s no descri pti on
about where those el ectrons are wi thi n the 2p subl evel . Orbi tal di agrams provi de us wi th a
useful way to map the orbi tal s wi thi n i ndi vi dual orbi tal s. I n these di agrams, boxes (or
someti mes ci rcl es) are used to represent i ndi vi dual orbi tal s. Arrows are used to represent
el ectrons, and the heads of the arrows i ndi cate the spi n. I n Fi gure 4.9, note the orbi tal
di agrams for the el ectrons i n el ements 110.
A shorthand notati on i s someti mes used to shorten the l ength of the confi gurati ons. I n thi s
notati on, the symbol for the nobl e gas appears at the end of the peri od just before the el ement
you are l ooki ng for, and then the remai nder of the confi gurati on wi l l conti nue as above. For
exampl e, a shorter way to wri te the confi gurati on for sul fur, el ement 16, woul d be: [Ne]3s
2
3p
4
.
Notethe nobl e gas i s wri tten i n brackets.
UNUSUAL ELECTRON CONFIGURATIONS
There are a few el ectron confi gurati ons that dont fol l ow the pattern l i sted above. These
bel ong to some of the transi ti on metal s. For atoms wi th el ectrons i n the d-orbi tal s, there are
two very stabl e confi gurati ons of el ectronswhen the d-orbi tal s are hal f-fi l l ed and when they
Note: According to thePauli exclusion principle, the3
rd
electron
in lithiumcant go in the1s sublevel.
Note: Because of Hunds rule, the 5
th
electron must enter a
separateorbital. Also notehow spins areparallel.
Very stable: half-filled p orbitals
The8
th
electron is forced to pair up with another.
Very stable: filled orbitals
Figure4.9
72 PART III: AP Chemistry Review
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are compl etel y fi l l ed. Thi s causes an unexpected confi gurati on for some el ements l i ke
chromi um and copper. I n the exampl e bel ow, noti ce the di fference i n el ectron confi gurati ons
between el ement 23, vanadi um, and el ement 24, chromi um:
Vanadi um: [Ar]4s
2
3d
3
You woul d expect that chromi um woul d conti nue the pattern and have the confi gurati on of
[Ar]4s
2
3d
4
. I nstead, i t i s:
Chromi um: [Ar]4s
1
3d
5
Thi s i s because i n thi s confi gurati on, the two subl evel s, 4s and 3d, are hal f-fi l l eda very
stabl e confi gurati on. The same phenomenon i s seen i n copper:
Copper: [Ar]4s
1
3d
10
The compl etel y fi l l ed d subl evel and hal f-fi l l ed 4s subl evel i s a very stabl e confi gurati on.
ELECTRON CONFIGURATIONS AND THE PERIODIC TABLE
A careful i nspecti on of the peri odi c tabl e and Fi gure 4.10 wi l l al l ow us to see some very cl ear
rel ati onshi ps between the el ements and thei r el ectron confi gurati ons. Note the confi gurati ons
for H, Li , Na, and K (al l group 1A el ements). For each el ement, the l ast part of the el ectron
confi gurati on shows s
1
, representi ng a si ngl e el ectron i n the outer s orbi tal . The other groups
of el ements show si mi l ar patterns. The patterns hel p us to better understand certai n
properti es of atoms that you wi l l revi ew i n the next secti on. The peri odi c tabl e i s arranged
accordi ng to the chart shown bel ow:
2A
2
3B
3
4B
4
5B
5
Lanthanide series
Actinide series
6B
6
7B
7 8
8B
9 10
1B
11
2B
12
3A
13
4A
14
5A
15
6A
16
7A
17
8A
18
1A
1
1s 1s
2s
3s
4s
5s
6s
2p
3p
4p
5p
6p
7s
5f
4f
3d
4d
5d
6d
Figure4.10 Patterns in outer shell electron configurations found in the Periodic Table of
theElements.
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Chapter 4: Atomic Structure 73
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When wri ti ng the el ectron confi gurati ons for an atom, there are a coupl e of shortcut
techni ques that can be used to hel p you remember the order i n whi ch the orbi tal s wi l l fi l l up.
The fi rst i s the chart i n Fi gure 4.10. I f you were goi ng to wri te the el ectron confi gurati on for
Sel eni um, Se, atomi c number 34, you woul d fi rst l ocate i t on the peri odi c tabl e. Second, you
woul d begi n goi ng l eft to ri ght across each peri od, fi l l i ng i n el ectrons as you go unti l you reach
Se. Goi ng across peri od one produces 1s
2
. Movi ng l eft to ri ght across peri od 2 produces 2s
2
and
2p
6
. Conti nui ng on unti l you reach Se, you woul d end up wi th 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
4
, or
[Ar]4s
2
3d
10
4p
4
. At thi s poi nt, you may be wonderi ng i f you shoul d wri te the 3d orbi tal s before
the 4s or after i t. Wri ti ng i t before i s a way to show the confi gurati ons i n order by energy l evel ,
whereas pl aci ng i t after shows them i n order of i ncreasi ng energi es. I f you l ook at enough
resources, you wi l l fi nd that i t i s done both ways, each source cl ai mi ng that i ts i s the correct
way. I n the past, the Col l ege Board has wri tten them both ways, so be prepared for ei ther. I t
i s not i ncorrect to wri te them ei ther way. What the questi ons on the AP tests of the past have
been testi ng i s whether you know the Aufbau pri nci pl e, the Paul i excl usi on pri nci pl e, and
Hunds rul e.
The second method uses what i s often cal l ed the Aufbau chart. You can easi l y produce thi s
from memory by constructi ng i t as fol l ows:
1. You begi n row 1 by wri ti ng 1s. 1s
2. I n row 2, you are goi ng to have two 1s
subl evel s l i sted, 2s and 2p. 2s 2p
3. I n row 3, you wi l l have three 1s
subl evel s, 3s, 3p, and 3d. 2s 2p
3s 3p 3d
4. For the remai ni ng rows, you are
goi ng to go up to f i n energy l evel s
4 and 5, then begi n goi ng down.
For exampl e, i n row 6, you onl y 1s
go to d, i n row 7 onl y to p. There
i s no row 8. 2s 2p
5. To fi ni sh the chart, you wi l l pl ace arrows
di agonal l y through the numbers so that 3s 3p 3d
the arrows begi n on the ri ght si de of the
chart and move di agonal l y to the l eft, 4s 4p 4d 4f
droppi ng one l evel each col umn. When
you fol l ow the arrows to determi ne the 5s 5p 5d 5f
order of fi l l i ng, you begi n at the top and
move down to the l eft, and when you 6s 6p 6d
reach the end of the arrow, move
back up to the arrow that i s bel ow 7s 7p
the one you just fi ni shed. I n other
words, 1s, then back to 2s, then 2p,
3s, then 3d, 4p, 5s, and so on.

Sample: Wri te the el ectron confi gurati on for Ba, atomi c number 56.
Answer: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
2
4d
10
5p
6
6s
2
or [Xe]6s
2
74 PART III: AP Chemistry Review
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You Try It!
Wri te the el ectron confi gurati on for Radon, Rn.
Answer: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
2
4d
10
5p
6
6s
2
4f
14
5d
10
6p
6
PERIODIC TRENDS
Factors Affecting the Behavior and Structure of Atoms
There are two factors that are cl osel y associ ated wi th the structure and behavi or of atoms.
The fi rst of these i s known as effecti venucl ear charge. The nucl ear charge i s rel ated to the
number of charged parti cl es (protons) i n the nucl eus. As the nucl ear charge i ncreases, there i s
an i ncrease i n the attracti ve force between the nucl eus and the el ectrons. Nucl ear charge
i ncreases from l eft to ri ght across a peri od.
The second of these i s known as nucl ear shi el di ng. Nucl ear shi el di ng occurs when el ectrons
i n a l ower energy l evel shi el d the el ectrons i n a hi gher energy l evel from the effecti ve
charge of the nucl eus. As a resul t, the attracti ve force fel t by those outer el ectrons i s l ess than
i t woul d be had those i nner el ectrons not been present. As more energy l evel s fi l l , more
shi el di ng i s seen between the nucl eus and the outermost el ectrons i n an atom. Therefore,
nucl ear shi el di ng i ncreases, goi ng from top to bottom i n a group. I ncreases i n nucl ear
shi el di ng are seen onl y after an energy l evel i s fi l l ed and el ectrons begi n to fi l l i n a further
energy l evel . Therefore, nucl ear shi el di ng does not change goi ng from l eft to ri ght across
a peri od.
Variations in Atomic Radius
The atomi c radi us i s the di stance between the nucl eus and the outermost el ectron. Atomi c
radi i are measured i n nanometers (10
29
meters). I n some fi el ds, atomi c radi i are measured i n
a uni t known as an angstrom, (10
210
m or
1
10
of a nanometer). Hydrogen i s the smal l est
atom, measuri ng onl y 0.037 nm or 0.37 .
TRENDS IN ATOMIC RADII
Peri odi c trendsGoi ng from l eft to ri ght across a peri od, atomi c si ze tends to decrease. Thi s
occurs because of an i ncrease i n nucl ear charge, whi ch pul l s the el ectrons i n more ti ghtl y
(thus maki ng the atoms smal l er). The nobl e gases are the smal l est el ements i n each peri od.
Group trendsGoi ng from top to bottom i n a group, atomi c si ze i ncreases. Thi s i s because
el ectrons begi n fi l l i ng i n energy l evel s that are farther from the nucl eus (thus maki ng the
atoms bi gger). (See Fi gure 4.11.)
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Chapter 4: Atomic Structure 75
www.petersons.com
Sr
2.15
In
1.63
Sn
1.40
Sb
1.41
Te
1.43
I
1.33
Xe
1.30
Rb
2.47
Ca
1.97
Ga
1.22
Ge
1.22
As
1.21
Se
1.17
Br
1.14
Kr
1.10
Al
1.43
Si
1.17
P
1.10
S
1.04
Cl
0.99
Ar
0.97
K
2.27
Mg
1.60
Na
1.86
B
0.88
C
0.77
N
0.75
O
0.73
F
0.71
Ne
0.69
Be
1.13
Li
1.52
He
0.32
H
0.37
Figure4.11 Atomic radii for thefirst fiveperiods of therepresentativeelements. All units are
in angstroms ().
Sample: Arrange the fol l owi ng atoms i n order of i ncreasi ng atomi c radi us: S, P, O
Answer: I f you note the arrangement of these atoms, S and P are i n the same peri od, whi l e
O and S are i n the same group. Therefore, P i s l arger than S, and S i s l arger than
O. Therefore O , S , P.
You Try It!
Arrange the fol l owi ng el ements i n order of decreasi ng radi us: Si , Na, Mg.
Answer: Na . Mg . Si
Ionization Energy
I oni zati on energy i s the amount of energy necessary to remove an el ectron from a gaseous
atom. Thi s quanti ty of energy wi l l fl uctuate i n di rect proporti on to the amount of attracti on
between the nucl eus and the el ectrons. When the force of attracti on i s strong, the i oni zati on
energy wi l l be a l arger number. When the force of attracti on i s weak, the i oni zati on energy
wi l l be a smal l number.
TRENDS IN IONIZATION ENERGIES
Peri odi c trendsI oni zati on energi es i ncrease goi ng from l eft to ri ght across a peri od. Thi s i s
because of the i ncrease i n nucl ear charge. As the nucl ear charge i ncreases, the attracti on
between the el ectrons and the nucl eus i ncreases. Thi s makes i t more di ffi cul t to remove an
el ectron from the atom.
Group trendsI oni zati on energi es decrease goi ng from top to bottom i n a group. Thi s i s due
to the i ncrease i n nucl ear shi el di ng. Wi thi n a group, as atomi c number i ncreases, the amount
of shi el di ng i ncreases. Thi s greater shi el di ng causes a decrease i n the amount of attracti on
between the nucl eus and the el ectrons. As a resul t, i t becomes easi er to remove the outermost
el ectrons of the atom (see Fi gure 4.12).
76 PART III: AP Chemistry Review
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Sr
503
In
558
Sn
709
Sb
834
Te
869
I
1008
Xe
1170
Rb
376
Ca
1.97
Ga
579
Ge
762
As
947
Se
941
Br
1140
Kr
1351
Al
578
Si
786
P
1012
S
1000
Cl
1251
Ar
1521
K
2.27
Mg
738
Na
496
B
801
C
1086
N
1402
O
1314
F
1681
Ne
2081
Be
899
Li
520
He
2372
H
1312
Figure4.12 First ionization energies for the first five periods of representative elements. All
units arein angstroms.
MULTIPLE IONIZATION ENERGIES
The energy requi red to remove one el ectron from the outermost energy l evel of an atom i s
known as the fi rst i oni zati on energy. The energy requi red to remove the next el ectron (2nd
el ectron) i s known as the second i oni zati on energy. The energy requi red to remove the 3rd
el ectron i s the thi rd i oni zati on energy, and so on. By compari ng mul ti pl e i oni zati on
energi es of atoms, i t i s possi bl e to determi ne the charge of an atom.
El ements i n group 1A al l have a si ngl e el ectron i n thei r outermost energy l evel s. Due to the
rel ati vel y smal l nucl ear charge, i t i s fai rl y easy to remove thi s outer el ectron. However, once
thi s el ectron i s removed, the atoms al l have el ectron confi gurati ons si mi l ar to a nobl e gas.
Nobl e gases have some of the hi ghest i oni zati on energi es. Therefore, a l arge amount of energy
wi l l be requi red to remove subsequent el ectrons. When these el ements are i nvol ved i n
reacti ons, they wi l l al ways l ose one el ectron and no more (si nce addi ti onal el ectrons woul d be
extremel y di ffi cul t to remove).
Summary: Group 2A el ements have a smal l fi rst i oni zati on energy and a very l arge second
i oni zati on energy. They wi l l l ose one el ectron i n a chemi cal reacti on and have a 1
1
charge.
El ements i n group 2A al l have two el ectrons i n thei r outermost energy l evel s. Agai n, due to
the rel ati vel y smal l effecti ve nucl ear charge, i t i s fai rl y easy to remove these outermost
el ectrons. After removal of two el ectrons, however, these el ements wi l l have el ectron
confi gurati ons l i ke nobl e gases. Therefore, a l arge i ncrease i n i oni zati on energi es i s seen
between the second and thi rd i oni zati on energi es. I n reacti ons, these el ements wi l l l ose two
el ectrons.
Summary: Group 2A el ements have rel ati vel y smal l fi rst and second i oni zati on energi es and
l arger thi rd i oni zati on energi es. They wi l l l ose two el ectrons i n a chemi cal reacti on and have
a +2 charge.
I n a si mi l ar fashi on, el ements i n group 3A wi l l l ose 3 el ectrons i n a chemi cal reacti on and
acqui re a +3 charge. Beyond group 3, however, the nucl ear charge begi ns to be much greater,
whi ch makes removal of the outermost el ectrons qui te di ffi cul t, especi al l y for the el ements
wi th l ower atomi c numbers. As a resul t, these atoms wi l l tend to resi st gi vi ng up thei r outer
el ectrons and i nstead tend to have a strong attracti on for el ectrons of other atoms.
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Chapter 4: Atomic Structure 77
www.petersons.com
Sample: Whi ch atom shoul d have a smal l er fi rst i oni zati on energy, oxygen or sul fur?
Answer: Si nce oxygen and sul fur are i n the same group, you must recal l the group trends.
Si nce the outer el ectron i n sul fur experi ences more shi el di ng, i t wi l l be easi er to
pul l off. Therefore, S has the smal l er fi rst i oni zati on energy.
You Try It!
Whi ch atom shoul d have a l arger fi rst i oni zati on energy: N or P?
Answer: N (l ess shi el di ng)
IONIC RADIUS
Al though there are patterns for the si zes of the i oni c radi i , these are not as easy to see as the
patterns for other peri odi c trends. The patterns can real l y be di vi ded i nto two mai n categori es
(other than peri odi c trends and group trends). These two categori es are posi ti vel y charged
i ons (cati ons), and negati vel y charged i ons (ani ons). The mai n di fference i s that cati ons wi l l
l ose el ectrons, l eavi ng them wi th an i ncreased effecti ve nucl ear charge per el ectron (more
protons i n the nucl eus per el ectron). Ani ons wi l l gai n el ectrons, l eavi ng them wi th a decreased
effecti ve nucl ear charge. As a resul t, cati ons are smaller (more protons pul l i ng fewer
el ectrons) than thei r correspondi ng neutral atoms, and ani ons are larger (fewer protons
pul l i ng more el ectrons) than thei r correspondi ng neutral atoms. Therefore, i n groups 1A
through 3A, each i on i s smal l er than i ts correspondi ng neutral atom. Al l cati ons get smal l er
goi ng across a peri od and l arger goi ng down a group. For groups 5A through 7A, the i ons are
l arger than thei r correspondi ng atoms; however, they sti l l get smal l er goi ng across the peri od
and l arger movi ng down a group.
Sample: Rank the fol l owi ng from smal l est to l argest: N
32
, Be
21
, O
22
Answer: These el ements are al l i n the same peri od. When beryl l i um l oses two el ectrons, i t
wi l l then l ose them from the 2s orbi tal , l eavi ng onl y 2 el ectrons i n the 1s orbi tal .
These wi l l be acted on by 4 protons, however, maki ng a very smal l i on. Oxygen and
ni trogen wi l l both be recei vi ng el ectrons i nto 2p orbi tal s; however, oxygen has a
l arger effecti ve nucl ear charge. Therefore, the oxygen i on wi l l be sl i ghtl y smal l er
than the ni trogen i on. The answer, therefore, i s Be
21
, O
22
, N
32
.
You Try It!
Rank the fol l owi ng from smal l est to l argest: Mg
21
, Ca
21
, Al
31
Answer: Al
31
, Mg
21
, Ca
21
ELECTRON AFFINITY
Whi l e i oni zati on energy represents the amount of energy requi red to remove an el ectron from
an atom, the el ectron affi ni ty i s the energy change that occurs when an el ectron i s added to
78 PART III: AP Chemistry Review
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www.petersons.com
a gaseous atom. I t i s a measure of the amount of an atoms attracti on for el ectrons. The val ues
for an el ectron can be negati ve or posi ti ve. Negati ve val ues correspond to a rel ease of energy,
whi l e posi ti ve val ues correspond to energy requi red to form an i on. For atoms that have a
hal f-fi l l ed or fi l l ed subl evel , or energy l evel , the addi ti on of el ectrons i s energeti cal l y
unfavorabl e. Thus, the atoms wi th these confi gurati ons, groups 2A, 5A, and 8A, tend to have
sl i ghtl y negati ve or even posi ti ve el ectron affi ni ty val ues. Atoms that are i n the groups just to
the l eft of these have much more negati ve el ectron affi ni ti es. Thi s i s because the addi ti on of
an el ectron wi l l gi ve these el ements the stabl e hal f-fi l l ed or fi l l ed subl evel s (see Fi gure 4.13).
Sr
11
In
30
Sn
107
Sb
103
Te
190
I
295
Xe
0
Rb
47
Ca
4
Ga
30
Ge
119
As
78
Se
195
Br
325
Kr
0
Al
43
Si
134
P
72
S
200
Cl
349
Ar
0
K
48
Mg
0
Na
53
B
27
C
122
N
0
O
141
F
328
Ne
0
Be
0
Li
60
He
0
H
73
Figure4.13 Electron affinities of thefirst fiveperiods of representativeelements. All units are
given in kJ / mol.
Sample: Why i s i t that sodi um has a negati ve el ectron affi ni ty whi l e magnesi um has a
posi ti ve val ue?
Answer: Sodi um onl y has a si ngl e el ectron i n the 3s orbi tal . I t can easi l y accommodate one
more. Magnesi um, on the other hand, has to add el ectrons to the 2p orbi tal s, whi ch
i s not nearl y as favorabl e.
You Try It!
Expl ai n the di fference i n el ectron affi ni ti es between ni trogen and oxygen.
Answer: Ni trogen has a very stabl e 2p
3
arrangement (one el ectron i n each p orbi tal ).
Addi ng an el ectron means a l oss i n some of that stabi l i ty.
ELECTRONEGATIVITY
El ectronegati vi ty i s a measure of the tendency of an el ement to attract addi ti onal el ectrons
i n a chemi cal reacti on. Nonmetal s (el ements on the upper ri ght porti on of the peri odi c tabl e)
attract el ectrons more than metal s because of thei r rel ati vel y hi gher nucl ear charges and
smal l shi el di ng effects. The scal e for measuri ng el ectronegati vi ti es goes from 0.7 to 4.0 (wi th
4.0 bei ng the hi ghest val ue). The el ement wi th the l argest el ectronegati vi ty i s fl uori ne. Thi s i s
because fl uori ne has the hi ghest effecti ve nucl ear charge and the l east amount of shi el di ng.
Whi l e the nobl e gases do have a hi gher nucl ear charge, they are unabl e to react wi th other
el ements due to thei r el ectron confi gurati on (thi s wi l l be covered i n Chapter 6). By defi ni ti on,
the attracti on for other el ectrons has to be i n a chemi cal reacti on. The el ement wi th the
smal l est el ectronegati vi ty i s cesi um. Thi s i s because i ts el ectrons are hi ghl y shi el ded and
experi ence a smal l effecti ve nucl ear charge (see Fi gure 4.14).
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Chapter 4: Atomic Structure 79
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TRENDS IN ELECTRONEGATIVITIES
Sr
1.0
In
1.7
Sn
1.8
Sb
1.9
Te
2.1
I
2.5
Rb
0.8
Ba
0.9
Tl
1.8
Pb
1.9
Bi
1.9
Po
2.0
At
2.2
Cs
0.7
Ca
1.0
Ga
1.6
Ge
1.8
As
2.0
Se
2.4
Br
2.8
Al
1.5
Si
1.8
P
2.1
S
2.5
Cl
3.0
K
0.8
Mg
1.2
Na
0.9
B
2.0
C
2.5
N
3.0
O
3.5
F
4.0
Be
1.5
Li
1.0
H
2.1
Figure4.14 Electronegativity values for thefirst six periods of representativeelements
Peri odi c trendsEl ectronegati vi ti es i ncrease goi ng from l eft to ri ght across a peri od. Thi s i s
due to the i ncreasi ng nucl ear charge, whi ch causes a stronger attracti on between the nucl eus
and el ectrons.
Group trendsEl ectronegati vi ti es decrease goi ng from top to bottom i n a peri od. Thi s i s due
to the i ncreased shi el di ng, whi ch weakens the attracti on between the nucl eus and the
el ectrons.
Sample: Rank the fol l owi ng by i ncreasi ng el ectronegati vi ty: N, P, O
Answer: N and P represent group trends, whi l e N and O represent peri odi c trends. N i s
more el ectronegati ve than P (l ess shi el di ng), whi l e O i s more el ectronegati ve than
N (greater effecti ve nucl ear charge). Therefore, P , N , O.
You Try It!
Expl ai n why H has an el ectronegati vi ty so much l arger than Li .
Answer: H has onl y one el ectron. I t has no shi el di ng; therefore any el ectrons can be
i ncorporated i nto the cl osest s orbi tal to the nucl eus.
Summary of Periodic Trends
1. Goi ng from l eft to ri ght across a peri od, nucl ear charge i ncreases, whi l e nucl ear shi el d-
i ng i s unaffected (see Fi gure 4.13). As a resul t,
a. atomi c radi us decreases.
b. i oni zati on energy i ncreases.
c. el ectronegati vi ty i ncreases.
80 PART III: AP Chemistry Review
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2. Goi ng from top to bottom down a group, nucl ear charge i s unaffected whi l e nucl ear
shi el di ng i ncreases (see Fi gure 4.15). As a resul t,
a. atomi c radi us i ncreases.
b. i oni zati on energy decreases.
c. el ectronegati vi ty decreases.
56
Ba
137.33
57
La
138.91
72
Hf
178.49
73
Ta
180.95
74
W
183.85
75
Re
186.21
76
Os
190.2
77
Ir
192.2
78
Pt
195.08
79
Au
196.97
80
Hg
200.59
81
Tl
204.38
82
Pb
207.2
83
Bi
208.98
84
Po
(209)
85
At
(210)
86
Rn
(222)
109
Une
(266)
108
Uno
(265)
107
Uns
(262)
106
Unh
(263)
105
Unp
(262)
104
Unq
(261)
89
Ac
227.03
88
Ra
226.02
87
Fr
(223)
55
Cs
132.91
38
Sr
87.62
39
Y
88.91
40
Zr
91.22
41
Nb
92.91
42
Mo
95.94
43
Tc
(98)
44
Ru
101.1
45
Rh
102.91
46
Pd
106.42
47
Ag
107.87
48
Cd
112.41
49
In
114.82
50
Sn
118.71
51
Sb
121.75
52
Te
127.60
53
I
126.91
54
Xe
131.29
37
Rb
85.47
20
Ca
40.08
21
Sc
44.96
22
Ti
47.90
23
V
50.94
24
Cr
52.00
25
Mn
54.938
26
Fe
55.85
27
Co
58.93
28
Ni
58.69
29
Cu
63.55
30
Zn
65.39
31
Ga
69.72
32
Ge
72.59
33
As
74.92
34
Se
78.96
35
Br
79.90
36
Kr
83.80
13
Al
26.98
14
Si
28.09
15
P
30.974
16
S
32.06
17
Cl
35.453
18
Ar
39.948
19
K
39.10
2A
2
3B
3
4B
4
5B
5
6B
6
7B
7 8
8B
9 10
1B
11
2B
12
3A
13
4A
14
5A
15
6A
16
7A
17
8A
18
1A
1
12
Mg
24.30
11
Na
22.99
5
B
10.811
6
C
12.011
7
N
14.007
8
O
16.00
9
F
19.00
10
Ne
20.179
4
Be
9.012
3
Li
6.941
2
He
4.0026
1
H
1.0079
A
t
o
m
i
c

r
a
d
i
u
s

i
n
c
r
e
a
s
e
s
I
o
n
i
z
a
t
i
o
n

e
n
e
r
g
y

d
e
c
r
e
a
s
e
s
E
l
e
c
t
r
o
n
e
g
a
t
i
v
i
t
y

d
e
c
r
e
a
s
e
s
Atomic radius decreases
Ionization energy increases
Electronegativity increases
Figure4.15 Summary of periodic trends
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Chapter 4: Atomic Structure 81
www.petersons.com
EXERCISES: ATOMIC STRUCTURE
Multiple Choice
QUESTIONS 14
(A) F
(B) O
(C) Li
(D) Na
(E) K
1. Whi ch el ement i s the l east el ectronegati ve?
2. Whi ch el ement has the l owest i oni zati on energy?
3. Whi ch has the smal l est natural l y occurri ng i on?
4. Whi ch atom has the smal l est atomi c radi us?
5. Whi ch of the fol l owi ng pai rs of atoms represents an i sotope?
Atomi c number Mass number
(A) I 8 18
I I 9 18
(B) I 8 9
I I 18 18
(C) I 8 18
I I 18 36
(D) I 9 18
I I 9 19
(E) I 6 12
I I 12 18
IN QUESTIONS 68, REFER TO THE ELECTRON CONFIGURATIONS SHOWN BELOW.
(A) 1s
2
2s
2
2p
6
3s
2
3p
4
(B) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
5
(C) 1s
2
2s
2
2p
8
3s
2
3p
6
(D) 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
4
(E) 1s
2
2s
2
2p
6
3s
2
3p
6
6. el ectron confi gurati on of Cr
7. vi ol ates Paul i excl usi on pri nci pl e
8. nobl e gas confi gurati on
82 PART III: AP Chemistry Review
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IN QUESTIONS 911, SELECT THE SCIENTIST PRIMARILY RESPONSIBLE FOR THE FINDINGS IN
EACH QUESTION.
(A) Dal ton
(B) Ei nstei n
(C) Hei senberg
(D) Thomson
(E) Rutherford
9. Made i mportant di scoveri es about the properti es of cathode rays
10. Proposed the exi stence of a nucl eus
11. Determi ned that i t was i mpossi bl e to know si mul taneousl y i nformati on about the
l ocati on and movement of el ectrons
12. Whi ch set of quantum numbers (n, l, m
l
, m
s
) i s not possi bl e?
(A) 1, 0, 0,
1
2
(B) 1, 1, 0,
1
2
(C) 1, 0, 0, 2
1
2
(D) 2, 1, 21,
1
2
(E) 3, 2, 1,
1
2
Free Response
(A) Chl orophyl l a, a photosyntheti c pi gment found i n pl ants, absorbs l i ght wi th a
wavel ength of 660 nanometers.
(i) Determi ne the frequency, i n s
21
, of chl orophyl l a.
(ii) Cal cul ate the energy of a photon of l i ght wi th a wavel ength of 660 nm.
(B) I n the Bal mer seri es of hydrogen, one spectral l i ne i s associ ated wi th the transi ti on of an
el ectron from the fourth energy l evel (n 5 4) to the second energy l evel (n 5 2).
(i) I ndi cate whether energy i s absorbed or emi tted as the el ectron moves from
n 5 4 to n 5 2. Expl ai n.
(ii) Determi ne the wavel ength of thi s spectral l i ne.
(iii) I ndi cate whether the wavel ength cal cul ated i n (i i ) i s l onger or shorter than the
wavel ength associ ated wi th an el ectron movi ng from n 5 5 to n 5 2. Expl ai n.
e
x
e
r
c
i
s
e
s
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Chapter 4: Atomic Structure 83
www.petersons.com
ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. E
2. E
3. C
4. A
5. D
6. B
7. C
8. E
9. D
10. E
11. C
12. B
1. The correct answer is (E). Potassi um wi l l be the l east el ectronegati ve el ement. The
el ectronegati vi ty val ue of an el ement i s determi ned by the strength of attracti ons the
atom has for other el ectrons i n a chemi cal bond. Atoms wi th the hi ghest el ectronegati ve
val ues have a combi nati on of a l arge effecti ve nucl ear charge and a smal l amount of
shi el di ng. I n general , the el ements at the upper ri ght porti ons of the Peri odi c Tabl e of
the El ements have the hi ghest el ectronegati vi ty val ues, whi l e the el ements i n the l ower
l eft regi ons have the l owest val ues. Of the fi ve choi ces, potassi um has a combi nati on of
the smal l est effecti ve nucl ear charge and the greatest amount of shi el di ng.
2. The correct answer is (E). For the same reasons that i t has the l owest
el ectronegati vi ty, potassi um has the l owest i oni zati on energy. The outermost el ectron
has the most shi el di ng between i t and the nucl eus wi th the smal l est effecti ve
nucl ear charge.
3. The correct answer is (C). Li thi um has the smal l est i on. When a l i thi um atom l oses
i ts outermost el ectron, i t l oses the enti re second energy l evel . I ts onl y remai ni ng
el ectrons are i n the fi rst energy l evel and have one more proton than hel i um wi th whi ch
to attract them.
4. The correct answer is (A). Fl uori ne has the smal l est atomi c radi us. The fl uori ne
atom has the hi ghest effecti ve nucl ear charge of the el ements i n the l i st. Because there
are no el ements on the l i st wi th a greater effecti ve nucl ear charge or a smal l er amount
of shi el di ng, fl uori ne wi l l have the smal l est atomi c radi us.
5. The correct answer is (D). I sotopes of an el ement have the same atomi c number
(numbers of protons), but di fferent mass numbers (numbers of neutrons). The onl y
choi ce that represents the same el ement i s (D), where each i sotope has 9 protons. One
i sotope has 9 neutrons, whi l e the other has 10 neutrons.
6. Thecorrect answer is(B).Al though choi ces (B) and (D) each have 24 el ectrons, (B) i s
the better answer because of chromi ums excepti onal el ectron confi gurati on. The
chromi um atom gai ns i ncreased stabi l i ty by promoti ng one of the 4s el ectrons to the
vacant 3d orbi tal . Thi s promoti on creates hal f-fi l l ed orbi tal s, whi ch i ncrease stabi l i ty.
7. Thecorrect answer is(C). By pl aci ng 8 el ectrons i n the 2p orbi tal s, (C) i s i n vi ol ati on
of the Paul i excl usi on pri nci pl e, whi ch states that each orbi tal may onl y contai n
2 el ectrons and that those must have opposi te spi ns. Ei ght el ectrons exceed the
maxi mum si x.
84 PART III: AP Chemistry Review
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www.petersons.com
8. The correct answer is (E). Choi ce (E) has the nobl e gas confi gurati on (of argon),
whi ch characteri sti cal l y has fi l l ed s and p subl evel s.
9. The correct answer is (D). Thomsons work wi th cathode rays l ed to hi s eventual
di scovery of many i mportant properti es of the el ectron and hi s subsequent devel opment
of the pl um puddi ng model of the atom.
10. The correct answer is (E). Rutherford, based on the resul ts of hi s gol d-foi l
experi ment, devel oped a model of the atom that i ncl uded a posi ti vel y charged dense
core (the nucl eus).
11. The correct answer is (C). The statement i n 11 i s the essence of the Hei senberg
uncertai nty pri nci pl e.
12. The correct answer is (B). Choi ce (B) i s an i mpossi bl e confi gurati on because of the
val ue of the l quantum number. The val ue of l i s onl y permi tted to go from n-1 to 0.
Therefore, l cannot have the same val ue as n.
Free Response
(A) Chl orophyl l a, a photosyntheti c pi gment found i n pl ants, absorbs l i ght wi th a
wavel ength of 660 nanometers.
(i) Determi ne the frequency, i n s
21
, of chl orophyl l a. The frequency can be
determi ned usi ng the equati on bel ow:
n 5
c
l
One i mportant consi derati on i s that the wavel engths and speed of l i ght are
expressed wi th di fferent uni ts of l ength. One of them wi l l have to be converted
before the frequency i s cal cul ated:
n 5
3.00 3 10
28
m s
21
660 nm
S
1 m
10
9
nm
D
5 4.54 3 10
14
s
21
(ii) Cal cul ate the energy of a photon of l i ght wi th a wavel ength of 660 nm. To sol ve
thi s one, you are goi ng to mul ti pl y your answer from (i ) by Pl ancks constant, h:
E 5 hn 5 (6.626 3 10
234
J s)(4.54 3 10
14
s
21
) 5 3.01 3 10
219
J
(B) I n the Bal mer seri es of hydrogen, one spectral l i ne i s associ ated wi th the transi ti on of
an el ectron from the fourth energy l evel (n54) to the second energy l evel (n 5 2).
(i) Energy i s absorbed when an el ectron moves from a l ower energy l evel to a hi gher
energy l evel . When an el ectron moves from a hi gher energy to a l ower energy
l evel , the atom wi l l rel ease energy (i n the form of a photon). That i s what
provi des the dri vi ng force to move the el ectron. Si nce n 5 4 corresponds to a
hi gher energy l evel than n 5 2, the atom wi l l rel ease energy i n thi s transi ti on.
a
n
s
w
e
r
e
x
e
r
c
i
s
e
s
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Chapter 4: Atomic Structure 85
www.petersons.com
(ii) The sol uti on to thi s probl em i s a l engthy one. The energy l evel data wi l l al l ow us
to use the Rydberg equati on, but thi s wi l l onl y sol ve for E. I n order to determi ne
the wavel ength, the energy (E) wi l l be used to cal cul ate the frequency, whi ch can
then be used to determi ne the wavel ength. The fi rst step i s to use the Rydberg
equati on to determi ne the energy emi tted by the transi ti on:
DE 5 RH
S
1
n
i
2
2
1
n
f
2D
DE 5 2.18 3 10
218
S
1
4
2
2
1
2
2D
5 24.01 3 10
219
J
The next step i s to use the energy you just obtai ned to cal cul ate the frequency:
n 5
E
h
5
4.01 3 10
219
J
6.626 3 10
234
J s
5 6.05 3 10
14
s
21
Fi nal l y, you can use the frequency to determi ne the wavel ength:
l 5
c
n
5
3.0 3 10
8
m s
21
6.05 3 10
14
s
21
5 4.96 3 10
27
m 5 496 nm
(iii) The transi ti on from n 5 5 to n 5 2 i s a l arger transi ti on than from n 5 4 to n 5 2,
and, as a resul t, the photon wi l l possess more energy. Because the photon has
more energy, i t wi l l al so have a hi gher frequency (n 5
E
h
). Thi s hi gher frequency
corresponds to a shorter wavel ength (l 5
c
n
).
86 PART III: AP Chemistry Review
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SUMMING IT UP
Our concept of an atom has changed qui te a bi t si nce Dal ton fi rst provi ded evi dence for
the exi stence of atoms. You shoul d be fami l i ar wi th the major contri buti ons to the
devel opment of modern atomi c theory. They do pop up on the test from ti me to ti me.
Tabl e 4.1 provi des a good overvi ew of these i ndi vi dual s and thei r contri buti ons.
The peri odi c tabl e provi des us wi th an excel l ent way to organi ze i nformati on about the
el ements. You shoul d be fami l i ar wi th the basi c l ayout of the tabl e as wel l as the names
for speci fi c groups of el ements.
The quantum mechani cal model of atomi c structure i s far too di ffi cul t to be expl ai ned i n
detai l i n an AP Chemi stry course. However, some aspects of the theory are appropri ate,
and you shoul d know them. These i ncl ude the predi cted number and shapes of orbi tal s i n
each energy l evel ; the number of el ectrons found i n each orbi tal , subl evel , and energy
l evel ; and the meani ng of the four quantum numbers.
El ectron confi gurati ons provi de us wi th a conveni ent way to map the posi ti ons of
el ectrons. Most of the el ements on the peri odi c tabl e fol l ow a very si mpl e pattern i n the
bui l dup of el ectrons; however, there are a few excepti ons, whi ch you shoul d try to
memori ze.
Because of the arrangement of el ements on the peri odi c tabl e, there are several patterns
that can be seen between the el ements. These patterns, or peri odi c trends, can be
observed for atomi c radi us, i oni c radi i , i oni zati on energi es, el ectron affi ni ti es, and
el ectronegati vi ti es. You shoul d be fami l i ar wi th the peri odi c and group trends for each
of these.
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Chapter 4: Atomic Structure 87
www.petersons.com
Nuclear Chemistry
OVERVIEW
The discovery of radioactivity
Rutherford discovers different types of radiation
Different types of radioactive emissions
Radioactive decay
Half-life
Nuclear reactions
Summing it up
The AP test requi res you to know about nucl ear equati ons, hal f-l i ves,
radi oacti vi ty, and chemi cal appl i cati ons of nucl ear properti es. Thi s chapter
begi ns wi th a bri ef revi ew of the hi story of the nucl eus and how we came to
know about i t and then moves i nto the requi red topi cs.
THE DISCOVERY OF RADIOACTIVITY
A si mpl e, but worki ng, defi ni ti on of radi oacti vi ty i s the spontaneous decay
of parti cl es from the nucl eus of an atom. Henri Becquerel fi rst di scovered
radi ati on i n 1896 whi l e doi ng research on the fl uorescence of di fferent
materi al s. One day, he set a sampl e of urani um ore i n a drawer atop some
unexposed photographi c pl ates. Upon l ater devel opi ng the fi l m, he di scovered
that the fi l m had been exposed i n the l ocati on where the ore had been si tti ng.
He concl uded that there must be some hi gh-energy emi ssi ons emergi ng from
the materi al . Becquerel di d not wi sh to pursue thi s separate l i ne of research,
so he passed the work on to one of hi s graduate students, Mari e Curi e, and her
husband, Pi erre. The Curi es pai nstaki ngl y worked wi th l arge sampl es of the
urani um ore to i sol ate the materi al responsi bl e for the emi ssi ons (the materi al
they i sol ated was radi um).
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
5
89
RUTHERFORD DISCOVERS DIFFERENT TYPES OF RADIATION
The next major di scoveri es about radi ati on came from Ernest Rutherford. These experi ments
came before hi s famous gol d-foi l experi ment. He di scovered that an el ectri cal fi el d affected the
emi ssi ons from radi oacti ve materi al . By pl aci ng a sampl e of materi al near two charged pl ates
(si mi l ar to the desi gn of Thomsons cathode ray studi es), he was abl e to observe the behavi or
of the radi oacti ve emi ssi ons i n an el ectri c fi el d. He accompl i shed thi s by fi ri ng a sampl e of
radi oacti ve materi al i n a thi n stream between two charged pl ates. He pl aced a photographi c
pl ate on the opposi te si de of the charged pl ates to observe the defl ecti ons of any parti cl es. (See
Fi gure 5.1.)
From the defl ecti ons, he determi ned that some of the parti cl es were posi ti vel y charged, some
were negati vel y charged, and some were not charged at al l . He di scovered that the posi ti vel y
charged parti cl es were much more massi ve than the others, and when combi ned wi th
el ectrons, they formed hel i um atoms. He cal l ed these parti cl es al pha parti cl es (a-parti cl es),
and today we know them to be hel i um nucl ei . The negati vel y charged parti cl es were l i ghter
and faster-movi ng than al pha parti cl es and behaved l i ke cathode rays. Rutherford cal l ed
these beta parti cl es (b-parti cl es), and today we know them to be el ectrons. The thi rd,
neutral emi ssi on was determi ned to be extremel y hi gh-energy radi ati on, unaffected by an
el ectri cal fi el d. These emi ssi ons became known as gamma rays (g rays).
Al pha parti cl es are rel ati vel y l arge and sl ow-movi ng and are easi l y stopped. Beta parti cl es
are much smal l er, much faster, and about 100 ti mes more penetrati ng than al pha parti cl es.
Gamma rays (often referred to as gamma photons) are massl ess and extremel y fast and
possess hi gh energy. They are by far the most penetrati ng radi ati onabout 100 ti mes greater
than a beta parti cl e, or 10,000 ti mes more penetrati ng than an al pha parti cl e.
The remai nder of thi s chapter wi l l be devoted to the process of radi oacti ve decay.
DIFFERENT TYPES OF RADIOACTIVE EMISSIONS
There are fi ve mai n types of emi ssi ons: al pha emi ssi on, beta emi ssi on, posi tron emi ssi on,
el ectron capture, and gamma emi ssi on. Four of these produce changes i n the el ements
undergoi ng decay, and the end resul t i s a more stabl e atomi c structure.
Figure5.1
90 PART III: AP Chemistry Review
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Alpha Emission
These emi ssi ons resul t i n the rel ease of an al pha parti cl e from the atom. Recal l that an
a-parti cl e i s a hel i um nucl eus. The resul t i n al pha decay i s the atoms atomi c number
decreasi ng by two and the mass number decreasi ng by four. An exampl e of an a-decay i s:
92
238
2
4
90
234
U He+ Th
You Try It!
Fi l l i n the mi ssi ng i sotope i n the reacti on that fol l ows:
83
211
Bi He + ______
2
4
Answer:
81
207
Tl
Beta Emission
Al though there are two types of b-parti cl es (b
1
and b
2
), the former i s usual l y referred to as a
posi tron, so wel l refer to onl y the b
2
parti cl e as a beta parti cl e. I n a beta emi ssi on, a beta
parti cl e i s ejected from the atom. A beta parti cl e has al l of the properti es of an el ectron
(vi rtual l y massl ess, negati ve charge), yet i t i s created by the conversi on of a neutron i n the
nucl eus to a proton and an el ectron (beta parti cl e). The proton remai ns i n the nucl eus, and the
beta parti cl e i s ejected from the nucl eus. An exampl e of a beta emi ssi on i s:
89
227
1
0
90
227
Ac e+ Th

Noti ce that si nce the number of nucl eons i n the atom does not change, the mass number
remai ns unchanged. However, the gai n of a proton i ncreases the atomi c number by one (and
consequentl y changes the el ement).
You Try It!
Fi l l i n the mi ssi ng i sotope i n the reacti on that fol l ows:
82
209
1
0
Pb e + ______

Answer:
83
209
Bi
Positron Emission
Posi tron emi ssi ons are al so known as b
1
emi ssi ons. The posi tron i s known as an
anti parti cl e. Anti parti cl es are the exact opposi tes of parti cl es. The posi tron i s the
anti parti cl e to an el ectron and i s represented by the symbol
+1
0
e. The el ectron has vi rtual l y no
mass and a charge of 21 (rel ati ve to a proton). A posi tron has vi rtual l y no mass and a charge
of 11. When an el ectron and i ts anti parti cl e, the posi tron, col l i de, they di si ntegrate and thei r
matter i s converted enti rel y i nto energy i n the form of two gamma rays. I n a posi tron
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Chapter 5: Nuclear Chemistry 91
www.petersons.com
emi ssi on, a proton i n the nucl eus i s converted i nto a neutron and a posi tron. The neutron
remai ns i n the nucl eus, and the posi tron i s ejected. The l i fe span of the posi tron i s very bri ef
si nce i t wi l l di si ntegrate upon col l i si on wi th an el ectron. An exampl e of a posi tron emi ssi on
can be seen i n the exampl e showi ng the breakdown of carbon-11:
6
11
1
0
5
11
C e+ B
+
Noti ce that the number of nucl eons doesnt change here, ei ther. As a resul t, the mass number
of the atom does not change. However, the conversi on of a proton to a neutron decreases the
atomi c number by one (and changes the el ement).
You Try It!
Fi l l i n the mi ssi ng i sotope i n the reacti on that fol l ows:
29
58
1
0
Cu e + ______
+
Answer:
28
58
Ni
Electron Capture
The fourth type of emi ssi on i s cal l ed el ectron capture. I n thi s process, an i nner shel l el ectron
i s pul l ed i nto the nucl eus, and when thi s occurs, the el ectron combi nes wi th a proton to form
a neutron. I n el ectron capture reacti ons, the atomi c number decreases by one, the mass
number remai ns the same, and the el ement changes. One di fference i n thi s type of reacti on i s
that the el ectron i s wri tten to the l eft of the arrow to show that i t i s consumed, rather than
produced, i n the process. An exampl e of el ectron capture can be seen i n the fol l owi ng reacti on:
80
201
1
0
79
201
Hg e Au +

You Try It!


Fi l l i n the mi ssi ng i sotope i n the reacti on that fol l ows:
32
68
1
0
Ge e ______ +

Answer:
31
68
Ga
Gamma Radiation
The fi fth type of radi oacti ve emi ssi on, gamma radi ati on, does not resul t i n a change i n the
properti es of the atoms. As a resul t, they are usual l y omi tted from nucl ear equati ons. Gamma
emi ssi ons often accompany other al pha or beta reacti onsany decay that has an excess of
energy that i s rel eased. For exampl e, when a posi tron col l i des wi th an el ectron, two gamma
rays are emi tted, a phenomenon usual l y referred to as anni hi l ati on radi ati on.
92 PART III: AP Chemistry Review
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RADIOACTIVE DECAY
There are a vari ety of reasons why radi oacti ve decay occurs, but the pri mary reason i s
i ncreased nucl ear stabi l i ty. To bri efl y revi ew, attracti ve forces must overcome el ectrostati c
repul si ons between the l i ke-charged protons. These attracti ve forces are provi ded by gl uons
(but you neednt concern yoursel f wi th knowi ng about gl uons). Neutrons seem to pl ay a rol e i n
thi s attracti ve process as wel l , both by attracti ng nei ghbori ng nucl eons (i ncl udi ng protons)
and by di l uti ng the el ectrostati c repul si ons between the protons, by spreadi ng them out a
bi t. Smal l atoms tend to have stabl e structures wi th equal numbers of neutrons and protons.
As atoms get l arger, the number of neutrons exceeds the number of protons. There are al so
two other properti es that seem to determi ne stabi l i ty of atomi c nucl ei . These are based on a
model of nucl ear stabi l i ty known as the shel l model of the nucl eus. Just as there are stabl e
el ectron confi gurati ons, there seem to be stabl e confi gurati ons of nucl eons. These two
properti es fal l i nto two categori es:
Magi c numbersThere are certai n numbers of protons and neutrons that are found
i n the most stabl e nucl ei . These are known as the magi c numbers for protons and
neutrons. For protons, the numbers are 2, 8, 20, 28, 50, and 82. For neutrons, the
numbers are 2, 8, 20, 28, 50, 82, and 126.
Nucl ei wi th even numbers of protons AND neutrons are more stabl e than atoms
wi th odd numbers of neutrons. I t i s bel i eved that perhaps proton-proton pai rs and
neutron-neutron pai rs form stabl e rel ati onshi ps, much l i ke el ectron-el ectron pai rs
i n mol ecul es. Above atomi c number 83 (el ements 84 and up), al l el ements are
radi oacti ve.
The Band of Stability
Fi gure 5.2 shows the pattern of stabl e nucl i des of the el ements. The shaded area of the graph
Figure5.2
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Chapter 5: Nuclear Chemistry 93
www.petersons.com
i ndi cates stabl e i sotopes and i s known as the bel t (or band) of stabi l i ty. Most radi oacti ve
i sotopes are l ocated outsi de thi s regi on. The fi gure may al so hel p you to see that there are
three mai n si tuati ons that determi ne the types of decay that el ements are l i kel y to undergo:
Atoms whose nucl ei are above the band of stabi l i ty (hi gh neutron-to-proton rati o)
can l ower thei r numbers of neutrons by undergoi ng beta emi ssi ons. The typi cal
pattern for these i s that the mass number (number of neutrons 1 number of
protons) i s greater than the atomi c wei ght. Remember that beta emi ssi ons convert
neutrons i nto protons and beta parti cl es.
Atoms whose nucl ei are bel ow the band of stabi l i ty (l ow neutron-to-proton rati o)
can rai se thei r numbers of neutrons by undergoi ng posi tron emi ssi ons, or el ectron
capture. The typi cal pattern here i s that the mass number i s l ess than the atomi c
wei ght. Remember that both processes i nvol ve the conversi on of a proton i nto a
neutron.
Atoms wi th atomi c numbers hi gher than 84 are too l arge to remai n stabl e. The
easi est way to decrease si ze i s to undergo al pha emi ssi on. Remember that al pha
emi ssi ons el i mi nate two protons and two neutrons.
A l arge sampl e of radi oacti ve materi al wi l l spontaneousl y decay. Over ti me, the amount of the
ori gi nal sampl e wi l l decrease and the amount of products wi l l i ncrease. I n the next secti on,
you wi l l l ook at the di fferent ways thi s decay i s descri bed.
HALF-LIFE
A common way to descri be the rate at whi ch radi oacti ve decay i s occurri ng i s a measurement
known as the hal f-l i fe. Hal f-l i fe i s defi ned as the ti me necessary for one hal f of a radi oacti ve
sampl e to undergo decay i nto new el ements. Di fferent i sotopes have di fferent decay rates.
Some are as l ong or l onger than 4.5 bi l l i on years (urani um-238) to as short as 10 mi croseconds
(astati ne-215). I t i s not necessary to understand the factors that contri bute to the l ength of the
hal f-l i fe, but you are expected to be abl e to perform vari ous cal cul ati ons i nvol vi ng hal f-l i fe.
There i s al so no way to real l y predi ct when an atom wi l l undergo a si ngl e decay, but i t i s
possi bl e to observe l arge amounts of decay and come up wi th an average rate. I f the amount
of a radi oacti ve substance i s measured over ti me and the resul ts are pl otted, the resul ti ng
graph i s known as a decay curve. Fi gure 5.3 shows the decay pattern more cl earl y.
From a conceptual approach, we can l ook at hal f-l i fe as the ti me i t takes for
1
2
of a sampl e to
decay i nto some other substance. For i nstance, i f we start out wi th 1.0 g of a radi oacti ve
sampl e, after one hal f-l i fe has el apsed, we wi l l be l eft wi th onl y 0.5 g of the ori gi nal materi al .
After two hal f-l i ves, we wi l l have 0.25 g. After 3, 0.125 g. As you can see, thi s coul d go on for
some ti me, but i t i s general l y accepted that after about 10 hal f-l i ves have el apsed, there i s a
negl i gi bl e amount of the ori gi nal radi oacti ve materi al l eft.
Most of the probl ems on past AP tests that contai n hal f-l i ves are rel ati vel y si mpl e to sol ve,
usi ng ei ther conceptual or mathemati cal approaches. On the test, you are not provi ded wi th
any equati ons rel ated to nucl ear chemi stry. Therefore, any cal cul ati ons you wi l l have to make
shoul d be fai rl y si mpl i sti c and easy to sol ve usi ng a few si mpl e rul es. From a conceptual
94 PART III: AP Chemistry Review
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perspecti ve, thi s means that hal f-l i fe probl ems can be sol ved by repeatedl y cutti ng the
starti ng amount i n hal f. For exampl e, after one hal f-l i fe, a sampl e wi l l have
1
2
the number of
radi oacti ve nucl ei that i t started wi th. After two hal f-l i ves, the sampl e wi l l have (
1
2
)(
1
2
), or (
1
2
)
2
,
ti mes the number of radi oacti ve nucl ei l eft. After three hal f-l i ves, the sampl e wi l l have
(
1
2
)(
1
2
)(
1
2
), or (
1
2
)
3
, ti mes the number of radi oacti ve nucl ei l eft. I f you havent al ready spotted the
pattern here, i t i s that the amount of sampl e l eft after ti me t wi l l be
N
t
5 N
0
(
1
2
)
n
where n 5 the number of hal f-l i ves that have el apsed duri ng ti me i nterval t. Thi s can al so be
rewri tten as
N
t
N
0
5 (
1
2
)
n
whi ch i s the same thi ng as sayi ng
Fracti on remai ni ng 5 (
1
2
)
n
Sample: I f you start wi th 64 g of a materi al wi th a hal f-l i fe of 10 years, how much wi l l be l eft
at the end of 40 years?
Answer: Conceptual l y, you can work through thi s step-by-step:
At end of You wi l l have l eft
10 years 32 g
20 years 16 g
30 years 8 g
40 years 4 g
Or you can use the formul a:
40 years 5 4 hal f-l i ves, so
N
t
5 N
0
(
1
2
)
n
5 (64 g)(
1
2
)
4
5 (64 g)(
1
16
) 5 4 g
The conceptual approach i s parti cul arl y effecti ve when sol vi ng probl ems that have hal f-l i ves
that are whol e number val ues. For more compl ex probl ems, we need to use some i deas
Figure5.3
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NOTE
These are just
general
guidelines. They
do not work for
all elements.
Chapter 5: Nuclear Chemistry 95
www.petersons.com
borrowed from chemi cal ki neti cs. Radi oacti ve decay can be descri bed as a fi rst order process,
whi ch means i t can be descri bed wi th the equati on:
Rate 5 kN
t
where k i s a constant, known as the decay constant, and N i s the number of radi oacti ve nucl ei
i n the sampl e at ti me t. Note that the rate i s proporti onal to the si ze of the sampl e.
By appl yi ng some basi c cal cul us, we can i ntegrate thi s equati on i nto a new formul a (i t i s not
necessary for you to know how thi s was deri ved):
l n
N
t
N
0
5 2kt or l og
N
t
N
0
5
2kt
2.303
where t i s the ti me i nterval , k i s the decay constant, N
0
i s the i ni ti al number of nucl ei , and N
t
i s the number of nucl ei after ti me t. Mass val ues can be substi tuted for the N val ues si nce the
mass wi l l be proporti onal to the number of nucl ei .
I f you are goi ng to be consi deri ng the hal f-l i fe of a substance, then the quanti ti es of nucl ei wi l l
be rel ated by the expressi on N
t
5
1
2
N
0
, or 2N
t
5 N
0
. Remember, after one hal f-l i fe, the number
of nucl ei of a parti cul ar radi oi sotope wi l l have decreased by hal f. Thi s rel ati onshi p wi l l al l ow
us to si mpl i fy the above expressi ons through substi tuti on (agai n, i t i s not necessary for you to
know the deri vati on) i nto the fol l owi ng expressi on:
k 5
0.696
t1
2
or t1
2
5
0.693
k
(the number 0.693 5 l n 2)
Sample: The hal f-l i fe of i odi ne-125 i s 60 days. I f the ori gi nal sampl e had a mass of
50.0 grams, how much i s l eft after 360 days?
Answer: I f you compare the hal f-l i fe to the ti me el apsed, you wi l l see that the number of
hal f-l i ves that el apse duri ng the ti me i nterval i s a whol e number (
60
360
5 6). The
easi est way to approach thi s probl em, then, i s to use the equati on:
N
t
5 N
0
(
1
2
)
n
Gi ven i nformati on:
N
0
5 50.0 g
n 5 6 hal f-l i ves We can now substi tute these val ues i nto the equati on to sol ve for N
t
.
N
t
5 ?
N
t
5 50.0 g (
1
2
)
6
5 50.0 g (
1
64
) 5 0.781 g
You Try It!
Ti tani um-51 has a hal f-l i fe of 6 mi nutes. I f 98 g of the materi al are obtai ned, how
many grams of the sampl e wi l l remai n after 1 hour?
Answer: 0.096 g
96 PART III: AP Chemistry Review
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Sample: I odi ne-131, a radi oacti ve i sotope of i odi ne, has a hal f-l i fe of 8.07 days. A l ab worker
di scovers that a sampl e of i odi ne-131 has been si tti ng on a shel f for 7 days. What
fracti on of the ori gi nal nucl ei i s sti l l present after 7 days?
Answer: To sol ve thi s probl em, you wi l l want to begi n wi th the equati on:
l og
N
t
N
0
5
2kt
2.303
We wi l l use thi s equati on because we are concerned wi th the rati o of the i ni ti al to the fi nal
sampl e. We dont know k, so we can substi tute the expressi on k 5
0.693
t
1
2
for k i n the equati on.
Doi ng so wi l l produce the new expressi on:
l og
N
t
N
0
5
20.693t
2.303t1
2
5
20.693~7.0 days!
2.303~8.07 days!
5 20.2610
Therefore, we need to rearrange the equati on so that:
N
t
N
0
5 10
20.2610
5 0.548 0.548 3 100%5 55%
We al so coul d have used thi s equati on:
l n
N
t
N
0
5 2kt; substi tuti ng k 5
0.693
t1
2
we obtai n l n
N
t
N
0
5 2
0.693
t1
2
t
l n
N
N
t
0
5
0 693 .
8.07 days
(7 days) 5 20.601
N
N
t
0
5 e
2.601
5 0.548 5 55%
Thi s i s about what we predi cted, so chances are weve done i t correctl y!
You Try It!
The hal f-l i fe of phosphorus-30 i s 2.5 mi n. What fracti on of phosphorus-30 nucl i des
woul d remai n after 14 mi nutes?
Answer: 2.1%
Sample: I f a 1.0 3 10
23
g sampl e of techneti um-99 has a decay rate of 6.3 3 10
5
nucl ei s
21
,
what i s i ts decay constant?
Answer: We want to use the formul a: Rate 5 kN
t
The fi rst thi ng we wi l l need to do i s rearrange the equati on to sol ve for k:
k 5
Rate
N
t
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TIP
Beforebeginning,
it helps toconsider
what youare
doing. If youknow
that thehalf-lifeis
about 8days and
thesampleis 7
days old, you
knowthereshould
bejust morethan
half of thesample
present inthe
sample. Whenyou
finishyour work,
check tomake
sureyour answer is
closetoyour
estimate.
Chapter 5: Nuclear Chemistry 97
www.petersons.com
We know the rate, but we sti l l need to determi ne the number of nucl ei present at ti me t (we
onl y know the mass of the sampl e). To do thi s, we wi l l need to determi ne how many
techneti um-99 atoms are present i n 1.0 3 10
23
g of the substance). Thi s i s a mol e-conversi on
probl em (see Chapter 12):
1.0 10 g Tc
1 mol Tc
99 g Tc
6.02 10 Tc nuclei
1 mol Tc
3
43
99 43
99
43
99
23
43
99
43
99


5 6.1 3 10
18
43
99
Tc nuclei
Now, we have al l of the i nformati on we need to sol ve the probl em:
k 5
Rate
N
t
5
6.3 3 10
5
nucl ei /s
6.1 3 10
18
nucl ei
5 1.0 3 10
213
s
21
You Try It!
A 2.8 3 10
26
g col l ecti on of pl utoni um-238 i s decayi ng at a rate of 1.8 3 10
6
di si nte-
grati ons per second. What i s the decay constant (k) of pl utoni um-238 i n s
21
?
Answer: 2.5 3 10
210
s
21
Sample: What i s the hal f-l i fe of techneti um-99?
Answer: We know from probl em 3 that the decay constant of Tc-99 i s 1.0 3 10
213
s
21
. We
al so know from the earl i er equati on that:
t1
2
5
0.693
k
Therefore, by substi tuti on, we wi l l get:
t1
2
5
0.693
k
5
0.693
1.0 3 10
213
s
21
5 6.9 3 10
12
s
Dependi ng on your needs, you mi ght need to convert thi s i nto more sui tabl e uni ts.
For i nstance:
6.9 3 10
12
s 3
1 min
60 s
3
1 h
60 min
3
1 day
24 h
5 7.99 3 10
7
days
Thi s sti l l i snt a very useful amount si nce i t i s so l arge, so we can convert i t further
i nto years:
7.99 3 10
7
days 3
1 yr
365.25 days
5 2.2 3 10
5
years
98 PART III: AP Chemistry Review
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www.petersons.com
You Try It!
A sampl e of curi um-243 was produced for transport to a l ab. When i t was fi rst produced,
the acti vi ty of the sampl e was measured at 3012 dps (di si ntegrati ons per second). After
one year, the l ab needed to use the sampl e. The l ead sci enti st measured the acti vi ty as
2921 dps. What i s the hal f-l i fe of curi um-243?
Answer: 22.6 years
Radioactive Isotope Dating
Because radi oacti ve i sotopes seem to decay at very constant rates, they can be used as
cl ocks. One of the fi rst radi oacti ve dati ng techni ques i nvol ved the use of the radi oi sotope
carbon-14. Carbon-14 i s produced i n the upper atmosphere when neutrons (produced by
cosmi c rays from space) col l i de wi th ni trogen-14 mol ecul es i n the reacti on shown bel ow:
7
14
0
1
6
14
1
1
N n C+ H +
Carbon-14 i ncorporates i nto mol ecul es just as carbon-12 (ordi nary carbon), i ncl udi ng CO
2
gas.
Thi s carbon di oxi de becomes i ncorporated i nto pl ants (and subsequentl y ani mal s). I t i s
assumed that the rati o of C-14 to C-12 wi thi n an organi sm i s si mi l ar to the rati o i n the
atmosphere, about 1:10
12
(i t i s bel i eved to have been at thi s rati o for about 50,000 years).
When a l i vi ng organi sm di es, carbon no l onger cycl es i nto or out of i t. Si nce carbon-12 does not
decay and carbon-14 does, the change i n rati o of C-14 to C-12 can be used to esti mate the ti me
of death of l i vi ng organi sms. There are other radi oi sotopes that are used for radi oacti ve
dati ng that i ncl ude i norgani c compounds i n nonl i vi ng thi ngs, but the mechani sms for
obtai ni ng dates are si mi l ar. We wi l l onl y exami ne C-14 dati ng.
The carbon-14 atom has a hal f-l i fe of 5730 years and decays at a rate of 15.3 di si ntegrati ons
per mi nute per gram of total carbon i n l i vi ng organi sms. What thi s tel l s us i s that i f an
organi sm di es, the carbon-14 i n i t wi l l decay at a rate of 15.3 di si ntegrati ons per mi nute per
gram. As more carbon-14 decays, thi s rate wi l l decrease. After one hal f-l i fe has el apsed (5730
years), onl y hal f of the ori gi nal C-14 wi l l be l eft. Thi s means that the total decay rate wi l l be
7.65 di si ntegrati ons/mi nute/gram. After two hal f-l i ves, the di si ntegrati on wi l l have dropped to
3.825, etc. Lets see how thi s i nformati on can be used to determi ne the date of an object.
Sample: How ol d i s a pi ece of anci ent wood that i s gi vi ng off beta emi ssi ons from carbon-14
at the rate of 1.9 di si ntegrati ons/mi nute/gram?
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Chapter 5: Nuclear Chemistry 99
www.petersons.com
Answer: We know that the rate of di si ntegrati ons i s proporti onal to the number of nucl ei .
Therefore, we can substi tute the acti vi ty for the N val ues i n the equati on
l n
N
t
N
0
5 2kt; substi tuti ng k 5
0.693
t1
2
we obtai n l n
N
t
N
0
5 2
0.693
t1
2
t
l n
1.9 di s/mi n/g
15.3 di s/mi n/g
5 2
0.693
t1
2
t
2
t1
2
0.693
5
1.9 di s/mi n/g
15.3 di s/mi n/g
5 t 2
5730 y
0.693
l n
1.9 di s/mi n/g
15.3 di s/mi n/g
5 1.7 3 10
4
y
Thi s object i s about 17,000 years ol d (rounded for si gni fi cant di gi ts).
You Try It!
A wooden arti fact found i n a mummys tomb i s found to have 9.4 di si ntegrati ons/mi n/g.
How ol d i s the arti fact?
Answer: 4030 years ol d (rounded)
Transuranium Elements
I n al most al l of the previ ous exampl es, we have l ooked at nucl ear reacti ons that occur by
spontaneous decay. There are other types of nucl ear reacti ons that can occur, known as
transmutati on reacti ons. These reacti ons can be i nduced by forci ng a reacti on between the
nucl eus of an el ement and nucl ear parti cl es (such as neutrons), or nucl ei . Ernest Rutherford
carri ed out the fi rst transmutati on by bombardi ng ni trogen-14 nucl ei wi th al pha parti cl es.
Thi s resul ted i n the producti on of oxygen-17 and a proton, as shown bel ow:
7
14
2
4
8
17
1
1
N He O+ H +
Thi s process has been used to produce countl ess i sotopes, i ncl udi ng many radi oacti ve
i sotopes. I n addi ti on, i t has al l owed sci enti sts to produce el ements wi th atomi c numbers that
are hi gher than that of the l argest natural l y occurri ng el ement, urani um. These el ements are
known as transurani um el ements. I n 1940, E. M. McMi l l an and P. H. Abel son of the
Uni versi ty of Cal i forni a, Berkel ey produced the fi rst transurani um el ement, neptuni um (Np,
Z593), by bombardi ng urani um-238 wi th neutrons. The nucl ei that captured the neutrons
were converted to urani um-239, whi ch decayed i nto neptuni um-239 duri ng a beta emi ssi on.
The reacti on i s shown bel ow:
Step 1:
92
238
0
1
92
239
U n U +
Step 2:
92
239
93
239
1
0
U Np e +

100 PART III: AP Chemistry Review


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www.petersons.com
NUCLEAR REACTIONS
Energy Relationships
Nucl ear decay al l ows a nucl eus to form products wi th l ower energy. However, accordi ng to
Al bert Ei nstei ns famous equati on E 5 mc
2
, any change i n energy must be accompani ed by a
correspondi ng change i n mass. I n chemi cal reacti ons, thi s change i n mass i s negl i gi bl e
(though i t does occur), but i t i s much more pronounced i n nucl ear reacti ons. I f E changes by a
certai n amount, DE, then mass wi l l have to change proporti onal l y by an amount Dm(c bei ng
constant at al l ti mes). Thus:
DE 5 (Dm)c
2
I f we exami ne a speci fi c reacti on, we can see how thi s works. Take for i nstance:
92
238
90
234
2
4
U Th He +
The masses of each of the parti cl es i n the equati on are:
92
238
U 5 238.0003 g mol
21
,
90
234
Th 5 233.9942 g mol
21
,
and
2
4
He 5 4.00150 g mol
21
The change i n mass can be determi ned by subtracti ng the mass of the reactant (parent
nucl ei i n thi s case, urani um-238), from the combi ned masses of the products:
Dm5 (233.9942 g 1 4.00150 g) 2 238.0003 g 5 20.0046 g
To determi ne the energy change, we can now use Ei nstei ns equati on and sol ve for DE. Before
we can do thi s, we must convert the mass to ki l ograms (because the energy uni t of joul es
requi res the mass i n ki l ograms):
DE 5 24.6 3 10
26
kg (3.0 3 10
8
m s
21
)
2
5 24.14 3 10
11
J
Thi s i s an enormous amount of energy!
You wi l l not be expected to perform these cal cul ati ons on the AP test, but you shoul d
appreci ate from a conceptual l evel that there i s an enormous amount of energy rel eased
duri ng nucl ear reacti ons. I n addi ti on, you shoul d understand that the amount of energy
rel eased i n nucl ear reacti ons i s much l arger than that rel eased i n chemi cal reacti ons. The
mai n reason i s that duri ng chemi cal reacti ons, the onl y energy rel eased duri ng a reacti on wi l l
resul t from el ectrostati c forces between the protons and el ectrons i n the atom. Duri ng nucl ear
reacti ons, the energy resul t i s dependent on the energi es associ ated wi th the strong nucl ear
force, whi ch i s many orders of magni tude l arger than el ectrostati c forces. On the atomi c l evel ,
we can see the effects of these strong nucl ear forces when we l ook at the phenomena of
bi ndi ng energi es and mass defect.
BINDING ENERGY
I t turns out that the mass of an i ndi vi dual atom i s al ways l ess than the sum of i ts parts. That
i s, i f you add up the masses of al l the components of an atom, you wi l l not get the total mass
of the atom. As an exampl e, l ets l ook at oxygen-16.
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Chapter 5: Nuclear Chemistry 101
www.petersons.com
Oxygen-16 contai ns 8 protons and 8 neutrons. Therefore, we woul d expect the mass to equal :
mass of 8 protons 1 mass of 8 neutrons 5 total mass
8(1.0078252 amu) 1 8(1.0086652 amu) 5 16.1319232 amu
However, the actual mass of oxygen-16 i s 15.9949150 amu
So, what happened to the 0.1370082 amu that shoul d have been present? I t turns out that
when the neutrons and protons come together to form the nucl eus, they form a more stabl e
enti ty. Thi s means that energy i s rel eased. When that energy i s rel eased, there must be a
correspondi ng l oss of mass. The more energy that i s rel eased, the more stabl e the nucl eus i s.
I n order to break apart a nucl eus, you woul d have to add that much energy. The amount of
energy you must add to break a nucl eus i nto i ts consti tuent neutrons and protons i s known as
the bi ndi ng energy. The di fference i n mass between the expected and actual masses i s
known as the mass defect.
I t i s not necessary to be abl e to perform these cal cul ati ons for the AP test. However, i t i s very
i mportant that you understand the underl yi ng i dea that l arge amounts of energy are rel eased
when atomi c nucl ei are broken apart. I t i s al so i mportant to understand that the di fference i n
mass between the components of a nucl eus and the actual mass of the nucl eus can be
accounted for by a change i n the energy state of those components. The nature of that
rel ati onshi p i s captured i n Ei nstei ns equati on E 5 mc
2
.
NUCLEAR FISSION
We have seen so far that the process of heavy nucl ei spl i tti ng apart (known as fi ssi on) i s
hi ghl y exothermi c. I n addi ti on, the joi ni ng of l i ghter nucl ei (known as fusi on) i s al so a hi ghl y
exothermi c process. Fi ssi on i s typi cal l y accompl i shed by bombardi ng heavy nucl ei wi th
sl ow-movi ng neutrons. Once the neutron i s absorbed, the resul ti ng unstabl e nucl eus breaks
i nto smal l er nucl ei . One of the most wel l -known fi ssi ons i nvol ves the spl i tti ng of
urani um-235, shown i n the reacti on bel ow:
92
235
0
1
56
139
36
94
0
1
U n Ba Kr + 3 n + +
The neutrons produced by thi s fi ssi on reacti on can potenti al l y col l i de wi th other U-235 nucl ei .
The l i kel i hood of the extra neutrons stri ki ng other nucl ei i ncreases as the mass of the sampl e
i ncreases. At a characteri sti c mass, the neutrons are assured to col l i de wi th U-235 nucl ei , and
as a resul t, a chai n reacti on begi ns. I n thi s chai n reacti on, the neutrons from one fi ssi on wi l l
stri ke other nucl ei and cause addi ti onal fi ssi on reacti ons. The mass at whi ch a sel f-sustai ni ng
chai n reacti on wi l l occur i s known as the cri ti cal mass. Fi ssi on reacti ons are responsi bl e for
the producti on of nucl ear power and for the desi gn of nucl ear weapons.
NUCLEAR FUSION
I n a fusi on reacti on, l i ght nucl ei wi l l combi ne to form heavi er ones. Whi l e thi s process i s qui te
commonpl ace on stars (i ncl udi ng our sun), i t i s very di ffi cul t to accompl i sh i n a l aboratory
setti ng. I n order to fuse nucl ei (such as hydrogen), extremel y hi gh temperatures are necessary
(around 100 mi l l i on degrees Cel si us) to overcome the repul si ve forces between nucl ei . These
temperatures are very di ffi cul t to achi eve and to mai ntai n l ong enough to achi eve the reacti on.
102 PART III: AP Chemistry Review
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www.petersons.com
EXERCISES: NUCLEAR CHEMISTRY
Multiple Choice
Directions: For questi ons 15, determi ne the mi ssi ng i nformati on.
1.
90
230
88
226
Th Ra + ______ The mechani sm
of thi s reacti on i s
(A) al pha decay.
(B) beta decay.
(C) posi tron emi ssi on.
(D) el ectron capture.
(E) gamma photon emi ssi on.
2.
29
58
1
0
Cu e + ______
+
I f copper-29
undergoes a posi tron emi ssi on, what
i s the resul ti ng product nucl i de?
(A)
29
59
Cu
(B)
28
58
Ni
(C)
30
58
Zn
(D)
29
57
Cu
(E)
29
60
Cu
3.
89
277
1
0
Ac e + ______

The mi ssi ng
product i n thi s equati on i s
(A)
90
227
Th
(B)
89
227
Ac
(C)
88
227
Ra
(D)
87
223
Fr
(E)
89
228
Ac
4.
32
68
1
0
Ge e ______ +

What wi l l the
resul ti ng product be when an
el ectron i s captured by a germa-
ni um-68 nucl eus?
(A)
33
68
As
(B)
32
69
Ge
(C)
32
68
Ge
(D)
31
68
Ga
(E)
34
72
Se
5.
88
225
89
225
Ra Ac ______ + What i s the
mi ssi ng product i n thi s reacti on?
(A)
+1
0
e
(B)
1
0
e
(C)
2
4
He
(D)
0
0

(E)
0
1
n
6. I f you begi n wi th 300.0 g of a sampl e
of a radi oi sotope and have 37.5 g
remai ni ng after a peri od of 90
mi nutes, what i s the hal f-l i fe of the
radi oi sotope?
(A) 90 mi nutes
(B) 60 mi nutes
(C) 30 mi nutes
(D) 45 mi nutes
(E) 3.4 mi nutes
7. Carbon-14 has a hal f-l i fe of 5730
years. I f you fi nd a sampl e gi vi ng off
0.96 di si ntegrati ons/mi nute/gram,
what i s the age of the sampl e?
(Ori gi nal l y the carbon-14 gave off
15.3 di si ntegrati ons/mi nute/gram.)
(A) 2.9 3 10
4
years
(B) 2.3 3 10
4
years
(C) 1.7 3 10
4
years
(D) 9.9 3 10
3
years
(E) 2.9 3 10
3
years
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Chapter 5: Nuclear Chemistry 103
www.petersons.com
8. Stronti um-90 i s a radi oacti ve i sotope
that was created by atomi c weapons
testi ng duri ng Worl d War I I . The
hal f-l i fe of stronti um-90 i s 28.8 years.
The fi rst atomi c weapons test took
pl ace i n New Mexi co on Jul y 16,
1945. What fracti on of the ori gi nal
stronti um-90 remai ned i n the desert
on Jul y 16, 2000?
(A) 77%
(B) 50%
(C) 27%
(D) 25%
(E) 12.5%
9. For the types of radi ati on gi ven,
whi ch of the fol l owi ng i s the correct
order of i ncreasi ng penetrabi l i ty?
(A) Gamma rays , al pha parti cl es
, beta parti cl es
(B) Beta parti cl es , al pha parti cl es
, gamma rays
(C) Beta parti cl es , gamma rays
, al pha parti cl es
(D) Al pha parti cl es , gamma rays
, beta parti cl es
(E) Al pha parti cl es , beta parti cl es
, gamma rays
10. I f 87.5 percent of a sampl e of pure
99
Rh decays i n 48 days, what i s the
hal f-l i fe of
99
Rh?
(A) 6 days
(B) 8 days
(C) 12 days
(D) 16 days
(E) 24 days
11. The radi oacti ve decay of
8
19
O to
9
19
F occurs by the process of
(A) beta parti cl e emi ssi on.
(B) al pha parti cl e emi ssi on.
(C) posi tron emi ssi on.
(D) el ectron capture.
(E) neutron capture.
12. The fi rst part of the decay seri es of
94
240
Pu i nvol ves three al pha emi ssi ons
fol l owed by two beta emi ssi ons. What
nucl i de has been formed at thi s
i ntermedi ate stage of the decay se-
ri es?
(A)
88
228
Ra
(B)
88
224
Ra
(C)
89
228
Ac
(D)
90
232
Th
(E)
90
228
Th
104 PART III: AP Chemistry Review
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www.petersons.com
ESSAY 1
The most common and stabl e form of oxygen i s
8
16
O, accounti ng for about 99.8 percent of al l
oxygen. Two of the many unstabl e i sotopes of oxygen are
8
14
O and
8
21
O. Each of these
undergoes a radi oacti ve decay, but the end products are di fferent from each.
(A) I denti fy the type of radi oacti ve decay that oxygen-14 wi l l undergo, and wri te a
bal anced nucl ear equati on for the process.
(B) I denti fy the type of radi oacti ve decay that oxygen-21 wi l l undergo, and wri te a
bal anced nucl ear equati on for the process.
(C) The decay of oxygen-21 i s al so accompani ed by gamma ray emi ssi ons. Expl ai n why i t i s
not necessary to i ncl ude thi s i n the nucl ear equati on.
(D)
The most stabl e form of oxygen,
8
16
O, has an atomi c wei ght of
15 99 .
. However, addi ng
the wei ghts of i ts components (8 protons and 8 neutrons) gi ves a wei ght of 16.13.
Account for thi s di screpancy between the predi cted and actual wei ghts.
ESSAY 2
(A) Expl ai n why beta parti cl es are more potenti al l y harmful to ski n than al pha parti cl es.
(B) Expl ai n why carbon dati ng i s not a very useful techni que for determi ni ng the age of
objects that were never al i ve.
(C) I t has been proposed by some that transurani um el ements, l i ke neptuni um and
pl utoni um, were once present on Earth i n fai rl y si gni fi cant quanti ti es. Expl ai n why
they are not found today.
(D) Fusi on offers great promi se as a cl ean, renewabl e energy source. However, for al l of i ts
promi se, there are tremendous obstacl es to be overcome before i ts use becomes
possi bl e. Expl ai n why fusi on i s so much more di ffi cul t to accompl i sh than fi ssi on, a
process al ready i n wi despread use for energy producti on.
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Chapter 5: Nuclear Chemistry 105
www.petersons.com
ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. A
2. B
3. A
4. D
5. B
6. C
7. B
8. C
9. E
10. D
11. A
12. E
1. Thecorrect answer is (A). You can tel l that thi s i s an al pha decay by the decrease of
4 i n the mass number and 2 i n the atomi c number.
2. Thecorrect answer is (B). Remember, posi trons are formed from the conversi on of a
proton to a neutron and a posi tron. Thi s wi l l cause the atomi c number to decrease by
one but the mass number to remai n unchanged.
3. Thecorrect answer is (A). Beta emi ssi ons are the resul t of a neutron converti ng to a
proton and an el ectron. The formati on of the proton causes an i ncrease i n atomi c
number, but the mass number remai ns unchanged.
4. The correct answer is (D). The captured el ectron combi nes wi th a proton to form a
neutron. Thi s causes a decrease i n the atomi c number but no change i n the mass
number.
5. Thecorrect answer is(B). Beta decay i s the onl y decay that causes an i ncrease i n the
atomi c number.
6. The correct answer is (C). You can answer thi s conceptual l y or mathemati cal l y.
Conceptual l y, try to determi ne i f the number of hal f-l i ves i s a whol e number. Begi n by
successi vel y di vi di ng the sampl e i n hal f. Hal f of 300 g i s 150 g. Hal f of 150 g i s 75 g. Hal f
of 75 g i s 37.5 g. Therefore, after 3 hal f-l i ves, the sampl e has decayed to i ts present
amount. I f 3 hal f-l i ves el apse i n 90 mi nutes, each one must be 30 mi nutes.
Mathemati cal l y, the probl em i s sol ved by usi ng the equati on l n
N
t
N
0
5 2kt; substi tuti ng
k 5 2
0.693
t
1
2
, we obtai n l n
N
t
N
0
5 2
0.693
t
1
2
t. Sol vi ng the equati on for t1
2
resul ts i n 30 mi nutes.
7. The correct answer is (B). You can sol ve the probl em conceptual l y, begi nni ng wi th a
qui ck determi nati on of the number of hal f-l i ves. Successi ve di vi si ons of the
di si ntegrati ons wi l l determi ne the approxi mate number of hal f-l i ves: 15.3 4 2 5 7.65 4
2 5 3.825 4 2 5 1.9125 4 2 5 0.95625. Thi s i s approxi matel y 0.96, so about 4 hal f-l i ves
have el apsed. Mul ti pl yi ng 5730 by 4 yi el ds 22,920whi ch rounds to 2.3 3 10
4
years.
The mathemati cal sol uti on i nvol ves the equati on l n
N
t
N
0
5 2kt; substi tuti ng k 5
0.693
t
1
2
,
we obtai n l n
N
t
N
0
5 2
0.693
t
1
2
t. Substi tuti ng the data i nto the equati on, we see that
l n
0.96 d/m/g
15.3 d/m/g
~
25730
0.693
!
5 2.3 3 10
4
years.
106 PART III: AP Chemistry Review
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www.petersons.com
8. The correct answer is (C). A qui ck i nspecti on of the probl em wi l l tel l you that the
number of hal f-l i ves that have el apsed i s not a whol e number. Fi fty-fi ve years wi l l have
el apsed si nce Jul y 16, 1945; however, two hal f-l i ves i s equal to 57.6 years. Gi ven the fi ve
choi ces, one answer i s obvi ousl y correct, even wi thout doi ng any cal cul ati ons. I f two
hal f-l i ves had el apsed, the sampl e woul d be 25 percent of the ori gi nal amount. Si nce the
ti me el apsed i s just shy of two hal f-l i ves, we woul d expect there to be sl i ghtl y more than
25 percent of the ori gi nal sampl e l eft. Therefore, 27 percent i s the obvi ous answer.
Mathemati cal l y, the probl em can be sol ved usi ng the fol l owi ng equati on: Fracti on
remai ni ng 5 (
1
2
)n. The val ue of n can be cal cul ated by di vi di ng the ti me el apsed by the
hal f-l i fe : 55 years 4 28.8 years 5 1.91. Thi s can be substi tuted for n, so that the
fracti on remai ni ng 5 (
1
2
)
1.91
5 26.6, whi ch rounds to 27 percent.
9. Thecorrect answer is (E). Al pha parti cl es are the l east penetrati ng parti cl e because
they have the greatest mass and the l owest vel oci ty. Beta parti cl es, bei ng much smal l er
than al pha parti cl es, travel much more qui ckl y and meet l ess resi stance due to thei r
si ze, but they do encounter some resi stance due to thei r charge. Gamma rays are the
most penetrati ng si nce they have nei ther mass nor charge and travel at near
l i ght speed.
10. The correct answer is (D). Conceptual l y, you can see that 87.5 percent has decayed,
whi ch i s the same as sayi ng there i s 12.5 percent remai ni ng. You shoul d recogni ze that
12.5 percent i s one hal f of 25 percent, whi ch i s one hal f of 50 pecent, whi ch i s one hal f
of 100 percent. Thus, 3 hal f-l i ves have el apsed duri ng the 48-day i nterval . Di vi di ng the
total ti me by the number of hal f-l i ves yi el ds 16 days. Mathemati cal l y, use the equati on
l n
N
t
N
0
5 2
0.693
t
1
2
t. Substi tuti ng the gi ven i nformati on, you get l n 0.125 5 2
~0.693! ~48 days!
t
1
2
.
Sol vi ng for t
1
2
yi el ds 16 days.
11. The correct answer is (A). Beta decay i s the onl y process that wi l l i ncrease the
atomi c number.
12. The correct answer is (E). The porti on of the decay seri es descri bed i n the probl em
consi sts of the fol l owi ng reacti ons:
94
240
92
236
Pu He U +
2
4
(a-decay)
92
236
90
232
U He Th +
2
4
(a-decay)
90
232
88
228
Th He Ra +
2
4
(a-decay)
88
228
89
228
Ra e Ac +
1
0
(b-decay)
89
228
90
228
Ac e Th +
1
0
(b-decay)
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Chapter 5: Nuclear Chemistry 107
www.petersons.com
ESSAY 1
(A) Stabl e oxygen has an atomi c wei ght of about 16 amu. Oxygen-14 has too few neutrons
and so wi l l need to i ncrease the number of neutrons. Thi s can occur by posi tron
emi ssi on or el ectron capture. Posi tron emi ssi on i s much more l i kel y:
8
14
1
0
7
14
O N e
+
+
Al ternati ve sol uti on:
8
14
1
0
7
14
O N e +

(B) Oxygen-21 has too many neutrons, so i t wi l l need to l ose some. By undergoi ng beta
emi ssi on, oxygen-21 can convert the neutrons to protons i n the fol l owi ng reacti on:
8
21
1
0
9
21
O F e+

(C) Si nce gamma rays do not affect the chemi cal nature of the reactants or products, i t i s
not necessary to i ncl ude them.
(D) The di fference i n masses, known as the mass defect, i s due to the conversi on of mass
that accompani es the formati on of the nucl eus. That i s, the energy that i s rel eased as
the more stabl e nucl eus i s formed by a conversi on of mass accordi ng to the equati on
DE 5 c
2
Dm.
ESSAY 2
(A) Beta parti cl es are much smal l er and travel much faster than al pha parti cl es. They are
about 100 ti mes more penetrati ng than al pha parti cl es and are more di ffi cul t to stop.
(B) Carbon dati ng rel i es on the rati o of carbon-14 to carbon-12 i n organi sms. Carbon-14,
produced mostl y i n the atmosphere, i s i ncorporated i nto l i vi ng organi sms through
carbon di oxi de formed from the radi oacti ve i sotope. When the organi sm di es, no more
exchange of gases wi l l take pl ace, so at the ti me of death, the quanti ty of carbon-14 i s
fi xed. I f an organi sm was never a l i vi ng organi sm, i t i s much l ess l i kel y to (A) contai n
carbon, and (B) even i f i t does have carbon, i t i s much l ess l i kel y to have i ncorporated
the radi oacti ve carbon di oxi de.
(C) These el ements are not present today because they have undergone decay i nto smal l er
el ements. Over ti me, al l l arger radi oacti ve el ements wi l l eventual l y decay i nto smal l er,
more stabl e el ements.
(D) The very l arge repul si ve force between nucl ei must be overcome i n order to al l ow
fusi on to occur. Thi s requi res enormous amounts of energy. Fi ssi on, on the other hand,
requi res much l ess energy because i t i s breaki ng apart al ready unstabl e nucl ei .
108 PART III: AP Chemistry Review
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www.petersons.com
SUMMING IT UP
Atomi c nucl ei are composed of neutrons and protons.
For each nucl ei , there are some i sotopes that are more stabl e than others. The stabi l i ty of
each nucl eus i s determi ned by the rati o of neutrons to protons. The bel t of stabi l i ty can be
used to esti mate the stabi l i ty of any gi ven nucl eus.
To gai n stabi l i ty, neutrons undergo decay reacti ons: al pha emi ssi on, beta emi ssi on,
posi tron emi ssi on, and el ectron capture are possi bl e.
Al though i t i s not possi bl e to predi ct when a si ngl e decay wi l l occur, the overal l rate of
decay for any i sotope i s rel ati vel y consi stent.
The rate of decay can be used to determi ne the hal f-l i fe of an i sotope; that i s the ti me
duri ng whi ch one hal f of a radi oacti ve sampl e i s converted i nto a di fferent materi al .
The hal f-l i ves of certai n materi al s, l i ke carbon-14, can be used to determi ne the ages of
arti facts.
The sum of the masses of the i ndi vi dual components of an atom i s greater than the actual
mass of the atom. Thi s i s due to the mass that i s converted i nto energy as the nucl eons
bi nd together.
Nucl ear fi ssi on i s a process whereby unstabl e nucl ei are bombarded by neutrons i n order
to spl i t them i nto smal l er nucl ei .
Nucl ear fusi on i s a process where smal l nucl ei are forced together wi th an extremel y
l arge amount of energy i n an effort to joi n them i nto a l arger nucl eus.
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Chapter 5: Nuclear Chemistry 109
www.petersons.com
Chemical Bonding
OVERVIEW
Lewis symbols
Octet rule
Ionic bonds
Covalent bonds
Using Lewis structures to determine molecular bonding
Resonance structures
Intermolecular forces
Summing it up
I n thi s chapter, you wi l l revi ew the basi c pri nci pl es of chemi cal bondi ng. The
underl yi ng theme to remember as you go through thi s chapter i s that
chemi cal bonds form for a reason. Thei r formati on i s nei ther di sorgani zed nor
haphazard. Chemi cal bonds al l ow atoms to exi st at l ower energy states that
are more stabl e. The mai n types of bonds fal l i nto three categori es: i oni c,
coval ent, and metal l i c. Whether an atom wi l l form i oni c or coval ent bonds
depends on a vari ety of factors, the most i mportant bei ng i ts current el ectron
confi gurati on and the strength of the attracti ve force between the protons i n
the nucl eus and the el ectrons. We wi l l refer back to materi al from Chapter 4:
Atomi c Structure as we di scuss these rel ati onshi ps. These same atomi c
properti es wi l l al so determi ne more compl ex behavi or, i ncl udi ng the physi cal
properti es of i oni c and coval ent compounds, the shapes of the structures
formed, and the attracti ve forces that wi l l exi st between the compounds. Thi s
chapter i s goi ng to focus on basi c bondi ng pri nci pl es and i ntermol ecul ar forces
(attracti ons or repul si ons that occur between coval ent or mol ecul ar
compounds). Chapters 7, 8, and 9 wi l l deal wi th the other topi cs.
The fi rst thi ng we need to l ook at i s the stabi l i ty of the atom. Lets begi n thi s
by revi ewi ng some detai l s about el ectron confi gurati ons.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
6
111
LEWIS SYMBOLS
The el ectrons that are responsi bl e for the formati on of chemi cal bonds are the outermost
el ectrons i n an atom, al so known as the val ence el ectrons. Duri ng our present di scussi on,
we are goi ng to l i mi t oursel ves to the representati ve el ements. Later i n the chapter we wi l l
take on the much more chal l engi ng transi ti on el ements. For the representati ve el ements, the
outermost el ectrons are found i n the s and p orbi tal s. G. N. Lewi s devi sed a cl ever method for
di agrammati cal l y representi ng the val ence el ectrons i n an atom. Hi s system uses the symbol
of the el ement, around whi ch dots are pl aced i n symmetri cal patterns. These dots can be used
to better understand the transfer or shari ng of el ectrons i n bond formati on. These structures,
known as el ectron-dot structures, or Lewi s-dot structures, are shown i n Tabl e 6.1. The tabl e
shows the dot structures for the ei ght groups, or fami l i es, of representati ve el ements. Al l dot
structures down a group i n the peri odi c tabl e are the same, wi th the excepti on of He, whi ch
onl y has two el ectrons. So al though i t i s i n group 8A, hel i um woul d have a dot structure
i denti cal to the group 2A el ements.
Al though the dot structures are shown wi th a parti cul ar ori entati on and pl acement of dots,
there i s some fl exi bi l i ty to dot pl acement. The onl y rul e that governs the pl acement of dots i s
that no more than 2 dots can be pl aced next to each other i n a symbol (remember two
el ectrons per orbi tal ). There are some si tuati ons, for exampl e, i n whi ch oxygen woul d be
drawn wi th the symbol or even . The pl acement of dots wi l l become more apparent
when you begi n maki ng Lewi s structures of mol ecul es. Noti ce from the chart above that the
number of dots (and therefore the number of el ectrons) i s equal to the group number of the
el ement. As we begi n to di scuss bondi ng, we wi l l use dot structures to fol l ow the movement of
el ectrons.
TABLE 6.1 DETAILS ABOUT THE VALENCE ELECTRONS FOR THE PERIOD 2 ELEMENTS. THE
DATA IN EACH COLUMN IS APPLICABLE TO ALL REPRESENTATIVE ELEMENTS ON
THE PERIODIC TABLE (EXCEPT He, WHICH WILL HAVE THE SAME INFORMATION
AS GROUP 2A ELEMENTS).
Group
Number
Valence
Electrons
Outer Shell
Electron
Configuration
Lewis Structure
(Period 2)
All Periods are the Same
1A 1 s
1
Li Li
2A 2 s
2
Be Be
3A 3 s
2
p
1
B B
4A 4 s
2
p
2
C C
5A 5 s
2
p
3
N N
6A 6 s
2
p
4
O O
7A 7 s
2
p
5
F F
8A 8 s
2
p
6
Ne Ne
112 PART III: AP Chemistry Review
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OCTET RULE
The nobl e gases have a very stabl e structure. The reason for thi s, i f you remember from
Chapter 4, i s that thei r ful l outer s and p orbi tal s provi de the hi ghest effecti ve nucl ear charge,
whi ch means a very ti ght hol d on el ectrons. I oni zati on energi es for the nobl e gases are the
hi ghest of any group. A cl oser l ook at groups 1A and 7A wi l l al so hel p to see the stabi l i ty of the
nobl e gases. Removal of an outer el ectron from a nobl e gas creates an el ement wi th an
el ectron confi gurati on of a group 7A el ement. The hi gh el ectron affi ni ti es of the el ements i n
these groups are evi dence that these el ements have a very great attracti on for nearby
el ectrons. A nobl e gas wi th the same el ectron confi gurati on as a group 7A el ement woul d have
an even greater attracti on for el ectrons because of the extra proton i n the nucl eus. Because of
thi s, any el ectron that i s removed from a nobl e gas woul d be rapi dl y repl aced from a
surroundi ng atom.
Consi der the opposi te case, the addi ti on of an el ectron. Addi ng an el ectron to a nobl e gas
woul d mean addi ng an el ectron to a hi gher energy l evel (remember that s and p subl evel s are
fi l l ed i n the nobl e gas confi gurati on). Thi s l one el ectron woul d have a si mi l ar confi gurati on to
a group 1A el ement; however, the atom woul d have a l ower effecti ve nucl ear charge (because
i t wi l l have one l ess proton than the correspondi ng group 1A el ement). As a resul t, thi s outer
el ectron woul d be very l oosel y bound to the atom and woul d be stri pped away rapi dl y. Because
the nobl e gas el ectron confi gurati on i s so stabl e, atoms tend to react i n ways that wi l l al l ow
them to achi eve thi s nobl e gas confi gurati on. I n order to achi eve thi s number of el ectrons,
atoms wi l l gai n, l ose, or share el ectrons. And because nobl e gases have ei ght val ence
el ectrons, thi s pattern of reacti ng i s cal l ed the octet rul e.
Whether atoms gai n, l ose, or share el ectrons i s determi ned by a number of factors, the mai n
one bei ng how ti ghtl y they hol d on to thei r el ectrons. Thi nk of i t thi s way: the more ti ghtl y
bound an el ectron i s, the l ess l i kel y i t i s to be taken away from an atom. Conversel y, the l ess
ti ghtl y bound an el ectron i s, the more l i kel y that el ectron i s to be taken away. I t i s i mportant
to remember, however, that el ectrons dont just fal l off or jump on to atoms i n a vacuumthey
have to come from somewhere and they must go somewhere. When we say that a sodi um atom
l oses an el ectron, what must al so be understood i s that some other atom took that el ectron
away from sodi um. And, at an even deeper l evel , that other atom must have a pretty strong
attracti on for el ectrons (el ectron affi ni ty or el ectronegati vi ty) to be abl e to do that. Before we
get i nto the more techni cal descri pti ons of i oni c and coval ent bondi ng, however, l ets try to get
a handl e on the mai n i deas.
I f one atom has a very weak attracti on for i ts val ence el ectron(s) (e.g., sodi um, Na), and
another atom has a very strong attracti on for i ts val ence el ectrons (e.g., fl uori ne, F), then the
weakl y hel d el ectron i s l i kel y to be stri pped away from the fi rst atom by the second atom
(fl uori ne wi l l stri p sodi ums val ence el ectron). Thi s wi l l usual l y resul t i n the formati on of an
i oni c bond. I f an atom wi th a weak attracti on for i ts val ence el ectron(s) (e.g., sodi um, Na) i s
around another atom that al so has a weak attracti on on i ts val ence el ectron(s) (e.g., Mg), then
nei ther has enough attracti ve force to take the others val ence el ectron away. Thi s means that
under normal ci rcumstances, these atoms wont react. But i f both atoms have strong
attracti ons for el ectrons, they wi l l attract each others el ectrons. The resul t of thi s type of
atomi c tug-of-war general l y i s that the two atoms wi l l hol d on to each other and share
el ectrons. Thi s type of i nteracti on i s the basi s for a coval ent (or mol ecul ar) bond.
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Chapter 6: Chemical Bonding 113
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IONIC BONDS
I oni c bonds are formed by el ectrostati c attracti ons between opposi tel y charged i ons. These
i ons are formed when atoms of l ow i oni zati on energy (weak attracti on for val ence el ectrons)
l ose one or more el ectrons to atoms wi th hi gh el ectron affi ni ty (strong attracti on for el ectrons).
At thi s poi nt, we can use the octet rul e to gui de us through the process.
Lets begi n wi th a very typi cal and si mpl e exampl ethe formati on of sodi um chl ori de (NaCl ),
ordi nary tabl e sal t. Sodi um i s a group 1A el ement wi th one val ence el ectron. The el ectron
confi gurati on of sodi um i s 1s
2
2s
2
2p
6
3s
1
. The outermost el ectron i n the 3s orbi tal i s weakl y
hel d. Chl ori ne, a group 7A el ement (hal ogen), has seven val ence el ectrons. The el ectron
confi gurati on for chl ori ne i s 1s
2
2s
2
2p
6
3s
2
3p
5
. The outermost el ectrons i n the 3p orbi tal s are
ti ghtl y hel d. Now, remember that the nobl e gas el ectron confi gurati on, s
2
p
6
, i s the most stabl e
el ectron confi gurati on. Careful exami nati on of the el ectron confi gurati ons for sodi um and
chl ori ne wi l l show that the l oss of one el ectron by sodi um wi l l resul t i n thi s confi gurati on, and
the gai n of one el ectron by chl ori ne wi l l al so resul t i n thi s confi gurati on. Sodi um wi l l become
i soel ectroni c (have the same el ectron confi gurati on) to neon, whi l e chl ori ne wi l l become
i soel ectroni c to argon:
Sodi um: 1s
2
2s
2
2p
6
3s
1
2 el ectron 1s
2
2s
2
2p
6
5 stabl e, octet
Chl ori ne: 1s
2
2s
2
2p
6
3s
2
3p
5
1 el ectron 1s
2
2s
2
2p
6
3s
2
3p
6
5 stabl e, octet
Usi ng dot structures to represent thi s equati on, the reacti on l ooks l i ke thi s:
Cl Na Cl Na


The si mpl e transfer of an el ectron does not expl ai n why the two atoms (now i ons) bi nd
together. To expl ai n thi s, we need to l ook at the el ectrostati c i nteracti on between the parti cl es.
Sodi um, upon l osi ng i ts el ectron, becomes a cati on, or posi ti vel y charged i on. Chl ori ne, upon
gai ni ng an el ectron, becomes an ani on, or negati vel y charged i on. When the i ons form, the
resul t i s that a negati vel y charged i on i s next to a posi ti vel y charged i on. These two opposi tel y
charged parti cl es wi l l attract each other, provi di ng the basi s for the bond between the two
i ons. Thi s exampl e was conveni ent because sodi um onl y needed to l ose one el ectron to form an
octet and chl ori ne onl y needed to gai n one. Thi s made for a perfect one-to-one transfer.
However, a si mi l ar process can be used for other atoms that are l ess conveni ent. For exampl e,
take magnesi um and chl ori ne. Magnesi um, wi th a confi gurati on [Ne]3s
2
, must l ose two
el ectrons to become i soel ectroni c to neon. Chl ori ne, as you saw i n the l ast exampl e, onl y needs
one el ectron. So, i f magnesi um i s stri pped of one el ectron by a chl ori ne atom, what becomes of
i ts other el ectron? As we see i n the exampl e bel ow, i t can be stri pped by another chl ori ne
atom. Thi s resul ts i n a compound composed of one magnesi um i on and two chl ori de i ons:
Cl Cl Cl Mg Mg
2
Cl

The same pattern i s fol l owed when other combi nati ons of i ons produce l arger compounds,
l i ke Al Cl
3
.
114 PART III: AP Chemistry Review
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Properties of Ionic Compounds
We saw i n the previ ous exampl es that the i ons are hel d together by el ectrostati c attracti ons.
What you have to remember i s that posi ti vel y charged parti cl es attract any negati vel y
charged parti cl esthey are not speci fi c. Li kewi se, negati vel y charged parti cl es wi l l attract
any posi ti vel y charged parti cl es. As a resul t, when the sodi um i on bi nds to the chl ori de i on, i t
wi l l al so bi nd to any other chl ori de i on i n the vi ci ni ty. The chl ori de i ons bi nd to the sodi um
i ons i n the vi ci ni ty. As a resul t, the i ons begi n sti cki ng together i n l arger cl usters, whi ch we
know as crystal s. These crystal s, composed of cl usters of i ons, are known as sal ts. I n a sal t,
you wont fi nd a si ngl e cati on or ani on, but rather l arge groupi ngs of each. However, as you
saw i n the previ ous exampl e of sodi um chl ori de, the groupi ngs of sodi um and chl ori ne occur i n
one-to-one rati os (because of the octet rul e). What thi s tel l s you i n terms of crystal l i ne
structure i s that whi l e a sodi um chl ori de crystal may contai n vast numbers of sodi um and
chl ori de i ons, they wi l l be found i n a 1:1 rati o. The resul ti ng structures are known as a
crystal l i ne l atti ce:
Sodium ion
Chloride ion
(two-dimensional view)
I n the sol i d state, these substances are unabl e to conduct el ectri ci ty (whi ch requi res a fl ow of
el ectrons). Thi s i s onl y possi bl e when these compounds are i n the mol ten state or when they
are di ssol ved i n sol uti on. The packi ng of the i ons l eads to crystal l i ne structures. The rel ati vel y
strong forces hol di ng the i ons together al so gi ve most of these structures hi gh mel ti ng and
boi l i ng temperatures. The strength of the attracti ve force hol di ng the i ons together i nto the
crystal l i ne l atti ce i s measured by the l atti ce energy, or the energy requi red to separate a
mol e of a sol i d i oni c compound i nto i ts consti tuent gaseous i ons. The l arger the l atti ce energy,
the stronger the attracti on between the i ons.
Transition Metals
Transi ti on metal s do not fol l ow the octet rul e si mpl y because thei r outer el ectron structures
i nvol ve both s and d orbi tal s. The transi ti on metal s form cati ons, so they are al l l osi ng
el ectrons. The typi cal pattern for the l oss of el ectrons i n these el ements i s for the fi rst
el ectron(s) to come out of the s orbi tal and then for al l remai ni ng el ectrons to come out of the
d orbi tal s. I n addi ti on, most of the transi ti on metal s can form more than one type of i on. An
exampl e woul d be copper, whi ch can form i ons of ei ther 1
1
or 2
1
charge.
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Chapter 6: Chemical Bonding 115
www.petersons.com
COVALENT BONDS
Remember, i n i oni c bondi ng, el ectrons from one atom are stri pped away by el ectrons of
another atom. Thi s requi res a l arge di fference i n the amount of attracti on each atom has for
i ts own el ectronsone has to have a very strong attracti on and the other a rel ati vel y weak
attracti on. Typi cal l y, i oni c bonds form between metal s and nonmetal s. However, when both
atoms have rel ati vel y strong attracti ons for el ectrons, nei ther atom can stri p el ectrons away
from the other. I nstead, the el ectrons from one atom are attracted to the other and vi ce-versa.
The orbi tal s of each atom wi l l actual l y overl ap, and the el ectrons wi l l be shared between the
atoms. Thi s process wi l l be descri bed i n much greater detai l i n Chapter 7.
There are two mai n ways that these el ectrons can be shared, and these wi l l determi ne the
characteri sti cs of each mol ecul e formed. Each of these two ways can be descri bed by way of an
anal ogy between shari ng el ectrons and a tug-of-war game. The fi rst type of shari ng i nvol ves
an equal shari ng of el ectrons between atoms. That i s, one atom attracts the other atoms
el ectrons wi th the same amount of force that the other atom attracts i ts el ectrons. I n the
tug-of-war anal ogy, thi s woul d be equi val ent to havi ng two evenl y matched teams. Each si de
i s pul l i ng on the rope wi th the same amount of force, and as a resul t, the teams are bound
together, but there i s no movement i n ei ther di recti on. Thi s type of shari ng produces what are
known as nonpol ar coval ent bonds. O
2
, N
2
, and Cl
2
are exampl es of these compounds.
The second type of shari ng i s where one team has a strength advantage over the other, and
the rope begi ns movi ng toward that team. I f the team has a sl i ght advantage over the other,
there wi l l be a sl i ght movement of the rope. I f i t has a l arge advantage, there wi l l be a l arge
movement of one team toward the other. I n the case of coval ent bondi ng, the factor that gi ves
one team an advantage over the other i s the el ectronegati vi ti es of each atom. Recal l from
Chapter 4 that el ectronegati vi ty i s the measure of the strength of the attracti on an atom wi l l
have for the el ectrons of another atom duri ng a chemi cal reacti on. Thi s means that
compounds wi th hi gh el ectronegati vi ti es wi l l have strong attracti ons for el ectrons, and those
wi th l ow el ectronegati vi ti es wi l l have weak attracti ons.
I f we l ook at our fi rst exampl e of the di atomi c el ements, O
2
, N
2
, and Cl
2
, the
el ectronegati vi ti es of each atom are the same (si nce they are the same el ement). We can l ook
at methane gas, CH
4
, to see an exampl e of a weak attracti on. The el ectronegati vi ty for
hydrogen i s 2.1, and for carbon i t i s 2.5. The di fference between carbon and hydrogen i s
rel ati vel y smal l ; therefore, the carbon atom wi l l have onl y a sl i ghtl y stronger attracti on for
hydrogens el ectrons than hydrogen wi l l have for carbons. Thi s uneven shari ng of el ectrons i s
known as pol ari ty. Hydrogen i s sl i ghtl y posi ti ve and carbon i s sl i ghtl y negati ve. I f we l ook at
the case of water, we see a much greater di fference i n el ectronegati vi ti es. Oxygen has an
el ectronegati vi ty of 3.5, whi ch i s much l arger than hydrogens 2.1. Consequentl y, water i s a
much more pol ar mol ecul e than methane. So, pol ari ty vari es accordi ng to di fferences i n
el ectronegati vi ti es. On one end of the spectrum, there are nonpol ar mol ecul es wi th no
di fference i n el ectronegati vi ti es between atoms. As the di fference i n el ectronegati vi ti es
becomes greater, so does the pol ari tythe el ectrons are pul l ed more toward the atom wi th the
hi gher el ectronegati vi ty. Fi nal l y, i f the di fference i n el ectronegati vi ty between atoms becomes
great enough, one atom si mpl y removes the el ectron from the other, resul ti ng i n the formati on
of an i oni c bond.
116 PART III: AP Chemistry Review
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Polarity
I n the l ast secti on, we l earned how pol ar coval ent bonds are formed. Lets l ook at an exampl e
and l earn more of the consequences of formi ng these bonds. When two atoms share el ectrons
unequal l y, they create what i s cal l ed a di pol e. A di pol e i s a mol ecul e that has a sl i ghtl y
posi ti ve end and a sl i ghtl y negati ve end. When two atoms form a pol ar coval ent bond, the
more el ectronegati ve el ement acqui res a hi gher el ectron densi ty. The l ess el ectronegati ve
el ement acqui res a l ower el ectron densi ty. Thi s unequal di stri buti on of the el ectrons causes
one atom (the more hi ghl y el ectronegati ve) to acqui re a parti al negati ve charge whi l e the
other atom acqui res a parti al posi ti ve charge. I t i s not a ful l negati ve or posi ti ve charge
because the el ectrons are not compl etel y transferred from one atom to the other. A very
common exampl e of a pol ar coval ent bond i s seen i n the water mol ecul e. The hi ghl y
el ectronegati ve oxygen atom attracts the hydrogen atoms el ectrons much more than the
moderatel y el ectronegati ve hydrogen can attract oxygens. As a resul t, we see a parti al
negati ve charge on the oxygen atom and a parti al posi ti ve charge on the hydrogen atoms.
Because of these pol ar bonds, the water mol ecul e i s sai d to be a pol ar mol ecul e:

partial charge

H H
O
Metallic Bonds
I n metal s, the typi cal structure has numerous free-fl oati ng val ence el ectrons that surround
posi ti vel y charged metal i ons. Si nce the el ectrons are free to fl ow, metal s are good conductors
of el ectri ci ty. The atoms i n a metal are not ti ghtl y bound together (as they are i n a sal t).
I nstead they are free to move past one another, whi ch gi ves metal s the property of
mal l eabi l i ty (abl e to be shaped) and ducti l i ty (abl e to be drawn i nto thi n wi re). I oni c sal ts
do not have these properti es and wi l l shatter i f they are hammered or pul l ed.
USING LEWIS STRUCTURES TO DETERMINE MOLECULAR BONDING
I n order to ful l y appreci ate and understand mol ecul ar structure, you wi l l need to be abl e to
construct representati ons of vari ous mol ecul es. One of the easi est ways to do thi s i s usi ng
Lewi s structures. The procedure i s a bi t more compl i cated than for i oni c compounds because
of the i ncreasi ng compl exi ty of coval ent compounds. The basi c procedure for constructi ng
Lewi s di agrams of mol ecul es consi sts of 4 steps:
Determi ne the total number of val ence el ectrons for the enti re mol ecul e. For
el ements, use the group number from the peri odi c tabl e. I n the event that you have
charged components (l i ke pol yatomi c i ons) i n the mol ecul e, add one el ectron for
every negati ve charge on the i on (e.g., for SO
4
22
, add two el ectrons to the total
because the i on has two more negati ve charges than a neutral speci es). For any
posi ti vel y charged components, subtract one el ectron from the total for each posi -
ti ve charge (e.g., for NH
4
1
, subtract one el ectron from the total si nce i t i s goi ng to
be taki ng one away from the total ). I n thi s step, i t doesnt matter where the
el ectrons are comi ng from, just that you know the total .
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NOTE
The lowercase
Greek letter delta
(d) is used to
represent a
partical charge.
Chapter 6: Chemical Bonding 117
www.petersons.com
Wri te a skel eton structure of the mol ecul e. For thi s step, you wi l l need to wri te the
symbol s for each atom i n the mol ecul e and connect each usi ng a pai r of dots or a
dash. Thi s i s one of the more di ffi cul t steps si nce you are not tol d di rectl y whi ch
atom i s attached to whi ch. I n general , the chemi cal formul a i s wri tten i n the same
order that the el ements are connected i n the mol ecul e. When mul ti pl e atoms are
connected to the same atom, the central atom i s usual l y wri tten fi rst (e.g., i n the
CCl
4
mol ecul e, the carbon i s the central atom and the four chl ori ne atoms are
bonded around i t). Very often, the central atom i s the l east el ectronegati ve el ement.
Make octets around al l surroundi ng atoms (not the central atom). Use the octet rul e
to fi l l i n al l 8 dots on al l atoms surroundi ng the central atom (the one excepti on
bei ng hydrogen, whi ch shoul d onl y have two).
Put the rest of the el ectrons on the central atom. The remai ni ng number of
el ectrons i s the total number (from step 1) mi nus the number you pl aced on the
surroundi ng atoms i n step 3. I f you dont have enough el ectrons, you wi l l need to
determi ne i f doubl e or tri pl e bonds are present. I f you have too many el ectrons on
the central atom, dont worry about i t. You wi l l see l ater i n the chapter why thi s i s
possi bl e.
Sample: Draw a Lewi s structure for the mol ecul e CF
4
, carbon tetrafl uori de.
a. Count the total val ence el ectrons. Carbon has 4 and each fl uori ne has 7, for a total
of 4 1 (7 3 4) 5 32
b. A skel eton structure wi l l pl ace the carbon as the central atom, wi th each fl uori ne
atom around i t. Thi s formati on i s chosen because carbon appears fi rst and i s the
l east el ectronegati ve el ement:
F
F
F
F
c. Compl ete the octets around each fl uori ne atom:
C F F
F
F
d. After compl eti ng the octets for each fl uori ne atom, al l 32 el ectrons have been used.
Therefore, youre done.
You Try It!
Draw a Lewi s structure for the mol ecul e PCl
3
.
Answer:
P Cl Cl Cl Cl
Cl
P
Cl
118 PART III: AP Chemistry Review
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Sample: Draw a Lewi s structure for H
2
CO.
a. The total number of val ence el ectrons i s 12. Each hydrogen has 1, the carbon has 4,
and the oxygen has 6. (2 3 1) 1 4 1 6 5 12
b. Thi s skel eton i s a l i ttl e more di ffi cul t, but you wi l l di scover that i n carbon com-
pounds, the carbon i s usual l y the central el ement. Therefore, the skel eton di agram
wi l l l ook l i ke:
C O H
H
C H O or
H
c. Compl ete the val ence shel l s (remember, onl y 2 el ectrons total for hydrogen, so i t
wont get any more):
C O H
H
C H O or
H
d. Counti ng the el ectrons, we determi ne that wi th al l 12 el ectrons used, there i s an
i nsuffi ci ent number for ei ther carbon or oxygen. I f oxygen recei ves an octet, then
carbon i s mi ssi ng two el ectrons. Li kewi se, i f you shi fted the el ectrons so that carbon
had an octet, oxygen woul d be mi ssi ng two. The sol uti on i s to form a mul ti pl e bond.
By creati ng a doubl e bond between oxygen and carbon, al l atoms have an octet:
C O H
H
O or C H
H
You Try It!
Draw the Lewi s structure for carbon di oxi de, CO
2
.
Answer:
C O O or C O O
RESONANCE STRUCTURES
The bondi ng i n some mol ecul es cannot be adequatel y descri bed by one Lewi s structure. An
exampl e i s sul fur tri oxi de, SO
3
. Lets begi n by maki ng a Lewi s structure of the compound.
a. Count the val ence el ectrons. S 5 6, O 5 6, so 6 1 (3 3 6) 5 24
b. Draw the skel eton mol ecul e:
S O O or S O O
O
O
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Chapter 6: Chemical Bonding 119
www.petersons.com
c. Compl ete the octets:
S or S O O O O
O
O
d. After compl eti ng thi s porti on, you may note that sul fur does not have an octet, whi ch
requi res you to create mul ti pl e bonds. You may al so noti ce that i n creati ng the
mul ti pl e bonds, there are actual l y three confi gurati ons that are equal l y possi bl e:
O
O O O
S
O
O O
S
O
O
S
So, whi ch structure shoul d be drawn? The answer i s al l three. Experi mental evi dence
suggests that somethi ng di fferent happens i n mol ecul es l i ke SO
3
the measured bond l engths
between each S and O are actual l y somewhere i n between the l ength of a si ngl e and doubl e
bond. What i s bel i eved to happen i n mol ecul es such as thi s i s a process known as
del ocal i zati on, or resonance. The el ectrons shown i n the doubl e bond actual l y spread out
so that they are equal l y shared among al l consti tuents. Thi s i s the onl y expl anati on that
seems to account for the i ntermedi ate bond l engths. When drawi ng resonance structures, i t i s
appropri ate to draw al l possi bl e Lewi s structures. When l ooki ng at them, you shoul d thi nk of
them as bei ng superi mposed on one another as opposed to bei ng three di sti nct, i sol ated states.
Exceptions to the Octet Rule
Of course, now that youre getti ng the hang of i t, you need to know about those ever-present
excepti ons to the rul e. There are some cases i n whi ch the octet rul e i s not obeyed. You shoul d
be fami l i ar wi th the exampl es, and there are some patterns you can l earn to hel p you
memori ze thi s.
ODD NUMBERS OF ELECTRONS
Some mol ecul es and i ons have an odd number of el ectrons. That i s, after al l el ectrons are
pai red up as bondi ng pai rs or l one pai rs, there i s an extra el ectron. The most common
exampl es of these compounds contai n ni trogen, such as NO and NO
2
.
MOLECULES WITH FEWER THAN EIGHT VALENCE ELECTRONS
There are a few mol ecul es i n whi ch an atom wi l l have l ess than ei ght val ence el ectrons. The
most common exampl es of these contai n H, Be, B, and Al . For exampl e, boron tri fl uori de, BF
3
,
has a central boron atom surrounded by three fl uori ne atoms. After fi l l i ng the octets around
the fl uori ne atoms, there are two possi bl e sol uti ons. One i s to l eave boron wi th onl y si x
val ence el ectrons, whi l e the second i s to draw resonance structures for the mol ecul e.
120 PART III: AP Chemistry Review
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Experi mental data suggests that the fi rst sol uti on i s more correct because the bond l engths
i ndi cate si ngl e bonds:
F
F
F B or
F
F
F F B
F
F
F B
F
F
B
MOLECULES WITH MORE THAN EIGHT VALENCE ELECTRONS
These are the most common excepti ons to the octet rul e. I n these mol ecul es, the atoms use
empty d orbi tal s to hol d more than ei ght val ence el ectrons. These tend to form from l arge
central atoms surrounded by smal l , hi ghl y el ectronegati ve el ements (such as F, Cl , and O).
Some common exampl es are PF
5
and SF
6
:
F
F
F
F P
F
F
F
F
F
F
S
F
INTERMOLECULAR FORCES
The pol ari ty of mol ecul es l i ke water has very si gni fi cant effects on the behavi or of these
compounds. I f you recal l i n i oni c compounds, the opposi tel y charged i ons attract each other
and form l arge crystal l i ne structures. A si mi l ar process occurs between pol ar mol ecul es, but
we descri be these as i ntermol ecul ar forces. There are three mai n i ntermol ecul ar forces we
need to exami ne. Al l three of these forces are known as van der Waal s forces and are
speci fi cal l y cal l ed hydrogen-bondi ng forces, di pol e-di pol e i nteracti ons, and London di spersi on
forces.
Hydrogen Bonding
Hydrogen bondi ng wi l l be seen i n si tuati ons i n whi ch a hydrogen atom i s bonded to a smal l ,
hi ghl y el ectronegati ve el ement wi th l one pai r el ectrons. I n hydrogen bonds, the hydrogen
atom (wi th i ts parti al posi ti ve charge), wi l l be attracted to the l one pai r el ectrons of the
nearby parti al l y negati ve atom. One of the more common and si gni fi cant pl aces where
hydrogen bondi ng occurs i s the water mol ecul e. I f two water mol ecul es are near each other,
the parti al l y posi ti ve hydrogen atoms wi l l be attracted to the l one-pai r el ectrons of the nearby
parti al l y negati ve oxygen atoms. These el ectrostati c attracti ons wi l l cause weak bonds to form
between the water mol ecul es. Hydrogen bonds, whi ch are weak compared to coval ent or i oni c
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Chapter 6: Chemical Bonding 121
www.petersons.com
bonds, are the strongest of the i ntermol ecul ar forces. They are responsi bl e for a number of
i mportant chemi cal phenomena, some of whi ch are l i sted i n Tabl e 6.2.
H H
O
H
H
O
O H H H
H
H
O
H-bond
H-bonds
Dipole-dipole Interactions
Di pol e-di pol e i nteracti on i s sti l l caused by forces between pol ar mol ecul es. However, thi s ti me
the mol ecul es are not l i mi ted to hydrogen-contai ni ng mol ecul es. Any pol ar mol ecul e can be
attracted to any other pol ar mol ecul e. Li kewi se, i ons wi l l al so be attracted to pol ar mol ecul es.
The strength of these attracti ons wi l l vary wi th the pol ari ty of the mol ecul es and wi l l
determi ne many physi cal properti es si mi l ar to those l i sted i n Tabl e 6.2. I n a di pol e-di pol e
i nteracti on, the atoms wi th parti al posi ti ve charges are attracted to nearby atoms wi th parti al
negati ve charges (or l one-pai r el ectrons).
London Dispersion Forces
London di spersi on forces are the weakest of the i ntermol ecul ar forces and occur between al l
mol ecul es. These are the onl y types of i ntermol ecul ar forces that are possi bl e between
nonpol ar mol ecul es and are caused by momentary di pol es. Experi mental evi dence suggests
that el ectrons are not symmetri cal l y di stri buted about the nucl eus at al l ti mes. On average,
the el ectrons may be spread out evenl y around the nucl eus, but there are bri ef i nstants when
the el ectron densi ty may be greater on one si de of the atom than another. Duri ng these
peri ods of ti me, the atoms devel op a temporary or i nstantaneous pol ari ty. The temporary
pol ari ty (whi ch i s the cause of the momentary di pol e) al l ows for attracti on between parti cl es
that are normal l y nonpol ar. London di spersi on forces tend to i ncrease as the si ze and mass of
the mol ecul e i ncrease.
TABLE 6.2 EXAMPLES OF THE EFFECTS OF HYDROGEN BONDING.
I ncreased Boi l i ng
Temperatures
A perfect exampl e i s the di fference between methane (CH
4
),
ammoni a (NH
3
), and water (H
2
O). The dramati c di fference i n
boi l i ng temperatures of CH
4
(2162C), NH
3
(233C), and H
2
O
(100C) i s due to the greater hydrogen bondi ng between the more
pol ar mol ecul es.
Surface Tensi on Hydrogen bondi ng i s not responsi bl e for surface tensi on i n al l
substances, but i t i s responsi bl e for i t i n many substances. The
tensi on found on the surface of l i qui ds and the roundi ng of drops
of l i qui ds are due to an uneven amount of hydrogen bondi ng
between the mol ecul es on the surface wi th mol ecul es beneath the
surface and mol ecul es i n the ai r. Thi s uneven attracti on creates a
net force that i s i nward.
122 PART III: AP Chemistry Review
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EXERCISES: CHEMICAL BONDING
Multiple Choice
1. The energy requi red to remove an
el ectron from a gaseous atom i s
known as
(A) acti vati on energy.
(B) free energy.
(C) i oni zati on energy.
(D) ki neti c energy.
(E) l atti ce energy.
2. The energy requi red to separate an
i oni c sol i d i nto gaseous i ons i s known
as
(A) acti vati on energy.
(B) free energy.
(C) i oni zati on energy.
(D) ki neti c energy.
(E) l atti ce energy.
3. For whi ch of the fol l owi ng mol ecul es
are resonance structures necessary to
descri be the bondi ng sati sfactori l y?
(A) H
2
O
(B) SO
2
(C) C
2
H
6
(D) HCN
(E) PF
3
4. Whi ch of the fol l owi ng has the most
pol ar bond?
(A) N
2
(B) F
2
(C) HF
(D) HCl
(E) PCl
3
5. Whi ch of the fol l owi ng woul d most
l i kel y have the hi ghest boi l i ng poi nt?
(A) NH
3
(B) CH
4
(C) PCl
5
(D) HF
(E) Li Cl
USE THESE ANSWERS FOR QUESTIONS 68.
(A) Hydrogen bondi ng
(B) Hybri di zati on
(C) I oni c bondi ng
(D) Resonance
(E) London di spersi on forces
6. I s used to expl ai n why bromi ne
mol ecul es are hel d together i n the
l i qui d state at room temperature
7. I s used to expl ai n why the boi l i ng
poi nt of n-propanol , C
3
H
7
OH, i s
greater than the boi l i ng poi nt of
propane, C
3
H
8
8. I s used to expl ai n the fact that the
S-O bonds i n SO
3
are i denti cal
9. Whi ch of the fol l owi ng el ements, i f
pl aced as the central atom i n a
mol ecul e, i s capabl e of havi ng more
than ei ght val ence el ectrons?
(A) N
(B) F
(C) O
(D) Te
(E) H
10. Whi ch mol ecul e has a Lewi s struc-
ture that does NOT obey the octet
rul e?
(A) NO
(B) CS
2
(C) PF
3
(D) HCN
(E) CCl
4
e
x
e
r
c
i
s
e
s
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Chapter 6: Chemical Bonding 123
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Free Response
Usi ng the pri nci pl es of chemi cal bondi ng and/or i ntermol ecul ar forces, expl ai n each of the
fol l owi ng.
(A) Neon has a boi l i ng poi nt of 2246C, argon has a boi l i ng poi nt of 2186C, and krypton
has a boi l i ng poi nt of 2153C.
(B) I n i ts metal l i c form, copper i s used to make el ectri cal wi re because of i ts excel l ent
conducti vi ty, yet the compound copper I I chl ori de, CuCl
2
, does not conduct el ectri ci ty.
(C) H
2
O has a boi l i ng poi nt of 100C, whi l e the si mi l ar H
2
S has a boi l i ng poi nt of 260C.
(D) The mel ti ng poi nt data i n the tabl e bel ow:
Melting point data for four lithiumsalts
Substance Melting point (C)
Li F 848
Li Cl 610
Li Br 552
Li I 469
124 PART III: AP Chemistry Review
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ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. C
2. E
3. B
4. C
5. E
6. E
7. A
8. D
9. D
10. A
1. The correct answer is (C).
2. The correct answer is (E).
3. The correct answer is (B). S O O S O O
4. Thecorrect answer is(C). H and F have the greatest di fference i n el ectronegati vi ti es.
5. The correct answer is (E). Li Cl i s an i oni c sol i d. The others, al l mol ecul ar
compounds, wi l l have l ower boi l i ng poi nts.
6. The correct answer is (E). Bromi ne, Br
2
, i s a nonpol ar mol ecul e. The onl y
i ntermol ecul ar forces that are possi bl e are London di spersi on forces. The l arger the
mol ecul e, the more i nteracti ons that are possi bl e between atoms/mol ecul es.
7. The correct answer is (A). The propane mol ecul e i s essenti al l y nonpol ar. The pol ar
OH bond i n propanol al l ows for the formati on of hydrogen bonds that wi l l i ncrease i ts
boi l i ng poi nt.
8. The correct answer is (D). SO
3
has three resonance structures. The concept of
resonance expl ai ns why al l three of these bonds are i denti cal as opposed to havi ng one
shorter S5O doubl e bond and two l onger S-O si ngl e bonds.
9. Thecorrect answer is(D).Te i s the onl y one wi th dorbi tal s capabl e of an expanded octet.
10. Thecorrect answer is (A). NO has an odd number of el ectrons. I t cant obey the octet
rul e. N O
Free Response
(A) Neon, argon, and krypton al l are nobl e gases wi th i ncreasi ng atomi c number. London
di spersi on forces are responsi bl e for the i ntermol ecul ar forces that can cause attrac-
ti ons between the atoms. Di spersi on forces i ncrease as the si ze of an atom i ncreases.
(B) The metal l i c bonds al l ow for free movement of val ence el ectrons wi thi n el emental
copper. Thi s al l ows greater conducti vi ty. Copper chl ori de, on the other hand, i s an i oni c
sol i d, where the el ectrons are al l hel d ti ghtl y wi thi n the crystal l i ne structure of the
compound. Ti ghtl y bound el ectrons cant support the fl ow of el ectri c current.
(C) Al though the mol ecul es are structural l y si mi l ar, the pol ari ty of the bonds i n each i s
dramati cal l y di fferent. Oxygen i s a much more el ectronegati ve el ement than sul fur.
Therefore, the pol ari ty of each OH bond i s much hi gher than the pol ari ty of the S-H
bonds. Thi s al l ows for a hi gher degree of hydrogen bondi ng between the water
mol ecul es and, hence, a hi gher boi l i ng poi nt.
(D) The trend i n the tabl e i s that l i thi um i s bonded to el ements that become progressi vel y
l arger. For i oni c compounds, the strength of the bonds decreases as atomi c si ze i ncreases.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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Chapter 6: Chemical Bonding 125
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SUMMING IT UP
Lewi s symbol s, or el ectron dot symbol s, are useful ways to represent the val ence el ectrons
i n many el ements.
Atoms form bonds that al l ow them to acqui re a stabl e octet (or ei ght val ence el ectrons).
I oni c bonds, based on el ectrostati c attracti on between opposi tel y charged parti cl es, form
when el ectrons are transferred from one atom to another.
I oni c compounds are crystal l i ne and tend to have hi gh boi l i ng poi nts.
Coval ent bonds form between atoms wi th fai rl y si mi l ar el ectronegati vi ti es. El ectrons are
shared between atoms i n coval ent compounds. When the el ectrons are shared equal l y, the
bond i s nonpol ar, and when they are shared unequal l y, the resul ti ng bond i s pol ar.
Lewi s structures can be used to draw the structures of coval ent compounds. You shoul d
l earn the rul es for drawi ng these structures.
Resonance structures exi st for mol ecul es i n whi ch el ectrons are del ocal i zed.
There are a few notabl e excepti ons to the octet rul e that you shoul d be aware of:
mol ecul es wi th odd numbers of el ectrons, i ncompl ete octets, and expanded octets.
There are three mai n types of i ntermol ecul ar forces you need to be aware of: hydrogen
bondi ng, di pol e-di pol e i nteracti ons, and London di spersi on forces. The fi rst two onl y occur
i n pol ar mol ecul es, whereas di spersi on forces exi st among al l types of mol ecul es.
I ntermol ecul ar forces can be used to expl ai n many physi cal properti es of compounds.
126 PART III: AP Chemistry Review
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Molecular Geometry
OVERVIEW
VSEPR theory
Molecular geometry
Dipole moments
Valence bond theory
Sigma and pi bonds
Molecular orbital theory
Summing it up
Thi s chapter revi ews mol ecul ar geometry and the two mai n theori es of
bondi ng. The model used to determi ne mol ecul ar geometry i s the VSEPR
(Val ence Shel l El ectron Pai r Repul si on) model . There are two theori es of
bondi ng: the val ence bond theory, whi ch i s based on VSEPR theory, and
mol ecul ar orbi tal theory. A much greater amount of the chapter i s based on
val ence bond theory, whi ch uses hybri di zed orbi tal s, si nce thi s i s the pri mary
model addressed on the AP test.
There are a few attri butes of mol ecul es that must be i ncl uded i n a di scussi on
of mol ecul ar geometry. These i ncl ude the three-di mensi onal arrangement of
the atoms, the bond angl es, the bond l engths, and the l ocati ons and effects of
l one pai rs of el ectrons. These i ssues are expl ai ned i n the VSEPR model .
VSEPR THEORY
As i ts name mi ght suggest, VSEPR theory i s based on the assumpti on that
mol ecul es wi l l be constructed i n ways that mi ni mi ze el ectron pai r repul si ons.
That i s, pai rs of el ectrons wi l l repel each other to the farthest possi bl e
di stance. Wi th thi s understandi ng, there are some very cl ear patterns that
emerge when l ooki ng at di fferent types of mol ecul ar structures.
When constructi ng mol ecul ar model s, i t hel ps to revi ew the Lewi s structures
for the mol ecul e. I f you recal l from Chapter 6, Lewi s structures di spl ay two
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
7
127
types of el ectrons: bondi ng pai rs (those shared between atoms) and nonbondi ng pai rs (those
that exi st as l one pai rs on an atom).
Electron-Pair Arrangements
Before l ooki ng at mol ecul ar geometry i t i s hel pful to exami ne the way that VSEPR theory
treats si ngl e atoms. Accordi ng to the theory, the el ectrons are goi ng to ori ent themsel ves as far
away from one another as possi bl e. I n Tabl e 7.1, you wi l l noti ce the effect thi s has on di fferent
amounts of el ectron pai rs.
The Relationship Between Bond Angles and Nonbonding Electrons
The basi c techni que for predi cti ng mol ecul ar geometri es i s to use one of the structures shown
i n Tabl e 7.1 and i nsert atoms i n the posi ti ons of some el ectron pai rs whi l e i nserti ng l one pai rs
for the remai nder. Thi s wi l l automati cal l y recl assi fy some of the el ectron pai rs as bondi ng
pai rs and others as nonbondi ng pai rs. The bondi ng pai rs determi ne the geometry of the
mol ecul e onl y, whi l e the nonbondi ng pai rs wi l l contri bute to the bond angl es. Lets construct
a model of a water mol ecul e:
O H H
Figure7.1
As you can see i n Fi gure 7.1, there are two pai rs of bondi ng el ectrons (one pai r between each
hydrogen and the central oxygen). There are al so two pai rs of nonbondi ng el ectrons. The
el ectron pai rs wi l l ori ent themsel ves i n a tetrahedral confi gurati on. Si nce two of the pai rs of
el ectrons are goi ng to be bonded to hydrogen atoms, the resul ti ng mol ecul e wi l l be a shape
known as bent as shown i n Tabl e 7.2:
Figure7.2
The water mol ecul e hel ps to i l l ustrate two i mportant facets of VSEPR theory: that the
mol ecul ar shape i s not al ways goi ng to be the same as the el ectron pai r geometry and that the
nonbondi ng pai rs of el ectrons tend to have a l arger effect on the overal l mol ecul e and are
drawn l arger as a resul t. Thi s second poi nt about the effect of the nonbondi ng pai rs can be
seen i n Fi gure 7.3 by compari ng the bond angl es of water, ammoni a, and methane agai nst
the predi cted bond angl es of 109.5 (the predi cted angl e for a tetrahedral arrangement
of el ectrons):
Figure7.3
128 PART III: AP Chemistry Review
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TABLE 7.1 ARRANGEMENTS OF ELECTRONS AROUND CENTRAL ATOMS
Electron
Pairs Electron-Pair Arrangement Geometry
Bond
Angles
2 Li near 180
3 Tri gonal pl anar 120
4 Tetrahedral 109.5
5
Tri gonal
bi pyrami dal
120
90
6 Octahedral
90
180
Each of these mol ecul es has a tetrahedral arrangement of el ectrons. The di fference between
them i s the number of nonbondi ng pai rs i n the mol ecul e. As you have just seen, water has two
nonbondi ng pai rs of el ectrons and two bondi ng pai rs. Ammoni a (NH
3
) has one nonbondi ng
pai r and three bondi ng pai rs. Methane (CH
4
) has no nonbondi ng pai rs and four bondi ng pai rs.
As you can see i n Fi gure 7.3, the bond angl es between hydrogen atoms i n methane are i ndeed
109.5. However, ammoni a i s onl y 107, whi l e water i s 104.5. The accepted expl anati on for
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NOTE
Remember from
Chapter 6 that
there are some
atoms that have
more than an
octet around
them.
Chapter 7: Molecular Geometry 129
www.petersons.com
thi s phenomenon i s that the nonbondi ng el ectrons have a l arger repul si ve force than the
bondi ng el ectrons. As a resul t, the bondi ng el ectrons between the hydrogen atoms and the
central atoms are squeezed more ti ghtl y together. The more nonbondi ng pai rs, the greater
the decrease i n bond angl e. Thi s same effect can be seen wi th mul ti pl e bonds. Mul ti pl e bonds
al so have the effect of compressi ng bond angl es by exerti ng a greater repul si ve force on
nei ghbori ng el ectrons.
MOLECULAR GEOMETRY
The shapes of most mol ecul es can be predi cted usi ng the si x model s for el ectron pai r
arrangements. What you need to do for each one i s:
Determi ne the number of el ectron pai rs on the central atomthi s determi nes the
el ectron pai r arrangements.
Determi ne the number of bondi ng pai rs and nonbondi ng pai rs on the central atom.
You cannot i gnore the nonbondi ng pai rs around the central atom when
determi ni ng the shape of the mol ecul e (si nce they have a l i ttl e more repul si ve
strength and change the shape of the mol ecul e). The nonbondi ng pai rs wi l l al so
become si gni fi cant i f you need to determi ne i nformati on about bond angl es.
Tabl e 7.2 l i sts representati ve structures and exampl es. One thi ng to note that wi l l save you
some ti me memori zi ng i nformati on i s that for mol ecul es wi th no nonbondi ng pai rs, the
mol ecul ar geometry i s i denti cal to the el ectron pai r geometry.
Samples: Determi ne the mol ecul ar geometri es of the fol l owi ng mol ecul es:
a. CF
4
b. TeF
4
c. KrF
2
Answers:
a. Drawi ng a Lewi s structure l ets you know qui ckl y that there are four pai rs of
el ectrons surroundi ng the central atom and no nonbondi ng pai rs. Therefore,
the structure wi l l be tetrahedral .
b. Te has si x val ence el ectrons. The Lewi s structure shoul d i ndi cate that four of
these wi l l be i n bondi ng pai rs wi th the fl uori ne atoms and the remai ni ng two
wi l l exi st as a nonbondi ng pai r. Therefore, the structure shows fi ve el ectron
pai rs, one of whi ch i s nonbondi ng, i ndi cati ng a seesaw shape.
c. Kr has ei ght val ence el ectrons. The Lewi s structure shoul d i ndi cate that two
of these wi l l be used i n bonds wi th fl uori ne atoms, l eavi ng si x. These si x wi l l
form three nonbondi ng pai rs. Therefore, there are fi ve el ectron pai rs, two
of whi ch are bondi ng and three of whi ch are nonbondi ng. The structure
i s l i near.
130 PART III: AP Chemistry Review
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TABLE 7.2
Electron
Pairs
Electron-Pair
Arrangement
Bonding
Pairs
Nonbonding
Pair
Molecular
Geometry
Example
2 2 0
CO
2
BeH
2
3
3 0
BCI
3
SO
3
2 1 SnCl
2
4
4 0 CH
4
3 1 NH
3
2 2 H
2
O
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Chapter 7: Molecular Geometry 131
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TABLE 7.2 ( c ontinue d )
Electron
Pairs
Electron-Pair
Arrangement
Bonding
Pairs
Nonbonding
Pair
Molecular
Geometry
Example
5
5 0 PCl
5
4 1 SF
4
3 2 Cl F
3
2 3 XeF
2
132 PART III: AP Chemistry Review
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TABLE 7.2 ( c ontinue d )
Electron
Pairs
Electron-Pair
Arrangement
Bonding
Pairs
Nonbonding
Pair
Molecular
Geometry
Example
6
6 0 SF
6
5 1 BrF
5
4 2 XeF
4
You Try It!
Determi ne the mol ecul ar geometri es of the fol l owi ng mol ecul es:
1. H
2
Se
2. BrF
3
3. SCl
4
Answers:
1. bent
2. T-shaped
3. seesaw
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Chapter 7: Molecular Geometry 133
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DIPOLE MOMENTS
I n Chapter 6, you l earned about di pol es. A natural extensi on of that topi c i s a di scussi on of the
di pol e moment. I f you recal l , a di pol e i s created when there i s an uneven di stri buti on (or
shari ng) of el ectrons i n a coval ent bond between atoms of unequal el ectronegati vi ti es. The
strength of a di pol e depends partl y on the degree of di fference i n el ectronegati vi ti es between
the two atoms. That i s, for two atoms whose di fferences i n el ectronegati vi ti es are rather l arge,
l i ke H and F, the magni tude of the di pol e wi l l be l arger than that of a bond between H and O
(i n whi ch the el ectronegati vi ty di fference i s not as l arge).
Di pol es, i n addi ti on to havi ng a certai n si ze, al so exi st i n speci fi c di recti ons. For exampl e, the
di pol e between H and F poi nts toward F si nce F has a l arger el ectronegati vi ty and draws the
el ectron densi ty toward i tsel f. So the di pol e has both a si ze and a di recti on. Measurements
that possess both a si ze and a di recti on are known as vectors. The magni tude of the di pol e i s
usual l y expressed as the di pol e moment. A di pol e moment i s defi ned as the product of the
charge, Q, ti mes the di stance between the charges, r:
Di pol e moment 5 Q 3 r
The uni t of measure for di pol e moments i s known as a debye (D).
You are not asked to cal cul ate the di pol e moment on the AP test, but you do need to
understand what i t represents and how to work wi th i t. What fol l ows i s a descri pti on of the
types of i nformati on that usual l y appear on the AP test for di pol e moments.
Working with Vectors
I f you are l ooki ng at the di pol es i n a di atomi c el ement, l i ke O
2
, you shoul d qui ckl y noti ce that
there i s no di pol e moment. One oxygen atom pul l s the other el ectrons toward i t wi th a certai n
amount of force, but the other atom pul l s back wi th an equal amount of force. Therefore, there
i s no net force between the two oxygen atomsthe forces cancel . For two di fferent atoms, such
as H and F, the el ectrons are defi ni tel y pul l ed more toward F than back toward H. As a resul t,
there i s a di pol e moment toward the F i n Fi gure 7.4:
H F
Figure7.4
Any di atomi c mol ecul e contai ni ng two di fferent el ements wi l l have a di pol e moment. More
compl ex mol ecul es have to be careful l y consi dered before determi ni ng thei r di pol e moments.
For exampl e, l ets compare the mol ecul es CO
2
and H
2
O. Both contai n three atoms, but the
di pol e moments are very di fferent. As you just l earned i n the previ ous secti on, CO
2
has a
l i near mol ecul ar geometry. Si nce C and O have di fferent el ectronegati vi ty val ues, there wi l l
be a di pol e between C and O. However, a cl oser l ook at the mol ecul e, the di pol es, and the
geometry reveal the nature of the di pol e momenti n Fi gure 7.5:
O C O
Figure7.5
134 PART III: AP Chemistry Review
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NOTE
The dipole mo-
ment equation is
derived from Cou-
lombs law, which
states that force is
equal to the prod-
uct of the charges
on twoparticles di-
vided by the
squared distances
between them,
F 5 k
q
1
q
2
r
2
, where k
is a constant, q
1
and q
2
represent
the electrical
charges on two
charged particles,
and r
2
is the
squared distance
between the par-
ticles. Coulombs
law helps to deter-
mine the amount
of electrostatic at-
traction (or repul-
sion) between
charged particles.
But it is not neces-
sary for youtowork
with this equation.
www.petersons.com
Because the magni tude of each di pol e i s equal and thei r di recti ons are exactl y opposed to one
another, the two vectors cancel each other out. Therefore, the CO
2
mol ecul e has no di pol e
moment. Now, consi der the H
2
O mol ecul e. Si nce there i s an el ectronegati vi ty di fference
between H and O, there wi l l be a di pol e between each H and the oxygen atom. However, the
mol ecul ar geometry of the water mol ecul e i s bent. Thi s means that the vectors l ook l i ke the
ones i n Fi gure 7.6:
O
H H
Figure7.6
I n thi s mol ecul e, the vectors are not opposi te each other and therefore do not cancel
each other out. They wi l l add together to produce a net di pol e moment for the mol ecul e i n
Fi gure 7.7:
O
H H
Figure7.7
A geometry that has angl es i n i t does not necessari l y mean the mol ecul e has to have a di pol e
moment. Take, for i nstance, BF
3
. The mol ecul ar geometry for thi s mol ecul e i s tri gonal pl anar.
There i s a di fference i n el ectronegati vi ti es between boron and fl uori ne, so there wi l l be di pol es
between boron and fl uori ne. I f you consi der the mol ecul ar geometry, however, you wi l l noti ce
that the di pol es cancel each other out, gi vi ng the BF
3
mol ecul e a di pol e moment of zero i n
Fi gure 7.8:
F
F F
B
Figure7.8
There are a few other i tems worth menti oni ng about di pol e moments. I n addi ti on to the
geometry of the mol ecul e, you must consi der the presence of nonbondi ng el ectrons.
Nonbondi ng el ectrons al so create a shi ft i n el ectron densi ty away from an atom and toward
the nonbondi ng pai r. These l one pai rs wi l l affect any mol ecul es that contai n nonbondi ng
el ectrons. For exampl e, i f you l ook at the mol ecul e NF
3
, you mi ght expect to see a rather l arge
di pol e moment. The shape of the mol ecul e i s tri gonal pyrami dal . Si nce there i s a substanti al
el ectronegati vi ty di fference between N and F, the di pol es wi l l be toward each fl uori ne atom.
Therefore, there wi l l be three di pol es movi ng downward, away from the ni trogen atom i n
Fi gure 7.9:
N
F F
F
Figure7.9
The di pol e moment of the NF
3
mol ecul e, however, i s rather smal l , onl y about 0.2 D. The factor
that reduces the effect of the fl uori ne atoms i s the nonbondi ng pai rs, whi ch al so create a force
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Chapter 7: Molecular Geometry 135
www.petersons.com
goi ng upward (or opposi te the net force of the fl uori ne atoms). Thi s i s nearl y enough to cancel
the force of the fl uori ne atoms i n Fi gure 7.10:
Figure7.10
Al so, mol ecul es are consi dered pol ar i f they have a di pol e moment and nonpol ar i f they have
no di pol e moment. You coul d say that mol ecul es that are pol ar have a di pol e moment, and
mol ecul es that are nonpol ar do not have a di pol e moment.
The AP test does not ask you to cal cul ate the di pol e moments of any mol ecul es. What i t does
askal most every yearare questi ons such as Whi ch of the fol l owi ng has the greatest di pol e
moment or Whi ch of the fol l owi ng has no di pol e moment. To answer those questi ons, you
have to consi der the geometry and the si ze of the attracti ons between the atoms.
Sample: Of the fol l owi ng mol ecul es, whi ch has the l argest di pol e moment?
a. CN
2
b. CO
2
c. N
2
d. HF
e. F
2
Answer: HF i s correct. N
2
and F
2
can be rul ed out i mmedi atel y si nce they are di atomi c
mol ecul es and nonpol ar. CO
2
i s the onl y tri atomi c mol ecul e here, but i t i s a l i near
mol ecul e, and therefore i t i s nonpol ar. Between CN
2
and HF, the el ectronegati vi ty
di fferences between H and F are far greater than between C and N. Therefore, the
di pol e wi l l be much l arger between those two, creati ng a l arger di pol e moment.
136 PART III: AP Chemistry Review
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www.petersons.com
You Try It!
Whi ch of the fol l owi ng has a zero di pol e moment?
1. HCN
2. H
2
S
3. SO
2
4. NO
5. PF
5
Answer: PF
5
VALENCE BOND THEORY
The VSEPR model makes some assumpti ons. Pri mari l y, i t assumes that orbi tal s from
nei ghbori ng atoms overl ap and el ectrons are shared wi thi n the common regi on of space.
Another assumpti on i s that onl y unpai red el ectrons are i nvol ved i n bondi ng. Thi s l atter
assumpti on i s where thi ngs get a bi t sti cky, so an al ternati ve approach i s needed. Take the
fl uori ne atom, for i nstance, whose orbi tal di agram i s shown i n Fi gure 7.11:
Figure7.11
Fl uori ne has one unpai red el ectron and, as you know, forms one bond. Si mi l arl y oxygen,
whose orbi tal di agram i s
1s 2s 2p 22
Figure7.12
has two unpai red el ectrons and forms two bonds (see Fi gure 7.12). Fol l owi ng thi s l ogi c, you
woul d expect that carbon, whose orbi tal di agram i s
1s 2s 2p 22
Figure7.13
woul d onl y form two bonds (see Fi gure 7.13). However, i t i s very rare that thi s occurs. Carbon
most often forms four bonds. So, i s the assumpti on about unpai red el ectrons i ncorrect, or i s
somethi ng el se goi ng on? I t turns out that somethi ng el se seems to be goi ng on (though there
i s sti l l a fai r amount of argument about thi s). For your purposes on the AP test, you can
assume that what fol l ows i s an acceptabl e expl anati on.
The answer comes from a process known as hybri di zati on of orbi tal s. The basi c premi se i s
that i n order to gai n the stabi l i ty of addi ti onal coval ent bonds, some el ectrons can be
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Chapter 7: Molecular Geometry 137
www.petersons.com
promoted to hi gher orbi tal s i n the same energy l evel . Whi l e some energy i s requi red to
promote el ectrons to hi gher energy l evel s, the stabi l i ty of the extra bonds compensates
suffi ci entl y to al l ow the process to occur. The four bonds of carbon can be expl ai ned by
showi ng the promoti on of an el ectron to a hi gher orbi tal , as seen i n thi s new orbi tal di agram
of carbon, Fi gure 7.14:
1s 2s 2p 22
Figure7.14
The di agram i ndi cates that there are sti l l separate s and p orbi tal s. Experi mental evi dence
i ndi cates that the bonds formed between carbon and other atoms (for exampl e, four hydrogen
atoms) are al l the same. That i s, they al l behave as though they are the same type of orbi tal .
The accepted expl anati on for thi s i s that the four orbi tal s form a new type of orbi tal known as
a hybri d. I n thi s case, because the new orbi tal s i nvol ve one s orbi tal and three p orbi tal s, the
new orbi tal s are known as sp
3
(pronounced s-p-threedont mi stake i t for an exponent)
hybri di zed orbi tal s, shown i n Fi gure 7.1:
1s sp
3
Figure7.15
Other combi nati ons of hybri d orbi tal s are possi bl e. For exampl e, boron, whose normal orbi tal
confi gurati on i s:
1s 2s 2p 22
normal boron atom
Figure7.16
wi l l promote a 2s el ectron to form hybri d orbi tal s, but there wi l l sti l l be an empty 2p orbi tal
(see Fi gure 7.16). Thi s confi gurati on, whi ch i nvol ves combi ni ng one s orbi tal and two p
orbi tal s, i s known as sp
2
hybri di zati on i n Fi gure 7.17:
1s sp
2
2p 22
hybridized boron atom
Figure7.17
As you may have predi cted, there i s al so an sp hybri di zed orbi tal . An exampl e of thi s can be
seen wi th beryl l i um (whi ch can vi ol ate the octet rul e). The normal beryl l i um orbi tal
confi gurati on i s Fi gure 7.18:
1s 2s 2p 22
normal beryllium atom
Figure7.18
138 PART III: AP Chemistry Review
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After promoti ng one of the s el ectrons to an unoccupi ed p orbi tal , the resul ti ng orbi tal s
become sp hybri ds. Thi s al l ows beryl l i um to form two bonds whi l e l eavi ng two unoccupi ed 2p
orbi tal s i n Fi gure 7.19:
1s 2s 2p 22
hybridized beryllium atom
Figure7.19
As you saw i n Chapter 6, some atoms can vi ol ate the octet rul e by usi ng unoccupi ed d orbi tal s
i n the same energy l evel . Thi s process actual l y occurs by hybri di zati onpromoti ng el ectrons
i nto the unoccupi ed d orbi tal s. For exampl e, l ook at the hybri di zati on of orbi tal s i n the
phosphorus atom as i t i s seen i n PCl
5
i n Fi gure 7.20:
1s 2s 3s 2p 22 3p 3 3d
Normal phosphorus atom
1s 2s sp
3
d 2p 22 3d
Hybridized phosphorus atom
Figure7.20
Thi s type of hybri di zati on i s known as sp
3
d (or dsp
3
, dependi ng on where you l ook). The
remai ni ng type of hybri di zati on, known as sp
3
d
2
(d
2
sp
3
), can be seen i n the hybri di zati on of
sul fur i n the compound sul fur hexafl uori de, SF
6
. I n Fi gure 7.21 bel ow, note how two el ectrons
are promoted to the d orbi tal s:
1s 2s 3s 2p 22 3p 33 3d
Normal sulfur atom
1s 2s sp
3
d
2
2p 22 3d
Hybridized sulfur atom
Figure7.21
Conveni entl y, the shapes of the hybri di zed orbi tal s are i denti cal to the shapes shown i n Tabl e
7.1. A qui ck summary i s shown i n Tabl e 7.3.
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Chapter 7: Molecular Geometry 139
www.petersons.com
Samples: Determi ne the hybri di zati on of the central atom i n the fol l owi ng mol ecul es:
a. CF
4
b. TeF
4
c. KrF
2
Answers:
a. sp
3
c. The central carbon atom has two el ectrons i n the 2s orbi tal and two
unpai red el ectrons i n the 2p orbi tal s. By promoti ng an el ectron from the s
orbi tal to the unoccupi ed p orbi tal , carbon can form four sp
3
orbi tal s.
b. sp
3
d. The mol ecul e requi res four bondi ng pai rs of el ectrons and one
nonbondi ng pai r. By promoti ng an el ectron to the d orbi tal s, Te wi l l have fi ve
hybri di zed orbi tal s. I n those sp
3
d orbi tal s, one wi l l contai n a pai r of el ectrons
(the l one pai r), whi l e the other four wi l l contai n unpai red el ectrons (whi ch wi l l
become bondi ng pai rs wi th the fl uori ne atoms).
c. sp
3
d. By promoti ng one el ectron to a d orbi tal , krypton wi l l have two unpai red
el ectrons (that can bond to fl uori ne). The three remai ni ng sp
3
d orbi tal s wi l l be
fi l l ed by nonbondi ng pai rs of el ectrons.
You Try It!
Determi ne the hybri di zati on of the central atom i n the fol l owi ng mol ecul es:
1. AsF
5
2. BF
3
3. Si Cl
4
Answers:
1. sp
3
d
2. sp
2
3. sp
3
TABLE 7.3
Hybridization
Number of
Hybridized Orbitals Geometry
sp 2 Li near
sp
2
3 Tri gonal pl anar
sp
3
4 Tetrahedral
sp
3
d 5 Tri gonal bi pyrami dal
sp
3
d
2
6 Octahedral
140 PART III: AP Chemistry Review
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www.petersons.com
SIGMA AND PI BONDS
The bonds that you have seen so far are al l known as si gma (s) bonds. Si gma bonds are
al most al ways si ngl e bonds that occur by orbi tal s that are di rectl y overl appi ng al ong an axi s.
I n the Fi gure 7.22, noti ce the four exampl es of s bonds. Si gma bonds can form between
nei ghbori ng orbi tal s, whether those are s orbi tal s, p orbi tal s, or hybri d orbi tal s:
Figure7.22
The other type of bond that can form i s a pi (p) bond. Pi bonds are the type of bonds that
make up mul ti pl e bonds and are formed when p orbi tal s on nei ghbori ng atoms al i gn wi th one
another i n a paral l el fashi on. The el ectrons i n the p orbi tal s di stri bute themsel ves above and
bel ow the axi s (where the s bond has occurred). Pi bonds are weaker than si gma bonds. Atoms
that have onl y si ngl e avai l abl e p orbi tal s can form a si ngl e p bond, where atoms wi th two
avai l abl e p orbi tal s can form two p bonds. The formati on of pi bonds prevents mol ecul es from
rotati ng around the i nternucl ear axi s i n Fi gure 7.23:
Figure7.23
I n summary, s bonds form si ngl e bonds and are much stronger than p bonds. Doubl e bonds
contai n one s bond and one p bond. Tri pl e bonds are composed of one s bond and two p bonds.
Sample: Ethyl ene gas, used i n the ri peni ng of frui ts, has the formul a CH
2
CH
2
. How many
s and p bonds are present i n the mol ecul e?
Answer: I f you construct a Lewi s di agram, you can see that the structure of the ethyl ene
mol ecul e contai ns si ngl e bonds between each carbon and two hydrogens and a
doubl e bond between the two carbon atoms. Therefore, between each carbon and
hydrogen there i s one s bond, for a total of four. Between the carbon atoms, there i s
one s bond and one p bond. I n al l , that makes fives bonds and onep bond.
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Chapter 7: Molecular Geometry 141
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You Try It!
Li st the number and types of bonds found i n a mol ecul e of hydrogen cyani de, HCN.
Answer: Two s bonds and two p bonds are found i n a mol ecul e of hydrogen
cyani de, HCN.
Bond Length, Bond Order, and Bond Dissociation Energy
Compl ete coverage of these topi cs woul d get a bi t compl i cated at thi s poi nt. The AP test does
not cover these at a very great depth, so you wi l l onl y need a general i dea of the topi cs to be
successful . Bond l ength i s the measured di stance between the nucl ei of the atoms i nvol ved i n
the bond. Bond order i s the number of pai rs of el ectrons i n a bond. For exampl e, i n a H-H
bond, the bond order i s 1; i n a O5O bond, the bond order i s 2; and i n a N[N bond, the bond
order i s 3. Bond di ssoci ati on energy (al so known as bond enthal py) i s the amount of
energy necessary to break a chemi cal bond (energy i s al ways requi red to break a chemi cal
bond). The mai n i dea i s that the more ti ghtl y atoms are bound together, the shorter the bond
becomes and the l arger the bond di ssoci ati on energy becomes. As a general rul e, thi s means
that as the number of bonds between two atoms i ncreases (that i s, the bond order), the bond
l engths get shorter and the bond energi es greater.
MOLECULAR ORBITAL THEORY
I f you are pressed for ti me, then ski p thi s topi c. I t rarel y appears on the AP test, and i t i s
rather compl i cated. However, because i t has appeared on the test and i t i s menti oned i n the
requi red subject matter, i t wi l l be di scussed i n thi s book.
Mol ecul ar orbi tal theory i s an al ternati ve to val ence bond theory that more adequatel y
expl ai ns a few di fferent phenomena. One of the i nadequaci es of the theory i nvol ves
paramagneti c and di amagneti c properti es of mol ecul es. Recal l from Chapter 3 that
paramagneti sm (attracti on to a magnet) resul ts from an odd number of el ectrons, whi l e
di amagneti sm (non-attracti on to a magnet) resul ts from an even number of el ectrons. There
are some cases where a few mol ecul es wi th even numbers of el ectrons are very strongl y
attracted to magnets. Oxygen (O
2
) i s one of the better-known mol ecul es to behave thi s way.
Mol ecul ar orbi tal theory does a much better job expl ai ni ng thi s than val ence bond theory.
A mol ecul ar orbi tal i s an al l owed energy state where el ectrons can be found. Mol ecul ar
orbi tal s form from overl appi ng atomi c orbi tal s. When orbi tal s overl ap, there are two
possi bi l i ti es for the regi on of space between the nucl ei . The fi rst i s that the el ectron densi ty i s
greater i n that regi on than the rest of the orbi tal . When thi s condi ti on occurs, the bond i s
qui te stabl e, whi ch provi des a l ower energy state than the i ndi vi dual orbi tal s possessed pri or
to overl appi ng. Thi s i s known as a bondi ng orbi tal . When orbi tal s exi st al ong an axi s between
the two nucl ei , they are known as s (si gma) bondi ng orbi tal s. I f the orbi tal s that were
overl appi ng were 1s orbi tal s, they woul d be l abel ed s
1s
orbi tal s.
The second possi bi l i ty i s that the el ectron densi ty i n the overl appi ng regi ons between the
nucl ei i s l ess than el sewhere. Thi s regi on now has a hi gher energy than the overl appi ng
142 PART III: AP Chemistry Review
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orbi tal s and i s known as an anti bondi ng orbi tal . Si mi l ar to bondi ng orbi tal s, i f an
anti bondi ng orbi tal exi sts on the i nternucl ear axi s, i t i s l abel ed as s*
1s
. (Note: The * i ndi cates
anti bondi ng.)
Orbi tal di agrams can be created for mol ecul ar orbi tal s much as they were created for atomi c
orbi tal s. Each mol ecul ar orbi tal possesses a certai n amount of energy, and el ectrons are fi l l ed
i nto these orbi tal s usi ng the same rul es as were used for atomi c orbi tal s (aufbau pri nci pl e,
Paul i excl usi on pri nci pl e, and Hunds rul e). You wont need to worry about anythi ng past the
second energy l evel , so you can l ook at a short l i st to determi ne the order of fi l l i ng (from
l owest to hi ghest energi es). The order of fi l l i ng i s:
s
1s
s*
1s
s
2s
s*
2s
p
2p
s
2p
p*
2p
s*
2p
Fi rst, l ets l ook at the si mpl est exampl e, an H
2
mol ecul e. I n thi s mol ecul e, two 1s orbi tal s wi l l
overl ap. The el ectrons wi l l fi l l i n the s
1s
orbi tal , as seen i n Fi gure 7.24:

1s
*
1s
H
2
molecule
Hatom
1s 1s
E
n
e
r
g
y
Figure7.24
Another way to represent thi s i s to use orbi tal di agrams that l ook l i ke atomi c orbi tal
di agrams. The same H
2
mol ecul e can be shown as fol l ows i n Fi gure 7.25:

1s

1s
Figure7.25
Bond Order
Earl i er i n thi s chapter, you l earned the defi ni ti on of bond order i n the val ence bond theory. I n
mol ecul ar orbi tal theory, the bond order i s defi ned as one-hal f the di fference between the
number of el ectrons i n bondi ng orbi tal s and the number of el ectrons i n anti bondi ng orbi tal s.
Mathemati cal l y, thi s can be expressed as
bond order 5
1
2
(n
b
2 n
a
)
where n
b
i s the number of el ectrons i n bondi ng orbi tal s and n
a
i s the number of el ectrons i n
anti bondi ng orbi tal s.
For hydrogen, the bond order i s
1
2
(2 2 0) 5 1. Thi s i s no di fferent from what woul d be
predi cted i n val ence bond theory.
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Chapter 7: Molecular Geometry 143
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Electron Configurations for the Period 2 Diatomic Molecules
To fi ni sh up thi s secti on on mol ecul ar orbi tal theory, l ets l ook at the confi gurati ons for the
el ements from l i thi um to neon. (See Tabl e 7.4.) These shoul d provi de you wi th suffi ci ent
exampl es to see the mai n pri nci pl es behi nd mol ecul ar orbi tal theory.
TABLE 7.4 MOLECULAR ORBITAL CONFIGURATIONS AND OTHER DATA ABOUT PERIOD
2 ELEMENTS. IT IS UNDERSTOOD THAT EACH MOLECULE HAS A COMPLETE s
1s
AND
s*
1s
ORBITAL. NOTE THAT OXYGEN, FLUORINE, AND NEON HAVE A SLIGHTLY
DIFFERENT ORDER DUE TO INTERACTIONS BETWEEN 2s AND 2p ORBITALS.
Substance Configuration
Bond
Order
Bond
Energy
(kJ mol
21
)
Bond
Length
() Magnetism
Li
2
s
2s
s*
2s
p
2p
s
2p
p*
2p
s*
2p
1 110 2.67 Di a-
Be
2
s
2s
s*
2s
p
2p
s
2p
p*
2p
s*
2p
0* 59 * *
B
2
s
2s
s*
2s
p
2p
s
2p
p*
2p
s*
2p
1 297 1.59 Para-
C
2
s
2s
s*
2s
p
2p
s
2p
p*
2p
s*
2p
2 607 1.24 Di a-
N
2
s
2s
s*
2s
p
2p
s
2p
p*
2p
s*
2p
3 945 1.10 Di a-
O
2
s
2s
s*
2s
s
2p
p
2p
p*
2p
s*
2p
2 498 1.21 Para-
F
2
s
2s
s*
2s
s
2p
p
2p
p*
2p
s*
2p
1 159 1.42 Di a-
Ne
2
s
2s
s*
2s
s
2p
p
2p
p*
2p
s*
2p
0* 4 * *
* wi l l not mai ntai n di atomi c structure
144 PART III: AP Chemistry Review
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EXERCISES: MOLECULAR GEOMETRY
Multiple Choice
1. Types of hybri di zati on exhi bi ted by
the C atoms i n acetyl ene, C
2
H
2
,
i ncl ude whi ch of the fol l owi ng?
I . sp
I I . sp
2
I I I . sp
3
(A) I onl y
(B) I I I onl y
(C) I and I I
(D) I I and I I I
(E) I , I I , and I I I
2. Whi ch of the fol l owi ng di atomi c
mol ecul es has the l argest bond-
di ssoci ati on energy?
(A) Li
2
(B) Be
2
(C) B
2
(D) N
2
(E) O
2
3. Whi ch of the fol l owi ng di atomi c
mol ecul es has the shortest bond
l ength?
(A) Li
2
(B) Be
2
(C) B
2
(D) N
2
(E) O
2
4. Whi ch of the fol l owi ng di atomi c
el ements contai ns onl y 1 si gma (s)
and 1 pi (p) bond?
(A) Li
2
(B) Be
2
(C) B
2
(D) N
2
(E) O
2
5. I n a mol ecul e i n whi ch the central
atom exhi bi ts sp
3
d hybri d orbi tal s,
the el ectron pai r arrangements form
the shape of a(n)
(A) tetrahedron.
(B) square-based pyrami d.
(C) tri gonal bi pyrami d.
(D) square.
(E) octahedron.
6. Mol ecul es that have pl anar confi gura-
ti ons i ncl ude whi ch of the fol l owi ng?
I . BF
3
I I . XeF
4
I I I . NH
3
(A) I onl y
(B) I I I onl y
(C) I and I I
(D) I I and I I I
(E) I , I I , and I I I
7. The el ectron-dot structure (Lewi s
structure) for whi ch of the fol l owi ng
mol ecul es woul d have one unshared
pai rs of el ectrons on the central
atom?
(A) H
2
O
(B) NH
3
(C) CH
4
(D) C
2
H
2
(E) CO
2
8. Whi ch of the fol l owi ng mol ecul es has
a tri gonal pyrami dal shape?
(A) PCl
5
(B) N
2
O
(C) NH
3
(D) CCl
4
(E) H
2
O
2
e
x
e
r
c
i
s
e
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Chapter 7: Molecular Geometry 145
www.petersons.com
9. The AsF
5
mol ecul e has a tri gonal
bi pyrami dal structure. Therefore, the
hybri di zati on of As orbi tal s shoul d be
(A) sp
2
(B) sp
3
(C) sp
2
d
(D) sp
3
d
(E) sp
3
d
2
CCl
4
, BeF
2
, PCl
3
, SbCl
5
, XeF
4
10. Whi ch of the fol l owi ng does NOT
descri be any of the mol ecul es above?
(A) Li near
(B) Octahedral
(C) Square pl anar
(D) Tetrahedral
(E) Tri gonal pyrami dal
11. The geometry of the H
2
S mol ecul e i s
best descri bed as
(A) tri gonal pl anar.
(B) tri gonal pyrami dal .
(C) square pyrami dal .
(D) bent.
(E) tetrahedral .
12. Al l of the mol ecul es bel ow di spl ay
sp
3
d hybri di zati on EXCEPT
(A) NF
3
(B) PF
5
(C) SF
4
(D) BrF
3
(E) XeOF
2
13. Pi bondi ng occurs i n each of the
fol l owi ng speci es EXCEPT
(A) N
2
F
2
(B) C
2
H
2
(C) HCN
(D) C
6
H
6
(E) CCl
4
14. Anti bondi ng orbi tal s are found
(A) between the nucl ei of atoms.
(B) surroundi ng the nucl ei of
atoms.
(C) nowhere; they onl y exi st
theoreti cal l y.
(D) on the outsi des of atoms (the
si des opposi te the overl appi ng
regi ons).
(E) above the bondi ng orbi tal s.
15. Whi ch of the fol l owi ng has a di pol e
moment of zero?
(A) CCl
4
(B) HCN
(C) NO
2
(D) NH
3
(E) H
2
O
Free Response
1. Use si mpl e structure and bondi ng model s to account for each of the fol l owi ng.
(A) The bond l ength between the two carbon atoms i s shorter i n C
2
H
2
than i n C
2
H
4
.
(B) The H-O-H bond angl e i s 104.5, as opposed to the expected 109.
(C) The bond l engths i n the ni trate i on, NO
3
2
, are al l i denti cal and shorter than a
ni trogen-oxygen si ngl e bond.
(D) The ethyl ene mol ecul e, C
2
H
4
, does not rotate around the C-C axi s.
2. Di scuss bri efl y the rel ati onshi p between the di pol e moment of a mol ecul e and the pol ar
character of the bonds wi thi n i t. Wi th thi s as the basi s, account for the di fference
between the di pol e moments of CH
2
Cl
2
and CCl
4.
146 PART III: AP Chemistry Review
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ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. A
2. D
3. D
4. E
5. C
6. C
7. B
8. C
9. D
10. B
11. D
12. A
13. E
14. D
15. A
1. Thecorrect answer is (A). Onl y two hybri di zed orbi tal s are formedone for the C-H
bond and the other for the C-C bond. The remai ni ng hal f-fi l l ed p orbi tal s are used to
make the two p bonds, whi ch compl ete the tri pl e bond.
2. The correct answer is (D). Ni trogen has a tri pl e bond and a bond order of 2. Thi s
makes i t the strongest bond, requi ri ng i t to have the l argest bond-di ssoci ati on energy.
3. Thecorrect answer is (D). The tri pl e bond i n ni trogen i s the strongest and wi l l cause
the ni trogen atoms to be the cl osest together.
4. The correct answer is (E). One s bond and one p bond are characteri sti c of a doubl e
bond. The onl y doubl e-bonded di atomi c el ement l i sted as a choi ce i s oxygen.
5. The correct answer is (C).
6. The correct answer is (C). BF
3
has a tri gonal pl anar confi gurati on, and XeF
4
has a
square pl anar confi gurati on. NH
3
has a tri gonal pyrami dal confi gurati on.
7. Thecorrect answer is(B). H
2
O has two pai rs, and al l others have no unshared pai rs.
8. The correct answer is (C).
9. The correct answer is (D). Make sure you read al l choi ces careful l y; choi ce (C) i s a
very cl ose di stracter, but i t represents a nonexi stent hybri di zati on.
10. The correct answer is (B). Be careful on questi ons l i ke thi s. SbCl
5
represents a
tri gonal bi pyrami dal structure, but thi s has been thrown i n as a di stracter. Of the fi ve
answer choi ces, four are representedmeani ng the fi fth choi ce, octahedral , must be the
correct one.
11. The correct answer is (D). Thi s i s a characteri sti c structure for four el ectron pai rs
wi th two nonbondi ng pai rs.
12. The correct answer is (A). Perhaps the bi ggest ti mesavi ng cl ue i s that ni trogen i s
onl y a peri od 2 el ement. Si nce peri od 2 does not have d orbi tal s, i t i s not possi bl e for
ni trogen to promote an el ectron to a d orbi tal to form a bond. The l ong route to sol vi ng
thi s probl em woul d be to determi ne the hybri di zati on of each separatel y.
13. The correct answer is (E). Al l the other choi ces have mul ti pl e bonds.
14. The correct answer is (D). Bondi ng orbi tal s exi st i n the overl appi ng regi on (where
el ectron densi ty i s greatest). Anti bondi ng orbi tal s exi st opposi te thi s regi on, or on the
outsi des of the atoms.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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Chapter 7: Molecular Geometry 147
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15. Thecorrect answer is (A). Al l the other choi ces ei ther contai n bond angl es that wont
al l ow for cancel l ati on of bond di pol es or di fferent atoms (i .e., atoms wi th di fferent
el ectronegati vi ti es).
Free Response
1. (A) C
2
H
2
has a tri pl e bond between the two carbons, whi l e C
2
H
4
has doubl e bonds.
Thi s al l ows for i ncreased overl ap and the formati on of an addi ti onal pi bond. Thi s
has the effect of shorteni ng the bond l ength.
(B) The two nonbondi ng pai rs of el ectrons on the central oxygen atom exert a
stronger repul si ve force than the bondi ng pai rs between oxygen and hydrogen.
Thi s has the effect of pushi ng the hydrogen atoms cl oser together, decreasi ng the
H-O-H bond angl e.
(C) A questi on that i s worded thi s way shoul d be a red fl ag that the test-makers may
be aski ng about resonance structures, whi ch, i n fact, i s happeni ng here. There
are three possi bl e resonance structures. I f the el ectron were l ocal i zed to any one
ni trogen and oxygen, the bond l ength of that bond woul d be shorter than the
other two, and the other two woul d have bond l engths the same as a N-O si ngl e
bond. Del ocal i zati on of the el ectron al l ows for the three resonance structures and
al so creates three equal bonds, each of whi ch i s l ess than a si ngl e bond but
greater than a doubl e bond:
O
O O
N
O
O O
N
O
O
N
(D) The ethyl ene mol ecul e, C
2
H
4
, i s not abl e to rotate around the C-C axi s because
of the presence of the pi bond that forms from the overl ap of the 2p orbi tal s of
each carbon. The pi bonds prevent rotati on and l ock the mol ecul e i nto i ts
pl anar structure.
2. Thi s questi on real l y has at l east two di sti nct parts, the fi rst about di pol e moments,
and the second to address the exampl es.
The di pol e moment of a mol ecul e represents the combi ned effects of the i ndi vi dual
vectors for each pol ar bond. A mol ecul e can have very pol ar bonds, yet no di pol e
moment, i f the confi gurati on of the mol ecul e i s such that the vectors al l cancel . I t i s the
resul tant of the i ndi vi dual vectors that determi nes the moment.
I n the CCl
4
mol ecul e, the i ndi vi dual bond pol ari ti es are rel ati vel y l arge si nce there i s
a l arge di fference i n el ectronegati vi ty between carbon and chl ori ne. However, the
tetrahedral confi gurati on of the mol ecul e causes the i ndi vi dual pol ari ti es to cancel
each other out. Thi s i s not the case i n the CH
2
Cl
2
mol ecul e. Thi s mol ecul e al so has a
tetrahedral geometry, but the forces do not cancel out thi s mol ecul e. The i nteracti ons
between the carbon and hydrogen atoms are i nsuffi ci ent to cancel the di pol es between
carbon and chl ori ne. As a resul t, there i s a di pol e moment for that mol ecul e.
148 PART III: AP Chemistry Review
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www.petersons.com
SUMMING IT UP
VSEPR theory i s the pri mary theory used to expl ai n the structure of most mol ecul es. The
underl yi ng assumpti on i s that mol ecul es form wi th geometri es that try to mi ni mi ze
el ectron-el ectron repul si ons.
There are fi ve mai n structures on whi ch al most al l mol ecul es are based. These are rel ated
to the fi ve geometri es associ ated wi th el ectron pai r arrangements, whi ch are l i near,
tri gonal pl anar, tetrahedral , tri gonal bi pyrami dal , and octahedral .
I n mol ecul es, both nonbondi ng pai rs and mul ti pl e bonds compress bond angl es.
You shoul d become fami l i ar wi th the materi al i n Tabl e 7.2. Duri ng the test, you wi l l need
to be abl e to recogni ze the shapes of many mol ecul es i n a very short peri od of ti me.
A di pol e moment i s a measure of the pol ari ty of a mol ecul e. I ndi vi dual bond pol ari ti es are
determi ned, and then the vectors are used to determi ne the net force.
Val ence bond theory predi cts the hybri di zati on of orbi tal s, whi ch occurs when an atom
promotes an el ectron from a l ower to a hi gher energy l evel i n order to form more bondi ng
pai rs. You shoul d be fami l i ar wi th the fi ve types of hybri di zati ons (sp, sp
2
, sp
3
, dsp
3
,
d
2
sp
3
).
When orbi tal s overl ap, bonds form. When the overl ap i s al ong the i nternucl ear axi s, thi s
i s known as a s (si gma) bond. Si gma bonds can form between s, p, or hybri di zed orbi tal s.
When the overl ap i s between paral l el orbi tal s that l i e perpendi cul ar to the nucl ear axi s,
thi s i s known as a p (pi ) bond.
Si gma bonds are associ ated wi th si ngl e bonds, and pi bonds are associ ated wi th doubl e
and tri pl e bonds.
As the number of bonds between two atoms (bond order) i ncreases, bond l engths get
shorter and bond energi es get greater.
Mol ecul ar orbi tal theory i s an al ternati ve approach to bondi ng than val ence bond theory.
Accordi ng to thi s theory, mol ecul ar orbi tal s form when orbi tal s overl ap. Thi s overl ap
gi ves ri se to bondi ng orbi tal s and anti bondi ng orbi tal s.
Mol ecul ar orbi tal s fi l l i n a prescri bed sequence, al though the sequence can vary based on
the degree of i nteracti on between s and p mol ecul ar orbi tal s (but you dont actual l y need
to know any detai l s about thi s).
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Chapter 7: Molecular Geometry 149
www.petersons.com
States of Matter
Gases
OVERVIEW
Units of measure
The gas laws
The ideal gas law
Gas density
Daltons law of partial pressures
Kinetic-molecular theory
Grahams law of effusion
Deviations from the ideal gas laws
Summing it up
Thi s chapter i s the fi rst of two devoted to speci fi c states of matter, and i n i t
you wi l l focus your attenti on on the gaseous state of matter. However, al l of
the states wi l l be descri bed wi thi n a l arger framework that l ooks at the state
of matter as a seri es of i nterrel ated factors, i ncl udi ng ki neti c energy (or
temperature), pressure, and i ntermol ecul ar forces. Gases are usual l y
descri bed by a seri es of postul ates known as ki neti c mol ecul ar theory, whi ch
consti tute the i deal gas l aw. To begi n the chapter, you wi l l l ook at a hi stori cal
devel opment of the i deal gas l aw, duri ng whi ch you wi l l revi ew some of the
equati ons used to create the i deal gas l aw.
UNITS OF MEASURE
The three uni ts descri bed i n the gas l aws are temperature, vol ume, and
pressure.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
8
151
Temperature
Temperaturei s defi ned as the average ki neti c energy of movi ng parti cl es. I n a hot object, the
parti cl es i n the object are movi ng more (and hence possess more energy) than your hand.
There wi l l be a net fl ow of energy i nto your hand, and your hand wi l l have the sensati on of
hotness. The opposi te i s true of col d objects. Energy fl ows from your hand i nto the object
causi ng a cool i ng sensati on i n your hand.
I n most i nstances, temperature i s measured i n the uni t of C (degrees Cel si us), but for the
descri pti on of any gas, i t i s i mperati ve to use the Kel vi n scal e. The Kel vi n temperature, al so
referred to as the absol ute temperature, bears a di rect rel ati onshi p to ki neti c energy. For
exampl e, 0 K (Note: I t i s not appropri ate to use the symbol ), known as absol ute zero,
represents zero ki neti c energy. A doubl i ng of Kel vi n temperature represents a doubl i ng of
ki neti c energy (e.g., 50 K to 100 K i s twi ce the ki neti c energy). Thi s i s not true for Cel si us
temperatures (50C to 100C i s not a doubl i ng of ki neti c energy.) Absol ute zero, 0 K, i s
2273.15C, so the conversi on from a Cel si us temperature to a Kel vi n temperature i s:
Kel vi n 5 Cel si us 1 273.15
(I t i s suffi ci ent to use 273 i n the probl ems you wi l l have.)
Volume
Vol ume does not need such a l engthy di scussi on. The vol ume of a substance i s si mpl y the
amount of space that i t occupi es. There are numerous uni ts of measure that can descri be
vol ume, i ncl udi ng cubi c centi meters (cm
3
), cubi c meters (m
3
), mi l l i l i ters (mL), and l i ters (L).
One cm
3
i s equal to 1 mL. I deal gas probl ems need to be sol ved i n l i ters, si nce the i deal gas
constant R uses l i ters as a uni t (more on thi s l ater).
Pressure
Pressure i s defi ned as the force per uni t of area, that i s Equati on 8.2:
P
F
A

For gases, thi s force can be a factor of thei r moti on or thei r wei ght. Atmospheri c pressure i s
caused by the wei ght of ai r parti cl es that are attracted toward earth. I nsi de a seal ed
contai ner, pressure i s exerted by the col l i si ons of parti cl es on the si des of the contai ner. By
determi ni ng the force of those col l i si ons on a gi ven area, you can determi ne the pressure
exerted by the parti cl es. There are many uni ts that descri be pressure. The SI uni t of pressure
i s the pascal , Pa. The ki l opascal i s a bi t more practi cal as a uni t, however, si nce a pascal i s
qui te smal l . Other uni ts of pressure i ncl ude mi l l i meters of Hg (mm Hg), torr, bar, and
atmospheres. The rel ati onshi p between the uni ts i s as fol l ows:
1 atm 5 760 mm Hg 5 760 torr 5 1.01 bar 5 101.325 kPa
You mi ght have noti ced that torr and mm Hg have the same val ue. On the AP test, uni ts of
pressure are usual l y expressed as atm i n the i deal gas probl ems (R uses atm as the pressure
uni t) and mm Hg i n parti al pressure probl ems.
152 PART III: AP Chemistry Review
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(Equati on 8.1)
(Equati on 8.2)
TIP
Equation8.1is
providedfor youin
theAPformulas.
Althoughthegas
lawquestions on
theAPtest usually
providethe
temperaturein
Kelvins, youshould
beonthelookout
for degrees
Celsius.
www.petersons.com
THE GAS LAWS
Many of the gas l aw probl ems on the AP test are conceptual questi ons rather than
cal cul ati ons. Make sure you understand each of these topi cs at a conceptual l evel as wel l as at
a mathemati cal l evel .
Boyles Law
One of the earl i est di scoveri es of the behavi or of gases came from Robert Boyl e i n 1661. Boyl e
di scovered that the vol ume of a gas i s i nversel y proporti onal to the pressure pl aced on i t. That
i s, i n a system where vol ume i s al l owed to change, an i ncrease i n pressure wi l l decrease the
vol ume. Li kewi se, i f you thi nk of a cl osed system, such as a cyl i nder wi th a pi ston above i t,
pushi ng down on the pi ston (i .e., decreasi ng the vol ume) wi l l have the effect of i ncreasi ng the
pressure. Thi s rel ati onshi p can be expressed mathemati cal l y as Equati on 8.3:
PV 5 constant
Thi s condi ti on, however, requi res that temperature and the number of gas parti cl es remai n
constant. A change i n ei ther of those wi l l al so change the pressure and vol ume. From a
conceptual perspecti ve, consi der the pi ston as shown i n Fi gure 8.1. I f you thi nk about a fi xed
number of parti cl es i nsi de the chamber, these parti cl es are movi ng about, col l i di ng wi th the
si des of the contai ner. As they do so, they exert a force. Thi s force, as measured per uni t of
area that the parti cl es are stri ki ng, represents the pressure exerted by the gas i nsi de the
pi ston. As the pl unger i s pushed down, note how the densi ty of the parti cl es i ncreases. Thi s
means that the parti cl es, sti l l travel i ng the same speed, wi l l not have to travel as far to col l i de
wi th the si des of the contai ner. As a resul t, the number of col l i si ons they have wi l l i ncrease.
Thi s i ncrease i n col l i si ons wi l l cause an i ncrease i n pressure that i s proporti onal to the change
i n vol ume.
Figure8.1
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(Equati on 8.3)
Chapter 8: States of MatterGases 153
www.petersons.com
Charless Law
The next di scoveri es about gases came from Jacques Charl es, who i n 1787 di scovered what i s
today known as Charl ess l aw. Thi s l aw states that for a fi xed amount of gas at constant
pressure, the rel ati onshi p between vol ume and temperature i s di rectl y proporti onal . Wri tten
as a formul a Charl ess l aw, Equati on 8.4, takes the form:
V
T
5 constant
You probabl y have some fami l i ari ty wi th thi s l aw. Perhaps you have observed a bal l oon
expandi ng on a hot day or a bag of mi crowave popcorn swel l i ng as the contents begi n to
heat up.
Pressure and Temperature Relationships
You may have noti ced that vol ume appears i n both Boyl es and Charl ess l aws. I f we know
that pressure and vol ume are i nversel y rel ated and vol ume and temperature are di rectl y
rel ated, then we can say that pressure and temperature are i nversel y rel ated, or as i n
Equati on 8.5:
P
T
5 constant
Thi s rel ati onshi p i s frequentl y referred to as Gay-Lussacs Law, named after Joseph Loui s
Gay-Lussac, one of the earl y gas researchers. Gay-Lussac al so performed some experi ments
that hel ped Amadeo Avogadro create what i s now referred to as Avogadros l aw.
Avogadros Law
I n 1811, Avogadro formul ated what i s now known as Avogadros hypothesi s, whi ch states
that equal vol umes of gases at the same temperature and pressure wi l l contai n equal
numbers of mol ecul es. I t has been experi mental l y determi ned that 22.4 l i ters of any gas at
0C and 1 atm (standard temperature and pressure, STP) contai n 1 mol e of mol ecul es
(6.02 3 10
23
). Thi s hypothesi s al l ows for the statement of Avogadros l aw, whi ch says that
the vol ume of a gas, kept at constant pressure and temperature, i s di rectl y proporti onal to the
number of mol es of the gas. As a formul a, Equati on 8.6 reads:
V
n
5 constant
Combined Gas Law
Al l four of these l aws, when taken together, al l ow us to make a new formul a that contai ns al l
four vari abl espressure, vol ume, temperature, and the number of mol es. Thi s new
expressi on, Equati on 8.7 (typi cal l y cal l ed the combi ned gas l aw), reads as fol l ows:
PV
nT
5 constant
154 PART III: AP Chemistry Review
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TIP
Remember, Kelvin
temperatures must
beusedfor this to
beaccurate.
(Equati on 8.4)
(Equati on 8.5)
(Equati on 8.6)
(Equati on 8.7)
www.petersons.com
Si nce the outcome of the equati on remai ns constant, you can use thi s equati on to determi ne
the behavi or of a gas as condi ti ons change (i .e., changi ng temperature, pressure, vol ume, or
quanti ty of gas). To use the equati on thi s way, i t i s hel pful to rewri te i t as Equati on 8.8:
PV
n T
PV
n T
1 1
1 1
2 2
2 2

where the subscri pt 1 i ndi cates the i ni ti al state of the gas and 2 represents the fi nal state.
Thi s equati on can be used to sol ve any probl em where a change i n condi ti ons i s i ndi cated,
regardl ess of how much i nformati on i s gi ven. For exampl e, i f onl y pressure and vol ume were
gi ven i n the probl em, the number of mol es and temperature woul d be omi tted. I f onl y vol ume
and temperature were gi ven, then pressure and number of mol es woul d be omi tted. Thi s
equati on (wi thout the n) i s provi ded i n the AP formul as.
Sample: I f 1.50 mol es of a gas at 300 K and under a pressure of 1.5 atm occupy 0.5 l i ters, at
what temperature wi l l 3.00 mol es of the same gas occupy 1.5 l i ters and exert a
pressure of 3.0 atm?
Answer: To begi n, you must set up the fol l owi ng equati on:
PV
n T
PV
n T
1 1
1 1
2 2
2 2

Probl ems l i ke thi s have a l ot of gi ven i nformati on, and i t i s i mportant you di sti ngui sh the
i ni ti al condi ti ons from the fi nal condi ti ons pri or to substi tuti on. Whi l e youre practi ci ng, i t i s
hel pful to make a l i ttl e chart or to wri te your gi ven i nformati on i n some organi zed fashi on,
but on the AP test you usual l y wont have ti me to do thi s step on paper. Practi ci ng the
techni que shoul d make you more careful about your work.
Gi ven:
P
1
5 1.5 atm P
2
5 3.0 atm
V
1
5 0.5 l i ters V
2
5 1.5 l i ters
n
1
5 1.50 mol es n
2
5 3.00 mol es
T
1
5 300 K T
2
5 ?
Rearrangi ng the equati on to sol ve for T
2
, produces the fol l owi ng expressi on:
T
PV n T
n PV
2
2 2 1 1
2 1 1

Substi tuti ng the gi ven i nformati on i nto the equati on produces:


3.0 atm 1.5 liters 1.50 mol 300 K
3.00 moles 1.5 atm 0.5 liters
( )( )( )( )
( )( )( )
= 900 K
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(Equati on 8.8)
Chapter 8: States of MatterGases 155
www.petersons.com
I f you have di ffi cul ty rearrangi ng equati ons wi th thi s many vari abl es, another techni que i s to
substi tute numbers di rectl y i n the equati on and attempt to make the equati on more
manageabl e before rearrangi ng. Sol vi ng the same equati on, you can observe thi s techni que:
PV
n T
PV
n T
1 1
1 1
2 2
2 2

1.5 atm 0.5 liters


1.50 mol 300 K
3.0 atm 1.5 liters
3.00 moles
( )( )
( )( )

( )( )
( )T
2
Thi s can be si mpl i fi ed to:
1 667 10
4 5
3 00
3
2
.
.
.


( )T
The equati on i s much easi er to rearrange now, gi vi ng:
T
2
3
4 5
3 00 1 67 10

( )
( )

.
. .

900 K
You Try It!
3H N 2NH
2 2 3
+
The Haber process i s a method of produci ng ammoni a from i ts el ements hydrogen and
ni trogen and takes pl ace accordi ng to the reacti on shown above. I t i s performed at hi gh
temperature and pressure. I f 500 l i ters of ammoni a are produced at 200 atmospheres
and 800 K, what vol ume woul d the sampl e be at i f the temperature was l owered to 300
K and the pressure decreased to 100 atm?
Answer: 375 l i ters
THE IDEAL GAS LAW
The i deal gas equati on i s not much of a stretch from what you have al ready seen wi th the
combi ned gas l aw. I f you recal l , when the combi ned gas l aw was fi rst presented, i t was wri tten
i n the form:
PV
nT
5 constant
Thi s constant can be repl aced by a val ue, known as the i deal gas constant, R, to yi el d the
equati on:
PV
nT
5 R
156 PART III: AP Chemistry Review
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www.petersons.com
where the val ue of R i s 0.0821 L-atm mol
21
K
21
. R can al so have a val ue of 8.31 joul es/mol e
Kel vi n or 8.31 vol t coul omb/mol e K, but these l atter forms of the gas equati on are not used i n
sol vi ng gas l aw probl ems.
Equati on 8.8 can be rearranged to l ook more l i ke the equati on as you have l earned i t:
PV 5 nRT
Wi th thi s equati on, i t i s possi bl e to determi ne any property of a gas, i f provi ded wi th the other
three properti es. An i mportant thi ng to remember i s the uni ts of the i deal gas constant.
Because R has uni ts of L atm mol
21
K
21
, i t i s i mportant that you have vol umes i n l i ters,
pressure i n atmospheres, and temperatures i n kel vi ns. The probl ems general l y are set up that
way, but you shoul d sti l l be al ert.
Sample: Determi ne the vol ume of 4.50 mol es of an unknown gas that exerts 7.50 atm
pressure at 350 K.
Answer: The gi ven i nformati on i s as fol l ows:
P 5 7.50 atm T 5 350 K n 5 4.50 mol V 5 ?
Rearrange the i deal gas equati on to sol ve for V and substi tute the gi ven i nformati on:
V 5
nRT
P
5
~4.50 mol !~0.0821 L 2 atm mol
21
K
21
!~350 K!
7.50 atm
5 17.2 L
You Try It!
A gas i s pl aced i n a contai ner at 5.00 atm and 300 K. I f the vol ume of the contai ner i s
2.00 L, how many mol es of gas must there be?
Answer: 0.406 mol
GAS DENSITY
The densi ty of a gas can be measured i n the same way as the densi ty of a sol i d or l i qui dby
di vi di ng i ts mass by i ts vol ume. Because the parti cl es i n a gas are very spread out, gas
densi ti es are very smal l numbers and are usual l y descri bed i n uni ts of grams per l i ter as
opposed to grams/mL or grams/cm
3
(as woul d be the case for sol i ds or l i qui ds). The AP test
occasi onal l y has gas densi ty questi ons on i t, so you shoul d be fami l i ar wi th the method for
sol vi ng them. The equati on for cal cul ati ng gas densi ty can be deri ved from the i deal gas
equati on.
To begi n, l ook at the i deal gas equati on i n i ts usual form:
PV 5 nRT
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(Equati on 8.9)
Chapter 8: States of MatterGases 157
www.petersons.com
By rearrangi ng i t, you wi l l noti ce that the uni ts on the l eft si de of the equati on now are mol es
per l i ter (whi ch i s getti ng cl ose to grams per l i ter):
n
V
P
RT

You may al so remember the expressi on bel ow (i f you dont, wel l revi ew i t i n Chapter 14):
n
m

M
, where m5 mass and M 5 mol ecul ar wei ght.
(Thi s equati on i s provi ded for you on the AP test.)
Substi tuti ng thi s val ue for n, you obtai n:
m
V
P
RT M

I f you l ook careful l y at thi s equati on, you wi l l note that the l eft si de of the equati on now
contai ns mass di vi ded by vol ume, whi ch i s equal to the densi ty of a materi al . I f we move the
mol ar mass (M) to the ri ght si de of the equati on, we get:
m
V
P
RT
M
=
Si nce d 5
m
V
, we can substi tute d i nto Equati on 8.10, yi el di ng:
P
RT
M
d =
One of the l aboratory procedures that you are expected to know i nvol ves the determi nati on of
mol ar mass from gas densi ty. I n the sampl e cal cul ati on that fol l ows, you wi l l sol ve for the
densi ty of a gas, but understand that a si mpl e rearrangement of the equati on al l ows you to
sol ve for the mol ar mass.
Sample: A sampl e of oxygen gas, O
2
, i s i n a contai ner, i nsi de whi ch the pressure i s 0.75 atm
and the temperature i s 323 K. Determi ne the densi ty of thi s sampl e of O
2
i n grams
per l i ter.
Answer: The gi ven i nformati on i s l i sted as:
P 5 0.75 atm T 5 323 K M 5 32.0 g mol
21
Note that the mol ar mass was not gi ven, but si nce i t i s needed, we can fi nd i t from
the peri odi c tabl e. I f you have forgotten how to do thi s, see Chapter 14.
Substi tuti ng our gi ven i nformati on i nto the equati on, we can sol ve for d:
d 5
P
RT
M
5
0.75 atm 32 g mol
0.0821 L atm mol K 323 K
1
1 1
( )
( )
( )
( )
5 0.91 g L
21
158 PART III: AP Chemistry Review
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(Equati on 8.10)
ALERT!
Make sure you
are on the
lookout for
diatomic
elements when
you obtain
molar masses!
www.petersons.com
You Try It!
A sampl e of butane gas, C
4
H
10
, was col l ected from a di sposabl e l i ghter. What i s the
densi ty of butane at 1.00 atm and 300 K?
Answer: 2.36 g L
21
DALTONS LAW OF PARTIAL PRESSURES
So far, weve l i mi ted our di scussi on to sampl es contai ni ng a si ngl e gas. Qui te often, however,
you are confronted wi th mi xtures of gases (e.g., ai r). I n 1801, John Dal ton determi ned a
rel ati onshi p between gases i n a mi xture that i s now referred to as Dal tons l aw of parti al
pressures. What he di scovered i s that the total pressure of a mi xture of gases i s equal to the
sum of the parti al pressures that each gas woul d exert i f i t were present al one. Expressed
mathemati cal l y, thi s means that:
P
t
5 P
A
1 P
B
1 P
C
. . .
(Equati on 8.11 i s gi ven to you on the AP test.)
Where P
t
i s the total pressure, P
A
i s the pressure of gas A, and so on.
Whi l e i t may be obvi ous to you, i t i s worth stati ng that the total number of mol es of gas i n the
sampl e i s al so equal to the sum of the number of mol es of each gas i n the sampl e:
n
t
5 n
A
1 n
B
1 n
C
. . .
From thi s expressi on, i t i s possi bl e to determi ne what percentage of a mi xture i s accounted for
by a gi ven substance. Thi s i s done by determi ni ng a quanti ty known as the mol e fracti on,
whi ch i s defi ned as X
A
(where A i s a vari abl e that represents a gas i n the mi xture):
X
A
5
n
A
N
t
Equati on 8.12 i s useful because i t al l ows us to determi ne the parti al pressure of a gas i f we
know the total pressure and the amount present. The parti al pressure of the gas wi l l be
proporti onal to the mol e fracti on of the gas i n the mi xture. Thi s can be expressed as
Equati on 8.13:
P
a
5 P
t
X
a
(Equati on 8.13 i s gi ven to you on the AP test.)
Fi nal l y, there i s one more aspect of parti al pressures that must be i ncl uded. Most of the
parti al pressure probl ems that appear on the AP test i nvol ve gases that have been col l ected
over a l i qui d. (I n other words, they have been col l ected by di spl acement of the l i qui d, usual l y
water.) The si gni fi cance of thi s i s that i n the contai ner, al ong wi th the col l ected gas, i s vapor
from the l i qui d, so the pressure i n the col l ecti on vessel i s the sum of the pressure of the gas
and the vapor. Si nce we know that the total pressure i n the contai ner i s equal to the sums of
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(Equati on 8.11)
(Equati on 8.12)
(Equati on 8.13)
Chapter 8: States of MatterGases 159
www.petersons.com
the i ndi vi dual pressures, i t i s possi bl e to determi ne the pressure of the gas usi ng
Equati on 8.14:
P
gas
5 P
t
2 P
H
2
O
Thi s equati on can be used whether the gas i s col l ected over water or some other l i qui d. I f i t i s
another l i qui d, substi tute the vapor pressure of that l i qui d for the vapor pressure of water.
Sample: Oxygen gas i s col l ected over water at 28C. The total pressure of the sampl e i s 785
mm Hg. At 28C, the vapor pressure of water i s 28 mm Hg. What pressure i s the
oxygen gas exerti ng?
Answer: Usi ng Equati on 8.14, si mpl y substi tute the gi ven val ues i nto the equati on:
P
gas
5 P
t
2 P
H
2
O
5 785 mm Hg 2 28 mm Hg 5 757 mm Hg
Thi s probl em i s fai rl y representati ve of the parti al pressure probl ems on the mul ti pl e-choi ce
porti on of the test. On the free response, the questi ons are more compl ex.
You Try It!
Hydrogen gas, l i berated from a reacti on between hydrochl ori c aci d and zi nc, i s bubbl ed
through water and col l ected i n an i nverted graduated cyl i nder at 22C. The pressure of
the gas mi xture i s 765 mm Hg. The vapor pressure of water at 22C i s 20 mm Hg. What
i s the parti al pressure of the hydrogen gas?
Answer: 743 mm Hg
Sample: A mi xture of gases contai ns 1.5 mol es of oxygen, 7.5 mol es of ni trogen, and 0.5
mol es of carbon di oxi de. I f the total pressure exerted by the mi xture i s 800 mm Hg,
what are the parti al pressures of each gas i n the mi xture?
Answer: To sol ve thi s probl em, we need to use Equati ons 8.12 and 8.13. The percentage of
the total pressure exerted by each gas wi l l be proporti onal to i ts percentage of the
number of mol es.
To begi n, we can cal cul ate the total number of mol es (whi ch i s needed i n Equati on 8.12). The
total number i s 5 (1.5 mol O
2
) 1 (7.5 mol N
2
) 1 (0.5 mol CO
2
) 5 9.5 mol es.
Thi s wi l l be used to determi ne the mol e fracti ons.
For oxygen, the cal cul ati on i s compl eted by:
P
O
2
5 P
t
X
O
2
5 800 mm Hg
S
1.5 mol
9.5 mol
D
5 126 mm Hg
Repeati ng thi s process for ni trogen and carbon di oxi de we fi nd:
P
N
2
5 P
t
X
N
2
5 800 mm Hg
S
7.5 mol
9.5 mol
D
5 632 mm Hg
P
CO
2
5 P
t
X
CO
2
5 800 mm Hg
S
0.5 mol
9.5 mol
D
5 42 mm Hg
160 PART III: AP Chemistry Review
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(Equati on 8.14)
www.petersons.com
As a qui ck check, you can add the three parti al pressures togetherthey shoul d equal the
total pressure:
126 mm Hg 1 632 mm Hg 1 42 mm Hg 5 800 mm Hg
You Try It!
A mi xture of gases contai ns 1.00 mol es H
2
, 4.00 mol es of O
2
, and 1.50 mol es N
2
. I f the
total pressure of the mi xture i s 760 mm Hg, what i s the parti al pressure of the
oxygen gas?
Answer: 468 mm Hg
KINETIC-MOLECULAR THEORY
The ki neti c-mol ecul ar theory consi sts of fi ve postul ates about gases. These postul ates are
assumpti ons from whi ch gas behavi or i s expl ai ned. Everythi ng di scussed so far i n thi s
chapter i s consi stent wi th ki neti c-mol ecul ar theory. The fi ve postul ates of the theory are:
The si ze of a gas mol ecul e i s negl i gi bl e i n compari son to the di stance between gas
mol ecul es. That i s, i n a sampl e of a gas, most of the sampl e consi sts of empty space.
Gas parti cl es are very smal l and very far apart.
Gas mol ecul es move randoml y i n strai ght-l i ne paths i n al l di recti ons and at di ffer-
ent speeds. Thi s means that i n a sampl e of gas, there i s an equal probabi l i ty of
fi ndi ng gas parti cl es wi th si mi l ar properti es anywhere i n the sampl e. You wont
have a cl osed fl ask where al l of the gas parti cl es are on one si de of the fl ask.
The attracti ve or repul si ve forces between gas parti cl es are consi dered very weak or
negl i gi bl e. Thi s can be expl ai ned because the parti cl es are movi ng qui ckl y and are
far apart.
When gas parti cl es do col l i de, the col l i si ons are el asti c. An el asti c col l i si on i s one
i n whi ch the parti cl es bounce off each other i n such a way that the energy each
parti cl e l eaves a col l i si on wi th i s exactl y the same as the energy i t had just before i t
col l i ded. No ki neti c energy i s l ost.
The average ki neti c energy of a mol ecul e i s proporti onal to the absol ute temperature.
I n your AP Chemi stry cl ass you may have di scussed the deri vati ons for the equati ons that
fol l ow. The AP test does not have any questi ons that requi re depth of understandi ng of the
physi cs of parti cl e movement. You are requi red to be fami l i ar wi th and comfortabl e usi ng a
few equati ons, and we wi l l di scuss thei r use. Thei r ori gi ns are a combi nati on of experi mental
data and some basi c physi cs i nvol vi ng the properti es of gas parti cl es, such as force, vel oci ty,
and accel erati on.
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Chapter 8: States of MatterGases 161
www.petersons.com
Kinetic Energy of a Gas Sample
Postul ate 5 states that the average ki neti c energy of a mol ecul e i s proporti onal to the absol ute
temperature. Thi s al so means that the ki neti c energy of a sampl e of mol ecul es wi l l be
proporti onal to the absol ute temperature. Equati on 8.15 that descri bes thi s behavi or i s:
KE
avg
5
3
2
RT
Thi s equati on requi res the use of one of the other val ues for R. Ki neti c energy i s measured i n
joul es, so the expressi on on the ri ght si de of the equati on must yi el d joul es. The val ue of R,
referred to as the mol ar gas constant i n thi s expressi on, shoul d be 8.31 J mol
21
K
21
. Thus, the
expressi on wi l l yi el d the joul es per mol e of a sampl e. I f the average ki neti c energy of an enti re
sampl e of gas i s requi red, then the number of mol es of gas must be entered i nto the equati on.
Equati on 8.16, whi ch i s provi ded on the AP test formul a sheet, i s:
KE
avg
5
3
2
nRT
Note how the uni ts on the ri ght wi l l now equal joul es. Al so note how the average ki neti c
energy wi l l be di rectl y proporti onal to the absol ute temperature.
Behavior of Single Molecules
Si ngl e gas mol ecul es move randoml y i n strai ght-l i ne paths. Each ti me they col l i de, ei ther
wi th another gas mol ecul e or wi th the si des of a contai ner, they wi l l bounce off wi th no l oss i n
ki neti c energy (i .e., undergo an el asti c col l i si on). The ki neti c energy of a parti cl e can be
determi ned usi ng Equati on 8.17:
KE 5
1
2
mv
2
where v i s the vel oci ty of the mol ecul e. Vel oci ty i s a vector that represents di stance travel ed
per ti me i nterval . The reason i t i s a vector i s that the di stance actual l y represents a change i n
the mol ecul es posi ti on through three-di mensi onal space, thereby gi vi ng i t a di stance and a
di recti on. For your purposes, you neednt worry about thi s di sti ncti on. I f you thi nk of vel oci ty
as bei ng equi val ent to speed (speed i s a scal ar quanti tythat i s, i t doesnt i ncl ude the
di recti on of moti on), youl l be fi ne.
I f you recal l postul ate 5 of the ki neti c-mol ecul ar theory, the average ki neti c energy of a
mol ecul e i s proporti onal to the absol ute temperature. Nothi ng i s sai d about the mass or
vel oci ty, whi ch are the terms i n Equati on 8.17. What thi s means i s that al l gas parti cl es
present i n a sampl e possess the same average ki neti c energy, regardl ess of thei r si ze. Thi s
al so means that i n order for Equati on 8.17 to be val i d, mol ecul es of l arger mass must be
movi ng more sl owl y than smal l mol ecul es.
162 PART III: AP Chemistry Review
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(Equati on 8.15)
(Equati on 8.16)
(Equati on 8.17)
www.petersons.com
Root Mean Square Velocity
An i mportant consi derati on about energy and speed wi thi n a sampl e of a gas i s that the
parti cl es wi thi n the sampl e do not al l have the same energy or the same speeds. I nstead, they
possess a vari ety of speeds and energi es. However, i t has been observed that most of the
parti cl es i n a sampl e tend to have speeds and energi es near the average speeds and
energi es. There are i ncreasi ngl y fewer parti cl es found farther away (ei ther hi gher or l ower)
from the averages. The speed of an i ndi vi dual parti cl e, possessi ng an average ki neti c
energy, i s descri bed as the root-mean-square (rms) mol ecul ar speed and can be descri bed by
the equati on:
u
rms
5
3RT
M
Some i mportant conceptual i nformati on you shoul d know from thi s equati on i s that the speed
of a mol ecul e i s di rectl y rel ated to the absol ute temperature and i nversel y rel ated to the mol ar
mass. More massi ve parti cl es are, on average, sl ower.
Sample: Cal cul ate the rms speed of ni trogen gas (N
2
) parti cl es i n a tank that has a
temperature of 27C.
Answer: The fi rst i mportant thi ng to note i s that the temperature i s gi ven i n degrees Cel si us
and must be converted to Kel vi n. The second i mportant consi derati on i s the uni ts of
the mol ar gas constant, R. The joul e i s a uni t of energy that represents a Newton
meter (N-m) i n physi cs. The Newton i s a uni t of force equi val ent to the amount of
force requi red to accel erate a 1 kg mass at 1 m/s
2
. Why does thi s matter, you mi ght
ask? Because i t means that a joul e can be descri bed as a Newton meter, whi ch i s 1
kg m
2
/s
2
. Can you see the probl em yet? The mass uni t associ ated wi th joul es i s the
ki l ogram. Mol ar mass i s usual l y expressed i n grams/mol e. To use the rms equati on,
you have to convert your mass uni ts to kg.
Once you have converted the temperature to Kel vi ns, you need onl y substi tute the numbers
i nto Equati on 8.18:
u
rms
5
3RT
M
5
3~8.31 J mol
21
K
21
!~300 K!
28.0 3 10
23
kg mol
21
5 517 m s
21
You Try It!
A sampl e of carbon di oxi de was i n a contai ner, hel d at a constant 57C. What i s the
rms speed of the CO
2
?
Answer: 432 m s
21
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ALERT!
While the AP test
tends to convert
temperatures to
Kelvins for gas law
problems, they will
often leave them
in Celsius, on ki-
netic-molecular
theory questions.
Be on the lookout
for that. Any prob-
lems involving
temperature of
gases require
absolute term-
perature, regard-
less of what you
are given!
(Equati on 8.18)
Chapter 8: States of MatterGases 163
www.petersons.com
GRAHAMS LAW OF EFFUSION
I t i s i mportant that you understand the di fference between di ffusi on and effusi on, al though
the terms are si mi l ar. Di ffusi on i s the movement of parti cl es from an area of hi gh
concentrati on (hi gh parti al pressure) to an area of l ow concentrati on (l ow parti al pressure). A
good exampl e of di ffusi on woul d be when a student wal ks i nto a cl assroom weari ng way too
much fragrancepretty soon, everyone becomes aware of i t. The hi gh concentrati on of
parti cl es on the person moves throughout the room to areas of l ower concentrati on unti l the
concentrati on becomes uni form (hopeful l y, by thi s ti me your nose wi l l have become
desensi ti zed to the odor).
After readi ng the previ ous secti on, you may wonder why i t takes so l ong for parti cl es to
spread around a room. After al l , you just sol ved probl ems where speeds average around 400 to
500 meters per second. Mol ecul es shoul d be abl e to move across a room i n a fracti on of a
second at that rate. They woul di f there were no other mol ecul es i n the room. Because there
are other parti cl es, each mol ecul e wi l l encounter a number of col l i si ons al ong the way. Thi s
conti nual l y changes the di recti on of mol ecul es, whi ch affects the ti me i t takes for them to
reach you.
I f a gas was pl aced i n a contai ner that had a ti ny hol e i n i t, and thi s contai ner was pl aced i nto
a second evacuated contai ner, the gas woul d l eak out of the hol e and i nto the second contai ner.
Thi s process, where a gas escapes through a ti ny hol e, i s known as effusi on. I f you have ever
woken up and been terri bl y di sappoi nted by a hel i um bal l oon (the l atex ones especi al l y) l yi ng
on the fl oor i nstead of fl oati ng ni cel y as i t had the day before, you have seen the resul ts of
effusi on. The hel i um atoms effused through the ti ny pores i n the l atex. Myl ar bal l oons dont
have as many pores, whi ch sl ows the effusi on. Grahams l aw of effusi on states that when a
gas, mai ntai ned at a constant temperature and pressure, l eaks through a parti cul ar hol e, the
rate of effusi on i s i nversel y proporti onal to the square root of the mol ecul ar wei ght of the gas.
The mathemati cal expressi on of Grahams l aw i s deri ved from Equati on 8.18 and has
the form:
Rate of effusi on
1
M
Thi s expressi on i s rarel y used i n thi s form, but i nstead has been transformed i nto an
expressi on that al l ows you to compare the rates of effusi on of two gases. Equati on 8.19, whi ch
i s provi ded for you on the AP formul a sheet, i s:
r
r
1
2
2
1

M
M
From a conceptual standpoi nt, the equati on tel l s you that l arger mol ecul es wi l l effuse more
sl owl y than smal l er parti cl es. Mathemati cal l y, the equati on provi des a number that tel l s you
the rati o and the effusi on rates of gases 1 and 2. I f the rati o i s greater than 1.00, gas 1 i s
effusi ng more qui ckl y than gas 2. I f the rati o i s l ess than 1.00, gas 2 i s effusi ng more qui ckl y
than gas 1.
Because both conceptual and numeri cal probl ems have appeared on the AP test, l ets do a
sampl e probl em of each type.
164 PART III: AP Chemistry Review
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(Equati on 8.19)
www.petersons.com
Sample: Equal numbers of mol es of He(g), O
2
(g), and CO
2
(g) are pl aced i n a gl ass vessel at
room temperature. The vessel has a pi nhol e-si zed l eak, and the gases are al l owed to
effuse for a bri ef peri od of ti me. Rank order the gases remai ni ng i n the contai ner, from
the gas wi th the hi ghest parti al pressure to the gas wi th the l owest parti al pressure.
Answer: Si nce you know that the rate of effusi on i s i nversel y rel ated to the square root of the
mol ar mass, you know that the l arger the mol ar mass, the sl ower the rate of effusi on.
Therefore, the gas wi th the smal l est mol ar mass wi l l effuse at the greatest rate.
The tri ck i n the questi on i s that you are asked for the amounts that remai n i n the contai ner.
Thi s means that the gas wi th the fastest rate of effusi on wi l l be the l east pl enti ful gas i n the
contai ner (more of i t wi l l have effused).
The mol ar masses of each gas are: He 5 4 g mol
21
, O
2
5 32 g mol
21
, and CO
2
5 44 g mol
21
.
Therefore, He wi l l have the greatest rate of effusi on, fol l owed by oxygen, and fi nal l y CO
2
. Thi s
means that hel i um wi l l have the l owest parti al pressure, fol l owed by O
2
, and fi nal l y CO
2
,
whi ch wi l l have the hi ghest parti al pressure.
You Try It!
A bal l oon i s fi l l ed up wi th one mol e of hydrogen (H
2
) mol ecul es. A second i denti cal
bal l oon i s fi l l ed wi th one mol e of He
2
mol ecul es. After some ti me has el apsed, whi ch
bal l oon i s smal l er?
Answer: H
2
, because the smal l er mol ecul es escape more qui ckl y.
Sample: Two gases, SO
2
and NO
2
, are pl aced i n a contai ner at a constant temperature and
pressure. Cal cul ate the rati o of effusi on rates of the mol ecul es.
Answer: The fi rst thi ng to noti ce here i s that the equati on for cal cul ati ng the rati o of
effusi on rates requi res a di sti ncti on between gas 1 and gas 2. Si nce no such
di sti ncti on i s made i n the probl em, the deci si on about what to l abel each gas i s
arbi trary. However, because the l i ghter gas i s typi cal l y l abel ed as gas 1, thats how
we shal l proceed.
You wi l l use Equati on 8.19 to sol ve thi s:
r
r
1
2
2
1

M
M
We wi l l assi gn NO
2
as gas 1 and SO
2
as gas 2. Therefore:
rate of effusion of NO
rate of effusion of SO
64.1 g mol
46.0 g mol
2
2
SO
NO
1
1

M
M
2
2
1 18 .
What thi s means i s that NO
2
effuses at a rate 1.18 ti mes greater than SO
2
. Thi s i s because, on
average, NO
2
parti cl es move 1.18 ti mes faster than SO
2
parti cl es.
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NOTE
Typically, the
lighter gas is
assigned as
gas 1. This assures
that your ratio will
be greater
than 1.00.
Chapter 8: States of MatterGases 165
www.petersons.com
You Try It!
Cal cul ate the rati o of effusi on rates of hel i um (He) and neon (Ne) gases from the same
contai ner and at the same temperature and pressure.
Answer: 2.25
DEVIATIONS FROM THE IDEAL GAS LAWS
Most of the ti me, real gases approxi mate the i deal gas cl osel y enough to use the i deal gas l aw
equati on. There are some ci rcumstances, however, when the devi ati ons between real and
i deal gases become si gni fi cant. The mai n sources for devi ati on ari se from postul ates 1 and 3.
Postul ate 1 asserts that the si ze of a gas mol ecul e i s negl i gi bl e i n compari son to the di stance
between gas mol ecul es. Under most ci rcumstances, thi s i s true because the parti cl es i n a gas
are very far apart. The di stance between parti cl es i s al so cri ti cal i n postul ate 3, whi ch asserts
that the attracti ve or repul si ve forces between gas parti cl es are negl i gi bl e and al so reasonabl e
when the gas parti cl es are very far apart. Probl ems start to occur, however, when the
mol ecul es get cl oser together. There are two si tuati ons when thi s wi l l occur: hi gh pressures
and l ow temperatures.
When a gas i s under hi gh pressure, the di stance between gas parti cl es becomes much smal l er,
whi ch al l ows for more opportuni ti es for parti cl es to i nteract. These i nteracti ons can be
si gni fi cant, especi al l y when the gases are capabl e of i ntermol ecul ar attracti ons. For exampl e,
a pol ar mol ecul e, l i ke SO
2
i n the gaseous state, i s capabl e of attracti ng other SO
2
mol ecul es by
di pol e-di pol e i nteracti ons i f the parti cl es get cl ose enough together. Hi gh pressures force the
mol ecul es cl oser together and i ncrease the l i kel i hood of attracti ons, whi ch decrease the i deal
nature of a gas. (I n the next chapter, you wi l l exami ne i n more depth the rol e of pressure on
the state of a substance.)
Loweri ng the temperature al so has an i mpact on the i deal nature of a gas. At l ow
temperatures, the movement of gas parti cl es begi ns to decrease. As the movement decreases,
there are more opportuni ti es for i ntermol ecul ar attracti ons.
So, at hi gh pressures or l ow temperatures, the behavi or of gases wi l l tend to devi ate from
i deal gas behavi or. The amount of devi ati on al so depends on the type of gas. Johannes van der
Waal s proposed an equati on that was based on the i deal gas equati on but that made
correcti ons for the vol ume of a mol ecul e (postul ate 1) and the amount of mol ecul ar attracti on
(postul ate 3). The van der Waal s equati on (whi ch i s provi ded for you on the AP test) i s
Equati on 8.20:
P
n a
V
V nb nRT +

_
,

( )
2
2
where a and b are known as van der Waal s constants and are di fferent for each gas. The
constant a i s associ ated wi th the devi ati ons due to mol ecul ar attracti ons, and constant b i s
associ ated wi th devi ati ons due to mol ecul ar vol umes. Val ues of a and btend to i ncrease as the
166 PART III: AP Chemistry Review
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(Equati on 8.20)
www.petersons.com
mass and compl exi ty of a gas i ncreases. Thi s shoul d make sense si nce these condi ti ons woul d
be the most l i kel y to affect postul ates 1 and 3 of the ki neti c-mol ecul ar theory.
Sample: The van der Waal s constants for He and SO
2
are l i sted bel ow:
Substance a (L
2
-atmmol
22
) b (L mol
21
)
He 0.03412 0.02370
SO
2
6.714 0.05636
Assume that you have separate sampl es of 1.00 mol es of the gas i n a 22.4 L
contai ner at 273 K. I f these gases were i deal gases, they woul d exert a pressure of
1.00 atm (per the equati on PV 5 nRT). Usi ng the van der Waal s equati on, cal cul ate
the pressures exerted by 1.00 mol es of He and SO
2
i n i denti cal 22.4 L contai ners
at 273 K.
Answer: Thi s i s a very l ong probl emand you wont be asked to sol ve a probl em thi s
compl ex on the AP test. I t can al so show you the degree to whi ch di fferent gases
devi ate from i deal behavi or.
Lets begi n wi th He. The fi rst thi ng you need to do i s rearrange the equati on to sol ve for P.
Thi s i s easi l y done i n two steps:
P
n a
V
V nb nRT +

_
,

( )
2
2
; di vi de each si de by (V 2 nb)
S
P 1
n
2
a
V
2 D
5
nRT
~V 2 nb!
; next, i sol ate P by subtracti ng
n
2
a
V
2
from each si de
P 5
nRT
~V 2 nb!
2
n
2
a
V
2
Substi tute the gi ven i nformati on. (Note: Because of the uni ts of a and b, i t i s necessary to use
the i deal gas constant R 5 0.0821 L-atm mol
21
K
21
):
P
( )( )( )
(
1.00 mol 0.0821 L-atm mol K 273 K
22.4 L- 1.00 mol
1 1
))( ) ( )
( ) ( )
0.02370 L mol
1.00 mol 0.03412 L -atm mol
22.
1
2 2
2
44 L ( )
2
P 5 1.002 atm 2 6.80 3 10
25
atm 5 1.002 atm
I n thi s case, the second val ue, 6.80 3 10
25
atm, i s very smal l , whi ch i ndi cates that the mai n
cause for the ti ny devi ati on from i deal behavi or i s due to the vol umes of the mol ecul es rather
than i ntermol ecul ar attracti ons. Thi s shoul d make sense i f you recal l that a ti ny atom, l i ke
He, i s nearl y i ncapabl e of creati ng any London di spersi on forces.
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Chapter 8: States of MatterGases 167
www.petersons.com
Now for the second gas, SO
2
. Thi s i s a much l arger mol ecul e, so we wi l l predi ct some
di fferences from He. Fol l owi ng the same procedure as you di d for He, substi tute the val ues for
SO
2
i nto thi s fi nal equati on:
P 5
nRT
~V 2 nb!
2
n
2
a
V
2
P
( )( )( )
(

1.00 mol 0.0821 L-atm mol K 273 K
22.4 L- 1.00 mol
1 1
))( ) ( )
( ) ( )

0.05636 L mol
1.00 mol 6.714 L -atm mol
22.4
2
1
2
2
LL ( )
2
P 5 1.003 atm 2 0.0134 atm 5 0.9896 atm
The val ue of 1.003 atm i s sl i ghtl y l arger than that of He, owi ng to the fact that the l arger SO
2
mol ecul es occupy more total space, whi ch means they wi l l experi ence more col l i si ons wi th the
contai ner than He atoms. The much hi gher correcti on factor for mol ecul ar attracti ons (0.0134
atm) i s hi gher than He because the much l arger mol ecul e i s more capabl e of i ntermol ecul ar
i nteracti ons than He.
You Try It!
1.00 mol es of ni trous oxi de gas, N
2
O, i s i ntroduced i nto a 22.4 L contai ner at a
temperature of 273 K. Determi ne the pressure usi ng the van der Waal s equati on. The
van der Waal s constants for N
2
O are a 5 3.782 L
2
-atm mol
22
, and b 5 0.04415 L mol
21
Answer: 0.995 atm
168 PART III: AP Chemistry Review
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www.petersons.com
EXERCISES: STATES OF MATTERGASES
Multiple Choice
1. A sampl e of hel i um gas i s i n a
contai ner at 30C. I f the temperature
i s rai sed to 60C, the average ki neti c
energy of the atoms wi l l change by a
factor of
(A)
1
2
(B)
333
303
(C)
333
303
(D) 2
(E) 4
2. Exactl y 4.0 g of hel i um gas, He, i s
pl aced i nto a contai ner at constant
temperature and pressure. Next to
the contai ner of hel i um i s a 28.0 g
sampl e of ni trogen gas, N
2
, pl aced i n
an i denti cal contai ner at the same
temperature and pressure as the
hel i um. From the l i st of statements
bel ow, sel ect al l that are TRUE:
I . The number of atoms of He i s
i denti cal to the number of
mol ecul es of N
2
.
I I . The average ki neti c energy of
the He atoms i s the same as the
average ki neti c energy of the
ni trogen mol ecul es.
I I I . The average speed of the
hel i um atoms i s the same as
the average speed of the
ni trogen mol ecul es.
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I , I I , and I I I
3. A sampl e of hel i um gas i s col l ected
i n a contai ner wi th a ti ny hol e i n i t.
The hel i um gas (M 5 4 grams)
effuses at a rate of 0.2 mol es per
mi nute. I f a sampl e of methane gas
(M 5 16 grams) i s al l owed to effuse
under the same condi ti ons, the rate
of CH
4
effusi on wi l l be
(A) 0.1 mol es per mi nute.
(B) 0.14 mol es per mi nute.
(C) 0.2 mol es per mi nute.
(D) 0.4 mol es per mi nute.
(E) 0.8 mol es per mi nute.
4. A sampl e of 13.40 grams of a gas at
127.0 C and 2.00 atmospheri c pres-
sure has a vol ume of 5.00 l i ters. What
i s the i denti ty of the gas? Assume
i deal behavi or. The gas constant, R, i s
0.0821 L atm mol
21
K
21
).
(A) He ( mol ar mass 5 4.00 g mol
21
)
(B) N
2
(mol ar mass 5 28.0 g mol
21
)
(C) O
2
(mol ar mass 5 32.0 g mol
21
)
(D) Ne (mol ar mass 5 20.2 g mol
21
)
(E) CO
2
(mol ar mass 544.0 g mol
21
)
5. I f you col l ected a sampl e of
3.50 mol es of hydrogen gas, H
2
, and
heated i t i n a 10.00 L contai ner to a
temperature of 300 K, how much
pressure woul d the H
2
exert on
the contai ner?
(A) 873 atm
(B) 86.2 atm
(C) 16.5 atm
(D) 8.62 atm
(E) 0.776 atm
e
x
e
r
c
i
s
e
s
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Chapter 8: States of MatterGases 169
www.petersons.com
6. 3.00 mol es of ni trogen gas, N
2
, and
an unknown amount of hydrogen gas,
H
2
, are mi xed together i n a
contai ner. The total pressure i n the
contai ner i s 1000 mm Hg. I f the
parti al pressure of ni trogen i n the
contai ner i s 750 mm Hg, how
many mol es of hydrogen gas must
be present?
(A) 0.5 mol es
(B) 1.0 mol es
(C) 1.5 mol es
(D) 2.0 mol es
(E) Not enough i nformati on
7. A chunk of cal ci um carbi de i s pl aced
i nto a contai ner of water, and the
acetyl ene gas that i s formed i s
bubbl ed through water i nto an
i nverted graduated cyl i nder. The
pressure i nsi de the graduated
cyl i nder i s 800 mm Hg, and the
temperature i s 27C. What i s the
parti al pressure exerted by the
acetyl ene gas? (The vapor pressure of
water at 27C i s 27 mm Hg.)
(A) 800 mm Hg
(B) 827 mm Hg
(C) 27 mm Hg
(D) 773 mm Hg
(E) 54 mm Hg
8. A sampl e of carbon di oxi de gas, CO
2
,
i s i n a contai ner, i nsi de whi ch the
pressure i s 1.25 atm and the tem-
perature i s 300 K. What i s the
densi ty of thi s sampl e of CO
2
i n
grams per l i ter?
(A) 0.022 g L
21
(B) 1.42 g L
21
(C) 2.23 g L
21
(D) 5.00 g L
21
(E) 24.8 g L
21
9. An unknown quanti ty of methane
gas, CH
4
, i s hel d i n a 2.00-l i ter
contai ner at 77C. The pressure
i nsi de the contai ner i s 3.00 atm. How
many mol es of methane must be i n
the contai ner?
(A) 0.21 mol es
(B) 0.95 mol es
(C) 1.05 mol es
(D) 4.8 mol es
(E) 0.5 mol es
10. Whi ch of the fol l owi ng i s most l i kel y
to devi ate from i deal gas behavi or?
(A) H
2
(B) He
(C) Ne
(D) N
2
(E) CCl
4
170 PART III: AP Chemistry Review
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Free Response
1. Three l arge, i denti cal bal l oons are fi l l ed wi th 22.4 L of gas at STP. The three gases are
hel i um (He), hydrogen (H
2
), and sul fur hexafl uori de (SF
6
). What fol l ows i s a l i st of
statements about those three bal l oons. Comment on the accuracy of the statements,
usi ng speci fi c detai l s to support your argument/comments.
(A) Because hydrogen i s the smal l est parti cl e, the bal l oon wi th hydrogen wi l l contai n
the l argest number of mol es of gas.
(B) The ki neti c energi es of the mol ecul es compare as fol l ows: SF
6
, He , H
2
(C) SF
6
wi l l devi ate the most from i deal gas behavi or.
(D) One day after fi l l i ng the bal l oons, al l three wi l l have decreased i n si ze by the
same amount.
Figure8.2
2. A smal l sampl e of mossy zi nc was pl aced i nto a reacti on vessel , as shown i n Fi gure 8.2.
Hydrochl ori c aci d was added, and the hydrogen gas that was generated was bubbl ed
through water i nto a gas col l ecti on tube fi l l ed wi th water. When the reacti on reached
compl eti on, the gas col l ecti on tube was nearl y ful l . The gas was al l owed to si t for several
mi nutes. The col l ecti on tube was then adjusted so that the l evel of water i n the tube was
equal to the l evel of the water outsi de the tube. The vol ume of gas was determi ned to be
47 mL, and the temperature of the water was 22C. The barometri c pressure i n the
l aboratory was 745 mm Hg. The vapor pressure of water at 22C i s 19.4 mm Hg.
(A) Cal cul ate the number of mol es of hydrogen gas produced.
(B) Expl ai n why i t was necessary to al l ow the gas to si t i n the tube for several
mi nutes before determi ni ng i ts vol ume.
(C) Expl ai n why i t was necessary to adjust the l evel of the tube so that water l evel s
i nsi de and outsi de of i t were the same.
(D) Expl ai n why the vapor pressure of water i s gi ven.
e
x
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Chapter 8: States of MatterGases 171
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ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. C
2. D
3. A
4. E
5. D
6. B
7. D
8. C
9. A
10. E
1. Thecorrect answer is (C). The bi g trap here i s the degrees Cel si us. The fact that the
second temperature i s exactl y two ti mes greater than the fi rst temperature makes i t
very attracti ve to thi nk that the ki neti c energy wi l l doubl e. Wrong! The ki neti c energy
i s proporti onal to the absol ute temperature scal e. On thi s scal e, the rati o of
60
30
becomes
~60 1 273!
~30 1 273!
or
333
303
.
2. Thecorrect answer is (D). There are two ways that you can gai n support for I . Fi rst,
the mass of each sampl e represents one mol e of the gas. Knowi ng that there i s one mol e
i n each contai ner al l ows you to say that the number of parti cl es i n each contai ner i s the
same. However, a second way to get the same answer i s Avogadros hypothesi s, whi ch
states that equal vol umes of gases at the same temperature and pressure wi l l contai n
equal numbers of mol ecul es. Because the contai ners are the same si ze (vol ume) and at
the same temperature and pressure, you can assume they have equal numbers of
parti cl es. Support for I I comes from the ki neti c-mol ecul ar theory, whi ch states that the
average ki neti c energy of gas parti cl es i s proporti onal to the absol ute temperature.
Because the contai ners are at the same temperature, i t can be sai d the gases have the
same average ki neti c energi es. There i s no support for I I I , however. Ki neti c energy i s
measured usi ng the formul a
1
2
mv
2
, where vrepresents the speed of the parti cl es. Ki neti c
mol ecul ar theory tel l s us that the product of these numbers wi l l be the same for both
gases, but because the masses of each gas are di fferent, i t i s i mpossi bl e for them to have
the same speeds. Ni trogen, the heavi er gas, wi l l , on average, travel much sl ower than
hel i um.
3. Thecorrect answer is(A). There i s a qui ck way to sol ve thi s and al so a l ong way. The
qui ck way i s to remember that Grahams l aw states that the rate of effusi on i s i nversel y
proporti onal to the square root of the mol ar mass. You can see pretty qui ckl y that the
mol ar mass of methane i s 4 ti mes that of hel i um. The square root of 4 i s 2, meani ng that
hel i um wi l l di ffuse two ti mes faster than methane. The l onger way i s to actual l y set up
the equati on
r
1
r
2
5
M
2
M
1
and sol ve for r
2
.
4. Thecorrect answer is (E). Usi ng the i deal gas equati on PV 5 nRT, and sol vi ng for n,
you get 0.3045 mol es. Di vi di ng the mass of the sampl e by the mol ar mass yi el ds
44.0 g mol
21
, whi ch i s the mol ar mass of CO
2
.
5. Thecorrect answer is(D).Another i deal gas equati on. Thi s ti me, al l val ues are i n the
appropri ate uni ts, so you just need to pl ug and chug.
172 PART III: AP Chemistry Review
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6. Thecorrect answer is(B). You know that P
A
5 P
t
X
A
. I f you try setti ng thi s up for the
hydrogen, i t gets a l i ttl e more compl i cated. Al ways remember what you are gi ven i n a
probl em. You know how many mol es of ni trogen gas you have. You al so know the total
pressure and the parti al pressure of ni trogen. Therefore, you can use the gi ven
i nformati on to fi gure out the total number of mol es i n the mi xture. Once you know thi s,
you can qui ckl y determi ne the amount of hydrogen. 750 mm Hg 5 1000 mm Hg
~
3
X
!
.
Sol vi ng for X, you fi nd i t to be 4. That means there are four mol es i n the mi xture. Three
of these are ni trogen, so the other one must be hydrogen. Note: There are other ways to
sol ve thi s probl emthi s one i s rel ati vel y strai ghtforward and easy to sol ve, so i t
was sel ected.
7. Thecorrect answer is (D). Remember, whenever you col l ect a gas sampl e over water
(or another l i qui d), the total pressure refl ects the pressure of the gas sampl e AND the
vapor pressure of the water. To determi ne the pressure of the gas, you must subtract the
vapor pressure of the water from the total pressure:
P
gas
5 P
t
2 P
water
5 800 mm Hg 2 27 mm Hg 5 773 mm Hg
8. The correct answer is (C). Densi ty can be cal cul ated usi ng the equati on d 5
PM
RT
. Al l
val ues are al ready i n the uni ts of R, so pl ug and chug:
~1.25 atm!~44.0 g mol
21
!
~0.0821 L atm mol
21
K!~300 K!
5 2.23 g L
2
9. The correct answer is (A). I deal gas equati on. Temperature i s i n Cel si us, so i t wi l l
need to be converted to Kel vi n:
n 5
PV
RT
5
~3.00 atm!~2.00 L!
~0.0821 L atm mol
21
K!~350 K!
5 0.21 mol es
10. Thecorrect answer is(E). When consi deri ng parti cl es, remember that l arger or more
compl ex mol ecul es wi l l most l i kel y devi ate from i deal gas behavi or. Thi s i s due both to
thei r i ncreased vol ume and to thei r i ncreased l i kel i hood of mol ecul ar attracti on.
Free Response 1
(A) Wrong! Avogadros hypothesi s tel l s us that equal vol umes of gases at constant
temperature and pressure wi l l contai n equal numbers of mol es of the gases. These
bal l oons al l have equal vol umes, and each i s at the same temperature and pressure.
Therefore, si ze has nothi ng to do wi th thi s.
(B) Wrong agai n! One of the postul ates of ki neti c-mol ecul ar theory i s that the average
ki neti c energy of a gas i s di rectl y rel ated to the absol ute temperature of the gas. Mass
and vol ume have nothi ng to do wi th i t. The gases are al l at the same absol ute
temperature; therefore, they wi l l al l have the same average ki neti c energi es.
a
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Chapter 8: States of MatterGases 173
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(C) Thi s statement i s correct. The sul fur hexafl uori de mol ecul e has a much l arger vol ume
than the other mol ecul es and i s much more l i kel y to experi ence mol ecul ar attracti ons
than the other two mol ecul es. These two factors wi l l make thi s mol ecul e most l i kel y to
devi ate from the key postul ates i n the ki neti c-mol ecul ar theory (si ze of the mol ecul e i s
negl i gi bl e and mol ecul ar attracti ons are negl i gi bl e).
(D) Wrong! Grahams l aw of effusi on states that the rates of effusi on are i nversel y rel ated
to the square root of the mol ar mass. Thi s means that smal l er parti cl es wi l l effuse
more qui ckl y than l arger parti cl es. Al l three bal l oons wi l l get smal l er at di fferent
rates, whi ch means they wi l l be di fferent si zes on the next day (hydrogen wi l l be
smal l est, fol l owed by hel i um, and then sul fur hexafl uori de).
Free Response 2
(A) Thi s i s a l aboratory procedure that you are expected to have performed and know for
the AP test. Whi l e setti ng up thi s cal cul ati on, we wi l l actual l y be answeri ng some of
the fol l owi ng questi ons. You wi l l use the i deal gas equati on to sol ve the probl em.
Therefore, you wi l l need to know the pressure, vol ume, and temperature of the gas.
The pressure of the gas wi l l equal the total pressure of the mi xture mi nus the vapor
pressure of water (whi ch i s present i n the gas col l ecti on tube, al ong wi th the
hydrogen). The total pressure of the gas i s equal to the atmospheri c pressure i n the
room. Therefore, the pressure of the hydrogen gas i s equal to 745 mm Hg 2 19.4 mm
Hg 5 725.6 mm Hg (726 mm Hg). Remember, the i deal gas equati on requi res
atmospheres, so thi s wi l l need to be converted to atmospheres:
726 mm Hg 3 1 atm
760 mm Hg
5 0.955 atm.
The vol ume of the mi xture i s 47 mL, but the i deal gas equati on requi res l i ters, so thi s
wi l l need to be converted to l i ters:
47 mL 5 4.7 3 10
22
L.
The temperature of the gas i s assumed to be the temperature of the water, whi ch i s
22C. Thi s wi l l need to be converted to K. 22C 5 295 K. Now you are ready to
substi tute your data i nto the equati on:
PV 5 nRT
n 5
PV
RT
5
~0.955 atm!~4.7 3 10
22
L!
~0.0821 L atm mol
21
K!~295 K!
5 1.85 3 10
23
mol H
2
(B) The gas must si t i n the tube so that the temperature of the gas wi l l equi l i brate
wi th the temperature of the water. Thi s i s necessary because the temperature of the
water i s the onl y known temperature and therefore i s the temperature used i n the
gas equati on.
174 PART III: AP Chemistry Review
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(C) When the water l evel i nsi de the tube i s the same as the water l evel outsi de the tube,
thi s i s an i ndi cator that the gas pressure i nsi de the tube i s equal to the ai r pressure
outsi de the tube. Because i n your l ab there i s no way to di rectl y measure the gas
pressure i nsi de the tube, thi s al l ows you to determi ne the pressure by di rect
compari son to atmospheri c pressure. Atmospheri c pressure can therefore be
substi tuted i nto the gas equati on.
(D) The vapor pressure of water must be gi ven because the gas i n the col l ecti on tube i s
actual l y a mi xture of hydrogen gas and water vapor. By subtracti ng the vapor pressure
of water, you can determi ne the parti al pressure of the hydrogen gas i n the mi xture.
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Chapter 8: States of MatterGases 175
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SUMMING IT UP
The gas l aws and the ki neti c mol ecul ar theory descri be gas temperatures usi ng the
Kel vi n, or absol ute, temperature scal e. Gas vol umes are usual l y descri bed i n l i ters, and
gas pressures are descri bed i n terms of atmospheres, or mm Hg.
Boyl es l aw states that pressure and vol ume are i nversel y proporti onal at constant
temperatures.
Charl ess l aw states that vol ume and temperature are di rectl y proporti onal at constant
pressures.
Gay-Lussacs l aw states that pressure and temperature are di rectl y proporti onal at
constant vol umes.
Avogadros hypothesi s states that equal vol umes of gases at the same temperature and
pressure wi l l contai n equal numbers of mol ecul es. At STP, the vol ume of one mol e of gas
i s approxi matel y 22.4 l i ters.
Avogadros l aw states that vol ume i s di rectl y proporti onal to the number of mol es of a gas
at constant temperature and pressure.
The i deal gas l aw, PV 5 nRT, descri bes the behavi or of any i deal gas. The equati on can be
used to deri ve any of the other gas l aws.
Dal tons l aw of parti al pressures states that the total pressure i n a mi xture of gases i s
equal to the sum of the pressures that each i ndi vi dual gas exerts.
When gas sampl es are col l ected over a l i qui d, the total pressure exerted by the gas
sampl e i ncl udes the vapor pressure of the l i qui d. I n order to determi ne the pressure
exerted by the gas al one, the parti al pressure of the l i qui d must be subtracted.
The ki neti c mol ecul ar theory consi sts of these postul ates:
The si ze of a gas mol ecul e i s negl i gi bl e i n compari son to the di stance between
gas mol ecul es.
Gas mol ecul es move randoml y i n strai ght-l i ne paths i n al l di recti ons and at
di fferent speeds.
The attracti ve or repul si ve forces between gas parti cl es are consi dered very
weak or negl i gi bl e.
When gas parti cl es do col l i de, the col l i si ons are el asti c.
The average ki neti c energy of a mol ecul e i s proporti onal to the absol ute
temperature.
Grahams l aw of effusi on states that the rate at whi ch a gas effuses i s i nversel y
proporti onal to the mol ecul ar wei ght of the gas.
Under condi ti ons of hi gh pressure and l ow temperature, real gases begi n to devi ate from
i deal gas behavi or. The van der Waal s equati on can be used to determi ne the behavi or of
a real gas.
176 PART III: AP Chemistry Review
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States of Matter
Liquids and Solids
OVERVIEW
General characteristics of gases, liquids, and solids
Energy and phase changes
Heating curves
Vapor pressure
Phase diagrams
The solid state
Summing it up
I n previ ous chapters, you l ooked at the basi c composi ti on of matter and the
characteri sti cs of the gaseous state of matter. One common theme i n each of
those chapters was the presence of i ntermol ecul ar forces that occur between
parti cl es. I n Chapter 6, you were i ntroduced to the three mai n types of these
forces: hydrogen bondi ng, di pol e-di pol e i nteracti ons, and London di spersi on
forces. I n Chapter 8, you saw how real gases dont behave qui te l i ke i deal
gases. That i s, real parti cl es do have mass and vol ume and exert attracti ons
on other parti cl es. Thi s accounts for devi ati ons between real behavi or and
i deal behavi or. I t al so expl ai ns why gases under di fferent combi nati ons of
pressure and temperature can be l i quefi ed. I n thi s chapter, we wi l l revi si t
i ntermol ecul ar forces and di scuss thei r rol es i n the l i qui d and sol i d states. I n
addi ti on, we wi l l l ook at the effects of chemi cal bondi ng on the behavi or of
sol i ds. We wi l l al so l ook at di fferent di agrams that are useful when studyi ng
the di fferent states of matter.
GENERAL CHARACTERISTICS OF GASES, LIQUIDS,
AND SOLIDS
Before you conti nue, you shoul d have a good feel for the di fferences between
the three mai n states of matter at the parti cl e l evel . Fi gure 9.1 provi des a
graphi c representati on of what i s descri bed i n the next three paragraphs.
Gases, you wi l l recal l from Chapter 8, are characteri zed by parti cl es that are
free to move about i n constant, random, strai ght-l i ne moti on. Under normal
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
9
177
atmospheri c condi ti ons, the parti cl es are very spread out. Gases can be thought of as bei ng
fl ui d, not i n the sense that they are l i qui ds, but that they can fl ow. They can fl ow freel y
because the parti cl es can move past one another wi th ease. Because there i s a l arge amount
of empty space between the parti cl es, gases are hi ghl y compressi bl e. Gases essenti al l y fi l l any
contai ner they are pl aced i nto.
I n l i qui ds, the parti cl es are much cl oser together. Li qui ds sti l l share some of the same
characteri sti cs as gases. Al though the parti cl es are much cl oser together than they are i n the
gaseous state, they are general l y free to sl i de past one another. Remember, the forces hol di ng
the parti cl es together i n the l i qui d state are not chemi cal bonds but i ntermol ecul ar forces.
They can keep the parti cl es together, but not ti ghtl y enough to prevent them from movi ng.
Because the parti cl es can sl i de past one another, l i qui ds can fl ow. Thi s wi l l al l ow them to take
the shape of any contai ner that they are pl aced i nto, but unl i ke gases, they are not abl e to
change thei r vol ume to fi l l the contai ner. Parti cl es of a l i qui d are much cl oser together than a
gas. As a resul t, l i qui ds are al most compl etel y i ncompressi bl e.
Sol i ds are nei ther fl ui d nor compressi bl e. The parti cl es i n a sol i d, whi ch mi ght be atoms,
mol ecul es, or i ons, dependi ng on the materi al , are ti ghtl y packed together i nto a ri gi d
structure. The movements i n a sol i d are l i mi ted to osci l l ati ons, or vi brati ons. Sol i ds wi l l
mai ntai n thei r shape wi thout a contai ner.
I n the previ ous chapter, you l ooked at the van der Waal s equati on as a way of taki ng i nto
account the si zes of parti cl es as wel l as mol ecul ar attracti ons. I n thi s chapter, these properti es
become even more i mportant i n the consi derati on of l i qui ds and sol i ds.
ENERGY AND PHASE CHANGES
So far, we have tal ked about the three di fferent phases of matter, but i n a di sconnected way,
as though the three states have nothi ng to do wi th one another. As you wi l l see, however, the
three states are very much connected to one another. Energy i s the thread that bi nds them al l
together and separates them. There are some terms associ ated wi th the transi ti ons from one
state of matter to another that you shoul d be fami l i ar wi th.
Mel ti ng, al so known as fusi on, i s the term used to descri be a change from the sol i d state to
the l i qui d state. A certai n amount of energy i s necessary to break the parti cl es from the ri gi d
Figure9.1
178 PART III: AP Chemistry Review
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NOTE
Occasionally,
pla sma , the gas-
eous mixture of
ions and electrons
that exists at
extremely high
temperatures, is
classified as a
fourth state of
matter. Because it
is irrelevant to our
discussion, we are
limiting the topic
to the three
clearly recog-
nized states.
www.petersons.com
sol i d state i nto thi s fl ui d state. I f you take an i ce cube from the freezer and set i t on the
counter, you wi l l wi tness mel ti ng as the cube changes from the sol i d state to the l i qui d state.
The hi gher ki neti c energy of the parti cl es on the counter and i n the ai r wi l l conti nue to
transfer energy to the i ce cube, causi ng i t to mel t.
I f the l i ttl e puddl e of water i s put i nto a smal l contai ner and pl aced back i nto the freezer, the
water, now at a hi gher ki neti c energy than the ai r i n the freezer, wi l l l ose energy to the ai r
parti cl es i n the freezer. When the parti cl es have l ost suffi ci ent energy, they wi l l no l onger be
abl e to overcome the attracti ve forces that wi l l cause them to change back i nto a ri gi d sol i d
structure once agai n. Thi s process of movi ng from the l i qui d state to the sol i d state i s known
as freezi ng. One thi ng you have to be careful of i s associ ati ng the word freezi ng wi th col d.
Many thi ngs you are fami l i ar wi th, l i ke i ce cubes, dont freeze unti l they become col d. Thi s i s
not true for al l substances, however. Pi cture mol ten l ava runni ng down the si des of a vol cano.
As i t cool s, i t i s freezi ng, but you woul d hardl y consi der i t to be col d! You wi l l al so l earn l ater
i n thi s chapter that terms such as boi l i ng and freezi ng are rel ated to pressure as wel l as
to temperature.
I f you have ever seen dry i ce mel t, you may have noti ced that there i s no puddl e l eft behi nd.
The word mel ts i s i n quotes because the process that dry i ce undergoes i s not known as
mel ti ng. Dry i ce, or sol i d carbon di oxi de, at normal atmospheri c pressure passes di rectl y from
the sol i d state to the gaseous state, wi thout passi ng through the l i qui d state. Thi s process i s
known as subl i mati on. The reverse process i s possi bl e as wel l . The conversi on of a gas i nto
a sol i d i s known as deposi ti on.
When a l i qui d changes to a gas, the process i s known as vapori zati on (remember the term
vapor i s used to descri be a gas that i s normal l y a sol i d or l i qui d at room temperature). Had
our mel ted i ce cube sat on the counter for an extended amount of ti me, the water woul d have
eventual l y vapori zed i nto water vapor. (We frequentl y cal l thi s evaporati on.) When the
reverse process occurs, that i s, when a gas converts i nto a l i qui d, the process i s known as
condensati on. A few types of condensati on that you are probabl y qui te fami l i ar wi th woul d
be the formati on of l i qui d on the outsi de of col d dri nk gl asses and dew formi ng on grass
or pl ants.
HEATING CURVES
A heati ng curve provi des you wi th a ni ce summary of the previ ous i nformati on whi l e al so
presenti ng you wi th some new i nformati on. Heati ng curves are obtai ned from the gradual
heati ng of a substance from the sol i d state to the gas state at a constant atmospheri c
pressure. As youl l see i n a l ater secti on, changes i n pressure have an i mpact on changes of
state. For now, we wi l l l i mi t oursel ves to atmospheri c pressure.
You may have done a l ab at one poi nt where you made a heati ng curve for water or a si mi l ar
substance. The way you woul d do thi s woul d be to obtai n a sampl e of i ce at a temperature
bel ow zero and begi n to sl owl y heat i t whi l e cl osel y moni tori ng the temperature. Heati ng
curves are someti mes pl otted wi th temperature over ti me. The di agram we are referri ng to
has temperature pl otted agai nst energy. I f you fol l ow Fi gure 9.2, you wi l l see that i ni ti al l y the
added heat i s used to change the temperature of the i ce, but, at thi s poi nt, no mel ti ng takes
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Chapter 9: States of MatterLiquids and Solids 179
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pl ace. Once the temperature of the i ce reaches 0C, i t wi l l begi n to mel t. There i s a peri od of
ti me, however, when the i ce i s mel ti ng and heat i s conti nual l y added, but the temperature
does not i ncrease. Thi s i s seen as the fi rst pl ateau on the graph. What i s happeni ng duri ng
thi s pl ateau, and why doesnt the temperature change? The temperature remai ns constant
because al l of the energy that i s bei ng added to the system i s bei ng used to break the strong
attracti ve forces that l ock the parti cl es i n the ri gi d sol i d state. The amount of energy that i s
requi red to compl etel y convert the sol i d to the l i qui d i s known as the heat of fusi on.
Once al l the parti cl es have broken free from thi s sol i d state (i .e., the sol i d has mel ted), then
the added heat causes an i ncrease i n the moti on of the parti cl es and a subsequent i ncrease i n
temperature. Thi s temperature i ncrease wi l l conti nue at a fi xed rate (determi ned by the type
of substance). Whi l e the substance i s getti ng hotter, a smal l number of parti cl es are
evaporati ng, but the bul k of the materi al remai ns i n the l i qui d state. Once the water or other
materi al reaches i ts boi l i ng temperature (at atmospheri c pressure), vapori zati on wi l l take
pl ace. Once agai n, however, the heati ng curve experi ences a pl ateau. As l ong as there i s l i qui d
present, the temperature of the l i qui d/vapor mi xture remai ns at the boi l i ng temperature (for
water, 100C at 1.00 atm pressure). The heat that i s bei ng added i s used to break apart the
i ntermol ecul ar attracti ons hol di ng the parti cl es together i n the l i qui d state. The quanti ty of
heat requi red to compl etel y convert the l i qui d to a gas i s known as the heat of vapori zati on.
The greater the i ntermol ecul ar attracti ons between parti cl es i n the l i qui d state, the greater
the heat of vapori zati on wi l l be. Because of the l arge amount of hydrogen bondi ng between
water mol ecul es, the heat of vapori zati on for water i s very l arge. I f youve ever been burned by
steam, you know i t i s extremel y pai nful . Thats because as the water vapor hi ts you and
condenses, al l of the heat that was absorbed i n the vapori zati on process i s rel eased duri ng
condensati on.
There i s a si mi l ar type of pl ot known as a cool i ng curve. Thi s provi des the same data, except
i t i nvol ves heat bei ng removed, or l ost from the system, rather than heat bei ng added. I t i s
essenti al l y a mi rror i mage of the heati ng curveal l parts are exactl y the same and represent
the same processes, onl y i n reverse. These types of graphs occasi onal l y appear on the AP test.
You shoul d know how to read and i denti fy al l of the parts on them.
Energy/Heat added
D
E
C
B
A
F
T
e
m
p
e
r
a
t
u
r
e
Figure9.2
180 PART III: AP Chemistry Review
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Sample: The questi ons that fol l ow are based on Fi gure 8.3.
Energy/Heat added
D
E
C
B
A
F
T
e
m
p
e
r
a
t
u
r
e
Figure9.3
I denti fy the l ocati ons on the heati ng curve of the fol l owi ng processes or quanti ti es:
a. Mel ti ng
b. Vapori zati on
c. A mi xture of sol i d and l i qui d exi sts
d. The substance just begi ns to boi l
e. The heat of vapori zati on
f. Condensati on
g. The substance i s total l y i n the l i qui d state
Answers:
a. Li ne BC. Mel ti ng begi ns at poi nt B and conti nues unti l poi nt C i s reached.
b. Li ne DE. Duri ng vapori zati on there i s no temperature change. The process of
vapori zati on begi ns to occur ri ght at poi nt D.
c. Li ne BC. Mel ti ng begi ns at poi nt B, when the substance begi ns to convert to l i qui d. I t
does not become compl etel y l i qui d unti l poi nt C.
d. Poi nt D.
e. Li ne DE. The heat of vapori zati on i s the amount of energy added between poi nts D and
E that represents al l energy used to overcome al l i ntermol ecul ar forces hol di ng the
substance i n the l i qui d state.
f. Li ne ED. Al though condensati on can occur at temperatures bel ow the boi l i ng
temperature, a heati ng curve i s not desi gned to show changes. Those are more
apparent i n a phase di agram (di scussed l ater i n the chapter). Condensati on begi ns at
poi nt E, where energy i s rel eased as parti cl es begi n to rejoi n i nto the l i qui d state.
g. Li ne CD. Duri ng thi s peri od, al l added energy i ncreases the temperature of the l i qui d.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 9: States of MatterLiquids and Solids 181
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You Try It!
Exami ne the cool i ng curve i n Fi gure 9.4, and answer the questi ons that fol l ow:
Energy/Heat added
V
U
Y X
W
Z
T
T
e
m
p
e
r
a
t
u
r
e
Figure9.4
I denti fy the l ocati ons on the heati ng curve of the fol l owi ng processes or quanti ti es:
1. Freezi ng
2. Condensati on
3. A mi xture of sol i d and l i qui d exi sts
4. The heat of vapori zati on
5. The substance i s total l y i n the l i qui d state
Answers:
1. W to Y
2. U to V
3. W to Y
4. U to V
5. V to W
VAPOR PRESSURE
I n the previ ous chapter, you l earned that i n a sampl e of a gas, the i ndi vi dual gas parti cl es had
vari ous amounts of ki neti c energy. Some had more than average, some had l ess. The same i s
true for any col l ecti on of parti cl es, even l i qui ds and sol i ds. I f you consi der a contai ner of water,
thi s means that some of the water mol ecul es have more ki neti c energy than others. Si nce the
parti cl es are constantl y i n moti on, they col l i de wi th one another, transferri ng some ki neti c
energy as they do (these col l i si ons are not el asti c). Occasi onal l y, at the surface of the water, a
parti cl e gai ns enough ki neti c energy to overcome the attracti ve forces exerted on i t by
nei ghbori ng water mol ecul es. When i t does, i t escapes from the water i nto the ai r, becomi ng a
gaseous mol ecul e. The amount of energy requi red to break free from the water i s known as
escapeenergy. Thi s process can occur at any temperature; however, one thi ng that shoul d be
remembered i s that at hi gher temperatures, a l arger percent of mol ecul es i n the l i qui d wi l l be
abl e to attai n the escape energy (theyre al ready cl oser to i t i n a hotter l i qui d). Another thi ng
182 PART III: AP Chemistry Review
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that shoul d be remembered i s that when a mol ecul e possessi ng a hi gher ki neti c energy l eaves,
the total ki neti c energy of the water decreases. Thi s i s why evaporati on i s consi dered a cool i ng
process. I f you have ever fel t a breeze bl ow by when you are wet, ei ther wi th sweat or wi th
water, you know that you get cool er. I n dry cl i mates, l i ke the desert Southwest, many homes
use evaporati ve cool ers. These cool i ng systems use a l arge fan and speci al pads that are
housed i n a uni t atop the house that are constantl y soaked wi th water. Hot ai r from the
outsi de, wi th the hel p of the l arge fan, i s cool ed through evaporati on as i t passes through the
web pads. The cool ed ai r i s then bl own i nto the house.
Now consi der a contai ner of water that i s seal ed, l i ke a ti ghtl y seal ed jar that i s hal f-fi l l ed
wi th water. I f you l eave the jar on a shel f for an extended peri od of ti me, the l evel of water
shoul d remai n constant (assumi ng there i s a good seal on the jar). Does thi s mean that
evaporati on i s not taki ng pl ace i n the jar? Certai nl y not! Heres how i t works: Parti cl es on the
surface sti l l l eave the l i qui d and begi n to enter the gas (ai r) above the l i qui d. However, i n the
seal ed jar they have nowhere to escape to, so they wi l l conti nual l y bounce around up i n the
top of the jar. Some may bounce off of the l i d; others may bounce off the gl ass, whi l e some wi l l
col l i de wi th other mol ecul es of gas i n the ai r space. And then there are those that wi l l col l i de
wi th the water surface. Some of the water mol ecul es that stri ke the surface, especi al l y those
that have l ost some ki neti c energy due to col l i si ons, wi l l not have suffi ci ent energy to l eave
agai n. That i s, they wi l l reenter the l i qui d state. For a peri od of ti me after the jar i s seal ed,
the number of parti cl es movi ng from the l i qui d to gas state wi l l exceed the number of parti cl es
returni ng from the gas state to the l i qui d state. However, as the number of parti cl es enteri ng
the gas state i ncreases, so wi l l the number of gas parti cl es enteri ng the l i qui d state. Thi s wi l l
happen unti l the parti cl es i n the jar reach a certai n poi nt, known as dynami c equi l i bri um,
where the rates at whi ch parti cl es are l eavi ng and reenteri ng the l i qui d wi l l be equal . Many
peopl e share the mi sconcepti on that everythi ng stops at thi s poi nt. Nonsense! I t onl y l ooks
that way because the rate at whi ch evaporati on and condensati on occur are equal , but both
processes are sti l l occurri ng. I f youre not convi nced, poke a hol e i n the bottom of a Styrofoam
cup. Then try fi l l i ng i t wi th water. I f you fi l l i t faster than i t can drai n, i t wi l l fi l l up. I f you fi l l
i t up sl ower than i t can drai n, i t wi l l stay empty. But i f you fi l l i t up at the exact same rate as
i t i s drai ni ng, the water l evel wi l l stay the same, even though i t i s fi l l i ng and drai ni ng at the
same ti me.
The parti cl es that have entered the gas state are now bounci ng around i n the top part of the
jar. As they do so, they are col l i di ng wi th everythi ng around them. Thi s creates vapor
pressure, whi ch i s the pressure exerted by the vapor when the l i qui d and gas states are i n
dynami c equi l i bri um.
Factors Affecting Vapor Pressure
I f you thi nk about i t a bi t, the factors that affect vapor pressure shoul d not come as any
surpri se. The fi rst one i s temperature. As temperature i ncreases, so does the average ki neti c
energy of the parti cl es i n the l i qui d (and the gas above i t). As a resul t, more parti cl es can
reach escape energi es and those that have escaped can exert more force (due to thei r
i ncreased energy) on thei r surroundi ngs. I f you recal l from the chapter on gases, for any
probl em where a gas was col l ected over a l i qui d (l i ke water), you had to take i nto account the
vapor pressure of water. Thats because you had a cl osed contai ner over the water catchi ng
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 9: States of MatterLiquids and Solids 183
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the gas. Whi l e i t was catchi ng the gas, i t was al so catchi ng the water vapor that had escaped
from the l i qui d. You al so may have noti ced that the amount of water vapor was l i sted for gi ven
temperatures. That was because the vapor pressure of water (or any l i qui d) i s affected
by temperature.
Another thi ng that affects vapor pressure i s vol ati l i ty. A vol ati l e l i qui d i s defi ned as a l i qui d
that attai ns rel ati vel y hi gh vapor pressures at normal temperatures. An easy way to thi nk of
i t i s that l i qui ds evaporate qui ckl y at room temperature. I f youve ever seen a gasol i ne spi l l on
the ground on a hot day, you may have noti ced that i t dri es up qui ckl y. Gasol i ne i s a vol ati l e
l i qui d and evaporates qui ckl y. I n a cl osed contai ner, i t acqui res a hi gh vapor pressure. Thi ngs
that dont evaporate qui ckl y, l i ke cooki ng oi l , have a very l ow vol ati l i ty. There are some sol i ds
that are consi dered vol ati l e, such as sol i d room deodori zers and mothbal l s (whi ch contai n
naphthal ene or para-di chl orobenezene). These materi al s subl i me; therefore, they can be
consi dered to have a vapor pressure at standard temperatures and pressures.
RELATIONSHIP BETWEEN BOILING POINT AND VAPOR PRESSURE
You may have been a l i ttl e confused by the sudden swi tch from cool i ng curves to vapor
pressure, but here i s where the two topi cs come together. When does a l i qui d boi l ? I f you are
thi nki ng of your experi ence wi th water, you may answer, When i t gets hot enough or When
i t reaches the boi l i ng temperature. However, nei ther of these i s real l y correct. A l i qui d boi l s
when the vapor pressure of the l i qui d equal s the external pressure. I f youre tal ki ng about an
open contai ner, l i ke a pot on a stove, external pressure means atmospheri c pressure. When
the two pressures are equal , thats when you see the bubbl es start to form i n the boi l i ng
l i qui d. Now, i f the atmospheri c pressure happens to be 1.00 atmospheres and the water i s
pure, then water wi l l boi l at 100C. However, water can be made to boi l at room temperature
i f you drop the pressure l ow enough (l i ke i n a bel l jar over a vacuum pump). By affecti ng the
boi l i ng temperature, vapor pressure affects the way food i s cooked (no, thi s i snt tri vi a
ti methi s has actual l y been on previ ous AP tests!). At hi gh el evati ons, there i s l ess
atmospheri c pressure. That means that the vapor pressure of the water does not have to be as
hi gh for boi l i ng to occur. I f you recal l from the heati ng curve, once the water starts to boi l , i t
wont get any hotter. That means at hi gher al ti tudes, water boi l s at a l ower temperature than
at l ower al ti tudes. I t takes l onger to cook foods at hi gh al ti tudes. There i s al so a cooki ng
devi ce known as a pressure cooker. These are pots that seal up ti ghtl y so that the pressure
above the l i qui d can bui l d up hi gher than atmospheri c pressure (there are val ves that prevent
them from expl odi ng). Because the external pressure i s hi gher, the l i qui d i n the pot can heat
above the normal boi l i ng temperature and cook more qui ckl y.
Pressure does not have nearl y the same effect on the mel ti ng/freezi ng poi nt of a l i qui d as i t
does on the boi l i ng poi nt.
Sample: I f you l i ved on top of a very hi gh mountai n and you made a cup of hot coffee usi ng
water boi l ed i n an open pot on the stove, how woul d i ts temperature compare to a
cup of coffee made at sea l evel ?
184 PART III: AP Chemistry Review
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Answer: I t woul d be l ower. At hi gh al ti tudes, the vapor pressure reaches equi l i bri um wi th
the atmospheri c pressure and l ower temperatures (because of the decreased
atmospheri c pressure at hi gh al ti tudes). At sea l evel , water boi l s at a hi gher
temperature.
You Try It!
How wi l l the ti me i t takes to hard-boi l an egg compare at hi gher al ti tudes?
Answer: I t wi l l take l onger because of the l ower boi l i ng temperature of the water.
Other Properties of Liquids
Weve l ooked at the vapor pressure of l i qui ds, but we havent real l y di scussed i n detai l the
factors that contri bute to the vapor pressures or vol ati l i ti es that are characteri sti cs of l i qui ds.
The factors are al l based on the i ntermol ecul ar forces from Chapter 6. Perhaps a few thi ngs
wi l l start to fal l i nto pl ace for you. I n the l ast secti on, we were l ooki ng at the mol ecul ar
processes that occur duri ng evaporati on. I f you recal l , a parti cl e had to possess enough energy
to escape from the l i qui d state to enter the gas state. But what keeps i t from l eavi ng? I n other
words, what i s keepi ng i t i n the l i qui d state? Most of thi s can be answered wi th the key words
i ntermol ecul ar attracti ons. The stronger the attracti ve forces are that hol d parti cl es
together, the more force wi l l need to be exerted to pul l them apart. Looki ng back at some of
the questi ons i n Chapter 6 about boi l i ng poi nts, thi s mi ght make more sense to you now.
Consi der the exampl es of methane, ammoni a, and water. Water i s the onl y l i qui d at room
temperature. (Dont confuse ammoni a wi th ammoni um hydroxi de, the sol uti on we cal l ed
househol d ammoni a.) Why? Because i t i s a very pol ar mol ecul e, i t i s capabl e of formi ng
strong hydrogen bonds between nei ghbori ng mol ecul es. I t takes a l ot more energy to get the
parti cl es apart. Thats why i t remai ns i n the l i qui d state at hi gher temperatures than the
others. Ammoni a i s capabl e of some hydrogen bondi ng, but not at the same degree as water.
I ts boi l i ng temperature i s between water and methane. Methane has the l owest boi l i ng poi nt
because i t i s a nonpol ar mol ecul e, bound onl y by di spersi on forces.
VISCOSITY
I ntermol ecul ar attracti ons are the pri mary cause of thi s phenomenonvi scosi ty or the
thi ckness of a l i qui d. I n general , l i qui ds contai ni ng l arger mol ecul es or l i qui ds wi th greater
i ntermol ecul ar forces between mol ecul es are thi cker l i qui ds. Motor oi l and corn syrup are
fai rl y vi scous l i qui ds. I ncreasi ng the temperature of a l i qui d general l y decreases i ts vi scosi ty.
SURFACE TENSION
Cohesi ve forces between parti cl es i n a l i qui d cause the phenomenon known as surface
tensi on. The term cohesi ve refers to the forces between parti cl es of a substance. I ts what
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Chapter 9: States of MatterLiquids and Solids 185
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weve been cal l i ng i ntermol ecul ar attracti ons. Surface tensi on occurs because there i s an
uneven attracti on between parti cl es on the surface of a l i qui d (see Fi gure 9.5).
Figure9.5
These uneven forces on the surface cause the mol ecul es to pack more ti ghtl y together and
create a more ri gi d surface.
Another type of force that can occur i s known as adhesi on, or adhesi ve force. These are the
forces that bi nd di fferent substances together. An exampl e of adhesi ve forces (other than
adhesi ve tape!) i s the way that water adheres to di fferent materi al s. When you fi rst l earned
how to read a graduated cyl i nder, you had to l earn to compensate for the meni scus, or the
curved part on the surface of the l i qui d. The meni scus forms when you put water i nto a
graduated cyl i nder because the adhesi ve force between the water mol ecul es and the gl ass i s
stronger than the cohesi ve forces hol di ng the water mol ecul es together.
PHASE DIAGRAMS
For the most part, our di scussi on about states of matter and phase changes has been l i mi ted
to temperature effects. The heati ng and cool i ng curves are i l l ustrati ons of temperature effects
on state. I n the secti on on vapor pressure, you were i ntroduced to the i dea that vari ati ons i n
pressure can al so cause changes i n state. When water boi l s at l ow temperatures, i t cl earl y
i l l ustrates that there are real l y two external factors i nvol ved i n changes of the state of water:
temperature and pressure. I n thi s secti on, you wi l l begi n to revi ew the effects of pressure on
state. Thi s wi l l be done wi th the hel p of phase di agrams, whi ch are di agrams that provi de
a graphi cal representati on of the states of matter for a substance under al l vari ati ons of
temperature and pressure.
Temperature
Vaporization
Freezing
Liquid Solid D
Critical
point
Condensation
Melting
Triple point
Deposition
Sublimation
A
C
B
Gas
P
r
e
s
s
u
r
e
Figure9.6
186 PART III: AP Chemistry Review
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Phase di agrams contai n a vari ety of i nformati on at vari ous l evel s of compl exi ty. The broadest
di sti ncti ons are the three l arge areas that are contai ned on the graph. Referri ng to Fi gure 9.6,
most of the l eft si de of the chart (those porti ons above and to the l eft of the l i nes connecti ng
poi nts B-A-C) represents those temperatures and pressures at whi ch the substance bei ng
shown exi sts as a sol i d. On the ri ght, bel ow the l i nes connecti ng B-A-D, are the temperatures
and pressures at whi ch the substance exi sts as a gas. The V-shaped regi on between the l i nes
connecti ng C-A-D represents the l i qui d state. The l i nes themsel ves represent the
temperatures and pressures at whi ch the states on ei ther si de are i n equi l i bri um. For
exampl e, the l i ne B-A represents the temperatures and pressures where the gas state and the
sol i d state are i n equi l i bri um. Li ne A-C represents the temperatures and pressures at whi ch
the sol i d and l i qui d states are at equi l i bri um, and the curve A-D represents the equi l i bri um
states between l i qui d and gas.
Two other speci al features on the di agram are desi gnated by bl ack dots. The dot at poi nt D,
known as the cri ti cal poi nt, represents the cri ti cal temperature and the cri ti cal
pressure (the poi nt at whi ch the l i qui d state no l onger exi sts, regardl ess of the amount of
pressure). The other dot represents the i ntersecti on of the three l i nes, known as the tri pl e
poi nt. The tri pl e poi nt represents the temperature and pressure at whi ch al l three phases
coexi st si mul taneousl y.
Al l of the phase changes l i sted earl i er i n the chapter are al so detectabl e on the phase
di agrams. The equi l i bri um l i nes, menti oned earl i er i n thi s secti on, represent those pl aces
where phase changes occur. For exampl e, at any of the l ocati ons al ong l i ne A-C, a transi ti on
from l eft to ri ght represents mel ti ng.
The phase di agram i n Fi gure 9.6 i s the di agram for water, whi ch i s not representati ve of most
substances. The mai n di fference i s the transi ti on from sol i d to l i qui d, l i ne A-C. For most
substances, thi s wi l l have a sl i ghtl y posi ti ve sl ope. You wi l l note that i n the di agram for water,
the sl ope i s negati ve. The posi ti ve sl ope for most substances means that as pressure i ncreases,
so does the mel ti ng temperature. Thi s shoul d make sense on an i ntui ti ve l evel . I ncreasi ng
pressure wi l l squeeze the parti cl es cl oser together, meani ng i t wi l l take more energy to break
them apart. Water, however, i s one of the few substances whose l i qui d state i s more compact
than the sol i d state. I n the sol i d state, water i s l ess dense than i t i s i n the l i qui d state, whi ch
i s why i ce fl oats on top of water. The reason that i ce expands i s because the crystal s i n sol i d
H
2
O arrange themsel ves i n an organi zed hexagonal structure that takes up more space than
the l ess organi zed, but more compact, arrangement of the l i qui d water mol ecul es.
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Chapter 9: States of MatterLiquids and Solids 187
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Sample: Use Fi gure 9.7 to answer the fol l owi ng questi on:
Temperature
D
E
C
B
A
P
r
e
s
s
u
r
e
Figure9.7
Whi ch poi nt represents the equi l i bri um between the l i qui d and gas phases duri ng
vapori zati on?
Answer: The correct answer i s D. The enti re l i ne from C to the cri ti cal poi nt E represents
equi l i bri um between the l i qui d and gas phases.
You Try It!
Referri ng to Fi gure 9.7, i ndi cate the poi nt on the graph that represents a pure sol i d
bel ow i ts mel ti ng poi nt.
Answer: The correct answer i s A.
THE SOLID STATE
The parti cl es i n a sol i d are hel d together wi th suffi ci ent force to mai ntai n a ri gi d structure. I n
some cases, these forces consi st of i ntermol ecul ar forces, whi l e i n others, chemi cal bonds.
Sol i ds are typi cal l y cl assi fi ed accordi ng to the types of forces that hol d the parti cl es together.
When cl assi fi ed thi s way, the four types of sol i d are mol ecul ar, i oni c, coval ent network, and
metal l i c.
Molecular Solids
Just l i ke the name suggests, these sol i ds are composed of mol ecul es that are hel d together by
i ntermol ecul ar forces of attracti on. I ce woul d be a perfect exampl e. Rel ati ve to the other
sol i ds, these tend to have much l ower mel ti ng temperatures. Thi s i s easy to remember
because they are not hel d together wi th chemi cal bonds, whereas the others are.
Ionic Solids
I oni c sol i ds are actual l y crystal l i ne sal ts composed of opposi tel y charged i ons that are hel d
together by el ectrostati c attracti on (i oni c bonds). I f you recal l from Chapter 6, the charged
parti cl es i ndi scri mi natel y bond to other opposi tel y charged parti cl es, formi ng l arge groupi ngs
of charged parti cl es. The arrangements tend to be hi ghl y regul ar, a resul t of the si mi l ar
188 PART III: AP Chemistry Review
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attracti ons and repul si ons that each speci fi c i on has i n the crystal . A crystal l atti ce i s
composed of a number of i denti cal subuni ts, known as uni t cel l s, that stack l i ke bui l di ng
bl ocks around and about each other i n a hi ghl y ordered fashi on. The i oni c bonds are very
strong bonds, and, as a resul t, i oni c sol i ds have hi gh mel ti ng poi nts. As you read i n Chapter 6,
the strength of the bonds i s usual l y measured i n terms of the l atti ce energy, or energy
requi red to separate a mol e of a sol i d i oni c compound to a mol e of gaseous i ons. The stronger
the attracti on i s between the i ons i n a crystal l i ne sol i d, the l arger the l atti ce energy. Another
characteri sti c of sal ts i s that they are fai rl y easy to shatter. The reason for thi s i s that the uni t
cel l s are arranged al ong pl anes, and when the crystal i s hi t, these pl anes wi l l sl i de past one
another sl i ghtl y, causi ng el ectrostati c repul si ons between nei ghbori ng i ons. These repul si ons,
whi ch occur when i ons that were al i gned wi th opposi tel y charge i ons pri or to bei ng hi t, move
sl i ghtl y so that they are bri efl y real i gned wi th l i ke-charged i ons.
Covalent Network Solids
These sol i ds are formed from atoms that are bonded coval entl y i nto l arge structures. These
are some of the strongest sol i ds due to thei r very stabl e coval ent bonds. Some of the most
common exampl es are graphi te (carbon atoms), di amond (carbon atoms), and quartz (si l i con
di oxi de). These mostl y have hi gh mel ti ng temperatures. Many of these structures, l i ke
di amond, are extremel y hard and resi st shatteri ng. The atoms i n the sol i d do not necessari l y
determi ne the properti es of the sol i d. For exampl e, graphi te and di amond are both composed
of carbon atoms, yet thei r properti es are enti rel y di fferent. Thi s i s due to the arrangement of
the carbon atoms i n the sol i d. I n di amond, the carbon atoms arrange themsel ves i n ri gi d
three-di mensi onal structures, whereas i n graphi te, the carbon atoms arrange themsel ves i n
l ong fl at sheets.
Metallic Solids
Metal l i c sol i ds have a very wi de vari ety of properti es. Thei r structures tend to be hi ghl y
ordered; the metal atoms arrange themsel ves i nto regul arl y packed structures, wi th the
l oosel y hel d val ence el ectrons del ocal i zed about the nucl ei . Whi l e mel ti ng poi nts vary a
tremendous amount (mel ti ng temperatures range from bel ow room temperature to above
3500C), there are some characteri sti cs that are shared. Most metal s are good conductors of
el ectri ci ty due to the l oosel y hel d val ence el ectrons. I n addi ti on, metal s are mal l eabl e (they
can be hammered/mol ded i nto di fferent shapes) and ducti l e (they can be drawn i nto wi res).
Thi s i s because the atoms are free to sl i de past each other and are not restri cted by ri gi d i oni c
or coval ent bonds.
Sample: I n whi ch of the fol l owi ng processes are coval ent bonds broken?
a. Br
2
(l) Br
2
(g)
b. H
2
O(s) H
2
O(g)
c. KCl (s) KCl (l)
d. Si O
2
(quartz) Si O
2
(g)
e. Cu(s) Cu(l)
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Chapter 9: States of MatterLiquids and Solids 189
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Answer: The correct answer i s Si O
2
(quartz) Si O
2
(g). S
i
O
2
(quartz) i s a coval ent network
sol i d. Therefore, i n i ts crystal l i ne form, the ri gi d sol i d structure i s mai ntai ned by
coval ent bonds. The other exampl es onl y i nvol ve the breaki ng of vari ous
i ntermol ecul ar forces.
You Try It!
Sel ect the process that woul d requi re the most energy:
1. Au(s) Au(l)
2. CH
3
OH(l) CH
3
OH(g)
3. SrCl
2
(s) SrCl
2
(l)
Answer: The correct answer i s SrCl
2
(s) SrCl
2
(l). Mel ti ng a stabl e i oni c compound
wi l l requi re much more energy than breaki ng most i ntermol ecul ar forces,
especi al l y the vapori zati on of an al cohol , choi ce 2, and the mel ti ng of a soft
metal l i ke gol d.
190 PART III: AP Chemistry Review
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EXERCISES: STATES OF MATTERLIQUIDS AND SOLIDS
Multiple Choice
1. 1-propanol , CH
3
CH
2
CH
2
OH, boi l s at
97C and ethyl methyl ether,
CH
3
CH
2
OCH
3
, boi l s at 7C, al though
each compound has an i denti cal
chemi cal composi ti on. The di fference
that i s responsi bl e for the hi gher
boi l i ng temperature i s
(A) mol ar mass.
(B) hydrogen bondi ng.
(C) densi ty.
(D) speci fi c heat.
(E) enthal py.
2. Whi ch of the fol l owi ng i s true at the
tri pl e poi nt of a pure substance?
(A) The temperature i s equal to the
normal mel ti ng poi nt.
(B) Al l three states have i denti cal
densi ti es.
(C) The sol i d-l i qui d equi l i bri um wi l l
al ways have a posi ti ve sl ope
movi ng upward from the tri pl e
poi nt.
(D) The vapor pressure of the sol i d
phase al ways equal s the vapor
pressure of the l i qui d phase.
(E) The pressure i s exactl y one-hal f
the cri ti cal pressure.
FOR QUESTIONS 35, USE THE KEY BELOW.
SELECT THE DESCRIPTION THAT BEST
DESCRIBES THE SUBSTANCE.
(A) A network sol i d wi th coval ent
bondi ng
(B) A mol ecul ar sol i d
(C) An i oni c sol i d
(D) A metal l i c sol i d
3. Dry i ce, sol i d carbon di oxi de, CO
2
4. Di amond, sol i d C
5. Brass, a mi xture of copper and zi nc
6. The cri ti cal temperature of a sub-
stance i s the
(A) temperature at whi ch the vapor
pressure of the l i qui d equal s
normal atmospheri c pressure.
(B) hi ghest temperature at whi ch a
substance can exi st i n the l i qui d
state, regardl ess of pressure.
(C) temperature at whi ch boi l i ng
occurs at 1.0 atmosphere of
pressure.
(D) temperature and pressure
where sol i d, l i qui d, and vapor
phases are al l i n equi l i bri um.
(E) poi nt at whi ch pressure and
temperature are l ess than 0.
7.
Figure9.8
When the l i qui d metal mercury, Hg,
i s pl aced i n a smal l tube, the meni s-
cus actual l y curves upward (see
Fi gure 9.8), just the opposi te of
water. The reason for thi s i s that
(A) the cohesi ve force i s greater
than the adhesi ve force.
(B) the adhesi ve force i s greater
than the cohesi ve force.
(C) the densi ty of mercury i s much
l arger than water.
(D) the densi ty of mercury i s much
greater where i t i s i n contact
wi th the gl ass.
(E) mercury i s l ess vol ati l e than
water.
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Chapter 9: States of MatterLiquids and Solids 191
www.petersons.com
QUESTIONS 811 REFER TO THE PHASE
DIAGRAM (FIGURE 9.9) SHOWN BELOW:
Temperature (C)
20
.5
2.5
1.0
1.5
2.0
120 60 100 140 40 80
P
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a
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m
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Figure9.9
USE THE KEY TO ANSWER QUESTIONS 810
(A) Subl i mati on
(B) Condensati on
(C) Sol vati on
(D) Fusi on
(E) Freezi ng
8. I f the temperature i ncreases from
10C to 60C at a constant pressure
of 0.5 atm, whi ch process occurs?
9. I f the temperature decreases from
100C to 60C at a constant pressure
of 1.5 atm, whi ch process occurs?
10. I f the pressure i ncreases from 0.5
atm to 1.5 atm at a constant tem-
perature of 100C, whi ch process
occurs?
11. The normal boi l i ng poi nt of the
substance i s approxi matel y
(A) 55C
(B) 65C
(C) 75C
(D) 85C
(E) 95C
12. Whi ch of the fol l owi ng expl ai ns why,
at room temperature, I
2
i s a sol i d,
Br
2
i s a l i qui d, and Cl
2
i s a gas?
(A) Hydrogen bondi ng
(B) Hybri di zati on
(C) I oni c bondi ng
(D) Resonance
(E) London di spersi on forces
Free Response
QUESTION 1
The normal mel ti ng and boi l i ng poi nts of oxygen are 55 K and 90 K, respecti vel y. The tri pl e
poi nt i s 54 K and 1 mm Hg (1.5 3 10
23
atm). The cri ti cal poi nt of O
2
i s 154 K and 50 atm.
(A) Use the data above to draw a phase di agram for oxygen. Label the axes and l abel
the regi ons i n whi ch the sol i d, l i qui d, and gas phases are stabl e.
(B) I f oxygen i s heated from 75 K to 130 K at 1.00 atm pressure, descri be any
changes that may occur.
(C) I f pressure i s i ncreased from 1.00 atm to 40 atm at a constant temperature of 110
K, descri be any changes that may occur.
(D) How does the densi ty of l i qui d oxygen, O
2
(l), compare to the densi ty of sol i d
oxygen, O
2
(s)? Expl ai n your answer usi ng both the data and your phase di agram.
192 PART III: AP Chemistry Review
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www.petersons.com
QUESTION 2
Gi ve sci enti fi c expl anati ons for each of the fol l owi ng i tems:
(A) Students worki ng i n a l ab i n a mountai nous regi on of Nevada measure the
boi l i ng temperature of water as 93C, whi l e students i n San Di ego, Cal i forni a,
measure the boi l i ng temperature of water as 100C. Both groups have accurate
thermometers.
(B) Pi oneers i n the hot, dry, desert Southwest used to dampen thei r bed sheets at
ni ght to keep cool er whi l e they sl ept.
(C) Graphi te, C(s), i s a very soft materi al used as a dry l ubri cant and i n the
producti on of penci l l eads. Di amond, al so C(s), i s an extremel y hard materi al ,
often used i n the producti on of i ndustri al dri l l bi ts and saws.
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Chapter 9: States of MatterLiquids and Solids 193
www.petersons.com
ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. B
2. D
3. B
4. A
5. D
6. B
7. A
8. A
9. E
10. B
11. D
12. E
1. The correct answer is (B). I n 1-propanol , the oxygen i s bonded to a carbon and a
hydrogen, whereas i n ethyl methyl ether, the oxygen i s bonded to two carbons. The
more pol ar O-H bond al l ows for greater hydrogen bondi ng than the C-H bonds al one.
2. The correct answer is (D). Because the tri pl e poi nt represents the temperature and
pressure at whi ch sol i d, l i qui d, and gas al l coexi st, the vapor pressures wi l l be i denti cal
at thi s poi nt.
3. The correct answer is (B).
4. The correct answer is (A).
5. The correct answer is (D). Brass, bei ng an al l oy, i s si mpl y a mi xture of the two
metal s. Because i t i s a mi xture, the metal s sti l l retai n thei r properti es as metal s.
6. The correct answer is (B).
7. The correct answer is (A). The cohesi ve forces between mercury atoms are much
stronger than the adhesi ve forces of mercury and gl ass. Thi s creates a strong surface
tensi on i n mercury as wel l as the upward bul ge i n the test tube. I n water, the adhesi ve
forces are greater, whi ch causes the mol ecul es on the edge of the test tube to cl i ng to the
gl ass whi l e the rest hang down from the si des. Thi s i s why water curves i n the
opposi te di recti on.
8. The correct answer is (A). Refer to l i ne 8 i n Fi gure 9.10.
9. The correct answer is (E). Refer to l i ne 9 i n Fi gure 9.10.
10. The correct answer is (B). Refer to l i ne 10 i n Fi gure 9.10.
11. The correct answer is (D). Note that thi s i s the temperature at whi ch l i qui d and
vapor states are i n equi l i bri um at 1 atm pressure.
Temperature (C)
20
.5
2.5
1.0
1.5
2.0
120
10
9
8
60 100 140 40 80
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s
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(
a
t
m
)
Figure9.10
194 PART III: AP Chemistry Review
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www.petersons.com
12. The correct answer is (E). These are nonpol ar di atomi c mol ecul es. The onl y
i ntermol ecul ar force between them i s London di spersi on force. The l argest mol ecul e, I
2
,
wi l l have the greatest forces, fol l owed by Br
2
and I
2
.
Free Response
QUESTION 1
(A) See Fi gure 9.11:
Temperature (K)
154 90 55
Liquid Solid
Triple
point
1.5 10
3
50
1
(c)
(b)
Gas
P
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s
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e

(
a
t
m
)

(
n
o
t

t
o

s
c
a
l
e
)
Critical
point
Figure9.11
(B) Note l i ne (b) i n Fi gure 9.11. The l i qui d oxygen wi l l vapori ze to oxygen gas under
these condi ti ons.
(C) Note l i ne (c) i n Fi gure 9.11. The oxygen gas wi l l condense to l i qui d oxygen.
(D) The densi ty of l i qui d oxygen i s l ower than sol i d oxygen. You can tel l thi s by the
posi ti ve sl ope of the equi l i bri um l i ne separati ng the sol i d and l i qui d states.
I ncreasi ng pressure al ong thi s l i ne l eads to an i ncrease i n the mel ti ng
temperature, i ndi cati ng a more dense state wi th addi ti onal i ntermol ecul ar
attracti ons.
QUESTION 2
(A) At hi gher el evati ons, atmospheri c pressure i s l ower. As a resul t, the boi l i ng poi nt
(whi ch i s the poi nt at whi ch the vapor pressure i s at equi l i bri um wi th the
atmospheri c pressure) wi l l al so be l ower. I n San Di ego, the ci ty i s essenti al l y at
sea l evel , where you woul d expect to fi nd atmospheri c pressures very cl ose to 1.0
atmosphere.
(B) Thi s process takes advantage of the cool i ng effects of evaporati on. As the water
evaporates from the sheet (whi ch i t i s guaranteed to do, gi ven the hot, dry
cl i mate), the average ki neti c energy of the water mol ecul es sti l l i n the sheet wi l l
decrease. Thi s decrease i n average ki neti c energi es i s fel t as a decrease i n
temperature, or a cool i ng.
(C) Whi l e both forms of carbon are network sol i ds, the structure of graphi te i s l arge
sheets of mol ecul es that easi l y sl i de past one another. I n di amonds, however, the
carbon atoms bond both verti cal l y and hori zontal l y, al l owi ng for much more ri gi d
three-di mensi onal structures, some of the hardest known.
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Chapter 9: States of MatterLiquids and Solids 195
www.petersons.com
SUMMING IT UP
Gases are characteri zed by thei r l ow densi ty, hi gh compressi bi l i ty, and fl ui di ty.
Li qui ds are vi rtual l y i ncompressi bl e and fl ui d and mai ntai n a constant vol ume.
Sol i ds are i ncompressi bl e and mai ntai n a constant vol ume.
Mel ti ng and freezi ng are terms to descri be the conversi ons between the sol i d and l i qui d
states. The amount of energy that i s absorbed or rel eased i n thi s process i s known as the
heat of fusi on.
Vapori zati on and condensati on are terms used to descri be the conversi ons between the
l i qui d and gaseous states. The amount of energy absorbed or rel eased i n thi s process i s
known as the heat of vapori zati on.
When matter converts di rectl y from the sol i d to the gaseous state i t i s known as
subl i mati on. The reverse i s cal l ed deposi ti on.
Heati ng curves are graphi cal representati ons of the temperature changes of a substance
as i t changes state from sol i d to gas, pl otted as a functi on of energy absorbed (or ti me).
Cool i ng curves show the reverse of thi s process.
The vapor pressure of a substance i n a cl osed system i s the pressure exerted by a vapor
that i s i n dynami c equi l i bri um wi th the l i qui d state. I ntermol ecul ar forces are the mai n
factors that determi ne vapor pressure.
The boi l i ng poi nt of a l i qui d i s the poi nt at whi ch the vapor pressure of the l i qui d i s equal
to the external pressure. As a resul t, the boi l i ng temperature i s affected by pressure,
i ncl udi ng pressure changes due to al ti tude.
Phase di agrams are graphi cal representati ons of the rel ati onshi ps between pressure,
temperature, and the state of a substance. You shoul d be abl e to read and i nterpret phase
di agrams for the AP test.
Sol i ds are usual l y descri bed accordi ng to the forces that hol d the parti cl es together. The
four types of sol i ds are mol ecul ar sol i ds, i oni c sol i ds, coval ent network sol i ds, and
metal l i c sol i ds.
196 PART III: AP Chemistry Review
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Solutions
OVERVIEW
Measuring concentration
Solvation
Colligative properties
Summing it up
I n the l ast two chapters, you revi ewed properti es of sol i ds, l i qui ds, and gases.
I n thi s chapter, you wi l l revi ew the processes that occur when two di fferent
substances mi x together to form a homogeneous mi xture. Remember from
your general chemi stry cl ass: homogeneous mi xtures are uni form throughout,
whi l e heterogeneous mi xtures have separate parts (or phases). An exampl e of
a homogeneous mi xture i s sal twater. The sal t and water are mi xed together,
but you cant di sti ngui sh the sal t from the water. Homogeneous mi xtures are
al so cal l ed sol uti ons. An i mportant characteri sti c of a sol uti on (homogeneous
mi xture) i s that you can separate i t usi ng ordi nary means. The sal t can be
separated from the water by evaporati ng the water away. Heterogeneous
mi xtures have di sti nct parts, l i ke a handful of i ron fi l i ngs mi xed i n wi th a
handful of sugar. Li ke homogeneous mi xtures, the materi al s have not reacted
chemi cal l ythey just happen to be i n the same pl ace at the same ti me. The
sugar and i ron can be separated easi l y ei ther wi th a magnet (attract the i ron)
or by throwi ng the mi xture i n water (di ssol ves the sugar).
There are two major di vi si ons i n a di scussi on of sol uti ons: sol uti on formati on
and sol ubi l i ty equi l i bri a. The fi rst topi c deal s wi th the mechani sms by whi ch
sol uti ons formdi fferent ways to descri be sol uti ons, factors that affect
sol uti on formati on, and some of the physi cal properti es of sol uti ons. Those are
the domai n of thi s chapter. Sol ubi l i ty equi l i bri a are di scussed i n Chapter 15,
after youve had a chance to revi ew the concept of equi l i bri um.
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c
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197
MEASURING CONCENTRATION
A sol uti on i s a mi xture of two or more thi ngs that bl end together i n a uni form way. When thi s
occurs, one materi al di ssol ves i n the other. The materi al that i s di ssol vi ng i s known as the
sol ute. The substance that i t i s di ssol vi ng i n i s cal l ed the sol vent. There are a vari ety of ways
to descri be the amount of sol ute that i s found i n the sol vent.
Popular Terminology
You may see concentrati on descri bed i n common terms out i n the real worl d. For exampl e, you
mi ght see a bottl e of vi negar that says 5 percent on i t. That means that out of 100 percent of
the sol uti on, 5 percent i s actual l y vi negar (aceti c aci d). Other percentages are gi ven by mass.
The concentrated hydrochl ori c aci d that you use i n the l ab i s purchased i n bottl es that are 37
percent HCl . That means that for every 100 g of sol uti on, 37 g are actual l y HCl . Sti l l another
popul ar descri pti on of sol uti ons i s parts per mi l l i on (ppm). Thi s i s used to descri be very
di l uted sol uti ons, for exampl e, the amount of avai l abl e chl ori de i on found i n a swi mmi ng pool
of water. On the AP test, you are unl i kel y to encounter these terms, but they hel p to gi ve you
a broader understandi ng of uni ts of concentrati on.
Chemistry Terminology
The three typi cal ways to descri be sol uti ons i n chemi stry are the mol e fracti on, mol ari ty, and
mol al i ty. The term normal i ty i s occasi onal l y used, but the Col l ege Board speci fi cal l y states
that i t i s not on the test, so wel l ski p i t. The mol e fracti on i s the same mol e fracti on we
di scussed earl i er. The mol e fracti on of substance A i s expressed i n Equati on 10.1:
X
A
moles A
total moles

Mol ari ty descri bes the number of mol es of sol ute per l i ter of sol uti on. Many students get thi s
l ast part mi xed up. They thi nk i t means per l i ter of sol vent. No! To cl ari fy, we can consi der an
exampl e of maki ng a sol uti on. I f you wanted to make a 2.0 M sol uti on of sodi um hydroxi de
(NaOH), you woul d wei gh out 2.0 mol es (80.0 g) of sol i d sodi um hydroxi de and transfer i t to a
1.00-l i ter vol umetri c fl ask. You woul d then add water unti l you had exactl y 1.00 l i ters of
sol uti on. You dont add 1.00 l i ters of water! To cal cul ate mol ari ty, you si mpl y di vi de the mol es
of sol ute by the l i ters of sol uti on. For substance A as expressed i n Equati on 10.2, the mol ari ty
woul d be:
M
A
moles A
liters of solution

Sample: Your l ab partner has just made a sol uti on for you to use i n a l ab but says she forgot
the mol ari ty. She remembers that she wei ghed out 83.0 g of KI and added enough
di sti l l ed water to equal 500 ml of sol uti on. What i s the mol ari ty of the KI ?
198 PART III: AP Chemistry Review
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(Equati on 10.1)
ALERT!
Molarity and mo-
lality are very simi-
lar words, so be
very careful to
knowthe
difference.
(Equati on 10.2)
www.petersons.com
Answer: Fi rst, remember that mol ari ty i s expressed i n mol es of sol ute per l i ter. You know
that the mass i s expressed i n a gram val ue, so the fi rst thi ng to do i s convert that
to mol es. Once youve done that, you wi l l be abl e to determi ne the mol ari ty:
83.0 g KI
1 mol
166 g KI

5 0.5 mol
At thi s poi nt, you are ready to substi tute your i nformati on i nto the mol ari ty equati on:
M
A
moles A
liters of solution
0.5 mol KI
0.5 liters of solution
5 1.0 M KI
Your l ab partner has mi xed a 1.0 M sol uti on of KI .
You Try It!
You are supposed to mi x 250 ml of a 0.1 M sol uti on of Pb(NO
3
)
2
sol uti on (mol ar mass
5 331.2 g mol
21
). You woul d need to mi x _____g of Pb(NO
3
)
2
wi th enough water to
make 250 ml sol uti on.
Answer: 8.28 g
Mol al i ty i s a bi t di fferent. I t i s cal cul ated as the mol es of sol ute per ki l ogram of sol vent. Two
mai n di fferences here: fi rst, you are measuri ng uni ts of mass i nstead of uni ts of vol ume, and
second, you are usi ng onl y the amount of sol vent i n the denomi nator. Thats where the
confusi on usual l y comes from wi th mol ari ty. Wi th mol ari ty, you are di vi di ng the mol es by the
amount of sol uti on, whereas i n mol al i ty, you are di vi di ng the mol es by the amount of
sol vent. To cal cul ate the mol al i ty of a sol uti on where substance A i s di ssol ved i n some sol vent,
you woul d use Equati on 10.3:
m
A
moles A
kilograms of solvent
=
The AP formul a sheet does not use the vari abl e for mol al i ty because i t woul d be the same as
mass. I nstead, the sheet wri tes the word mol al i ty i n the equati on.
For di l ute aqueous sol uti ons (sol uti ons where water i s the sol vent), the mol ari ty and mol al i ty
are very si mi l ar. Thi s i s because 1.00 L of water has a mass of 1.00 ki l ograms (at 4C,
anyway).
Because mol al i ty i s onl y based on mass val ues, i t does not vary wi th the temperature of the
sol uti on. Mol ari ty, on the other hand, does vary sl i ghtl y due to changes i n the vol ume of a
sol uti on at di fferent temperatures.
Sample: What i s the mol al i ty of a sol uti on that has 27.0 g of potassi um chromate (K
2
CrO
4
,
mol ar mass 194.2) di ssol ved i n 110.0 g of water?
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TIP
On the AP test for-
mula sheet, the
symbols for molar
mass and molarity
are nearly identi-
cal. The only dif-
ference is that the
molar mass is a
bold italic M, while
the molarity is just
an italic M. Make
sure you know
your formulas well
enough that you
dont confuse
the two.
(Equati on 10.3)
Chapter 10: Solutions 199
www.petersons.com
Answer: There i s more than one way to sol ve thi s probl em. There are certai n steps i n
common wi th al l of them, however. The fi rst step wel l perform i s to determi ne the
number of mol es i n 27.0 g of K
2
CrO
4
:
27.0 g K CrO
1 mol
194.2 g K CrO
mol K CrO
2 4
2 4
2 4
0 139 .
The mol al i ty requi res us to know the mol es of sol ute per ki l ogram of sol vent. We wi l l convert
our i nformati on i nto mol es per g of sol vent, and then i nto ki l ograms:
0 139 . mol K CrO
110 g H O
1000 g
1 kilogram
2 4
2
5 1.26 m
Note: Thi s fi nal step coul d al so have been cal cul ated wi thout the conversi on factor by
expressi ng the mass of water i n ki l ograms:
0 139 . mol K CrO
0.110 kg H O
2 4
2
5 1.26 m
You Try It!
A sol uti on i s prepared by di ssol vi ng 25.0 g of methanol (CH
3
OH, mol ar mass 32.0 g) wi th
80 g of ethanol (C
2
H
5
OH, mol ar mass 46.1 g). What i s the mol al i ty of the sol uti on?
Answer: 9.77 m
SOLVATION
Sol vati on i s the name of the process where a sol ute i s di ssol ved by a sol vent. An easy
exampl e to start wi th i s the di ssol vi ng of a pol ar sol ute, l i ke NaCl , i n a pol ar sol vent, H
2
O.
When the sodi um chl ori de crystal s are added to water, the pol ar water mol ecul es are
i mmedi atel y attracted to the crystal s. At the same ti me, the parti cl es i n the crystal are al so
attracted to the water, but the water mol ecul es are free to move about whi l e the sodi um and
chl ori de i ons are bound to the rest of the crystal . The water mol ecul es are attracted to the i ons
on the surfaces of the crystal . The oxygen atom i n the water mol ecul e, wi th i ts parti al
negati ve charge, i s attracted to the posi ti vel y charged sodi um i ons, whi l e the hydrogen atoms,
wi th thei r parti al posi ti ve charges, are attracted to the negati ve chl ori de i ons. I f the
attracti ons between water and the i ons i n the crystal are suffi ci ent, the i ons wi l l be removed
from the crystal l i ne l atti ce and wi l l move out i nto the l i qui d (i .e., be di ssol ved) as i n
Fi gure 10.1.
What happens next i s very si mi l ar to the equi l i bri um you read about i n the l ast chapter
between the l i qui d and vapor i n a cl osed contai ner. When the sal t i s added to the water, the
water has no sal t di ssol ved i n i t. Wi thi n a short ti me, the water i s fi l l ed wi th a number of
sodi um and chl ori de i ons. To real l y understand what happens next, thi nk of the fol l owi ng
exampl e: Pi cture yoursel f throwi ng a handful of sal t i nto a smal l contai ner of water. You can
probabl y i magi ne that no matter what you do to the water, there wi l l be a pi l e of sal t i n the
200 PART III: AP Chemistry Review
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www.petersons.com
bottom of the contai ner. Not al l of i t wi l l di ssol ve. (Thi s i s a l ot l i ke what happens when you
try to make chocol ate mi l k wi th too much chocol ate and not enough mi l k. No matter what you
do, there i s al ways that bi g gl ob of chocol ate on the bottom!) The l arge quanti ty of sal t begi ns
to di ssol ve i nto the water. However, as the sodi um and chl ori de i ons (surrounded by water
mol ecul es) move about i n the sol uti on, occasi onal l y they wi l l col l i de wi th the sal t crystal s.
Someti mes they wi l l bounce off, whi l e other ti mes they wi l l get stuck to the crystal agai n. The
greater number of sodi um and chl ori de i ons that are di ssol ved i n the water, the greater the
probabi l i ty that some wi l l col l i de wi th the sal t crystal . So whi l e the crystal i s di ssol vi ng i n the
water, i t i s bei ng reformed si mul taneousl y.
The reason for usi ng the exampl e of the bi g pi l e of sal t i n the water i s to make you aware of
the equi l i bri um that occurs. You may be tempted to thi nk that once the sal t stops di ssol vi ng
(i .e., when i t just si ts i n the bottom of the contai ner) al l acti vi ty has stopped i n the contai ner.
Dont thi nk i t! Remember the equi l i bri um system between water and water vapor? Remember
that when that system l ooked l i ke i t was not doi ng anythi ng, i t was real l y i n dynami c
equi l i bri um? Remember that the vapor was formi ng at the same rate as the l i qui d? Wel l , the
same thi ng i s occurri ng here. The crystal s are bei ng di smantl ed at the same rate that they are
bei ng reconstructed. As a resul t, you dont see any changes taki ng pl ace.
A sol uti on that i s i n thi s state, where i t has di ssol ved as much sol ute as i t possi bl y can at a
gi ven temperature, i s cal l ed a saturated sol uti on. What i f you onl y put a smal l pi nch of sal t
i nto a l arge contai ner of water? Do you thi nk i t woul d al l di ssol ve? I f you sai d yes, youre ri ght.
Do you thi nk you coul d get a l i ttl e more sal t to di ssol ve i n the l arge contai ner of water? I f you
sai d yes, youd be ri ght agai n. Sol uti ons that are not yet saturated, that i s, sol uti ons that can
di ssol ve more sol ute, are known as unsaturated sol uti ons. There i s a thi rd type of sol uti on,
known as a supersaturated sol uti on. These sol uti ons actual l y have more di ssol ved i n them
than they can hol d at a gi ven temperature. The way these sol uti ons are typi cal l y made i s to
heat the sol vent (whi ch wi l l al l ow you to di ssol ve more sol ute), saturate the sol uti on, and then
Figure10.1
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Chapter 10: Solutions 201
www.petersons.com
very careful l y cool the sol uti on. Most supersaturated sol uti ons are very unstabl e. By droppi ng
i n a smal l seed crystal or by scratchi ng the gl ass i nsi de the contai ner (whi ch creates
vi brati ons i n the sol uti on and ti ny pi eces of gl ass), you can usual l y get the sol ute to rapi dl y
preci pi tate out of the sol uti on.
You may have mi xed some sol uti ons before where, upon addi ng the sol vent to the sol ute, the
temperature began to i ncrease. Sodi um hydroxi de rel eases a great deal of heat when
di ssol vi ng. So do Epsom sal ts (magnesi um sul fate). There are even some substances, such as
ammoni um ni trate, that get col d when di ssol vi ng. Where does thi s heat come from? I t i s
known as the heat of sol uti on, and there are three separate processes that determi ne how
much heat wi l l be generated and al so whether the process wi l l be exothermi c or endothermi c.
At thi s poi nt i n the revi ew, we have not yet di scussed enthal py, H. A more detai l ed descri pti on
wi l l occur i n Chapter 17. For our purposes i n thi s chapter, you real l y onl y need to remember
two thi ngs. Fi rst, enthal py represents the heat associ ated wi th a process. (Later we wi l l tal k
about the heats associ ated wi th chemi cal reacti ons, but at thi s poi nt were l i mi ti ng the focus
to heats of sol uti on, H
sol uti on
, al so abbrevi ated H
sol n
.) The second thi ng you need to remember
i s that an exothermi c process, one that rel eases heat, has a negati ve enthal py (DH
sol n
, 0).
An endothermi c process i s one that requi res heat or takes i t from the envi ronment
(DH
sol n
. 0). The di ssol vi ng of sodi um hydroxi de i s exothermi c and ammoni um ni trate i s
endothermi c.
The heat of sol uti on i s determi ned by three separate enthal pi es associ ated wi th sol vati on. The
fi rst i s the energy associ ated wi th pul l i ng the sol ute apart. The second i s associ ated wi th
pul l i ng the sol vent apart, so that i t can accommodate the sol ute. The thi rd i s the heat
associ ated wi th sol ute and sol vent i nteracti ons. I f these i nteracti ons are very favorabl e, then
di ssol vi ng i s l i kel y to occur. I f they are not, di ssol vi ng i s not l i kel y to occur. Returni ng to our
sal twater exampl e, thi s process i s l i kel y to occur because there i s such a strong attracti on
between the pol ar water mol ecul es and the sodi um and chl ori de i ons. However, i f you throw a
handful of sal t i nto a cup of cooki ng oi l , very l i ttl e i s l i kel y to happen. Thats because the
attracti on between the sol ute and sol vent i s so much l ess than the attracti ons between the
mol ecul es i n the oi l and the sodi um and chl ori de i ons for each other. As a resul t, sal t, a pol ar
substance, wont di ssol ve i n a nonpol ar sol vent.
Like Dissolves Like
Though there are some excepti ons, i n most cases the rul e l i ke di ssol ves l i ke appl i es. That i s,
pol ar sol vents (l i ke water) can di ssol ve pol ar sol utes (l i ke sal ts), and nonpol ar sol vents (l i ke
gasol i ne) can di ssol ve nonpol ar sol utes (l i ke grease). These sol vent-sol ute i nteracti ons have
other effects on the properti es of sol uti ons that are the topi c of the upcomi ng secti on on
col l i gati ve properti es.
The Effects of Temperature and Pressure on Solubility
I n the previ ous secti on, you read about saturated, unsaturated, and supersaturated sol uti ons.
These terms are al l rel ated to the amount of sol ute that i s di ssol ved i nto a sol vent. However,
you probabl y al so know that the temperature of a sol vent affects the amount of sol ute that can
di ssol ve i n i t. The degree to whi ch the temperature affects di ssol vi ng i s somethi ng speci fi c to
each substance, but for most sol i d sol utes, an i ncrease i n temperature wi l l l ead to an i ncrease
202 PART III: AP Chemistry Review
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i n sol ubi l i ty. There are some substances that actual l y decrease i n sol ubi l i ty wi th i ncreased
temperature, but these are the excepti on rather than the rul e.
The effect of temperature i s opposi te for gases di ssol ved i n water. Gases become l ess sol ubl e at
hi gher temperatures. One of the mai n reasons that carbonated soft dri nks are usual l y served
wi th i ce (even when they are al ready col d), i s to keep them col d l onger. Thi s not onl y makes for
a more refreshi ng dri nk, i t mai ntai ns hi gher l evel s of di ssol ved CO
2
i n the beverage. Many
peopl e who try to get more dri nk for thei r money by orderi ng a soft dri nk wi thout i ce often fi nd
out that they have a warm, fl at, syrupy mess by the ti me they get near the bottom of the cup.
Pressure onl y affects sol uti ons of gases di ssol ved i n l i qui d sol vents. I f you have ever watched
a gl ass of soda, you probabl y saw the bubbl es fl oati ng to the top of the l i qui d. These were
bubbl es of di ssol ved carbon di oxi de comi ng out of the sol uti on. Because the gl ass i s open, the
carbon di oxi de that bubbl es out of the l i qui d wi l l move i nto the surroundi ng ai r. Over ti me,
nearl y al l of the CO
2
wi l l be gone. However, you know that a can of soda can si t on the shel f
for a very l ong ti me and sti l l remai n carbonated. The reason i s the contai ner i s cl osed. Whi l e
thats probabl y obvi ous to you, what i s goi ng on i nsi de the can may not be.
The process i nsi de a seal ed contai ner of a l i qui d-gas sol uti on i s very si mi l ar to the process of
equi l i bri um between the l i qui d and vapor states that we di scussed i n Chapter 9. The gas that
i s di ssol ved i n the l i qui d begi ns to come out of sol uti on and enter the ai r space above the
l i qui d. Over ti me, more and more parti cl es begi n to enter thi s space. However, as ti me
progresses, gas mol ecul es wi l l reenter the sol uti on. The system wi l l come to equi l i bri um, at
whi ch poi nt the rate at whi ch gas parti cl es are l eavi ng sol uti on wi l l be the same as the rate at
whi ch parti cl es are returni ng to sol uti on. I f the pressure above the l i qui d was suddenl y
i ncreased, the mol ecul es above the surface woul d exert more force and therefore return to
sol uti on more qui ckl y. The rate of di ssol vi ng woul d i ncrease whi l e the rate of gas formati on
woul d decrease unti l a new equi l i bri um was reached. Usual l y, carbonated beverages are
bottl ed at sl i ghtl y hi gher pressures than standard atmospheri c pressure. The hi ss you hear
when you open the bottl e or can i s the hi gh pressure ai r rushi ng out of the contai ner, comi ng
to equi l i bri um wi th the atmospheri c pressure.
COLLIGATIVE PROPERTIES
I n Chapter 9, you revi ewed heati ng and cool i ng curves i n addi ti on to phase di agrams. You al so
l ooked at factors that affect the boi l i ng temperatures of di fferent substances. Those
substances i n Chapter 9 were al l pure substances. I n thi s secti on, wel l l ook at how the
behavi ors of sol uti ons di ffer from those of a si ngl e substance. These properti es that are
affected by the presence (and amount) of a sol ute are known as col l i gati ve properti es. The
four col l i gati ve properti es are vapor-pressure reducti on, boi l i ng-poi nt el evati on, freezi ng-
poi nt depressi on, and osmoti c pressure.
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Chapter 10: Solutions 203
www.petersons.com
Vapor-Pressure Reduction
When a nonvol ati l e sol ute i s added to a sol vent, the vapor pressure of the resul ti ng sol uti on
wi l l be l ower than the vapor pressure of the pure sol vent. Why does thi s occur? To answer thi s,
you have to remember back to our di scussi on of the equi l i bri um between vapor and l i qui d i n
a cl osed system. I f you recal l , equi l i bri um i s reached when the rate that parti cl es are escapi ng
the l i qui d i s equal to the rate that the parti cl es are returni ng to the l i qui d. Al so recal l that
these transi ti ons take pl ace on the surface of the l i qui d. Now, suppose you add a nonvol ati l e
sol ute to the sol vent. (The AP curri cul um speci fi es that onl y the effects of nonvol ati l e sol utes
are requi red.) Because the sol ute i s nonvol ati l e, i t wi l l not enter the gaseous phase above the
l i qui d. What thi s means i s that at the surface of the l i qui d, where parti cl es of the sol vent can
escape, there are now some parti cl es of the sol ute mi xed i n wi th the sol vent. As a resul t, the
number of sol vent mol ecul es that are abl e to escape wi l l be l ess than the number that coul d
have escaped i n the pure sol vent (they are bl ocked by the sol ute parti cl es). The addi ti on of a
nonvol ati l e sol ute decreases the abi l i ty of sol vent mol ecul es to form vapors. Thi s means that
not as much vapor can form, whi ch al so means that there wi l l be fewer gaseous mol ecul es
returni ng to the l i qui d state. Thus, the vapor pressure i s reduced.
One of the fi rst to i nvesti gate the mathemati cal rel ati onshi p between the vapor pressure
reducti on and the amount of sol ute was Franoi s Raoul t. The mathemati cal rel ati onshi p he
determi ned i s known as Raoul ts l aw. What the l aw states i s that the parti al pressure of the
sol vent over a sol uti on equal s the vapor pressure of the pure sol vent ti mes the mol e fracti on
of sol vent i n the sol uti on. As Equati on 10.4, thi s becomes
P
A
5 P
A
X
A
where P
A
i s the vapor pressure of pure sol vent and X
A
the mol e fracti on of the sol vent. Put
very si mpl y, i f the mol e fracti on i s equi val ent to 99 percent of the pure sol vent concentrati on,
the new vapor pressure wi l l be 99 percent what i t was before the sol ute was added. Note, the
decrease of 1 percent woul d al so equal the mol e fracti on of the sol ute. Thus, the decrease i n
vapor pressure woul d be 1 percent.
Sample: A sol uti on of sugar water i s made by di ssol vi ng 200.0 g of sucrose, C
12
H
22
O
11
(mol ar
mass 342.3 g), i n 710.0 g of pure water at 25C. The vapor pressure of water at 25C
i s 23.76 mm Hg. Cal cul ate the vapor pressure of the sugar water, assumi ng al l of
the sucrose di ssol ves i n the water.
Answer: Were goi ng to use Raoul ts l aw to sol ve the probl em, but we need to determi ne the
mol e fracti on of water fi rst. Therefore, we need to determi ne the number of mol es of
sucrose present i n the sol uti on, and then the number of mol es of water present.
For the number of mol es of sucrose:
Mol es sucrose 5 200.0 g sucrose 3
1
3
mol sucrose
42.3 g sucrose
5 0.5843 mol sucrose
Mol es water 5 710.0 g water 3
1
1
mol water
8.01 g water
5 39.42 mol water
204 PART III: AP Chemistry Review
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(Equati on 10.4)
www.petersons.com
The mol e fracti on of water:
X
H O
2
2
2
mol H O
mol H O + mol sucrose

5
39.42 mol H O
39.42 mol H O + 0.5843 mol sucrose
2
2
5 0.9854
Now that we have thi s number, we can use the Raoul ts l aw:
P
H
2
O
5 P
H
2
O
X
H
2
O
5 (23.76 mm Hg)(0.9854) 5 23.41 mm Hg
The vapor pressure has been l owered 0.35 mm Hg by the addi ti on of sucrose.
You Try It!
Gl ucose, C
6
H
12
O
6
, i s commonl y mi xed wi th water to make i ntravenous feedi ng
sol uti ons. What woul d be the vapor pressure of a sol uti on where 60.0 g of gl ucose (mol ar
mass 180.16 g) i s di ssol ved i n 700.0 g H
2
O at 22C? The vapor pressure of pure water at
22C i s 19.83 mm Hg.
Answer: 19.66 mm Hg
Ideal Solutions
Li ke gases, sol uti ons can al so be thought of as i deal . Raoul ts l aw onl y works for i deal
sol uti ons. I deal sol uti ons are descri bed as those sol uti ons that fol l ow Raoul ts l aw. Sol uti ons
that devi ate from Raoul ts l aw are noni deal . What makes a sol uti on devi ate from i deal
behavi or? The mai n reason i s i ntermol ecul ar attracti ons between sol ute and sol vent. When
the attracti on between sol ute and sol vent i s very strong, the parti cl es attract each other a
great deal . Thi s makes i t more di ffi cul t for sol ute parti cl es to enter the vapor phase. As a
resul t, fewer parti cl es wi l l enter that state and the vapor pressure wi l l be l ower than
expected. Remember, Raoul ts l aw operates on the assumpti on that the reason for a decrease
i n the number of parti cl es l eavi ng the sol uti on i s that fewer can be on the surface i n order to
l eave. I f, i n addi ti on to thi s, the sol ute parti cl es are al so hol di ng more ti ghtl y to the sol vent
parti cl es, then fewer wi l l l eave the surface than expected. The most i deal sol uti ons are those
where the sol vent and sol ute are chemi cal l y si mi l ar.
I f the attracti on between the sol ute and sol vent i s l ess than the attracti on between sol vent
parti cl es or between sol ute parti cl es, then more parti cl es wi l l be abl e to l eave the l i qui d and
the vapor pressure wi l l be hi gher than predi cted. You shoul d defi ni tel y keep these two
condi ti ons i n mi nd as we go i nto the next secti on.
Boiling-Point Elevation
I f you remember, the boi l i ng poi nt for a substance i s the poi nt where the vapor pressure of the
l i qui d equal s the external pressure above the l i qui d. Changi ng the external pressure changes
the boi l i ng temperature, as we saw i n exampl es of di fferent boi l i ng temperatures at di fferent
al ti tudes. Now you have just l earned that addi ng a nonvol ati l e sol ute to a sol vent decreases
the vapor pressure of the sol uti on. That means that i f you are goi ng to try to boi l a sol uti on,
you wi l l have to heat i t to a greater temperature than you woul d a pure sol vent. To i ncrease
the amount of parti cl es l eavi ng the sol uti on to a l evel equal to that of the pure sol vent, you
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Chapter 10: Solutions 205
www.petersons.com
have to add more heat to the sol uti on. I n other words, the l i qui d wont boi l unti l youve added
that extra heat (i .e., rai sed i ts temperature).
From the conceptual l evel , thats why the boi l i ng temperature i ncreases when you add a
sol ute to a sol vent. Thats why you pour anti freeze i nto a car radi ator (i t al l ows the
temperatures of the water to i ncrease past the normal boi l i ng temperature). From a
mathemati cal l evel , however, there i s another consi derati on you must make. When you are
sol vi ng probl ems about boi l i ng-poi nt el evati on, you need to know how much the temperature
i s goi ng to i ncrease and what i t i s goi ng to be after a certai n amount or type of sol ute i s added.
For thi s, i t i s i mportant to consi der the nature of the sol ute.
Electrolytic Solutes
I f you throw a scoop of tabl e sugar i nto water and heat i t, wi l l i t have the same effect as a
scoop of tabl e sal t? Not qui te. The reason i s that when sugar i s di ssol ved, the crystal s break
apart i nto i ndi vi dual sucrose mol ecul es. When sal t di ssol ves, because i t i s an i oni c sol ute (al so
known as an el ectrol yte), i t does somethi ng a l i ttl e di fferent. I t breaks i nto two types of
parti cl es, sodi um i ons and chl ori de i ons, whi ch means that there wi l l be twi ce as many
parti cl es rel eased i nto the sol uti on as wi th sugar. A sal t l i ke magnesi um chl ori de, MgCl
2
, wi l l
rel ease three parti cl es, one magnesi um i on and two chl ori de i ons. When you cal cul ate the
boi l i ng poi nt el evati on, you must take the nature of the sol ute i nto account. The way you do
thi s i s wi th the vant Hoff factor (i). For your purposes you can assume that the vant Hoff
factor i s equal to the number of i ons that are produced from each uni t of sol ute di ssol ved. For
sucrose, i i s 1; for sodi um chl ori de, i i s 2; and for magnesi um chl ori de, i i s 3. Thi s i s an
oversi mpl i fi cati on of the vant Hoff factor, but thi s expl anati on i s more than suffi ci ent for the
AP test. The equati on for cal cul ati ng the boi l i ng poi nt el evati on, DT
b
, for a sol uti on, whi ch i s
gi ven to you on the AP test, i s Equati on 10.5:
DT
b
5 iK
b
m
where i i s the vant Hoff factor, K
b
i s the boi l i ng-poi nt el evati on constant, and m i s the
mol al i ty (not the mass; on the AP test, the equati on i s wri tten wi th the word molality, i nstead
of m). K
b
i s speci fi c to the sol vent and i s expressed i n vari ous uni ts. The probl ems i n thi s book
and others use C m
21
as uni ts for K
b
. The AP formul a sheet uses K kg mol
21
. However,
because a change of 1 degree Cel si us i s i denti cal to a change of 1 kel vi n and the uni ts for
mol al i ty are mol kg
21
, you shoul d see that the uni ts are real l y i denti cal to one another. Thi s
appl i es to K
f
, the freezi ng-poi nt depressi on constant, as wel l .
Sample: A cook adds 50.0 g of sal t (NaCl , mol ar mass 58.4 g) i nto a pot contai ni ng 1.00 kg of
water. She then bri ngs i t to a boi l . What wi l l be the temperature of the boi l i ng
sal ted water (assumi ng that pure water boi l s at 100)? K
b
for water i s 0.512C m
21
.
Answer: You wi l l use the boi l i ng-poi nt el evati on formul a to sol ve thi s. Because sodi um
chl ori de i s an el ectrol yte, i t wi l l be necessary to use the vant Hoff factor i n thi s
probl em. Each NaCl di ssoci ates i nto one Na
1
i on and one Cl
2
i on. Therefore, the
vant Hoff factor wi l l be 2.
206 PART III: AP Chemistry Review
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(Equati on 10.5)
www.petersons.com
Before we can substi tute the data i nto the equati on, we al so need to know the mol al i ty of the
sol uti on. To cal cul ate the mol al i ty, we need to determi ne the number of mol es of sal t per
ki l ogram of water. The fi rst step wi l l be to cal cul ate the number of mol es of sal t:
Mol es NaCl 5 50.0 g NaCl 3
1 mol NaCl
58.4 g NaCl
5 0.856 mol NaCl
Now, youre ready to determi ne the mol al i ty:
Mol al i ty 5
moles NaCl
kg H O
2
5
0.856 mol NaCl
1.000 kg H O
2
5 0.856 m
Now that the mol al i ty i s known, you can determi ne the boi l i ng poi nt el evati on:
DT
b
5 iK
b
m5 (2)(0.512C m
21
)(0.856 m) 5 0.877C
Therefore, the new boi l i ng poi nt wi l l be 100C 1 0.877C 5 100.877 or 100.9C.
You Try It!
A sol uti on i s made by mi xi ng 255 g of stronti um ni trate [Sr(NO
3
)
2
, mol ar mass 211.6 g]
i n 1.00 kg of water. I f the boi l i ng poi nt of pure water i s assumed to be 100.0C,
cal cul ate the predi cted boi l i ng poi nt of the stronti um ni trate sol uti on. K
b
for water i s
0.512C m
21
.
Answer: 101.9C (Remember, the vant Hoff factor wi l l be 3.)
Freezing-Point Depression
I n addi ti on to rai si ng the boi l i ng temperature of a sol uti on, the presence of a sol ute wi l l cause
a decrease i n the freezi ng temperature of a sol uti on. The decrease i n freezi ng temperature,
known as the freezi ng-poi nt depressi on, DT
f
, i s best expl ai ned usi ng a phase di agram, l i ke
those you revi ewed earl i er. I f you refer to Fi gure 10.2, note how the addi ti on of a nonvol ati l e
sol ute shi fts the posi ti on of the curve separati ng the l i qui d and gas states:
Temperature
Liquid
T
f
T
b
Solid
Gas
P
r
e
s
s
u
r
e
Figure10.2
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Chapter 10: Solutions 207
www.petersons.com
Thi s represents the vapor-pressure reducti on that you al ready read about. I f you trace i t down
to l ower temperatures, however, you wi l l noti ce that i t now meets the l i ne separati ng the sol i d
and gas states at a l ower posi ti on. Keep i n mi nd that above the l i ne (represented by the dotted
l i ne i n the fi gure), thi s sti l l represents the equi l i bri um between gas and l i qui d. Note that the
tri pl e poi nt has al so changed. The new freezi ng/mel ti ng poi nt for the substance must shi ft to
the l eft and begi n at the poi nt where the new dotted vapor pressure l i ne crosses. As a resul t,
the freezi ng temperatures for the substance change. Just as the presence of di ssol ved sol ute
parti cl es di srupted the vapori zati on process, they al so di srupt the freezi ng process. The added
parti cl es i nhi bi t the sol vents abi l i ty to crystal l i ze and therefore shi ft the freezi ng
temperature. Li ke the boi l i ng-poi nt el evati on, freezi ng-poi nt depressi on i s al so affected by the
number of sol ute parti cl es rel eased duri ng sol vati on. As a resul t, the formul a for the
freezi ng-poi nt depressi on wi l l al so have to i ncl ude the vant Hoff factor. Equati on 10.6 i s
wri tten as
DT
f
5 iK
f
m
where i i s the vant Hoff factor, K
f
i s the freezi ng-poi nt depressi on constant, and m i s the
mol al i ty. K
f
vari es wi th the sol vent.
Sample: A cool di p (col d pool that i s next to a hot tub) can be made by di ssol vi ng l arge
amounts of sal t i n water and then chi l l i ng i t. The resul ti ng sol uti on can be cool ed
bel ow 0C, the normal freezi ng temperature of water. I f a sal twater sol uti on was
made wi th 300 g of sal t (NaCl , mol ar mass 58.4 g) di ssol ved i n 1.00 kg of water, how
col d coul d the sal twater get before freezi ng? K
f
for water i s 1.86C m
21
.
Answer: Once agai n, the sol ute i s an el ectrol yte, so the vant Hoff factor must be used. Si nce
NaCl wi l l di ssoci ate i nto one Na
1
and one Cl
2
i on, the val ue of i i s 2.
The next step i s to determi ne the mol al i ty of the sol uti on. To do thi s, we need to di vi de the
mol es of NaCl by the ki l ograms of sol vent. Fi rst, however, we must know the number of mol es
of NaCl . Thi s can be cal cul ated by:
Mol es NaCl 5 300 g NaCl 3
1 mol NaCl
58.4 g NaCl
5 5.14 mol NaCl
The mol al i ty, therefore, wi l l be:
mol al i ty NaCl 5
5.14 mol NaCl
1.00 kg H O
2
5 5.14 m
The l ast step i s to cal cul ate the freezi ng-poi nt depressi on:
DT
f
5 iK
f
m5 (2)(1.86C m
21
)(5.14 m) 5 19.1C
The l owest the temperature can get, therefore, i s 0C 2 19.1C 5 2 19.1C
208 PART III: AP Chemistry Review
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(Equati on 10.6)
www.petersons.com
You Try It!
A sol uti on i s made by di ssol vi ng 250.0 g of potassi um chromate crystal s (K
2
CrO
4
mol ar
mass 194.2 g) i n 1.00 kg of water. What wi l l the freezi ng poi nt of the new sol uti on be?
K
f
for water i s 1.86C m
21
.
Answer: 27.18C
Osmotic Pressure
You may remember l earni ng about osmosi s i n a bi ol ogy cl ass. The term descri bes the
movement of water across semi permeabl e membranes. Semi permeabl e membranes al l ow
certai n si zes, or types, of parti cl es to pass through, but not others. I n chemi stry, the term can
refer to any sol vent; however, most appl i cati ons of the concept that are rel evant to you i nvol ve
water. The movement of water across the membrane hel ps to restore equi l i bri um to the
system. I n a system where two concentrati ons of a sol uti on are separated by a semi permeabl e
membrane, water can fl ow back and forth through the membrane. Water, on the si de of the
membrane wi th the l ower sol ute concentrati on, passes through the membrane to the si de wi th
the hi gher sol ute concentrati on. Li kewi se, water can pass from the si de wi th hi gher sol ute
concentrati on to the si de wi th l ower sol ute concentrati on. However, the presence of addi ti onal
sol ute parti cl es on the si de wi th hi gher concentrati on reduces the amount of sol ute parti cl es
that are abl e to pass through the membrane to the si de wi th l ower concentrati on (much l i ke
the sol ute parti cl es preventi ng the escape of sol vent from the l i qui d to vapor phase). Thi s
creates a net fl ow of sol vent i nto the area of hi ghest sol ute concentrati on. However, the net
fl ow of water al so creates an i ncrease i n pressure on the si de of the membrane wi th hi gher
concentrati on of sol ute.
The cause of thi s i ncrease i n pressure can vary dependi ng on the system. I f the system i s an
open contai ner wi th a membrane separati ng the si des, the fl ow of water to one si de wi l l
i ncrease the vol ume on that si de. That wi l l cause the water to ri se to a hi gher l evel . The mass
of sol uti on pushi ng down (due to gravi ty) provi des the pressure i n thi s case. I f the system
consi sts of the sol uti ons on the i nsi de and outsi de of a l i vi ng cel l , the membrane of the
swel l i ng cel l wi l l exert a pressure. The ori gi n of the pressure makes no di fference to us. The
i mportant thi ng i s that the i ncreased pressure i ncreases the fl ow of water back i nto the area
of l ower concentrati on. Thus, the pressure wi l l conti nue to i ncrease unti l equi l i bri um i s
establ i shed. The amount of pressure that i s requi red to just establ i sh equi l i bri um, or to stop
the net fl ow of water, i s known as osmoti c pressure, p. Osmoti c pressure can be cal cul ated
usi ng an equati on that i s very si mi l ar to the i deal gas l aw equati on. The equati on, al so
provi ded for you on the AP test, i s Equati on 10.7:

nRT
V
i
where R i s the i deal gas constant and T i s the absol ute temperature. The equati on i s often
si mpl i fi ed so that the
n
V
i s converted to the mol ari ty, M. Rewri tten, i t appears as:
p 5 MRTi
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(Equati on 10.7)
(Equati on 10.8)
Chapter 10: Solutions 209
www.petersons.com
Sample: A sol uti on i s made by pl aci ng 220.0 g of gl ucose (C
6
H
12
O
6
, mol ar mass 5 180.16 g)
i n a vol umetri c fl ask and addi ng di sti l l ed water to equal 1.00 L of sol uti on.
Cal cul ate the osmoti c pressure at 25C. Gl ucose i s a nonel ectrol yte.
Answer: Because you are gi ven a mass of gl ucose and a vol ume of sol uti on, you can
determi ne the mol ari ty of the sol uti on, whi ch al l ows us to use Equati on 10.8. I n
order to determi ne the mol ari ty of the sol uti on, you wi l l need to determi ne the
number of mol es of gl ucose i n the sol uti on:
220.0 g gl ucose 3
1 mol glucose
180.16 g glucose
5 1.221 mol gl ucose
From thi s, you can determi ne the mol ari ty of the sol uti on:
Mol ari ty 5
moles solute
liters of solution
5
1.221 mol glucose
1.00 L solution
5 1.221 mol L
21
p 5 MRTi 5 (1.221 mol L
21
)(0.0821 L atm mol
21
K
21
)(298 K)(1) 5 29.9 atm
You Try It!
I f you were to add 50.0 g of sodi um chl ori de, an el ectrol yte (NaCl , mol ar mass 58.44
g), to enough water to make 1.00 L of sol uti on, what woul d be the osmoti c pressure of
the sol uti on at 22C?
Answer: 41.4 atm
Applications of Colligative Properties
One of the l aboratory requi rements for the course, and al so the topi c of former test questi ons,
i s the determi nati on of the mol ar mass of a substance from the freezi ng-poi nt depressi on.
Actual l y, any of the col l i gati ve properti es can be used to determi ne the mol ar mass, but the
onl y one that you are requi red to know i s the freezi ng-poi nt depressi on method. I t i s easi er to
i l l ustrate the techni que wi thi n the framework of a probl em, so the di scussi on of thi s process
wi l l be done wi thi n a sampl e probl em.
Sample: 100 grams of an unknown substance was di ssol ved i n 900 g of water. The freezi ng
temperature of the sol uti on was determi ned to be 23.76C. What i s the mol ar mass
of the unknown substance? Assume that K
f
5 1.86C kg mol
21
.
Answer: Fi rst of al l , the val ue of K
f
(or K
b
for that matter) wi l l be gi ven to you. The val ues
for water are i ncl uded on the AP equati on sheet. Second, you need to set up your
equati on.
Begi nni ng wi th the formul a for cal cul ati ng the freezi ng-poi nt depressi on
DT
f
5 iK
f
m
210 PART III: AP Chemistry Review
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NOTE
The units for molar-
ity have been left
as mol L
21
so you
can see howthe
units of R, the
ideal gas con-
stant, will cancel
them. Because
glucose is a non-
electrolyte, the
vant Hoff
factor is 1.
www.petersons.com
you must determi ne what you have been gi ven and what you need to use to sol ve the probl em.
Because a formul a i s not present, nor i s the vant Hoff factor, you have to assume that i t i s not
needed. Because of thi s, you wi l l drop i t from the equati on. The equati on now becomes:
DT
f
5 K
f
m
We have been gi ven K
f
and DT
f
. I f you substi tute the gi ven i nformati on ri ght now, you wi l l
know the mol al i ty of the sol uti on. Youl l be hal fway there at that poi nt:
DT
f
K
f
5 m5
3.76C
1.86C kg mol
21
5 2.02 mol kg
21
Thi s tel l s us that there are 2.02 mol es of the unknown substance di ssol ved i n each kg of
water. The probl em i s that the substance i snt di ssol ved i n 1 kg of water. I ts di ssol ved i n
900 g. I n the next step, you need to fi gure out how many mol es are di ssol ved i n the 900 g of
water. Thi s i s accompl i shed by si mpl y mul ti pl yi ng the val ues together (usi ng common uni ts,
however):
2.02 mol kg
21
3 0.900 kg 5 1.82 mol
At thi s poi nt, you now know that 100 g of the substance i s equal to 1.82 mol , so you can easi l y
cal cul ate the mol ar mass of the sol ute as fol l ows:
n 5
m
M
M 5
m
n
5
100 g
1.82 mol
5 54.9 g mol
21
You Try It!
1.00 g of a nonel ectrol yte i s di ssol ved i n 100.0 g of pure water. What i s the mol ar mass of
the sol ute i f the freezi ng poi nt of the sol uti on i s 20.103C? K
f
for H
2
O i s 1.86C m
21
.
Answer: 181 g
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Chapter 10: Solutions 211
www.petersons.com
EXERCISES: SOLUTIONS
Multiple Choice
1. An aqueous sol uti on of potassi um
i odi de, KI , i s heated from 25C to
85C. Duri ng the ti me peri od whi l e
the sol uti on i s bei ng heated, whi ch of
the fol l owi ng i s true?
(A) The mol e fracti on of sol ute
decreases.
(B) The mol e fracti on of sol vent
i ncreases.
(C) The densi ty of the sol uti on
i s constant.
(D) The mol ari ty of the sol uti on
i s constant.
(E) The mol al i ty of the sol uti on
i s constant.
2. I f you were tryi ng to i ncrease the
amount of di ssol ved carbon di oxi de
gas, CO
2
(g), i n water, whi ch set of
condi ti ons woul d al l ow you the
hi ghest l evel s of di ssol ved CO
2
?
Pressure of
CO
2
(g)
above
H
2
O(l) (atm)
Temperature
of
H
2
O(l) (C)
(A) 10.0 90
(B) 10.0 10
(C) 5.0 90
(D) 5.0 10
(E) 1.0 10
3. Whi ch of the fol l owi ng pai rs of
l i qui ds forms the most i deal sol uti on
(the sol uti on that most cl osel y fol l ows
Raoul ts l aw)?
(A) C
6
H
14
(l) and H
2
O(l)
(B) CH
3
CH
2
CH
2
OH(l) and H
2
O(l)
(C) CH
3
CH
2
OH(l) and C
6
H
14
(l)
(D) C
6
H
6
(l) and C
6
H
5
CH
3
(l)
(E) H
3
PO
4
(l) and H
2
O(l)
4. Whi ch of the fol l owi ng sol uti ons has
the l owest freezi ng poi nt?
(A) 0.50 m C
12
H
22
O
11
(B) 0.50 m KNO
3
(C) 0.50 m MgSO
4
(D) 0.50 m Na
3
PO
4
(E) 0.50 m K
2
CrO
4
5. 100.0 mi l l i l i ters of a 4.00 mol ar
sol uti on of KBr (mol ar mass 119.0 g)
woul d contai n _______of KBr.
(A) 2.98 g
(B) 4.76 g
(C) 47.6 g
(D) 476 g
(E) 500 g
6. An aqueous sol uti on of si l ver ni trate
(AgNO
3
, mol ar mass 169.9 g) i s
prepared by addi ng 200.0 g AgNO
3
to
1,000 g H
2
O. I f K
f
for H
2
O i s
1.86C m
21
, the freezi ng poi nt of
the sol uti on shoul d be
(A) 0.00C
(B) 2 0.219C
(C) 2 0.438C
(D) 2 2.19C
(E) 2 4.38C
7. A sol uti on of gl ucose (mol ecul ar
wei ght 180.16) i n water (mol ecul ar
wei ght 18.01) i s prepared. The mol e
fracti on of gl ucose i n the sol uti on i s
0.100. What i s the mol al i ty of
the sol uti on?
(A) 0.100 m
(B) 0.162 m
(C) 3.09 m
(D) 6.17 m
(E) 10.0 m
212 PART III: AP Chemistry Review
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www.petersons.com
8. Your teacher has asked you to
prepare 1.00 l i ters of a 0.100-mol ar
aqueous sol uti on of sodi um hydroxi de
(mol ar mass 40.0 g). You shoul d
wei gh out
(A) 4.00 g NaOH and add 1.00 l i ter
of di sti l l ed H
2
O.
(B) 2.50 g NaOH and add 1.00 l i ter
of di sti l l ed H
2
O.
(C) 4.00 g NaOH and add 1.00
ki l ogram of di sti l l ed H
2
O.
(D) 4.00 g NaOH and add di sti l l ed
H
2
O unti l the sol uti on has a
vol ume of 1.00 l i ters.
(E) 2.50 g NaOH and add di sti l l ed
H
2
O unti l the sol uti on has a
vol ume of 1.00 l i ters.
9. Whi ch of the fol l owi ng aqueous
sol uti ons has the hi ghest boi l i ng
poi nt?
(A) 0.10 M sodi um fl uori de, NaF
(B) 0.10 M ni tri c aci d, HNO
3
(C) 0.10 M ammoni um hydroxi de,
NH
4
OH
(D) 0.10 M magnesi um chl ori de,
MgCl
2
(E) 0.20 M gl ucose, C
6
H
12
O
6
10. The vapor pressure of water at 50C
i s 92.5 mm Hg. I f 400.0 g of sucrose
(C
12
H
22
O
11
, mol ar mass 342.3 g) i s
added to 900.0 g of H
2
O at 50C,
what wi l l the vapor pressure of the
sol uti on be?
(A) 94.6 mm Hg
(B) 92.3 mm Hg
(C) 90.4 mm Hg
(D) 88.3 mm Hg
(E) 27.4 mm Hg
11. How much pure water (H
2
O, mol ar
mass 18.01 g) woul d 81.1 g of i ron
(I I I ) chl ori de (FeCl
3
, mol ar mass
162.2) be di ssol ved i n to make a
sol uti on wi th a mol al i ty of 1.5 m?
(A) 333 kg
(B) 333 g
(C) 3.33 kg
(D) 666 g
(E) 500 ml
12. What i s the osmoti c pressure of a
0.100-mol ar sal i ne sol uti on (NaCl
di ssol ved i n H
2
O) at 27C?
(A) 0.22 atm
(B) 0.44 atm
(C) 2.5 atm
(D) 4.9 atm
(E) 9.8 atm
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Chapter 10: Solutions 213
www.petersons.com
Free Response
QUESTION 1
A 0.562 g sampl e of an unknown substance was di ssol ved i n 17.4 g benzene. The freezi ng
poi nt of the sol uti on was 4.075C. The freezi ng poi nt of pure benzene i s 5.455C. For benzene,
K
f
5 5.065C m
21
, and K
b
5 2.61C m
21
. Assume that the sol ute i s a nonel ectrol yte.
(A) What i s the mol al i ty of the sol uti on?
(B) What i s the mol ar mass of the unknown?
(C) I f the boi l i ng temperature of pure benzene i s 80.2C, what i s the boi l i ng
temperature of the sol uti on?
(D) What i s the vant Hoff factor? Expl ai n whether the use of one was necessary i n
these cal cul ati ons.
Fi gure 10.3
QUESTION 2
A hi gh school student was goi ng to determi ne the mol ar mass of an unknown compound usi ng
the freezi ng-poi nt depressi on techni que. A sampl e of sol vent was fi rst chi l l ed to i ts freezi ng
temperature i n a smal l test tube that was pl aced wi thi n a second test tube as shown i n Fi gure
10.3. Fol l owi ng the i ni ti al tri al , a careful l y measured amount of water was added to the test
tube and the tube and i ts contents wei ghed. A smal l amount of sol ute was wei ghed and added
to the test tube contai ni ng the water. The freezi ng temperature was measured agai n i n the
same way as the i ni ti al tri al wi th the pure water. Assume that:
the sol ute was a nonel ectrol yte.
the temperature of the l i qui d i n the smal l test tube was uni form throughout.
a graduated cyl i nder and an anal yti cal bal ance are avai l abl e.
214 PART III: AP Chemistry Review
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www.petersons.com
(A) Wri te the equati on(s) needed to cal cul ate the mol ar mass of the sol ute.
(B) Li st the measurements that must be made i n order to cal cul ate the mol ar mass of
the sol ute.
(C) Expl ai n the purpose of pl aci ng the test tube contai ni ng the l i qui ds i nsi de the
l arger test tube.
(D) The student determi nes the mol ar mass of the sol ute to be 170 g mol
21
. Show the
setup you woul d use to cal cul ate the percent error for the experi ment i f the mass
of the unknown was actual l y 180 g mol
21
(i t i s not necessary for you to perform
the cal cul ati on).
(E) I f the student had used the mol ari ty rather than the mol al i ty i n the
determi nati on of the mol ar mass, how woul d thi s have affected hi s resul ts.
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Chapter 10: Solutions 215
www.petersons.com
ANSWER KEY AND EXPLANATIONS
Multiple Choice
1. E
2. B
3. D
4. D
5. C
6. E
7. D
8. D
9. D
10. C
11. B
12. D
1. The correct answer is (E). The mol al i ty, because i t i s onl y dependent on the mass of
the sol ute and sol vent, does not change as temperature changes. Vol ume does vary wi th
temperature, whi ch i s why choi ces (C) and (D) are not appropri ate. Mol e fracti ons are
unaffected by vol ume changes, but they do remai n constant duri ng heati ng (unl ess
vapori zati on accompani es the heati ng).
2. The correct answer is (B). Gases are most sol ubl e i n l i qui ds at l ower temperatures
and when hi gher parti al pressures of the gas are present above the l i qui d. Choi ce (B)
represents the condi ti ons of hi ghest pressure and l owest temperature.
3. Thecorrect answer is(D). The two l i qui ds shown i n D represent the most chemi cal l y
si mi l ar el ements l i sted. The others i n the l i st wi l l experi ence more i ntermol ecul ar forces.
4. Thecorrect answer is (D). Whi l e at fi rst gl ance al l of the sol uti ons may l ook si mi l ar,
on cl oser i nspecti on there are i mportant di fferences. Wi th the excepti on of sucrose, the
other sol utes are el ectrol ytes. Thi s means they wi l l separate i nto i ons when they
di ssol ve. The vant Hoff factor must be consi dered when determi ni ng freezi ng poi nts.
Sodi um phosphate, Na
3
PO
4
wi l l separate i nto 4 i ons, 3 Na
1
and 1 PO
4
23
. That wi l l
create more sol ute parti cl es i n the sol uti on than any of the others, whi ch wi l l l ower the
freezi ng poi nt.
5. Thecorrect answer is(C).A 4.00 mol ar sol uti on of KBr woul d contai n 4 mol es of KBr
per l i ter. Thi s i s the equi val ent of 4 mol 3 119 g/mol 5 476 g of KBr. Because we are
onl y goi ng to obtai n 100.0 mi l l i l i ters of the sol uti on (
1
10
of a l i ter), the amount of KBr wi l l
be
1
10
the amount. Hence, 0.10 L 3 476 g/L 5 47.6 g.
6. The correct answer is (E).
200 g AgNO
3
169.9 g mol
21
5 1.177 mol AgNO
3
1.177 mol AgNO
3
1.00 kg H
2
O
5 1.1777 m
DT
f
5 iK
f
m5 (2)(1.86C m
21
)(1.177 m) 5 24.38C.
The vant Hoff factor of 2 was needed because of the di ssoci ati on of AgNO
3
i nto one
Ag
1
i on and one NO
3
2
i on.
216 PART III: AP Chemistry Review
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7. The correct answer is (D). I f the mol e fracti on of gl ucose i s 0.100, that means that
the mol e fracti on of water must be 1.00 2 0.100 5 0.900. Knowi ng thi s, you can
determi ne the mass of the sol vent, and from that the mol al i ty:
0.900 mol H
2
O 3 18.01 g mol
21
5 16.209 g H
2
O
mol al i ty 5 mol gl ucose/kg H
2
O 5
0.100 mol
0.016209 kg H
2
O
5 6.17 m.
8. The correct answer is (D). I ts very i mportant that you remember the defi ni ti on of
mol ari ty: mol ari ty i s the number of mol es of sol ute per l i ter of sol uti on. That means that
the contents of the sol ute and sol vent must equal 1.00 l i ters. I n thi s probl em, the
sol uti on i s to be 0.100 mol ar, whi ch means that there are 0.100 mol es of sol ute per 1.00
l i ters. 0.100 mol 3 40.0 g mol
21
5 4.00 g.
9. The correct answer is (D). The sol ute that produces the most parti cl es i n sol uti on
wi l l produce the sol uti on wi th the hi ghest boi l i ng poi nt. (E) i s a tempti ng choi ce because
the concentrati on i s twi ce that of any other. Gl ucose, however, i s not an el ectrol yte. (A),
(B), and (C) wi l l al l have vant Hoff factors of 2, whi l e MgCl
2
has a vant Hoff factor of
3, whi ch wi l l produce the greatest boi l i ng-poi nt el evati on.
10. Thecorrect answer is (C). Thi s i s a vapor-pressure reducti on probl em. The fi rst step
i s to determi ne the mol e fracti on of water i n the sol uti on. Thi s wi l l then be used to
determi ne the vapor pressure of the sol uti on:
400 g sucrose 3
1 mol
342.3 g
5 1.169 mol sucrose
900 g H
2
O 3
1 mol
18.01 g
5 49.972 mol H
2
O
mol e fracti on 5
S
mol H
2
0
mol sucrose 1 mol H
2
O
D
5
49.972 mol
~1.169 mol 1 49.972 mol !
5 0.9771
P
A
5P
H
2
O
X
A
5 (92.5 mm Hg)(0.9771) 5 90.4 mm Hg.
11. The correct answer is (B). Mol al i ty i s mol es of sol ute per ki l ogram of sol vent.
Therefore, you fi rst need to cal cul ate the number of mol es of FeCl
3
that are i n 81.1 g.
After a qui ck eyebal l i ng you mi ght noti ce that 81.1 i s hal f of 162.2, whi ch means that
you have 0.5 mol es of FeCl
3
. Wi th thi s i nformati on, you can use the mol al i ty equati on to
cal cul ate the answer:
mol al i ty 5
mol es FeCl
3
kg H
2
O
1.5 m 5
0.5 mol FeCl
3
X kg H
2
O
X kg H
2
O 5
0.5 mol FeCl
3
1.5 m
X 5 0.333 kg H
2
O or 333 g.
a
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Chapter 10: Solutions 217
www.petersons.com
12. Thecorrect answer is (D). You need to use the vant Hoff factor i n thi s because NaCl
i s an el ectrol yte. Therefore, you wi l l use p 5 MRTi 5 (0.100 mol L
21
)(0.0821 L atm
mol
21
K
21
)(300 K)(2) 5 4.9 atm.
Free Response
QUESTION 1
(A) 0.272 m. The mol al i ty i s cal cul ated as the number of mol es of unknown per
ki l ogram of benzene. Because the number of mol es of the unknown substance i s
not known, the mol al i ty wi l l be cal cul ated from the freezi ng-poi nt depressi on of
the sol uti on. Thi s i s done usi ng the equati on DT
f
5 K
f
m. Because the sol uti on i s
a nonel ectrol yte, the vant Hoff factor i s unnecessary. Thi s expressi on can be
rearranged to yi el d DT
f
5 K
f
5 m. Mol al i ty i s determi ned to be:
~5.455C 2 4.075C!
5.065C m
21
5 0.272 m.
(B) 119 g mol
21
. The mol ar mass of the unknown i s cal cul ated from the mol al i ty of
the sol uti on. Accordi ng to the gi ven i nformati on, 0.562 g i s di ssol ved i n the
benzene. I n part A, i t was determi ned that the mol al i ty of the sol uti on i s 0.272 m.
Thi s tel l s you that there are 0.272 mol es of unknown per ki l ogram of benzene. We
know that we have 0.562 g unknown per 17.4 g of benzene. These two pi eces of
i nformati on wi l l al l ow us to cal cul ate the mol ar mass of the unknown:
mol al i ty 5
mol es unknown
kg benzene
thi s can be rewri tten as
mol al i ty 5
~grams sol ute/mol ar mass!
kg benzene
.
Thi s can be rearranged to yi el d the fi nal equati on:
mol ar mass 5
grams sol ute
~mol al i ty!~kg benzene!
Substi tuti ng i n the data, we get:
mol ar mass 5
0.562 g
~0.272 m!~0.0174 kg benzene!
5 119 g mol
21
(C) 80.9C. The boi l i ng temperature of the sol uti on i s cal cul ated usi ng the
boi l i ng-poi nt el evati on equati on: DT
b
5 K
b
m. The vant Hoff factor i s not needed
si nce the sol ute i s a nonel ectrol yte. From part A we know the mol al i ty, so the data
can be substi tuted di rectl y i nto the equati on: DT
b
5 (2.61C m
21
)(0.272 m) 5
0.710C. The el evated boi l i ng temperature wi l l be 80.2C 1 0.710C 5 80.9C.
(D) The vant Hoff factor i s i n the cal cul ati ons for col l i gati ve properti es of sol uti ons.
Because the number of sol ute parti cl es i n sol uti on affects these factors, an
adjustment must be made for el ectrol yti c sol utes. Thi s i s due to the fact that
el ectrol ytes, when di ssol ved, yi el d as many parti cl es as the number of i ons i n the
218 PART III: AP Chemistry Review
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www.petersons.com
sol ute. For exampl e, the el ectrol yte sodi um chl ori de, NaCl , wi l l di ssol ve to yi el d
one sodi um i on, Na
1
, and one chl ori de i on, Cl
2
, per sodi um chl ori de. Because the
probl em decl ared that the unknown sol ute was a nonel ectrol yte, no vant Hoff
factor was needed.
QUESTION 2
(A) Mol ar mass can be cal cul ated i n two steps. Fi rst the mol al i ty i s determi ned from
the freezi ng-poi nt depressi on, usi ng the expressi on DT
f
5 K
f
3 m. Once the
mol al i ty i s known, the equati on to determi ne the mol ar mass wi l l be deri ved
from the mol al i ty equati on. Si nce mol al i ty 5
mol es sol ute
kg sol vent
, and mol es sol ute 5
grams sol ute
mol ar mass sol ute
, we can substi tute
~
grams sol ute
mol ar mass sol ute
!
for mol es sol ute i n the
mol al i ty equati on. Thi s produces the equati on:
mol al i ty 5
~grams sol ute/mol ar mass sol ute!
kg sol vent
Rearrangi ng thi s equati on, we obtai n:
mol ar mass sol ute 5
grams sol ute
~mol al i ty!~kg sol vent!
(B) I n order for thi s to work, you need several measurements. To cal cul ate the
mol al i ty, two temperature readi ngs are requi red. The fi rst i s for the pure sol vent,
and the second for the sol uti on. Subtracti ng these val ues wi l l produce DT
f
. The
val ue of K
f
i s al so needed, but i t i s obtai ned from a reference book, not the
experi ment. I n order to compl ete the cal cul ati ons, two other pi eces of data are
requi red. The fi rst i s the mass of the sol ute. The second i s the mass of the
sol vent. By usi ng these two val ues, al ong wi th the mol al i ty (just cal cul ated), we
wi l l be abl e to cal cul ate the mol ar mass of the unknown.
(C) The purpose of the outer test tube i s to sl ow down the rate of temperature
decrease to al l ow for more uni form cool i ng and al so greater accuracy of the
temperature at the freezi ng poi nt. Submerged di rectl y i n the water, the test tube
wi th the sol uti on wi l l cool too rapi dl y.
(D) The percent error i s determi ned by usi ng the equati on:
measured resul t 2 theoreti cal resul t
theoreti cal resul t
3 100 percent
The absol ute val ue i s used because we are not concerned i f the error was above or
bel ow the theoreti cal val ueonl y about how much i t i s above or bel ow the theo-
reti cal val ue. I f the numbers were substi tuted i nto thi s equati on, i t woul d read:
170 g mol
21
2 180 g mol
21
180 g mol
21
3 100 percent
(E) Mol ari ty and mol al i ty are di fferent measures, al though there are some condi ti ons
where they are very si mi l ar. Mol al i ty depends on the mass of the sol vent and
mol ari ty depends on the vol ume of the sol vent. Si nce vol ume i s affected by
temperature, there may be some fl uctuati ons i n the vol ume of a sol uti on as i t
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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Chapter 10: Solutions 219
www.petersons.com
heats or cool s. Mass, and therefore mol al i ty, i s unaffected by temperature
changes. Another area where probl ems can possi bl y ari se i s the defi ni ti ons. For
mol ari ty, the sol ute i s added and the vol ume of the sol ute 1 sol vent shal l equal
1.00 L (or some other amount). For mol al concentrati ons, the sol ute i s added to
1.00 kg of water. There are a coupl e of condi ti ons where the di fference between
mol al i ty and mol ari ty i s very smal l . The mai n one worth noti ng i s when the
amount of sol ute i s smal l , rel ati ve to the amount of water. Water has the uni que
property that, by defi ni ti on, 1.00 L of water i s equal to 1.00 kg of water (onl y at
4C, but the numbers are sti l l very cl ose at other temperatures). Therefore, i f a
ti ny amount of sol ute i s pl aced i n a contai ner and water i s fi l l ed unti l a 1.00 l i ter
of sol uti on i s produced, the amount of water wi l l be very cl ose to 1.00 l i ters, and
therefore 1.00 kg. Therefore, i n the speci al case where a sol uti on i s very di l ute
and the sol vent i s water, mol al i ty and mol ari ty are nearl y the same. Thi s i s a
fai rl y di l ute sol uti on, so the error woul d have been very smal l i f mol ari ty
was used.
220 PART III: AP Chemistry Review
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www.petersons.com
SUMMING IT UP
Sol uti ons are homogeneous mi xtures.
Sol uti ons are usual l y measured i n di fferent concentrati on uni ts. The two most common
are mol ari ty (mol es of sol ute per l i ter of sol uti on) and mol al i ty (mol es of sol ute per
ki l ogram of sol vent).
The process of di ssol vi ng, sol vati on, occurs when the attracti ve forces between sol vent
and sol ute exceed the attracti ve forces between sol vent and sol vent or sol ute and sol ute.
I n the process of di ssol vi ng, there i s a maxi mum amount of sol ute that can be di ssol ved i n
a sol vent at any gi ven temperature. When thi s maxi mum i s reached, the rate of
di ssol vi ng i s at equi l i bri um wi th the rate of crystal l i zati on. At thi s poi nt, the sol uti on i s
saturated. No addi ti onal sol ute wi l l di ssol ve (actual l y di ssol vi ng sti l l occurs, but si nce i t
i s i n equi l i bri um wi th crystal l i zati on, there i s no net change i n the amount of sol ute).
A sol uti on that has l ess than the amount of sol ute requi red to reach equi l i bri um i s
unsaturated, and a sol uti on wi th excess sol ute i s supersaturated. Nei ther of these
condi ti ons i s at equi l i bri um.
Many ti mes, the di ssol vi ng process generates heat, whi ch i s to say i t i s exothermi c.
Occasi onal l y sol uti on formati on i s endothermi c.
I ncreases i n temperature are usual l y associ ated wi th i ncreased sol ubi l i ty of sol i d sol utes
and decreased sol ubi l i ty of gaseous sol utes. Decreases i n temperature are associ ated wi th
decreased sol ubi l i ty of sol i d sol utes and i ncreased sol ubi l i ty of gaseous sol utes.
I ncreases i n pressure i ncrease the sol ubi l i ty of gaseous sol utes, but have l i ttl e effect on
sol i d sol utes. Si mi l arl y, decreases i n pressure decrease the sol ubi l i ty of gases i n l i qui ds
and have l i ttl e effect on sol i d sol utes.
There are four mai n col l i gati ve properti es, or properti es of a sol vent that are affected by
the presence of a sol ute: vapor-pressure reducti on, boi l i ng-poi nt el evati on, freezi ng-poi nt
depressi on, and osmoti c pressure.
I n general , the addi ti on of sol ute to a sol vent decreases the vapor pressure, i ncreases
the boi l i ng poi nt, decreases the freezi ng poi nt, and i ncreases the osmoti c pressure of
the sol vent.
I n Raoul ts l aw, sol uti ons are bel i eved to be i deal . That i s, the vapor pressure of a sol vent
i s di rectl y proporti onal to the mol e fracti on of sol ute.
I n sol uti ons where the sol ute-sol ute i nteracti ons, or sol vent-sol vent i nteracti ons, affect
the vapor pressure, Raoul ts l aw i s not observed and the sol uti ons cannot be cl assi fi ed
as i deal .
Sol uti ons where the sol vent and sol ute are chemi cal l y si mi l ar are the most i deal
sol uti ons.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 10: Solutions 221
www.petersons.com
Reaction Types
OVERVIEW
Nomenclature
Molecular compounds
Chemical equations
Major reaction types
Ionic equations
Oxidation-reduction reactions
Summary of the main reaction types
Summing it up
Thi s chapter i s di vi ded i nto two major secti ons. The fi rst, nomencl ature, i s a
revi ew of materi al you shoul d have l earned i n your fi rst-year chemi stry course
but that you wi l l be expected to know for the AP test. I n the second secti on,
you wi l l revi ew the major types of chemi cal reacti ons.
NOMENCLATURE
Nomencl ature, or the nami ng system, i s fai rl y uni form. The body that i s most
wi del y recogni zed for devel opi ng and mai ntai ni ng the rul es for nami ng
compounds i s the I nternati onal Uni on of Pure and Appl i ed Chemi stry
(I UPAC). The rul es that you wi l l need to be fami l i ar wi th were devel oped by
I UPAC. I n thi s chapter, you wi l l onl y revi ew the procedures for nami ng
i norgani c compounds. Organi c compounds, whose nami ng system i s qui te a bi t
di fferent, wi l l be addressed i n Chapter 19. There are di fferent procedures for
nami ng i oni c and coval ent compounds. Wel l begi n wi th i oni c compounds.
Ionic Compounds
I oni c compounds are composed of two or more atoms that have l ost or gai ned
el ectrons to become charged parti cl es. The opposi tel y charged parti cl es are
hel d together by el ectrostati c attracti ons. I n general , i oni c compounds consi st
of a metal l i c cati on (posi ti vel y charged i on), bonded to a nonmetal l i c ani on
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
1
1
223
(negati vel y charged i on) or a negati vel y charged pol yatomi c i on. Pol yatomi c i ons are stabl e
arrangements of atoms that are coval entl y bonded together but that mai ntai n a net charge.
Most of the pol yatomi c i ons are negati vel y charged. The ammoni um i on, NH
4
1
, i s one of the
onl y posi ti vel y charged pol yatomi c i ons. Tabl e 11.1 shows a l i st of some of the more common
pol yatomi c i ons:
TABLE 11.1 COMMON POLYATOMIC IONS
Charge Formula Name
11 NH
4
1
ammoni um
12 Hg
2
21
mercury (I )
BrO
3
2
bromate
C
2
H
3
O
2
2
acetate
Cl O
2
hypochl ori te
Cl O
2
2
chl ori te
Cl O
3
2
chl orate
Cl O
4
2
perchl orate
CN
2
cyani de
21 HCO
3
2
hydrogen carbonate (common name i s bi carbonate)
HSO
4
2
hydrogen sul fate (common name i s bi sul fate)
H
2
PO
4
2
di hydrogen phosphate
MnO
4
2
permanganate
NO
2
2
ni tri te
NO
3
2
ni trate
OH
2
hydroxi de
SCN
2
thi ocyanate
CO
3
22
carbonate
C
2
O
4
22
oxal ate
CrO
4
22
chromate
22 Cr
2
O
7
22
di chromate
HPO
4
22
hydrogen phosphate
SO
3
22
sul fi te
SO
4
22
sul fate
AsO
4
32
arsenate
23 PO
4
32
phosphate
PO
3
32
phosphi te
224 PART III: AP Chemistry Review
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As you saw i n Chapter 6, the rati o of i ons i n an i oni c compound i s determi ned by the charges
on the i ons. I n a sal t, the i ons wi l l combi ne to form compounds wi th a net charge of zero.
Before l i sti ng the speci fi c rul es for nami ng compounds, l ets revi ew a few thi ngs about i ons
and el ectri cal charges:
Metal s i n groups 1A and 2A on the peri odi c tabl e form cati ons wi th the same posi ti ve
charge as thei r group numbers (1A 5 1
1
and 2A 5 2
1
).
Most transi ti on metal s, as wel l as the metal s i n groups 3A26A, have mul ti pl e
charges possi bl e; however, there are four very commonl y used el ements that have
onl y one charge and shoul d be memori zed: Ag
1
, Zn
21
, Cd
21
, and Al
31
. I f you l ocate
these on the peri odi c tabl e, you wi l l fi nd that they are very cl ose to one another.
For the representati ve metal l i c el ements i n groups 3A26A, most have two posi ti ve
charges that fol l ow a pattern. The two charges consi st of a charge equal to the group
number and a second charge equal to the group number mi nus two. For exampl e,
the el ement ti n, Sn i n group 4A, can have two charges, 4
1
(i ts group number) and 2
1
(i ts group number mi nus two).
BINARY IONIC COMPOUNDS
Bi nary i oni c compounds are compounds composed of two monatomi c i ons. These usual l y are a
metal l i c cati on and a nonmetal l i c ani on. When nami ng these compounds, there are a few
rul es that need to be fol l owed:
Cati ons that onl y have one possi bl e charge bear the same name as thei r neutral
atoms. For exampl e, a l i thi um atom, a group 1A el ement, can onl y have a 1
1
charge.
A l i thi um i on i s referred to as si mpl y a l i thi um.
Cati ons that can have more than one charge are named by pl aci ng a Roman
numeral equal to the posi ti ve charge after the name of the el ement. For i nstance,
the el ement copper can have two possi bl e charges, 1
1
and 2
1
. A Cu
21
i on i s cal l ed a
copper (I I ) i on. The Roman numeral i s pl aced i n parentheses.
Monatomi c ani ons are named after the el ement, but the endi ng has been modi fi ed
and an 2i de endi ng added as a repl acement. For exampl e, the S
22
i on becomes a
sul fi de i on. There are no cl ear rul es that can be fol l owed about whi ch part of the
root to remove before addi ng the 2i de endi ng, so i t i s easi est to memori ze these
ani ons. There arent very many, so i t i s not that l arge a task. The charges on the
monatomi c ani on are usual l y equal to the negati ve resul t of 8 mi nus the group
number. For exampl e, oxygen, a group 6A el ement, has a charge of 2(826), or 22.
The reason for thi s i s that i t i s how many negati vel y charged el ectrons are acqui red
i n the formati on of a stabl e octet (8 val ence el ectrons).
Bi nary aci ds, aci ds that are formed from a hydrogen i on bondi ng to a monatomi c
ani on, are named by pl aci ng the term hydro i n front of the root of the ani on
endi ng i n i c. For i nstance, HCl i s cal l ed hydrochl ori c aci d.
These are the mai n rul es that are used to name bi nary i oni c compounds. I n most cases, the
procedure i s qui te si mpl e. For exampl e, Li Cl i s named l i thi um chl ori de. Li thi um i s a group 1A
el ement, so i ts name doesnt change, and the chl ori de comes from addi ng an 2i de endi ng to
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Chapter 11: Reaction Types 225
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a monatomi c, nonmetal l i c ani on. There are some cases, however, where the procedure i s not
as readi l y apparent. These are the compounds formed from the metal s wi th more than one
possi bl e charge. For exampl e, the compound FeCl
3
has an i ron i on i n i t. I ron has more than
one possi bl e i oni c charge, so i ts name requi res the use of a Roman numeral . Thi s i s a fai rl y
easy one to fi gure out because you know that a chl ori de i on has a 1
2
charge. You al so know
that the net charge i n an i oni c compound i s zero. Therefore, i f i t takes three chl ori de i ons
(wi th a total charge of 3
2
) to neutral i ze one i ron i on, the i ron i on must have a charge of 3
1
.
Therefore, the name woul d be wri tten as i ron (I I I ) chl ori de. I n the next secti on, wel l l ook
more cl osel y at thi s process of determi ni ng the Roman numeral s to assi gn cati ons wi th more
than one possi bl e charge.
Writing Formulas for Binary Ionic Compounds
The formul a for an i oni c compound actual l y represents the si mpl est rati o of i ons wi thi n a
crystal . I t i s i mportant to remember that the formul as you wri te for the test must represent
the si mpl est rati o of i ons. There are two mai n ways to wri te the formul as for i oni c compounds.
The fi rst method uses conservati on of charge, whi l e the second i s a shortcut method often
cal l ed the cri sscross method.
I n the conservati on of charge method, you come up wi th the si mpl est rati o of i ons to have a
net charge of zero. Thi s i s basi cal l y a tri al and error method, but, i f you do i t enough, you wi l l
di scover patterns that make the process very effi ci ent. I t wi l l be easi er to revi ew thi s wi th a
few di fferent exampl es.
Sample: Determi ne the formul a for l i thi um chl ori de.
Answer: To begi n, you need to determi ne the charges on each i on. Li thi um, a group 1A
el ement, has a charge of 1
1
, and the chl ori de i on has a charge of 1
2
. So, we begi n by
l ooki ng at the two i ons, Li
1
and Cl
2
. You shoul d qui ckl y noti ce that a charge of 1
1
wi l l exactl y bal ance a charge of 1
2
. Therefore, for every one Li
1
, there wi l l be one
Cl
2
. As a resul t, the formul a wi l l read Li Cl .
Sample: Determi ne the formul a for magnesi um chl ori de.
Answer: Magnesi um, a group 2A el ement, has a charge of 2
1
. Chl ori de has a charge of 1
2
.
Thi s ti me we have Mg
21
and Cl
2
. I f one chl ori de i on combi nes wi th a magnesi um
i on, there wi l l sti l l be a net charge of 1
1
. Therefore, i n order to bal ance the two
posi ti ve charges of magnesi um, you wi l l need to have two chl ori de i ons, each wi th a
1
2
charge. The formul a for magnesi um chl ori de wi l l be MgCl
2
.
Sample: Determi ne the formul a for magnesi um oxi de.
Answer: Magnesi um i s Mg
21
. Oxi de represents the oxygen i on wi th a charge of 2
2
, or O
22
.
I f you l ook at thi s exampl e, onl y one magnesi um i on i s needed to bal ance the charge
of one oxi de i on. Therefore, the formul a i s MgO.
226 PART III: AP Chemistry Review
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Sample: Determi ne the formul a for al umi num oxi de.
Answer: Al umi num has a charge of 3
1
and oxygen has a charge of 2
2
. I n the previ ous
exampl es, you coul d mani pul ate the quanti ti es of one of the i ons to make the
charges bal ance. Cl earl y, that wont work here. I n thi s exampl e, you need to
bal ance the charges by changi ng the quanti ti es of both i ons. I f you doubl e the
quanti ty of al umi num, the two al umi num i ons wi l l have a total charge of 2(3
1
)or
6
1
. I f you l ook at the negati ve charge of 2
2
, you mi ght qui ckl y see that 2 goes i nto
6 three ti mes. I f you tri pl e the quanti ty of oxygen, you wi l l have a charge of 3(2
2
) or
6
2
. Now the posi ti ve and negati ve charges are bal anced. The fi nal formul a must
have two al umi num i ons for every three oxi de i ons, or Al
2
O
3
.
THE CRISSCROSS METHOD
The cri sscross method of formul a wri ti ng makes wri ti ng formul as for compounds l i ke
al umi num oxi de an easi er process. I n thi s method, the fi rst step i s to wri te the i oni c symbol s
next to each other. Once thi s i s done, the number of the charge on the cati on i s wri tten as a
subscri pt for the ani on and the number of the charge on the ani on i s wri tten as a subscri pt for
the cati on.
Sample: Wel l use al umi num oxi de agai n:
Al
3
Al
2
O
3
OOO
2
Answer: Noti ce how the arrows cri sscross as they move toward the subscri pt posi ti on. That
i s where the name comes from. The method makes formul a wri ti ng for i oni c
compounds qui ck and easy. There i s one thi ng you need to pay attenti on to as you
use thi s method, as the next exampl e wi l l demonstrate.
Sample: Wri te the formul a for ti n (I I ) oxi de.
Usi ng the cri sscross method, we see that:
Sn
2
Sn
2
O
2
OOO
2
The fi rst thi ng to poi nt out i s the charge on ti n. Whi l e ti n has more than one possi bl e charge,
you know i t has to be two i n thi s case because of the Roman numeral (I I ) that appears i n the
name. The formul a Sn
2
O
2
does not represent the smal l est rati o of i ons. You shoul d noti ce that
i f each one of these subscri pts i s reduced by
1
2
, the new formul a wi l l be SnO. You can onl y
reduce these subscri pts i f al l subscri pts i n a formul a can be reduced by the same amount (thi s
wi l l be more cri ti cal wi th ternary i oni c compounds).
Goi ng back to the previ ous secti on, where you were l ooki ng at how to determi ne the Roman
numeral s wri tten after some el ements, you may see how thi s can be done usi ng the cri sscross
method. To determi ne the Roman numeral , you use a reverse cri sscross techni que to
determi ne the charge on the cati on. Thi s charge then becomes the val ue of the Roman
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Chapter 11: Reaction Types 227
www.petersons.com
numeral . Whi l e you can probabl y eyebal l a sol uti on to these, wel l l i st a set of rul es that wi l l
work for al l exampl es:
a. Determi ne the total (2) charge by mul ti pl yi ng the charge on each ani on by the
total number of ani ons present.
b. The total (2) must equal the total (1).
c. Determi ne the (1) charge on each cati on by di vi di ng the total (1) charge by the
number of cati ons present i n the compound (subscri pt).
d. Thi s answer i s the charge that shoul d be wri tten as a Roman numeral i n the
name.
Sample: Wri te the name of PbO
2
.
Answer: Fol l owi ng the four rul es:
a. Determi ne the total (2) charge by mul ti pl yi ng the charge on each ani on by the
total number of ani ons present (2 3 22 5 42).
b. The total (2) must equal the total (1) (42 5 41).
c. Determi ne the (1) charge on each cati on by di vi di ng the total (1) charge by the
number of cati ons present i n the compound (subscri pt) (41 4 1 5 4).
d. Thi s answer i s the charge that shoul d be wri tten as a Roman numeral i n the
name (l ead (I V) oxi de).
You Try It!
Wri te the formul as for the fol l owi ng compounds:
1. cal ci um oxi de
2. magnesi um i odi de
3. chromi um (I I I ) oxi de
4. sodi um bromi de
5. ti n (I V) oxi de
6. zi nc i odi de
7. ni ckel (I I ) oxi de
8. hydrobromi c aci d
9. cal ci um sul fi de
10. si l ver chl ori de
11. l ead (I I ) fl uori de
12. cadmi um bromi de
228 PART III: AP Chemistry Review
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Answers:
1. CaO
2. MgI
2
3. Cr
2
O
3
4. NaBr
5. SnO
2
6. ZnI
2
7. Ni O
8. HBr
9. CaS
10. AgCl
11. PbF
2
12. CdBr
2
You Try It!
Wri te the names represented by the fol l owi ng formul as:
1. Na
2
S
2. Al N
3. MgBr
2
4. Co
2
S
3
5. CuI
2
6. SrI
2
7. Hg
3
N
8. MnO
9. FeO
10. Ba
3
N
2
11. H
2
S
12. BeI
2
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Chapter 11: Reaction Types 229
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Answers:
1. sodi um sul fi de
2. al umi num ni tri de
3. magnesi um bromi de
4. cobal t (I I I ) sul fi de
5. copper (I I ) i odi de
6. stronti um i odi de
7. mercury (I ) ni tri de
8. manganese (I I ) oxi de
9. i ron (I I ) oxi de
10. bari um ni tri de
11. hydrosul furi c aci d
12. beryl l i um i odi de
TERNARY IONIC COMPOUNDS
Ternary i oni c compounds are i oni c compounds contai ni ng one or more pol yatomi c i ons. The
possi bl e combi nati ons are a monatomi c cati on bonded to a pol yatomi c ani on, a pol yatomi c
cati on bonded to a monatomi c ani on, or a pol yatomi c cati on bonded to a pol yatomi c ani on.
There are addi ti onal rul es that must be added to the rul es i n the previ ous secti on:
Si nce pol yatomi c i ons al ready have speci fi c names, these names are not changed when
the i on becomes part of a compound. For exampl e, i f the sul fate i on, SO
4
22
, combi nes
wi th a cal ci um i on, Ca
21
, the resul ti ng compound, CaSO
4
, i s cal l ed cal ci um sul fate.
Because the atoms i n a pol yatomi c i on are a stabl e uni t, i f more than one i on i s
needed to bal ance the charge of the opposi tel y charged i on, parentheses are pl aced
around the pol yatomi c i on to i ndi cate that the subscri pt pl aced outsi de the
parentheses refers to the enti re pol yatomi c i on. For exampl e, i f the hydroxi de i on,
OH
2
, combi nes wi th a l i thi um i on, Li
1
, the resul ti ng formul a i s Li OH. However, i f
the hydroxi de i on combi nes wi th a magnesi um i on, Mg
21
, the resul ti ng formul a wi l l
be Mg(OH)
2
. The parentheses i ndi cate that there are two hydroxi de i ons requi red to
bal ance the 2
1
charge of the magnesi um i on. Leavi ng out the parentheses woul d
create the formul a MgOH
2
, whi ch onl y i ndi cates the presence of an extra hydrogen
atom. For ternary aci ds, the prefi x hydro i s dropped. The aci d i s named accordi ng
to the pol yatomi c i on. I f the pol yatomi c i on ends i n ate, the aci d i s named usi ng
the root of the pol yatomi c i on endi ng i n i c, fol l owed by the word aci d. For
exampl e, when H
1
combi nes wi th the ni trate i on, NO
3
2
, the resul ti ng aci d i s cal l ed
ni tri c aci d. I f the pol yatomi c i on ends i n i te, the aci d i s named usi ng the root of
the pol yatomi c i on endi ng i n ous, fol l owed by the word aci d. For exampl e, when
H
1
combi nes wi th the ni tri te i on, NO
2
2
, the resul ti ng aci d i s cal l ed ni trous aci d.
230 PART III: AP Chemistry Review
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The cri sscross or conservati on of charge methods are used i n the same way to determi ne the
rati o of i ons i n the compound.
You Try It!
Wri te the formul as for the fol l owi ng compounds:
1. potassi um acetate
2. cal ci um hydrogen sul fate
3. stronti um ni tri te
4. ni ckel (I I ) sul fate
5. manganese (I I I ) cyani de
6. zi nc hydroxi de
7. perchl ori c aci d
8. l i thi um phosphate
9. ammoni um oxi de
10. sodi um hydrogen phosphate
11. zi nc oxal ate
12. ammoni um carbonate
Answers:
1. KC
2
H
3
O
2
2. Ca(HSO
4
)
2
3. Sr(NO
2
)
2
4. Ni SO
4
5. Mn(CN)
3
6. Zn(OH)
2
7. HCl O
4
8. Li
3
PO
4
9. (NH
4
)
2
O
10. Na
2
HPO
4
11. ZnC
2
O
4
12. (NH
4
)
2
CO
3
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Chapter 11: Reaction Types 231
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You Try It!
Wri te the names for the compounds represented by the fol l owi ng equati ons:
1. Pb(OH)
2
2. Al
2
(SO
4
)
3
3. NaHCO
3
4. Co(NO
3
)
2
5. CrCO
3
6. H
2
SO
3
7. Sn
3
(PO
4
)
4
8. Mg(OH)
2
9. Fe(C
2
H
3
O
2
)
3
10. NH
4
NO
2
11. Mn
3
(PO
3
)
2
12. NaHSO
4
Answers:
1. l ead (I I ) hydroxi de
2. al umi num sul fate
3. sodi um hydrogen carbonate
4. cobal t (I I ) ni trate
5. chromi um (I I ) carbonate
6. sul furous aci d
7. ti n (I V) phosphate
8. magnesi um hydroxi de
9. i ron (I I I ) acetate
10. ammoni um ni tri te
11. manganese (I I ) phosphi te
12. sodi um hydrogen sul fate
MOLECULAR COMPOUNDS
The nomencl ature for mol ecul ar compounds i s much l ess compl i cated than for i oni c
compounds. Mol ecul ar compounds are formed from coval entl y bonded nonmetal l i c el ements.
The formul a for a mol ecul e represents a stabl e uni t of atoms, unl i ke a formul a for an i oni c
compound, whi ch onl y represents the si mpl est whol e number rati o of i ons. As a resul t,
mol ecul ar formul as cannot be si mpl i fi ed l i ke formul as for i oni c compounds. An exampl e woul d
232 PART III: AP Chemistry Review
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www.petersons.com
be hydrogen peroxi de, H
2
O
2
. Al though the formul a coul d be reduced to HO, thi s woul d be
i nappropri ate because H
2
O
2
i s a mol ecul e. Changi ng the structure to HO woul d change the
chemi cal composi ti on.
Another source of di ffi cul ty i s that the atoms i n mol ecul es do not form i ons. Therefore, the use
of Roman numeral s i s not possi bl e. And because nonmetal s have mul ti pl e oxi dati on states
possi bl e (ni trogen has 8), i t i s too di ffi cul t to determi ne the possi bl e combi nati ons of atoms i n
a mol ecul e. Al l of thi s i s meant to i l l ustrate why a di fferent nami ng system i s requi red for
mol ecul ar compounds.
The rul es for nami ng mol ecul es are very si mpl e:
The second atom i n the mol ecul e i s al ways wri tten wi th an i de endi ng.
The fi rst atom i n the mol ecul e i s gi ven the name of the el ement.
Prefi xes are used to i ndi cate the number of atoms of each type i n a compound. These
prefi xes, l i sted i n Tabl e 11.2, shoul d be commi tted to memory.
Prefi xes are wri tten before the names of al l atoms wi th one excepti on: i f there i s onl y
one of the fi rst atom i n the mol ecul e.
When determi ni ng the name of a mol ecul ar compound from the formul a, the
subscri pt determi nes the prefi x you wi l l use i n the name.
Sample: Wri te the formul a for the compound di ni trogen pentoxi de.
Answer: Si nce di 5 2, there wi l l be two ni trogen atoms i n the mol ecul e. Penta i s 5, so
there wi l l be 5 oxygen atoms. The resul ti ng formul a wi l l be N
2
O
5
.
TABLE 11.2 PREFIXES USED TO INDICATE THE NUMBER OF ATOMS OF EACH TYPE IN
A COMPOUND
Number Prefix
1 mono
2 di
3 tri
4 tetra
5 penta
6 hexa
7 hepta
8 octa
9 nona
10 deca
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Chapter 11: Reaction Types 233
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Sample: Wri te the name of the compound SO
3
.
Answer: There i s onl y one sul fur atom. Because i t i s the fi rst atom i n the formul a, no prefi x
wi l l be used. There are three oxygen atoms, so the prefi x tri wi l l be used. The
resul ti ng name wi l l be sul fur tri oxi de.
You Try It!
Wri te formul as for the fol l owi ng compounds:
1. ni trogen di oxi de
2. carbon monoxi de
3. di ni trogen monoxi de
4. si l i con di oxi de
5. sul fur hexafl uori de
6. phosphorous pentachl ori de
7. si l i con monocarbi de
8. carbon di sul fi de
9. di ni trogen tri oxi de
10. tetrasul fur di ni tri de
11. di hydrogen mononi tri de
12. tetraboron monocarbi de
Answers:
1. NO
2
2. CO
3. N
2
O
4. Si O
2
5. SF
6
6. PCl
5
7. Si C
8. CS
2
9. N
2
O
3
10. S
4
N
2
11. H
2
N
12. B
4
C
234 PART III: AP Chemistry Review
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www.petersons.com
You Try It!
Wri te the names of the fol l owi ng compounds:
1. NF
3
2. S
2
Cl
2
3. CF
4
4. BCl
3
5. P
4
H
10
6. O
2
F
2
7. SF
4
8. B
2
O
3
9. Si
3
N
4
10. B
2
O
3
11. Cl O
7
12. Si F
4
Answers:
1. ni trogen tri fl uori de
2. di sul fur di chl ori de
3. carbon tetrafl uori de
4. boron tri chl ori de
5. tetraphosphorous decahydri de
6. di oxygen di fl uori de
7. sul fur tetrafl uori de
8. di boron tri oxi de
9. tri si l i con tetrani tri de
10. di boron tri oxi de
11. chl ori ne heptoxi de
12. si l i con tetrafl uori de
CHEMICAL EQUATIONS
A chemi cal equati on i s a way to represent, i n symbol s, a chemi cal reacti on. By usi ng
combi nati ons of symbol s to represent chemi cal s and processes, you can express i n a uni versal
l anguage the events i n a chemi cal reacti on. Before revi ewi ng the di fferent types of reacti ons,
i t wi l l be hel pful to revi ew some of the symbol s that are used i n chemi cal equati ons.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 11: Reaction Types 235
www.petersons.com
A basi c chemi cal equati on consi sts of a few components. I n every reacti on, there i s at l east one
reactant and one product. I n order to better i l l ustrate the features of a chemi cal equati on, we
wi l l use an exampl e of a chemi cal reacti on that has two reactants and two products. I n the
equati on, the formul as of each reactant and product wi l l represent the chemi cal s. The
reactants are pl aced on the l eft si de of the equati on and the products on the ri ght si de of the
equati on. An arrow () pl aced i n the center, between the reactants and products, i ndi cates a
reacti on i s taki ng pl ace. A pl us (1) si gn on the l eft si de of the equati on, pl aced between the
reactants (i f there are more than one), i s used to si gni fy that the reactants are added together.
A pl us (1) si gn on the ri ght, or products si de, of the equati on si gni fi es that the products are
separate enti ti es. An exampl e of a chemi cal reacti on i s the addi ti on of sodi um metal to water
to form sodi um hydroxi de and hydrogen gas. When wri tten as a chemi cal equati on, thi s word
equati on i s transl ated to:
Na 1 H
2
O NaOH 1 H
2
Thi s type of equati on i s often cal l ed a skel eton equati on. I t i ndi cates whi ch reactants were
i nvol ved and what products were formed, but l i ttl e el se. The addi ti on of a few more symbol s
can provi de much more i nformati on. Whats mi ssi ng i n the chemi cal equati on that was
present i n the word equati on i s the states of the chemi cal s. The word equati on speci fi ed
sodi um metal and hydrogen gas, yet the chemi cal equati on does not i ndi cate thi s. By
rewri ti ng the equati on, we can convey thi s i nformati on:
Na(s) 1 H
2
O(l) NaOH(aq) 1 H
2
(g)
These symbol s are frequentl y added to chemi cal equati ons to provi de the states of the
reactants and products. Sol i ds are represented by (s), l i qui ds by (l), aqueous sol uti ons
(sol uti ons where water i s the sol vent) by (aq), and gases by (g).
Another i ssue wi th the skel eton equati on above i s that the reacti on, as wri tten, vi ol ates the
l aw of conservati on of matter. Accordi ng to the equati on, one sodi um atom reacts wi th one
oxygen atom and two hydrogen atoms to produce one sodi um atom, one oxygen atom, and
three hydrogen atoms. A hydrogen atom has been created, i n di rect vi ol ati on of the l aw of
conservati on of matter. I n real i ty, thi s i s not how the chemi cal s react. The reacti on real l y
takes pl ace l i ke thi s:
2Na(s) 1 2H
2
O(l) 2NaOH(aq) 1 H
2
(g)
I f you count up the atoms of each el ement on ei ther si de of the arrow, you see that there are
now 2 sodi um atoms, 4 hydrogen atoms, and 2 oxygen atoms on the l eft si de of the arrow and
2 sodi um atoms, 4 hydrogen atoms, and 2 oxygen atoms on the ri ght si de of the arrow. Matter
has been conserved! I n case you have forgotten, the coeffi ci ents i n front of a component i n an
equati on tel l you how many of the atoms or mol ecul es are present. 2Na means two sodi um
atoms, and 2H
2
O represents two water mol ecul es. Subscri pts, l i ke the 2 after the H i n 2H
2
O,
i ndi cate the number of atoms of the el ement that are i n the mol ecul e (i n water, the 2 means
there are two hydrogen atoms). Thi s type of equati on, where matter i s conserved, i s known as
a bal anced equati on. I n the next secti on, we wi l l revi ew the procedures for bal anci ng
equati ons.
236 PART III: AP Chemistry Review
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www.petersons.com
The other symbol s that can add i nformati on to an equati on are shown i n Tabl e 11.3:
TABLE 11.3 OTHER SYMBOLS THAT CAN ADD INFORMATION TO AN EQUATION
Symbol Meaning

or
heat Reactants are heated.
50 atm
Reacti on i s carri ed out at a certai n pressure.
Reacti on i s carri ed out at a speci fi c temperature.
MnO2 A catal yst i s used i n the reacti on.
Product i s a sol i d preci pi tate.
Product i s a gas.
Reacti on can proceed i n both di recti ons, nei ther di recti on endi ng
i n compl eti on.
Balancing Equations
I n the upcomi ng chapters, the chemi cal equati ons you wi l l be worki ng wi th wi l l be bal anced
equati ons. That i s because the topi cs covered i n these chapters are al l concerned wi th
quanti tati ve aspects of chemi cal reacti ons. I n thi s chapter, you are l ooki ng at di fferent
reacti on types and l earni ng how to predi ct the outcomes of vari ous reacti ons. As you just read,
chemi cal reacti ons must be bal anced i n order to fol l ow the l aw of conservati on of matter. The
process i s, i n pri nci pl e, just an el ementary form of record keepi ng to assure that there are
equal numbers of atoms of each el ement goi ng i nto and comi ng out of a chemi cal reacti on. I n
practi ce, bal anci ng equati ons i s not al ways as easy. Many reacti ons are qui te si mpl e and
requi re very l i ttl e to bal ance them, but some are qui te compl ex. There are a few procedures
that you shoul d fol l ow whi l e bal anci ng equati ons as wel l as a few strategi es that wi l l al l ow
you to bal ance equati ons more qui ckl y.
Rules for Balancing Equations
The bottom l i ne i s that you must adjust the equati on so that the number of atoms of each
el ement i s the same on each si de of the equati on. There are some rul es that must be fol l owed
whi l e bal anci ng equati ons:
You can onl y change the coeffi ci ents that appear before an el ement or compound.
You are never al l owed to change any subscri pts i n a formul a. Changi ng subscri pts
changes the chemi cal nature of the substance, whereas changi ng a coeffi ci ent si mpl y
changes the amount of a substance.
Coeffi ci ents shoul d be wri tten as the l owest numeri cal rati os.
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Chapter 11: Reaction Types 237
www.petersons.com
Sample: Zn 1 HCl ZnCl
2
1 H
2
Answer: I f you l ook at thi s equati on, there i s one zi nc atom on the l eft si de and one on the
ri ght si de. At the moment, al l zi nc atoms are accounted for. Whi l e l ooki ng at the
zi nc chl ori de on the ri ght si de, you may have noti ced the subscri pt 2 by the
chl ori ne. There are two chl ori ne atoms i n zi nc chl ori de, but onl y one on the reactant
si de of the equati on. You can begi n by pl aci ng a coeffi ci ent of 2 i n front of HCl :
Zn 1 2HCl ZnCl
2
1 H
2
Thi s gi ves you the two chl ori ne atoms that you need, but i t has now al so gi ven you two
hydrogen atoms on the reactants si de. A vi sual i nspecti on of the products i ndi cates that you
need two hydrogen atoms to bal ance the equati on, so hydrogen i s now bal anced.
A qui ck tal l y of the atoms i ndi cates that al l are bal anced. Mental l y, you shoul d go through a
process si mi l ar to the chart i n Tabl e 11.4.
The basi c process of bal anci ng equati ons i s, by nature, a tri al and error affai r, but you can
streaml i ne the process by usi ng a few di fferent strategi es.
The most i mportant approach i s to begi n by bal anci ng substances that onl y appear once on
each si de of the equati on. El ements that appear more than once are more di ffi cul t. Qui te
often, you may fi nd that by bal anci ng the easi est el ements fi rst, the others wi l l bal ance
themsel ves. One el ement that often appears i n more than one compound i n an equati on i s
oxygen. I t i s a good i dea to wai t on the oxygen atoms unti l the end.
A second strategy i s to l ook for any pol yatomi c i ons. I f a pol yatomi c i on appears on each si de
of the equati on, you can treat i t l i ke an i ndi vi dual el ement whi l e bal anci ng the equati on.
Sample: NaHCO
3
1 H
2
SO
4
Na
2
SO
4
1 H
2
O 1 CO
2
Answer: I n thi s equati on, you shoul d noti ce two thi ngs. Fi rst, oxygen appears i n several
pl aces i n the equati on. Second, the sul fate i on i s present on each si de of the
equati on. Our fi rst step i s to l ook for an el ement that appears onl y once. Sodi um i s
a good starti ng poi nt. You wi l l very often fi nd that metal cati ons are the best pl ace
to start. We begi n by pl aci ng a 2 i n front of the sodi um atom on the reactants si de
of the equati on:
2NaHCO
3
1 H
2
SO
4
Na
2
SO
4
1 H
2
O 1 CO
2
TABLE 11.4
Reactants Products
Zn 5 1 atom Zn 5 1 atom
H 5 2 atoms H 5 2 atoms
Cl 5 2 atoms Cl 5 2 atoms
238 PART III: AP Chemistry Review
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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TIP
This mental
checkist helps
you keep track of
the atoms you
are trying to
balance. As
reactions
become more
complex, it may
help you to write
this list down
on paper.
www.petersons.com
Pl aci ng thi s 2 i n front of sodi um bal ances the sodi um atoms, but i t al so adds two addi ti onal
hydrogen atoms, two carbon atoms, and si x oxygen atoms (al l from the bi carbonate i on).
Carbon i s another atom that appears onl y once on each si de. There are now two carbon atoms
on the reactants si de and onl y one on the products si de. We can conti nue by pl aci ng a 2 i n
front of the carbon di oxi de mol ecul e, CO
2
, on the products si de:
2NaHCO
3
1 H
2
SO
4
Na
2
SO
4
1 H
2
O 1 2CO
2
The carbon atoms and the sodi um atoms are now bal anced. Ti me to pi ck another el ement. Our
choi ces are hydrogen, oxygen, and sul fur. Si nce sul fur i s ti ed up i n a sul fate i on, we wi l l l eave
that one al one for now. Hydrogen i s the next easi est el ement. On the reactants si de of the
equati on, there are a total of 4 hydrogen atoms (2 i n sodi um bi carbonate and 2 i n sul furi c
aci d). On the products si de, there are onl y 2. We can bal ance the hydrogen by pl aci ng a
coeffi ci ent of 2 i n front of the water mol ecul e on the products si de:
2NaHCO
3
1 H
2
SO
4
Na
2
SO
4
1 2H
2
O 1 2CO
2
At thi s poi nt, we have bal anced everythi ng except sul fur and oxygen. Here i s where we can
take advantage of the sul fate i on. Because sul fate appears on each si de of the equati on, you
can treat i t as a si ngl e el ement. There i s one on the reactants si de and one on the products
si de, so i ts bal anced. When we check the oxygen atoms, we can i gnore the oxygen atoms i n
the sul fate i ons for now. On the reactants si de, we have 6 oxygen atoms. On the products si de,
we have 2 i n the water mol ecul e, and 4 i n the carbon di oxi de mol ecul es, for a total of 6. Doi ng
some qui ck mental checki ng, we see that al l of the atoms i n the equati on are now bal anced.
By wai ti ng to bal anci ng the oxygen atoms, they bal anced themsel ves!
Another hel pful strategy i s to l ook for odd numbers of atoms on one si de of the equati on. I f
there i s an odd number of atoms on one si de of the equati on but an even number on the other,
there i s no way to bal ance the equati on by addi ng coeffi ci ents i n front of the even-numbered
el ement. An even number mul ti pl i ed by any number wi l l al ways be even. I n these equati ons,
you need to work on the odd si de. When you mul ti pl y an odd number by an even, the product
i s al ways even. An exampl e of thi s sort i s shown bel ow:
Cl
2
1 Al I
3
Al Cl
3
1 I
2
For both chl ori ne and i odi ne, each has an odd number of atoms on one si de of the equati on
and an even number on the opposi te. I f we l ook at chl ori ne, Cl
2
, on the reactants si de, there i s
no coeffi ci ent you can put i n front of i t to make i t an odd number. So our efforts are best spent
on the other si de of the equati on. Because bal anced equati ons must show the l owest whol e
number rati o of reactants and products, you shoul d al ways start wi th the smal l est coeffi ci ent
possi bl e. I f we put a coeffi ci ent of 2 i n front of the Al Cl
3
, i t wi l l gi ve us an even number of
chl ori ne atoms. I t al so gi ves us 2 al umi num atoms, maki ng al umi num out of bal ance:
Cl
2
1 Al I
3
2Al Cl
3
1 I
2
The next step wi l l be to bal ance chl ori ne and al umi num. To get 6 chl ori ne atoms on the
reactants si de, we must put a coeffi ci ent of 3 i n front of the Cl
2
. You wi l l fi nd that thi s i s a
fai rl y common pattern i n bal anci ng (fi ndi ng the l east common mul ti pl e). Next, we need to put
a 2 i n front of the Al I
3
to bal ance the al umi num:
3Cl
2
1 2Al I
3
2Al Cl
3
1 I
2
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Chapter 11: Reaction Types 239
www.petersons.com
Everythi ng i s bal anced now, except for i odi ne. There are 6 on the l eft and onl y 2 on the ri ght.
Thi s i s easi l y remedi ed by pl aci ng a coeffi ci ent of 3 i n front of I
2
:
3Cl
2
1 2Al I
3
2Al Cl
3
1 3I
2
Doi ng a qui ck check, al l atoms are now bal anced and the coeffi ci ents are i n the si mpl est whol e
number rati o.
The l ast strategy for bal anci ng equati ons i s used for bal anci ng combusti on reacti ons. Later i n
the chapter, we wi l l di scuss combusti on reacti ons, but for now, assume that a hydrocarbon i s
reacti ng wi th oxygen to form carbon di oxi de and water vapor. These are parti cul arl y nasty
reacti ons to bal ance as the coeffi ci ents can get qui te l arge. There i s a shortcut that makes
the process very si mpl e i f the fuel contai ns onl y carbon and hydrogen. The steps to bal anci ng
thi s type of combusti on reacti on are shown i n the exampl e bel ow of the combusti on of
benzene, C
6
H
6
:
C
6
H
6
1 O
2
CO
2
1 H
2
O
Step 1: Bal ance the carbon and hydrogen atoms. To do thi s, you wi l l need to pl ace a coeffi ci ent
of 6 i n front of the CO
2
and a coeffi ci ent of 3 i n front of the water:
C
6
H
6
1 O
2
6CO
2
1 3H
2
O
Step 2: Count the number of atoms on the ri ght si de of the equati on. (You are goi ng to have to
cheat a l i ttl e bi t here to make thi s work out.) I n thi s equati on, there are a total of 15 oxygen
atoms on the ri ght si de of the equati on (12 i n CO
2
and 3 i n H
2
O).
Step 3: Take the number of oxygen atoms from the ri ght si de of the equati on and pl ace a
coeffi ci ent i n front of the O
2
on the l eft si de that i s that number over 2. For thi s, you wi l l make
a coeffi ci ent of
15
2
(dont worryyoure not goi ng to l eave i t l i ke that):
C
6
H
6
1
15
2
O
2
6CO
2
1 3H
2
O
Step 4: Change the
15
2
coeffi ci ent to a whol e number, mul ti pl yi ng i t by 2. When you do that,
however, you have to mul ti pl y everythi ng el se by 2 as wel l . When fi ni shed, you shoul d have
somethi ng l i ke thi s:
2C
6
H
6
1 15O
2
12CO
2
1 6H
2
O
Thi s shortcut wi l l save you a l ot of tri al and error!
240 PART III: AP Chemistry Review
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www.petersons.com
You Try It!
Bal ance the fol l owi ng equati ons:
1. Au
2
O
3
Au 1 O
2
2. Na
3
PO
4
1 ZnSO
4
Na
2
SO
4
1 Zn
3
(PO
4
)
2
3. MnO
2
1 HCl MnCl
4
1 H
2
O
4. CaO 1 P
4
O
10
Ca
3
(PO
4
)
2
5. C
6
H
5
OH 1 O
2
CO
2
1 H
2
O
6. (NH
4
)
2
S 1 Co(NO
3
)
2
CoS 1 NH
4
NO
3
7. Al 1 O
2
Al
2
O
3
8. C
2
H
6
1 O
2
CO
2
1 H
2
O
Answers:
1. 2Au
2
O
3
4Au 1 3O
2
2. 2Na
3
PO
4
1 3ZnSO
4
3Na
2
SO
4
1 Zn
3
(PO
4
)
2
3. MnO
2
1 4HCl MnCl
4
1 2H
2
O
4. 6CaO 1 P
4
O
10
2Ca
3
(PO
4
)
2
5. C
6
H
5
OH 1 7O
2
6CO
2
1 3H
2
O
6. (NH
4
)
2
S 1 Co(NO
3
)
2
CoS 1 2NH
4
NO
3
7. 4Al 1 3O
2
2Al
2
O
3
8. 2C
2
H
6
1 7O
2
4CO
2
1 6H
2
O
MAJOR REACTION TYPES
There are a few di fferent ways to cl assi fy chemi cal reacti ons. We wi l l l ook at the most
tradi ti onal method of cl assi fyi ng reacti ons, whi ch di vi des reacti ons i nto fi ve categori es, based
on the behavi or of the chemi cal s duri ng the reacti ons:
Combi nati on (synthesi s) reacti onstwo or more substances reacti ng to form a
si ngl e compound
Decomposi ti on reacti onsreacti ons i n whi ch a si ngl e compound i s broken down
i nto two or more si mpl er products
Combusti on reacti onsreacti ons where oxygen reacts wi th another substance,
often produci ng energy i n the form of heat and l i ght
Di spl acement reacti ons (si ngl e-repl acement reacti ons)chemi cal reacti ons
i n whi ch atoms of one el ement repl ace the atoms of a second el ement i n a compound
Metathesi s reacti ons (doubl e-repl acement reacti ons)chemi cal change that
i nvol ves an exchange of posi ti ve i ons between two compounds
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Chapter 11: Reaction Types 241
www.petersons.com
Combination or Synthesis Reactions
These are reacti ons i n whi ch two or more substances combi ne to form a si ngl e product. A
general equati on for a combi nati on reacti on i s:
A 1 B AB
Example: N
2
(g) 1 3H
2
(g) 2NH
3
(g)
Decomposition Reactions
These are reacti ons i n whi ch a si ngl e compound i s broken down i nto two or more si mpl er
products. The products of a decomposi ti on reacti on can be any combi nati on of el ements and
compounds. I t i s usual l y di ffi cul t to predi ct the products of decomposi ti on reacti ons, but i f a
si mpl e bi nary compound breaks down, the products wi l l usual l y be the consti tuent el ements.
(Consti tuent el ements are those el ements that make up a compound.) Most decomposi ti on
reacti ons requi re energy to occur. A general equati on for a decomposi ti on reacti on i s:
AB A 1 B
Example: 2HgO(s)

2Hg(l) 1 O
2
(g)
Combustion Reactions
These are reacti ons where oxygen reacts wi th another substance, often produci ng energy i n
the form of heat and l i ght. These reacti ons typi cal l y i nvol ve hydrocarbons, whi ch are
compounds of hydrogen and carbon. When hydrocarbons react wi th oxygen, they generate
water vapor and ei ther carbon di oxi de or carbon monoxi de as products. For the combusti on of
hydrocarbons, there are two types: compl ete and i ncompl ete.
Compl etecombusti on occurs when there i s ampl e oxygen and the reacti on generates carbon
di oxi de and water as products. A general equati on for the compl ete combusti on of a
hydrocarbon i s:
C
x
H
y
1 O
2
CO
2
1 H
2
O
Example: 2C
6
H
6
1 15O
2
12CO
2
1 6H
2
O
I ncompl ete combusti on occurs when there i s i nsuffi ci ent oxygen. Carbon monoxi de and
water are generated as products. A general equati on for the i ncompl ete combusti on of a
hydrocarbon i s:
C
x
H
y
1 O
2
CO 1 H
2
O
Example: C
2
H
4
1 2O
2
2CO 1 2H
2
O
Metathesis Reactions
The term metathesi s l i teral l y means to transpose. The term doubl e repl acement i s often
used to descri be these reacti ons because the cati ons swi tch pl aces wi th each other. These are
chemi cal reacti ons that i nvol ve an exchange of posi ti ve i ons between two compounds and that
general l y take pl ace between two i oni c compounds i n an aqueous sol uti on. The dri vi ng force
that causes these reacti ons to occur i s a decrease i n the number of i ons from the reactants to
242 PART III: AP Chemistry Review
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NOTE
The characteristic
feature of these
reactions is that
only one product
is formed. No
other type of re-
action has this
outcome.
NOTE
The distinguishing
feature of these
reactions is that
there is a single
reactant. No
other reaction
has a single
reactant.
www.petersons.com
products. Thi s wi l l occur when a stabl e product forms from the i oni c reactants. The three
types of stabl e products that can form are a preci pi tate (or an i nsol ubl e sol i d), a gas (gaseous
materi al s wi l l bubbl e out of the sol uti ons and l eave the reacti on mi xture), or a stabl e mol ecul e
(a weak el ectr ol yte, or nonel ectr ol yte, such as water ). A gener al equati on for a doubl e-
repl acement reacti on i s:
AB 1 CD AD 1 CB
Example: BaCl
2
(aq) 1 K
2
CO
3
(aq) BaCO
3
(s) 1 2 KCl (aq)
Note how the bari um and potassi um i ons have si mpl y been exchanged between the two
negati ve i ons. Al so note that on both si des of the equati on there are two i oni c compounds. Thi s
i s a good i ndi cator that an equati on represents a doubl e-repl acement reacti on.
Precipitation Reactions
One of the three types of metathesi s reacti ons i s dri ven by the producti on of an i nsol ubl e sol i d.
Whi l e we are goi ng to go much more i n depth about sol ubi l i ty i n Chapter 15, there are some
basi c rul es you can l earn now that wi l l provi de you wi th more than enough i nformati on to
predi ct the products of chemi cal reacti ons. These basi c rul es, usual l y referred to as sol ubi l i ty
rul es, are l i sted i n Tabl e 11.5. When readi ng the chart, keep i n mi nd that al l the sol uti ons
l i sted are aqueous sol uti ons (water i s the sol vent). The term i nsol ubl e i s not exactl y correct.
TABLE 11.5 SOLUBILITIES OF COMMON IONS
Soluble Compounds Exceptions
Al l compounds of the al kal i metal s (group
1A) are sol ubl e.
Al l sal ts contai ni ng NH
4
1
, NO
3
2
, Cl O
4
2
,
and C
2
H
3
O
2
2
are sol ubl e.
Al l chl ori des, bromi des, and i odi des (sal ts
contai ni ng Cl
2
, Br
2
, or I
2
) are sol ubl e.
Hal i des where Ag
1
, Pb
21
, Hg
2
21
, are the
cati ons are i nsol ubl e.
Al l sul fates (sal ts contai ni ng SO
4
22
) are
sol ubl e.
Sul fates wi th the cati ons Hg
21
, Pb
21
,
Ca
21
, Sr
21
, and Ba
21
.
Insoluble Compounds Exceptions
Al l hydroxi des (OH
2
compounds) and al l
metal oxi des (O
22
compounds) are
i nsol ubl e.
Hydroxi des and metal oxi des combi ned
wi th group 1A el ements and Ca
21
, Sr
21
,
and Ba
21
.
NOTE: When metal oxi des do di ssol ve,
they react wi th water to form hydroxi des.
Group 1A and NH
4
1
compounds are
sol ubl e.
For exampl e:
Na
2
O(s) 1 H
2
O(l) 2NaOH(aq)
Al l compounds that contai n PO
4
32
,
CO
3
22
, SO
3
22
, and S
22
are i nsol ubl e.
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Chapter 11: Reaction Types 243
www.petersons.com
Al l materi al s are sol ubl e to a certai n degree, though, for some materi al s, the degree of
sol ubi l i ty i s so smal l i t i s negl i gi bl e. I n these cases, we refer to the materi al as i nsol ubl e. You
wi l l l earn more about thi s i n Chapter 15.
When you attempt to determi ne products of a preci pi tati on reacti on, you need to thi nk back to
what the sol uti ons l ook l i ke. For exampl e, suppose you have two beakers, one contai ni ng an
aqueous sol uti on of l ead (I I ) ni trate, Pb(NO
3
)
2
, and the other contai ni ng an aqueous sol uti on
of potassi um i odi de, KI . Pri or to mi xi ng, the contents of the contai ners l ook somethi ng l i ke the
di agram i n Fi gure 11.1.
Each beaker contai ns a sol ubl e sal t, whi ch means that each i oni c sal t wi l l di ssol ve i n the
water. Crystal l i ne Pb(NO
3
)
2
, when added to water, di ssol ved. The same happened to KI . I n
each beaker, si nce the sal ts are sol ubl e, the i ons are di ssol ved i n water and fl oati ng about. I n
the fi rst beaker, i f a l ead i on encounters a ni trate i on, i t may sti ck together bri efl y, but
because the sal t i s sol ubl e, i t wi l l qui ckl y di ssol ve i nto sol uti on agai n. The same i s true for the
KI beaker. I f you dump some of each beaker i nto a thi rd beaker, you are goi ng to mi x al l four
of the i ons together l i ke i n Fi gure 11.2.
Pb
2
Pb

Pb
2
Pb
2
Pb
2
Pb
2
Pb
2
Pb

Pb
2
2
I

K
I

K
I

K
I

NO

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

NO
3

Figure11.1
Pb
2
Pb
2
Pb
2
2
Pb
2
2
Pb
2
2

NO

NO
3

NO
3

NO
3

NO

NO
3
NO
3

NO
3

Figure11.2
244 PART III: AP Chemistry Review
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www.petersons.com
At thi s poi nt, al l four i ons are free to i nteract, so there wi l l be two i nteracti ons that were not
possi bl e before. The fi rst i s K
1
and NO
3
2
i ons, and the second Pb
21
and I
2
i ons. To determi ne
what wi l l happen next, you need to refer to Tabl e 11.5, the sol ubi l i ty rul es. I f you l ook up the
fi rst possi bl e pai ri ng of i ons, K
1
and NO
3
2
, you can determi ne i f potassi um ni trate i s an
i nsol ubl e product. For two reasons, i t i s not: al l sal ts made from group 1A el ements are
sol ubl e, and al l ni trates are sol ubl e. The next possi bl e product, then, i s l ead (I I ) i odi de. For
thi s compound, the tabl e says that al l i odi des are sol ubl e except those formed wi th Ag
1
, Pb
21
,
and Hg
21
. Therefore, l ead (I I ) i odi de i s an i nsol ubl e product. What that means, i n terms of our
beaker, i s that when l ead i ons encounter i odi de i ons, they wi l l sti ck together (see Fi gure 11.3).
They wi l l conti nue to sti ck together i n l arger and l arger numbers unti l vi si bl e crystal s appear.
You probabl y have seen the bri ght yel l ow preci pi tate, l ead (I I ) i odi de. What wi l l be l eft i n the
beaker i s an aqueous sol uti on of potassi um ni trate and any l eftover l ead or i odi de i ons (thi s
wi l l be di scussed i n Chapter 12).
The reacti on that we have just descri bed can be wri tten as:
Pb(NO
3
)
2
(aq) 1 2KI (aq) PbI
2
(s) 1 2KNO
3
(aq)
To determi ne i f these reacti ons wi l l occur, you need to wri te the equati on as though the
cati ons swi tch pl aces and then determi ne i f ei ther of the newl y formed products i s i nsol ubl e.
I f i t i s not, then the reacti on wi l l not occur (unl ess one of the next two productswater or a
gasi s formed).
Neutralization Reactions
These reacti ons wi l l onl y be di scussed bri efl y at thi s poi nt, si nce they wi l l be di scussed i n
detai l i n Chapter 14. I n neutral i zati on reacti ons, an aci d and a base are combi ned to form
a sal t and water. These reacti ons appl y to aci ds that di ssoci ate to form free hydrogen i ons i n
sol uti on and bases that di ssoci ate to form free hydroxi de i ons. For exampl e, when
hydrochl ori c aci d, HCl , i s combi ned wi th sodi um hydroxi de, NaOH, the reacti on proceeds
as fol l ows:
HCl (aq) 1 NaOH(aq) H
2
O(l) 1 NaCl (aq)
K

NO
3

PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
PbI
2
NO
3

NO
3

NO
3

NO
3

NO
3
NO
3

NO
3

Figure11.3
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Chapter 11: Reaction Types 245
www.petersons.com
Some other neutral i zati on reacti ons can occur that are not as obvi ous as thi s one, but these
wi l l be addressed i n Chapter 14.
Gas-forming Reactions
These reacti ons are al so aci d-base i nteracti ons. One of these that may i mmedi atel y come to
mi nd i n thi s category i s a reacti on that you more than l i kel y di d as a chi l dmi xi ng vi negar
and baki ng soda. Now that you are an AP Chemi stry student, you know that you were real l y
mi xi ng aceti c aci d, HC
2
H
3
O
2
, and sodi um bi carbonate, NaHCO
3
. When these two substances
are mi xed, the reacti on proceeds as fol l ows:
HC
2
H
3
O
2
(aq) 1 NaHCO
3
(aq) NaC
2
H
3
O
2
(aq) 1 H
2
CO
3
(aq)
Al though the sodi um bi carbonate i s a sol i d when i t i s added to the aceti c aci d, i t must di ssol ve
i n the aqueous sol uti on before the reacti on can occur. That i s why i t i s shown as (aq) i n the
reacti on. Now that you have wri tten thi s out, you may be tryi ng to fi gure out where the gas i s.
The gas i s produced when the unstabl e product, carboni c aci d, decomposes to form water and
carbon di oxi de gas:
H
2
CO
3
(aq) H
2
O(l) 1 CO
2
(g)
I f you combi ne the two equati ons, you can see that the reacti on i s a neutral i zati on reacti on
and produces a gas:
HC
2
H
3
O
2
(aq) 1 NaHCO
3
(aq) NaC
2
H
3
O
2
(aq) 1 H
2
O(l) 1 CO
2
(g)
IONIC EQUATIONS
The equati ons you have been l ooki ng at up to thi s poi nt have been known as mol ecul ar
equati ons. They are cal l ed thi s because al l of the substances are wri tten as though they are
mol ecul es, even when they may not presentl y be i n that state. For exampl e, i n the previ ous
secti on, two substances we were di scussi ng were l ead (I I ) ni trate and potassi um i odi de. I n the
exampl e that used the two substances, both were i n an aqueous sol uti on. When the two
sol uti ons were mi xed, the reacti on occurred and crystal l i ne l ead (I I ) i odi de was formed.
However, i f you had taken the crystal l i ne forms of each reactant, Pb(NO
3
)
2
and KI , and
thrown them together, they woul d have sat there for an i ndefi ni te amount of ti me wi th l i ttl e
or no reacti on occurri ng. The two materi al s need to be di ssol ved (or i n a mol ten state) for the
reacti on to occur. I n the equati on for the reacti on, though, the materi al s are wri tten as though
they were mol ecul es:
Pb(NO
3
)
2
(aq) 1 2KI (aq) PbI
2
(s) 1 2KNO
3
(aq)
Potassi um ni trate, KNO
3
, i s wri tten as a mol ecul e, even though that materi al cant form i n
water. For thi s reason, there i s another type of equati on that i s often used to descri be
reacti ons that i nvol ve i ons. I t i s known as an i oni c equati on. I nstead of wri ti ng the formul as
for the substances as mol ecul es (or sal ts), we wi l l wri te the formul as for the i ons that woul d
be present i n aqueous sol uti on. I f the previ ous equati on i s rewri tten as an i oni c equati on, i t
wi l l become:
Pb
21
(aq) 1 2NO
3
2
(aq) 1 2K
1
(aq) 1 2I
2
(aq) PbI
2
(s) 1 2K
1
(aq) 1 2NO
3
2
(aq)
246 PART III: AP Chemistry Review
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Note that i n the i oni c equati on, ni trate i ons on the reactant si de of the equati on acqui red a
coeffi ci ent of 2. Thi s i s because when Pb(NO
3
)
2
di ssoci ates, i t forms one Pb
21
i on and two
NO
3
2
i ons. Al so noti ce that the l ead i odi de, PbI
2
, i s wri tten as a sol i d on the products si de of
the equati on. Al l preci pi tates wi l l be wri tten thi s way. Al though thi s doesnt appear i n the
previ ous exampl e, when nonel ectrol ytes or weak el ectrol ytes l i ke water appear i n an i oni c
equati on, they are wri tten i n thei r appropri ate state, such as H
2
O(l).
Net Ionic Equations
I f you l ook at the equati on i n the previ ous exampl e, there are a few i ons that havent done
anythi ng. Lets l ook at the equati on agai n, wi th these hi ghl i ghted so you can see that they do
nothi ng:
Pb
21
(aq) 1 2NO
3
2
(aq) 1 2K
1
(aq) 1 2I
2
(aq) PbI
2
(s) 1 2K
1
(aq) 1 2NO
3
2
(aq)
I ons that havent done anythi ng are known as spectator i ons. Just l i ke spectators watch a
footbal l game wi thout taki ng part i n i t, these spectator i ons watch the reacti on wi thout
taki ng part i n i t. The equati on can be rewri tten wi thout the spectator i ons. When i t i s
wri tten thi s way, i t i s known as a net i oni c equati on. The previ ous equati on, wri tten as a net
i oni c equati on, i s:
Pb
21
(aq) 1 2I
2
(aq) PbI
2
(s)
Thi s equati on onl y shows the i ons that are actual l y i nvol ved i n the reacti on. I t al so hel ps to
poi nt out other reacti ons that are possi bl e. For exampl e, any sol ubl e l ead sal t, when combi ned
wi th any sol ubl e i odi de sal t, wi l l produce the i nsol ubl e l ead (I I ) i odi de.
You Try It!
Wri te net i oni c equati ons from the fol l owi ng pai rs of reactants. Use the sol ubi l i ty to
determi ne the products when necessary. Al l pai rs wi l l react to form products:
1. H
2
SO
4
(aq) 1 BaCl
2
(aq)
2. Pb(NO
3
)
2
(aq) 1 MgSO
4
(aq)
3. NaOH(aq) 1 HNO
3
(aq)
4. Sr(C
2
H
3
O
2
)
2
(aq) 1 Ni SO
4
(aq)
5. Fe(OH)
3
(s) 1 HCl O
4
(aq)
Answers:
1. Ba
21
(aq) 1 HSO
4
2
(aq) BaSO
4
(s) 1 H
1
(aq)
2. Pb
21
(aq) 1 SO
4
22
(aq) PbSO
4
(s)
3. H
1
(aq) 1 OH
2
(aq) H
2
O(l)
4. Sr
21
(aq) 1 SO
4
22
(aq) SrSO
4
(s)
5. Fe(OH)
3
(s) 1 3H
1
(aq) Fe
31
(aq) 1 3H
2
O(l)
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Chapter 11: Reaction Types 247
www.petersons.com
Single-Replacement Reactions
These reacti ons are part of a l arger category of reacti ons known as redox reacti ons (redox i s
short for oxi dati on-reducti on). Someti mes these are cal l ed di spl acement reacti ons. These are
chemi cal reacti ons i n whi ch atoms of one el ement repl ace the atoms of a second el ement i n a
compound. A general equati on for a si ngl e-repl acement reacti on i nvol vi ng a metal (A),
repl aci ng a metal l i c cati on i n sol uti on (B) i s:
A 1 BC AC 1 B
Example: Zn(s) 1 2AgNO
3
(aq) Zn(NO
3
)
2
(aq) 1 2Ag(s)
Whether one metal wi l l repl ace another metal from a compound i s determi ned by the
reducti on potenti al of the metal , found on a tabl e of standard reducti on potenti al s (l i ke the
one avai l abl e to you on the AP test). I f the metal l i c el ement i s hi gher on the chart than the
cati on, i t wi l l repl ace i t. I f i t i s not hi gher on the chart, no reacti on wi l l occur.
For a nonmetal (D) repl aci ng a nonmetal l i c ani on, the general form of the reacti on i s:
D 1 BC BD 1 C
Example: Cl
2
1 2NaBr 2NaCl 1 Br
2
These reacti ons are typi cal l y l i mi ted to the hal ogens. The procedure for predi cti ng the
outcome of these reacti ons i s the same as for the metal s. The hal ogens al so appear on the
tabl e of standard reducti on potenti al s, but for reasons we wi l l di scuss i n Chapter 18, the
hal ogens get more reacti ve as you go up the tabl e of reducti on potenti al s. An easy way to
remember the reacti vi ti es of the hal ogens i s they are l ess reacti ve goi ng down the group (as
atomi c number i ncreases).
You Try It!
Predi ct the outcome of the fol l owi ng reacti ons. Not al l substances may react. When a
reacti on does occur, wri te the compl ete and bal anced equati on, fol l owed by the net
i oni c equati on:
1. Fe 1 NaCl (aq)
2. F
2
1 Al Cl
3
(aq)
3. K 1 CuSO
4
(aq)
4. Pb 1 KCl (aq)
5. Mg 1 HCl (aq)
248 PART III: AP Chemistry Review
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www.petersons.com
Answers:
1. No reacti on
2. 3F
2
(g) 1 2Al Cl
3
(aq) 2Al F
3
(aq) 1 3Cl
2
(g); 3F
2
1 6Cl
2
6F
2
1 3Cl
2
3. 2K(s) 1 CuSO
4
(aq) K
2
SO
4
(aq) 1 Cu(s); 2K 1 Cu
21
2K
1
1 Cu
4. No reacti on
5. Mg(s) 1 2HCl (aq) MgCl
2
(aq) 1 H
2
(g); Mg 1 2H
1
Mg
21
1 H
2
OXIDATION-REDUCTION REACTIONS
Redox reacti ons are not l i mi ted to si ngl e repl acement reacti ons. They real l y descri be a wi de
vari ety of reacti ons, but each shares the common theme of i nvol vi ng an oxi dati on and a
reducti on. An oxi dati on occurs when a substance l oses el ectrons and becomes more
posi ti vel y charged. Earl i er i n the book we di scussed a si mi l ar phenomenon i n the formati on of
i oni c compounds. Substances dont just l ose el ectrons for no reason. They l ose el ectrons
because another substance takes them. When a substance acqui res addi ti onal el ectrons and
becomes more negati vel y charged, i t i s cal l ed a reducti on. An oxi dati on cannot take pl ace
wi thout a reducti on, so these processes must occur si mul taneousl y. These reacti ons descri be
the si mul taneous oxi dati on and reducti on of materi al s, whi ch has earned them the name
oxi dati on-reducti on reacti ons.
Two terms you shoul d be fami l i ar wi th are oxi di zi ng agent and reduci ng agent. An
oxi di zi ng agent i s a substance that oxi di zes another substance. Thi s means i t i s causi ng the
other substance to l ose el ectrons. The onl y way to do thi s i s for the oxi di zi ng agent to gai n the
el ectrons or become reduced. Therefore, oxi di zi ng agents oxi di ze other materi al s whi l e they
are bei ng reduced. Si mi l arl y, a reduci ng agent i s a substance that reduces other materi al s by
becomi ng oxi di zed. I n other words, reduci ng agents are gi vi ng away el ectrons. We are goi ng to
l ook at thi s more cl osel y i n Chapter 18, but there i s one i mportant appl i cati on for thi s chapter.
The tabl e of standard reducti on potenti al s that you are gi ven on the AP test i s a hel pful way
to predi ct the outcome of redox reacti ons. The way i t i s set up, the strongest reduci ng agents
are at the top of the chart (have the most negati ve val ues), and the strongest oxi di zi ng agents
are l ocated at the bottom of the chart (have the most posi ti ve val ues).
Oxidation Numbers
An oxi dati on-reducti on reacti on has to be accompani ed by a change i n the oxi dati on state of
the reactants. Someti mes, these changes arent that obvi ous. I t hel ps i f you l earn how to
fol l ow the oxi dati on states of an el ement duri ng a chemi cal reacti on. I n i oni c compounds, i t i s
very obvi ous where the el ectrons have been transferred. However, i n mol ecul ar compounds,
el ectrons are bei ng shared. Oxi dati on numbers are real l y fi cti ti ous creati ons that hel p us
better understand atomi c behavi or. I f you remember back to Chapter 6 when we di scussed
coval ent bonds, you may recal l that el ectrons are bei ng shared between atoms i n a coval ent
bond. I n many cases, one atom i s more el ectronegati ve than the other, resul ti ng i n a pol ar
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TIP
If you have
trouble
remembering the
definitions of the
terms oxidation
and reduction,
just remember
the little
mnemonic
device: LEO says
GER which
stands for Losing
Electrons is
Oxidation, and
Gaining Electrons
is Reduction.
Chapter 11: Reaction Types 249
www.petersons.com
bond. When you determi ne the oxi dati on number of an atom, you pretend that the more
el ectronegati ve el ement actual l y got the enti re charge of the el ectron and the l ess
el ectronegati ve el ement l ost i t. Therefore, i n a water mol ecul e, the more el ectronegati ve
oxygen woul d be assi gned both of the el ectrons from the hydrogen atoms, gi vi ng i t an
oxi dati on number of 22. Hydrogen woul d have an oxi dati on number of 11. Oxi dati on
numbers are usual l y wri tten wi th the si gn of the charge wri tten before the number i nstead of
after i t. Thi s i s so you dont confuse them wi th real charges found on i ons. There are four rul es
that are fol l owed to si mpl i fy the process of assi gni ng oxi dati on numbers:
The oxi dati on number of an el ement i n i ts normal state i s zero. A pi ece of copper,
Cu, woul d have an oxi dati on number of 0. Chl ori ne gas, Cl
2
, wi l l al so have an
oxi dati on number of 0. Even though some el ements are di atomi c, remember that
the el ectrons i n those bonds are shared evenl y, so no number i s assi gned.
Oxi dati on numbers for monatomi c i ons are the same as thei r charges. K
1
has an
oxi dati on number of 11, and O
22
has an oxi dati on number of 22.
I n a bi nary compound, the more el ectronegati ve el ement i s assi gned a negati ve
oxi dati on number equal to the charge i t woul d have i n si mpl e i oni c compounds. For
exampl e, i n CCl
4
, the chl ori ne atoms are assi gned oxi dati on numbers of 21 because
i n i oni c compounds, chl ori de i ons have a 1
2
charge.
For any el ectri cal l y neutral compound, the sum of the oxi dati on numbers wi l l
al ways equal zero. For any i oni c speci es (l i ke pol yatomi c i ons), the sums of the
oxi dati on states of the el ements wi l l equal the charge of the i on. I n CCl
4
, i f each
chl ori ne i s assi gned a 21 oxi dati on number, then carbon must be assi gned a 14 so
the net charge wi l l be zero. I n a pol yatomi c i on, l i ke ni trate, NO
3
2
, oxygen i s the
more el ectronegati ve el ement, so i t wi l l be assi gned a 22 oxi dati on number. Be-
cause there are three oxygen atoms i n a ni trate i on, the total oxi dati on state for
oxygen i s 26. Si nce the sum of the oxi dati on states must equal the charge of the
i on, ni trogen must have an oxi dati on number of 15 so that the sum wi l l be
21: 26 1 5 5 21
Sample: Assi gn oxi dati on numbers to al l atoms i n the fol l owi ng:
a. SF
6
b. Cr
2
O
7
22
c. P
2
O
5
Answers:
a. Fl uori ne i s al ways goi ng to have an oxi dati on number of 21. I t i s the most
el ectronegati ve el ement, so nothi ng wi l l ever have a hi gher el ectronegati vi ty.
Therefore, the 6 fl uori ne atoms wi l l gi ve a total of 6(21) 5 26. Because thi s i s
a neutral mol ecul e, the sum of sul furs oxi dati on number and the si x fl uori nes
must be zero. That means sul fur must be 16.
b. Oxygen i s more el ectronegati ve, so i t wi l l have the negati ve oxi dati on number.
I t wi l l have the charge i t has i n i oni c compounds, whi ch i s 22. Oxygen wi l l
250 PART III: AP Chemistry Review
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al ways have a 22 oxi dati on number, except when i t appears as a peroxi de i on
(O
2
22
), where i t wi l l have a 21. Si nce there are 7 of them, the total wi l l be
7(22) 5 214. The sum of the two chromi um atoms and oxygen must equal the
charge of the i on (2
2
). Therefore, each chromi um must have a 16 oxi dati on
number. 2(16) 1 7(22) 5 22.
c. P
2
O
5
i s a neutral mol ecul e i n whi ch oxygen i s the more el ectronegati ve
el ement. Wi th 5 oxygen atoms, the total negati ve oxi dati on number i s 5(22) 5
210. Si nce there are two phosphorous atoms, each wi l l have an oxi dati on state
of 15.
You Try It!
Assi gn oxi dati on numbers to the atoms i n the fol l owi ng:
1. PbS
2. MnO
4
22
3. N
2
O
5
Answers:
1. Pb 5 12, S 5 22
2. Mn 5 16, O 5 22
3. N 5 15, O 5 22
One of the mai n purposes for usi ng oxi dati on numbers i s to fol l ow the movement of el ectrons
duri ng an oxi dati on-reducti on reacti on. Doi ng so hel ps to predi ct the products and determi ne
the outcomes of such reacti ons. There are a few di fferent ways to anal yze redox reacti ons, but
we wi l l focus on onl y one: the i on-el ectron method (al so cal l ed the hal f-reacti on method).
The procedure requi res that you know the reactants and products of the reacti on, but, by
goi ng through the process, you wi l l gai n a better understandi ng of the mechani sms by whi ch
these reacti ons proceed.
Understanding the Oxidation-Reduction Process
These reacti ons al l proceed by the transfer of el ectrons from one substance to another. Part of
understandi ng the process i s recogni zi ng when these transfers are taki ng pl ace. For exampl e,
i f you l ook at the equati on for the reacti on that takes pl ace between magnesi um metal and
hydrochl ori c aci d, you may not noti ce the transfers unl ess you l earn to l ook for them. The
equati on i s wri tten as:
Mg(s) 1 2HCl (aq) MgCl
2
(aq) 1 H
2
(g)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 11: Reaction Types 251
www.petersons.com
Youve probabl y seen thi s reacti on, and you may have even performed i t. There are no charged
parti cl es vi si bl e. However, l ets begi n by l ooki ng at the oxi dati on states of each substance i n
the reacti on. Rewri ti ng the equati on wi th the oxi dati on states wri tten above each el ement, we
can see that there are a few changes:
0 11 12 0
Mg(s) 1 2HCl (aq) MgCl
2
(aq) 1 H
2
(g)
You can see that magnesi um has l ost two el ectrons and hydrogen has pi cked up one el ectron.
Another way to see the process i s to wri te an i oni c equati on, l i ke you l earned i n the
l ast secti on:
Mg(s) 1 2H
1
(aq) 1 2Cl
2
(aq) Mg
21
(aq) 1 2Cl
2
(aq) 1 H
2
(g)
Looki ng at the i oni c equati on, you can see that el ectrons are actual l y bei ng transferred. I f we
wri te the net i oni c equati on, you wi l l see that the onl y atoms parti ci pati ng i n the reacti on are
those whose oxi dati on numbers have changed:
Mg(s) 1 2H
1
(aq) Mg
21
(aq) 1 H
2
(g)
I n thi s reacti on, you may be abl e to see the movement of el ectrons just by l ooki ng at the
equati on. Some other equati ons are more di ffi cul t and wi l l requi re you to fol l ow a seri es of
procedures to compl ete them. We wi l l begi n to l ook at those rul es usi ng thi s rel ati vel y
easy exampl e.
The fi rst step i n bal anci ng the equati on i s to wri te an unbal anced net i oni c equati on for the
reacti on. Wel l di spense wi th the states for now:
Mg 1 H
1
Mg
21
1 H
2
The second step requi res you to separate the equati on i nto two separate hal f-reacti ons. A
hal f-reacti on onl y shows what i s goi ng on i n hal f of the reacti on. The fi rst hal f-reacti on shows
the oxi dati on and the second hal f-reacti on the reducti on:
Oxi dati on: Mg Mg
21
Reducti on: H
1
H
2
I n the thi rd step, you need to make sure you have the same number of each atom on each hal f
of the equati on:
Oxi dati on: Mg Mg
21
~thi s one doesnt change!
Reducti on: 2H
1
H
2
I n the fourth step, you need to add el ectrons to the equati on to bal ance the charges. Wri te
them i n the equati on as though they are el ements wi th the symbol e
2
:
Oxi dati on: Mg Mg
21
1 2e
2
Reducti on: 2H
1
1 2e
2
H
2
You may be abl e to l ook at these two equati ons and thi nk, Hey, magnesi um l ost two el ectrons,
and the hydrogen atoms gai ned two el ectrons. Coi nci dence? Nope. Thats why thi s method i s
252 PART III: AP Chemistry Review
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hel pful . I t expl ai ns where the el ectrons go, and how thi s di ctates the outcome of the reacti on.
I n thi s si mpl e reacti on, we l eft out a few steps because they werent requi red. Wel l fi ni sh thi s
secti on by tackl i ng two more chal l engi ng exampl es that wi l l requi re you to use al l of the rul es.
Reactions in Acidic Solutions
I n thi s fi rst reacti on, an aci di fi ed sol uti on of potassi um di chromate, K
2
Cr
2
O
7
, reacts wi th a
sol uti on of potassi um chl ori de, KCl . Thi s type of probl em peri odi cal l y appears on the AP test.
The skel eton equati on for thi s reacti on i s:
Cr
2
O
7
22
1 Cl
2
Cl
2
1 Cr
31
Step 1: Just l i ke the l ast exampl e, we need to begi n by wri ti ng the unbal anced skel eton
equati on i n i oni c form:
Cr
2
O
7
22
1 Cl
2
Cl
2
1 Cr
31
Step 2: Same as l ast ti meconvert the reacti on i nto hal f-reacti ons:
Oxi dati on: Cl
2
Cl
2
Reducti on: Cr
2
O
7
22
Cr
31
(I f you dont recogni ze i t, the oxi dati on state of chromi um has changed from 16 to 13.)
Step 3: At thi s poi nt, thi ngs get a l i ttl e di fferent. Bal ance the atoms other than O i n each
hal f-reacti on:
Oxi dati on: 2Cl
2
Cl
2
Reducti on: Cr
2
O
7
22
2Cr
31
Step 4: Thi s step was not i n the previ ous exampl e. For reacti ons i n an aci di c medi um, add
H
2
O to bal ance the oxygen atoms. I n doi ng thi s, you wi l l create some hydrogen atoms. You wi l l
need to bal ance those next, by addi ng H1 i ons to the other si de of the equati on. Al l of these
speci es are present i n aci di c sol uti ons:
Cr
2
O
7
22
2Cr
31
1 7H
2
O
You have to bal ance the hydrogen atoms now, so add H
1
to the other si de:
14H
1
1 Cr
2
O
7
22
2Cr
31
1 7H
2
O
Step 5: Add el ectrons to the hal f-reacti ons to bal ance the charges:
Oxi dati on: 2Cl
2
Cl
2
1 2e
2
The total number of negati ve charges on the l eft si de i s 2 and on the ri ght i s 0. We need to add
2e
2
to the ri ght to bal ance the charges:
Reducti on: 14H
1
1 Cr
2
O
7
22
1 6e
2
2Cr
31
1 7H
2
O
The total charge on the l eft i s 12
1
, obtai ned from 14
1
on hydrogen pl us 2
2
on the di chromate
i on. The total charge on the ri ght i s 6
1
, from the two chromi um (I I I ) i ons. To bal ance the
charges on the ri ght and l eft, we must add 6e
2
to the l eft, maki ng the total charge 6
1
, the
same as the ri ght si de.
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Chapter 11: Reaction Types 253
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Step 6: At thi s poi nt, you need to remember what we sai d about oxi dati on and reducti on. One
substance i s oxi di zed and the other reduced. As the equati ons exi st ri ght now, the chl ori de
i ons have l ost 2 el ectrons, but the chromi um atoms have gai ned 6 el ectrons. Thats i mpossi bl e!
The 6 el ectrons had to come from the chl ori de i ons. I n step 6, therefore, we need to equal i ze
the number of el ectrons i n each hal f-reacti on. We need to i ncrease the total number of
el ectrons l ost by the chl ori de i ons to 6. To do thi s, we have to mul ti pl y the enti re hal f-reacti on
by 3:
Oxi dati on: 6Cl
2
3Cl
2
1 6e
2
Reducti on: 14H
1
1 Cr
2
O
7
22
1 6e
2
2Cr
31
1 7H
2
O
Step 7: I n the fi nal step, youre goi ng to combi ne the two hal f-reacti ons. After you have done
thi s, you want to doubl e check to make sure that al l charges are bal anced and that the
number of atoms i s bal anced. Once you have done that, remove the el ectrons, and youre l eft
wi th the bal anced net i oni c equati on:
14H
1
1 Cr
2
O
7
22
1 6Cl
2
1 6e
2
2Cr
31
1 3Cl
2
1 7H
2
O1 6e
2
Net i oni c equati on: 14H
1
1 Cr
2
O
7
22
1 6Cl
2
2Cr
31
1 3Cl
2
1 7H
2
O
Reactions in Basic Solutions
Occasi onal l y, you wi l l have probl ems where the reacti on takes pl ace i n a basi c medi um. I n
these probl ems, when you reach step 4, you add the water mol ecul es to bal ance the oxygen
atoms, and then add the hydrogen atoms to bal ance the hydrogen atoms i n water (thats the
same as what you normal l y do i n step 4 for an aci di c sol uti on). After that, however, you add
hydroxi de (OH
2
) i ons on both si des of the equati on to bal ance out the hydrogen atoms. After
you do thi s, there wi l l be H
1
i ons and OH
2
i ons on the same si de of the equati on. You combi ne
them together to form water mol ecul es (as many as you can form) and cancel the number of
water mol ecul es that appear on both si des of the equati on. I n thi s exampl e, we wi l l l ook at a
reacti on that takes pl ace i n basi c sol uti on. I f youre pressed for ti me, you can probabl y ski p
thi sthese rarel y appear on the test.
The skel eton equati on: MnO
4
2
1 I
2
MnO
2
1 I O
3
2
Step 1: Wri te the unbal anced i oni c equati on:
MnO
4
2
1 I
2
MnO
2
1 I O
3
2
Step 2: Convert the reacti on i nto hal f-reacti ons:
Oxi dati on: I
2
I O
3
2
I odi de has changed oxi dati on states from 21 to 15:
Reducti on: MnO
4
2
MnO
2
(The oxi dati on state of manganese has changed from 17 to 14.)
Step 3: Bal ance the atoms other than oxygen:
Both atoms are al ready bal anced.
254 PART III: AP Chemistry Review
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www.petersons.com
Step 4: Bal ance the oxygen atoms wi th water:
Oxi dati on: 3H
2
O 1 I
2
I O
3
2
Reducti on: MnO
4
2
MnO
2
1 2H
2
O
Next, bal ance the hydrogen atoms wi th H
1
:
Oxi dati on: 3H
2
O 1 I
2
I O
3
2
1 6H
1
Reducti on: MnO
4
2
1 4H
1
MnO
2
1 2H
2
O
Thi s next part i s whats di fferent for a basi c sol uti onaddi ng OH
2
i ons to both si des of the
equati on for every H
1
:
Oxi dati on: 3H
2
O 1 I
2
1 6OH
2
I O
3
2
1 6H
1
1 6OH
2
Reducti on: MnO
4
2
1 4H
1
1 4OH
2
MnO
2
1 2H
2
O 1 4OH
2
Now, you form water mol ecul es where you can add H1 and OH2 together:
Oxi dati on: 3H
2
O 1 I
2
1 6OH
2
I O
3
2
1 6H
2
O
Reducti on: MnO
4
2
1 4H
2
O MnO
2
1 2H
2
O 1 4OH
2
Fi nal l y, we wi l l cancel the extra water mol ecul es and proceed to step 5:
Oxi dati on: I
2
1 6OH
2
I O
3
2
1 3H
2
O
Reducti on: MnO
4
2
1 2H
2
O MnO
2
1 4OH
2
Step 5: Add el ectrons to each hal f-reacti on to bal ance the charges:
Oxi dati on: I
2
1 6OH
2
I O
3
2
1 6e
2
1 3H
2
O
Reducti on: MnO
4
2
1 3e
2
1 2H
2
O MnO
2
1 4OH
2
Step 6: Modi fy the hal f-reacti ons, so the total el ectrons are the same:
Oxi dati on: I
2
1 6OH
2
I O
3
2
1 6e
2
1 3H
2
O
Reducti on: 2MnO
4
2
1 6e
2
1 4H
2
O 2MnO
2
1 8OH
2
Step 7: Combi ne the hal f-reacti ons and bal ance al l el ectrons and atoms. Wel l remove any
excess water mol ecul es or hydroxi de i ons i n thi s step:
2MnO
4
2
1 6e
2
1 4H
2
O 1 I
2
1 6OH
2
2MnO
2
1 8OH
2
1 I O
3
2
1 6e
2
1 3H
2
O
Net i oni c equati on: 2MnO
4
2
1 H
2
O 1 I
2
2MnO
2
1 2OH
2
1 I O
3
2
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Chapter 11: Reaction Types 255
www.petersons.com
You Try It
Bal ance the fol l owi ng redox reacti ons, usi ng the hal f-reacti on method. Wri te your
answers as net i oni c equati ons.
1. Mn(s) 1 H
2
SO
4
(aq) MnSO
4
(aq) 1 H
2
(g)
2. Pb(s) 1 AgNO
3
(aq) Pb(NO
3
)
2
(aq) 1 Ag(s)
3. MnO
4
2
(aq) 1 Cl
2
(aq) Mn
2
1
(aq) 1 Cl
2
(aq) i n aci di c sol uti on
Answers:
1. Mn(s) 1 2H
1
(aq) Mn
21
(aq) 1 H
2
(g)
2. Pb(s) 1 2Ag
1
(aq) Pb
21
(aq) 1 2Ag(s)
3. 2MnO
4
2
(aq) 1 10Cl
2
(aq) 1 16H
1
(aq) 2Mn
21
(aq) 1 5Cl
2
(g) 1 8H
2
O
What You Are Going to Be Accountable For on the AP Test
Thi s topi c rarel y appears i n the mul ti pl e-choi ce porti on of the AP test. I t i s al ways found i n
the free response secti on of the test, where you are presented wi th 3 reacti ons. You are gi ven
the reactants and condi ti ons for three di fferent possi bl e reacti ons. The reactants are wri tten
as words, and you need to transl ate them i nto symbol s and answer a questi on about the
reacti on. Each of the three reacti ons that you wri te i s worth 5 poi nts. Over the years, averages
on thi s secti on are usual l y between 6 and 7 out of 15. What that means to you i s i f you get two
of these correct, you are doi ng about as wel l as someone who has a cumul ati ve score of 3 on
the AP test. Many of the reacti ons may seem very strange, but you shoul dnt pani c when you
get to thi s part. Here are fi ve strategi es you can use to hel p you i mprove your chances on
thi s secti on:
The i nstructi ons say that you are to assume that sol uti ons are aqueous unl ess
otherwi se i ndi cated. Thi s means i t i s not necessary to wri te (aq) next to each
reactant and product i n sol uti on. The same i s true for the phases of the substances.
You do not need to wri te (s), (l), or (g).
The i nstructi ons al so say to represent substances i n sol uti on as i ons i f the sub-
stances are extensi vel y i oni zed. That means that i f the substance di ssol ves, you
shoul d use an i oni c equati on to descri be the consti tuent i ons.
The i nstructi ons al so say to omi t formul as for any i ons or mol ecul es that are
unchanged by the reacti on. Thi s i s the equi val ent of usi ng a net i oni c equati on.
Fi nal l y, the i nstructi ons say that you need to bal ance the equati on.
Of the 5 poi nts for each questi on, one of the poi nts i s for correctl y wri ti ng the
reactants. Two other poi nts are for correctl y wri ti ng the products. There are some
thi ngs you shoul d know about how these poi nts are awarded. Fi rst, i f you i ncl ude
any spectator i ons on the reactant si de, you wi l l l ose the reactant poi nt for that
questi on. I f a reacti on i s wri tten as a mol ecul ar equati on i nstead of an i oni c
equati on, you wi l l onl y earn one poi nt, even i f the products are correct. When you
256 PART III: AP Chemistry Review
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wri te the charges for i ons, they must be correct or you wont earn any poi nts. The
other poi nt, wi l l be gi ven for bal anci ng the equati on and for correctl y answeri ng the
questi ons. Three poi nts are gi ven for wri ti ng the correct net i oni c equati on, and one
poi nt i s gi ven for bal anci ng the si mpl est whol e number rati o and answeri ng a
questi on about the equati ons.
Now that you have some awareness of what wi l l be expected of you on the AP test, l ets revi ew
the materi al i n the chapter. There are far too many chemi cal reacti ons to worry about
memori zi ng i ndi vi dual reacti ons. I nstead, you shoul d focus your attenti on on l earni ng the
i denti fyi ng characteri sti cs of the di fferent types of reacti ons so that you can more effecti vel y
predi ct the possi bl e products. I n addi ti on, you shoul d l earn the basi c mechani sms for each
type of equati on to hel p you wi th your response.
SUMMARY OF THE MAIN REACTION TYPES
Tabl e 11.6 summari zes the di sti ngui shi ng characteri sti cs of the di fferent reacti on types.
Combination
I n combi nati on reacti ons, the reactants combi ne to form a si ngl e product. Because a
combi nati on of an el ement and a compound or two compounds woul d be di ffi cul t to cl assi fy as
a combi nati on reacti on, the reacti ons on the AP test that are combi nati on reacti ons tend to
use two el ements. So, i f you encounter two el ements on the test, they wi l l undergo a
combi nati on reacti on.
Sample: Magnesi um metal i s heated strongl y i n the presence of ni trogen gas.
Answer: When you read thi s, you have to know that ni trogen gas i s a di atomi c el ement. You
al so have to assume that strong heat means the reactants probabl y woul dnt react
otherwi se. When you wri te the reactants and products, you do not need to wri te the
states of condi ti ons of the reacti on:
3Mg 1 N
2
Mg
3
N
2
The formul a Mg
3
N
2
was obtai ned by usi ng the cri sscross method. You can use the peri odi c
tabl e on thi s part of the test, so you shoul d real l y make an effort to memori ze the common
charges of i ons, or oxi dati on states, by an el ements posi ti on on the chart.
Decomposition
These are probabl y the easi est to detect, even i f they arent the easi est to determi ne the
products for. The reason they are easi est to detect i s there wi l l onl y be a si ngl e reactant. You
wi l l usual l y be tol d somethi ng i s bei ng done to i t, l i ke heati ng, but no other reactant i s
menti oned. There may be a catal yst menti oned, but i t wi l l be l abel ed as a catal yst.
Sample: Potassi um chl orate crystal s are heated strongl y i n the presence of the catal yst
manganese di oxi de.
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TIP
An easy
mnemonic
device to
remember the
diatomic
elements is Dr.
Brinclhof. If you
spell the last
name this way,
BrINClHOF, you
should quickly
recognize the
seven diatomic
elements:
Br(omine),
I(odine),
N(itrogen),
Cl(chlorine),
H(ydrogen),
O(xygen),
and F(luorine).
Chapter 11: Reaction Types 257
www.petersons.com
Answer: Theres onl y one reactant, so thi s must be a decomposi ti on reacti on. The mai n
probl em i s to try to determi ne the correct products. Usual l y, decomposi ti on
reacti ons are goi ng to produce gases and sal ts. I f nothi ng el se, you are guaranteed
one poi nt i f you can correctl y wri te the formul a of the reactant:
2KCl O
3
2KCl 1 3O
2
Combustion Reactions
The key term to l ook for i n these questi ons i s the word burn. Combusti on reacti ons can occur
wi th di fferent types of materi al s, but the most common and the most wi del y used on the AP
test i s combusti on of hydrocarbons. Whi l e the products are easi l y predi ctabl e, you have to
have an understandi ng of organi c chemi stry nomencl ature (we wi l l di scuss that l ater i n the
book) to be abl e to wri te the formul as of the reactants.
I n al l of these combusti on reacti ons, the hydrocarbon reacts wi th oxygen. I f suffi ci ent oxygen
i s avai l abl e for the hydrocarbon to react compl etel y wi th the oxygen, a compl ete combusti on
occurs, where the products are CO
2
and H
2
O. I f i nsuffi ci ent oxygen i s present, carbon
monoxi de, CO, wi l l form i nstead. Occasi onal l y, the AP questi ons wi l l speci fy an excess of
oxygen gas to l et you know that a compl ete combusti on i s expected.
Sample: Butane gas i s burned i n ai r.
TABLE 11.6
Reaction Type General Equation Distinguishing Characteristics
Combi nati on A 1 B AB On the test, these wi l l usual l y have
two el ements as reactants.
Decomposi ti on AB A 1 B Youre onl y gi ven a si ngl e reactant.
Youl l most l i kel y be gi ven a set of
condi ti ons as wel l (i .e., heati ng, etc.).
Si ngl e Repl acement A 1 BC AC 1 B
or
D 1 BC BD 1 C
A neutral el ement combi ned wi th an
i oni c compound (usual l y i n sol uti on).
Metathesi s
(doubl e repl acement)
AB 1 CD AD 1 CB These wi l l have di fferent combi na-
ti ons we wi l l l ook at i n more detai l . A
key feature though i s the presence of
two bi nary reactants (usual l y both
i oni c, but not al ways).
Combusti on CxHy 1 O
2
CO(2) 1 H
2
O The 2 i n CO
2
i s wri tten i n parenthe-
ses because someti mes CO i s a prod-
uct. Not al l combusti on reacti ons
i nvol ve hydrocarbons. These ques-
ti ons usual l y use the word burn i n
the condi ti ons of the reacti on.
258 PART III: AP Chemistry Review
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Answer: Past AP tests have used the word ai r i n combusti on questi ons. Assume that the
word ai r represents oxygen when you answer the questi on. The onl y other
di ffi cul t part on a questi on l i ke thi s wi l l be rememberi ng the structure of butane.
The reacti on proceeds as:
2C
4
H
10
1 13O
2
8CO
2
1 10H
2
O
Occasi onal l y, other compounds wi l l be burned besi des hydrocarbons. I f the compound contai ns
carbon, assume that one of the products i s l i kel y to be carbon di oxi de (or carbon monoxi de).
Sample: Carbon di sul fi de vapor i s burned i n oxygen.
Answer: CS
2
1 3O
2
CO
2
1 2SO
2
Double-Replacement Reactions
These wi l l take a vari ety of forms. The one thi ng they wi l l al l have i n common i s that two
compounds wi l l be reacti ng. What those compounds are wi l l gi ve you cl ues about how the
reacti on wi l l proceed.
PRECIPITATION REACTIONS
I n these reacti ons, you wi l l see two sal t sol uti ons added together. You need to use the
sol ubi l i ty rul es to determi ne the i nsol ubl e sol i d. Remember that i n these reacti ons there are
spectator i ons, so make sure you l eave them out of your equati on.
Sample: A test tube contai ni ng a sol uti on of si l ver ni trate i s added to a beaker contai ni ng a
sol uti on of sodi um chromate.
Answer: Fi rst thi ng to do i s l ook at the possi bl e products here: sodi um ni trate and si l ver
chromate. I f you remember your sol ubi l i ty rul es, you wi l l know that si l ver
chromate i s the sol i d here. Therefore, the reacti on wi l l l ook l i ke:
2Ag
1
1 CrO
4
22
Ag
2
CrO
4
Remember, si l ver i s one of the four metal s that onl y have one charge. I f you forget the charge,
i t does appear on the reducti on potenti al s chart. Al so note that the spectator i ons are omi tted.
NEUTRALIZATION REACTIONS
I n a neutral i zati on reacti on, an aci d or a base wi l l combi ne to form neutral products. There
are several vari ati ons here, but we have not yet gone over the speci fi cs of aci d-base chemi stry.
At thi s poi nt, we wi l l onl y l ook at a si mpl e neutral i zati on between a strong aci d and a strong
base. I n Chapter 14, we wi l l take a deeper l ook at aci d-base chemi stry.
STRONG ACID AND STRONG BASE
These are l i ke the exampl es we l ooked at earl i er i n the chapter. An aci d and a base react to
yi el d water and a sal t.
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Chapter 11: Reaction Types 259
www.petersons.com
Sample: A sol uti on of hydrochl ori c aci d i s added to an equi mol ar sol uti on of sodi um
hydroxi de.
Answer: Hydrochl ori c aci d i s a strong aci d, therefore i t compl etel y di ssoci ates i n sol uti on.
The hydrogen i ons react wi th the hydroxi de i ons rel eased from the sodi um
hydroxi de to form water. The remai ni ng sodi um and chl ori ne i ons combi ne to form
the sal t sodi um chl ori de. Thi s process i s cal l ed hydrol ysi s. Therefore, the reacti on
wi l l l ook l i ke:
H
1
1 OH
2
H
2
O
GAS-FORMING REACTIONS
I n these reacti ons, a gas i s formed as a product, whi ch dri ves the reacti on. A very common
exampl e i s used i n the i denti fi cati on of l i mestone.
Sample: A pi ece of sol i d cal ci um carbonate i s added to a sol uti on of di l ute hydrochl ori c aci d.
Answer: Whi l e HCO
3
2
i s an acceptabl e answer for a product, i t i s very unstabl e and rapi dl y
decomposes to form water and carbon di oxi de. Therefore, the reacti on wi l l l ook l i ke:
CO
3
22
1 H
1
H
2
O 1 CO
2
Displacement Reactions
These reacti ons wi l l take a few di fferent forms, but there are some thi ngs i n common. The
mai n thi ng i s the presence of an el ement and a compound. Usual l y, the el ement wi l l be a
metal , but someti mes i t wi l l be a hal ogen. The compound wi l l ei ther be a di ssol ved sal t or
water. You wi l l be abl e to use the chart of standard reducti on potenti al s on thi s secti on, so you
shoul d be abl e to determi ne the acti vi ty of the el ements. You shoul d make a poi nt of
memori zi ng the cutoff poi nts for the repl acement of hydrogen. I n general , the materi al s above
hydrogen on the chart wi l l repl ace H i n aci ds, but onl y those from sodi um through the top wi l l
repl ace H i n l i qui d water.
One type that i s a bi t more compl ex but that shows up a fai r amount i s the addi ti on of a metal
to a strong oxoaci d sol uti on (usual l y ni tri c or sul furi c). The reason these are sel ected as often
as they are i s that they vi ol ate the typi cal rul es for the repl acement of hydrogen i n sol uti on.
Thi s i s because the aci ds act as strong oxi di zi ng agents that wi l l i oni ze the metal . Copper or
si l ver typi cal l y appear on the test because they wont react wi th other aci ds but they wi l l wi th
the oxoaci ds. Both metal s are oxi di zed by these aci ds.
Sample: A pi ece of cal ci um metal i s dropped i nto a contai ner of pure water.
Answer: Noti ce how one of the reactants i s a si ngl e el ement. Thi s i s your cl ue that thi s may
be a repl acement. Next, you need to deci de i f cal ci um i s capabl e of repl aci ng the
hydrogen i n water. Looki ng at the l i st of reducti on potenti al s, you noti ce that
cal ci um i s above sodi um on that l i st, so i t wi l l repl ace the hydrogen. The reacti on,
therefore, i s:
Ca 1 2H
2
O Ca
21
1 2OH
2
1 H
2
260 PART III: AP Chemistry Review
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www.petersons.com
Noti ce how the cal ci um hydroxi de i s wri tten i n i oni c form i nstead of mol ecul ar. Thi s i s a
requi rement for the AP test. Hydrogen gas i s a mol ecul ar compound and shoul d be wri tten
as such.
Sample: A stri p of magnesi um ri bbon i s l owered i nto a test tube of si l ver ni trate sol uti on.
Answer: Agai n, noti ce the si ngl e el ement as a reactant and a sol uti on of an i oni c compound
as the other reactant. These are cl ues for a repl acement. You shoul d check to make
sure that magnesi um i s capabl e of repl aci ng si l ver i n sol uti on. A qui ck gl ance at
the reducti on potenti al s i ndi cates that i t wi l l easi l y repl ace si l ver, so the reacti on
shoul d be compl eted:
Mg 1 2Ag
1
Mg
21
1 2Ag
Noti ce that the ni trate i on i s not wri tten, as i t i s onl y a spectator i on. I ts very i mportant that
you know the charges of the el ements. For some of the el ements, the tabl e of reducti on
potenti al s shows the charges, but thi s wont hel p you as much wi th the transi ti on metal s.
Sample: Chl ori ne gas i s bubbl ed through a sol uti on of sodi um i odi de.
FLOWCHART TO DETERMINE A COMPOUND FORMULA WHEN GIVEN A NAME
This is an IONIC compound. This is a MOLECULAR compound.
Does the name contain Roman numerals?
Does the formula contain Greek prefixes?
Write the symbol of the cation followed by the symbol of the
anion. Be sure to include the element symbol and the charge.
The Roman numeral represents
the charge on the cation ().
The Greek prefixes attached to each element represent the
number of atoms of that element present in the molecule.
The one exception is when the first element in the name
has NO prefix, meaning that there is only one atom of that
element in the molecule.
No Yes
No Yes
Write the formula, using the number of the charge of the cation
as the subscript of the anion. The number of the charge of the
anion becomes the subscript of the cation. If a polyatomic ion
requires a subscript (other than an understood 1), parentheses
must be placed around the entire ion. Reduce the subscripts to
the lowest whole number ratio. (But do not reduce subscripts
that are a part of a polyatomic ion!)
Figure11.4
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Chapter 11: Reaction Types 261
www.petersons.com
Answer: A careful l ook here wi l l show you an el ement and a di ssol ved sal t for reactants.
Another careful l ook wi l l hel p you recogni ze that the el ement i s a hal ogen, whi ch
means i t i s goi ng to repl ace the ani on from sol uti on, i n thi s case i odi de. Sodi um i s
a spectator i n thi s reacti on and wi l l be omi tted:
Cl
2
1 2I
2
2Cl
2
1 I
2
Sample: A smal l pi ece of copper metal i s dropped i nto a beaker contai ni ng concentrated
ni tri c aci d.
Answer: You have probabl y seen thi s reacti on, ei ther as a l i ve demonstrati on or i n a vi deo. I t
i s a very dramati c reacti on. When the metal i s pl aced i n the aci d, i t begi ns to get
very hot, i t fi zzes, the ni tri c aci d turns green, and a very poi sonous brown gas i s
formed. Chemi cal l y, the reacti on i s wri tten as:
Cu 1 4H
1
1 2NO
3
2
Cu
21
1 2NO
2
1 2H
2
O
Had the reacti on occurred i n di l ute ni tri c aci d, the product ni trogen di oxi de, NO
2
, woul d be
repl aced wi th ni trogen monoxi de, NO. Noti ce that thi s i s not a typi cal repl acement, where
hydrogen gas i s rel eased. These gases are characteri sti c of the reacti on. I f sul furi c aci d was
used i nstead of ni tri c aci d, the gas woul d be SO
2
.
FLOWCHART TO DETERMINE A COMPOUND NAME WHEN GIVEN A FORMULA
This formula represents an IONIC compound. This formula represents a MOLECULAR compound.
Does the formula contain a metal or an ammonium ion?
If the cation is a metal
with more than 1 charge
(any other metal)
If the cation is an
ammonium ion
If the cation is in
Group IA, IIA, A1,
Zn, Cd, or Ag
Combine the name of
the cation followed by a
Roman numeral equal to
the charge
Combine the name of the cation
The subscript for each element in the molecule must
be converted into a prefix for that element. The only
exception is when the first element in the molecule
has an understood 1 for a subscript t no prefix is
used. The name of the second element must be
changed to end in -ide.
Yes No
with the name of the monatomic anion ending in -ide, or the name of
the polyatomic ion.
Figure11.5
262 PART III: AP Chemistry Review
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www.petersons.com
EXERCISES: REACTION TYPES
Because thi s topi c onl y appears as Free Response questi ons, no mul ti pl e-choi ce questi ons are
i ncl uded i n thi s chapter. As you work through these, dont try to memori ze them. The
reacti ons change every year, and they are very di verse. Make sure you are l earni ng how to
wri te your answers and al so the major pri nci pl es that gui de al l reacti ons. Learni ng these wi l l
hel p you better predi ct the products of any reacti on.
Gi ve the formul as to show the reactants and the products for the fol l owi ng chemi cal
reacti ons. Each occurs i n aqueous sol uti on unl ess otherwi se i ndi cated. Represent substances
i n sol uti on as i ons i f the substance i s extensi vel y i oni zed. Omi t formul as for any i ons or
mol ecul es that are unchanged by the reacti on. I n al l cases a reacti on occurs. Bal anci ng the
equati ons i s worth one poi nt. As you work through the book, thi nk of a possi bl e questi on 1.
1. A cl ean pi ece of magnesi um ri bbon i s
burned i n ni trogen gas.
2. A beaker of ammoni um sul fate
sol uti on i s added to a saturated
sol uti on of bari um hydroxi de.
3. A sampl e of sol i d cal ci um fl uori de i s
mi xed wi th di l ute sul furi c aci d.
4. A cruci bl e contai ni ng sol i d ammo-
ni um carbonate i s heated.
5. A pea-si zed chunk of sodi um metal i s
dropped i nto a beaker of water.
6. Ammoni a gas i s added to a contai ner
of boron tri fl uori de gas.
7. A beaker contai ni ng di l ute hydrochl o-
ri c aci d i s poured i nto a beaker
contai ni ng a sol uti on of potassi um
sul fi te.
8. Sol i d sodi um oxi de i s spri nkl ed i nto a
contai ner of pure water.
9. A cl ean i ron rod i s submerged i n a
sol uti on of i ron (I I I ) sul fate.
10. Si l ver turni ngs are dropped i nto a
contai ner of di l ute ni tri c aci d (6M)
sol uti on.
11. Ethanol i s burned compl etel y i n ai r.
12. A sol uti on of potassi um i odi de i s
added to an aci di fi ed sol uti on of
potassi um di chromate.
13. A sol uti on of potassi um carbonate i s
added to a contai ner of di l ute
hydrochl ori c aci d.
14. A sampl e of potassi um sul fi te
sol uti on i s mi xed wi th an excess of
di l ute hydrochl ori c aci d.
15. Ti n (I I ) chl ori de sol uti on i s sl owl y
poured i nto an aci di fi ed sol uti on of
potassi um permanganate.
16. A sol uti on of ammoni a i s added to a
sol uti on of ferri c chl ori de.
17. A test tube of hydrogen peroxi de
sol uti on i s gentl y heated.
18. Crystal s of di ni trogen pentoxi de are
sti rred i nto water.
19. Copper (I I ) sul fi de crystal s are
strongl y heated i n oxygen gas.
20. A concentrated sol uti on of ammoni a
i s added to a sol uti on of zi nc i odi de.
21. Sol i d l i thi um hydri de i s added to water.
22. A sol uti on of tetraami necopper (I I )
sul fate i s combi ned wi th an excess of
ni tri c aci d sol uti on.
23. An excess amount of chl ori ne gas i s
sl owl y passed over hot i ron fi l i ngs.
24. Methanol i s burned i n oxygen.
25. Hydrogen sul fi de gas i s bubbl ed through
a sol uti on of mercury (I I ) chl ori de.
e
x
e
r
c
i
s
e
s
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Chapter 11: Reaction Types 263
www.petersons.com
ANSWERS AND EXPLANATIONS
1. 3Mg 1 N
2
Mg
3
N
2
. Two el ementssuggests a combi nati on reacti on.
2. 2NH
4
1
1 SO
4
22
1 Ba
21
1 2OH
2
BaSO
4
1 2NH
3
1 2H
2
O (or NH
4
1
1 OH
2
). The AP
test frequentl y i ncl udes questi ons wi th an ammoni a sol uti on (what youre deal i ng wi th
as products i n thi s reacti on). Ammoni a and water are actual l y i n equi l i bri um wi th the
ammoni um and hydroxi de i ons.
3. 2H
1
1 SO
4
22
1 CaF
2
2HF 1 CaSO
4
4. (NH
4
)
2
CO
3
H
2
O
1
1 CO
2
1 2NH
3
. You know i t has to be a decomposi ti on, so the
chal l enge i s to fi gure out what products wi l l form. They have to be gases/vapors, so you
start wi th ammoni a gas. Any ti me you have a carbonate i n a decomposi ti on, fi gure i t
wi l l probabl y decompose to carbon di oxi de gas. After those are gone, that l eaves you
wi th enough materi al s to produce water vapor.
5. 2Na 1 2H
2
O 2Na
1
1 2OH
2
1 H
2
. Youve probabl y seen thi s reacti on at some poi nt.
The reactants shoul d ti p you off that i t has to be a repl acement reacti on. The di spl aced
hydrogen i ons wi l l combi ne to form hydrogen gas.
6. BF
3
1 NH
3
BF
3
NH
3
. I n the ammoni a mol ecul e there i s a nonbondi ng pai r of
el ectrons that can react i n a vari ety of ways. Later i n the book, you wi l l l earn about
compl exes that can form wi th ammoni a. I n thi s reacti on, boron tri fl uori de i s a mol ecul e
that i s usual l y represented wi th onl y 6 el ectrons around the central boron, maki ng i t a
perfect mate for the ammoni a mol ecul e. As tempted as you mi ght be to try to appl y a
doubl e-repl acement strategy here, remember that they are both mol ecul ar substances.
Thi s suggests another approach: a combi nati on reacti on.
7. H
1
1 SO
3
22
HSO
3
2
. A doubl e-repl acement reacti on (KCl i s sol ubl e).
8. Na
2
O 1 H
2
O 2Na
1
1 2OH
2
. A very characteri sti c reacti on for metal oxi des. Sol ubl e
metal oxi des (l i ke thi s one) are known as basi c anhydri des because they di ssol ve i n
water to form basi c sol uti ons. You can al so treat i t l i ke a doubl e-repl acement reacti on.
9. 2Fe
31
1 Fe 3Fe
21
. The reactants shoul d ti p you off that thi s has to be a si ngl e
repl acement reacti on. Thi s i s a redox reacti on, where i ron i s reduced. These are the onl y
two possi bl e oxi dati on states for i ron.
10. 3Ag 1 4H
1
1 NO
3
2
3Ag
1
1 NO (or NO
2
) 1 2H
2
O. Remember, ni tri c aci d i s a strong
oxoaci d, maki ng i t a strong oxi di zi ng agent. Even though si l ver wont react wi th most
aci ds, i t wi l l react wi th ni tri c aci d. I n these reacti ons, l ook for the metal to be oxi di zed.
Most l i kel y, NO wi l l be the product because of the di l ute sol uti on of ni tri c aci d, but i t i s
al so possi bl e that some NO
2
wi l l form. I n cases l i ke thi s, the graders usual l y wont mark
you down for l i sti ng both (or ei ther one separatel y).
11. C
2
H
5
OH 1 3O
2
2CO
2
1 3H
2
O. Cl assi c compl ete combusti on reacti on.
264 PART III: AP Chemistry Review
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12. 14H
1
1 6I
2
1 Cr
2
O
7
22
3I
2
1 2Cr
31
1 7H
2
O. Questi ons pop up peri odi cal l y that
contai n an aci di fi ed sol uti on of potassi um di chromate (or potassi um permanganate) or
ei ther of those two added to an aci di fi ed sol uti on of some other compound. Thi s i s a
redox reacti on si mi l ar to the exampl es i n the chapter. The H
1
and H
2
O come from the
aci di c sol uti on.
13. 2H
1
1 CO
3
22
CO
2
1 H
2
O. Doubl e-repl acement reacti on. Remember, carbonates tend
to form CO
2
.
14. 2H
1
1 SO
3
22
H
2
O 1 SO
2
. Another doubl e repl acement. A di fferent gas i s formed, but
note the si mi l ari ty to number 13.
15. 5Sn
21
1 16H
1
1 2MnO
4
2
5Sn
41
1 2Mn
21
1 8H
2
O. Another redox reacti on i n
aci di fi ed sol uti on. Look back to the redox secti on, i f you have troubl e here.
16. Fe
31
1 3NH
3
1 3H
2
O Fe(OH)
3
1 3NH
4
1
. The ammoni um i on i s i n sol uti on.
17. 2H
2
O
2
2H
2
O 1 O
2
. Decomposi ti on of hydrogen peroxi de. Thi s i s a very common
reacti on and i s the reason why hydrogen peroxi de has a very poor shel f l i fe.
18. N
2
O
5
1 H
2
O 2H
1
1 2NO
3
2
. Nonmetal l i c oxi des are often cal l ed aci d anhydri des.
Most, parti cul arl y those where the nonmetal has a hi gher oxi dati on state, produce aci ds
when di ssol ved i n water.
19. 2CuS 1 3O
2
2CuO 1 2SO
2
. You coul d al so have Cu as a product, or Cu
2
O. Sul fur
di oxi de must be present as the other product.
20. Zn
21
1 4NH
3
Zn(NH
3
)
4
21
or Zn
21
1 NH
3
1 2H
2
O Zn(OH)
2
1 NH
4
1
. There are
two possi bl e outcomes here. One i s the formati on of a compl ex i on and the other i s the
formati on of i nsol ubl e zi nc hydroxi de. Ei ther woul d be gi ven credi t. On thi s probl em,
remember the ammoni a and water sol uti on i s i n equi l i bri um and can be wri tten as
NH
3
1 H
2
O, or NH
4
1
1 OH
2
. Ei ther i s consi dered correct. The i mpl i cati ons on the
reacti on are when the ammoni a i s i n the NH
3
state, the formati on of the compl ex i s
favored. The other, NH
4
1
state, frees the hydroxi de i ons to form the i nsol ubl e sol i d.
21. Li H 1 H
2
O Li
1
1 OH
2
1 H
2
. Just l i ke pure metal s i n water, metal hydri des wi l l al so
produce basi c sol uti ons. Thi s one behaves l i ke a doubl e-repl acement reacti on.
22. 4H
1
1 Cu(NH
3
)
4
21
Cu
21
1 4NH
4
1
. I f the name of the compound confused you, wel l
be goi ng over compl ex i ons l ater. Thi s i s a redox reacti on.
23. 2Fe 1 3Cl
2
2FeCl
3
. Remember, two el ements are reactants. Theres not much to do
except combi ne them.
24. CH
3
OH 1 O
2
CO
2
1 2H
2
O (CO al so acceptabl e). Combusti on reacti on.
25. H
2
S 1 Hg
21
HgS 1 2H
1
. Formati on of a preci pi tate.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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Chapter 11: Reaction Types 265
www.petersons.com
SUMMING IT UP
Nomencl ature, the nami ng system for chemi cal compounds, i s summari zed i n Fi gures
11.4 and 11.5. Nomencl ature for aci ds i s not i ncl uded i n the chart.
Bal anced chemi cal equati ons obey the l aw of conservati on of matter by pl aci ng equal
numbers of atoms of each el ement on both si des of a chemi cal equati on.
The fi ve mai n types of equati ons are summari zed i n Tabl e 11.6.
A shortened form of chemi cal equati on, known as a net i oni c equati on, shows onl y the
atoms that are di rectl y i nvol ved i n an equati on. I t al so represents al l materi al s as they
exi st i n the reacti on (e.g., as i ons when i n sol uti on, etc.).
There are three mai n types of metathesi s reacti ons, al l di sti ngui shed by the products.
One forms a preci pi tate, another a nonel ectrol yte, and the thi rd a gas.
Redox reacti ons, al so known as oxi dati on-reducti on reacti ons, i ncl ude al l reacti ons where
oxi dati ons and reducti ons occur si mul taneousl y.
There are speci fi c rul es for wri ti ng equati ons that need to be fol l owed on the AP test. You
shoul d be fami l i ar wi th these rul es.
266 PART III: AP Chemistry Review
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Stoichiometry
OVERVIEW
The mole
Determining chemical formulas
Calculations in chemical reactions
Limiting reactants
Summing it up
Thi s chapter shoul d be thought of as more of a starti ng poi nt than a
sel f-contai ned uni t. Stoi chi ometry i s just a strange word that refers to record
keepi ng duri ng chemi cal reacti ons. I t i s the cal cul ati ons that i l l ustrate the
rel ati onshi ps between reactants and products i n chemi cal reacti ons. The i deas
from thi s chapter wi l l be used i n the next several chapters.
THE MOLE
Fundamental to any di scussi on of the amount of reactants and products must
be the mol e. The mol e (abbrevi ated as mol ) i s a term used to descri be an
amount of parti cl es, typi cal l y atoms, mol ecul es, or formul a uni ts. The Engl i sh
l anguage i ncl udes many terms that descri be speci fi c numbers. For exampl e, a
dozen doughnuts means 12 doughnuts. One gross of somethi ng i s 144. The
mol e i s just a much bi gger number. A mol e represents 6.02 3 10
23
parti cl es,
al so known as Avogadros number of parti cl es. I f you remember from earl i er i n
the book, the atomi c mass uni t was based on 1
1
2
the mass of a carbon-12 atom.
Wel l , Avogadros number i s based on the number of atoms i n a 12 g sampl e of
carbon-12 atoms. Thi s al so rel ates to the second way to descri be mol es. One
mol e of a substance wi l l wei gh, i n grams, the same amount as the wei ght
expressed i n atomi c mass uni ts. The mass of a water mol ecul e i s 18.01 amu, so
the mol ar mass (the mass of one mol e of water mol ecul es) i s 18.01 g. As
covered i n Chapter 8, one mol e of any gas at STP wi l l have a vol ume of 22.4.
So, mol es hel p demonstrate the rel ati onshi p of the number of parti cl es, mass,
and vol ume of di fferent substances.
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c
h
a
p
t
e
r
1
2
267
Calculating the Molar Mass of a Substance
To cal cul ate a mol ar mass, add the total wei ghts of al l atom(s) i n an el ement or compound.
These wei ghts are obtai ned from the Peri odi c Tabl e of the El ements.
Sample: Cal cul ate the gram formul a mass of K
2
Cr
2
O
7
.
Answer: K 2 2 3 39.10 5 78.20
Cr 2 2 3 52.00 5 104.00
O 2 7 3 16.00 5 112.00
294.20 g K
2
Cr
2
O
7
You Try It!
1. Cal cul ate the gram formul a mass of Na
2
CrO
4
.
2. Cal cul ate the gram formul a mass of C
9
H
18
.
3. Cal cul ate the gram formul a mass of Ba
3
(PO
4
)
2
.
Answers:
1. 162.00 g
2. 126.27 g
3. 601.93 g
Mole Calculations
The most basi c mol e cal cul ati on i s the mol e-to-mass (or mass-to-mol e) conversi on. I t i s si mpl y
a matter of usi ng di mensi onal anal ysi s and the mol ar mass of the substance to make the
conversi on.
C onve rting M ole s to G ra m s
To convert a mol e val ue to a mass val ue you wi l l need to mul ti pl y by the mol ar mass:
Mol es of gi ven substance 3
molar mass of given
1 mol given
5 mass of gi ven
Sample: How many grams are i n 7.20 mol of di ni trogen tri oxi de?
Answer: Fi rst cal cul ate the mol ar mass of di ni trogen tri oxi de:
N: 2 3 14.01 g N 5 28.02 g N
O: 3 3 16.00 g O 5 48.00 g O
28.02 1 48.00 5 76.02 g N
2
O
3
Next i nsert the mol ar mass i nto the equati on:
7.20 mol N
2
O
3
3
76.02 g N O
1 mol N O
2 3
2 3
5 547.34 g N
2
O
3
268 PART III: AP Chemistry Review
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www.petersons.com
You Try It!
1. Fi nd the mass i n grams of 3.32 mol K.
2. Fi nd the mass i n grams of 5.08 mol Ca(NO
3
)
2
.
3. Fi nd the mass i n grams of 4.52 3 10
23
mol C
20
H
42
.
Answers:
1. 129.81 g
2. 833.6 g
3. 1.28 g
C onve rting G ra m s to M ole s
Thi s procedure i s very si mi l ar to the mol e to gram conversi on, except i n thi s one you di vi de by
the mol ar mass:
Mass of gi ven substance 3
1 mol given
molar mass of given
5 mol es of gi ven
Sample: Cal cul ate the number of mol es i n 922 g of i ron (I I I ) oxi de, Fe
2
O
3
.
Answer: Fi rst, cal cul ate the mol ar mass of Fe
2
O
3
:
Fe: 2 3 55.85 g Fe 5 111.7 g Fe
O: 3 3 16.00 g 5 48.00 g O
111.7 g Fe 1 48.00 g O 5 159.7 g Fe
2
O
3
Next, convert 922 grams i nto mol es:
922 g Fe
2
O
3
3
1 mol Fe O
159.7 g Fe O
2 3
2 3
5 5.77 mol Fe
2
O
3
You Try It!
1. Cal cul ate the number of mol es 187 g Al .
2. Cal cul ate the number of mol es i n 333 g SnF
2.
3. Cal cul ate the number of mol es i n 847 g (NH
4
)
2
CO
3
.
Answers:
1. 6.93 mol es
2. 2.12 mol es
3. 8.81 mol es
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Chapter 12: Stoichiometry 269
www.petersons.com
OTHER MOLE CALCULATIONS
The cal cul ati ons shown i n the previ ous two secti ons as wel l as the cal cul ati ons i n thi s next
secti on are summari zed i n a conveni ent chart, Fi gure 12.1. I n thi s fi gure, the mol e i s i nsi de a
star i n the center of the di agram. I n the preceedi ng cal cul ati ons, when converti ng from mol es
to grams, you si mpl y fol l ow the arrow from the star to ei ther one of the l eft corners (upper l eft
i f the substance i s an el ement, l ower l eft i f i t i s a compound). For exampl e, to convert from
mol es of an el ement to grams of that el ement, fol l ow the arrow from the star to the upper l eft
corner. Noti ce that above the arrow i t says 3 atomi c mass i f you read i t i n the di recti on you
are movi ng. That means you take the number of mol es 3 the atomi c mass to obtai n the mass
of the el ement. I f you are converti ng i n the other di recti on, from grams of the el ement to
mol es, you fol l ow the arrow back to the mi ddl e, whi ch says /atomi c mass. Thi s means to
take the mass you are gi ven and di vi de i t by the atomi c mass of that el ement to determi ne the
number of mol es. Someti mes, you wi l l need to do other cal cul ati ons usi ng the mol e. These are
based on the other two equal i ti es for mol es, whi ch are that 1 mol e i s equal to 6.02 3 10
23
parti cl es and 1 mol e of a gas at STP occupi es a vol ume of 22.4 l i ters. These two rel ati onshi ps
are al so found i n Fi gure 12.1 and are read the same way as the mass to mol e exampl es. The
fol l owi ng i s a bri ef l ook at these probl ems.
M ole s to Pa rtic le s
Sample: How many atoms of magnesi um are i n a sampl e of magnesi um contai ni ng 2.75
mol es of magnesi um atom?
Answer: To make thi s conversi on, usi ng the chart i n Fi gure 12.1, si mpl y mul ti pl y the mol es
of magnesi um by Avogadros number (6.02 3 10
23
parti cl es):
2.75 mol es Mg 3 6.02 3 10
23
mol Mg 5 1.66 3 10
24
atoms Mg
Pa rtic le s to M ole s
To go i n the other di recti on, you just di vi de by Avogadros number.
Figure12.1
270 PART III: AP Chemistry Review
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www.petersons.com
Sample: I f you have 4.86 3 10
22
mol ecul es of water, how many mol es of water do you have?
Answer: 4.86 3 10
22
mol ecul es H
2
O / 6.02 3 10
23
mol ecul es
I f you used di mensi onal anal ysi s, thi s same procedure woul d be done wi th the cal cul ati on:
4.86 3 10
22
mol H
2
O 3
1 mol H O
. mc H O
2
23
2
6 02 10
5 0.0801 mol H
2
O
M ole s to Volum e
I n these cal cul ati ons, you wi l l convert from the number of mol es of a gaseous substance to the
number of l i ters of that substance. Agai n, you can use Fi gure 12.1 to assi st you wi th your
cal cul ati on.
Sample: What i s the vol ume of 0.372 mol es of oxygen gas?
Answer: You woul d use the chart to move from mol es to l i ters, whi ch means you wi l l need to
mul ti pl y by 22.4 l i ters:
0.372 mol es 3
22.4 liters
1 mol
5 8.33 l i ters
Volum e to M ole s
Thi s i s si mpl y the conversedetermi ni ng the number of mol es of gas present i n a certai n
vol ume. The procedure requi res di vi di ng by 22.4 l i ters i nstead of mul ti pl yi ng.
Sample: How many mol es of hel i um gas, He, are contai ned i n a bal l oon that has a vol ume of
15.8 l i ters?
Answer: 15.8 l i ters 3
1 mol
22.4 liters
5 0.703 mol es
ADDITIONAL CALCULATIONS
The chart can al so be used to make more compl ex cal cul ati ons. I f, for exampl e, you were
tryi ng to determi ne the vol ume, i n l i ters, of hydrogen gas i n a sampl e of 2.23 g H
2
, you woul d
begi n on the upper l eft corner of the chart, convert grams to mol es, and then move from the
mol es to the vol ume. I t i nvol ves two separate cal cul ati ons rather than the si ngl e cal cul ati ons
i n the exampl es. To sol ve the probl em just menti oned, you coul d combi ne the two steps i nto a
si ngl e equati on or sol ve i t i n two steps. Here i s an exampl e of i t sol ved i n a si ngl e equati on
usi ng di mensi onal anal ysi s:
2.23 g H
2
3
1 mol
1.01 g
22.4 liters
1 mol

5 49.5 l i ters
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NOTE
This same result
can be obtained
using the ideal
gas law PV 5 nRT.
Chapter 12: Stoichiometry 271
www.petersons.com
DETERMINING CHEMICAL FORMULAS
Percent Composition
Thi s next type of probl em occurs qui te frequentl y on the AP test. Thi s cal cul ati on i s the
steppi ng-stone toward determi ni ng the empi ri cal or mol ecul ar formul a for a compound. The
procedure al l ows you to determi ne the percentage by mass that a gi ven substance exi sts i n a
compound or what percentage of a compound i s composed of a parti cul ar substance. I n the
procedure, you need to determi ne the mass percentage of each el ement that i s i n the
compound. You do so wi th the fol l owi ng cal cul ati on:
Mass % of substance 5
mass of substance i n compound
mass of compound
3 100%
Sample: Determi ne the percentage composi ti on for each el ement i n the compound i ron (I I )
carbonate (FeCO
3
).
Answer: Thi s requi res you to determi ne the mass percentage of each component i n the
compound. The fi rst step i s to cal cul ate the mol ar mass of the substance:
Fe: 1 3 55.85 5 55.85 g
C: 1 3 12.01 5 12.01 g
O: 3 3 16.00 5 48.00 g
Mol ar mass FeCO
3
5 115.86
Next, you wi l l di vi de the mol ar mass of each substance by the mol ar mass of the compound:
Mass %Fe 5
55.85 g Fe
115.86 g FeCO
3
3 100% 5 48.20%
Mass %C 5
12.01 g Fe
115.86 g FeCO
3
3 100% 5 10.37%
Mass %O 5
48.00 g Fe
115.86 g FeCO
3
3 100% 5 41.43%
You Try It!
Cal cul ate the percent composi ti on of Mg
3
(PO
4
)
2
.
Answer:
Mg 5 27.74%
P 5 23.57%
O 5 48.70%
272 PART III: AP Chemistry Review
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