AP-Master AP Chemistry

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
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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
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
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
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
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
Summing It Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
10 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Measuring Concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
Solvation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Colligative Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Exercises: Solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
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
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
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
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
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
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
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
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
Practice Test 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Section I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Section II Reference Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
Section II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
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
2000 Lenox Dri ve
Lawrencevi l l e, NJ 08648
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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
1
3
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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www.petersons.com
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
www.petersons.com
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
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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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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.
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www.petersons.com
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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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.
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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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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
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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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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.
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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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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
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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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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).
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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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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
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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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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
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
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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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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.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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)
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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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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?
(D) Resonance
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
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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?
(D) Resonance
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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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)
ni sm shown above?
(A) Rate 5 k[NO][Cl
2
]
(B) Rate 5 k[NO]
2
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
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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
(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.
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
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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
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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.
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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
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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
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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
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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.
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?
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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
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
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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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
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
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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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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.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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
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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
www.petersons.com
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.
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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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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.
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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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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.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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.
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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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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.
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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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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
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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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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.
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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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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
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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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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
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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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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).
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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
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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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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.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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
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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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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.
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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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(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
).
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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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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
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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!
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!
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!

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.
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www.petersons.com
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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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
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www.petersons.com
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.
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
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www.petersons.com
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.
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
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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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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
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 +

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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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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.
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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
e
x
e
r
c
i
s
e
s
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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
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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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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
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.
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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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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 .
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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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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
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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
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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
www.petersons.com
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
.
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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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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.
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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.
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
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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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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.
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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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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.
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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.
(D) Resonance
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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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
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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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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.
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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
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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.
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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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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
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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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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
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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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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.
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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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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
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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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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
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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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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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
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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
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
mol ecul es has the shortest bond
l ength?
(A) Li
2
(B) Be
2
(C) B
2
(D) N
2
(E) O
2
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
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
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
s
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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.
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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.
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.
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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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.
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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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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.
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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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)
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
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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)
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
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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)
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
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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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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.
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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)
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.
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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.
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
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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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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
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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
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
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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
to devi ate from i deal gas behavi or?
(A) H
2
(B) He
(C) Ne
(D) N
2
(E) CCl
4
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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
e
r
c
i
s
e
s
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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.
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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
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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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.
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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.
a
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s
w
e
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s
e
x
e
r
c
i
s
e
s
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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.
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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
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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
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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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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
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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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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 ?
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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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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
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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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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
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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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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.
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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.
e
x
e
r
c
i
s
e
s
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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
r
e
s
s
u
r
e

(
a
t
m
)
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?
(D) Resonance
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.
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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.
e
x
e
r
c
i
s
e
s
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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
P
r
e
s
s
u
r
e

(
a
t
m
)
Figure9.10
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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
r
e
s
s
u
r
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.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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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.
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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
h
a
p
t
e
r
1
0
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 ?
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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
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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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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
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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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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
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(Equati on 10.4)
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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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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
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.
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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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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
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
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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
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)
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
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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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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
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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
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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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.
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(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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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.
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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.
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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
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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
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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.
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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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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
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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.
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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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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
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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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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.
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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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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
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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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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
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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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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.
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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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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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!
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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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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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.
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
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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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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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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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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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
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www.petersons.com
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).
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.
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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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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
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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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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
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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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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.
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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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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.
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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.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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
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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
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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.
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%
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Empirical Formulas
An empi ri cal formul a shows the si mpl est rati o of atoms i n a mol ecul e (or an i oni c
compound). For a mol ecul ar substance, the empi ri cal formul a onl y tel l s you the rati o of atoms,
so i t may not be very hel pful at i denti fyi ng the nature of a substance. For exampl e, take any
of the group of hydrocarbons known as the al kenes. Al l of the di fferent compounds have a
1-to-2 rati o of carbon to hydrogen. Ethene i s C
2
H
4
, propene i s C
3
H
6
, and butene i s C
4
H
8
. I f you
reduce al l of the subscri pts, they each come out to CH
2
. Knowi ng the empi ri cal formul a hel ps
to tel l you that thi s substance i s an al kene, but i t doesnt tel l you whi ch one. How can you
determi ne what a compound i s from the empi ri cal formul a? The mol ecul ar wei ght wi l l sol ve
your probl em. I f you know the empi ri cal formul a and the mol ecul ar wei ght, you can
determi ne the mol ecul ar formul a for a compound. The fi rst type of cal cul ati on we wi l l l ook at
i s the determi nati on of the empi ri cal formul a. The second type i s the determi nati on of a
mol ecul ar formul a.
DETERMINING AN EMPIRICAL FORMULA
Anal ysi s of a compound contai ni ng potassi um, chromi um, and oxygen determi nes that i n a
3.34 g sampl e, 0.89 g i s potassi um, 1.18 g i s chromi um, and 1.27 g i s oxygen. What i s the
empi ri cal formul a of the compound?
Our fi rst step wi l l be to cal cul ate the number of mol es of each compound:
K: 0.89 g K 3
1 mol K
39.10 g K
5 0.0228 mol K
Cr: 1.18 g Cr 3
1 mol Cr
52.00 g Cr
5 0.0227 mol Cr
O: 1.27 g O 3
1 mol O
16.00 g O
5 0.0794 mol O
The next step i s to di vi de al l of the numbers of mol es by the smal l est one:
K:
0.0228 mol
0.0227 mol
5 1.00
Cr:
0.0227 mol
0.0227 mol
5 1.00
O:
0.0794 mol
0.0227 mol
5 3.50
At thi s poi nt, you need to make a deci si on. I f the outcome of your cal cul ati on produces al l
i ntegers wi thi n a smal l degree of experi mental error, you are ready to use these numbers as
the subscri pts i n the empi ri cal formul a. I f they are not, then you need to determi ne what you
can mul ti pl y al l of the numbers by to produce al l i ntegers. I n most cases, i t i s fai rl y obvi ous.
For i nstance, i n our exampl e, you can see that by doubl i ng 3.50, i t becomes 7.00an i nteger.
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Therefore, to compl ete the empi ri cal formul a, you need to mul ti pl y al l of the numbers by 2.
Thi s produces the empi ri cal formul a K
2
Cr
2
O
7.
Si nce thi s i s an i oni c compound, the empi ri cal formul a i s the onl y formul a that i s possi bl e.
However, for a mol ecul ar compound, i t i s possi bl e to have an empi ri cal formul a that does not
represent the mol ecul ar formul a. Here i s a l ook at such an exampl e. I n the fi rst probl em, we
wi l l al so show the procedure for begi nni ng wi th a percentage composi ti on, whi ch i s qui te
typi cal for these probl ems.
Sample: The percentage composi ti on of ci tri c aci d found i n l emons and other frui ts i s
37.5 percent C, 58.3 percent O, and 4.20 percent H by mass. What i s the mol ecul ar
formul a of ci tri c aci d i f the mol ecul ar mass i s 192.14 g?
Answer: The fi rst step i s to cal cul ate the empi ri cal formul a. To begi n, we need to determi ne
the number of mol es of each el ement. However, the percentage composi ti on does
not tel l us a mass. To get around thi s, the commonl y used techni que i s to assume
that you have a 100.0-gram sampl e of the substance. Because 100.0 grams i s equal
to 100%, you can si mpl y take the percentages and say that the masses are equal to
that same amount i n grams. From there, the probl em proceeds just l i ke the
previ ous exampl e:
C: 37.5 g 3
1 mol C
12.01 g C
5 3.122 mol C
H: 4.20 g 3
1 mol H
1.01 g H
5 4.158 mol H
O: 58.3 g 3
1 mol O
16.00 g C
5 3.644 mol O
The next step i s to di vi de al l numbers by the smal l est number:
C:
3.122 mol
3.122 mol
5 1.000
H:
4.158 mol
3.122 mol
5 1.332
O:
3.644 mol
3.122 mol
5 1.167
Thi s i s a good exampl e of one that does not jump off the page at you. The numbers are
defi ni tel y not i ntegers; nei ther can they be expl ai ned by experi mental error. A cl oser l ook
di spl ays a pattern, however. I f you l ook at the H, .332 i s extremel y cl ose to the deci mal
equi val ent of the fracti on
1
3
. The 0.167 endi ng i n oxygen i s extremel y cl ose to the deci mal
equi val ent of the fracti on
1
6
. Because 6 i s a mul ti pl e of 3, the sol uti on appears to requi re al l
val ues to be mul ti pl i ed by 6. Therefore, the empi ri cal formul a for ci tri c aci d i s:
(C
1.000
H
1.332
O
1.167
)6 5 C
6
H
8
O
7
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The next step i s to compare the wei ght of the compound i n the empi ri cal formul a to the
mol ecul ar wei ght. The mol ecul ar wei ght of C
6
H
8
O
7
i s:
C: 6 3 12.01 g 5 72.06
H: 8 3 1.01 g 5 8.08
O: 7 3 16.00 g 5 112
72.06 1 8.08 1 112 5 192.14 g
For thi s formul a, the empi ri cal formul a has the same mass as the mol ecul ar formul a, so they
must be the same. The mol ecul ar formul a of ci tri c aci d i s C
6
H
8
O
7
. So that you can see what
happens when the two arent the same, wel l do one more exampl e. I n thi s one, however, we
wi l l ski p the fi rst steps and go ri ght to the fi nal step.
Sample: The empi ri cal formul a of a compound i s CH
2
O. The mol ar mass of the compound i s
180.18 g. Fi nd the mol ecul ar formul a for thi s compound.
Answer: Fi rst, we need to cal cul ate the mol ar mass of CH
2
O:
C: 1 3 12.01 5 12.01 g
H: 2 3 1.01 5 2.02 g
O: 1 3 16.00 5 16.00 g
12.01 1 2.02 1 16.00 5 30.03 g
You can probabl y eyebal l thi s one and know the mol ecul ar formul a, but wel l sol ve i t formal l y
so you can see the procedure. I n order to determi ne how many ti mes you wi l l have to mul ti pl y
each subscri pt, you need to determi ne the rati o of the empi ri cal formul a and the mol ecul ar
formul a. Di vi di ng the mol ecul ar formul a by the empi ri cal formul a does thi s:
mol ecul ar formul a mass
empi ri cal formul a mass
5
180.18 g
30.03 g
5 6
Therefore, you need to mul ti pl y each subscri pt i n the empi ri cal formul a by 6:
(CH
2
O)6 5 C
6
H
12
O
6
The mol ecul ar formul a of the compound i s C
6
H
12
O
6
.
CALCULATIONS IN CHEMICAL REACTIONS
Thi s secti on begi ns to l ook at chemi cal reacti ons rather than si ngl e substances. Usi ng the
techni ques i n thi s secti on, you wi l l be abl e to convert from a gi ven amount of one substance to
an amount of any other substance i n a reacti on. By havi ng thi s abi l i ty, you wi l l be abl e to
better predi ct the outcome of many di fferent chemi cal reacti ons. Wel l begi n wi th the most
basi c procedure of converti ng from mol es of one substance to mol es of another and work our
way toward converti ng quanti ti es of one substance to quanti ti es of another.
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Mole-to-Mole Conversions
The most i mportant step to al l of these cal cul ati ons i s the use of a val ue known as the mol e
rati o. The mol erati o i s the rati o of mol es of one substance to mol es of second substance. I t i s
determi ned by the rati os of the coeffi ci ents from the bal anced chemi cal equati on. The mol e
rati o i s used i n al l conversi ons si nce i t al l ows you to swi tch from val ues that descri be the
gi ven substances to val ues that descri be the unknown substance. To faci l i tate thi s process,
there i s another chart, Fi gure 12.2, that provi des gui del i nes for sol vi ng most probl ems. I n thi s
fi rst type of cal cul ati on, we wi l l use the mol e rati o to convert from uni ts of mol es of the gi ven
substance to mol es of the unknown substance. Were goi ng to omi t the states of the reactants
and products so that you can focus your attenti on on the coeffi ci ents.
Sample: 2C
2
H
6
1 7O
2
4CO
2
1 6H
2
O
I n the equati on above, determi ne the number of mol es of carbon di oxi de produced i f
3.5 mol es of ethane, C
2
H
6
, react wi th an excess of oxygen.
Answer: I n the probl em, fi rst note the use of the term excess. Whenever you see thi s, the
reason you are bei ng tol d about an excess of a reactant i s so you know that the
other reactant can react compl etel y to yi el d the maxi mum amount of product. I n
some l ater exampl es i n thi s chapter, you wi l l see what happens when there i s a
l i mi ted amount of a reactant.
The next thi ng to determi ne are the gi ven and unknown substances. I n thi s probl em, ethane
i s the gi ven substance and carbon di oxi de i s the unknown. Our task wi l l be to convert from
mol es of ethane to mol es of carbon di oxi de. We wi l l do thi s usi ng the mol e rati o, whi ch i s based
on the equal i ty of 2 mol es C
2
H
6
5 4 mol es CO
2
. I n si mpl e terms, the rati o tel l s you that you
wi l l al ways produce twi ce as many mol es of CO
2
as the number of mol es of ethane. To sol ve
PROCEDURES FOR CONVERSIONS USING DIMENSIONAL ANALYSIS
If given moles
start here
If given grams
start here
If asked-for moles
end here
If asked-for grams
end here
Moles
Given
MOLE RATIO OR
convert to
Mass
Given Moles
Unknown
Mass
Unknown
convert to convert to
moles
given
moles
unknown
moles
given
moles unknown
moles given molar mass given
mass
given
1 mole moles
unknown
molar mass
unknown
mass given 1 mole
1 mole
molar mass unknown
molar mass
given
1 mole
Figure12.2
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the probl em, we wi l l use the mol e rati o as the conversi on factor to change uni ts from ethane
to carbon di oxi de:
3.50 mol es
C H
4 moles CO
2 moles C H
2 6
2
2 6
5 7.00 mol es CO
2
Mole-to-Mass or Mass-to-Mole Calculations
I n these cal cul ati ons, you wi l l be converti ng ei ther from mol es of the gi ven substance to grams
of the unknown or from grams of the gi ven substance to mol es of the unknown. Ei ther way,
you wi l l need to use the mol e rati o as the mechani sm for crossi ng over from one substance to
the next. Other than the step wi th the mol e rati o, these cal cul ati ons are the same as the
cal cul ati ons from earl i er i n the chapter that converted mass to mol es or mol es to mass for a
si ngl e substance. Wel l use the same equati on from the sampl e probl em to conti nue wi th
thi s exampl e.
Sample: Mol es to Mass:
2C
2
H
6
1 7O
2
4CO
2
1 6H
2
O
I n the reacti on shown above, how many grams of oxygen gas are requi red to compl etel y react
wi th 3 mol es of ethane, C
2
H
6
?
Answer: Before you can determi ne the number of grams of oxygen, you need to know the
number of mol es of oxygen that wi l l be requi red. You know that for every 2 mol es of
C
2
H
6
, you need 7 mol es of O
2
. Therefore, we can begi n wi th the mol e rati o:
3 mol
C H
7 moles CO
2 moles C H
2 6
2
2 6
5 10.5 mol O
2
Now that you know you wi l l need 10.5 mol O
2
, you can cal cul ate the mass of the O
2
:
10.5 mol O
2
3
16.00 g O
1 mol O
2
2
5 168.0 g O
2
Sample: Mass to Mol es:
2C
2
H
6
1 7O
2
4CO
2
1 6H
2
O
I n the equati on above, how many mol es of water vapor can be produced from the combusti on
of 147.0 g of ethane, C
2
H
6
?
Answer: Fi rst, you need to know how many mol es of ethane are bei ng burned. Once you
know thi s, you can use the mol e rati o to determi ne the mol es of water vapor:
147.0 g
C H
1 mol C H
30.08 g C H
2 6
2 6
2 6
5 4.89 mol C
2
H
6
Now that you know the mol es of C
2
H
6
, you can convert to mol es of H
2
O. 4.89 mol ,
C H
6 mol H O
2 mol C H
2 6
2
2 6
5 14.67 mol H
2
O wi l l be produced.
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Mass-to-Mass Conversions
These are by far the most common conversi ons that you wi l l be requi red to know. I n these
probl ems, you are gi ven the mass of one substance and asked for the mass of another
substance. The procedure i s real l y just the two previ ous procedures bl ended together. The
sampl e probl em wi l l demonstrate the procedures for sol vi ng these probl ems.
Sample: 4Al 1 3O
2
2Al
2
O
3
I n the reacti on shown above, how many grams of al umi num are requi red to produce
192.0 grams of Al
2
O
3
? Assume there i s adequate oxygen for a compl ete conversi on
of al umi num.
Answer: The steps you are goi ng to fol l ow are:
Fi rst, convert grams of Al
2
O
3
to mol es of Al
2
O
3
:
192.0 g Al
2
O
3
3
1 mol
101.96 g
5 1.883 mol Al
2
O
3
Second, convert mol es of Al
2
O
3
to mol es of Al (mol e rati o step):
1.883 mol
Al O
4 mol Al
2 mol Al O
2 3
2 3
5 3.766 mol Al
Thi rd, convert mol es of Al to grams of Al :
3.766 mol Al 3
26.98 g
1 mol
5 101.6 g Al are requi red
Thi s procedure can al so be set up as a one-step di mensi onal anal ysi s probl em as fol l ows:
192.0 g Al
2
O
3
1 mol Al
2
O
3
4 mol Al 26.98 g Al
5 101.6 g Al
101.96 g Al
2
O
3
2 mol Al
2
O
3
1 mol Al
Note how al l uni ts except g Al cross cancel .
Other Conversions
Once you know thi s basi c procedure, you can al so convert from any quanti ty of one substance
to any quanti ty of another. The secret i s to combi ne the two charts to one l arger chart.
Because the mol e rati o i s the pl ace that must be i ncl uded i n al l cal cul ati ons of thi s type, you
must know the number of mol es of the gi ven substance to be abl e to convert to the unknown
substance. I t doesnt matter what starti ng uni t you have (i .e., l i ters, atoms, g), you wi l l use
the procedures i n Fi gure 12.1 to convert to mol es. Once you know the mol es, you use the mol e
rati o to change from one substance to the other. At that poi nt, you use Fi gure 12.1 agai n to
convert to whatever endi ng uni t you desi re. I f you are converti ng from grams of the gi ven to
grams of unknown, or any i ntermedi ate step, you can use Fi gure 12.2 to do so.
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LIMITING REACTANTS
I n thi s secti on, we wi l l further i nvesti gate rel ati onshi ps between substances i n chemi cal
reacti ons. Up to thi s poi nt, we have been assumi ng that there i s a suffi ci ent amount of each
chemi cal to compl ete the reacti on. However, much of the ti me the amounts of chemi cal s dont
work out so ni cel y. There may be a defi ci ency of one substance that l i mi ts the amount of
product that can be formed. An anal ogy, one that has perpl exed consumers for years, i s the hot
dog and bun di l emma. Many packages of popul ar hot dogs come wi th 10 hot dogs. Most
packages of buns come wi th 8 buns. Al though you probabl y know whats comi ng, l ets go
through i t anyway. You cant make 10 compl ete hot dogs here. Even though you have 10 hot
dogs, you onl y have enough buns for 8, so the most hot dogs you can make i s 8. You wi l l have
2 bun-l ess hot dogs l eft over. The bun i s what we woul d cal l a l i mi ti ng reactant i n thi s
reacti on. The yi el d, or number of compl ete hot dogs, i s l i mi ted because of the number of buns
that we have. Thi s very same pri nci pl e appl i es to chemi cal reacti ons as wel l . The yi el d i s
l i mi ted by the amount of each reactant. Once a reactant i s used up, the reacti on wi l l stop, and
any amount of the other reactant(s) l eft over wi l l remai n i n the reacti on vessel . I n the fi rst
sampl e probl em, we wi l l determi ne the l i mi ti ng reactant i n a chemi cal reacti on.
I n the l ast chapter, we l ooked at the reacti on between l ead (I I ) ni trate and potassi um i odi de,
where the yel l ow preci pi tate l ead (I I ) i odi de was formed. We wi l l use thi s reacti on to l ook at
l i mi ti ng reactants. To refresh your memory, the reacti on proceeds as fol l ows:
Pb(NO
3
)
2
(aq) 1 2KI (aq) PbI
2
(s) 1 2KNO
3
(aq)
From the bal anced equati on, you can see that i t i s necessary to have twi ce as many mol es of
potassi um i odi de as l ead ni trate for the reacti on to compl ete. What i f you onl y had 1.5 mol es
of KI , and 1 mol e of Pb(NO
3
)
2
? Si nce the rati o of KI to Pb(NO
3
)
2
i s 2-to-1, i f you onl y have 1.5
mol es of KI , you coul d onl y combi ne wi th 0.75 mol es of Pb(NO
3
)
2
. Therefore, you woul d have
0.25 mol es of unreacted Pb(NO
3
)
2
l eft i n the reacti on vessel after al l KI had reacted. I n thi s
exampl e, KI was the l i mi ti ng reactant.
I ts fai rl y easy to conceptual i ze the i dea of l i mi ti ng reactants when you are gi ven mol es of the
reactants. When you are gi ven grams, i t i s not al ways so easy to see. When you have to sol ve
l i mi ti ng reactant probl ems, i t i s al ways necessary to determi ne the number of mol es of each
substance and compare that to the requi red rati os from the bal anced chemi cal equati on. Lets
use the same reacti on, but use masses i nstead of mol es.
Sample: A sol uti on of l ead (I I ) ni trate contai ni ng 286.4 g of Pb(NO
3
)
2
i s added to a sol uti on
of potassi um i odi de contai ni ng 138.9 g of KI .
a. How many grams of sol i d PbI
2
wi l l be formed duri ng the reacti on?
b. What i s the l i mi ti ng reactant?
c. How many grams of the excess reactant wi l l be remai ni ng?
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Answers:
a. A typi cal way to sol ve thi s probl em i s to cal cul ate the number of mol es of
product that can be produced from each quanti ty of reactant. The answer that
i s the smal l est wi l l i ndi cate the l i mi ti ng reactant:
286.4 g Pb(NO
3
)
2
3
1 mol
331.22 g
1 mol PbI
1 mol Pb(NO )
2
3 2
5 0.865 mol PbI

2
138.9 g KI 3
1 mol
166.01 g
1 mol PbI
2 mol KI
2
5 0.418 mol PbI

2
Because KI i s onl y capabl e of produci ng 0.418 mol of PbI
2
, i t i s the l i mi ti ng
reactant. The amount of PbI
2
that wi l l be formed i n thi s reacti on i s:
0.418 mol PbI
2
3
461.02 g
1 mol
5 192.71 g PbI
2
b. KI i s the l i mi ti ng reactant.
c. To determi ne the amount of excess reactant, we need to determi ne how much
Pb(NO
3
)
2
was actual l y used duri ng the reacti on and subtract thi s from the
starti ng amount:
0.418 mol PbI
2
3
1 mol Pb NO
1 mol PbI
3
2
2
( )
( )
( )
331.22 g Pb NO
1 mol Pb NO
3
2
3
2
5 138.4 g Pb(NO
3
)
2
Thi s answer tel l s us that 138.4 grams of Pb(NO
3
)
2
wi l l actual l y react wi th KI and that the
remai nder, (286.4 g 2 138.4 g) 5 148 g, wi l l remai n i n sol uti on. I f more KI were added to the
reacti on vessel , more preci pi tate woul d form.
The amount of PbI
2
cal cul ated i n part a, 192.71 g, i s known as the theoreti cal yi el d of the
substance. That i s the maxi mum amount that can form based on the stoi chi ometri c
rel ati onshi ps between reactants and products. The actual reacti on wi l l more than l i kel y
produce l ess than thi s, for a vari ety of reasons (whi ch are uni mportant to us).
You Try It!
Sol i d al umi num reacts vi gorousl y wi th aqueous copper (I I ) chl ori de. Use the reacti on
bel ow to answer questi ons 1, 2, and 3:
2Al (s) 1 3CuCl
2
(aq) 2Al Cl
3
(aq) 1 3Cu(s)
43.17 g of sol i d al umi num are added to an aqueous copper (I I ) chl ori de sol uti on
contai ni ng 302.51 g of CuCl
2
:
1. Whi ch i s the l i mi ti ng reactant?
2. What i s the theoreti cal yi el d of Cu?
3. How many grams of excess reactant are l eft i n the reacti on vessel ?
Answers:
1. CuCl
2
2. 2.25 mol 5 143.0 g Cu
3. 2.7 g Al
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EXERCISES: STOICHIOMETRY
Multiple Choice
1. I n whi ch of the fol l owi ng compounds
i s the mass rati o of ni trogen to
oxygen cl osest to 0.58:1.00?
(A) N
2
O
(B) NO
(C) NO
2
(D) N
2
O
3
(E) N
2
O
5
2. How many grams of stronti um
ni trate, Sr(NO
3
)
2
, contai n 40 grams
of oxygen atoms?
(A) 210 grams
(B) 96 grams
(C) 62 grams
(D) 24 grams
(E) 88 grams
3. 1.00 mol e of four di fferent compounds
contai ni ng el ement X were anal yzed
and found to contai n 36.0 grams,
54.0 grams, 72.0 grams, and
108 grams, respecti vel y. A possi bl e
atomi c wei ght of X i s
(A) 13.5
(B) 18.0
(C) 25.0
(D) 72.0
(E) 108
4. The si mpl est formul a for an oxi de of
chromi um that i s 61.9 percent
chromi um by wei ght i s
(A) CrO
3
(B) CrO
2
(C) CrO
(D) Cr
2
O
(E) Cr
2
O
3
5. Ahydrocarbon gas wi th an empi ri cal
formul a CH
2
has a densi ty of
2.51 grams per l i ter at STP. Apossi bl e
formul a for the hydrocarbon i s
(A) CH
2
(B) C
2
H
4
(C) C
3
H
6
(D) C
4
H
8
(E) C
5
H
10
6. When magnesi um metal i s heated i n
ai r, one product of the reacti on i s
found to contai n 72.2 percent Mg by
mass and 27.8 percent N by mass.
What i s the empi ri cal formul a for
thi s compound?
(A) MgN
(B) Mg
2
N
(C) MgN
2
(D) Mg
2
N
3
(E) Mg
3
N
2
7. A pi ece of sol i d sodi um metal wi th a
mass of 7.67 grams i s added to an
excess of hydrochl ori c aci d. What
vol ume of hydrogen gas i s produced
from thi s reacti on i f i t takes pl ace
at STP?
(A) 22.4 l i ters
(B) 11.2 l i ters
(C) 7.46 l i ters
(D) 5.60 l i ters
(E) 3.74 l i ters
8. ___Al (s) 1 ___HCl (g) ___Al Cl
3
(s) 1
___H
2
(g)
I f 2 mol es of al umi num metal
shavi ngs react wi th hydrogen
chl ori de gas, how many mol es of H
2
can be formed?
(A) 2
(B) 3
(C) 4
(D) 5
(E) 6
e
x
e
r
c
i
s
e
s
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9. 3Cu(s) 1 8HNO
3
(aq)
3Cu(NO
3
)
2
(aq) 1 2NO(g) 1 4H
2
O
Copper reacts wi th di l ute ni tri c aci d
accordi ng to the bal anced equati on
above. I f 2 mol es of copper metal are
al l owed to react wi th an excess of
ni tri c aci d, how many grams of NO
gas can be formed?
(A) 90.0 g
(B) 80.0 g
(C) 40.0 g
(D) 20.0 g
(E) 1.5 g
10. ___C
6
H
12
(l) 1 ___O
2
(g)
___CO
2
(g) 1 ___H
2
O(l)
Accordi ng to the reacti on represented
above, how many mol es of O
2
are
requi red to produce 2 mol es of H
2
O?
(A) 2 mol es
(B)
5
2
mol es
(C) 3 mol es
(D)
7
2
mol es
(E) 4 mol es
11. I n a very vi ol ent reacti on known as
the thermi te reacti on, powdered
al umi num metal reacts wi th i ron
(I I I ) oxi de to form mol ten i ron and
al umi num oxi de. How many mol es of
al umi num metal are requi red to
produce 13.96 g of mol ten i ron?
(A) 0.0500 mol e
(B) 0.0625 mol e
(C) 0.125 mol e
(D) 0.250 mol e
(E) 0.500 mol e
12. 4NH
3
(g) 1 5O
2
(g) 4NO(g) 1
6H
2
O(g)
I n the reacti on above, 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
Free Response
QUESTION 1
You are gi ven three unknown hydrocarbon compounds (unknowns A, B, and C), each
contai ni ng onl y carbon and hydrogen. Usi ng the data bel ow, answer the questi ons that wi l l
eventual l y al l ow you to determi ne the i denti ti es of the unknowns.
(A) Compl ete combusti on of 1.00 g of unknown A resul ted i n the formati on of 1.39
l i ters of CO
2
(at STP) and 2.23 g of H
2
O. What i s the most probabl e mol ecul ar
formul a of unknown A?
(B) Determi ne the mol ecul ar wei ght of unknown B i f the vapor densi ty of B at STP i s
3.13 grams per l i ter.
(C) The empi ri cal formul a for unknown B i s CH
2
. Determi ne the mol ecul ar formul a.
(D) 1.00 g of unknown C contai ns 0.817 g carbon. The compl ete combusti on of 1.00
mol e of unknown C requi res 5 mol es of O
2
. What i s the most l i kel y mol ecul ar
formul a of unknown C?
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QUESTION 2
The fol l owi ng questi ons refer to a l aboratory acti vi ty desi gned to determi ne concentrati on of
l ead i ons i n a sol uti on of l ead (I I ) ni trate usi ng gravi metri c anal ysi s. I n the experi ment, a 50.0
mL sampl e of the Pb(NO
3
)
2
sol uti on was added to an excess of potassi um i odi de sol uti on. The
resul ti ng preci pi tate, PbI
2
, was col l ected by vacuum fi l trati on, dri ed i n a dryi ng oven, and
wei ghed. Assume that:
both sol uti ons were pure.
no decomposi ti on took pl ace i n the dryi ng oven.
the fi l ter di d not al l ow any PbI
2
to pass through.
al l l ead i s l ead (I I ).
an anal yti cal bal ance was used to wei gh the product.
(A) I f 2.310 g of PbI
2
were col l ected, how many grams of l ead (I I ) ni trate must have
been i n the 50.0 mL sampl e?
(B) What was the mol ari ty of the l ead (I I ) ni trate sol uti on?
(C) How many grams of l ead (I I ) i ons were i n the l ead (I I ) ni trate sol uti on?
(D) What i s the mi ni mum number of mol es of potassi um i odi de that must be present
i n sol uti on to assure a compl ete preci pi tati on of al l l ead from sol uti on?
(E) I f the sol i d PbI
2
on the fi l ter paper was not thoroughl y ri nsed wi th di sti l l ed water
pri or to dryi ng, what i mpl i cati ons woul d that have on your answer i n questi on
(A)? Defend your response.
e
x
e
r
c
i
s
e
s
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Multiple Choice
1. D
2. E
3. B
4. B
5. D
6. E
7. E
8. B
9. C
10. C
11. D
12. A
1. The correct answer is (D). On a probl em l i ke thi s, you need to work qui ckl y. You
know that the rati o of ni trogen to oxygen i s supposed to be 0.58:1.00. Begi n by wri ti ng
the atomi c masses of ni trogen and oxygen, and then mul ti pl y them by rati os i n the
formul as. I f you round 0.58 to 0.6, thi s wi l l save ti me duri ng the i ni ti al probl em sol vi ng.
That gi ves you a rati o of 3:5 to work wi th. You wi l l qui ckl y rul e out most choi ces. When
you get to the l ast one, you can doubl e check. N
2
O
3
yi el ds the approxi mate rati o of
28:48, whi ch equal s 0.58:1.
2. Thecorrect answer is (E). I f you use the peri odi c tabl e, you can determi ne the mol ar
mass of Sr(NO
3
)
2
at 211.64. Duri ng the AP test, you can save ti me by roundi ng the
masses. A qui ck gl ance at the answers shows that none of them are that cl ose together.
Therefore, when determi ni ng the mol ar mass of stronti um ni trate, you can round Sr to
88 and N to 14; O i s al ready 16. The roundi ng of mass of 212 i s goi ng to be cl ose enough
to get the correct answer. From thi s, you can determi ne the mass percentage of oxygen
by di vi di ng 96 by 211.64 (212). The mass percentage i s 45.4 percent (di vi di ng by 212
yi el ds 45.3 percent). I f you know that oxygen i s 45.4 percent by mass of the compound,
then you just need to fi gure out what 40 grams i s 45.4 percent of. Di vi di ng 40 grams by
.454 yi el ds 88 grams.
3. Thecorrect answer is(B). I n thi s one, you are just l ooki ng for mul ti pl es of an answer.
Noti ce that al l of these numbers are mul ti pl es of 18.
4. Thecorrect answer is (B). Thi s i s si mi l ar to questi on 2. The qui ckest way to fi gure i t
out i s to wri te 52 (the mass of Cr) over 16 (the mass of O). You know that the mass of
chromi um i n the compound di vi ded by the mass of the compound must equal 0.619, so
you can eyebal l di fferent combi nati ons to see whi ch one woul d be cl ose. When you thi nk
you have one, you can do the math to confi rm i t. For exampl e, i f you l ook at CrO
3
, you
can fai rl y qui ckl y determi ne the mol ar mass: 52 1 (3 3 16 5 48) 5 100.
52
100
i s cl earl y not
the rati o you are l ooki ng for. So try another. CrO
2
yi el ds
52
84
5 .619.
5. The correct answer is (D). Remember, al l gases at STP have a vol ume of 22.4 l i ters
per mol e. Therefore, i f the densi ty i s 2.51 grams per l i ter, al l you need to do i s determi ne
the mass i n 22.4 l i ters. You can do thi s wi th a proporti on:
2.51 g
1 L
g
22.4 L
x
x 5 56.2 g, the mass of C
4
H
8
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6. Thecorrect answer is(E). There are two ways to work a probl em l i ke thi s. One i s the
correct way, and the other i s a qui ck eyebal l i ng (i f youre short on ti me). I n the
eyebal l i ng, you woul d wri te the rounded mass of Mg (24 amu) over the rounded mass of
N (14 amu). Then l ook qui ckl y at the mul ti pl es i n the probl em to see whi ch ones
produce mass percents around 75 percent and 25 percent (thi s wi l l get you very cl ose).
The correct way to sol ve the probl em, whi ch can al so be done very qui ckl y i f youve been
practi ci ng, i s as fol l ows:
72.2 g 3
1 mol
24.3 g
5 2.97
2.97
1.99
5 1.5 3 2 5 3
27.8 g 3
1 mol
14.0 g
5 1.99
1.99
1.99
5 1.0 3 2 5 2
7. Thecorrect answer is(E). Some probl ems on the AP test are goi ng to be l i ke thi s. You
need to determi ne the bal anced equati on for a reacti on even on the mul ti pl e-choi ce
secti on of the test.
Thi s reacti on i s 2Na 1 2HCl 2NaCl 1 H
2
.
The mol e rati o of Na to H
2
i s 2:1.
The cal cul ati on i s goi ng to be 7.67 g 3
1 mol
23 g
3
1 mol H
2 mol Na
2
5 0.167 mol H
2
.
I f one mol e occupi es 22.4 L, then 0.167 mol e 5 3.74 L.
8. The correct answer is (B). Fi rst you have to bal ance the equati on: 2Al 1 6HCl
2Al Cl
3
1 3H
2
. Now thi s becomes a very si mpl e mol e-to-mol e conversi on:
2 mol Al 3
3 mol H
2 mol Al
2
5 3 mol H
2
9.
The correct answer is (C). 2 mol Cu 3
2 mol NO
3 mol Cu
3
30 g NO
1 mol Cu
5 40 g
10. The correct answer is (C). The bal anced equati on i s C
6
H
12
(l) 1 9O
2
(g) 6CO
2
(g) 1
6H
2
O(l). Therefore, the cal cul ati on i s:
2 mol H
2
O 3
9 mol O
6 mol H O
2
2
5 3 mol O
2
11. Thecorrect answer is(D). The equati on for the reacti on i s Fe
2
O
3
12Al Al
2
O
3
12Fe.
The cal cul ati on, therefore, i s:
13.96 g Fe 3
1 mol Fe
55.85 g Fe
3
2 mol Al
2 mol Fe
5 0.250 mol
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12. Thecorrect answer is(A). I f you encounter a probl em i n whi ch two masses are gi ven,
suspect a l i mi ti ng reactant probl em. I n thi s probl em, the l i mi ti ng reactant i s O
2
. You
can determi ne thi s wi th the cal cul ati on shown bel ow or eyebal l i t. The mol ar mass of
NH
3
i s about 17 g. The mol ar mass of O
2
i s 32 g. I f you l ook at the bal anced equati on,
you wi l l see that you need more mol es of oxygen than ammoni a. You can al so l ook at the
masses you have and know that you have l ess mol es of oxygen than ammoni a. That tel l s
you that oxygen i s the l i mi ti ng reactant. The formal cal cul ati on i s:
3.10 g NH
3
3
1 mol NH
17 g NH
3
3
3
4 mol NO
4 mol NH
3
5 0.182 mol NO
2.50 g O
2
3
1 mol O
32 g O
2
2
3
4 mol NO
5 mol O
2
5 0.0625 mol NO
Knowi ng that O
2
i s the l i mi ti ng reactant, you can just compl ete the cal cul ati on usi ng
the val ue from O
2
: 0.0625 mol NO 3
30 g
1 mol NO
5 1.88 g NO
Free Response
QUESTION 1
(A) I n thi s probl em, you know a few thi ngs. The most i mportant i s that each
compound contai ns onl y hydrogen and carbon. Whats i mportant about that i s i t
means that al l of the carbon i n carbon di oxi de comes from the hydrocarbon and
al l of the hydrogen i n water comes from the hydrocarbon. Therefore we can work
backwards to get your answer. The fi rst thi ng to do i s to pi ck ei ther carbon
di oxi de or water to anal yze, si nce we know somethi ng about both. Arbi trari l y,
wel l pi ck carbon di oxi de. You have a vol ume at STP, whi ch means youl l have to
use the 1 mol 5 22.4 l i ters of gas rel ati onshi ps. We have 1.39 l i ters of gas, whi ch
means we have 1.39 l i ters 3
1 mol
22.4 l i ters
5 0.0621 mol CO
2
. Thi s means we have
0.0621 mol C.
For water, we have 2.23 g 3
1 mol
18.02 g
5 0.124 mol H
2
O. Thi s means we have twi ce
as many mol es of hydrogen atoms, or 0.248 mol H. Now we can see that we have
0.0621 mol C and 0.248 mol H. We have 4 ti mes as many mol es of hydrogen, so
the empi ri cal formul a for the compound i s CH
4
. Because we know the amount of
unknown that was anal yzed, we can use that i nformati on to determi ne the
mol ecul ar formul a of the unknown. We coul d set up an equati on and sol ve for an
unknown, but i nstead wel l just try to confi rm that CH
4
i s al so the mol ecul ar
formul a. I n doi ng so we use the cal cul ati on bel ow to see i f we obtai n the correct
amount of CO
2
or H
2
O:
1.00 g CH
4
3
1 mol CH
16.1 g CH
4
4
3
1 mol CO
1 mol CH
2
4
5 0.0621 mol
Si nce thi s matches our val ue from before, thi s must be the mol ecul ar formul a of
the compound.
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(B) Because thi s one i s at STP, i t makes i t a bi t easi er. You can al so sol ve for vapor
densi ti es that are not at STP by usi ng the i deal gas equati on and sol vi ng for
densi ty. However, because thi s one i s at STP, we know that one mol e of the gas
wi l l occupy 22.4 l i ters. Usi ng thi s i nformati on and the densi ty of the vapor, we
can determi ne the mol ar mass of B usi ng the equati on:
3.13 g B
1 L B
22.4 L
1 mol B
5 70.1 g mol
21
(C) The mass of CH
2
5 14.0 g mol
21
, so
70.1 g mol
21
14.0 g mol
21
5 5. Therefore, we need to
mul ti pl y everythi ng i n the empi ri cal formul a by 5. The mol ecul ar formul a for B i s
C
5
H
10
.
(D) I f 1.00 g of the unknown contai ns 0.817 g carbon, the mass percent of carbon i s
81.7 percent, l eavi ng the remai ni ng 18.3 percent as hydrogen. Therefore, we need
to use the procedures for determi ni ng an empi ri cal formul a from a percentage
composi ti on. The probl em wi l l progress as fol l ows (remember wi th percents,
assume a 100 g sampl e):
81.7 g C 3
1 mol
12.01 g C
5 6.80 mol
6.80
6.80
5 1
18.3 g H 3
1 mol
1.01 g H
5 18.12 mol
18.12
6.80
5 2.66
At thi s poi nt, you need to determi ne i ntegers that are mul ti pl es of 1 and 2.66.
Some qui ck cal cul ati ons determi ne that 3 3 2.66 5 7.98, whi ch i s wel l wi thi n
experi mental error of 8. Therefore, the empi ri cal formul a must be C
3
H
8
. To
determi ne the mol ecul ar formul a, we can use the i nformati on i n the probl em.
One mol e of the combusti on of unknown C requi res 5 mol es of O
2
. The bal anced
equati on for the compl ete combusti on of C
3
H
8
requi res 5 mol es of O
2
. The next
possi bl e formul a, C
6
H
16
, requi res 10 mol es. The number of mol es of oxygen wi l l
conti nue to i ncrease, so the mol ecul ar formul a must be C
3
H
8
.
QUESTION 2
(A) 1.656 g Pb(NO
3
)
2
Thi s i s a mass-to-mass conversi on. You must begi n by wri ti ng
the compl ete, bal anced equati on for the reacti on:
Pb(NO
3
)
2
(aq) 1 2KI (aq) PbI
2
(s) 1 2KNO
3
(aq)
Proceed wi th the conversi on:
2.310 g PbI
2
3
1 mol PbI
461.0 g PbI
2
2
3
1 mol Pb NO
1 mol PbI
3
2
2
( )
3
331.2 g Pb NO
1 mol Pb NO
3
2
3
2
( )
( )
5 1.660 g Pb(NO
3
)
2
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(B) 0.100 M. Thi s i s a mol ari ty cal cul ati on, whi ch, i f you recal l , requi res you to di vi de
the mol es of sol ute by the l i ters of sol uti on. We al ready know that we have 50 mL
of sol uti on (or 0.050 L sol uti on), so we just need the number of mol es of Pb(NO
3
)
2
represented by 1.660 g:
1.660 g Pb~NO
3
!
2
3
1 mol Pb~NO
3
!
2
331.2 g Pb~NO
3
!
2
5 5.01 3 10
23
mol
The mol ari ty i s M 5
5.01 3 10
23
mol
0.05 L
5 0.100M.
(C) The grams of l ead can be determi ned from the grams of l ead (I I ) ni trate from the
answer to part (A) and the mass percentage of l ead i n that compound:
Mass % Pb 5
207.2 g
331.2 g
5 0.6256 ~62.56%!
You can use thi s fi gure to determi ne the amount of l ead i n sol uti on:
1.660 g Pb(NO
3
)
2
3 0.6256 5 1.038 g Pb
(D) 1.660 g Pb~NO
3
!
2
3
1 mol Pb~NO
3
!
2
331.2 g Pb~NO
3
!
2
5 1.00 3 10
22
mol KI
(E) Fai l ure to adequatel y ri nse the l ead (I I ) i odi de thoroughl y wi l l i ncrease the
l i kel i hood that the sol i d wi l l be contami nated wi th some of the sol vent KI (aq) or
KNO
3
(aq). Upon dryi ng, thi s wi l l i ncrease the mass of the sol i d (whi ch wi l l be a
mi xture of sol i d Pb(NO
3
)
2
, sol i d KI , and sol i d KNO
3
). The i ncreased mass wi l l
l ead to an overesti mati on of the amount of l ead (I I ) i odi de formed, whi ch wi l l
cause an overesti mati on of the amount of starti ng materi al i n the l ead (I I )
ni trate sol uti on.
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SUMMING IT UP
A mol e i s equal to 6.02 3 10
23
parti cl es. The mass of one mol e of parti cl es i s known as the
mol ar mass of a substance, and the vol ume of one mol e of gas parti cl es at STP i s equal to
22.4 l i ters.
The mol ar mass of a substance i s cal cul ated by addi ng the wei ghts of the atoms of each
el ement mul ti pl i ed by the number of atoms of that el ement i n the compound.
The mol ar mass of a substance i s used to convert from mol es to grams of a si ngl e
substance or grams to mol es of a si ngl e substance.
Avogadros number, 6.02 3 10
23
, i s used to convert from mol es to parti cl es or parti cl es to
mol es for a si ngl e substance.
Mol ar vol umes can be determi ned by usi ng the equal i ty 22.4 l i ters 5 1 mol , provi ded the
gas i s at STP.
The percentage composi ti on of a compound tel l s you, by percentage, the mass of each
el ement i n a compound. I t al so al l ows you to determi ne empi ri cal and mol ecul ar
formul as.
The empi ri cal formul a i s the si mpl est whol e number rati o of el ements i n a compound.
The mol ecul ar formul a tel l s you the actual numbers of each atom i n a compound.
The same basi c formul as for mol e conversi on wi th one substance are used to compare two
substances i n a chemi cal reacti on. The onl y di fference i s that one substance must be
converted to another usi ng the mol e rati o before the cal cul ati on can be compl eted.
A l i mi ti ng reactant i s a reactant that i s compl etel y used up i n a chemi cal reacti on and
that prevents the remai nder of the other reactant(s) from formi ng products.
The theoreti cal yi el d of a reacti on i s the amount of product that i s predi cted usi ng the
stoi chi ometri c rati os of mol es from the bal anced chemi cal reacti on.
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www.petersons.com
Equilibrium
OVERVIEW
The equilibrium constant
The equilibrium constant, K
c
The equilibrium constant, K
p
The relationship between K
c
and K
p
The reaction quotient
Solving problems when not all equilibrium concentrations
are known
Le Chteliers Principle
Summing it up
Up to thi s poi nt, we have been l ooki ng at chemi cal reacti ons that have a start
and a fi ni sh. That i s, the reactants are combi ned, and a certai n amount of
product i s formed. After that, the reacti on i s fi ni shedno more products wi l l
be formed. I n addi ti on, these reacti ons tend to be i rreversi bl e. I f a pi ece of
sodi um i s pl aced i nto a contai ner of chl ori ne gas, a very vi ol ent reacti on
ensues, from whi ch a whi te powder (sal t) i s formed. Thi s whi te powder i s not
readi l y converted back to sodi um and chl ori ne. I t can be done, but i t i s not an
easy transformati on.
Many reacti ons, however, do not run to compl eti on. They wi l l reach a poi nt
where they stop, but i n thi s chapter you wi l l l earn that when they are i n thi s
state they are not real l y stopped at al l . These reacti ons, where the products
can readi l y reform the reactants, are known as reversi bl e reacti ons. The way
these reacti ons proceed i s anal ogous to the systems i n equi l i bri um that were
di scussed i n Chapters 8 and 10 (vapor equi l i bri um and sol uti ons). I n the next
three chapters, you wi l l study the equi l i bri um of chemi cal reacti ons and l earn
more about the factors associ ated wi th i t. The focus of thi s chapter i s to
i ntroduce the equi l i bri um constant, whi ch provi des data about the rel ati on-
shi ps between reactants and products i n a system at equi l i bri um, and Le
Chtel i ers Pri nci pl e, whi ch al l ows you to predi ct the effects of di fferent
stressors on reacti on equi l i bri a.
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c
h
a
p
t
e
r
1
3
291
THE EQUILIBRIUM CONSTANT
Chemi cal equi l i bri um i s the si tuati on where the concentrati on of reactants and products
remai ns constant. Thi s occurs when opposi ng reacti ons happen at the same rate. That i s, the
conversi on of reactants to products i s proceedi ng at the same rate as products are converted to
reactants. A system must be cl osed (not al l ow for the escape of reactants or products) to
achi eve equi l i bri um. Thi s i s very si mi l ar to our di scussi on of the l i qui d-vapor equi l i bri um i n
Chapter 8.
A reversi bl e reacti on takes the form:
X Y
At equi l i bri um, X forms Y at the same rate as Y forms X. Therefore, the concentrati on of [X]
wi l l remai n constant. Li kewi se, [Y] wi l l al so remai n constant.
Once a reacti on has reached equi l i bri um, the rates of the forward and reverse reacti ons wi l l
remai n constant (provi di ng that envi ronmental condi ti ons remai n constant). Thi s can be
expressed mathemati cal l y as:
Y
X
[ ]
[ ]
5 constant
THE EQUILIBRIUM CONSTANT, K
c
There are two mai n ways to descri be the equi l i bri um of a reacti on. The fi rst i s i n terms of the
concentrati ons of reacti ons and products. The expressi on that descri bes the equi l i bri um of a
reacti on where the concentrati ons of the materi al s are known i s K
c
. When the reactants and
products are i n the gaseous state, we can al so use the equi l i bri um constant expressi on, K
p
,
where parti al pressures are used i nstead of concentrati on uni ts. Sol i ds and pure l i qui ds (l i ke
water) are omi tted from equi l i bri um expressi ons because thei r concentrati ons do not change
duri ng chemi cal reacti ons.
Lets begi n by l ooki ng at how the equi l i bri um constant, K
c
, i s deri ved from a bal anced
chemi cal equati on. Lets use a reacti on wri tten i n the form:
aA 1 bB cC 1 dD
The equi l i bri um constant can be cal cul ated usi ng the general expressi on:
K
c
5
C D
A B
[ ] [ ]
[ ] [ ]
c d
a b
I n thi s reacti on Equati on 13.1, the coeffi ci ents from the bal anced equati on become the
exponents i n the equi l i bri um constant expressi on. The concentrati ons of the products go i n
the numerator, and the concentrati ons of the reactants go i n the denomi nator.
Sample: Wri te the equi l i bri um constant expressi on, K
c
, for the fol l owi ng reacti on:
2CO
2
(g) 2CO(g) 1 O
2
(g)
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NOTE
The
concentration of
a substance is
shown by placing
brackets, [ ],
around it.
ALERT!
The constant ratio
does NOT mean
the reaction has
stopped.
(Equati on 13.1)
www.petersons.com
Answer: Usi ng Equati on 13.1, we determi ne K
c
to be:
K
c
5
CO O
CO
2
2
2
2
[ ] [ ]
[ ]
Sample: Wri te the equi l i bri um constant expressi on, K
c
, for the fol l owi ng reacti on:
Ni (s) 1 4CO(g) Ni (CO)
4
(g)
Answer: Because Ni i s a sol i d, i t wi l l not be entered i nto the equati on:
K
c
5
Ni CO
CO
4
( )
[ ]
[ ]
4
You Try It!
Wri te the equi l i bri um constant expressi on, K
c
, for the fol l owi ng reacti ons:
1. H
2
(g) 1 I
2
(g) 2HI (g)
2. 2NH
3
(g) 1 3CuO(s) 3H
2
O(g) 1 N
2
(g) 1 3Cu(s)
3. NH
4
Cl (s) NH
3
(g) 1 HCl (g)
Answers:
1. K
c
5
HI
H I
2
2 2
[ ]
[ ][ ]
2. K
c
5
H O N
NH
2
3
2
3
2
[ ] [ ]
[ ]
3. K
c
5 [NH
3
][HCl ]
THE EQUILIBRIUM CONSTANT, K
p
The equi l i bri um constant, K
c
, i s used to descri be the concentrati ons of reactants and products
at equi l i bri um. When the reactants and products are gases, i t i s often useful to use the
expressi on K
p
i nstead, where the subscri pt p represents pressure. I n thi s expressi on, the
equi l i bri um i s descri bed i n terms of the parti al pressures of the reactants and products. The
equi l i bri um constant expressi on, K
p
, for the reacti on
aA 1 bB cC 1 dD
woul d be wri tten as Equati on 13.2
K
p
5
~P
C
!
c
~P
D
!
d
~P
A
!
a
~P
B
!
b
where P represents the parti al pressure of each substance.
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(Equati on 13.2)
Chapter 13: Equilibrium 293
www.petersons.com
Sample: Wri te the equi l i bri um constant, K
p
, for the fol l owi ng mi xture of gases at equi l i bri um:
2CO
2
(g) 2CO(g) 1 O
2
(g)
Answer: Usi ng Equati on 13.2, we determi ne K
p
to be:
K
p
5
P P
P
CO
2
O
CO
2
2
2
( ) ( )
( )
You Try It!
Wri te the equi l i bri um constant, K
p
, for the fol l owi ng mi xture of gases at equi l i bri um:
2 NO(g) 1 O
2
(g) 2NO
2
(g)
Answer: K
p
5
P
P P
NO
2
NO
2
O
2
2
( )
( ) ( )
THE RELATIONSHIP BETWEEN K
c
AND K
p
The i deal gas l aw can be used to convert between concentrati on (K
c
) and pressures (K
p
). I f you
recal l from Chapter 8, the i deal gas l aw i s PV 5 nRT. You do not need to know the deri vati ons
of these equati ons, but you shoul d know how to use both Equati ons 13.3 and 13.4:
K
p
5 K
c
(RT)
Dn
K
c
5 K
pS
1
RT
D
Dn
Where Dn 5 (total mol es of gaseous products) 2 (total mol es of gaseous reactants), R 5 i deal
gas constant (0.0821 L atm mol
21
K
21
), and T i s temperature i n Kel vi n.
Sample: A 3:1 starti ng mi xture of hydrogen, H
2
, and ni trogen, N
2
, comes to equi l i bri um at
500C. The mi xture at equi l i bri um i s 35.06 percent NH
3
, 96.143 percent N
2
, and
0.3506 percent H
2
by vol ume. The total pressure i n the reacti on vessel was 50.0
atm. What i s the val ue of K
p
and K
c
for thi s reacti on?
N
2
(g) 1 3H
2
(g) 2NH
3
(g)
Answer:
Note that the 3:1 i nformati on i s i rrel evant i n thi s probl emremember that we
are onl y concerned wi th the equi l i bri um condi ti ons i n thi s probl em. I t doesnt
matter what the starti ng condi ti ons were. Once equi l i bri um i s establ i shed, the
quanti ti es of the consti tuents are determi ned by K.
Use Dal tons l aw of parti al pressures to determi ne the parti al pressure of each
gas at equi l i bri um (percent of mi xture mul ti pl i ed by the total pressure).
Remember, the l aw states that the total pressure exerted by a mi xture of gases
i s equal to the sums of the i ndi vi dual pressures that each gas exerts. The
pressures exerted by the gases i n thi s mi xture wi l l equal thei r percentage of
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(Equati ons 13.3
and 13.4)
www.petersons.com
the total pressure. To determi ne the parti al pressures, we wi l l mul ti pl y each
percentage of gas by the total pressure:
P
NH
3
5 0.03506 3 50.0 atm 5 1.75 atm
P
N
2
5 0.96143 3 50.0 atm 5 48.1 atm
P
H
2
5 0.003506 3 50.0 atm 5 0.175 atm
Use the parti al pressures to cal cul ate K
p
:
K
p
5
~P
NH
3
!
2
~P
N
2
!~P
H
2
!
3
5
~1.75!
2
~48.1!~0.175!
3
5 11.9
Once you have cal cul ated K
p
, you can use the val ue i n Equati on 13.4 to
determi ne the val ue of K
c
:
K
c
5 K
pS
1
RT
D
Dn
5 11.9
S
1
0.0821 3 773
D
22
5 4.79 3 10
4
Note: Dn has a negati ve val ue because the mol es product 2 mol es reactant 5 2 2 (113) 5 22
You Try It!
2NO(g) 1 Cl
2
(g) 2NOCl (g)
I n the above reacti on, the total pressure of the mi xture of gases at equi l i bri um i s 1.55
atm. The percentages of each gas i n the mi xture are as fol l ows: NOCl 5 77.4 percent,
NO53.20 percent, and Cl
2
5 19.4 percent. Cal cul ate K
p
and K
c
for the reacti on.
Answer: K
p
5 1.9 3 10
3
; K
c
5 4.65 3 10
4
Calculating the Equilibrium Constant for Equilibrium Reactions Involving
Concentration Changes
The equi l i bri um constant for a reacti on works just as i t i s adverti sedi t i s al ways constant.
I t doesnt matter how much of the reactants or products are present at the begi nni ng of the
reacti on; when equi l i bri um i s reached, i f the equi l i bri um constant i s cal cul ated, i t wi l l al ways
be the same. I n these next cal cul ati ons, we wi l l be cal cul ati ng K
c
from the concentrati ons of
the reactants and products at equi l i bri um. When concentrati ons (or pressures) are known,
use Equati ons 13.1 and 13.2 to determi ne K.
Sample: At hi gh pressure (1000 atm) and temperature (450C), ni trogen and hydrogen gases
come to equi l i bri um accordi ng to the reacti on shown bel ow:
N
2
(g) 1 3H
2
(g) 2NH
3
(g)
I f, at equi l i bri um, the concentrati on of ni trogen (N
2
) i s 2.95 M, the concentrati on of
hydrogen (H
2
) i s 7.68 M, and the concentrati on of ammoni a (NH
3
) i s 5.78 M, what
i s the K
c
?
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www.petersons.com
Answer: K
c
5
NH
N H
3
2
2 2
3
[ ]
[ ][ ]

( )
( )( )
5 78
2 95 7 68
2
3
.
. .
5 2.50 3 10
22
You Try It!
At 425C, gaseous hydrogen i odi de (HI ) parti al l y decomposes i nto hydrogen (H
2
) and
i odi ne (I
2
) gases. What i s the val ue of K
c
at 425C i f the concentrati ons of the
consti tuents are [HI ] 5 7.06 3 10
23
M, [H
2
] 5 9.58 3 10
24
M, and [I
2
] 5 9.58 3 10
24
M?
Answer: K
c
5 1.84 3 10
22
Conceptual Interpretation of the Equilibrium Constant
When you are sol vi ng mathemati cal chemi stry probl ems, such as equi l i bri um probl ems, i t i s
easy to l ose the meani ng of the probl ems. I t i s i mportant to devel op a conceptual
understandi ng of the materi al that can gui de you as you work through the math probl ems.
Lets take a moment to revi ew some basi c i deas about equi l i bri um constants before we move
on to more di ffi cul t probl ems.
Si nce the expressi on for K i s i n the general form:
K 5
Products
Reactants
we can make some assumpti ons about the reacti on by exami ni ng the val ue of K.
For reacti ons where K i s very l arge (K . 1), we can concl ude that the amount of product i s
much l arger than the amount of reactants. Therefore, the reacti on to the ri ght i s favored
(equi l i bri um i s favored to the ri ght). Conversel y, i f K i s qui te smal l , (K , 1) i t tel l s us that the
amount of reactants i s much greater than the amount of products. Therefore, equi l i bri um i s
favored to the l eft. Keep these i deas i n mi nd when you see val ues for K.
THE REACTION QUOTIENT
Earl i er i n the chapter, you read that regardl ess of the i ni ti al concentrati ons of reactants i n an
equi l i bri um reacti on, the val ue for the equi l i bri um constant wi l l al ways be the same. The
equi l i bri um constant i s determi ned at equi l i bri um when the rates of the forward reacti on and
reverse reacti on are the same. I f the two reactants are put i n a reacti on vessel and there i s
i ni ti al l y no product(s), the reactants wi l l react for a peri od of ti me. After a whi l e, the amount
of product wi l l begi n to bui l d up, but whi l e thi s i s happeni ng the product(s) wi l l begi n formi ng
the reactants. Thi s process wi l l conti nue unti l the rates are the same. Usi ng the same l ogi c, i f
onl y the products of the previ ous reacti on were pl aced i n the reacti on vessel , the reverse
reacti on woul d proceed unti l the ti me when the reactants had accumul ated i n suffi ci ent
quanti ty to begi n formi ng products at the same rate as the reverse reacti on. The
concentrati ons of reactants and products wi l l change unti l equi l i bri um i s reached.
There are ti mes when you wi l l be gi ven i nformati on about the reactants and products when
they have not reached equi l i bri um. Under these condi ti ons, a val ue known as the reacti on
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www.petersons.com
quoti ent can be cal cul ated. The val ue of the reacti on quoti ent, Q, when compared to the
equi l i bri um constant, wi l l i ndi cate the di recti on the reacti on i s proceedi ng. The reacti on
quoti ent i s cal cul ated usi ng the same expressi on as K, but the concentrati ons of the reactants
and products are not equi l i bri um val ues. For the reacti on
aA 1 bB cC 1 dD
the reacti on quoti ent, Q, i s cal cul ated wi th Equati on 13.5:
Q 5
C D
A B
[ ] [ ]
[ ] [ ]
c d
a b
The val ue of Q can be hel pful i n determi ni ng the di recti on of a reacti on i n a nonequi l i bri um
state. For i nstance, i f the val ue of Q i s greater than K, i t means that the equati on i s top-heavy
or that there are too many products (or not enough reactants). I n thi s case, the reacti on wi l l
have to proceed to the l eft to l ower Q toward the val ue of K. I f Q i s smal l er than K, there are
too many reactants and not enough products, whi ch means the reacti on wi l l need to shi ft to
the ri ght to reach equi l i bri um. I f Q and K are equal to one another, the reacti on i s at
equi l i bri um.
Sample: N
2
(g) 1 3H
2
(g) 2NH
3
(g)
I n the reacti on shown above, the val ue of K
c
at 500C i s 6.0 3 10
22
. At some poi nt
duri ng the reacti on, the concentrati ons of each materi al were measured. At thi s
poi nt, the concentrati ons of each substance were [N
2
] 5 1.0 3 10
25
M, [H
2
] 5
1.5 3 10
23
M, and [NH
3
] 5 1.5 3 10
23
M. Cal cul ate the val ue of Q, and determi ne
the di recti on that the reacti on was most l i kel y to proceed when the measurements
were taken.
Answer: To sol ve thi s probl em, you need to begi n by determi ni ng the val ue of Q usi ng
Equati on 13.5:
Q 5
C D
A B
NH
N H
3
2
2 2
[ ] [ ]
[ ] [ ]

[ ]
[ ][ ]
c d
a b 3
5
1 5 10
1 0 10 1 5 10
3
2
5 3
3
.
. .
( )
( )

( )

5 6.67310
7
The val ue of Q i s nearl y 9 orders of magni tude l arger than K. Therefore, the onl y way that
equi l i bri um wi l l be reached i s i f the reacti on proceeds toward the l eft. That wi l l decrease the
numerator, i ncrease the denomi nator, and decrease the val ue of Q.
SOLVING PROBLEMS WHEN NOT ALL EQUILIBRIUM
CONCENTRATIONS ARE KNOWN
Occasi onal l y, not al l equi l i bri um concentrati ons are known. When thi s occurs you must use
equi l i bri um concepts and stoi chi ometry concepts to determi ne K. What you are tryi ng to do i n
these probl ems i s determi ne the amounts of materi al s at equi l i bri um. I n Chapter 12, you
l earned that the bal anced chemi cal equati on shows you the rel ati ve amounts of reactants and
products duri ng the chemi cal reacti on. For a reacti on at equi l i bri um, the l ogi c i s the same.
The mol e rati os sti l l appl y. There i s one major di fference, however, between the stoi chi ometry
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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(Equati on 13.5)
www.petersons.com
of reversi bl e and i rreversi bl e reacti ons. For reversi bl e reacti ons, the reactants wi l l not be
compl etel y converted to product(s), whi ch i s the case i n i rreversi bl e reacti ons (keepi ng i n
mi nd l i mi ti ng reactants, of course). So, i n the stoi chi ometry of equi l i bri um, the mol e rati os are
sti l l used to determi ne the rel ati ve amounts of each substance. However, because the
reactants are not compl etel y converted to products (and vi ce versa), the rati o wi l l onl y hel p us
to determi ne the di fference between the starti ng and endi ng amounts of a substance. Thi s
process wi l l be i l l ustrated i n the next sampl e probl em. Usi ng a tabl e and fol l owi ng some basi c
steps can si mpl i fy sol vi ng these probl ems:
Step 1. Wri te a bal anced equati on for the reacti on.
Step 2. Create a tabl e wi th three rows and as many col umns as there are
consti tuents (reactants and products). The three rows shoul d be l abel ed Start (for
i ni ti al concentrati on or pressure), D (change i n concentrati on or pressure), and
Fi ni sh (equi l i bri um concentrati on or pressure).
Step 3. Fi l l i n al l known parts of the tabl e.
Step 4. For any substances where the i ni ti al and equi l i bri um concentrati ons are
known, determi ne the change i n concentrati on (D).
Step 5. Use the stoi chi ometri c rel ati onshi ps (mol e rati os) i n the reacti on to fi l l i n
the remai ni ng bl anks (revi ew Chapter 12 i f you have forgotten thi s).
Step 6. Once the tabl e i s compl eted, use the val ues to determi ne the equi l i bri um
constant.
Sample: The equi l i bri um reacti on referred to i s:
H
2
(g) 1 I
2
(g) 2HI (g)
When 2.00 mol e each of hydrogen (H
2
) and i odi ne (I
2
) are mi xed i n an evacuated 1.00 L vessel ,
3.50 mol es of HI are produced. What i s the val ue of the equi l i bri um constant, K
c
?
Step 1. The equati on i s al ready bal anced.
Steps 2 and 3. Create a tabl e; fi l l i t i n wi th the known val ues:
H
2
I
2
2HI
Start 2.0 M 2.0 M 0
D
Fi ni sh 3.50
Dont forget, you can put a 0 i n the start for HI si nce there i s none i ni ti al l y
present. You al ways need to careful l y exami ne your gi ven i nformati on. Qui te often
there i s materi al that i s gi ven that i s not expl i ci tl y stated. I n thi s probl em, you are
not tol d that there i s no HI to start wi th, but you are tol d that H
2
and I
2
are
combi ned i n an evacuated vessel . That means nothi ng el se i s i n there. I n other
words, the starti ng concentrati on of HI i s zero.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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NOTE
The volume of the
vessel is used to
calculate the
concentrations.
www.petersons.com
Step 4. The onl y substance you can cal cul ate the change (D) for i s HI , so fi l l i n the
tabl e for i t:
H
2
I
2
2HI
Start 2.0 M 2.0 M 0
D 13.50
Fi ni sh 3.50
Step 5. Use the mol e rati os from the bal anced equati on to fi l l i n the remai ni ng
bl anks. You can use the rati os because you know, from the bal anced equati on, that
i f 3.50 mol es of HI are produced, one-hal f that amount of each reactant must have
been used up (mass sti l l has to be conserved):
3.50 mol HI 3
1 mol H
2 mol HI
2
5 1.75 mol H
2
3.50 mol HI 3
1 mol I
2 mol HI
2
5 1.75 mol I
2
Because H
2
i s bei ng converted i nto HI , thi s number shoul d be a negati ve number to
i ndi cate the decrease i n quanti ty. The same goes for I
2
. You can see here that
because the reacti on i s at equi l i bri um, not al l of the starti ng materi al s are
converted i nto the product HI . However, because of the l aw of conservati on of mass,
you know that whatever amount of product was gai ned must correspond to an
equi val ent l oss of reactants:
H
2
(mol ) I
2
(mol ) 2HI (mol )
Start 2.0 2.0 0
D 21.75 21.75 13.50
Fi ni sh 0.25 0.25 3.50
Step 6. The quanti ti es from the Fi ni sh row are used to cal cul ate K
c
:
K
c
5
HI
H I
[ ]
[ ][ ]
2
2 2
5
3 50
0 25 0 25
2
.
. .
( )
( )( )
5 196
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You Try It!
Ni tri c oxi de gas, NO, and oxygen gas, O
2
, react to form the poi sonous gas ni trogen
di oxi de, NO
2
, i n the reacti on shown bel ow:
2NO(g) 1 O
2
(g) 2NO
2
(g)
10.0 mol es of NO and 6.00 mol es of O
2
are pl aced i nto an evacuated 1.00 L vessel , where
they begi n to react. At equi l i bri um, there are 8.80 mol es of NO
2
present. Cal cul ate the
val ue of K
c
, assumi ng that the temperature remai ns constant throughout the reacti on.
Answer: 33.6
Determining Equilibrium Concentrations When Only Initial Concentrations
Are Known
I n thi s next secti on, we wi l l l ook at a si tuati on i n whi ch you have i nformati on about the
starti ng materi al s, but no i nformati on about the quanti ti es at equi l i bri um. I f you are thi nki ng
ahead, you may see that i n the charts you have just been revi ewi ng, i f you dont know the
quanti ti es at equi l i bri um, each substance wi l l be represented by a vari abl e. There are two
mai n ways to handl e these probl ems. The fi rst we wi l l l ook at i s to set up an equati on and
sol ve for x. Thi s i s by far the easi er of the two. I n the next sampl e we wi l l l ook at how to sol ve
such a probl em.
Sample: H
2
(g) 1 I
2
2HI
0.500 mol of H
2
and 0.500 mol e of I
2
are added to a 1.00-l i ter reacti on vessel . The
mi xture i s heated to 498C and al l owed to reach equi l i bri um accordi ng to the
reacti on shown above. At thi s temperature, K
c
5 49.7. What i s the composi ti on of
the reacti on mi xture at equi l i bri um i n thi s system?
Answer: To begi n, you wi l l need to make a chart wi th al l of the i nformati on. Thi s chart wi l l
be sl i ghtl y di fferent, however, because no endi ng amounts are known:
H
2
(g) 1 I
2
2HI
H
2
I
2
2HI
Start 0.50 0.50 0
D 2x 2x 12x
Fi ni sh 0.50 2 x 0.50 2 x 2x
Before conti nui ng, you shoul d take note of a few thi ngs. Fi rst, because the reacti on vessel i s
1.00 l i ters, we can substi tute the number of mol es for the mol ari ty. Second, because we dont
know the equi l i bri um concentrati ons of the two known substances (H
2
and I
2
), we must
represent the decrease i n each substance wi th the vari abl e x. Fi nal l y, the rati o 2:1 wri tten i n
the D row for HI represents the mol e rati o of HI to the other reactants.
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At thi s poi nt, were ready to substi tute the val ues i nto the equi l i bri um expressi on for K
c
:
K
c
5
@HI #
2
@H
2
# @I
2
#
49.7 5
~2x!
2
~0.50 x!
2
At thi s poi nt, you need to thi nk before proceedi ng. Dont jump ri ght i n and start mul ti pl yi ng
numbers and vari abl es. I f you l ook careful l y, you wi l l noti ce that the val ues on the ri ght are
both squared. Thi s means that you can take the square root of both si des and get ri d of those
squares. The resul t of thi s i s
49 7 . 5
2
0 50
2
2
x
x
( )
( ) .
whi ch i s rewri tten as 67.05 5
2
0 50
x
x
( )
( ) .
Both 1 and 2 7.05 val ues must be consi dered si nce they are both mathemati cal possi bi l i ti es.
67.05(0.50 2 x) 5 2x, whi ch we then can sol ve as two equati ons:
13.525 2 7.05x 5 2x and 23.525 1 7.05 5 2x
Sol vi ng for x, we fi nd that the two equati ons produce the fol l owi ng sol uti ons:
3.525 5 9.05x 23.525 5 25.05x
and
0.39 5 x 0.70 5 x
The second answer cant be correct because a val ue of x that l arge wi l l produce negati ve
concentrati ons of H
2
and I
2
at equi l i bri um. Therefore, the answer 0.39 i s accepted as the
answer for x. At thi s poi nt, the val ue must be substi tuted back i nto the tabl e to obtai n the
equi l i bri um concentrati ons.
Sol vi ng for x, we get 0.11 mol H
2
, 0.11 mol I
2
, and 0.78 mol HI .
You Try It!
0.500 mol es of NO gas are pl aced i nto a 1.00-l i ter reacti on vessel . The gas i s heated to
an extremel y hi gh temperature, where i t decomposes accordi ng to the reacti on shown
bel ow:
2NO(g) N
2
(g) 1 O
2
(g)
At equi l i bri um, K
c
5 2.4 3 10
3
. Determi ne the equi l i bri um composi ti on of the mi xture
at equi l i bri um.
Answer: 5.1 3 10
23
mol NO, 0.25 mol N
2
, 0.25 mol O
2
I n the l ast sampl e probl em and the You Try I t! probl em, the probl ems were desi gned so that
the val ues of x coul d be obtai ned by fi ndi ng the square roots of each si de of the equati on.
There are some probl ems where thi s i s not the case and you must cal cul ate x usi ng the
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quadrati c equati on. Whi l e you may have worked wi th these ki nds of probl ems i n your course,
they wi l l not be i ncl uded i n thi s book because they dont appear on the AP test.
LE CHTELIERS PRINCIPLE
Le Chtel i ers Pri nci pl e states that i f a system at equi l i bri um i s di sturbed, i t wi l l react i n such
a way as to mi ni mi ze the di sturbance. What causes these di sturbances? Changes i n pressure,
concentrati on, and temperature can affect the consti tuents i n a reacti on, each of whi ch i s
di scussed i n detai l bel ow.
Refer to the general reacti on shown bel ow i n the di scussi on that fol l ows:
aA 1 bB cC 1 dD
Effects of Changing Concentration
Addi ng A or B to the mi xture wi l l create an i ncreased concentrati on of A or B. The reacti on
wi l l respond by tryi ng to use up the excess; i n other words, the rate of the forward reacti on
wi l l i ncrease unti l equi l i bri um i s reestabl i shed. Li kewi se, addi ng C or D wi l l cause the reverse
reacti on to speed up.
Sample: Whi ch di recti on wi l l the reacti on shi ft i f substance A i s added to the reacti on
vessel ?
Answer: Addi ng A or B wi l l cause a shi ft i n equi l i bri um to the ri ght. Thi s wi l l use up the
extra A unti l equi l i bri um i s reestabl i shed.
Effects of Changing Pressure
I f the pressure of a system contai ni ng gaseous mol ecul es i s i ncreased, then the number of
mol ecul es must be reduced to rel i eve the stress. The reacti on wi l l shi ft to the si de wi th the
smal l est number of mol es of gaseous mol ecul es. I f the number of mol es i s the same i n the
forward and reverse reacti on, then no change wi l l occur. I n order for pressure changes to
affect the di recti on of the reacti on, the pressure must be i ncreased by ei ther decreasi ng the
vol ume of the contai ner or by changi ng the parti al pressures of the i ndi vi dual gases i n the
mi xture. For exampl e, addi ng an i nert gas to the reacti on vessel wi l l not affect the reacti on. I t
wi l l i ncrease the total pressure of the system, but i t wi l l not affect the parti al pressures of the
gases i nvol ved i n the reacti on.
Sample: I n the reacti on:
2Cl
2
(g) 1 2H
2
O(g) 4Cl (g) 1 O
2
(g)
i n whi ch di recti on wi l l the reacti on shi ft i f the pressure i ncreases?
Answer: I f you count the number of mol es of gas on each si de of the equati on, you wi l l note
that the l eft si de of the reacti on contai ns 4 mol es of gas, whi l e the ri ght si de has 5
mol es. An i ncrease i n pressure wi l l favor the si de wi th the fewer number of mol es,
so the reacti on wi l l shi ft to the l eft (the reverse reacti on i s favored).
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www.petersons.com
Effects of Changing Temperature
The effect a change i n temperature wi l l have on a system depends on the enthal py of reacti on.
Enthal py i s a concept that wi l l be di scussed i n detai l i n Chapter 17, but you wi l l be abl e to
understand thi s concept wi th just a smal l amount of i nformati on. There are two mai n types of
reacti ons: endothermi c and exothermi c. Endothermi c reacti ons requi re heat i n order to occur,
whi l e exothermi c reacti ons rel ease heat. Enthal py i s a measure of the amount of heat
l i berated or absorbed i n a chemi cal reacti on that occurs at constant pressure. I t can be
measured, and i t i s descri bed by the symbol H (DH for a reacti on whi ch i nvol ves a change i n
enthal py). A negati ve val ue for DH means the reacti on i s exothermi c, whi l e a posi ti ve val ue
for DH represents an endothermi c reacti on. The i mportant thi ng to remember i s that a change
i n temperature of a reacti on at equi l i bri um wi l l cause the reacti on to shi ft i n the di recti on
that wi l l undo the change of temperature. An i mportant note about temperature changes i s
that because the shi fts are based on the energeti cs (enthal pi es) of the reacti ons, the shi fts wi l l
cause changes i n rates that wi l l affect K. Changes i n temperature wi l l change the val ue of K.
Lets refer to the previ ous equati on to i l l ustrate:
aA 1 bB cC 1 dD
I f you wri te the equati on wi th the word heat i n i t, you can then treat the equi l i bri um the
same as you do for a change i n concentrati on. I f the forward reacti on i s endothermi c,
(DH . 0), wri te heat as a reactant. I f the reacti on i s exothermi c, (DH , 0), wri te heat as a
product.
Sample: What effect wi l l an i ncrease i n temperature have on the reacti on bel ow?
2 SO
3
(g) 2 SO
2
(g) 1 O
2
(g) DH 5 1196.6 kJ per 2 mol es SO
3
Fi rst, note that the reacti on i s endothermi c (DH . 0). I t can be rewri tten as:
Heat 1 2SO
3
(g) 2SO
2
(g) 1 O
2
(g)
The addi ti on of heat wi l l cause the reacti on to proceed i n a di recti on that wi l l use
up heat. I n thi s reacti on, the hi ghl y endothermi c forward reacti on wi l l use up the
heat and wi l l hence be favored. The reacti on wi l l shi ft to the ri ght, and K wi l l
i ncrease at the hi gher temperature.
Sample: What effect wi l l an i ncrease i n temperature have on the reacti on bel ow?
2NO(g) 1 O
2
(g) 2NO
2
(g) DH 5 2113 kJ
Answer: Note that the reacti on i s exothermi c (DH , 0). I t can be rewri tten as:
2NO(g) 1 O
2
(g) 2NO
2
(g) 1 Heat
Si nce the reacti on wi l l shi ft to use up the heat, you can see that the reverse reacti on
wi l l be favored. The reacti on wi l l shi ft to the l eft. For exothermi c reacti ons, K i s
smal l er at hi gher temperatures.
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www.petersons.com
Catalysis
Catal ysts do not affect equi l i bri um concentrati ons. The addi ti on of a catal yst speeds up the
rate of both the forward and reverse reacti ons. At equi l i bri um, these reacti on rates are equal .
The effect of the catal yst i s to make these equal rates faster.
You Try It!
Combi ni ng carbon monoxi de gas, CO, and hydrogen gas, H
2
, i n the reacti on shown
bel ow, produces methanol , CH
3
OH:
CO(g) 1 2H
2
(g) CH
3
OH(g) DH 5 221.7 kcal
Whi ch di recti on wi l l the reacti on proceed after the fol l owi ng di srupti ons to the
equi l i bri um?
1. Some of the methanol vapor i s condensed and removed from the reacti on vessel .
2. The pressure i s i ncreased by decreasi ng the vol ume of the reacti on vessel .
3. The temperature i s i ncreased.
Answers:
1. shi ft ri ght
2. shi ft ri ght
3. shi ft l eft
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EXERCISES: EQUILIBRIUM
Multiple Choice
1. 2CO
2
(g) 2CO(g) 1 O
2
(g)
After the equi l i bri um represented
above i s establ i shed, some pure O
2
(g)
i s i njected i nto the reacti on vessel at
constant temperature. After equi l i b-
ri um i s reestabl i shed, whi ch of the
fol l owi ng has a l ower val ue compared
to i ts val ue at the ori gi nal equi l i b-
ri um?
(A) K
eq
for the reacti on
(B) The total pressure i n the
reacti on vessel
(C) The amount of CO
2
(g) i n the
reacti on vessel
(D) The amount of O
2
(g) i n the
reacti on vessel
(E) The amount of CO (g)i n the
reacti on vessel
2. 2SO
2
(g) 1 O
2
(g) 2SO
3
(g)
DH 5 2197 kJ
Whi ch of the fol l owi ng changes al one
woul d cause a decrease i n the val ue
of K
eq
for the reacti on represented
above?
(A) Decreasi ng the temperature
(B) I ncreasi ng the temperature
(C) Decreasi ng the vol ume of the
reacti on vessel
(D) I ncreasi ng the vol ume of the
reacti on vessel
(E) Addi ng a catal yst
3. N
2
(g) 1 3H
2
(g) 2NH
3
(g) 1 energy
Some N
2
and H
2
are mi xed i n a
contai ner at 200C, and the system
reaches equi l i bri um accordi ng to the
equati on above. Whi ch of the fol l ow-
i ng causes an i ncrease i n the number
of mol es of NH
3
present at equi l i b-
ri um?
I . Decreasi ng the vol ume of the
contai ner
I I . Rai si ng the temperature
I I I . Addi ng a mol e of Ar gas at
constant vol ume
(A) I onl y
(B) I I onl y
(C) I and I I I
(D) I I and I I I
4. I
2
(g) 1 Br
2
(g) 2I Br(g)
I n the reacti on shown above, 0.50
mol es of Br
2
and 0.50 mol es of I
2
are
pl aced i n an evacuated 1.00-l i ter
vessel and al l owed to reach equi l i b-
ri um. What i s the val ue of K
c
i f the
vessel contai ns 0.84 mol es of I Br at
equi l i bri um?
(A) 2.0
(B) 8.8
(C) 11
(D) 110
(E) 130
e
x
e
r
c
i
s
e
s
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5. 4CuO(s) 1 CH
4
(g) CO
2
(g) 1
4Cu(s) 1 2H
2
O(g)
Whi ch i s the correct set up to
determi ne K
c
for the reacti on above?
(A)
CO Cu H O
CuO CH
2
4
2
2
4
4
[ ][ ] [ ]
[ ] [ ]
(B)
CuO CH
CO Cu H O
4
4
2
4
2
2
[ ] [ ]
[ ][ ] [ ]
(C)
CO H O
CH
2 2
2
4
[ ][ ]
[ ]
(D)
CO H O
CuO CH
2 2
2
4
4
[ ][ ]
[ ] [ ]
(E)
CO Cu H O
CuO CH
2
2
4
4
[ ] [ ] [ ]
[ ] [ ]
4 2
6. 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) 2SO
2
(g) 1 O
2
(g) 2SO
3
(g)
(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)
7. Cu
2
S(l) 1 O
2
(g) 2Cu(l) 1 SO
2
(g);
DH 5 2250 ki l ojoul es
The reacti on above i s used i n the
mi ni ng i ndustry to extract copper
from copper ore. Once the mi xture i s
al l owed to establ i sh equi l i bri um at
temperature T and pressure P, the
equi l i bri um can be shi fted to favor
the products by
(A) i ncreasi ng the pressure by
decreasi ng the vol ume of the
reacti on vessel at constant T.
(B) i ncreasi ng the pressure by
addi ng an i nert gas such as
hel i um.
(C) decreasi ng the temperature.
(D) al l owi ng some gases to escape
at constant T and P.
(E) addi ng a catal yst.
8. An evacuated 1.00-l i ter vessel i s
i njected wi th 0.777 mol es of sul fur
tri oxi de gas, SO
3
. The vessel i s then
heated to a hi gh temperature where
the SO
3
parti al l y decomposes to form
the products SO
2
and O
2
i n the
reacti on shown bel ow:
2SO
3
(g) 2SO
2
(g) 1 O
2
(g)
The temperature i s kept constant,
and the amount of SO
3
i n the vessel
at equi l i bri um i s 0.520 mol . What i s
the val ue of K
c
at thi s temperature?
(A) 0.031
(B) 0.062
(C) 0.125
(D) 0.257
(E) 31.9
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9. A 3.00-l i ter reacti on vessel i s fi l l ed
wi th carbon monoxi de gas, CO, and
chl ori ne gas, Cl
2
. The mi xture i s
heated to 670 K and al l owed to reach
equi l i bri um accordi ng to the bal anced
equati on shown bel ow:
CO(g) 1 Cl
2
(g) COCl
2
(g)
At equi l i bri um, the mi xture contai ns
0.036 mol es CO, 0.075 mol es Cl
2
, and
1.11 mol es COCl
2
. What i s K
c
at thi s
temperature?
(A) 8.11 3 10
24
(B) 2.43 3 10
23
(C) 12.0
(D) 411
(E) 1.23 3 10
3
10. 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
11. For the reacti on shown bel ow,
K
p
5 2.8 3 10
22
at 400 K.
2NH
3
(g) N
2
(g) 1 3H
2
(g)
What i s the val ue of K
c
at thi s
temperature?
(A) 1.3 3 10
25
(B) 2.6 3 10
25
(C) 8.5 3 10
24
(D) 1.3 3 10
22
(E) 30
12. At 373 K, the reacti on shown bel ow
has an equi l i bri um constant,
K
c
5 2.19 3 10
210
.
COCl
2
(g) CO(g) 1 Cl
2
(g)
After pl aci ng a mi xture of gases i n
the reacti on vessel , the concentra-
ti ons were measured to be [COCl
2
] 5
3.50 3 10
23
M, [CO] 5 1.11 3 10
25
M, and [Cl
2
] 5 3.25 3 10
26
M. Whi ch
statement bel ow accuratel y descri bes
the reacti on?
(A) The reacti on i s at equi l i bri um.
(B) The reacti on i s not at equi l i b-
ri um, and i t i s proceedi ng to
the l eft.
(C) The reacti on i s not at equi l i b-
ri um, and i t i s proceedi ng to
the ri ght.
(D) The reacti on quoti ent i s equal
to K
c
.
(E) The reacti on quoti ent i s l ess
than K
c
.
e
x
e
r
c
i
s
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Free Response
QUESTION 1
Sul fur tri oxi de gas, one of the causes of aci d rai n, i s produced i n the upper atmosphere when
oxygen reacts wi th sul fur di oxi de gas i n the reacti on shown bel ow:
2SO
2
(g) 1 O
2
(g) 2SO
3
(g) DH5 2197 kJ
The gases are pl aced i n a reacti on vessel and al l owed to come to equi l i bri um at temperature
T, pressure P, and vol ume V. Predi ct and expl ai n the effects that each of the fol l owi ng wi l l
have on the equi l i bri um composi ti on of the reacti on:
(A) The parti al pressure of SO
3
(g) i s i ncreased by the addi ti on of SO
3
(g).
(B) The pressure i n the vessel i s i ncreased by the addi ti on of He.
(C) The total pressure i n the vessel i s i ncreased by decreasi ng the vol ume of the
vessel .
(D) The temperature of the system i s decreased.
(E) The parti al pressure of O
2
(g) i s decreased.
QUESTION 2
A 1.00-l i ter evacuated reacti on vessel was fi l l ed wi th 0.034 mol each of H
2
and I
2
gases. The
reacti on proceeded to equi l i bri um accordi ng to the equati on shown bel ow. The equi l i bri um
constant, K
c
, at temperature T, was 45.0:
H
2
(g) 1 I
2
(g) 2HI (g)
(A) What i s the equi l i bri um composi ti on of the mi xture?
(B) Determi ne K
p
for the reacti on mi xture descri bed i n part (A), i f the temperature
T i s 500C.
(C) After equi l i bri um had been establ i shed, 0.008 mol of HI was i njected i nto the
reacti on vessel , and the system was al l owed to reestabl i sh equi l i bri um.
Determi ne the new composi ti on of the equi l i bri um mi xture after the new
equi l i bri um i s establ i shed.
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Multiple Choice
1. E
2. B
3. A
4. D
5. C
6. C
7. D
8. A
9. E
10. D
11. B
12. B
1. The correct answer is (E). A l arge percentage of the mul ti pl e-choi ce equi l i bri um
questi ons are based on Le Chtel i ers Pri nci pl e, l i ke thi s one. I f pure oxygen i s i njected
i nto the reacti on vessel , the concentrati on of one of the products i ncreases, whi ch wi l l
dri ve the reacti on to the l eft. You need to l ook for answers that are consi stent wi th that
shi ft. The amount of carbon monoxi de wi l l have to decrease because i t i s requi red to
react wi th the excess oxygen to restore equi l i bri um.
2. The correct answer is (B). Thi s i s another Le Chtel i er probl em. Because i t i s an
exothermi c reacti on (DH , 0), you can thi nk of the reacti on as havi ng heat as another
product. An i ncrease i n temperature wi l l dri ve the reacti on to the l eft. Thi s wi l l cause
an i ncrease i n the concentrati on of reactants (and a subsequent decrease i n products),
whi ch wi l l decrease the val ue of K
eq
.
3. Thecorrect answer is(A).A decrease i n pressure, caused by a decreased vol ume, wi l l
cause the reacti on to shi ft i n the di recti on that has fewer parti cl es, whi ch i s to the ri ght.
Thi s i s the onl y choi ce that i s true. Rai si ng the temperature of an exothermi c reacti on
wi l l dri ve the reacti on to the l eft, whi ch wi l l decrease the number of mol es of NH
3
;
addi ng an i nert gas l i ke argon wi l l have no effect on the reacti on because i t wont affect
the parti al pressures of any of the reacti on components.
4. The correct answer is (D). Thi s requi res the use of a chart, whi ch i s shown bel ow:
I
2
(g) 1 Br
2
(g) 2I Br(g)
I
2
Br
2
2I Br
Start 0.50 mol 0.50 mol 0 mol
D 2
1
2
(0.84) 2
1
2
(0.84) 10.84 mol
Fi ni sh 0.08 mol 0.08 mol 0.84 mol
Because the vol ume of the vessel i s 1.0 l i ters, the number of mol es i s the same as the
concentrati on (mol ari ty). Therefore, were ready to substi tute the numbers i nto the
equi l i bri um constant expressi on:
K
eq
5
IBr
I Br
2
2 2
[ ]
[ ][ ]
( )
( )( )
0 84
0 08 0 08
2
.
. .
5 110
5. The correct answer is (C). The sol i ds CuO and Cu must be omi tted from the
equati on.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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6. The correct answer is (C). The equati on i n choi ce (C) i s the onl y one i n whi ch the
number of mol es of products i s the same as the number of mol es of reactants. As a
resul t, i t wont shi ft i n response to pressure changes due to changes i n vol ume.
7. The correct answer is (D). There are two thi ngs that you shoul d note about thi s
equati on. Fi rst, i t i s exothermi c; second, i t i nvol ves a heterogeneous equi l i bri um (i t has
two sol i ds and two gases). Therefore, the equi l i bri um expressi on i s
@SO
2
#
@O
2
#
. A decrease i n
the temperature wi l l cause a shi ft toward the products. One of the bi gger tri cks i n thi s
questi on i s the use of sol i ds. I f you are l ooki ng at the number of mol es of each
substance, and not payi ng attenti on to the states, you wi l l be mi sl ed i nto thi nki ng that
a pressure change wi l l have an affect on thi s. I t wont, because there are equal numbers
of mol es of the onl y gaseous components.
8. The correct answer is (A). Thi s i s another chart probl em. Set i t up as fol l ows:
2SO
3
(g) 2SO
2
(g) 1 O
2
(g)
2SO
3
2SO
2
O
2
Start 0.777 mol 0 0
D 20.257 1
2
2
(0.257) 1
1
2
(0.257)
Fi ni sh 0.520 mol 0.257 0.1285
Now the substi tuti on:
K
c
5
SO
2
2
3
O
SO
[ ] [ ]
[ ]
( ) ( )
( )
0 257 0 1285
0 520
2
2
. .
.
5 0.031
9. The correct answer is (E). Be careful , there was a huge trap i n thi s probl emone
that the AP test occasi onal l y throws i n. I n thi s probl em, the vol ume of the reacti on
vessel i s not 1.0 l i ters. Therefore, to get the concentrati ons of the reactants and
products, you must use the number of mol es di vi ded by the vol ume
n
3
l i ters). Look out for
thi s on the AP test. The rest of the probl em i s as fol l ows:
K
c
5
COCl
CO Cl
2
2
[ ]
[ ][ ]
_
,
_
,
_
,
1 11
3
0 036
3
0 075
3
.
. .
5 1.23 3 10
3
10. The correct answer is (D). Thi s i s a strai ghtforward K
p
probl em:
K
p
5
P
P P
HOCl
H
2
O Cl
2
O
( )
( )( )
( )
( )( )
2
2
20
296 15
5 0.090
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11. The correct answer is (B). Conversi on of K
p
to K
c
:
K
c
5 K
pS
1
RT
D
Dn
where Dn 5 (number of mol es products 2 number of mol es reactants) 5 ((113) 2 2) 5
2. The equati on then becomes:
K
c
5 2.8 3 10
22
1
0 0821 400
2
. ( )( )
_
,
5 2.6 3 10
25
12. The correct answer is (B). Thi s i s a reacti on quoti ent, Q, probl em. You need to
cal cul ate Q and then compare i t to the equi l i bri um constant, K. The cal cul ati on i s as
fol l ows:
Q 5
CO Cl
COCl
2
2
[ ][ ]
[ ]
5
1.1 10 3.25 10
3.50 10
5 6
3

( )( )
( )
5 1.0 3 10
28
Thi s i s consi derabl y l arger than K. Therefore, the reacti on i s not at equi l i bri um, and i t
must be movi ng toward the l eft (whi ch wi l l i ncrease the reactants, decrease the
products, and decrease Q unti l i t equal s K).
Free Response
QUESTION 1
(A) The addi ti on of SO
3
to the reacti on vessel wi l l i ncrease the concentrati on of SO
3
and dri ve the reacti on to the l eft, causi ng the producti on of more SO
2
and O
2
,
i ncreasi ng thei r parti al pressures and concentrati ons.
(B) The addi ti on of an i nert gas wi l l not affect the equi l i bri um parti al pressures and,
as a resul t, wi l l not cause a shi ft i n the equi l i bri um.
(C) I ncreasi ng the pressure by changi ng the vol ume wi l l cause the reacti on to shi ft to
the ri ght. Thi s wi l l al l ow the number of parti cl es to decrease, whi ch wi l l reduce
the pressure.
(D) Thi s i s an exothermi c reacti on (DH , 0). A decrease i n temperature wi l l dri ve the
reacti on to the ri ght i n an attempt to generate more heat. Thus, the amount of
SO
3
wi l l i ncrease.
(E) Decreasi ng the parti al pressure of O
2
wi l l cause the equi l i bri um to shi ft to the
l eft i n order to restore equi l i bri um. Thi s wi l l cause an i ncrease i n SO
2
and a
decrease i n SO
3
.
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QUESTION 2
(A) You need to set up a tabl e for thi s one:
H
2
(g) 1 I
2
(g) 2HI (g)
H
2
I
2
2HI
Start 0.034 0.034 0
D 2x 2x 1
2
1
x
Fi ni sh 0.034 2 x 0.034 2 x 2x
The next step i s to set up the equi l i bri um expressi on:
K
c
5
HI
H I
2
2 2
[ ]
[ ][ ]
45 5
2
0 034
2
2
x
x
( )
( ) .
You can take the square root of both si des to determi ne the val ue of x:
45 5
2
0 034
2
2
x
x
( )
( ) .
66.71 5
2
0 034
x
x
( )
( ) .
Sol vi ng for 1 and 2 6.71, we fi nd x to be:
0.228 2 6.71x 5 2x 20.228 1 6.71 5 2x
0.228 5 8.71x 20.228 5 24.71x
0.026 5 x 0.049 5 x
0.049 must be rejected because i t woul d cause H
2
and I
2
to have negati ve
concentrati ons. Therefore, x50.026. Substi tuti ng thi s back i nto the val ues i n the
tabl e provi des:
0.008 mol H
2
, 0.008 mol I
2
, and 0.052 mol HI
(B) K
p
5 K
c
(RT)
Dn
K
p
5 45[(0.0821)(773 K)]
0
K
p
5 45
K
p
i s the same as K
c
. There i s no di fference i n the number of mol es of reactants
and products. Therefore, the parti al pressures wi l l be proporti onal to the
concentrati ons.
(C) You need to make another tabl e. One thi ng to be careful of i s that i n thi s probl em,
you dont have any starti ng materi al s equal to zero:
H
2
(g) 1 I
2
(g) 2HI (g)
H
2
I
2
2HI
Start 0.008 0.008 0.060
D 1 0.5x 1 0.5x 2x
Fi ni sh 0.008 1 0.5x 0.008 1 0.5x 0.060 2x
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www.petersons.com
Because you are starti ng wi th some hydrogen and i odi ne, you have to add the
new amount to the ori gi nal amount. I n the cal cul ati on that fol l ows, K
c
remai ns
the same si nce we are at the same temperature:
K
c
5
HI
H I
2
2 2
[ ]
[ ][ ]
45 5
0 060
0 008 0 5
2
2
.
. .
x
x
( )
+ ( )
Taki ng the square root of each si de:
45 5
0 060
0 008 0 5
2
2
.
. .
x
x
( )
+ ( )
66.71 5
0 060
0 008 0 5
.
. .
x
x
( )
+ ( )
Fi ni sh sol vi ng for x (26.71 i s excl uded because i t yi el ds a negati ve val ue for x):
16.71~0.008 1 0.5x! 5 0.06 2 x
4.355x 5 6.2 3 10
23
x 5 1.45 3 10
23
Substi tuti ng for the val ues i n the tabl e:
H
2
5 I
2
5 8.7 3 10
23
mol
HI 5 0.059 mol
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SUMMING IT UP
Chemi cal equi l i bri um occurs i n reversi bl e reacti ons when the rate of the forward reacti on
i s equal to the rate of the reverse reacti on.
The equi l i bri um constant, K, descri bes the rel ati onshi p between the reactants and
products of a reversi bl e reacti on at equi l i bri um.
K
c
descri bes equi l i bri um i n terms of the concentrati ons of reactants and products.
K
p
descri bes equi l i bri um i n terms of the parti al pressures of the reactants and products.
The reacti on quoti ent, Q, i s used to descri be the rel ati onshi ps between the reactants and
products i n a system that i s not necessari l y i n equi l i bri um.
When the val ue of Q , K, the reacti on proceeds to the ri ght; when the val ue of Q . K, the
reacti on proceeds to the l eft; and when Q 5 K, the reacti on i s at equi l i bri um.
Le Chtel i ers Pri nci pl e states that when a system at equi l i bri um i s di sturbed, i t wi l l
react i n a way that mi ni mi zes the di sturbance.
A change i n the concentrati on of reactants or products wi l l cause the reacti on to shi ft i n
the di recti on that compensates for the addi ti on or l oss of materi al . For exampl e, i f the
concentrati on of a reactant i s i ncreased, the reacti on wi l l proceed to the ri ght, toward the
formati on of more product. Thi s wi l l use up the excess reactant and restore equi l i bri um.
A change i n pressure of a gaseous mi xture wi l l shi ft equi l i bri um to the di recti on that
compensates for the pressure change. I ncreases i n pressure wi l l shi ft the reacti on to the
si de of the reacti on that has fewer mol es of gas, whi l e decreases i n pressure favor the si de
of the reacti on wi th more mol es of gas.
The effects of temperature changes are rel ated to the enthal py of the reacti on. I n
response to a temperature i ncrease, an endothermi c reacti on (DH . 0) wi l l shi ft to
produce more products, whi ch wi l l use up the excess heat. An exothermi c reacti on
(DH , 0) wi l l shi ft to product more reactants, whi ch uses up the heat i n the reverse
reacti on (or by sl owi ng down the forward reacti on, sl ows down the producti on of
addi ti onal heat).
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Acids and Bases
OVERVIEW
Definitions of acids and bases
The pH concept
Weak acids and bases
Salt solutions
The relationship between K
a
and K
b
The common-ion effect
Buffers
Acid-base titrations
Summing it up
DEFINTIONS OF ACIDS AND BASES
There are three defi ni ti ons for aci ds and bases that you must be fami l i ar wi th:
Arrheni us, Brnsted-Lowry, and Lewi s. I n the fol l owi ng secti on, you wi l l
revi ew the meani ng and appl i cati on of these di fferent defi ni ti ons.
Arrhenius
Arrheni us defi ni ti ons are the earl i est and the most si mpl i sti c of aci d-base
defi ni ti ons. Of the three defi ni ti ons, arrheni us defi ni ti ons are the l east
i ncl usi ve, but the most commonl y known aci ds and bases can be defi ned by
Arrheni us.
An Arrheni us aci d i s a substance that, when di ssol ved i n water, i ncreases
the concentrati on of H
1
i ons i n the sol uti on:
HCl H Cl
H O
2
g aq aq ( ) ( ) + ( )
+
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
1
4
315
An Arrheni us basei s a substance that, when di ssol ved i n water, i ncreases the concentrati on
of OH
2
i ons i n the sol uti on:
NaOH Na OH
H O
2
s aq aq ( ) ( ) + ( )
+
I n the Arrheni us defi ni ti ons for aci ds and bases, the strength of the aci d or base i s determi ned
by the degree of i oni zati on. For exampl e, HCl i s consi dered a strong aci d because when i t i s
pl aced i n water i t compl etel y i oni zes to H
1
and Cl
2
. The strongest aci ds and bases are al l
Arrheni us aci ds and bases.
Brnsted-Lowry
Whi l e the Arrheni us defi ni ti ons focus on the H
1
and OH
2
i ons, the Brnsted-Lowry
defi ni ti ons focus on the behavi or of protonsthat i s, the transfer of a proton from one
substance to another.
A Brnsted-Lowry aci d i s a substance that transfers a proton to another substance. Si nce a
hydrogen i on i s a proton, al l Arrheni us aci ds are Brnsted-Lowry aci ds. However, the sl i ght
di fference i n defi ni ti ons al l ows us to consi der addi ti onal substances as aci ds. We can al so
consi der reacti ons that do not occur i n aqueous sol uti ons:
NH
3
(g) 1 HCl (g) NH
4
Cl (s)
Noti ce how HCl sti l l acts as an aci d, but i n thi s reacti on i t i s doi ng so wi thout bei ng di ssol ved
i n water.
A Brnsted-Lowry basei s a substance that accepts a proton from another substance. Thi s i s
a si gni fi cant change from the Arrheni us defi ni ti on. Arrheni us bases possess an OH
2
, whereas
Brnsted-Lowry bases need not. I n the exampl e bel ow, noti ce how ammoni a i ncreases the
concentrati on of hydroxi de i on i n the resul ti ng sol uti on wi thout donati ng a OH
2
i on. I t does so
by accepti ng a proton from water:
NH
3
(aq) 1 H
2
O(l) NH
4
1
(aq) 1 OH
2
(aq)
Another si gni fi cant di fference between defi ni ti ons i s that Brnsted-Lowry aci ds and bases
need not be mol ecul ar substances. There are a vari ety of reacti ons i n whi ch i ons donate or
accept protons. I n the sampl e bel ow, note how the cyani de i on (CN
2
) acts as a base by
accepti ng a proton and the bi carbonate i on (HCO
3
2
) acts as an aci d by donati ng a proton:
CN
2
(aq) 1 HCO
3
2
(aq) HCN(aq) 1 CO
3
22
(aq)
Amphoterism
An amphoteri c substance i s a substance that acts as an aci d i n some reacti ons and a base
i n others. I n the two reacti ons bel ow, note how water donates a proton (maki ng i t an aci d) i n
the fi rst reacti on, whi l e i n the second reacti on i t recei ves a proton (maki ng i t a base):
NH
3
(aq) 1 H
2
O(l) NH
4
1
(aq) 1 OH
2
(aq)
HCl (g) 1 H
2
O(l) H
3
O
1
(aq) 1 Cl
2
(aq)
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Conjugate Acid-Base Pairs
One very i mportant thi ng to remember i s that an aci d and base are al ways present i n these
reacti ons. I n order for a mol ecul e or i on to donate a proton, there has to be another i on or
mol ecul e to recei ve i t. I n addi ti on, i n reversi bl e aci d-base reacti ons, the rol es of the
substances as proton donor or acceptor wi l l swi tch i n the reverse reacti on. I n the exampl e
bel ow, note how water (a Brnsted-Lowry base i n thi s reacti on) accepts a proton to form a
hydroni um i on i n the forward reacti on. I n the reverse reacti on, the hydroni um i on
(Brnsted-Lowry aci d) donates a proton and, after l osi ng the proton, becomes the water
mol ecul e once agai n:
H
2
CO
3
(aq) 1 H
2
O(l) H
3
O
1
(aq) 1 HCO
3
2
(aq)
Al so note how H
2
CO
3
donates a proton i n the forward reacti on to form a bi carbonate i on,
whi ch then wi l l accept a proton i n the reverse reacti on.
These pai rs of substancesH
2
O/H
3
O
1
and H
2
CO
3
/HCO
3
2
di ffer onl y by the presence (or
absence) of a proton, whi ch cl assi fi es them as conjugate aci d-base pai rs. A conjugate aci d i s
formed when a proton i s added to a Brnsted-Lowry base. Therefore, i n the previ ous exampl e
the conjugate aci d i s the hydroni um i on, si nce i t was formed by the addi ti on of a proton to the
water mol ecul e (the Brnsted-Lowry base i n the forward reacti on). Removi ng a proton from a
Brnsted-Lowry aci d forms a conjugate base. I n the previ ous exampl e, HCO
3
2
i s the
conjugate base of H
2
CO
3
.
Sample: I n the chemi cal reacti on shown bel ow, i denti fy the Brnsted-Lowry aci d,
Brnsted-Lowry base, conjugate aci d, and conjugate base:
H
3
PO
4
(aq) 1 NO
2
2
(aq) HNO
2
(aq) 1 H
2
PO
4
2
(aq)
Answer: Brnsted-Lowry aci d: H
3
PO
4
donates a proton
Brnsted-Lowry base: NO
2
2
accepts a proton
Conjugate aci d: HNO
2
formed by the addi ti on of a proton to NO
2
2
; wi l l donate a
proton i n the reverse reacti on
Conjugate base: H
2
PO
4
2
formed by the removal of a proton from H
3
PO
4
; wi l l
accept a proton i n the reverse reacti on
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NOTE
Removing a
proton from an
acid produces a
conjugate base,
and adding a
proton to a base
produces a
conjugate acid.
Chapter 14: Acids and Bases 317
www.petersons.com
You Try It!
I n the chemi cal reacti on shown bel ow, i denti fy the Brnsted-Lowry aci d, the Brnsted-
Lowry base, the conjugate aci d, and the conjugate base:
NH
3
(aq) 1 H
2
O(l) NH
4
1
(aq) 1 OH
2
(aq)
Answer:
Brnsted-Lowry aci d: H
2
Odonates a proton
Brnsted-Lowry base: NH
3
accepts a proton
Conjugate aci d: NH
4
1
formed by addi ng a proton to a base
Conjugate base: OH
2
formed by removi ng a proton from an aci d
STRENGTHS OF ACIDS AND BASES
Before conti nui ng on to the l ast defi ni ti on of aci ds and bases, i t wi l l be hel pful to consi der the
defi ni ti ons for strong and weak aci ds wi thi n the context of the Brnsted-Lowry model of aci ds
and bases. The defi ni ti ons are real l y an extensi on of the Arrheni us i deas. I n the Arrheni us
defi ni ti ons, strong aci ds and bases were those that i oni ze compl etel y. Most Brnsted-Lowry
aci ds and bases do not compl etel y i oni ze i n sol uti on, so the strengths are determi ned based on
the degree of i oni zati on i n sol uti on. For exampl e, aceti c aci d, found i n vi negar, i s a weak aci d
that i s onl y about 1 percent i oni zed i n sol uti on. That means that when aceti c aci d, HC
2
H
3
O
2
,
i s pl aced i n water, the reacti on l ooks l i ke:
HC
2
H
3
O
2
(aq) 1 H
2
O(l) C
2
H
3
O
2
2
(aq) 1 H
3
O
1
(aq)
Thi s equati on can actual l y provi de you wi th a weal th of i nformati on i f you know how to
i nterpret i t. Because the aceti c aci d i s onl y about 1 percent i oni zed, i t means that the reacti on
to the l eft i s much more favored than the reacti on to the ri ght. I n the reacti on goi ng to the
ri ght, HC
2
H
3
O
2
i s the aci d and H
2
O i s the base. I n the reacti on goi ng to the l eft, H
3
O
1
i s the
aci d and C
2
H
3
O
2
2
i s the base. Because the reacti on goi ng to the l eft i s favored, i t means that
H
3
O
1
i s a stronger aci d than HC
2
H
3
O
2
. I t al so means that C
2
H
3
O
2
2
i s a stronger base than
H
2
O. I n aci d-base equi l i bri um reacti ons, the domi nant di recti on of the reacti on i s from the
stronger aci d and base to the weaker aci d and base.
To summari ze, strong aci ds yi el d weak conjugate bases whi l e weak aci ds yi el d rel ati vel y
strong conjugate bases.
HOW STRENGTH RELATES TO THE MOLECULAR STRUCTURE
There are a few trends about aci d strengths that you shoul d be fami l i ar wi th. I f you consi der
the aci d HA, the bond between H and A wi l l have to be broken i n order for the hydrogen i on
to be donated. For bi nary aci ds (those contai ni ng onl y hydrogen and a nonmetal l i c el ement),
there are two mai n factors that determi ne the ease of thi s process: the pol ari ty of the bond
between H and A and the si ze of A. The factors can be summari zed as fol l ows:
The l arger the mol ecul e A i s, the stronger the aci d wi l l be.
The more pol ar the bond between H and A i s, the stronger the aci d wi l l be.
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For aci ds contai ni ng oxygen, known as oxoaci ds, the rul es are si mi l ar but have a sl i ght
di fference. I n the oxoaci ds, the hydrogen atom i s bonded to an oxygen atom, whi ch i s, i n turn,
bonded to somethi ng el se. Qui te often, the general symbol to descri be them i s HOX, where X
i s some el ement. For exampl e, the structure of perchl ori c aci d, seen i n Fi gure 14.1, shows the
posi ti oni ng of the aci di c hydrogen atom (the one that wi l l come off). Note how the oxygen atom
i t i s bonded to i s al so bonded to a chl ori ne atom. For the oxoaci ds, the basi c rul es for
determi ni ng the strengths of the aci ds are as fol l ows:
The more el ectronegati ve el ement X i s, the stronger aci d HOX wi l l be.
When compari ng aci ds where X i s bonded to addi ti onal oxygen mol ecul es (for
i nstance, compari ng perchl ori c aci d, HCl O
4
, to chl ori c aci d, HCl O
3
), the more
addi ti onal oxygen atoms that are bonded to X, the stronger the aci d wi l l be (HCl O
4
i s stronger than HCl O
3
).
For pol yproti c aci ds (aci ds where more than one proton can be removed), each
successi ve proton becomes more di ffi cul t to remove. I n H
2
SO
4
, the fi rst proton
readi l y di ssoci ates, formi ng the HSO
4
2
i on. The addi ti onal el ectron densi ty on the
i on has a stronger hol d on the addi ti onal hydrogen i on, so i t i s hel d much more
ti ghtl y. Therefore, for pol yproti c aci ds, the ani ons formed by the di ssoci ati on of the
aci di c hydrogen are al ways l ess aci di c than thei r parent mol ecul e.
Lewis Acids and Bases
The Lewi s concept of the aci d i s i ncl uded i n the AP curri cul um but i s not emphasi zed as much
as the other two descri pti ons. As a resul t, we wi l l just l ook at the mai n i deas.
The Lewi s concept deal s wi th the behavi or of el ectron pai rs i n chemi cal reacti ons. The same
el ectron pai rs we l ooked at when we di scussed mol ecul ar geometry (see Chapter 7) can be
i nvol ved i n many reacti ons. Substances that can form a coval ent bond by accepti ng an
el ectron pai r from another substance are known as Lewi s aci ds. Substances that can form a
coval ent bond by donati ng an el ectron pai r to another substance are known as Lewi s bases.
Be careful that you dont mi x these up wi th the Brnsted-Lowry aci ds and bases. I t i s easy to
do si nce the words donate and accept are used, except they are associ ated wi th the
opposi te speci es (Brnsted-Lowry aci ds donate protons, whi l e Lewi s aci ds accept el ectron
pai rs).
When you are worki ng on probl ems wi th Lewi s aci ds and bases, i t i s often useful to use Lewi s
di agrams (or at l east modi fi ed Lewi s di agrams) to determi ne the behavi or and l ocati on of the
el ectron pai rs. I n the reacti on shown i n Fi gure 14.2, note how the el ectron pai r from ni trogen
(i n ammoni a) i s donated to boron (i n BF
3
). Thi s transfer of the el ectron pai r al l ows for the
formati on of a coval ent bond.
Cl O O
O
OO
H
Figure14.1
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NOTE
The hydrogen ion
(H
1
) is often writ-
ten in acid-base
examples and
problems be-
cause it is simplis-
tic. In actuality, a
positively charged
hydrogen ion will
bind to a polar
water molecule to
forma hydronium
ion. (H
3
O
1
).
The expressions
(H
1
) and
(H
3
O
1
) can
be used
interchangeably.
www.petersons.com
I n the previ ous exampl e, note that the success of the reacti on depended upon the aci d (BF
3
)
havi ng an i ncompl ete octet. Many substances, i ncl udi ng metal i ons that have i ncompl ete
octets, can act as Lewi s aci ds i n the presence of Lewi s bases.
Sample: I denti fy the Lewi s aci d and base i n the reacti on shown bel ow:
CN
2
(aq) 1 H
2
O(l) HCN(aq) 1 OH
2
(aq)
Answer: Aci d: H
2
O (gai ned a pai r of el ectrons i n the reacti on)
Base: CN
2
(donated a pai r of el ectrons)
You Try It!
I n the fol l owi ng reacti on, i denti fy the Lewi s aci d and the Lewi s base:
B(OH)
3
(aq) 1 H
2
O(l) B(OH)
4
(aq) 1 H
1
(aq)
Answer:
Aci d: B(OH)
3
Base: H
2
O
THE pH CONCEPT
Self-Ionization of Water
A sampl e of pure water wi l l contai n a smal l quanti ty of i ons (H
1
and OH
2
) produced from the
sel f-i oni zati on of water. These i ons exi st onl y for a bri ef ti me peri od before rejoi ni ng to form
water mol ecul es. At any gi ven moment, onl y a very smal l proporti on of the sampl e of water
exi sts as i ons (onl y about one of every bi l l i on parti cl es). The fol l owi ng equati on descri bes
thi s process:
H
2
O(l) H
1
(aq) 1 OH
2
(aq)
Usi ng the equi l i bri um expressi on that you revi ewed i n Chapter 13, the equi l i bri um constant
for the sel f-i oni zati on of water can be expressed as:
K
[ ][ ]
[ ]
+
H OH
H O
2
N H B
B
B
N H
B
B
F
F
F
B F
F
F
Lewis
Base
Lewis
Acid
Figure14.2
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www.petersons.com
However, si nce the concentrati on of l i qui d water i s constant and so l arge rel ati ve to the
concentrati on of i ons, i t can be omi tted from the equi l i bri um expressi on. At 25C, the
equi l i bri um expressi on can be rewri tten as Equati on 14.1:
K
w
5 [H
1
][OH
2
] 5 [H
3
O
1
][OH
2
] 5 1.0 3 10
214
where the subscri pt w i n the equi l i bri um constant expressi on stands for water. Because
the amounts of hydrogen and hydroxi de i ons are equal i n water (and any neutral sol uti on), we
can wri te:
[H
1
] 5 [OH
2
] 5 1.0 3 10
27
M
Si nce the equi l i bri um constant expressi on (K
w
) remai ns constant, an i ncrease i n one i on wi l l
onl y occur at the expense of a decrease i n the other. An i ncrease i n [H
1
] must be accompani ed
by a correspondi ng decrease i n [OH
2
], such that the product of the two wi l l equal 1.0 3 10
214
.
The reverse wi l l occur as wel l a decrease i n [H
1
] wi l l be accompani ed by an i ncrease i n
[OH
2
]. Use the tabl e bel ow to hel p you remember the rel ati onshi ps between these two i ons:
Sol uti on
Neutral [H
1
] 5 [OH
2
]
Aci di c [H
1
] . [OH
2
]
Basi c [H
1
] , [OH
2
]
The pH Scale
pH stands for the power of hydrogen i on concentrati on i n a sol uti on. The numeri cal val ues for
pH range from 0 to 14 and can be cal cul ated usi ng Equati on 14.2 bel ow:
pH 5 2l og [H
1
]
We can use the [H
1
] for a neutral sol uti on to show how the pH equati on works (recal l that i n
a neutral sol uti on [H
1
] 5 1.0 3 10
27
):
pH 5 2l og [H
1
] 5 2l og (1.0 3 10
27
) 5 7
A pH of 7 i s representati ve of neutral sol uti ons. I n aci di c sol uti ons, where the [H
1
] . 1.0 3
10
27
, pH val ues l ess than 7 are obtai ned. Li kewi se, i n basi c sol uti ons, pH val ues greater than
7 are obtai ned.
Sample:
An unknown sol uti on has a hydrogen i on concentrati on of 5.40 3 10
26
M. Cal cul ate the pH
and determi ne i f the sol uti on i s aci di c or basi c.
Answer: pH 5 2l og [H
1
] 5 2l og (5.40 3 10
26
) 5 5.27
The pH i s l ess than 7, so the sol uti on i s aci di c. You can determi ne whether a sol uti on i s aci di c
or basi c by eyebal l i ng the [H
1
]. Any exponents l ess than 27 wi l l yi el d an aci di c pH, whi l e
exponents greater than 27 wi l l yi el d a basi c pH.
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(Equati on 14.1)
(Equati on 14.2)
www.petersons.com
You Try It!
An unknown sol uti on has a hydrogen i on concentrati on [H
1
] of 7.64 3 10
211
M.
Cal cul ate the pH and determi ne i f the sol uti on i s aci di c, basi c, or neutral .
Answer: pH 5 2l og [H
1
] 5 2l og (7.64 3 10
211
) 5 10.1, so the sol uti on i s basi c.
Calculating the Hydrogen Ion Concentration
There are a few vari ati ons on pH probl ems that you mi ght encounter. The si mpl est vari ati on
i s a reversal of the pH equati on to sol ve for the hydrogen i on concentrati on. To sol ve these
probl ems, rearrange the pH equati on to sol ve for [H
1
] i n Equati on 14.3:
[H
1
] 5 10
2pH
Sample:
What i s the hydrogen i on concentrati on of a sol uti on wi th a pH of 2.4?
Answer: [H
1
] 5 10
2pH
5 10
22.4
5 4.0 3 10
23
M
You Try It!
An unknown base has a pH of 10.6. Determi ne the [H
1
] of the sol uti on.
Answer: [H
1
] 5 10
2pH
5 10
210.6
5 2.5 3 10
211
M
Relationship Between pH and [OH
2
]
The second vari ati on i s to determi ne ei ther the pH or the hydrogen i on concentrati on of a
sol uti on when gi ven the hydroxi de i on concentrati on, [OH
2
], for the sol uti on. To sol ve these
probl ems you need to uti l i ze the equi l i bri um constant expressi on for the sel f-i oni zati on of
water (K
w
). Thi s expressi on wi l l al l ow you to convert from the hydroxi de i on concentrati on,
[OH
2
], to the hydrogen i on concentrati on, [H
1
]. The [H
1
] can then be used to cal cul ate pH i f
necessary. One of the free-response questi ons on the 1999 test requi red thi s cal cul ati on.
Sample: Orange jui ce has a hydroxi de i on concentrati on of 6.3 3 10
212
M. Determi ne the pH
of orange jui ce.
Answer: Thi s wi l l requi re two steps:
Fi rst, the hydroxi de i on concentrati on wi l l be used to cal cul ate the hydrogen i on
concentrati on. Second, the obtai ned val ue wi l l be used to determi ne pH:
K
w
5 [H
1
][OH
2
] 5 1.0 3 10
214
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(Equati on 14.3)
www.petersons.com
Sol ve for [H
1
]:
@H
1
# 5
1.0 3 10
214
@OH
2
#
5
1.0 3 10
214
6.3 3 10
212
5 1.6 3 10
23
M
Use thi s val ue to cal cul ate the pH:
pH 5 2l og [H
1
] 5 2l og (1.6 3 10
23
) 5 2.8
You Try It!
Househol d ammoni a has a hydroxi de i on concentrati on of 7.9 3 10
23
M. Cal cul ate the
pH of househol d ammoni a.
Answer: [H
1
]51.3 3 10
212
M; pH 5 11.9
Calculation of pOH
I n addi ti on to the pH val ue, a sol uti on can al so be descri bed accordi ng to i ts pOH (power of
hydroxi de i on concentrati on). Because of the rel ati onshi p between hydrogen i ons and
hydroxi de i ons, there are many si mi l ari ti es between pOH and pH. Fi rst, note the si mi l ari ty
between the cal cul ati on of pH and pOH i n Equati on 14.4 bel ow:
pOH 5 2l og [OH
2
]
Si mi l arl y, the [OH
2
] can be cal cul ated by rearrangi ng the pOH Equati on 14.5:
[OH2] 5 10
2pOH
Fi nal l y, there i s a rel ati onshi p that al l ows easy conversi on between pH and pOH i n
Equati on 14.6:
pH 1 pOH 5 14
Sample: A sol uti on of potassi um hydroxi de has a hydroxi de i on concentrati on of 2.5 310
25
M.
What are the pH, [H
1
], and pOH of the sol uti on?
Answer: There i s more than one way to sol ve thi s probl em. One possi bl e sol uti on woul d use
the gi ven [OH
2
] to cal cul ate the [H
1
], use the cal cul ated [H
1
] to determi ne the pH,
and then use the pH to determi ne the pOH. Another woul d be to use the [OH
2
] to
determi ne the pOH, then use the pOH to determi ne the pH, and fi nal l y use the pH
to determi ne the [H
1
]. Whi l e there are sti l l other vari ati ons possi bl e, we wi l l sel ect
the second one and sol ve the probl em:
pOH 5 2l og [OH
2
] 5 2l og (2.5 3 10
25
) 5 4.6
pH 5 14 2 pOH 514 2 4.6 5 9.4
[H
1
] 5 10
2pH
5 10
29.4
5 4.0 3 10
210
M
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(Equati on 14.4)
(Equati on 14.5)
(Equati on 14.6)
www.petersons.com
You Try It!
Drai n cl eaner, a strong base, has a pH of 13.0. Cal cul ate the pOH, [OH
2
], and [H
1
].
Answers:
pOH 5 1.0
[OH2] 5 1.0 3 10
21
M
[H1] 5 1.0 3 10
213
M
WEAK ACIDS AND BASES
When a strong aci d or base undergoes a compl ete i oni zati on i n sol uti on, the concentrati ons of
the newl y formed i ons can be understood usi ng basi c stoi chi ometry pri nci pl es. Thi s i s because
essenti al l y al l of the aci d i s converted to i ons. Wi th weaker aci ds and bases, equi l i bri um i s
establ i shed between the i ons, much l i ke the equi l i bri a studi ed i n the l ast chapter. The
concentrati ons of the i ons must be determi ned by usi ng an equi l i bri um constant, K. The
equi l i bri um constants used to descri bes aci d-base equi l i bri a are i n the same form as K
c
from
the l ast chapter. Wel l use the di ssoci ati on of aceti c aci d to begi n our descri pti on of the new
equi l i bri um constant.
The equati on that descri bes the i oni zati on of aceti c aci d i n water takes the form:
HC
2
H
3
O
2
(aq) 1 H
2
O(l) H
3
O
1
(aq) 1 C
2
H
3
O
2
2
(aq)
I f you were goi ng to determi ne the equi l i bri um constant, K
c
, for thi s reacti on, you woul d set i t
up as fol l ows:
K
c
3 2 3 2
2 3 2
H O C H O
HC H O
1
]

1
]
[ ]
+
Water i s omi tted from the expressi on because i ts concentrati on i s not l i kel y to be affected by
thi s equi l i bri um. When the equi l i bri um constant, K
c
, i s wri tten for an aci d-base equi l i bri um,
i t i s known as the aci d-di ssoci ati on constant, K
a
. The generi c equati on for the
aci d-di ssoci ati on constant i s wri tten wi th the symbol HA to represent the aci d. Thus for the
reacti on
HA(aq) 1 H
2
O(l) H
3
O
1
(aq) 1 A
2
(aq)
the aci d-di ssoci ati on constant, K
a
i s expressed i n Equati on 14.7
K
a
3
H O A
HA
1
]

1
]
[ ]
+
, whi ch i s general l y shortened to K
a
H A
HA
1
]

1
]
[ ]
+
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(Equati on 14.7)
www.petersons.com
Calculating the pH of Weak Acid Solutions
Youve al ready seen how to cal cul ate the pH of a sol uti on contai ni ng a strong aci d. Thi s was
rel ati vel y easy because the aci d compl etel y di ssoci ated. That meant for every mol e of aci d, you
generated a mol e of hydrogen i ons (for monoproti c aci ds). Wi th weak aci ds, the process i s not
as si mpl e, but you wi l l noti ce that i t i s very si mi l ar to the cal cul ati ons you di d i n the
l ast chapter for K
c
. Wel l revi ew the procedure usi ng the equi l i bri um of aceti c aci d i n water,
shown bel ow:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
I n a 0.10 M sol uti on of aceti c aci d, HC
2
H
3
O
2
, what are the concentrati ons of hydrogen i on, H
1
,
and acetate i on, C
2
H
3
O
2
2
? What i s the pH of the sol uti on i f K
a
5 1.7 3 10
25
?
As you approach the probl em, you need to thi nk about what i t i s you are cal cul ati ng. The
sol uti on i s 0.10 M aceti c aci d sol uti on. That means that 0.10 mol aceti c aci d was di ssol ved i n
enough water to make 1.00 l i ters of sol uti on. Some of that 0.10 mol has di ssoci ated, however.
Because we dont know how much, we have to determi ne the amount usi ng the expressi on for
K
a
. Thi s wi l l al l ow us to determi ne the concentrati ons, and eventual l y the pH. We wi l l begi n
by setti ng up a chart l i ke the ones you used i n the l ast chapter:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
HC
2
H
3
O
2
H
1
C
2
H
3
O
2
2
Start 0.10 0 0
D 2x 1x 1x
Fi ni sh 0.10 2 x x x
I n the cal cul ati ons, we have omi tted the sel f-i oni zati on of water. Si nce the equi l i bri um
concentrati on of hydrogen i on [H
1
] i s so smal l (1.0 3 10
27
), i t i s negl i gi bl e compared to the
mol ari ty of the aceti c aci d.
The next step i s to substi tute the val ues i nto the equati on for K
a
:
K
a

[ ][ ]
[ ]
+
H C H O
HC H O
2 3 2
2 3 2
1.7 3 10
25
5
x
x
( )
2
0 10 .
At thi s poi nt, we need to consi der a very i mportant i dea. As the equati on stands, we need to
use the quadrati c equati on to sol ve i t. Youre not goi ng to want to spend your preci ous ti me on
the AP test (or even now) cranki ng out quadrati c equati ons, so were goi ng to make an
esti mate. The onl y catch i s that we al ways have to check to make sure that we can get away
wi th the shortcut. The shortcut i s to assume that the val ue for x i s goi ng to be so smal l that
subtracti ng i t from 0.10 wont make a dent i n i t. For exampl e, pretend that x i s 0.00001.
Subtract that from 0.10. You get 0.09999, whi ch i s essenti al l y 0.1. So, were goi ng to forget
about the x i n the denomi nator of the fracti on. When we have sol ved for x, wel l go back and
see i f we can get away wi th i t. Our new equati on i s:
1.7 3 10
25
5
x ( )
2
0 10 .
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We can rearrange thi s so that
x
2
5 1.7 3 10
26
and then sol ve for x by taki ng the square root of both si des:
x 5 1.3 3 10
23
I f we check back to our assumpti on, we see that 0.10 2 x 5 0.10 2 0.0013 ' 0.10; good
enough! Now to fi ni sh the probl em:
x 5 [H
1
] 5 [C
2
H
3
O
2
2
] 5 1.3 3 10
23
M
Sol vi ng for pH, we use the pH equati on:
pH 5 2l og [H
1
] 5 2l og (1.3 3 10
23
) 5 2.9
You Try It!
Propi oni c aci d, HC
3
H
5
O
2
, has a K
a
of 1.3 3 10
25
. I f you started wi th a 0.25 M sol uti on
of propi oni c aci d, what woul d be the concentrati ons of hydrogen i ons, H
1
, and
propi onate i ons, C
3
H
5
O
2
2
. What woul d be the pH of the sol uti on?
Answer:
[H1] 5 [C
3
H
5
O
2
2
] 5 1.8 3 10
23
pH 5 2.7
Polyprotic Acids
For pol yproti c aci ds, the K
a
for the i ni ti al hydrogen i on i s usual l y much hi gher than the K
a
for
the second or thi rd hydrogen i ons. For exampl e, i n phosphori c aci d, H
3
PO
4
, the val ue of K
a
for
the fi rst hydrogen i on i s 6.9 3 10
23
. For the second i oni zati on, the hydrogen wi l l come off the
H
2
PO
4
2
i on, and the K
a
for thi s i s 6.2 3 10
28
. The thi rd i oni zati on, whi ch converts HPO
4
22
to
H
1
and PO
4
32
, has a K
a
of 4.8 3 10
213
. Just because there are three hydrogen atoms on
phosphori c aci d does not mean that al l three wi l l come off easi l y or that they wi l l contri bute
to the aci di c character of the substance. Thi s exampl e i s fai rl y typi cal , and from i t we wi l l
make a hel pful general i zati on about pol yproti c aci ds: when you want to determi ne the
hydrogen i on concentrati on of one of these, use the K
a
from the fi rst i oni zati on (someti mes
referred to as K
a1
). The other val ues are so much smal l er that they are negl i gi bl e.
Base Equilibria
So far, weve been l ooki ng at the equi l i bri a of weak aci ds, from whi ch we devel oped the
aci d-di ssoci ati on constant, K
a
. There i s a si mi l ar process for weak bases. Lets use the weak
base ammoni a. I n sol uti on, ammoni a establ i shes the equi l i bri um shown bel ow:
NH
3
(aq) 1 H
2
O(l) NH
4
1
(aq) 1 OH
2
(aq)
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Fol l owi ng the same process we used to l ook at the equi l i bri um of the aci d, l ets set up the
equi l i bri um constant expressi on for thi s reacti on:
K
c
4
3
NH OH
NH
1
]

1
]
[ ]
+
Agai n, because the concentrati on of water i s constant, we can say that K
c
5 K
b
for thi s
reacti on. I f wri tten i n a generi c format, where B i s to represent the base, the equi l i bri um
takes on the fol l owi ng form:
B(aq) 1 H
2
O(l) HB
1
(aq) 1 OH
2
(aq)
The base-di ssoci ati on constant, K
b
, i s wri tten as Equati on 14.8:
K
b
HB OH
B
1
]

1
]
[ ]
+
The base-di ssoci ati on constant expressi on can be used to cal cul ate the concentrati ons of i ons
just l i ke the aci d-di ssoci ati on expressi on. The probl em-sol vi ng strategy i s i denti cal .
SALT SOLUTIONS
I f you remember from Chapter 11, we sai d that i f an aci d and base are mi xed together, a
neutral i zati on reacti on occurs that produces water and a sal t. I n thi s secti on, we are goi ng to
l ook a bi t more cl osel y at the sal ts that form i n neutral i zati on reacti ons (and sal ts i n general ).
I f you remember, a neutral i zati on reacti on takes the form:
HA(aq) 1 BOH(aq) H
2
O(l) 1 BA(aq)
From thi s you can see that the cati on from the sal t comes from the base and the ani on comes
from the aci d. Sal ts can act as Brnsted-Lowry aci ds or bases to produce sol uti ons that are
aci di c or basi c. The sal ts react wi th water i n a reacti on known as hydrol ysi s to yi el d ei ther a
conjugate aci d and a hydroxi de i on or a conjugate base and a hydrogen (hydroni um) i on. I f you
know the ori gi ns of the components of a sal t, you can make some predi cti ons about the pH of
the sol uti on formed from a hydrol ysi s of a sal t i on.
Salts from Strong Acids and Strong Bases
To understand a l i ttl e bi t about how thi s works, l ook at the di ssoci ati on of hydrochl ori c aci d,
a strong aci d:
HCl (aq) 1 H
2
O(l) H
3
O
1
(aq) 1 Cl
2
(aq)
The reacti on onl y goes i n the forward di recti on (i f any movement occurs i n the reverse
di recti on, the amount i s so sl i ght that i t i s negl i gi bl e). Thi s means that chl ori de i ons are very
weak bases, so weak that they can be thought of as havi ng no basi c character. I n a si mi l ar
reacti on, l ook at the di ssoci ati on of sodi um hydroxi de, a strong base:
NaOH(aq) 1 H
2
O(l) Na
1
(aq) 1 OH
2
(aq)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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(Equati on 14.8)
www.petersons.com
Thi s reacti on onl y goes i n the forward di recti on. As a conjugate aci d, sodi um i s compl etel y
i neffecti ve. Now, put the two substances, HCl and NaOH, together:
HCl (aq) 1 NaOH(aq) H
2
O(l) 1 NaCl (aq)
The sal t formed, NaCl , i s qui te sol ubl e i n water, but we have just seen that nei ther of the i ons
i s capabl e of behavi ng as an aci d or a base. As a resul t, a sol uti on of sal twater (made by
di ssol vi ng sodi um chl ori de i n water) has a neutral pH.
Sal ts created from the conjugates of strong aci ds and bases wi l l produce neutral sol uti ons.
Salts from Strong Acids and Weak Bases
You al ready know that the conjugate base of a strong aci d i s extremel y weak. The conjugate
aci d of a weak base, however, i s rel ati vel y strong. Therefore, the conjugate i on from the weak
base wi l l hydrol yze to produce an aci di c sol uti on. The weaker the base, the stronger the
conjugate aci d wi l l be. An exampl e woul d be NH
4
Cl . The NH
4
1
i on, the cati on from a base,
hydrol yzes water as shown bel ow:
NH
4
1
(aq) 1 H
2
O(l) NH
3
(aq) 1 H
3
O
1
(aq)
Salts from Weak Acids and Strong Bases
From the fi rst exampl e, we know that the conjugate aci ds of strong bases are weak. The
conjugate bases of weak aci ds, however, are rel ati vel y strong. Therefore, the ani ons from the
weak aci ds wi l l hydrol yze water to form basi c sol uti ons. An exampl e woul d be NaC
2
H
3
O
2
. The
acetate i on, the ani on from the weak aci d, hydrol yzes water as shown bel ow:
C
2
H
3
O
2
2
(aq) 1 H
2
O(l) HC
2
H
3
O
2
(aq) 1 OH
2
(aq)
Salts from Weak Acids and Weak Bases
Thi s one i s not as cl ear-cut as the others. Both speci es wi l l hydrol yze water. The questi on here
i s whi ch one wi l l do i t more? The onl y way to real l y predi ct the nature of the sol uti on i s to l ook
at the K
a
of the cati on and the K
b
of the ani on. I f K
a
i s bi gger, the sol uti on wi l l be aci di c; but
i f K
b
i s bi gger, then the sol uti on wi l l be basi c.
THE RELATIONSHIP BETWEEN K
a
AND K
b
I n the previ ous secti on, you saw further evi dence of the rel ati onshi ps between aci ds, bases,
and thei r conjugates. The rel ati onshi p between aci ds and thei r conjugate bases and bases and
thei r conjugate aci ds wi l l al l ow us to better see another rel ati onshi p between K
a
and K
b
. I f you
consi der the aceti c aci d equi l i bri um agai n:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq) K
a
5 1.7 3 10
25
Next, consi der the hydrol ysi s of water by aceti c aci ds conjugate, the acetate i on:
C
2
H
3
O
2
2
(aq) 1 H
2
O(l) HC
2
H
3
O
2
(aq) 1 OH
2
(aq)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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What i f you wanted to cal cul ate the K
b
for thi s equi l i bri um? As i t turns out, you dont have to.
There i s a rel ati onshi p between these two expressi ons that may not have been obvi ous when
you l ooked at them i n thi s way. I f we pl ace them on top of one another, you mi ght see
somethi ng di fferent:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
C
2
H
3
O
2
2
(aq) 1 H
2
O(l) HC
2
H
3
O
2
(aq)1 OH
2
(aq)
I f you add the two equati ons together, you wi l l fi nd that the net equati on i s:
H
2
O(l) H
1
(aq) 1 OH
2
(aq)
Perhaps you recogni ze thi s equati on from the begi nni ng of the chapter. I f you dont, i t i s the
equati on for the sel f-i oni zati on of water, from whi ch K
w
was deri ved. What youve now seen
are three equati ons. The fi rst i s an equati on that woul d be used to cal cul ate the K
a
of aceti c
aci d. The second i s the equati on used to cal cul ate K
b
for the conjugate base. The thi rd, whi ch
i s deri ved from these two, i s the formul a for cal cul ati ng K
w
. There i s a very cl ear rel ati onshi p
between K
a
, K
b
, and K
w
. The three constants are al l rel ated i n Equati on 14.9, shown bel ow:
K
w
5 K
a
K
b
I f you wanted to determi ne K
b
for the acetate i on, you coul d use the K
a
of i ts conjugate aci d,
aceti c aci d. The K
a
of aceti c aci d i s 1.7 3 10
25
:
K
b
5
K
w
K
a
5
1.0 3 10
214
1.7 3 10
25
5 5.9 3 10
210
whi ch makes acetate a pretty weak base.
You Try It!
HF i s a fai rl y weak aci d wi th a K
a
of 6.8 3 10
24
. What i s the K
b
for the F
2
i on?
Answer: 1.5 3 10
211
THE COMMON-ION EFFECT
You wi l l see thi s topi c appear twi ce, once i n thi s chapter and once the next chapter. For now,
you wi l l see how thi s phenomenon affects aci d-base equi l i bri a. I n the next chapter, you wi l l
see i ts effects on sol ubi l i ty equi l i bri a. The common-i on effect i s not too di fferent from what
i ts name suggests. I f you have an equi l i bri um system and add a sol ute to i t that contai ns one
of the i ons i n the equi l i bri um, i t wi l l cause the equi l i bri um to shi ft. That i s the common-i on
effect (common because the sol ute has an i on i n common wi th the equi l i bri um system). From
a conceptual standpoi nt, thi s can be addressed usi ng Le Chtel i ers Pri nci pl e. For exampl e,
consi der our favori te equi l i bri um system bel ow:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
We can add a coupl e of di fferent thi ngs to the mi xture that wi l l affect i t and demonstrate the
common-i on effect. One of them woul d be sodi um acetate, NaC
2
H
3
O
2
. Another woul d be
hydrochl ori c aci d. Thi nk about thi s for a moment, keepi ng i n mi nd Le Chtel i ers Pri nci pl e. I f
sodi um acetate i s added to the mi xture, i t wi l l di ssoci ate i nto sodi um i ons and acetate i ons.
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(Equati on 14.9)
NOTE
The weaker the
acid, the stronger
the conjugate
base.
www.petersons.com
The i ncrease i n concentrati on of the acetate i ons wi l l dri ve the reacti on to the l eft, whi ch wi l l
further i nhi bi t the di ssoci ati on of aceti c aci d. Addi ng hydrochl ori c aci d wi l l have the same
effect because i t wi l l i ncrease the concentrati on of protons, whi ch wi l l al so dri ve the reacti on
to the l eft. Sodi um acetate and hydrochl ori c aci d have two features that al l ow them both to
cause the common-i on effect to occur. Fi rst, they are both strong el ectrol ytes, and second they
each have an i on i n common wi th the aceti c aci d equi l i bri um. These are the key i ngredi ents
that cause the common-i on effect.
Quantitative Treatment of the Common-Ion Effect
Havi ng a conceptual understandi ng of the effect i s a good starti ng poi nt, but we sti l l need to
be abl e to understand the quanti tati ve rel ati onshi ps between the di fferent components i n the
equi l i bri um mi xture. I n thi s secti on, we wi l l see how to deal wi th the common-i on effect i n
aci d-base equi l i bri um probl ems. You wi l l fi nd that these probl ems are very si mi l ar to the
weak aci d probl ems earl i er i n the chapter.
I n thi s sampl e, we wi l l see what happens when we make a sol uti on that contai ns both aceti c
aci d and sodi um acetate (whi ch was used i n our previ ous exampl e). Suppose you make a
sol uti on that contai ns 0.30 mol HC
2
H
3
O
2
and 0.30 mol NaC
2
H
3
O
2
di ssol ved i n 1.00 l i ters of
sol uti on. Lets compare the pH of thi s sampl e to the pH of a sol uti on that onl y has 0.30 mol
HC
2
H
3
O
2
. I f the conceptual expl anati on i n the l ast secti on i s val i d, we shoul d predi ct that the
pH of the sol uti on wi th the sodi um acetate wi l l be hi gher (l ess aci di c) than the aceti c aci d-onl y
sol uti on. To begi n, l ets set up the equati on for the equi l i bri um reacti on:
HC
2
H
3
O
2
(aq) 1 H
2
O(l) H
3
O
1
(aq) 1 C
2
H
3
O
2
2
(aq)
There are a few thi ngs that you need to pay attenti on to as you set up thi s probl em. Fi rst, the
sodi um need not be wri tten i n the equati on because i t doesnt do anythi ng (i ts a spectator).
Second, unl i ke the previ ous weak aci d probl ems, these probl ems arent starti ng out wi th no
products. The common i on i n thi s reacti on i s the acetate i on, whi ch i s a product of the aceti c
aci d di ssoci ati on. When you set up your chart, you need to i ncl ude al l amounts of al l
substances present at the start of the reacti on. Were goi ng to omi t water i n our chart because
i t i s not part of the equi l i bri um expressi on.
Lets make the chart:
HC
2
H
3
O
2
(aq) 1 H
3
O
1
(aq) 1 C
2
H
3
O
2
2
(aq)
HC
2
H
3
O
2
H
3
O
1
C
2
H
3
O
2
2
Start 0.30 0 0.30
D 2x 1x 1x
Fi ni sh 0.30 2 x x 0.30 1 x
At thi s poi nt, you are ready to pl ug these val ues i nto the K
a
expressi on. We saw earl i er i n the
chapter that the K
a
for aceti c aci d was 1.7 3 10
25
:
K
a
3 2 3 2
2 3 2
H O C H O
HC H O
1
]

1
]
[ ]
+
1.7 3 10
25
5
x x
x
0 30
0 30
.
.
( )
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Li ke the previ ous probl ems, we are goi ng to assume that x i s smal l enough that addi ng or
subtracti ng i t from or to 0.30 wi l l make an i nsi gni fi cant di fference. That wi l l al l ow us to sol ve
for x:
1.7 3 10
25
5
( . )
.
0 30
0 30
x
1.7 3 10
25
5 x
I f we check our earl i er approxi mati on, we see that 0.30 2 1.7 3 10
25
5 0.30 so we can go
wi th that.
Substi tuti ng our x back i nto the equati on for the [H
3
O
1
] (whi ch we have to do to get the pH),
we get [H
3
O
1
] 5 1.7 3 10
25
.
I f we use thi s hydroni um i on concentrati on, we can determi ne the pH:
pH 5 2l og [H
3
O
1
] 5 2l og (1.7 3 10
25
) 5 4.77
Now, l ets compare that to the pH of a 0.30 M sol uti on of aceti c aci d. Because you have al ready
done thi s type of cal cul ati on, wel l just show the setup and sol uti on wi th no further expl anati on:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
HC
2
H
3
O
2
H
1
C
2
H
3
O
2
2
Start 0.30 0 0
D 2x 1x 1x
K
a
3 2 3 2
2 3 2
H O C H O
HC H O
1
]

1
]
[ ]
+
1.7 3 10
25
5
x
x
( )
2
0 30 .
1.7 3 10
25
5
x ( )
2
0 30 .
x 5 1 7 10 0 30
5
. .
( )
( )
x 5 [H
3
O
1
] 5 2.26 3 10
23
pH 5 2l og [H
3
O
1
] 5 2l og (2.26 3 10
23
) 5 2.65
So, by addi ng sodi um acetate to the sol uti on, the pH of the aceti c aci d sol uti on changed from
2.65 to 4.77. Thi s was caused by the addi ti on of a common i on from a strong el ectrol yte and
behaved accordi ng to Le Chtel i ers Pri nci pl e.
Thi s same process can be seen i n bases. Consi der the equi l i bri um of a weak base i oni zati on, as
shown bel ow:
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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NH
3
(aq) 1 H
2
O(l) NH
4
1
(aq) 1 OH
2
(aq)
The addi ti on of a strong el ectrol yte contai ni ng ei ther an ammoni um i on (NH
4
1
) or a strong
base (contai ni ng OH
2
) wi l l shi ft the equi l i bri um to the l eft. I t wi l l al so shi ft pH i n the other
di recti on, whi ch wi l l make the basi c pH l ess basi c.
BUFFERS
The term buffer i s usual l y used to descri be a buffered sol uti on, whi ch i s a sol uti on that
resi sts changes to pH when aci ds or bases are added to i t. You know enough chemi stry ri ght
now to know that there are l i mi ts to the amount of aci d or base that a sol uti on can buffer. You
can probabl y i magi ne that a 100 ml beaker of buffered sol uti on wont be much good i f you mi x
i t wi th a l i ter of concentrated hydrochl ori c aci d! The amount of aci d of base that a buffered
sol uti on can handl e before appreci abl y changi ng pH i s known as the buffer capaci ty.
The purpose of thi s secti on i s to revi ew the nature of buffers and how thi s rel ates to the
buffer capaci ty.
What you saw i n the l ast secti on was an exampl e of how the presence of certai n i ons i n
sol uti on can regul ate the pH of a system. I n the aceti c aci d/sodi um acetate exampl e, we
started wi th a weak aci d and then added a sal t contai ni ng the conjugate base of the weak aci d
to the sol uti on. Thi s pai ri ng of the weak aci d and the conjugate base modi fi ed the pH of the
sol uti on. Thi s i s the pri nci pl e behi nd buffered sol uti ons. I f an aci d was added to the sol uti on
contai ni ng the aceti c aci d/acetate conjugates, the hydroni um i ons from the aci d woul d
combi ne wi th the acetate i ons to form more aceti c aci d. So, what shoul d have amounted to an
i ncrease i n hydroni um i ons i n the sol uti on was foi l ed by the acetate i ons.
The abi l i ty to dri ve the reacti on to the l eft, and thereby remove the hydroni um i ons from
sol uti on, hi nges on two factors. Fi rst, there has to be enough of the conjugate base to combi ne
wi th the aci d. Second, the K
a
of the aci d has to be smal l enough that the reacti on doesnt move
qui ckl y to the ri ght. I n other words, when the protons combi ne wi th the conjugate base, they
wi l l remai n that way (the aci d i s weak enough that i t does not readi l y i oni ze).
I n a basi c sol uti on, the pri nci pl e i s si mi l ar. The conjugate aci d of the weak base combi nes wi th
excess hydroxi de i on to dri ve the reacti on toward the weak base. The same factors govern the
process: the amount of the conjugate aci d and the K
b
of the base.
Buffers can be made that wi l l resi st changes to pH by aci ds and bases. To i l l ustrate thi s, l ets
l ook at an exampl e of a buffer that i s composed of HX, a weak aci d, and X
2
, the conjugate base
of the weak aci d. Normal l y, the sol uti on woul d exi st i n equi l i bri um as shown bel ow (water has
been omi tted to make the rel ati onshi ps more obvi ous):
HX(aq) H
1
(aq) 1 X
2
(aq)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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When you l ook at thi s equi l i bri um, though, you have to remember that the aci d has been
spi ked wi th a sal t that wi l l i ncrease the concentrati on of X
2
to much hi gher l evel s than woul d
normal l y be found (from the di ssoci ati on of the aci d). That means that the concentrati on of H
1
i ons i s rel ati vel y much smal l er than the concentrati on of X
2
. I f an aci d i s added to the
mi xture, the equi l i bri um wi l l be shi fted to the l eft as excess hydrogen (hydroni um) i ons
combi ne wi th the conjugate base:
HX(aq) H
1
(aq) 1 X
2
(aq)
The di sproporti onate arrow si zes i ndi cate that the reacti on i s movi ng much more to the l eft
after an aci d i s added. I f a strong base i s added i nstead of an aci d, the hydroxi de i on i n the
base wi l l react wi th the aci d i n a neutral i zati on, as shown bel ow:
OH
2
(aq) 1 HX(aq) H
2
O(l) 1 A
2
(aq)
The amount of aci d or base that a buffer i s abl e to neutral i ze before changi ng pH, the
bufferi ng capaci ty, i s rel ated to the amount of weak aci d/conjugate base or weak
base/conjugate aci d present i n the buffer sol uti on. The greater the concentrati on of the
conjugate pai rs, the more resi stant to a change i n pH the buffer wi l l be. I n the next secti on,
wel l l ook at some quanti tati ve aspects of buffer sol uti ons.
Quantitative Aspects of Buffers
On the AP test, aci d-base questi ons appear on a regul ar basi s, and buffer cal cul ati ons are
among the most common of those questi ons to pop up. One of the thi ngs you are expected to
be abl e to do i s cal cul ate the pH of a buffer sol uti on, and though you may not real i ze i t yet, you
have al ready done thi s cal cul ati on. I n the previ ous exampl e of the common-i on effect, when
you cal cul ated the pH of the sol uti on made wi th the 0.30 M aceti c aci d and the 0.30 M sodi um
acetate, that was a buffer sol uti on. That i s the fi rst type of buffer cal cul ati on you are expected
to know. The second type of cal cul ati on i s to determi ne the effect of addi ng a strong aci d or
base to a buffer, and the thi rd type i s to determi ne how to prepare a speci fi c buffer. Lets take
the second type of probl em now, where you wi l l see how to cal cul ate the effect of addi ng a
strong aci d or base to a buffer sol uti on.
As l ong as we al ready have mi xed up a batch of the aceti c aci d/sodi um acetate buffer, we
mi ght as wel l use i t. Wel l set up two di fferent reacti on vessel s. To the fi rst one, we wi l l add
0.01 mol of gaseous HCl , and to the second wel l add 0.01 mol of sol i d NaOH.
Vessel 1: Addi ti on of a strong aci d, HCl , to a buffer sol uti on
Two thi ngs are goi ng to occur i n the vessel , and sol vi ng the probl em requi res you to l ook at
both. Fi rst, the aci d wi l l i mmedi atel y di ssoci ate i nto H
1
i ons and Cl
2
i ons. Second, we wi l l
assume that the H
1
from the HCl wi l l react compl etel y wi th the acetate i on. Thi s has an
i mportant i mpl i cati on for our starti ng condi ti ons. I f we make these two assumpti ons, then the
starti ng concentrati on of acetate, C
2
H
3
O
2
2
, wi l l be (0.30 2 0.01) 5 0.29 M because i t reacts
wi th the H
1
from hydrochl ori c aci d. Thi s reacti on forms aceti c aci d, so the amount of aceti c
aci d i n the sol uti on wi l l i ncrease after the addi ti on of hydrochl ori c aci d to (0.30 1 0.01) 5
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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0.31 M. I n the next part of the probl em, we need to l ook at the effect of the i oni zati on of aceti c
aci d, whi ch requi res the use of an equi l i bri um cal cul ati on:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
HC
2
H
3
O
2
H
1
C
2
H
3
O
2
2
Start 0.31 0 0.29
D 2x 1x 1x
Fi ni sh 0.31 2 x x 0.29 1 x
K
a
5
H O C H O
HC H O
3 2 3 2
2 3 2
+
[ ][ ]
[ ]
1.7 3 10
25
5
x x
x
0 29
0 31
.
.
+ ( )
Assumi ng x i s much smal l er than 0.31 or 0.29:
1.7 3 10
25
5
0 29
0 31
.
.
x
x 5
1 7 10 0 31
0 29
5
. .
.
( )
5 1.8 3 10
25
Substi tuti ng thi s for x, we see that H
1
5 1.8 3 10
25
. Therefore, we can use thi s val ue to
cal cul ate the pH of the sol uti on:
pH 5 2l og [H
1
] 5 2l og (1.8 3 10
25
) 5 4.74
I f you recal l from the earl i er probl em, the pH of the sol uti on pri or to the addi ti on of the HCl
was 4.77.
I f you had added 0.01 mol HCl to pure water, the pH woul d have been:
pH 5 2l og [H
1
] 5 2l og (0.01) 5 2.0
Qui te a bi t di fferent!
Vessel 2: Addi ti on of a strong base, NaOH, to a buffer sol uti on
I n thi s exampl e, were addi ng 0.01 mol NaOH to the buffer sol uti on. Before we begi n wi th the
math, l ets consi der what i s goi ng to happen i n the vessel . Ri ght after the sodi um hydroxi de i s
added, i t wi l l di ssoci ate compl etel y i nto sodi um and hydroxi de i ons because i t i s such a strong
el ectrol yte and a strong base. We are al so goi ng to assume that the hydroxi de i ons react
compl etel y wi th the aceti c aci d to yi el d water and acetate i ons. Thi s wi l l cause an i ncrease i n
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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the concentrati on of acetate i ons at the expense of a decrease i n the concentrati on of aceti c
aci d. The setup wi l l be the opposi te of the addi ti on of aci d. Lets begi n the cal cul ati on wi th an
equi l i bri um cal cul ati on:
HC
2
H
3
O
2
(aq) H
1
(aq) 1 C
2
H
3
O
2
2
(aq)
HC
2
H
3
O
2
H
1
C
2
H
3
O
2
2
Start 0.29 0 0.31
D 2x 1x 1x
Fi ni sh 0.29 2 x x 0.31 1 x
Make sure you arent getti ng mi xed up about the changi ng concentrati ons of the buffer
consti tuents and the si gns i n the D col umn. The change i n concentrati on that occurs because
of the addi ti on of strong aci d or base takes pl ace i n a separate reacti on to the one i n the
equi l i bri um cal cul ati on tabl e. The effects of these changes are refl ected i n the di fferent
amounts i n the start row of the tabl e. The other events shown i n the tabl e onl y descri be
the equi l i bri um of the aceti c aci d sol uti on, whi ch wi l l al ways i ncrease the concentrati on of
acetate i on.
Wi th that out of the way, l ets fi ni sh the cal cul ati on. Set up the expressi on of K
a
to sol ve for x:
K
a
5
H O C H O
HC H O
3 2 3 2
2 3 2
+
[ ][ ]
[ ]
1.7 3 10
25
5
x x
x
0 31
0 29
.
.
+ ( )
Assumi ng x i s much smal l er than 0.31 or 0.29:
1.7 3 10
25
5
0 31
0 29
.
.
x
x 5
1 7 10 0 29
0 31
5
. .
.
( )
5 1.60 3 10
25
Substi tuti ng thi s for H
1
, we fi nd that the pH of the sol uti on i s:
pH 5 2l og [H
1
] 5 2l og (1.60 3 10
25
) 5 4.80
As you can see, the buffer sol uti on mai ntai ned the pH wi thi n a rel ati vel y smal l range. The
buffer sol uti on onl y has a pH of 4.77, the buffer wi th HCl was 4.74, and the buffer wi th NaOH
was 4.80. Al l of these were onl y sl i ght changes i n the pH.
Henderson-Hasselbalch Equation
Thi s equati on i s used to di rectl y cal cul ate the pH of a buffer wi thout usi ng an equi l i bri um
cal cul ati on. I t i s i mportant that you know how to do equi l i bri um cal cul ati ons before you use
thi s equati on. The equati on makes the cal cul ati on much faster, but there are frequentl y
conceptual questi ons about aci d-base equi l i bri a that requi re a sol i d understandi ng of the
topi c. Therefore, make sure you trul y understand what you are doi ng before usi ng thi s
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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cal cul ati on. The probl ems that use the Henderson-Hassel bal ch equati on can be sol ved usi ng
equi l i bri um cal cul ati on tabl es as wel l .
So what i s thi s equati on? Lets take a moment to show the deri vati on, so i t wi l l make more
sense to you. Wel l begi n wi th the formul a for K
a
that weve been usi ng:
K
a
5
H A
HA
+
[ ][ ]
[ ]
I f we rearrange thi s equati on, we can sol ve for [H
1
]. Thi s wi l l al l ow us to l ater use i t to
cal cul ate pH:
[H
1
] 5 K
a
HA
A
[ ]
[ ]
Before goi ng on to the next step, we need to l ook at a new vari abl e. So far, youve l earned
about pH and pOH. Remember, these were obtai ned by taki ng the 2l og of the [H
1
] and
[OH
2
], respecti vel y. Here, were goi ng to i ntroduce two new terms: pK
a
, and pK
b
. These terms
are used to descri be the K
a
and K
b
i n smal l , posi ti ve numbers, rather than very smal l
exponents (much l i ke the pH val ues of 014 represent the smal l [H
1
] i on amounts of 1.0 3
10
214
). pK
a
i s cal cul ated as the 2l og K
a
, and pK
b
i s the 2l og K
b
. You wi l l need these terms to
understand the rest of the deri vati on, whi ch wel l conti nue now.
We can take the negati ve l og of both si des of the equati on to reveal a fami l i ar rel ati onshi p:
2l og [H
1
] 5 2l og K
a
HA
A
[ ]
[ ]
I f we substi tute pH for 2l og[H
1
], and factor the ri ght si de, we end up wi th:
pH 5 2l og K
a
2 l og
HA
A
[ ]
[ ]
A careful l ook at thi s expressi on shoul d reveal the val ue for pK
a
that we menti oned earl i er
when we showed that pK
a
5 2l og K
a
. I f we substi tute that and add the l og, we get:
pH 5 pK
a
1 l og
A
HA
[ ]
[ ]
Equati on 14.10 i s known as the Henderson-Hassel bal ch equati on and i s provi ded for you on
the AP formul a sheet. You can use i t to cal cul ate the pH of a buffer. There i s a si mi l ar form of
the equati on that i s rewri tten to address the hydroxi de i on concentrati on
pOH 5 pK
b
1 l og
HB
B
+
[ ]
[ ]
where B i s the base and HB
1
i s the protonated base.
To show how the equati on i s used, l ets use the previ ous cal cul ati on to show how the equati on
coul d have been used i nstead of the equi l i bri um cal cul ati on method.
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(Equati on 14.10)
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I f you recal l , we were usi ng a buffer that was composed from 0.30 mol HC
2
H
3
O
2
and 0.30 mol
NaC
2
H
3
O
2
di ssol ved i n 1.0 l i ters of sol uti on. The K
a
of aceti c aci d i s 1.7 3 10
25
. Usi ng the
Henderson-Hassel bal ch equati on to determi ne the pH, we get
pH 5 pK
a
1 l og
A
HA
[ ]
[ ]
5 2l og (1.7 3 10
25
) 1 l og
0.30
0.30
_
,
5 4.77
The equati on to determi ne the pH after addi ti on of the aci d woul d become:
pH 5 pK
a
1 l og
A
HA
[ ]
[ ]
5 2l og (1.7 3 10
25
) 1 l og
0.29
0.31
_
,
5 4.74
The equati on to determi ne the pH after addi ti on of the base woul d become:
pH 5 pK
a
1 l og
A
HA
[ ]
[ ]
5 2l og (1.7 3 10
25
) 1 l og
0.31
0.29
_
,
5 4.80
Al l three produced i denti cal answers to the equi l i bri um cal cul ati on tabl es that we used.
ACID-BASE TITRATIONS
An aci d-base ti trati on i s a procedure that i s used where a base of known concentrati on i s
added to an aci d of unknown concentrati on (or vi ce-versa) i n order to determi ne the
concentrati on of the unknown. I n addi ti on, i t i s possi bl e to determi ne the K
a
of the aci d bei ng
ti trated (or K
b
of the base) as wel l as an appropri ate i ndi cator. Aci d-base ti trati ons are often
the topi c of AP test questi ons and are frequentl y used i n the l aboratory questi ons. You shoul d
know about ti trati ons from a conceptual l evel , be abl e to perform cal cul ati ons for ti trati ons,
and know how to properl y perform one i n the l aboratory. Wel l begi n wi th the conceptual
expl anati on of ti trati ons.
There are a few mai n types of ti trati ons: a strong aci d ti trated wi th a strong base (or a strong
base ti trated wi th a strong aci d); a weak aci d ti trated wi th a strong base; a weak base ti trated
wi th a strong aci d; and a pol yproti c aci d ti trated wi th a strong base. Each one of these
produces characteri sti c resul ts and wi l l need to be di scussed separatel y. For the sol uti ons of
weak aci ds and bases, the process i s compl i cated by the common-i on effect.
Strong Acid with a Strong Base
One of the most common ti trati ons of thi s type i s the ti trati on of hydrochl ori c aci d, HCl , wi th
sodi um hydroxi de, NaOH. I f you remember from earl i er, thi s i s a neutral i zati on reacti on.
However, you shoul d al so remember from earl i er that i n order for a compl ete neutral i zati on to
occur, the reacti on must use appropri ate stoi chi ometri c rati os. When we fi rst l ook at the
process, we wi l l do so wi th two sol uti ons of known concentrati on, but you wi l l see that thi s
process can be used to determi ne the concentrati on of one of the sol uti ons.
The way that thi s procedure i s typi cal l y done i s to obtai n a sampl e of strong base that has
been standardi zed (the exact concentrati on determi ned) and pl ace i t i nto a buret. Frequentl y,
questi ons appear on the test that deal wi th the procedures for ti trati ons. One procedural
questi on that has come up more than once i nvol ves the cl eani ng of the buret pri or to the
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ti trati on. After thorough cl eani ng wi th water and di sti l l ed water, the buret shoul d be ri nsed
wi th the sol uti on that i s goi ng i n i t. Thi s i s done by runni ng several smal l amounts of the
sol uti on through the ti p pri or to the ti trati on. Thi s assures that the concentrati on of every
drop i n the buret i s constant. The base i s sl owl y added to the aci d and the pH i s recorded after
the addi ti ons. I n most modern hi gh school l abs, the pH i s constantl y bei ng recorded wi th a
di gi tal pH meter or a computer probe.
The purpose of determi ni ng the pH i s to create a ti trati on curve for the reacti on. A ti trati on
curve i s a graph of the pH pl otted agai nst the amount of ti trant (whats i n the buret). Fi gure
14.5 shows the ti trati on curve for a strong aci d ti trated wi th a strong base. Wi th di gi tal pH
meters, thi s pl otti ng must be done by hand, but wi th computer probes, the computer usual l y
pl ots the curve whi l e you are performi ng the ti trati on.
Hopeful l y you have had the opportuni ty to do ti trati ons i n your l aboratory, but i f you havent
(or i f you were l ost whi l e you were tryi ng to do them!), heres a l i ttl e refresher. Duri ng the
i ni ti al stages of the ti trati on, there i s very l i ttl e change i n pH. You add rel ati vel y l arge
amounts of base to the fl ask or beaker contai ni ng the aci d, and the pH i ncreases onl y sl i ghtl y.
However, al most al l at once, the pH sharpl y ri ses from a l ow, aci di c pH to a hi gh, basi c pH.
The graph goes strai ght up at thi s poi nt and the stoi chi ometri c amounts of aci d and base are
equal . Thi s poi nt i s known as the equi val ence poi nt of the ti trati on. I n thi s ti trati on, at the
equi val ence poi nt, the pH of the sol uti on i s 7.0. Remember HCl and NaOH react to form water
and NaCl . Si nce nei ther Na
1
nor Cl
2
can hydrol yze water, the pH i s compl etel y neutral , or 7.
The typi cal procedure i s to use an i ndi cator sol uti on that wi l l change col ors duri ng thi s ti me
of the ti trati on. Once the equi val ence poi nt i s passed, the sol uti on qui ckl y becomes basi c
because al l of the excess H
1
i ons from the HCl have combi ned wi th OH
2
. Subsequent
addi ti ons of sodi um hydroxi de wi l l create an excess of OH
2
.
The ti trati on curve for a strong aci d wi th a strong base l ooks l i ke the one i n Fi gure 14.5, and
you shoul d be fami l i ar wi th the shape. I f you pl otted the curve for a strong base bei ng ti trated
wi th a strong aci d, the curve woul d be a mi rror i mage of Fi gure 14.5the curve woul d start
wi th a hi gh pH and gradual l y sl ope downward unti l at the equi val ence poi nt, i t woul d drop
sharpl y to an aci di c pH and then conti nue i ts gradual descent.
mL NaOH
Equivalence point
14
13
12
11
10
9
8
7
6
5
4
3
2
0
1
p
H
Figure14.5
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Weak Acids with Strong Base
For weak aci ds bei ng ti trated wi th a strong base, there are three mai n di fferences i n the
ti trati on. The fi rst i s that the pH at the begi nni ng of the ti trati on i s hi gher si mpl y because the
aci d i s not as strong as a strong aci d. As wi th strong aci ds, the pH ri ses sl owl y at fi rst and
then begi ns to ri se qui ckl y near the equi val ence poi nt. However, near the equi val ence poi nt,
when the change becomes most rapi d (verti cal on the ti trati on curve), the range of pH val ues
i s much smal l er than the range for a strong aci d/strong base pai ri ng. For the thi rd mai n
di fference, the pH at the equi val ence poi nt i s not 7.
The mai n reason for the unusual behavi or i s the composi ti on of the weak aci d. The conjugate
base of the weak aci d creates a bufferi ng effect. As the hydroxi de i ons from the base react wi th
the aci d, the concentrati on of the conjugate base i ncreases. When the base has reacted wi th
al l of the hydrogen i ons from the aci d, the sol uti on contai ns an excess of the conjugate (sal t).
I f you recal l from the previ ous secti on, the conjugate base of a weak aci d wi l l hydrol yze water
to create a basi c sol uti on. So, i nstead of bei ng neutral at the equi val ence poi nt, the pH wi l l be
basi c. Addi ng addi ti onal base wi l l onl y enhance thi s effect.
For the ti trati on of a weak base wi th a strong aci d, the effect i s fai rl y si mi l ar. The mai n
di fference i s that the pH wi l l be l ower than 7 at the equi val ence poi nt. As the hydrogen i ons
i n the aci d neutral i ze the hydroxi de from the base, the concentrati on of the conjugate aci d
from the base wi l l i ncrease. I f you recal l , the conjugate aci ds of weak bases wi l l hydrol yze
water to create aci di c sol uti ons. Thi s wi l l cause the pH at the equi val ence poi nt to be aci di c.
Addi ti on of further aci d to the mi xture wi l l enhance thi s effect.
Of consi derabl e di fference wi th the ti trati ons of weak aci ds and weak bases are the bufferi ng
effects of the conjugate sal ts. The ti trati on curves (see Fi gure 14.6) al l contai n a bufferi ng
regi on near the equi val ence poi nt where most of the sol uti on consi sts of the conjugate base
(for a weak aci d ti trati on; a conjugate aci d for a weak base ti trati on).
mL NaOH
p
H
Figure14.6
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EXERCISES: ACID AND BASES
Multiple Choice
1. A mol ecul e or an i on i s cl assi fi ed as a
Lewi s base i f i t
(A) donates a proton to water.
(B) forms a bond by accepti ng a
pai r of el ectrons.
(C) forms a bond by donati ng a pai r
of el ectrons.
(D) accepts a proton from water.
(E) has resonance Lewi s structures.
2. What i s the H
1
(aq) concentrati on i n
0.05 M HCl O (aq)? (The K
a
for HCl O
i s 3.0 3 10
28
)
(A) 1.5 3 10
9
(B) 2.5 3 10
10
(C) 3.9 3 10
9
(D) 3.9 3 10
5
(E) 3.9 3 10
3
3. A 50.0 mL sampl e of 0.15 M NaOH i s
added to 50.0 mL of 0.10 M Ba(OH)
2
.
What i s the mol ar concentrati on of
OH(aq) i n the resul ti ng sol uti on?
(Assume that the vol umes are
addi ti ve.)
(A) 0.10 M
(B) 0.13 M
(C) 0.18 M
(D) 0.36 M
(E) 0.55 M
4. A bottl e of di sti l l ed vi negar pur-
chased at a supermarket was ti trated
wi th a 0.50 M NaOH sol uti on to
determi ne the content of aceti c aci d,
HC
2
H
3
O
2
. For 20.0 mi l l i l i ters of the
vi negar, 24.0 mi l l i l i ters of 0.50-mol ar
NaOH sol uti on was requi red. What
was the concentrati on of aceti c aci d
i n the vi negar i f no other aci d was
present?
(A) 1.6 M
(B) 0.80 M
(C) 0.60 M
(D) 0.40 M
(E) 0.25 M
5. HCN(aq) 1 H
2
O(l) H
3
O
1
(aq) 1
CN(aq)
I n the equi l i bri um represented above,
the speci es that act as bases i ncl ude
whi ch of the fol l owi ng?
I . CN
I I . H
2
O
I I I . HCN
(A) I I onl y
(B) I I I onl y
(C) I and I I
(D) I and I I I
(E) I I and I I I
6. What vol ume of 0.150-mol ar HCl i s
requi red to neutral i ze 25.0 mi l l i l i ters
of 0.120-mol ar Ba(OH)
2
?
(A) 20.0 mL
(B) 30 0 mL
(C) 40.0 mL
(D) 60.0 mL
(E) 80.0 mL
7. For oxoaci ds that vary onl y by the
number of oxygens (i .e., HAO, HAO
2
,
HAO
3
), whi ch of the fol l owi ng occurs
as the number of oxygen atoms
i ncreases?
(A) I t i s i mpossi bl e to predi ct the
aci d strength.
(B) The strength of the aci d
i ncreases.
(C) The strength of the aci d
decreases onl y i f A i s a non-
metal .
(D) The strength of the aci d
decreases onl y i f A i s a metal .
(E) The strength of the aci d
decreases whether A i s a
nonmetal or a metal .
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QUESTIONS 810 REFER TO THE FOLLOWING
GRAPHS:
I .
mL NaOH
Equivalence point
14
13
12
11
10
9
8
7
6
5
4
3
2
0
1
p
H
I I .
mL NaOH
p
H
I I I .
mL HC1
p
H
I V.
mL NaOH
p
H
8. Thi s graph coul d represent the
ti trati on curve of HC
2
H
3
O
2
.
(A) I
(B) I I
(C) I I I
(D) I V
(E) None of the graphs are an
accurate representati on.
ti trati on of a pol yproti c aci d.
(A) I
(B) I I
(C) I I I
(D) I V
ti trati on of NH
3
.
(A) I
(B) I I
(C) I I I
(D) I V
QUESTIONS 1112 REFER TO AQUEOUS
SOLUTIONS CONTAINING 1:1 MOLE RATIOS
OF THE FOLLOWING PAIRS OF SUBSTANCES.
ASSUME ALL CONCENTRATIONS ARE 1 M.
(A) NH
3
and NH
4
Cl
(B) HC
2
H
3
O
2
and NaC
2
H
3
O
2
(C) HCl and KCl
(D) KOH and NH
3
(E) NH
3
and HCl
11. Thi s represents an aci di c sol uti on
that i s not a buffer.
12. Thi s represents a buffer at pH , 7.
e
x
e
r
c
i
s
e
s
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Free Response
QUESTION 1
(A) 4.60 g of formi c aci d, HCHO
2
, i s mi xed wi th enough pure water to create 1.00
l i ters of sol uti on. K
a
for formi c aci d i s 1.7 3 10
24
. Cal cul ate the pH of the
sol uti on.
(B) 100 mL of 0.1 M HCl sol uti on i s mi xed wi th 100 mL of the formi c aci d sol uti on
descri bed i n part (A). Cal cul ate the [H
3
O
1
] of the resul ti ng sol uti on.
(C) A new sol uti on was mi xed wi th 0.10 mol of formi c aci d, HCHO
2
, and 0.15 mol of
sodi um formate, NaCHO
2
, di ssol ved i n enough water to make 1.00 l i ter of
sol uti on. What i s the pH of the resul ti ng sol uti on?
(D) I f 0.005 mol HCl i s bubbl ed through 1.00 l i ters of the sol uti on descri bed i n part
(C), what i s the pH of the resul ti ng sol uti on?
QUESTION 2
A 50.00 mL sampl e of 0.25 M benzoi c aci d, HC
7
H
5
O
2
, i s ti trated wi th 0.199 M NaOH sol uti on.
The K
a
of benzoi c aci d i s 6.3 3 10
25
.
(A) What i s the pH, pOH, and [H
3
O
1
] of the benzoi c aci d sol uti on pri or to the
ti trati on?
(B) How many mi l l i l i ters of NaOH are requi red to reach the equi val ence poi nt?
(C) What i s the pH of the sol uti on at the equi val ence poi nt?
(D) Whi ch of the fol l owi ng woul d be the best i ndi cator to use for thi s ti trati on?
Methyl red K
a
5 1 3 10
25
Cresol red K
a
5 1 3 10
28
Al i zari n yel l ow K
a
5 1 3 10
211
Justi fy your response.
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Multiple Choice
1. C
2. D
3. C
4. C
5. C
6. C
7. B
8. B
9. D
10. C
11. C
12. B
1. Thecorrect answer is(C). By defi ni ti on, Lewi s aci ds accept el ectron pai rs, and Lewi s
bases donate el ectrons.
2. The correct answer is (D). The fol l owi ng equi l i bri um cal cul ati on tabl e can be
constructed:
HCl O(aq) H
1
(aq) 1 Cl O
2
(aq)
HCl O H
1
Cl O
2
Start 0.05 0 0
D 2x 1x 1x
Fi ni sh 0.05 2 x 1x 1x
K
a
5
H ClO
HClO
+
[ ][ ]
[ ]
3.0 3 10
28
5
x x
x
x
x
( )( )
( )

( ) 0 05 0 05
2
. .
x 5 0 05 3 0 10
8
. .

( )
5 3.9 3 10
25
Doubl e-checki ng the shortcut, 0.05 2 3.9 3 10
25
5 0.050, we were justi fi ed wi th the
assumpti on that x coul d be di sregarded.
3. The correct answer is (C). The total [OH
2
] of the sol uti on wi l l equal the hydroxi de
i on concentrati on of NaOH, added to that of Ba(OH)
2
. The bi ggest mi sl eadi ng factor
here i s that the bari um hydroxi de wi l l donate two hydroxi de i ons to sol uti on. That
means the probl em wi l l be sol ved as:
~0.050 L NaOH!
S
0.15 mol NaOH
1.00 L
D
1
S
2 mol OH
2
1 mol Ba~OH!
2
D
~0.050 L Ba~OH!
2
!
S
0.10 mol Ba~OH!
2
1.00 L
D
5 0.0175 mol es OH
2
Dont forget the l ast step: You onl y have 100 mL so:
0.0175 mol OH
0.10 L sol uti on
5 0.18 M
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4. The correct answer is (C). At the equi val ence poi nt, the amount of hydroxi de from
the base i s bal anced wi th the H
1
of the aci d. Thi s can be determi ned usi ng the equati on
bel ow:
~0.50 M NaOH!~0.024 mL! 5 0.012 mol NaOH
0.012 mol NaOH 5 ~0.020 mL!@H
1
#
@H
1
# 5 0.60 M
5. Thecorrect answer is (C). Bases i n thi s reacti on woul d be consi dered the substances
that are accepti ng protons (Brnsted-Lowry defi ni ti on). I n the forward reacti on, H
2
O
recei ves a hydrogen to become a hydroni um i on. I n the reverse reacti on, CN
2
recei ves a
proton to become HCN. HCN donates a proton, whi ch makes i t an aci d.
6. The correct answer is (C). Neutral i zati on wi l l occur when the number of mol es of
hydrogen i ons added to the base equal s the number of mol es of hydroxi de i ons present
i n the base. The tri ck i n thi s questi on i s that bari um hydroxi de di ssoci ates to form two
mol es of hydroxi de i on per mol e of Ba(OH)
2
. The cal cul ati on woul d l ook as fol l ows:
S
0.150
mol
L
HCl
D
~X! 5
S
0.120
mol
L
Ba~OH!
2DS
2 mol OH
2
1 mol Ba~OH!
2
D
~0.025 L Ba~OH!
2
!
X 5 0.040 L 5 40.0 mL
7. The correct answer is (B). For oxoaci ds, as the number of oxygen atoms attached to
atom A i n the mol ecul e i ncreases, i t becomes easi er to remove the proton. Thi s wi l l
i ncrease the aci di ty of the oxoaci d.
8. Thecorrect answer is (B). The curve shown as choi ce I I i s the most l i ke a weak aci d.
The characteri sti cs that di fferenti ate i t from a strong aci d are the sl i ght i ni ti al i ncrease
i n pH at the i ni ti al addi ti on of base and the el ongated regi on pri or to and after the
equi val ence poi nt. Thi s i s where the conjugate base exhi bi ts a bufferi ng effect.
9. Thecorrect answer is (D). Pol yproti c aci ds di spl ay more than one equi val ence poi nt.
The di agram i n I V i s a typi cal exampl e of a pol yproti c aci d.
10. The correct answer is (C). Choi ce I I I i s the onl y possi bl e base among four choi ces,
maki ng i t the onl y possi bl e answer. I t i s al so representati ve of a weak base because of
the i ni ti al drop i n pH and the el ongated regi ons around the equi val ence poi nt.
11. The correct answer is (C). HCl i s a very strong aci d, whi ch means that the chl ori de
i on i s a very weak conjugate base. Thi s means the sol uti on i s not a buffer sol uti on. The
potassi um chl ori de i s real l y a di stracter i n thi s questi on. Al though Cl
2
i s present i n
each sal t, the common-i on effect i s onl y seen i n equi l i bri um systems. The reverse
reacti on for the di ssoci ati on of ei ther of these two woul d be so sl i ght i t woul d be
negl i gi bl e. However, because KCl does nothi ng to neutral i ze the aci d, the sol uti on woul d
be both aci di c and not a buffer.
12. The correct answer is (B). I n thi s answer, the common-i on effect i s seen wi th the
addi ti on of sodi um acetate. The
HC
2
H
3
O
2
C
2
H
3
O
2
2
equi l i bri um creates a buffer, whi ch i s al so
aci di c.
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Free Response
QUESTION 1
(A) pH 5 2.9. I n order to cal cul ate pH, you must know the [H
1
] concentrati on. The
K
a
expressi on wi l l al l ow you to determi ne the [H
1
] i f you know the concentrati on
of HCHO
2
. I n order to sol ve thi s probl em, you need to determi ne the mol ari ty of
the formi c aci d and then use thi s val ue to cal cul ate the [H
1
] and, ul ti matel y, the
pH. The cal cul ati on proceeds as fol l ows:
4.60 g HCHO
2
3
1 mol HCHO
46.0 g HCHO
2
2
5
0.10 mol HCHO
2
i n 1.00-l i ter sol uti on 5 0.10 M
HCHO
2
(aq) H
1
(aq) 1 CHO
2
2
(aq)
HCHO
2
H
1
CHO
2
Start 0.10 mol 0 0
D 2x 1x 1x
Fi ni sh 0.10 2 x 1x 1x
K
a
5
[H
1
] [CHO
2
2
]
[HCHO
2
]
1.7 3 10
25
5
x
~0.10 2 x!
5
x
2
0.10
x
2
5 1.7 3 10
26
x 5 1.3 3 10
23
Therefore, pH 5 2.9
(B) [H
3
O
1
] 5 1.7 3 10
24
HCHO
2
H
1
1 CHO
2
2
I n thi s probl em, you are goi ng to be deal i ng wi th the common-i on effect. Assume
that al l of the H
1
from the HCl i s goi ng to push the equi l i bri um to the l eft:
HCHO
2
(aq) H
1
(aq) 1 CHO
2
2
(aq)
HCHO
2
H
1
CHO
2
2
Start 0.10 mol 0.10 mol 0
D 2x 1x 1x
Fi ni sh 0.10 2 x 0.10 1 x 1x
K
a
5
[H
1
] [CHO
2
2
]
[HCHO
2
]
1.7 3 10
24
5
~0.10 1 x!~x!
~0.10 2 x!
5
0.10x
0.10
x 5 [H
1
] 5 [H
3
O
1
] 5 1.7 3 10
24
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www.petersons.com
(C) pH 5 4.0. Thi s i s a buffer sol uti on contai ni ng a weak aci d and i ts conjugate base.
I n thi s probl em, you set up the equi l i bri um cal cul ati on tabl e wi th amounts for
HCHO
2
and CHO
2
2
i n the start col umn:
HCHO
2
(aq) H
1
(aq) 1 CHO
2
2
(aq)
HCHO
2
H
1
CHO
2
2
Start 0.10 mol 0 0.15
D 2x 1x 1x
Fi ni sh 0.10 2 x x 0.15 1 x
K
a
5
[H
1
] [CHO
2
2
]
[HCHO
2
]
1.7 3 10
24
5
~x!~0.15 1 x!
~0.10 2 x!
5
0.15x
0.10
x 5 [H
1
] 5 1.1 3 10
24
pH 5 2l og [H
1
] 5 2l og (1.1 3 10
24
) 5 4.0
(D) pH 5 3.9. I n thi s probl em, you have to assume that the aci d wi l l i oni ze and the
H
1
i ons wi l l react compl etel y wi th any formate i ons i n sol uti on. Therefore, the
starti ng concentrati on of formate i on shoul d be decreased and the starti ng
concentrati on of formi c aci d i ncreased:
I ni ti al [HCHO
2
] 5 0.10 mol 1 0.005 mol 5 0.105 mol
I ni ti al [CHO
2
2
] 5 0.15 mol 2 0.005 mol 5 0.145 mol
HCHO
2
(aq) H
1
(aq) 1 CHO
2
2
(aq)
HCHO
2
H
1
CHO
2
Start 0.105 mol 0 0.145
D 2x 1x 1x
Fi ni sh 0.105 2 x x 0.145 1 x
K
a
5
[H
1
] [CHO
2
2
]
[HCHO
2
]
1.7 3 10
24
5
~x!~0.145 1 x!
~0.105 2 x!
5
0.145x
0.105
x 5 [H
1
] 5 1.2 310
24
pH 5 2l og [H
1
] 5 2l og (1.2 3 10
24
) 5 3.9
The Henderson-Hassel bal ch equati on al so produces:
pH 5 pK
a
1 l og
A
HA
[ ]
[ ]
pH 5 2l og (1.7 3 10
24
) 1 l og
0 145
0 105
.
.
_
,
5 3.9
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QUESTION 2
(A) [H1] 5 8.9 3 10
24
; pH 5 3.1; pOH 5 10.9. Pri or to the ti trati on, the pH of the
benzoi c aci d sol uti on must be determi ned usi ng an equi l i bri um cal cul ati on tabl e.
I ni ti al concentrati on of benzoi c aci d: 0.05 L 3 0.25 M 5 0.0125 mol HC
7
H
5
O
2
HC
7
H
5
O
2
(aq) H
1
(aq) 1 C
7
H
5
O
2
2
(aq)
HC
7
H
5
O
2
H
1
C
7
H
5
O
2
2
Start 0.0125 0 0
D 2x 1x 1x
Fi ni sh 0.0125 2 x x x
K
a
5
H CHO
HCHO
+
2
2
[ ][ ]
[ ]
6.3 3 10
25
5
x x
x
x ( )( )
( )

0 0125 0 0125
2
. .
x 5 0 0125 6 3 10
5
. .

( )
( )
5 8.9 3 10
24
[H1] 5 8.9 3 10
24
pH 5 2l og (8.9 3 10
24
) 5 3.1
pOH can be cal cul ated from the equati on pH 1 pOH 5 14
pOH 5 14 2 pH 5 10.9
(B) NaOH 5 62.8 mi l l i l i ters. I n the ti trati on, the equati on for the neutral i zati on i s:
HC
7
H
5
O
2
(aq) 1 OH
2
(aq) H
2
O(l) 1 C
7
H
5
O
2
2
(aq)
The equi val ence poi nt wi l l be reached when the number of mol es of NaOH equal s
the number of mol es of HC
7
H
5
O
2
. Thi s i s cal cul ated as fol l ows:
Amount of benzoi c aci d to be neutral i zed:
0.05 L 3 0.25 M 5 0.0125 mol HC
7
H
5
O
2
Therefore, 0.0125 mol of NaOH are requi red to reach the equi val ence poi nt:
0.0125 mol NaOH 3
1 L soln
0.199 mol NaOH
5 0.0628 L or 62.8 mi l l i l i ters.
(C) pH 5 8.20. At the equi val ence poi nt, the equati on has essenti al l y reversed i tsel f.
Pri or to ti trati on, the equi l i bri um was as fol l ows:
HC
7
H
5
O
2
(aq) H
1
(aq) 1 C
7
H
5
O
2
2
(aq)
Upon addi ti on of the NaOH, the OH
2
i ons react compl etel y wi th the benzoi c aci d
i n a reacti on that can be consi dered i rreversi bl e:
HC
7
H
5
O
2
(aq) 1 OH
2
(aq) H
2
O(l) 1 C
7
H
5
O
2
2
(aq)
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The reacti on uses up al l OH
2
and converts al l HC
7
H
5
O
2
to C
7
H
5
O
2
2
. The
benzoate i ons then wi l l establ i sh an equi l i bri um system as fol l ows:
C
7
H
5
O
2
2
(aq) 1 H
2
O(l) HC
7
H
5
O
2
(aq) 1 OH
2
(aq)
The next step i s cri ti cal . When you determi ne the starti ng concentrati on of
benzoate i on, you must do so by di vi di ng the number of mol es of benzoate by the
vol ume of the new sol uti on, whi ch wi l l consi st of the 50.00 mL of the ori gi nal
sol uti on 162.8 mL of added sol uti on. The neutral i zati on created 0.0125 mol
C
7
H
5
O
2
2
, so the mol ari ty i s:
0.0125 mol C H O
0.050 L + 0.0628 L
7 5 2
( )
5 0.111 M C
7
H
5
O
2
2
Now, an equi l i bri um tabl e can be constructed as fol l ows:
C
7
H
5
O
2
2
(aq) HC
7
H
5
O
2
(aq) 1 OH
2
(aq)
C
7
H
5
O
2
2
HC
7
H
5
O
2
OH
2
Start 0.111 0 0
D 2x 1x 1x
At thi s poi nt, the cal cul ati on becomes a l i ttl e di fferent. Because the benzoate i on
i s a base, the equi l i bri um constant expressi on must be the base i oni zati on
constant, K
b
. You havent been gi ven the val ue of K
b
, however, so you wi l l have to
generate i t usi ng Equati on 13.8:
K
w
5 K
a
K
b
K
b
5
K
K
w
a
K
b
5
1 0 10
6 3 10
14
5
.
.
5 1.6 10
210
Now, the equi l i bri um expressi on can be set up:
K
b
5
HC H O OH
C H O
7 5
7 5
2
2
[ ][ ]
[ ]
1.6 3 10
210
5
x x
x
( )( )
( ) 0 0167 .
Maki ng the assumpti on that x wi l l be qui te smal l , we can then sol ve for x:
x 5 1 6 10 0 0167
10
. .
( )
( )
5 1.6 3 10
26
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At thi s poi nt, you know that the [OH
2
] 5 1.6 3 10
26
. There i s more than one way
to proceed from here. Two of the more obvi ous ways are to use the hydroxi de
concentrati on to cal cul ate the pOH, and then convert that to a pH val ue. The
other way i s to convert the hydroxi de i on concentrati on to the hydrogen i on
concentrati on and cal cul ate the pH di rectl y. We wi l l use the l atter to cal cul ate
the pH:
[OH
2
] 5 1.6 3 10
26
[OH
2
][H
1
] 5 1.0 3 10
214
[H
1
] 5
1.0 3 10
214
1.6 3 10
26
5 6.25 3 10
29
pH 5 2l og [H
1
] 5 2l og (6.25 3 10
29
) 5 8.20
(D) Because the pH at the equi val ence poi nt i s 8.20, the best i ndi cator to use (of the
three l i sted) i s cresol red. Wi th a K
a
of 1 3 10
28
, the pK
a
woul d be 8. Thi s
suggests that i t wi l l be effecti ve i n the pH ranges near 8. Because thi s i s a
ti trati on of a weak aci d, the equi val ence poi nt wi l l be found i n a more narrow
range of pH val ues than for a strong aci d. The other two i ndi cators are effecti ve
at pH val ues that may be too l ow (methyl red) or too hi gh (al i zari n yel l ow) to
detect the equi val ence poi nt.
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SUMMING IT UP
Arrheni us aci ds i ncrease the concentrati on of H
1
i ons i n sol uti on, whi l e Arrheni us bases
i ncrease the concentrati on of OH
2
i n sol uti on. The strongest aci ds and bases are
Arrheni us aci ds and bases.
Brnsted-Lowry aci ds donate protons i n sol uti on. Brnsted-Lowry bases accept protons i n
sol uti on. The defi ni ti ons for Brnsted-Lowry aci ds and bases are more broad and al l ow
for the consi derati on of many more substances than ei ther of the other two defi ni ti ons.
When a Brnsted-Lowry aci d donates a proton, the remai ni ng ani on i s known as a
conjugate base. When a Brnsted-Lowry base accepts a proton, the protonated base i s
known as a conjugate aci d.
Strong aci ds and bases i oni ze compl etel y i n sol uti on, whi l e weak aci ds and bases parti al l y
i oni ze. The parti al i oni zati on of weak aci ds and bases creates sol uti ons i n whi ch an
equi l i bri um i s establ i shed.
Lewi s aci ds are substances that form a coval ent bond by accepti ng an el ectron pai r from
another substance.
Lewi s bases are substances that form a coval ent bond by donati ng an el ectron pai r to
another substance.
The pH scal e consi sts of a range of val ues from 0214 that descri be the concentrati on of
hydrogen i ons i n a sol uti on. The equati on used to cal cul ate pH i s pH 5 2l og [H
1
].
The neutral pH of 7 i s based on the fact that water sel f-i oni zes to form hydroni um
(hydrogen) i ons and hydroxi de i ons i n equal amounts. The concentrati on of these i ons i s
equal to 1.0 3 10
27
, whi ch corresponds to a pH of 7.
The concentrati on of hydroxi de i ons can be expressed usi ng pOH val ues.
The hydrogen i on concentrati on of weak aci ds must be determi ned by consi deri ng the
equi l i bri um concentrati ons of al l i ons i n the equi l i bri um mi xture.
K
a
i s the term used as the equi l i bri um constant for weak aci d equi l i bri a.
K
b
i s the term used as the equi l i bri um constant for weak base equi l i bri a.
The sal ts of strong aci ds and strong bases produce neutral sol uti ons. Sal ts from strong
aci ds and weak bases yi el d aci di c sol uti ons, whi l e sal ts from weak aci ds and strong bases
yi el d basi c sol uti ons.
The common-i on effect i s observed when an equi l i bri um system i s di srupted by the
addi ti on of a sal t contai ni ng one of the i ons i n the equi l i bri um mi xture. The effect of thi s
addi ti on, as predi cted by Le Chtel i ers Pri nci pl e, i s to shi ft the equi l i bri um away from
the common i ons.
Buffer sol uti ons are created by pai ri ng a weak aci d wi th a sal t of i ts conjugate base or a
base wi th a sal t of i ts conjugate aci d. Buffer sol uti ons mai ntai n a rel ati vel y stabl e pH
when smal l amounts of aci ds or bases are added.
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An aci d-base ti trati on i s a procedure that i s typi cal l y used to determi ne the concentrati on
of an unknown aci d or base sol uti on. I n a ti trati on, a strong or base or known
concentrati on i s added to a base or aci d of unknown concentrati on. An i ndi cator sol uti on
i s typi cal l y uti l i zed to mark the equi val ence poi nt, or the poi nt at whi ch the
stoi chi ometri c amounts of aci d and base are equi val ent.
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Additional Equilibrium
Concepts
OVERVIEW
The solubility-product constant, K
sp
Solubility
The ion product
Factors that affect solubility
The common-ion effect
The effect of pH on solubility
Complex ions
Miscellaneous topics
Coordination complexes
Nomenclature of coordination complexes
Summing it up
I n thi s chapter, we wi l l extend the concepts of equi l i bri um that have been
di scussed i n previ ous chapters. I n Chapter 10 we di scussed the concept of
equi l i bri um i n rel ati on to saturated sol uti ons i n whi ch an equi l i bri um was
establ i shed between sol vated i ons and undi ssol ved sol ute. I n Chapter 11 we
di scussed the sol ubi l i ty of di fferent sal ts when we l ooked at the formati on of
preci pi tates. I n thi s chapter you wi l l see the connecti on between these two
i deas wi th the i ntroducti on of the sol ubi l i ty product constant, K
sp
, whi ch i s a
quanti tati ve means of descri bi ng sol ubi l i ty equi l i bri a. Thi s measure hel ps to
predi ct and expl ai n the preci pi tati on of di fferent sal ts from sol uti on. You wi l l
al so see how the common-i on effect, temperature, and pH affect sol ubi l i ty.
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c
h
a
p
t
e
r
1
5
353
THE SOLUBILITY-PRODUCT CONSTANT, K
sp
So far, you have l earned about a number of di fferent equi l i bri um constants, i ncl udi ng K
p
, K
c
,
K
a
, K
b
, and K
w
. I n thi s secti on, you wi l l l earn about another equi l i bri um constant, K
sp
. I f you
recal l from Chapter 10, when a sol ubl e sol ute i s pl aced i nto a sol vent i t wi l l di ssol ve unti l the
sol uti on becomes saturated. At the poi nt of saturati on, an amount of sol i d sol ute exi sts i n
equi l i bri um wi th the surroundi ng sol uti on. One thi ng you wi l l l earn i n thi s chapter i s that
even when a substance i s consi dered i nsol ubl e, a smal l amount of the substance wi l l sti l l
di ssol ve. One of the i nsol ubl e substances you l earned about i n Chapter 10 was the bri ght
yel l ow preci pi tate l ead (I I ) i odi de, PbI
2
. I f we assume for a moment that i t i s sol ubl e i n very
smal l amounts (whi ch i t i s), we can consi der the equi l i bri um shown bel ow:
PbI
2
(s) Pb
21
(aq) 1 2I
2
(aq)
Thi s equi l i bri um i s known as a heterogeneous equi l i bri um, whi ch i s to say that i t consi sts
of substances that are i n di fferent states (phases). I f you recal l from Chapter 13, the
equi l i bri um constant expressi ons for such equi l i bri a do not contai n the concentrati ons of
l i qui ds or sol i ds. The equi l i bri um expressi on for thi s reacti on wi l l descri be the degree to whi ch
the sol i d di ssol ves i n sol uti on, whi ch i s another way to say the degree to whi ch i t i s sol ubl e.
And si nce the sol i d i s not shown i n the equi l i bri um expressi on, the equi l i bri um constant wi l l
express the product of the concentrati ons of the di ssol ved sol ute i ons. For thi s reason, the
equi l i bri um constant i s referred to as the sol ubi l i ty-product constant. For thi s equi l i bri um,
the sol ubi l i ty-product constant, K
sp
i s:
K
sp
5 [Pb
21
][I
2
]
2
One i mportant consi derati on i s the absence of the sol i d from the expressi on. Even though the
sol i d (PbI
2
) i s not shown i n the equi l i bri um expressi on, i t must be present i n the sol uti on i n
order for the system to be at equi l i bri um. I n probl ems i nvol vi ng K
sp
, you wi l l usual l y
encounter the i nformati on that some undi ssol ved sol i d remai ns, whi ch i s your cue to know
that i t i s okay to use the K
sp
expressi on.
The val ue of K
sp
for PbI
2
at 25C i s 9.8 3 10
29
. Smal l numbers l i ke thi s are a good i ndi cator
that the materi al i s not very sol ubl e.
SOLUBILITY
I t i s i mportant to make the di sti ncti on between sol ubi l i ty and the sol ubi l i ty product constant.
Sol ubi l i ty refers to the amount of a substance that can di ssol ve to form a saturated sol uti on.
The sol ubi l i ty of a substance i s usual l y expressed i n grams sol ute per l i ter of sol uti on (g/L).
Someti mes, however, i t i s descri bed i n mol es sol ute per l i ter of sol uti on, i n whi ch case i t i s
referred to as the mol ar sol ubi l i ty of the substance. At any gi ven temperature, the
sol ubi l i ty-product constant, K
sp
, for a sol ute remai ns constant. The sol ubi l i ty of a sol ute i s not
necessari l y constant because i t i s affected by the concentrati ons of other di ssol ved substances.
I n the next secti on we wi l l l ook at some factors that affect the sol ubi l i ty of a sol ute.
One type of cal cul ati on that you may be asked to perform i s the determi nati on of the
concentrati on of an i on i n sol uti on when gi ven the K
sp
, or you may be asked to cal cul ate the
K
sp
when gi ven the concentrati on of an i on i n sol uti on. The two sampl e probl ems that fol l ow
wi l l demonstrate these techni ques.
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Sample: Sol i d cal ci um phosphate, Ca
3
(PO
4
)
2
, i s added to a sampl e of pure water at 25C and
sti rred for an extended peri od of ti me unti l i t i s certai n that equi l i bri um has been
establ i shed. After several days, a smal l amount of sol i d cal ci um phosphate i s sti l l
present on the bottom of the reacti on vessel . An anal ysi s of the sol uti on shows that
the concentrati on of cal ci um i on i s 3.42 3 10
27
M. Cal cul ate K
sp
for Ca
3
(PO
4
)
2
.
Answer: The fi rst thi ng you need to do i s wri te the bal anced equati on for the equi l i bri um:
Ca
3
(PO
4
)
2
(aq) 3Ca
21
(aq) 1 2PO
4
32
(aq)
From the bal anced equati on, the equi l i bri um expressi on can be wri tten as:
K
sp
5 [Ca
21
]
3
[PO
4
32
]
2
We know the concentrati on of Ca
21
, but we wi l l have to use stoi chi ometri c
rel ati onshi ps to determi ne the concentrati on of PO
4
32
:
[PO
4
32
] 5
3.42 10 mol Ca
L
7 2

_
,
+
2 mol PO
3 mol Ca
4
2
2+
_
,
5 2.28 3 10
27
M
Wi th thi s val ue, you can now cal cul ate K
sp
:
K
sp
5 [Ca
21
]
3
[PO
4
32
]
2
5 (3.42 3 10
27
)
3
(2.28 3 10
27
)
2
5 2.07 3 10
233
Cal ci um phosphate i s not a very sol ubl e compound.
Sample: The K
sp
for si l ver chromate, Ag
2
CrO
4
, i s 1.12 3 10
212
. What i s the mol ar sol ubi l i ty
of Ag
2
CrO
4
?
Answer: You sti l l must start out by wri ti ng the sol ubi l i ty equi l i bri um and sol ubi l i ty product
expressi on:
Ag
2
CrO
4
(s) 2Ag
1
(aq) 1 CrO
4
22
(aq) K
sp
5 [Ag
1
]
2
[CrO
4
22
]
Next, you wi l l set up an equi l i bri um cal cul ati on tabl e:
Ag
2
CrO
4
(s) 2Ag
1
(aq) 1 CrO
4
22
(aq)
Ag
2
CrO
4
2Ag
1
CrO
4
22
Start 0 0
D 12x 1x
Fi ni sh 2x x
Substi tuti ng the val ues i nto the K
sp
expressi on:
K
sp
5 [Ag
1
]
2
[CrO
4
22
]
1.12 3 10
212
5 [2x]
2
[x] 5 4x
3
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Chapter 15: Additional Equilibrium Concepts 355
www.petersons.com
Sol vi ng for x, we fi nd that x i s:
x 5
3
1.12 3 10
212
4
5 6.54 3 10
25
Si nce x i s the stoi chi ometri c equi val ent of Ag
2
CrO
4
, the mol ar sol ubi l i ty wi l l be
6.54 3 10
25
M.
THE ION PRODUCT
Before we begi n consi deri ng shi fts i n an equi l i bri um system, we need a quanti tati ve way to
descri be the state of the system at any ti me, whether i t has establ i shed equi l i bri um or not. I n
Chapter 13, you l earned about the reacti on quoti ent, Q, whi ch was used to descri be
equi l i bri um systems. I n sol ubi l i ty equi l i bri a, were not real l y deal i ng wi th a quoti entjust a
product. Because the expressi on i s the product of the concentrati ons of two di fferent i ons, the
equi l i bri um expressi on that descri bes sol ubi l i ty equi l i bri a i s known as the i on product. Q i s
cal cul ated i n the same way as K
sp
, except i t does not necessari l y descri be a system at
equi l i bri um. Referri ng to our i ni ti al exampl e, for the equi l i bri um shown bel ow
PbI
2
(s) Pb
21
(aq) 1 2I
2
(aq)
the i on product i s:
Q 5 [Pb
21
][I
2
]
2
The val ue of Q can be i nterpreted accordi ng to three possi bl e rel ati onshi ps between Q and
K
sp
:
Q . K
sp
Thi s condi ti on means that the concentrati on of i ons i s hi gher than i t i s at
equi l i bri um. The way to get ri d of the excess i ons i s for them to form
addi ti onal sol i d (preci pi tate). Thi s process wi l l occur unti l Q 5 K
sp
.
Q , K
sp
Thi s means that the concentrati on of i ons i s smal l er than i t shoul d be. The
way to i ncrease the concentrati on of i ons i s for more of the sol i d to di ssol ve
unti l Q 5 K
sp
.
Q 5 K
sp
The sol uti on i s at equi l i bri um. That means the sol uti on i s saturated and there
i s some sol i d present.
These rel ati onshi ps can be used for more than just descri bi ng the status of a sol i d and i ts
consti tuent i ons. Another useful appl i cati on i s to determi ne i f a preci pi tate wi l l form from two
di fferent sol uti ons. For i nstance, si l ver ni trate i s sol ubl e i n water. Potassi um chromate i s al so
sol ubl e (as are al l potassi um sal ts). I f these two sol uti ons are mi xed together, two possi bl e
products can form: potassi um ni trate and si l ver chromate. Potassi um ni trate i s sol ubl e, but
si l ver chromate i s not. But what i f very di l ute sol uti ons of each were added together? I s there
a poi nt at whi ch the sol uti ons woul d be so di l ute that no preci pi tate woul d form? The i on
product tel l s us that the answer i s a defi ni te, Yes. I n order for a preci pi tate to form, the
val ue of Q must exceed K
sp
. I f i t does not, no preci pi tate wi l l form. Lets take a l ook at a
probl em that shows thi s.
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Sample: Wi l l a preci pi tate form when 0.10 L of 1.0 3 10
24
M AgNO
3
i s mi xed wi th 0.10 L of
2.5 3 10
24
M K
2
CrO
4
? K
sp
for Ag
2
CrO
4
5 1.12 3 10
212
?
Answer: I n order for Ag
2
CrO
4
to preci pi tate, Q wi l l have to exceed K
sp
. The fi rst thi ng to do
i s cal cul ate Q.
The di ssoci ati on of Ag
2
CrO
4
wi l l establ i sh the fol l owi ng equi l i bri um:
Ag
2
CrO
4
(s) 2Ag
1
(aq) 1 CrO
4
22
(aq)
Therefore, the i on product wi l l be:
Q 5 [Ag
1
]
2
[CrO
4
22
]
We need to determi ne the concentrati ons of each i on to cal cul ate the i on product. There are a
few thi ngs to keep i n mi nd as we do thi s. Fi rst, when the two sol uti ons are added together, the
total vol ume i ncreases to 0.10 L 1 0.10 L 5 0.20 L. Second, we need to determi ne the number
of mol es of each i on, and then cal cul ate the mol ari ty based on the new vol umes.
I n 0.10 L of 1.0 3 10
24
M AgNO
3
, the number of mol es of Ag
1
i ons i s 0.10 L 3
1.0 10 mol
L
4
_
,
5 1 3
10
25
mol Ag
1
(we dont care about the ni trate).
The concentrati on of Ag
1
i n 0.20 L of sol uti on (the new vol ume) i s:
[Ag
1
] 5
1.0 10 mol
0.20 L
5
5 5.0 3 10
25
M
Next, we need the concentrati on of chromate, whi ch wel l determi ne i n the same way:
0.10 L 3
2 10 mol
L
4
.5
_
,
5 2.5 3 10
25
mol CrO
4
22
whi ch i n 0.20 L of sol uti on has the concentrati on:
[CrO
4
22
] 5
2 10 mol
0.20 L
5
.5
5 1.25 3 10
24
M
Wi th both concentrati ons, we can cal cul ate the i on product:
Q 5 [Ag
1
]
2
[CrO
4
22
] 5 (5.0 3 10
25
)
2
(1.25 3 10
24
) 5 3.1 3 10
213
Because Q , K
sp
, no preci pi tati on wi l l occur.
You Try It!
Wi l l the bri ght yel l ow preci pi tate, PbI
2
, form 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 ? K
sp
for PbI
2
i s 9.8 3 10
29
.
Answer: Q 5 5.4 3 10
26
; Q . K
sp
. Yes, a preci pi tate wi l l form.
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FACTORS THAT AFFECT SOLUBILITY
A major factor that affects the sol ubi l i ty of sol utes i s temperature. Most substances become
more sol ubl e at hi gher temperatures. Thi s i s somethi ng you have probabl y had experi ence
wi th i n the past as you tri ed to di ssol ve thi ngs (that you are ei ther goi ng to eat or dri nk).
There are some substances that become l ess sol ubl e at hi gher temperatures, but they are
more the excepti on than the rul e. The three addi ti onal factors that we are goi ng to consi der i n
thi s chapter are the common-i on effect, pH, and the presence of compl exi ng agents.
THE COMMON-ION EFFECT
You were fi rst i ntroduced to the common-i on effect i n the previ ous chapter on aci ds and bases.
The basi c pri nci pl e behi nd the effect rel ates back to Le Chtel i ers Pri nci pl e, whi ch was fi rst
i ntroduced i n Chapter 13. I f you recal l , one aspect of Le Chtel i ers Pri nci pl e states that an
i ncrease i n the concentrati on of a reactant wi l l shi ft the equi l i bri um of the system i n a way
that wi l l rel i eve the di stress, or that wi l l hel p reduce the concentrati on of the newl y added
reactant. When an i oni c sol ute di ssol ves, i t i s broken i nto i ts consti tuent i ons. When
equi l i bri um i s establ i shed, the di ssol ved sol ute i s i n equi l i bri um wi th i ts sol i d. At thi s poi nt,
i f any of the consti tuent i ons are added, they wi l l cause a shi ft i n the equi l i bri um.
I t i s not necessary that these i ons come from the ori gi nal sol ute, however. For exampl e, i n a
sol uti on of si l ver chl ori de at equi l i bri um, i f si l ver ni trate i s added i t wi l l di ssoci ate to generate
addi ti onal si l ver i ons. As Le Chtel i ers Pri nci pl e predi cts, the presence of these addi ti onal
si l ver i ons wi l l dri ve the equi l i bri um to the l eft, causi ng the preci pi tati on of si l ver chl ori de. Or,
as you l earned i n the l ast secti on, the i ncrease i n si l ver i ons wi l l i ncrease the i on product, Q,
maki ng i t greater than K
sp
. The system can onl y restore i tsel f by the preci pi tati on of si l ver
chl ori de. I n the sampl e that fol l ows, we wi l l l ook at a quanti tati ve exampl e of the common-i on
effect.
Sample: Cal cul ate the mol ar sol ubi l i ty of stronti um sul fate, SrSO
4
, i n 0.25 M sodi um
sul fate, Na
2
SO
4
. K
sp
for stronti um sul fate i s 3.44 3 10
27
.
Answer: Thi s probl em i s very si mi l ar to sampl e 2 i n the sol ubi l i ty secti on of the chapter. The
onl y di fference wi th thi s one i s that the starti ng concentrati on of sul fate i on i s not
zero. You must al so assume that because al l sodi um sal ts are hi ghl y sol ubl e, al l of
the sodi um sul fate has di ssol ved. Sol vi ng thi s probl em wi l l requi re us to determi ne
the concentrati ons of the consti tuent i ons at equi l i bri um. Our fi rst step i s to set up
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an equi l i bri um tabl e. The concentrati on of sul fate i on i s 0.25 M at the start of the
tabl e, si nce thi s i s the concentrati on of sul fate i n the sodi um sul fate sol uti on:
SrSO
4
(s) Sr
21
(aq) 1 SO
4
22
(aq)
SrSO
4
(s) Sr
21
SO
4
22
Start 0 0.25
D 1x 1x
Fi ni sh x 0.25 1 x
K
sp
5 [Sr
21
][ SO
4
22
] 5 (x)( 0.25 1 x)
Were goi ng to make the approxi mati on that x wi l l be smal l enough that
0.25 1 x ' 0.25; 3.44 3 10
27
5 (x)(0.25):
x 5
3 44 10
7
.

0.25
5 1.4 3 10
26
M
To hel p you get a feel for the common-i on effect, l ets compare the mol ar sol ubi l i ty
i n the sodi um sul fate sol uti on wi th that i n pure water. The equi l i bri um tabl e woul d
be si mi l ar except the i ni ti al concentrati on of sul fate i on woul d be 0, whi ch woul d
make the fi nal concentrati on of sul fate i on x. The mol ar sol ubi l i ty woul d be
cal cul ated as fol l ows:
K
sp
5 [Sr
21
][ SO
4
22
] 5 (x)(x) 5 x
2
x 5
3 44 10
7
.

5 5.9 3 10
24
Noti ce how the sol ubi l i ty i ncreases because of the absence of the addi ti onal
sul fate i on.
You Try It!
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,
K
2
SO
4
, K
sp
for BaSO
4
i s 1.08 3 10
210
.
Answer: 5.4 3 10
29
M
THE EFFECT OF pH ON SOLUBILITY
Thi s secti on wi l l i ntegrate materi al from thi s chapter wi th materi al from the previ ous
chapter. I n Chapter 14, we l ooked at sal ts composed of strong and weak aci ds and bases. We
saw that these sal ts have characteri sti c behavi ors i n sol uti on. So far i n thi s chapter, we have
not consi dered the pH of the sol uti ons. Were goi ng to connect these two i deas to consi der the
sol ubi l i ti es of sal ts i n non-neutral sol uti ons.
Lets begi n wi th a conceptual exampl e by consi deri ng the sal t magnesi um hydroxi de,
Mg(OH)
2
, whi ch i s a common i ngredi ent i n many over-the-counter antaci ds. Magnesi um
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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hydroxi de i s somewhat sol ubl e i n water, has a K
sp
5 5.61 3 10
212
, and mai ntai ns the
fol l owi ng equi l i bri um:
Mg(OH)
2
(s) Mg
21
(aq) 1 2OH
2
(aq)
I f a strong aci d, such as HCl i s added to the sol uti on, the hydrogen i ons wi l l react wi th the
hydroxi de i ons i n sol uti on to form water mol ecul es. Therefore, the addi ti on of a strong aci d
wi l l decrease the concentrati on of hydroxi de i ons. The i on product, Q, wi l l decrease. Our
fri end Le Chtel i er woul d tel l us that at thi s poi nt the equi l i bri um wi l l shi ft to the ri ght to
compensate for the l oss of the hydroxi de i ons. The Mg(OH)
2
wi l l conti nue to di ssoci ate unti l
equi l i bri um i s restored. I f addi ti onal HCl i s added to the sol uti on, i t wi l l dri ve the equi l i bri um
to the ri ght agai n. I f suffi ci ent aci d i s added, al l of the Mg(OH)
2
wi l l di ssol ve.
Thi s process wi l l occur wi th any sal t whose ani on i s basi c. Ani ons that are the most basi c are
affected the most by changes i n pH. Sal ts whose ani ons are from strong aci ds have vi rtual l y
no basi ci ty and wi l l therefore be unaffected by changes i n the pH.
Sample: For whi ch of the fol l owi ng i s pH l i kel y to affect the sol ubi l i ty?
a. BaSO
4
b. BaF
2
c. CaCO
3
d. MnS
e. AuCl
3
Answer: The cri teri a that must be consi dered for each of these i s the basi ci ty of the ani on.
The more basi c the ani on, the more pH wi l l affect the sol ubi l i ty.
a. The sul fate i on SO
4
22
i s a very weak base and wi l l not be affected much by
changes i n pH. However, because i t i s a very weak base, the sol ubi l i ty can be
affected sl i ghtl y i n very strong aci ds.
b. F
2
i s the conjugate base of a weak aci d, whi ch means i t i s a fai rl y strong base.
As a resul t, i t wi l l react wi th the excess hydrogen i n an aci di c sol uti on. Thi s
wi l l decrease the [F
2
], whi ch wi l l cause more BaF
2
to di ssol ve to restore
equi l i bri um.
c. CaCO
3
wi l l be affected by pH. CO
3
22
i s a basi c ani on and can combi ne wi th two
hydrogen i ons. Thi s wi l l cause addi ti onal CaCO
3
to di ssol ve i n order to restore
equi l i bri um.
d. S
22
i s the conjugate base of a weak aci d. I t wi l l combi ne wi th two hydrogen i ons
and force more MnS to di ssol ve.
e. Cl
2
i s the conjugate base of a very strong aci d and wont react wi th excess
hydrogen i on. The sol ubi l i ty of AuCl
3
wi l l be unaffected by pH.
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You Try It!
For each of the fol l owi ng three pai rs, sel ect the sal t whose sol ubi l i ty wi l l be affected
most by a change i n pH.
1. Ca(NO
3
)
2
, Ca(OH)
2
2. Mg
3
(PO
4
)
2
, MgCl
2
3. SrSO
4
, SrS
Answers:
1. Ca(OH)
2
2. Mg
3
(PO
4
)
2
3. SrS
COMPLEX IONS
I n the l ast secti on we focused on the ani ons of the di ssol ved sol utes, but i n thi s secti on we wi l l
l ook at the cati ons. Metal i ons can act as Lewi s aci dswhi ch, as you recal l , means they can be
el ectron-pai r acceptors when they are i n the presence of Lewi s bases (el ectron pai r donors).
One of the more common Lewi s bases to i nteract wi th metal i ons i n thi s way i s ammoni a.
These i nteracti ons are most common among the transi ti on metal s. One exampl e of such an
i nteracti on i s that of the si l ver i on and ammoni a. Si l ver chl ori de i s not very sol ubl e i n water
(the K
sp
i s 1.77 3 10
210
) but i s qui te sol ubl e i f ammoni a i s added to the sol uti on. The
phenomenon can be understood by l ooki ng at the fol l owi ng equati ons:
AgCl (s) Ag
1
(aq) 1 Cl
2
(aq)
Thi s i s the normal di ssol vi ng of si l ver chl ori de. Now, i f ammoni a i s added, an addi ti onal
equi l i bri um occurs:
Ag
1
(aq) 1 2NH
3
(aq) Ag(NH
3
)
2
1
(aq)
Because thi s second equi l i bri um removes si l ver i ons from sol uti on, i t shi fts the equi l i bri um of
the fi rst reacti on to the ri ght, causi ng addi ti onal AgCl to di ssol ve. Ag(NH
3
)
2
1
i s an exampl e of
a compl ex i on, whi ch i s a term used to descri be an i on that forms between a metal i on and
Lewi s bases. Whi l e the di ssol vi ng of si l ver chl ori de i s not hi ghl y favorabl e (as evi dent by the
smal l K
sp
), the formati on of the compl ex i on i s. The equi l i bri um constant used to descri be the
formati on of a compl ex i on i s known as the formati on constant, K
f
. The K
f
for the formati on of
Ag(NH
3
)
2
1
i s 1.7 3 10
7
and i s cal cul ated by the expressi on:
K
f
5
@Ag~NH
3
!
2
1
#
@Ag
1
# @NH
3
#
2
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Amphoterism
I f you recal l from Chapter 14, the term amphoteri c refers to a substance that can act as
ei ther an aci d or a base. Many metal oxi des and hydroxi des that are fai rl y i nsol ubl e i n water
are qui te sol ubl e i n strongl y aci di c and basi c sol uti ons. These materi al s can di ssol ve i n both
aci ds and bases because they are amphoteri cthat i s, they are capabl e of acti ng l i ke aci ds or
bases. One exampl e i s zi nc hydroxi de, Zn(OH)
2
. Zi nc hydroxi de i s qui te i nsol ubl e i n water
(K
sp
5 3 3 10
217
). However, i f pl aced i n a strong aci d, the hydroxi de i on reacts wi th the
hydrogen i on i n the aci d i n the fol l owi ng way:
Zn(OH)
2
(s) 1 2H
1
(aq) Zn
21
(aq) 1 2H
2
O(l)
However, zi nc hydroxi de can al so form a compl ex i on wi th hydroxi de i ons, maki ng i t sol ubl e i n
bases, as shown i n thi s reacti on:
Zn(OH)
2
(s) 1 2OH
2
(aq) Zn(OH)
4
22
(aq)
K
f
for Zn(OH)
4
22
i s 2.8 3 10
15
, maki ng thi s a very favorabl e reacti on.
MISCELLANEOUS TOPICS
There are two topi cs that are somewhat rel ated to the materi al i n thi s chapter. One of them i s
frequentl y referred to i n questi ons, whi l e the second onl y rarel y pops up. The fi rst deal s wi th
the col ors of vari ous substances; at l east one mul ti pl e-choi ce questi on usual l y refers to i t. The
second topi c i s the formati on of compl exes, l i ke the ones menti oned i n the previ ous secti on,
but i t goes a bi t beyond the subject as i t i s addressed here. Occasi onal l y a questi on about the
nomencl ature of compl ex i ons appears, so wel l address that here (for l ack of a better pl ace to
put i t).
Colors of Various Substances
The l i st bel ow i s by no means a comprehensi ve one, but i t does l i st some fai rl y characteri sti c
col ors.
These fl ame tests represent the col or of the fl ame, not the i ndi vi dual spectral l i nes:
Cation Flame Color
Li
1
Deep red (cri mson)
Na
1
Yel l ow
K
1
Vi ol et
Ca
21
Orange
Sr
21
Red
Ba
21
Green
Cu
21
Bl ue-green
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Colors of Ions
These are some typi cal col ors. Agai n thi s i s not a comprehensi ve l i st.
Cations Color
Cu Green to bl ue (dependi ng on ani on and charge on Cu)
Fe Yel l ow to red-orange (dependi ng on ani on and charge on Fe); i n rare
i nstances, can form compl ex i ons that produce a deep bl ue col or
Co Pi nk
Cr Green
Ni Green
Anions
CrO
4
22
Yel l ow
Cr
2
O
7
22
Orange
Assorted Compounds
NO
2
Brown gas; associ ated wi th reacti ons between metal s (l i ke copper) and
ni tri c aci d
PbI
2
Bri ght yel l ow preci pi tate
Cu(NH
3
)
4
21
Dark bl ue; produced as ammoni a i s added to l i ght bl ue copper
sol uti ons (e.g., CuSO
4
, Cu(NO
3
)
2
)
Thi s l i st i s not i ntended to l i st al l compounds that have characteri sti c col ors. These are some
that are qui te common and that have appeared i n some form on previ ous AP tests.
COORDINATION COMPLEXES
Earl i er i n the chapter, we di scussed the term compl ex i on, whi ch referred to the i ons formed
by a metal l i c cati on and an ani on acti ng as a Lewi s base. These Lewi s bases that surround
metal i ons i n a compl ex are known as l i gands. Some common l i gands are NH
3
, H
2
O, and
CN
2
. The most common metal s to form compl exes are the transi ti on metal s because they
have many empty val ence orbi tal s that al l ow them to functi on as Lewi s aci ds (accept el ectron
pai rs). I n these compounds, the central metal i on and the attached l i gands are wri tten i n
brackets to di sti ngui sh the compl ex from the rest of the compound. For i nstance, the formul a
for the sal t potassi um hexacyanoferrate (I I ) i s wri tten:
K
4
[Fe
3
(CN)
6
]
where the compl ex hexacyanoferrate (I I ) i on, Fe(CN)
6
42
, i s set asi de from the potassi um by
brackets. I n case you are wonderi ng where the charge 4
2
came from on thi s i on, i t came by
addi ng the charges on each consti tuent i on. The Fe(CN)
6
42
i on was formed by the addi ti on of
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si x cyani des to an Fe
21
i on. The procedure for determi ni ng the charge on the enti re i on (the
same procedure that i s used for al l compl ex i ons) can be demonstrated as fol l ows:
Fe
21
3 1 5 12
CN
2
3 6 5 26
The charge equal s 12 1 (26) 5 24.
Another term you shoul d be fami l i ar wi th i s the coordi nati on number of the metal i on. Thi s
number refers to the total number of bonds formed wi th the l i gands. I n the Fe(CN)
6
42
i on,
i ron has formed 6 bonds (one wi th each cyani de), so the coordi nati on number of i ron i n thi s
compl ex i s 6.
Compounds can al so be referred to by the type of l i gands they contai n. Many l i gands, l i ke NH
3
and Cl
2
, can onl y form si ngl e bonds to the metal l i c i ons. Thi s type of l i gand i s referred to as
a monodentate l i gand. Other l i gands, l i ke the ami ne group, NH
2
, can bi nd two ti mes and
are known as bi dentate (or pol ydentate) l i gands. Some of the more common pol ydentate
l i gands are known as chel ati ng agents. These chel ati ng agents bi nd to metal i ons i n such a
way that they l i teral l y wrap around them.
NOMENCLATURE OF COORDINATION COMPLEXES
I f pressed for ti me, youre better off ski ppi ng thi s secti on i n favor of another more i mportant
secti on, but i f you have the l uxury of ti me, read on. The name of a coordi nati on compl ex has
come up on the mul ti pl e-choi ce test before. There i s an establ i shed set of rul es for nami ng
these compounds that has been devel oped by the I UPAC, and i t consi sts of the fol l owi ng
fi ve parts:
When nami ng sal ts, the name of the cati on i s gi ven before the name of the ani on
(thi s i s the same as the other nomencl ature rul es).
The name of the compl ex i on, whether i t i s an ani on, cati on, or neutral , i s wri tten as
two parts that are combi ned i nto one word. The fi rst part consi sts of the name of the
l i gand, and the second part, the name of the metal i on. I f more than one of the same
type of l i gand appears, Greek prefi xes are used to i ndi cate the number of ti mes the
l i gand occurs. A Roman numeral i s used to i ndi cate the charge on the cati on. For
i nstance, the name of the i on i n the previ ous exampl e, Fe(CN)
6
42
, i s hexacyanofer-
rate (I I ) i on.
The prefi x hexa- represents the si x cyani de l i gands, the ani on appears before the
cati on, and the Roman numeral (I I ) i n parentheses i ndi cates the 2
1
charge on the
i ron i on.
One thi ng you may have noti ced i n the previ ous exampl e i s the endi ng -o on the end
of cyano. Most ani oni c l i gands are wri tten wi th an -o endi ng, l i ke chl oro, bromo,
cyano, and oxo. Neutral l i gands are usual l y gi ven the name of the mol ecul e. A few
notabl e excepti ons to thi s are NH
3
, known as ammi ne; H
2
O, known as aqua; and
CO, known as carbonyl .
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You may al so have noti ced the term ferrate to descri be i ron. Thi s i s a by-product
of the ol d nami ng system that used the Lati n terms for el ements i nstead of Roman
numeral s to i ndi cate thei r names (and charges). I n thi s nami ng system, these ol der
Lati n names of el ements are gi ven an ate endi ng. Most of these ol der forms have
been di scarded, except they do appear here. The Lati n names for el ements are
responsi bl e for the symbol s that may have been di ffi cul t for you to memori ze
because they dont start wi th the same l etters as the el ements, common names.
Some exampl es of these ol der names and thei r use i n nami ng ani ons i n compl exes
are seen bel ow:
Common
English Name
Latin Name
and Symbol
Anion Name
(used in complex)
Copper Cuprum, Cu Cuprate
Lead Pl umbum, Pb Pl umbate
I ron Ferrum, Fe Ferrate
Ti n Stannum, Sn Stannate
Gol d Aurum, Au Aurate
Si l ver Argentum, Ag Argentate
Even when the Lati n name i s used, the charge sti l l must be wri tten i n parenthe-
ses next to the ani ons name.
I n a compl ex i on or mol ecul e, i f more than one type of l i gand appears, the order of
appearance i s determi ned al phabeti cal l y. For exampl e, the compl ex i on
Pt(NH
3
)
4
Cl
2
21
contai ns two l i gands, NH
3
and Cl
2
. The name of the i on i s tetraam-
mi nedi chl oropl ati num (I V) i on.
Youl l noti ce that the ammi ne appears before chl oro (you use the root to determi ne
al phabeti c order) because a comes before c. The prefi xes tetra i s used to i ndi cate
the four NH
3
l i gands and di i ndi cates the two Cl
2
l i gands. Al so noti ce the o
endi ng on chl oro, whi ch i s not present on ammi ne. Fi nal l y, the Roman numeral (I V)
i ndi cates a 4
1
charge on pl ati num. The overal l charge on the i on, 2
1
, can be
determi ned by addi ng the 4
1
charge of pl ati num to the 2(1
2
), or 2
2
, charge of the
chl ori de i ons. I f thi s i on compl ex was attached to a chl ori de i on, the resul ti ng
compound, [Pt(NH
3
)
4
Cl
2
]Cl
2
, woul d be cal l ed tetraammi nedi chl oropl ati num (I V)
chl ori de.
Sample: Name the fol l owi ng coordi nati on compound, l i st the coordi nati on number of the
transi ti on el ement, and determi ne the charge of the compl ex i on:
K
4
[Mo(CN)
8
]
Answer: The name i s potassi um, octacyanomol ybdate (I V).
The name of the cati on, potassi um, i s wri tten fi rst, fol l owed by the ani on. The
compl ex i on i s wri tten wi th the l i gand fi rst, fol l owed by the metal i on. The l i gand
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has the Greek prefi x i ndi cati ng 8 and an o endi ng for the cyano term. The metal
i on, mol ybdenum, has been gi ven the ate endi ng and i s fol l owed wi th the Roman
numeral of i ts charge.
The coordi nati on number of mol ybdenum i s 8.
The charge of the compl ex i on i s 4
2
. Thi s i s determi ned by the rati o of i t to
potassi um. Potassi um al ways has a charge of 1
1
, whi ch means that the charge on
the compl ex i on must be 4
2
. The Roman numeral for mol ybdenum can be
determi ned from thi s number as wel l . The overal l charge i s 4
2
. The cyani de i on,
CN
2
, has a charge of 1
2
, so 8 of them woul d have a charge of 8
2
. The charge of Mo
must be 4
1
to gi ve an overal l charge of 4
2
.
Sample: Wri te the formul a for tetraammi nesul fatochromi um (I I I ) chl ori de.
Answer: You need to begi n di ssecti ng thi s pi ece by pi ece. Fi rst, you know there i s a
chromi um i on wi th a 3
1
charge i n the compl ex. There are al so two l i gands,
ammoni a (whi ch goes by the name ammi ne), NH
3
, and sul fate, (whi ch goes by
sul fato), SO
4
22
. The tetra before ammi ne i ndi cates that there are four ammoni a
mol ecul es i n the compl ex. Because the name of the compl ex appears fi rst, i t must
be the cati on. A qui ck check of the i ndi vi dual charges of each component wi l l
determi ne the charge of the compl ex i on as wel l as veri fy i ts i denti ty as a cati on. We
al ready know that chromi um has a 3
1
charge (by the Roman numeral ). We al so
know that ammoni a has no charge and sul fate has a charge of 2
2
. I n addi ti on, the
absence of a prefi x i n front of the sul fato term i n the name i ndi cates there i s onl y
one sul fate i on present. Therefore, the net charge on the compl ex i on i s 3
1
1 (2
2
) 5
1
1
. Because i t has a 1
1
charge, i t wi l l combi ne i n a one-to-one rati o wi th the
chl ori de i on, whi ch has a 1
2
charge. The formul a, therefore, i s:
[Cr(NH
3
)
4
SO
4
]Cl
You Try It!
1. Determi ne the name of [Cu(NH
3
)
4
]SO
4.
2. Wri te the formul a for ammoni um aquapentafl uoroferrate (I I I ).
Answers:
1. tetraammi necuprate (I I ) sul fate
2. (NH
4
)
2
[Fe(H
2
O)F
5
]
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EXERCISES: ADDITIONAL EQUILIBRIUM CONCEPTS
Multiple Choice
1. What i s the mol ar sol ubi l i ty of si l ver
oxal ate? (K
sp
for Ag
2
C
2
O
4
i s 5.4 3
10
212
)
(A) 1.1 3 10
24
(B) 1.4 3 10
24
(C) 1.6 3 10
26
(D) 1.4 3 10
212
(E) 5.4 3 10
212
2. What i s the fi nal concentrati on of
si l ver i ons, [Ag
1
], i n sol uti on when
100 mL of 0.10 M AgNO
3
(aq) i s
mi xed wi th 100 mL of 0.050 M
HCl (aq)?
(A) 0.00 M
(B) 0.012 M
(C) 0.025 M
(D) 0.075 M
(E) 0.10 M
3. I f the sol ubi l i ty of Fe(OH)
2
i n water
i s 7.7 3 10
26
M, what i s the val ue of
K
sp
(A) 7.7 3 10
26
(B) 2.4 3 10
210
(C) 9.1 3 10
216
(D) 1.8 3 10
215
(E) 4.6 3 10
216
4. The sol ubi l i ty of BaCO
3
i n water i s
i ncreased by whi ch of the fol l owi ng?
I . Addi ti on of NaOH
I I . Decreasi ng the pH of
the sol uti on
I I I . I ncreasi ng the pH of
the sol uti on
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I and I I I
5. A 30-mL sampl e of 0.40 M
Pb(C
2
H
3
O
2
)
2
sol uti on i s added to
20 mL of 0.20 M Na
2
CrO
4
sol uti on.
Lead chromate preci pi tates out of
sol uti on. The concentrati on of l ead
(I I ) i on, Pb
21
, i n sol uti on after the
l ead (I I ) chromate preci pi tates i s
(A) 0.150 M
(B) 0.160 M
(C) 0.200 M
(D) 0.240 M
(E) 0.267 M
6. When 100 mL of 1.0 M K
2
CrO
4
i s
mi xed wi th 100 mL of 1.0 M AgNO
3
,
a browni sh-red preci pi tate forms and
[Ag
1
] becomes qui te smal l . Of the
i ons remai ni ng i n sol uti on, whi ch of
the fol l owi ng i s the correct l i sti ng of
the i ons remai ni ng i n sol uti on, i n
order of i ncreasi ng concentrati on?
(A) [CrO
4
] , [NO
3
2
] , [K
1
]
(B) [CrO
4
] , [K
1
] , [NO
3
2
]
(C) [NO
3
2
] , [CrO
4
] , [K
1
]
(D) [K
1
] , [NO
3
2
] , [CrO
4
]
(E) [K
1
] , [CrO
4
] , [NO
3
2
]
7. A 1.0 L sampl e of an aqueous
sol uti on contai ns 0.20 mol of NaI and
0.20 mol of SrI
2
. What i s the mi ni -
mum number of mol es of AgNO
3
that
must be added to the sol uti on i n
order to remove al l avai l abl e I
2
as
the preci pi tate AgI (s)? (AgI i s very
i nsol ubl e i n water.)
(A) 0.10 mol
(B) 0.20 mol
(C) 0.30 mol
(D) 0.40 mol
(E) 0.60 mol
e
x
e
r
c
i
s
e
s
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8. What i s the mol ar sol ubi l i ty of AgCl
i n 3.0 3 10
22
M AgNO
3
sol uti on? K
sp
for AgCl i s 1.8 3 10
210
.
(A) 1.8 3 10
210
M
(B) 3.0 3 10
29
M
(C) 1.3 3 10
25
M
(D) 6.0 3 10
29
M
(E) 4.8 3 10
212
M
9. Whi ch of the fol l owi ng wi l l be more
sol ubl e at an aci di c pH than i n
water?
I . AgCl
I I . Mg(OH)
2
I I I . BaCO
3
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I I and I I I
10. When a sol uti on of potassi um
chl ori de i s vapori zed i n a fl ame, the
col or of the fl ame i s
(A) red.
(B) yel l ow.
(C) green.
(D) vi ol et.
(E) orange.
11. The formul a for sodi um tetrahy-
droxoal umi nate (I I I ) i s
(A) Na
4
[Al (OH)
4
]
(B) Na
3
[Al (OH)
4
]
(C) Na[Al (OH)
4
]
(D) Na
4
Al (OH)
3
(E) Na(OH)
4
12. Si l ver chl ori de i s l east sol ubl e i n a
0.1 M sol uti on of whi ch of the
fol l owi ng?
(A) FeCl
3
(B) MgCl
2
(C) NaCl
(D) H
2
O
(E) AgNO
3
Free Response
QUESTION 1
I n thi s probl em, assume that the temperature remai ns constant at 25C. K
sp
for bari um
sul fate, BaSO
4
, i s 1.1 3 10
210
, and K
sp
for bari um fl uori de, BaF
2
, i s 1.8 3 10
27
.
(A) What i s the mol ar sol ubi l i ty of BaSO
4
i n pure water?
(B) What i s the mol ar sol ubi l i ty of BaF
2
?
(C) I f an aqueous sol uti on of Ba(NO
3
)
2
i s added to 1.0 L of a sol uti on contai ni ng 0.05
mol F
2
and 0.075 mol SO
4
22
, whi ch sal t wi l l preci pi tate fi rst? (Assume that the
vol ume of the sol uti on remai ns 1.0 L.)
(E) Based on your cal cul ati ons i n part (C), what i s the concentrati on of Ba
21
i n the
sol uti on when the fi rst preci pi tate forms?
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QUESTION 2
The sol ubi l i ty of magnesi um hydroxi de, Mg(OH)
2
, i s 6.53 3 10
23
grams per l i ter at 25C.
Assume that thi s temperature i s mai ntai ned for al l parts of the questi on.
(A) Wri te a bal anced equati on for the sol ubi l i ty equi l i bri um.
(B) Wri te the expressi on for K
sp
, and determi ne i ts val ue.
(C) Cal cul ate the pH of a saturated sol uti on of Mg(OH)
2.
(D) I f 100 mL of 2.5 3 10
23
M Mg(NO
3
)
2
sol uti on i s added to 100 mL of a
3.5 3 10
24
M NaOH sol uti on, wi l l a preci pi tate of Mg(OH)
2
form? Justi fy your
response by usi ng your cal cul ated data.
e
x
e
r
c
i
s
e
s
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Multiple Choice
1. A
2. C
3. D
4. B
5. B
6. A
7. E
8. D
9. E
10. D
11. C
12. A
1. Thecorrect answer is (A). Fi rst you must set up an equati on for the equi l i bri um and
set up the equi l i bri um expressi on:
Ag
2
(C
2
O
4
) 2Ag
1
(aq) 1 C
2
O
4
22
K
sp
5 [Ag
1
]
2
[C
2
O
4
22
]
Next, set up an equi l i bri um tabl e for the two substances:
Ag
2
(C
2
O
4
) 2Ag
1
(aq) 1 C
2
O
4
22
Ag
2
C
2
O
4
2Ag
1
C
2
O
4
22
Start 0 0
D 12x 1x
Fi ni sh 2x x
Fi nal l y, the mol ar sol ubi l i ty (x) can be cal cul ated:
K
sp
5 [Ag
1
]
2
[C
2
O
4
22
]
5.4 3 10
212
5 (2x)
2
(x) 5 4x
3
x 5
1 35 10
12 3
.

5 1.1 3 10
24
2. The correct answer is (C). The fi rst assumpti on i s that the si l ver chl ori de wi l l
preci pi tate out of sol uti on. The second assumpti on i s that there i s an excess of si l ver
i ons so that there wi l l be some l eft over. I n order to determi ne thi s, you need to
determi ne the amount, i n mol es, of each substance, and then use the bal anced equati on
to determi ne what i s l eft over:
Ag
1
(aq) 1 Cl
2
(aq) AgCl (s)
To determi ne the number of mol es of Ag1 i n AgNO
3
, you can assume the number of
mol es of si l ver i ons i s the same as the number of mol es of si l ver ni trate because of the
1:1 rati o i n the di ssoci ati on:
0.100 L 3
0.10 mol
L
5 0.010 mol Ag
1
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Next, determi ne the number of mol es of Cl
2
, whi ch you can al so assume i s the same as
the number of mol es of HCl :
0.100 L 3
0.05 mol
L
5 0.005 mol Cl
2
The numbers tel l us that 0.005 mol of si l ver wi th react wi th al l 0.005 mol of chl ori de
i ons to yi el d 0.005 mol AgCl . Thi s wi l l l eave 0.005 mol of excess Ag
1
. The fi nal
cal cul ati on i s to determi ne what [Ag
1
] i s i n 200 mL of sol uti on. Dont forget to add the
vol umes together:
0.005 mol Ag
1
0.200 L sol n
5 0.025 M
3. The correct answer is (D). You are gi ven the val ue of x i n thi s probl em. You need to
set up an equi l i bri um tabl e to determi ne equi l i bri um concentrati ons of each substance,
and then you can substi tute the gi ven val ue of x to determi ne K
sp
:
Fe(OH)
2
(s) Fe
21
(aq) 1 2OH
2
(aq)
Fe(OH)
2
Fe
21
2OH
2
Start 0 0
D 1x 12x
Fi ni sh x 2x
K
sp
5 [Fe
21
][OH
2
]
2
5 (x)(2x)
2
5 4x
3
Therefore, K
sp
5 4(7.7 3 10
26
)
3
5 1.8 3 10
215
.
4. Thecorrect answer is (B). You shoul d pi ck up that the questi on i s seei ng i f you know
the effects of pH on the sol ubi l i ty of BaCO
3
. Wi th thi s i n mi nd, you need to consi der the
compound, l ooki ng i n parti cul ar at the ani on, CO
3
22
. Remember, i f the ani on i s the
conjugate of a weak aci d, i t wi l l be a strong base. Thi s means i t wi l l be affected by an
aci di c pH because the base wi l l combi ne wi th the H
1
, dri vi ng the equi l i bri um to the
ri ght (more di ssol vi ng of the sl i ghtl y sol ubl e sol i d). Choi ces I and I I both i ndi cate
changes i n the basi c di recti on, whi ch wont affect the sol ubi l i ty (or decrease i t i f
anythi ng). I I i s the onl y condi ti on that wi l l i ncrease the sol ubi l i ty of BaCO
3
.
5. The correct answer is (B). Thi s i s very much l i ke questi on 2. You need to determi ne
i f there i s excess Pb after the preci pi tati on.
The amount of Pb avai l abl e (each Pb(C
2
H
3
O
2
)
2
rel eases one Pb
21
):
0.030 L 3
0.40 mol
L
5 0.012 mol Pb
21
The amount of CrO
4
22
avai l abl e (each Na
2
CrO
4
rel eases one CrO
4
22
):
0.020 L 3
0.20 mol
L
5 0.004 mol CrO
4
22
a
n
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0.004 mol of Pb
21
wi l l react wi th CrO
4
22
and preci pi tate out of sol uti on, l eavi ng the
remai ni ng 0.008 mol i n sol uti on. Thi s 0.008 mol i s i n 50 mL of sol uti on, whi ch makes
the concentrati on:
0.008 mol
0.050 L
5 0.16 M
6. The correct answer is (A). Thi s doesnt requi re any cal cul ati onsjust some l ogi c.
Wel l l ook at some numbers to make the expl anati on easi er, but they are not necessary
to sol ve the probl em.
I f you have 100 mL of 1.0 M K
2
CrO
4
, you have 0.1 mol K
2
CrO
4
. Usi ng stoi chi ometri c
pri nci pl es, thi s means you have 0.2 mol K
1
and 0.1 mol CrO
4
22
i n sol uti on.
Si mi l arl y, i n 100 mL of 1.0 M AgNO
3
, you have 0.1 mol Ag
1
and 0.1 mol NO
3
2
.
The preci pi tate must be Ag
2
CrO
4
because al l potassi um and ni trate sal ts are sol ubl e.
An i mportant thi ng to noti ce i s the formul a of si l ver chromate. Each chromate wi l l
combi ne wi th two si l ver i ons. Si nce both start out wi th 0.1 mol , si l ver i s a l i mi ti ng
reactant. Onl y 0.05 mol of CrO
4
22
wi l l be abl e to preci pi tate. At the end of the reacti on
then, there wi l l be:
0.05 mol CrO
4
22
, 0.10 mol NO
3
2
, and 0.20 mol K
1
7. The correct answer is (E). You can sol ve thi s one i n your head as wel l , but you need
to understand the nature of the probl em. You have a 1.0-l i ter contai ner that has 0.20
mol e each of NaI and SrI
2
di ssol ved i n i t. The di ssoci ated si l ver i ons from si l ver ni trate
wi l l react wi th the I
2
i ons from the other two sal ts to produce the i nsol ubl e sol i d AgI . Al l
you have to do i s determi ne how many mol es of i odi de i ons are i n sol uti on, and thi s wi l l
be the number of mol es of si l ver that wi l l be requi red to react wi th i t (because AgI has
a 1:1 rati o of si l ver to i odi de).
NaI di ssoci ates to yi el d one Na
1
and one I
2
. SrI
2
di ssoci ates to yi el d one Sr
21
and two
I
2
. As a resul t, 0.20 mol NaI wi l l produce 0.20 mol I
2
, and 0.20 mol SrI
2
wi l l produce
0.40 mol I
2
. The total amount of I
2
generated i s 0.60 mol , whi ch i s the mi ni mum
amount of AgNO
3
requi red to react wi th i t.
8. The correct answer is (D). Thi s i s a common i on probl em. Before you sol ve i t, you
shoul d predi ct what you thi nk the answer wi l l be based on what you know about the
common-i on effect. I f you are tryi ng to di ssol ve AgCl i n a sol uti on of AgNO
3
, there wi l l
be si l ver i ons i n sol uti on before the AgCl starts to di ssol ve. Thi s wi l l l i mi t i ts abi l i ty to
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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di ssol ve. We woul d expect a fai rl y smal l mol ar sol ubi l i ty as a resul t. To sol ve the
probl em, we begi n by setti ng up an equi l i bri um tabl e, keepi ng i n mi nd that we are
starti ng out wi th some si l ver i ons:
AgCl (s) Ag
1
(aq) 1 Cl
2
(aq)
AgCl Ag
1
Cl 2
Start 0.03 0
D 1x 1x
Fi ni sh (0.03 1 x) x
The next step i s to set up the equi l i bri um expressi on:
K
sp
5 [Ag
1
][Cl
2
] 5 (0.03 1 x)(x)
We are goi ng to assume that the val ue of x i s smal l enough that the sum of 0.03 1 x i s
approxi matel y 0.03:
1.8 3 10
210
5 0.03x
x 5 6 3 10
29
M (our assumpti on i s val i d), so thi s i s the mol ar sol ubi l i ty.
9. The correct answer is (E). Thi s i s another questi on about the effect of pH on
sol ubi l i ty. Si nce the questi on i s aski ng whi ch woul d be more sol ubl e at aci di c pH, you
shoul d be l ooki ng for compounds whose ani ons are basi c or are amphoteri c substances.
Because Cl has negl i gi bl e basi ci ty, i t can be di sregarded. Magnesi um hydroxi de has a
basi c ani on (that wi l l react wi th H
1
to form water), as does BaCO
3
(the carbonate i on
wi l l react wi th H
1
). Therefore, both I I and I I I wi l l be more sol ubl e at aci di c pH. The
sol ubi l i ty of AgCl i s unaffected at aci di c pH. AgCl i s more sol ubl e i n sol uti ons contai ni ng
NH
3
because i t can form compl ex i ons wi th NH
3
.
10. The correct answer is (D). You ei ther know thi s or you dont. Most of the col or
i nformati on i ncl uded i n thi s chapter i s much easi er to remember i f you have done the
l abs that show the col ors. Even i f you havent, you shoul d try to commi t these to
memory. The AP test usual l y has one or two of these questi ons l urki ng about.
11. The correct answer is (C). The tetra tel l s you that there are four hydroxi de i ons
(i ndi cated by the hydroxo prefi x) combi ned wi th the metal al umi num. The al umi num
has a charge of 3
1
(i ndi cated by the Roman numeral ). The compl ex i on
tetrahydroxoal umi nate (I I I ) must have a charge of 1
2
because the charge of al umi num
i s 3
1
, and the charge of each hydroxi de i s 1
2
(there are four, so that makes 4
2
). Thi s i s
confi rmed because the term appears second i n the name, i ndi cati ng i ts status as the
ani on. The formul a then shoul d have one sodi um i on. (The 1
1
charge of sodi um
bal ances the 1
2
charge of the compl ex i on):
Na[Al (OH)
4
]
a
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12. The correct answer is (A). You have to consi der the factors that affect sol ubi l i ty
before you answer thi s one. Thi s hel ps cl ue you i n on what the questi on i s l ooki ng for.
The common-i on effect, pH, and compl ex i on formati on are the possi bl e i tems. Because
four of the fi ve compounds shown contai n a common i on, thi s i s the most l i kel y topi c the
questi on i s testi ng you on. I f you note, the fi rst three compounds di ffer by one chl ori de
i on. What you need to remember i s that the l arger the amount of common i on i n
sol uti on, the l ess sol ubl e the sal t wi l l be. FeCl
3
has three mol es of chl ori de i ons per mol e
of FeCl
3
. MgCl
2
has two mol es, and NaCl has one. AgNO
3
al so has a common i on, but
onl y one. Water has no common i ons, whi ch means that AgCl wi l l be the most sol ubl e i n
i t. AgCl i s l east sol ubl e i n FeCl
3
because the presence of the excess chl ori de i ons i n
sol uti on shi fts the equi l i bri um to the l eft (toward the sol i d).
Free Response
QUESTION 1
You shoul d al ways try to get the bi g pi cture of a free-response questi on before answeri ng i t.
I t hel ps you to focus and to determi ne i f al l parts of the probl em are rel ated. I n thi s probl em,
the onl y two parts that are compl etel y rel ated are (C) and (D). You are goi ng to need the gi ven
i nformati on i n al l parts of the probl em.
(A) To sol ve thi s one [and part (B)], you need to set up an equi l i bri um cal cul ati on
tabl e and sol ve for x:
BaSO
4
(s) Ba
21
(aq) 1 SO
4
22
(aq)
BaSO
4
Ba
21
SO
4
22
Start 0 0
D 1x 1x
Fi ni sh x x
You may have recogni zed that when the sol i d di ssoci ates i nto two i ons that have
no coeffi ci ents, the endi ng val ues wi l l al ways be x and the K
sp
expressi on wi l l
al ways come out so that K
sp
5 x
2
. I f you do recogni ze thi s, i t wi l l save you ti me on
the mul ti pl e-choi ce secti on where you dont have to show your cal cul ati ons:
K
sp
5 [Ba
21
][SO
4
22
] 5 (x)(x) 5 x
2
1.1 3 10
210
5 x
2
x 5 1.0 3 10
25
M (rounded for si gni fi cant fi gures)
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(B) Thi s requi res another equi l i bri um cal cul ati on tabl e:
BaF
2
(s) Ba
21
(aq) 1 2F
2
(aq)
BaF
2
Ba
21
2F
2
Start 0 0
D 1x 12x
Fi ni sh x 2x
K
sp
5 [Ba
21
][F
2
]
2
5 (x)(2x)
2
5 4x
3
1.8 3 10
27
5 4x
3
x 5
1.8 10
4
7

3
5 3.6 3 10
23
M
(C) To sol ve thi s, you need to determi ne the mi ni mum amount of Ba(NO
3
)
2
that must
be added to each one to cause a preci pi tate to form, and then you shoul d compare
these numbers. Whi chever substance has the smal l er number i s the one that wi l l
preci pi tate fi rst.
For BaF
2
, the concentrati on of bari um i ons that wi l l be requi red to form a
preci pi tate i s:
K
sp
5 [Ba
21
][F
2
]
2
Were gi ven the concentrati on of fl uori de i ons, so we can use thi s i n the
expressi on. I n addi ti on, because the sol uti on i s 1.0 L i n vol ume, the number of
mol es i s equal to the mol ari ty. Therefore, for BaF
2
:
1.8 3 10
27
5 [Ba
21
](0.05)
2
[Ba
21
] 5
1.8 10
2.5 10
7
3
5 7.2 3 10
25
M
For BaSO
4
, the concentrati on of Ba requi red i s:
K
sp
5 [Ba
21
][SO
4
22
]
1.1 3 10
210
5 [Ba
21
](0.075)
[Ba
21
] 5
1.1 10
10
0 075 .
5 1.5 3 10
29
Because 1.5 3 10
29
, 7.2 3 10
25
, BaSO
4
wi l l preci pi tate fi rst.
(D) For part (D), we need onl y provi de the cal cul ati on from part (C):
[Ba
21
] 5
1.1 10
10
0 075 .
5 1.5 3 10
29
a
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QUESTION 2
(A) 5Mg(OH)
2
(s) Mg
21
(aq) 1 2OH
2
(aq)
(B) K
sp
5 [Mg
21
][OH
2
]
2
. To cal cul ate the val ue of K
sp
, we need to know the mol ar
sol ubi l i ty. We can then set up an expressi on for K
sp
usi ng val ues from an
equi l i bri um cal cul ati on tabl e and substi tute the mol ar sol ubi l i ty, x, i nto the
expressi on.
Step 1: The mol ar sol ubi l i ty of Mg(OH)
2
i s:
6.53 10 g Mg OH
L
1 mol
5 g Mg OH
3
2
2
( )
_
,
( )
_
,
8 32 .
5 1.12 3 10
24
M
Step 2: Determi ne the expressi on for K
sp
:
Mg(OH)
2
(s) Mg
21
(aq) 1 2OH
2
(aq)
Mg(OH)
2
Mg
21
2OH
2
Start 0 0
D 1x 12x
Fi ni sh x 2x
K
sp
5 [Mg
21
][OH
2
]
2
5 (x)(2x)
2
5 4x
3
Step 3: Substi tute the mol ar sol ubi l i ty for x:
K
sp
5 4x
3
5 4(1.12 3 10
24
)
3
5 5.62 3 10
212
(C) We can sol ve thi s two di fferent ways. To start ei ther way, we use the val ue for the
mol ar sol ubi l i ty to determi ne the [OH
2
]. Once [OH
2
] i s known, we convert i t to
[H
1
] and sol ve for pH. The other way i s to cal cul ate pOH and convert thi s to pH.
Both methods are shown bel ow.
From the equi l i bri um tabl e, we know that the val ue of [OH
2
] i s 2x. Therefore, we
can substi tute the val ue of x i nto the expressi on to cal cul ate [OH
2
]:
[OH
2
] 5 2x 5 2(1.12 3 10
24
) 5 2.24 3 10
24
Usi ng pH:
1.0 3 10
214
5 [H
1
][OH
2
]
1.0 3 10
214
5 [H
1
](2.24 3 10
24
) [H
1
] 5
1 10
10
14
4
.
.
00
2 24
5 4.46 3 10
211
pH 5 2l og [H
1
] 5 2l og (4.46 3 10
211
) 5 10.4
Usi ng pOH:
pOH 5 2l og [OH
2
] 5 2l og (2.24 3 10
24
) 5 3.6
pH 5 14.0 2 pOH 5 14.0 2 3.6 5 10.4
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(D) Thi s i s an i on-product probl em. We need to cal cul ate Q and compare i t to K
sp
,
whi ch we cal cul ated i n part (B):
Q 5 [Mg
21
][OH
2
]
2
To obtai n the mol ar concentrati ons of each i on, we need to use the gi ven
i nformati on i n (D).
For [Mg
21
], each mol e of Mg(NO
3
)
2
di ssoci ates to form 1 mol e of Mg
21
, so:
0.100 L 3
2.5 10 mol Mg NO
0.200 L
4
3
2

( )
5 2.5 3 10
24
mol Mg(NO
3
)
2
I n 200 mL of sol uti on, thi s makes the [Mg
21
]:
[Mg
21
] 5
2.5 10 mol Mg NO
0.200 L
3
2

( )
4
5 1.25 3 10
24
M
For [OH
2
], each mol e of NaOH makes one mol e of OH
2
, so:
0.100 L 3
3.5 10 mol NaOH
L
4

5 3.5 3 10
24
mol NaOH
I n 200 mL of sol uti on, thi s wi l l make [OH
2
]:
[OH
2
] 5
3.5 10 mol NaOH
0.200 L
4

5 1.75 3 10
24
M
Now, you are ready to substi tute these val ues i nto the expressi on for Q:
Q 5 [Mg
21
][OH
2
]
2
5 (1.25 3 10
23
)(1.75 3 10
24
)
2
5 3.8 3 10
211
Because Q . K
sp
, thi s i ndi cates an excess of i ons i n sol uti on (compared to
equi l i bri um). The onl y way to restore equi l i bri um i s to remove the excess by
al l owi ng i t to preci pi tate as Mg(OH)
2
.
a
n
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w
e
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SUMMING IT UP
The equi l i bri um between i oni c sol utes and thei r consti tuent i ons can be summari zed
usi ng the equi l i bri um constant known as the sol ubi l i ty product constant, K
sp
.
Sol ubi l i ty, whi ch refers to the amount of a substance that can be di ssol ved i n sol uti on,
di ffers from the sol ubi l i ty product. K
sp
for a substance remai ns constant as l ong as
temperature i s constant, whi l e the sol ubi l i ty of a substance i s subject to change.
The i on product, Q, provi des a quanti tati ve descri pti on of the rel ati onshi p between sol ute
and the consti tuent i ons at any ti me, regardl ess of whether equi l i bri um has been
establ i shed. The rel ati onshi p between Q and K
sp
can al so be used to i ndi cate the status of
the mi xture (i .e., whether the sol ute i s di ssol vi ng at a faster rate than crystal s are
formi ng).
Three factors, other than temperature, that affect sol ubi l i ty are the common-i on effect,
pH, and the formati on of compl ex i ons.
The presence of sal ts that share a common i on to the consti tuent i ons of a sol ute wi l l
affect the sol ubi l i ty of a sol ute. Because of Le Chtel i ers Pri nci pl e, the addi ti on of
common i ons shi fts the equi l i bri um toward the formati on of addi ti onal sol ute (sol i d),
whi ch decreases i ts sol ubi l i ty.
Sol ubi l i ty can al so be affected by pH. Sal ts whose ani ons are basi c wi l l i ncrease i n
sol ubi l i ty i n aci di c sol uti ons. Thi s i s because the ani ons wi l l combi ne wi th excess
hydrogen i ons. Accordi ng to Le Chtel i ers Pri nci pl e, thi s wi l l shi ft the equi l i bri um to the
ri ght to restore equi l i bri um.
Some sal ts contai n metal i ons that can act as Lewi s aci ds i n sol uti on. These often form
compl ex i ons when i n sol uti ons wi th Lewi s bases l i ke water or ammoni a. I n the presence
of these Lewi s bases, the ani ons form compl ex i ons. The formati on of these compl ex i ons
reduces the concentrati on of the ani on, whi ch wi l l cause the equi l i bri um to shi ft ri ght (or
i ncrease di ssol vi ng).
The AP test frequentl y adds questi ons about the col ors of di fferent substances. You shoul d
fami l i ari ze yoursel f wi th some of the more col orful el ements and compounds.
Compl ex i ons combi ne wi th cati ons or ani ons to form coordi nati on compl exes. These
compl ex i ons usual l y consi st of a transi ti on metal i on attached to l i gands. You shoul d be
fami l i ar wi th the basi c nomencl ature for coordi nati on compl exes.
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Kinetics
OVERVIEW
Reaction rate
Using concentrations to describe rate
Units and rate constants
Determining rate laws
Reaction types
Half-life
The relationship between temperature and rate
Reaction mechanisms
Rate-determining steps and rate laws
The effect of catalysts on reaction rate
Summing it up
Up to thi s poi nt, we have pri mari l y studi ed the descri pti ve aspects of chemi cal
reacti ons. That i s, weve di scussed whats occurri ng duri ng reacti ons wi thout
much detai l about the dri vi ng forces behi nd the reacti ons. The purpose of the
next two chapters i s to provi de such detai l . I n thi s chapter, we wi l l l ook at the
major model s that have been devel oped to expl ai n the mechani sms by whi ch
reacti ons occur. The focus of thi s chapter i s ki neti cs, an area of chemi stry
that expl ores the rates at whi ch chemi cal reacti ons occur. I n the fi rst porti on
of the chapter, we wi l l focus on a few techni ques we use to descri be or defi ne
the rate of a reacti on. Once that i s establ i shed, we wi l l move our attenti on to
the factors that affect the rate of a reacti on: concentrati on, temperature,
surface area, and the presence of a catal yst.
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c
h
a
p
t
e
r
1
6
379
REACTION RATE
One thi ng that i s very i mportant to consi der as you proceed through thi s chapter i s that rate
and other i tems rel ated to rate (the rate constant or rate l aw) can onl y be determi ned
experi mental l y. Bal anced equati ons can provi de us wi th a means to specul ate about the rate
of a reacti on, but the onl y way to accuratel y descri be factors associ ated wi th rate i s to
determi ne them experi mental l y. On the AP test, you dont have the abi l i ty to perform any
measurements, so al l data i s gi ven to you, usual l y i n a tabl e.
The term rate i s usual l y associ ated wi th the occurrence of somethi ng per uni t of ti me. When
you move, the speed at whi ch you are movi ng i s a rate, determi ned by the di stance you have
travel ed di vi ded by the ti me i t took for you to travel that di stance (e.g., mi l es per hour or
meters per second). I n a chemi cal reacti on, rate i s usual l y associ ated wi th the rate at whi ch a
reactant i s bei ng used up (thi s i s usual l y referred to as the rate of di sappearance) or the
rate at whi ch a product i s bei ng created (usual l y cal l ed the rate of appearance). Al though
there are di fferent techni ques for maki ng these measurements, the end resul t i s the
sameyou want to col l ect data that tracks the appearance or di sappearance of a substance
over a ti me i nterval .
Thi s data i s qui te often pl aced on a graph to i l l ustrate the progressi on of the reacti on. Fi g-
ures 16.1 and 16.2 show typi cal curves for the appearance and di sappearance of a substance.
The graphs i n Fi gures 16.1 and 16.2 represent the most si mpl i sti c of reacti ons, those i n whi ch
there i s a 1:1 stoi chi ometri c rel ati onshi p among reactants and products. That i s, for every
mol e of reactant used up, there i s a mol e of product created. Not al l reacti ons proceed i n such
a manner, but these fi gures at l east gi ve you an i dea of how graphs can be used to di spl ay the
rate of reacti on. Most graphs that you wi l l be worki ng wi thand most reacti on ratesare
descri bed i n terms of changi ng concentrati ons over ti me (as opposed to mol es, as are seen i n
Fi gures 16.1 and 16.2). We wi l l spend more ti me on graphs i n a l ater secti on.
Time
#

o
f

m
o
l
e
s
Figure16.1: Typical curveshowingtherateof appearanceof a substance. Notethat therateis
highest when the concentrations of reactants is the highest (at the beginning
stages of thereaction).
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USING CONCENTRATIONS TO DESCRIBE RATE
Reacti ons are usual l y descri bed i n terms of changes i n concentrati on over ti me. I n the
hypotheti cal reacti on
aA 1 bB cC 1 dD
i f we were goi ng to moni tor the rate of reacti on, we coul d measure the concentrati on of one of
the substances over ti me. We coul d use stoi chi ometri c pri nci pl es to convert the data for the
other substances. However, i f we col l ected data about one of the substances, we coul d then
determi ne for vari ous i nterval s of ti me how the concentrati on i s changi ng. I f we were
measuri ng the concentrati on of A at 10-mi nute i nterval s, we woul d have a l i st of
concentrati ons as wel l as a l i st of ti mes. We coul d determi ne the rate of di sappearance of A by
usi ng Equati on 16.1:
Average rate 5

A [ ]
t
Remember that the Greek l etter del ta, D, means change i n a vari abl e. For thi s case, the
equati on can be rewri tten as:
Average rate 5
A A
final time initial time
[ ] [ ]
_
,
Thi s val ue i s cal l ed an average because the cal cul ati on i s onl y taki ng i nto account two
measurements and nothi ng i n between. The graph i s actual l y curvi ng duri ng thi s ti me
i nterval , whi ch means the rate i s changi ng. Taki ng a measurement of the average rate can
someti mes be mi sl eadi ng, dependi ng on the sl ope of the graph. For i nstance, l ook at Fi gure
16.3, whi ch represents the rate of di sappearance of a substance. I f the average rate i s
measured between poi nts 1 and 2, the average rate i s a very good approxi mati on of the
reacti on rate because the sl ope of the l i ne connecti ng the two poi nts i s a very cl ose fi t to the
curve. The sl ope i s used because i f you l ook at the formul a for average rate, the numerator,
D[A], represents the ri se of the sl ope (i n math i ts often referred to as Dy), whi l e Dt
represents the run (or Dxi n math terms). You may recal l from previ ous course work that the
ri se di vi ded by the run determi nes the sl ope of a l i ne.
Time
#

o
f

m
o
l
e
s
Figure16.2: Typical curve showing the rate of disappearance of a substance. This could be
superimposed over Figure16.1becauseit is showingthebehavior of thereactants
in thesamereaction for which theproduct is being shown in Figure16.1.
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(Equati on 16.1)
Chapter 16: Kinetics 381
www.petersons.com
For the l i ne connecti ng poi nts 1 and 3 i n Fi gure 16.3, you can see that the l i ne i s begi nni ng to
devi ate substanti al l y from the curve representi ng the reacti on. Thi s means that at any poi nt
al ong the dotted l i ne (the average rate), the rate i s di fferent from the experi mental l y
measured rate. The di fference grows more si gni fi cant when you l ook at the di fference between
poi nts 1 and 4. So the average rate i s much more accurate for smal l er ti me i nterval s than i t
i s for l arger ti me i nterval s.
There i s another way to graphi cal l y determi ne the rate of a reacti on, and that i s wi th the
i nstantaneous rate. As the term suggests, thi s i s the rate at a parti cul ar i nstance i n ti me, as
opposed to a ti me i nterval . The techni que of cal cul ati ng the i nstantaneous rate i s to draw a
tangent to the curved l i ne of the graph. Fi gure 16.4 shows such l i nes drawn on the curve from
Fi gure 16.3.
Sample: Consi der the reacti on aA 1 bB cC 1 dD. The concentrati on of C was recorded for
a peri od of ti me, and some of the data i s shown i n the tabl e bel ow:
Ti me (s) [C] M
2.0 0.00230
4.0 0.00275
Cal cul ate the average rate of reacti on of C duri ng thi s ti me i nterval .
Time
#

o
f

m
o
l
e
s
3
4
2
1
Figure16.3
Time
#

o
f

m
o
l
e
s
3
4
2
1
Figure16.4
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www.petersons.com
Answer: We are goi ng to use the equati on for average rate
Average rate 5
D@C#
Dt
whi ch i s the change i n the concentrati on of C duri ng ti me i nterval t, whi ch can be
cal cul ated usi ng the equati on:
Average rate 5
C C
final timeini
[ ] [ ]
ttial time
_
,

0 00275 0 00230
4 2
. .
5 2.3 3 10
24
M s
21
You Try It!
I n a di fferent experi ment, the concentrati on of D was measured. Determi ne the
average rate for D based on the data shown bel ow:
Ti me (s) [D] M
3.0 0.00470
7.0 0.00635
Answer: 4.1 3 10
24
M s
21
The Relationship Between Reaction Rate and Stoichiometry
I n the i ni ti al exampl e i n thi s chapter, the stoi chi ometri c rel ati onshi p between al l reactants
and products was one-to-one. For every mol e of reactant used, a mol e of product was
produced. From your work i n previ ous chapters, you know that many reacti ons do not fol l ow
thi s si mpl e pattern (i t sure woul d make bal anci ng equati ons easi er i f they di d, though!). How
do you set up an expressi on for a reacti on where the stoi chi ometri c rel ati onshi ps are not
one-to-one? I f we refer to the general reacti on shown bel ow
aA 1 bB cC 1 dD
the reacti on rates for each substance are determi ned usi ng the fol l owi ng equal i ti es i n
Equati on 16.2:
Rate 5 2
1
a
D@A#
Dt
5 2
1
b
D@B#
Dt
5
1
c
D@C#
Dt
5
1
d
D@D#
Dt
You may noti ce the negati ve si gns i n front of the A and B expressi ons. Thi s i s to denote that
these are rates of di sappearance whi l e C and D are rates of appearance. Al though these
formul as are often i ntroduced thi s way to hel p you get a better conceptual understandi ng of
the rate, reacti on rate i s usual l y expressed as a posi ti ve val ue, and the negati ve si gn i s
i mpl i ed (i f the rate i s a di sappearance).
Sample: For the reacti on 2N
2
O
5
(g) 4NO
2
(g) 1 O
2
(g), wri te the rate expressi on for each
substance as shown i n Equati on 16.2.
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(Equati on 16.2)
www.petersons.com
Answer: Equati on 16.2, though i t may l ook compl i cated, i s real l y qui te si mpl e. Each rate
consi sts of two parts: the fi rst part i s a stoi chi ometri c factor (
1
a
, etc.), and the second
part i s the average rate from Equati on 16.1. The reason the stoi chi ometri c factor i s
needed i s because the rates of di sappearance or appearance of each substance are
rel ated to the number of mol es of each that are present. For i nstance, for every two
mol es of N
2
O
5
that decompose, one mol e of O
2
i s produced. Thi s means that the rate
of di sappearance of N
2
O
5
wi l l be hal f the rate of appearance of oxygen. The
expressi on for the enti re equati on l ooks l i ke thi s:
Rate 5
1
2
1
4
N O NO O
2 5 2 2
[ ]
[ ]
[ ]
t t t
You Try It!
Wri te the rate expressi on for each substance i n the fol l owi ng reacti on:
2N
2
O(g) 2N
2
(g) 1 O
2
(g)
Answer:
Rate 5 2
1
2
D[N
2
O]
Dt
5
1
2
D[N
2
]
Dt
5
D[N
2
]
Dt
Sample: Wel l refer to the reacti on from the previ ous sampl e: 2N
2
O
5
(g) 4NO
2
(g) 1 O
2
(g).
I f, at one poi nt, the rate of di sappearance of N
2
O
5
was 1.3 3 10
23
M s
21
, what
woul d the rate of appearance of O
2
be at thi s poi nt?
Answer: I f we substi tute the val ue 1.3 3 10
23
M s
21
i n for the rate of di sappearance of
N
2
O
5
, we wi l l end up wi th:
1
2
N O O
2 5 2
[ ]
[ ]
t t
2
1
2
~1.3 3 10
23
M s
21
! 5
D[O
2
]
Dt
Rate O
2
5 6.5 3 10
24
Note that the negati ve si gn was dropped. I t i s customari l y omi tted from the
reacti on rate. I n thi s case, O
2
i s bei ng formed, so i t woul d be posi ti ve anyway.
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You Try it!
I n the reacti on 2NO(g) N
2
(g) 1 O
2
(g), the measured rate of appearance of N
2
duri ng
one experi ment was 0.12 M s
21
. At thi s poi nt, what woul d be the rate of di sappearance
of NO?
Answer: 0.24 M s
21
Rate Laws
I n thi s next secti on, we are goi ng to l ook a l i ttl e more cl osel y at the rel ati onshi ps between
concentrati on and reacti on rate. Were al so goi ng to i ntroduce some general procedures that
can hel p you understand these rel ati onshi ps i n al most any reacti on. To begi n, we wi l l l ook at
some data from a fi cti ti ous seri es of experi ments i n whi ch substance A was combi ned wi th
substance B to form substances C and D i n a reacti on that has the equati on:
A 1 2B C 1 D
I n these experi ments, the amounts of A and B were careful l y measured pri or to thei r
combi nati on. The i ni ti al rates for each experi ment were cal cul ated, and al l data was pl aced i n
Tabl e 16.1.
You may noti ce some di sti nct patterns i n the data. For i nstance, i n the fi rst two experi ments,
the A doubl ed whi l e B remai ned constant. The reacti on rate al so doubl ed duri ng thi s peri od.
I n experi ment 3, the A doubl ed agai n, and so di d the reacti on rate. I t seems that the reacti on
rate i s di rectl y proporti onal to the concentrati on of A.
I f you l ook at experi ment 4, the concentrati on of A i s back to i ts i ni ti al l evel s (experi ment 1),
but the concentrati on of B has been doubl ed (compared to experi ment 1). Thi s had the same
effect on the rate of reacti on as doubl i ng A. Doubl i ng B caused the reacti on rate to doubl e. I t
appears that the reacti on rate i s al so di rectl y proporti onal to B. We can check thi s assumpti on
wi th the l ast experi ment. I n thi s experi ment, the l evel s of A are twi ce what they were i n
experi ment 1, whi l e the l evel s of B are 4 ti mes l arger. I f the reacti on rate i s di rectl y
proporti onal to the concentrati on of each reactant, we woul d expect the new reacti on rate to
be 8 ti mes l arger than the ori gi nal val ue (2 3 4). Compari son of the two val ues reveal s that i t
TABLE 16.1
Experiment Initial [A] M Initial [B] M Initial Rate (M s
21
)
1 0.10 0.10 1.3 3 10
26
2 0.20 0.10 2.6 3 10
26
3 0.40 0.10 5.2 3 10
26
4 0.10 0.20 2.6 3 10
26
5 0.20 0.40 1.04 3 10
25
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i s i ndeed 8 ti mes l arger, val i dati ng our assumpti on that the concentrati on of each substance
i s di rectl y proporti onal to the reacti on rate.
The rel ati onshi p between the concentrati on of reactants and the reacti on rate i s descri bed by
a factor known as the reacti on order. I n the previ ous exampl e, the rel ati onshi p between the
reactants and the reacti on rate was di rectl y proporti onal , meani ng that an i ncrease i n the
concentrati on of one reactant caused proporti onal l y the same i ncrease i n the rate. Doubl i ng
the concentrati on of a reactant doubl ed the rate of the reacti on. Thi s di rectl y proporti onal
rel ati onshi p i s known as a fi rst-order rel ati onshi p. I f changi ng the concentrati on of a
reactant had no effect on the reacti on rate, the rel ati onshi p woul d be descri bed as a
zero-order rel ati onshi p. A second-order rel ati onshi p i s exponenti al ; i n other words,
doubl i ng the concentrati on of a reactant wi l l i ncrease the rate by 4. The reacti on order for a
parti cul ar reactant i s wri tten as an exponent next to the concentrati on of that reactant. For
i nstance, because the previ ous reacti on was fi rst order for substance A, we coul d represent
thi s symbol i cal l y as [A] (the exponent 1 i s understood). I f A had a zero-order or second-order
rel ati onshi p, the symbol s woul d be wri tten [A]
0
and [A]
2
, respecti vel y.
These symbol s can be used to create a general expressi on to descri be the rel ati onshi ps
between the concentrati on of the reactants and the reacti on rate. Thi s expressi on i s known as
a rate l aw, and for the previ ous reacti on i t woul d have the form of Equati on 16.3:
Rate 5 k[A][B]
The vari abl e k represents the rate constant. Note the order of each reactant i s 1. The
reacti on order, whi ch descri bes the order of the enti re reacti on, can be determi ned by addi ng
the order of each reactant. For i nstance, i n thi s exampl e each reactant i s fi rst order (meani ng
each has an understood exponent of 1). The reacti on order i s the sum of the exponents, or 1 1
1 5 2. Thi s i s a second-order reacti on. Most reacti ons have an order of 0, 1, or 2, but some
have fracti onal orders or l arger numbers (though these are qui te rare). The order of the
reacti on must be determi ned experi mental l y. Unl i ke equi l i bri um expressi ons, the exponents
have nothi ng to do wi th the coeffi ci ents i n the bal anced equati ons.
I t i s i mportant that you make a di sti ncti on between the reacti on rate and the rate constant.
The bi ggest di sti ncti on i s that the reacti on rate depends on the concentrati ons of each
reactant (whi ch you can see from the formul a), and i t wi l l al ways have the same uni ts, usual l y
M s
21
. The rate constant i s not affected by concentrati ons. I t mai ntai ns the same val ue as
l ong as temperature i s kept constant. The uni ts of the rate constant wi l l al so vary accordi ng
to the order of the reacti on.
UNITS AND RATE CONSTANTS
I f we were to cal cul ate the val ue of uni ts of the rate constant i n the previ ous exampl e, we
coul d do so wi th rel ati ve ease. Begi nni ng wi th the equati on and rearrangi ng i t to sol ve for k,
we obtai n the expressi on:
Rate 5 k[A][B]
k 5
Rate
@A#@B#
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(Equati on 16.3)
TIP
You are expected
to know how to
determine the
units of a rate
constant.
www.petersons.com
Substi tuti ng uni ts i nto thi s expressi on, we fi nd:
k 5
M s
M M
M s
M
M s
2

( )( )

1 1
1 1
The uni ts for the rate constant for thi s reacti on are M
21
s
21
.
You Try It!
For each rate l aw, determi ne a) the order of each reactant, b) the overal l order of the
reacti on, and c) the uni ts of the rate constant, k. Assume that al l reacti on rates have
been expressed i n M s
21
.
1. Rate 5 k[NO]
2
[O
2
]
2. Rate 5 k[O
3
]
2
[O
2
]
21
Answers:
1. a. NO 5 second order; O
2
5 fi rst order
b. reacti on i s (211) 5 thi rd order
c. M
22
s
21
2. a. O
3
5 second order; O
2
5 21 order;
b. reacti on i s (2 1 21) 5 fi rst order
c. s
21
DETERMINING RATE LAWS
I n the previ ous secti on, we used a very si mpl e method of eyebal l i ng the data to determi ne the
order of the reacti on (and eventual l y the rate l aw). On the AP test, you must be abl e to
cal cul ate the rate l aw from the i ni ti al rates of reacti on. The rate l aw that we showed i n the
l ast secti on can be made i nto a generi c versi on that i s appl i cabl e to any reacti on. For a
reacti on where A and B are reactants (e.g., A 1 B C), the rate l aw takes the form:
Rate 5 k[A]
m
[B]
n
The exponents m and n represent the reacti on order for each substance. By compari ng the
rates and concentrati ons from two di fferent experi ments, we can numeri cal l y cal cul ate the
val ues of mand n. I n the sampl e probl em, we wi l l determi ne the rate l aw of a reacti on based
on experi mental data.
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Sample:
Experiment [A]
m
[B]
n
Initial Rate M s
21
1 0.20 0.20 1 3 10
23
2 0.20 0.40 1 3 10
23
3 0.40 0.20 4 3 10
23
One name often used to descri be thi s techni que i s the i sol ati on method. The
method of sol uti on rel i es on one reactant bei ng i sol ated. The concentrati ons of al l
reactants but one are hel d constant, whi ch wi l l al l ow you to cancel them i n the
cal cul ati on. We can use the generi c rate l aw equati on, substi tuti ng the data i n for
the vari abl es. By setti ng up a cal cul ati on, we can try to sol ve for mor n:
Rate
Exp 1
5 k[A]
m
[B]
n
Rate
Exp 2
5 k[A]
m
[B]
n
I f we l ook at the rati o of the rates of two experi ments, we can usual l y sol ve the
equati on for ei ther mor n. We can use experi ments 1 and 2 for the fi rst exampl e:
Rate
Rate
1 10
1 10
Exp 2
Exp 1
3
3
1
Thi s al l ows us to set up the fol l owi ng equati on:
Rate
Rate
M M
M M
Exp 2
Exp 1
[ ] [ ]
[ ] [ ]

k
k
m n
m n
0 20 0 40
0 20 0 20
1
. .
. .
I n thi s equati on, we can cancel the fi rst two terms i n the numerator and
denomi nator, l eavi ng us wi th the expressi on:
0 40
0 20
1
.
.
M
M
[ ]
[ ]

n
n
Si mpl i fyi ng thi s expressi on gi ves us:
2
n
5 1
n 5 0
Anythi ng rai sed to the zero power yi el ds 1; therefore, thi s i s a zero-order reacti on
for B. We can perform a si mi l ar procedure i n experi ments 3 and 1 to determi ne the
reacti on order for A. Si nce [B] i s constant i n experi ments 3 and 1, we can cancel i t:
Rate
Rate
4 10
1 10
Exp 3
Exp 1
3
3
4
2
m
5 4
m5 2; the reacti on i s second order for A
The rate l aw can be wri tten as: Rate 5 k[A]
2
[B]
0
or Rate 5 k[A]
2
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You Try It!
For the reacti on 2A 1 B C, experi mental data was col l ected for three tri al s:
Experiment [A]
m
[B]
n
Initial 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?
Answer: Rate 5 k[A]
0
[B]
2
REACTION TYPES
I n thi s secti on, you wi l l l earn how to recogni ze, di sti ngui sh, and work wi th fi rst-order and
second-order reacti ons. The order i s referri ng to the overal l order of the reacti on, not the order
for one of the reactants. Remember, the overal l order of the reacti on i s determi ned by addi ng
the exponents of the i ndi vi dual reactants.
First-Order Reactions
Because the order i s the sum of the exponents of the reactants, a fi rst-order reacti on must
depend onl y on the concentrati on of a si ngl e reactant (were goi ng to i gnore fracti onal
exponents). An exampl e of such a reacti on mi ght be a decomposi ti on reacti on wi th onl y one
reactant. The rate l aw for such a reacti on woul d be as fol l ows:
Rate 5 k[A], where the exponent i s an i mpl i ed one. I n the fi rst secti on of thi s
chapter, we showed that the reacti on rate for such a reacti on woul d be cal cul ated
usi ng the formul a:
Average rate 5 2
D@A#
Dt
I f we put both of these equati ons together, we come up wi th:
Rate 5 2

A [ ]
t
5 k[A]
Thi s expressi on can be transformed, usi ng cal cul us, i nto an equati on that al l ows us
to determi ne the concentrati on of A at any ti me duri ng the reacti on. I t i s not
necessary for you to be abl e to perform thi s transformati on, but you shoul d be
fami l i ar wi th Equati ons 16.4 and 16.5
l n
[A]
t
[A]
0
5 2kt or l n [A]
t
5 2kt 1 l n [A]
0
where [A]
0
i s the concentrati on of A at the start of the reacti on and [A]
t
i s the
concentrati on of A at any l ater ti me, t.
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(Equati ons 16.4
and 16.5)
www.petersons.com
You may be thi nki ng that the equati on on the l eft (16.4) l ooks fami l i ar to you. I t
shoul d, because i t i s nearl y the same as the equati on from Chapter 5
l n
N
t
N
0
5 2kt
whi ch was used to show the decay of a radi oacti ve i sotope over ti me.
The other equati on, Equati on 16.5 (whi ch i s just 16.4 rearranged), i s desi gned to show you one
of the more i mportant features of thi s topi c, graphi cal i nterpretati on of reacti on data.
Equati on 16.5 has the form of the sl ope-i ntercept expressi on i n math: y 5 mx 1 b. I f you
recal l , i n thi s equati on, mrepresents the sl ope of the l i ne and b i s the y-i ntercept. Thi s i s an
expressi on for a strai ght l i ne. One purpose of transformi ng the expressi on i s to al l ow us to
anal yze i t based on a strai ght-l i ne graph. Compare the two graphs i n Fi gure 16.5. The graph
on the l eft shows a pl ot of the fi rst-order decomposi ti on of substance A over ti me. The y-axi s
l i sts the change i n concentrati on over ti me. The parabol i c curve i n the l eft graph can be
strai ghtened by usi ng the natural l ogari thm of the concentrati on i nstead of the concentrati on.
Thi s i s a characteri sti c of a fi rst-order reacti on, and you shoul d be abl e to recogni ze i t. I f the
pl ot of the natural l og of the concentrati on over ti me i s a strai ght l i ne, the reacti on must be
fi rst order.
Sample: The fi rst-order reacti on 2N
2
O
5
(g) 2N
2
O
4
(s) 1 O
2
(s) has a rate constant of 4.80 3
10
24
s
21
at a certai n temperature. I f, at thi s same temperature, a 2.50 3 10
23
M
sampl e of di ni trogen pentoxi de i s al l owed to decompose for 10.0 mi nutes, what wi l l
be the new concentrati on of N
2
O
5
?
Answer: Because you are sol vi ng for the concentrati on of N
2
O
5
at ti me t, i t i s probabl y best
to use the sl ope-i ntercept versi on of the formul a. Thi s equati on wi l l be set up as
fol l ows:
l n [N
2
O
5
]
600 s
5 2kt 1 l n [N
2
O
5
]
0
l n [N
2
O
5
]
600 s
5 2(4.80 3 10
24
s
21
)(600.0 s) 1 l n (2.50 3 10
23
M)
l n [N
2
O
5
]
600 s
5 20.288 1 (25.991) 5 26.28
To sol ve for [N
2
O
5
], we must rearrange the equati on:
Time
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

A
,

M
Time
l
n

c
o
n
c
e
n
t
r
a
t
i
o
n

o
f

A
Figure16.5
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NOTE
Radioactive
decay is a
first-order
process, too!
www.petersons.com
[N
2
O
5
] 5 e
26.28
[N
2
O
5
] 5 1.87 3 10
23
M
You Try It!
For the reacti on descri bed i n the previ ous sampl e, how l ong wi l l i t take for [N
2
O
5
] to
reach 1.25 3 10
23
, assumi ng the starti ng concentrati on i s 2.50 3 10
3
M, l i ke i t was i n
the sampl e?
Answer: 1.44 3 10
3
s
HALF-LIFE
I f you recal l , back i n Chapter 5 we di scussed hal f-l i fe i n the context of the decay of radi oacti ve
nucl ei . I n that chapter, we defi ned the hal f-l i fe as the amount of ti me i t took for one hal f of the
ori gi nal sampl e of radi oacti ve nucl ei to decay. Because the rate of decay onl y depends on the
amount of the radi oacti ve sampl e, i t i s consi dered a fi rst-order process. Usi ng the same l ogi c,
we can appl y the concept of hal f-l i fe to fi rst-order chemi cal reacti ons as wel l . I n thi s new
context, the hal f-l i fe i s the amount of ti me requi red for the concentrati on of a reactant to
decrease by one-hal f. The hal f-l i fe equati on from Chapter 5 can be used to determi ne the
hal f-l i fe of a reactant:
t
k
1
2
0 693
.
Noti ce, the onl y factor that affects the hal f-l i fe i s the rate constant, k.
Sample: For the reacti on i n the l ast sampl e probl em (2N
2
O
5
(g) 2N
2
O
4
(s) 1 O
2
(s)),
determi ne the hal f-l i fe for the decomposi ti on of N
2
O
5
(k 5 4.80 3 10
24
s
21
).
Answer: Thi s i s just a strai ght pl ug-and-chug:
t
1
2
0 693
.
4.80 10 s
4 1
5 1.44 3 10
23
s
You may have noti ced that thi s i s the same answer as the l ast sampl e. I f you l ook at the
concentrati on val ues i n the probl em, the second concentrati on i s one hal f of the fi rst.
You Try It!
Substance X has a rate constant of 1.67 3 10
23
and decomposes i n a fi rst-order reacti on.
I f the i ni ti al concentrati on of X i s 4.80 3 10
22
M, how l ong wi l l i t take to reach a fi nal
concentrati on of 2.40 3 10
22
M?
Answer: 415 s (5 t1
2
)
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Second-Order Reactions
There are di fferent rate l aws that can represent second-order reacti ons, but for our purposes
we need not consi der al l of these. We can pi ck the easi est one, the composi ti on of a si ngl e
reactant that proceeds i n a second-order reacti on. I n such a reacti on, the rate l aw can be
wri tten as Equati on 16.6:
Rate 5

A [ ]
t
5 k[A]
2
Remember, i n these reacti ons, the rate of the reacti on vari es as the square of the change i n
concentrati on, so doubl i ng the concentrati on wi l l i ncrease the rate four ti mes.
I n another transformati on i nvol vi ng cal cul us (whi ch you dont need to know), we can
transl ate the rate expressi ons i nto a si ngl e expressi on that wi l l al l ow us to cal cul ate the
concentrati on at any ti me duri ng the reacti on (l i ke the expressi on we had for fi rst-order
reacti ons) i n Equati on 16.7:
1 1
0
A A [ ]
+
[ ]
t
kt
Noti ce agai n that thi s i s wri tten i n the sl ope-i ntercept format, where the sl ope of the l i ne i s k
once agai n. The di fferences between the equati ons and graphs of a second-order reacti on and
a fi rst-order reacti on are frequentl y a topi c on the AP test i n some form or another.
The mai n di fference that you must remember i s that for a fi rst-order reacti on, a pl ot of l n [A]
agai nst t wi l l generate a strai ght l i ne, and for a second-order reacti on, a pl ot of
1
[A]t
agai nst t
wi l l generate a strai ght l i ne.
The hal f-l i fe of a second-order reacti on i s al so si gni fi cantl y di fferent from the hal f-l i fe of a
fi rst-order reacti on. As Equati on 16.8 shows, the hal f-l i fe of a second order reacti on depends
on the i ni ti al concentrati on of the reactant (for fi rst-order reacti ons i t does not):
t
k
1
2 0
1
[ ]
A
THE RELATIONSHIP BETWEEN TEMPERATURE AND RATE
Temperature has a defi ni te effect on the rate of chemi cal reacti ons. Most often, an i ncrease i n
temperature corresponds to an i ncrease i n rate, al though there are a smal l number of
excepti ons. One thi ng to keep i n mi nd i s that the rate constant i s affected by changes i n
temperature. Thi s i s someti mes confusi ng to remember because i t i s not affected by
concentrati ons.
Al though there i s a great deal of evi dence to show that temperature changes affect reacti on
rates, there i s no si ngl e theory that expl ai ns why. There are two mai n theori es that together
expl ai n the rel ati onshi ps between temperature and rates. Nei ther theory on i ts own i s
suffi ci ent to expl ai n the rel ati onshi p. The two theori es are the col l i si on theory and the
transi ti on-state theory.
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(Equati on 16.6)
(Equati on 16.7)
(Equati on 16.8)
www.petersons.com
Collision Theory
The central premi se behi nd thi s theory i s that mol ecul es need to crash i nto each other i n
order to col l i de. On many i ntui ti ve l evel s, thi s i s an appeal i ng theory. I f parti cl es must col l i de
i n order to react, then anythi ng that i ncreases the l i kel i hood of col l i si ons shoul d i ncrease the
reacti on rate. I ncreases i n concentrati on, whi ch cause i ncreases i n rate, al l ow more parti cl es
to come i n contact or col l i de wi th each other. I ncreases i n temperature wi l l cause parti cl es to
move faster, whi ch wi l l i ncrease the number of col l i si ons. More col l i si ons wi l l l ead to i ncreased
reacti on rates at hi gher temperatures.
Nei ther of these i deas i s di sputed when tryi ng to rel ate them to reacti on rates. The probl em
wi th the col l i si on theory i s i t i s unabl e to expl ai n certai n rel ati onshi ps between temperature
and rate. Some major fl aws are that some reacti ons experi ence huge changes i n reacti on rate
for rel ati vel y smal l changes i n temperature, whi l e others experi ence smal l changes i n rate for
l arge changes i n temperature. Another probl em i s that onl y a very smal l percentage of
col l i si ons actual l y resul t i n a reacti on. These two probl ems rai se concerns about why
temperature effects are not consi stent across di fferent materi al s and why so few col l i si ons
resul t i n reacti ons.
One factor that each theory shares i s the vi ew that two col l i di ng parti cl es wi l l react onl y i f
thei r combi ned ki neti c energi es meet or exceed a threshol d val ue known as the acti vati on
energy (E
a
). As Fi gure 16.6 shows, the number of parti cl es possessi ng the acti vati on energy
i ncreases as temperature i ncreases. I f the acti vati on energy cant be achi eved, the reacti on
wont occur. The gasol i ne that i s i n the gas tank of a parked car wi l l si t i ndefi ni tel y, despi te
the fact that the parti cl es are col l i di ng. However, i f a spark energi zes the same parti cl es, they
can gai n suffi ci ent acti vati on energy to start the chemi cal reacti on that wi l l al l ow the car to
dri ve. Thi s combusti on reacti on i s a hi ghl y exothermi c reacti on (gi ves off heat). I f the
potenti al energy of such a reacti on i s pl otted agai nst the progress of the reacti on, the
resul ti ng graph l ooks l i ke the graph (a) on the l eft i n Fi gure 16.7. The fi gure i l l ustrates a few
si gni fi cant poi nts. Fi rst, si nce the potenti al energy i n the graph i s di rectl y rel ated to the
transfer of ki neti c energy duri ng the col l i si on, the graph shows that the ki neti c energy must
be suffi ci ent to reach the top of the hi l l for the reacti on to conti nue. Second, the parti cl es
that col l i de sti ck together for a bri ef peri od, formi ng what i s known as an acti vated compl ex.
The acti vated compl ex i s a temporary speci es that forms as a resul t of the col l i si on between
parti cl es. I ts exi stence i s temporary, so i t wi l l eventual l y fal l apart. Fi nal l y note that potenti al
energy drops bel ow i ts ori gi nal l evel when the products are formed. Thi s i s characteri sti c of an
Kinetic energy
Minimum energy
needed for reaction, E
a
Higher temperature
Lower temperature
F
r
a
c
t
i
o
n

o
f

m
o
l
e
c
u
l
e
s
Figure16.6
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exothermi c reacti on, where the products are more stabl e than the reactants. The excess
energy i s rel eased mostl y as heat, though someti mes i t i s accompani ed by l i ght and sound.
The graph (b) on the ri ght i n Fi gure 16.7 shows an endothermi c reacti on. The products of an
endothermi c reacti on are l ess stabl e than the reactants, so the energy after the reacti on
occurs i s hi gher than the energy before the reacti on. Note how the acti vati on energy i s al so
much l arger for an endothermi c reacti on. I n a sense, you have to force reactants to do
somethi ng they real l y dont want to do.
Transition-State Theory
Col l i si on theory, as i ts name mi ght suggest, focuses on the col l i si ons between parti cl es. The
col l i si ons must be frequent, and the col l i di ng parti cl es must have suffi ci ent energy to form an
acti vated compl ex. The transi ti on-state theory focuses on the behavi or of the acti vated
compl ex. Accordi ng to the transi ti on-state theory, there are three mai n factors that determi ne
i f a reacti on wi l l occur:
The concentrati on of acti vated compl exes
The rate at whi ch the compl exes break apart
The di recti on that the compl exes fal l apart (whether they break apart i nto the
products or fal l back apart as reactants)
Transi ti on-state theory assumes that an equi l i bri um forms between the acti vated compl ex
and the reactants. Large acti vati on energi es shi ft the equi l i bri um to favor the reactants,
whi l e smal l er acti vati on energi es shi ft more toward the acti vated compl ex. The mathemati cs
that compri se the transi ti on-state theory are too compl ex for consi derati on i n the AP course,
but you shoul d have a conceptual understandi ng of the basi c premi ses. I n the next secti on of
the chapter, we wi l l l ook more careful l y at the stages that take pl ace duri ng the bri ef ti me
between the formati on of the acti vated compl ex and the formati on of products.
Reaction progress
(a)
A B
E
a
C D
C D
Activated
complex
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
Reaction progress
(b)
A B
E
a
Activated
complex
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
Figure16.7
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REACTION MECHANISMS
Most reacti ons do not occur i n the si mpl e fashi on that we descri be i n a bal anced chemi cal
equati on. Chemi cal equati ons show the reactants and products of the reacti on but do nothi ng
to descri be how the former converts to the l atter. A method that i s used to show the
i ntermedi ate processes that occur duri ng a reacti on i s a reacti on mechani sm. A reacti on
mechani sm l i sts the proposed changes that take pl ace to the reactants as the product(s) are
bei ng formed. Usual l y thi s consi sts of two or three chemi cal reacti ons, referred to as
el ementary reacti ons or el ementary steps, shown one on top of the other. For exampl e, i n the
reacti on of ni trogen di oxi de and carbon monoxi de, the bal anced chemi cal equati on l ooks l i ke
thi s:
NO
2
(g) 1 CO(g) NO(g) 1 CO
2
(g)
I t may seem perfectl y reasonabl e that the carbon monoxi de mol ecul e coul d crash i nto the
ni trogen di oxi de mol ecul e i n just the ri ght way and steal the oxygen atom for i tsel f. Anal ysi s
of the reacti on, however, has detected the presence of the substance NO
3
, whi ch i s nei ther a
reactant nor a product of the reacti on. One expl anati on for thi s fi ndi ng i s that the reacti on
proceeds i n two steps:
Step 1: NO
2
1 NO
2
NO
3
1 NO
Step 2: NO
3
1 CO NO
2
1 CO
2
These two steps are known as the reacti on mechani sm for thi s reacti on. A reacti on mechani sm
must correctl y represent the overal l chemi cal equati on i f i t i s to be consi dered correct. The
way ei ther to obtai n an overal l equati on from the el ementary steps or to veri fy that the
el ementary steps are possi bi l i ti es i s to add the two together. I n thi s process, al l reactants are
pl aced on the l eft si de of the equati on and al l products are pl aced on the ri ght si de of the
equati on. Any substances that are found on both si des may be cancel ed:
El ementary steps NO
2
1 NO
2
NO
3
1 NO
NO
3
1 CO NO
2
1 CO
2
Sum of steps NO
2
1 NO
2
1 NO
3
1 CO NO
3
1 NO 1 NO
2
1 CO
2
Overal l equati on NO
2
1 CO NO 1 CO
2
Any substance that i s nei ther a reactant nor a product but that exi sts duri ng the reacti on i s
known as a reacti on i ntermedi ate. The number of i ntermedi ates can vary dependi ng on the
compl exi ty of a reacti on.
I n each el ementary step, the number of mol ecul es that take part i n the reacti on determi nes
the mol ecul ari ty of that step. When a si ngl e mol ecul e i s i nvol ved (thi s usual l y i nvol ves some
type of rearrangement), the reacti on i s l abel ed uni mol ecul ar. I n the previ ous exampl e, each
step had two mol ecul es reacti ng, whi ch makes i t a bi mol ecul ar reacti on. Termol ecul ar
reacti ons i nvol ve three mol ecul es but are qui te rare because they requi re the si mul taneous
col l i si ons of three mol ecul es.
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You Try It!
Usi ng the two el ementary steps shown bel ow, construct the bal anced equati on, and
determi ne the mol ecul ari ty of each step:
NO 1 NO N
2
O
2
N
2
O
2
1 O
2
NO
2
1 NO
2
Answer: 2NO 1 O
2
2NO
2
; step 1 and 2 5 bi mol ecul ar
Determining Rate Laws for Elementary Steps
Whi l e i t i s not possi bl e to determi ne the rate l aw of a reacti on by i nspecti ng i ts bal anced
equati on, i t i s possi bl e to deduce the rate l aw i f you know the el ementary steps for the
reacti on or, i n other words, the reacti on mechani sm. Knowi ng the mol ecul ari ty of the
el ementary step wi l l hel p you determi ne the rate l aw for that step. For exampl e, consi der the
el ementary step that i nvol ves the decomposi ti on of substance A i nto one or more product:
A products
Remember, rate l aws are wri tten i n terms of the concentrati on of the reactants. How wi l l the
rate of thi s reacti on depend on the concentrati on of A? You may remember from earl i er i n the
chapter that i t wi l l vary di rectl y wi th the concentrati on. Thi s i s al so the same form as a
radi oacti ve decay. These reacti ons are fi rst order, and the reacti on rate can be summari zed as:
Rate 5 k[A]
The el ementary steps i n the You Try I t! reacti on that you just compl eted are exampl es of
bi mol ecul ar reacti ons. Each step represents one of the two di fferent types of rate l aws that
can be wri tten for bi mol ecul ar el ementary reacti ons. The fi rst:
NO 1 NO N
2
O
2
i nvol ves the col l i si on of two i denti cal mol ecul es. Thi s can be rewri tten i n a generi c form:
A 1 A products
An i ncrease i n the concentrati on of A shoul d cause a proporti onal i ncrease i n the number of
col l i si ons. Thi s wi l l create the rate l aw expressi on:
Rate 5 k[A][A] or Rate 5 k[A]
2
The second el ementary step i n the exampl e was:
N
2
O
2
1 O
2
NO
2
1 NO
2
I n thi s step, the two reactant mol ecul es are di fferent substances. The generi c equati on for the
rate of such a bi mol ecul ar reacti on i s:
A 1 B products
The reacti on i s fi rst-order for each reactant because the rate wi l l be proporti onal to each
reactants concentrati on, so the reacti on rate expressi on for thi s type of step wi l l be:
Rate 5 k[A][B]
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RATE-DETERMINING STEPS AND RATE LAWS
I n reacti on mechani sms, the di fferent el ementary steps tend to occur at di fferent rates. Some
are faster than others. The sl owest step i s known as the rate-determi ni ng step for the
reacti on and wi l l determi ne the overal l rate at whi ch the reacti on wi l l proceed. Lets l ook at
an anal ogy that you may be abl e to rel ate to.
I magi ne that you are a customer at a fast-food restaurant. You arri ve at a very busy ti me of
day, and there are l i nes standi ng at each cash regi ster. Suppose you have nothi ng better to do
than watch what the empl oyees are doi ng behi nd the counter. You noti ce that each cashi er
takes an order and then fi l l s up the dri nks. After pl aci ng the dri nks on the counter, the
cashi er grabs a tray or a bag and begi ns col l ecti ng the food for the order. Fi rst, he pi cks up the
burgers from a bi n that i s bei ng fi l l ed up by a very anxi ous-l ooki ng woman who appears to be
worki ng rather qui ckl y. Next, he wal ks over to the french fry area to pi ck up the fri es for the
order. There i s a young man i n charge of the fry area who i s cooki ng the fri es and fi l l i ng up the
fry bags and boxes for the cashi ers. Just when your hunger has reached i ts breaki ng poi nt,
you step up to the counter and pl ace your order wi th the eager cashi er. He goes to get your
dri nk, goes to the burger bi n and gets your burger, wal ks over to the fry area, and then stops.
For some reason, there are no fri es ready. Wi thi n seconds, the other cashi ers begi n pi l i ng up
around the fry stati on. The dri ve-thru i s starti ng to back up. The fry guy i s stari ng nervousl y
i nto the fry vats, hopi ng he can wi l l the fri es to cook more qui ckl y. I n thi s exampl e, nobody
who ordered fri es can be served unti l those fri es are done. Even though the dri nks can be
fi l l ed qui ckl y, the burgers are ready to go, and the cashi ers are movi ng qui ckl y, no one can get
served unti l the fri es are cooked. The fry stati on i s the rate-determi ni ng step i n thi s scenari o.
I n chemi cal reacti ons, the rate-determi ni ng step works i n much the same way. From a
conceptual standpoi nt, consi der a reacti on wi th two el ementary steps where the fi rst step i s
the sl ow one (the rate-determi ni ng step). The concentrati on of the reactants i n the fi rst step i s
far more i mportant than the concentrati on of the addi ti onal reactants i n the second step. That
i s because the second step cant start unti l the fi rst step has been compl eted. I n our fast-food
exampl e, i ts the equi val ent of sayi ng that you cant speed up the process by addi ng more
cashi ers. You can have fi fty cashi ers, but i f there are no french fri es for them to pi ck up, they
cant do anythi ng.
Usi ng a reacti on as an exampl e, consi der the reacti on that occurs between ni trogen di oxi de
and fl uori ne. The reacti on i s bel i eved to have the fol l owi ng el ementary steps:
NO
2
1 F
2

k
1
NO
2
F 1 F
F 1 NO
2

k
2
NO
2
F
The k
1
and k
2
wri tten above the arrow represent the rate constant for those el ementary steps,
and the subscri pts are used to di sti ngui sh them from the rate constant, k, for the overal l
reacti on.
I n thi s reacti on, i f the fi rst step i s the rate-determi ni ng step (sl ow), then as soon as F
2
reacts
to form NO
2
F, the F that i s produced wi l l qui ckl y react to form another NOF. Therefore, the
rate of appearance of NO
2
F i s di rectl y rel ated to the rate of di sappearance of F
2
. Thi s means
that the fi rst step i s consi dered the rate-determi ni ng step. I n the previ ous secti on, we saw
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that a bi mol ecul ar reacti on, l i ke the el ementary steps i n thi s reacti on, has a predi ctabl e rate
l aw that wi l l take the form:
Rate 5 k
1
[NO
2
][F
2
]
At thi s poi nt, the rate l aw i s just an educated guess. I t must be compared wi th experi mental
data to determi ne i f i t i s supported. k
1
shoul d equal the experi mental l y determi ned rate
constant, k. An i mportant note here i s that even i f the experi mental data matches our
predi cted rate l aw, i t does not mean that our rate l aw i s correct. I f the data di sagrees wi th
ours, i t does al l ow us to rul e out our reacti on mechani sm, but i f the data supports ours, i t onl y
al l ows us to know that we have produced the best expl anati on for the ti me bei ng. For your
purposes on the AP test, what thi s transl ates to i s that you shoul d be careful how you word
any responses when you are predi cti ng the rate l aw from a reacti on mechani sm. Al ways
reserve a l i ttl e room for doubt.
Mechanisms Where the Initial Step Is Fast
What i f the rate-determi ni ng step i s the second step? Thi s becomes a bi t more di ffi cul t to
determi ne because an i ntermedi ate i s i nvol ved i n the rate l aw. Because i ntermedi ates are
usual l y qui te unstabl e, i t i s di ffi cul t to predi ct thei r concentrati ons. I f the second step i s sl ow,
then you have to assume that the fi rst step qui ckl y produces an i ntermedi ate. However, i f the
second step i s sl ow, the i ntermedi ate may not be abl e to break apart to form products. What
general l y happens i n thi s case i s that the i ntermedi ate wi l l fal l apart i nto the reactants agai n.
The reactants wi l l reform the i ntermedi ate, and equi l i bri um wi l l begi n between the
i ntermedi ate and the reactants. For mechani sms where a sl ow step i s preceded by a fast one,
i t i s assumed that equi l i bri um i s establ i shed i n the fast reacti on. Lets see how thi s works i n
an exampl e. I n the reacti on
H
2
(g) 1 I
2
(g) 2HI (g)
the experi mental l y determi ned rate l aw i s:
Rate 5 k[H
2
][I
2
]
A possi bl e mechani sm that i ncl udes a fast i ni ti al step i s:
I
2
k
1
k
1
2I (fast)
I 1 I 1 H
2

k
2
2HI (sl ow)
Remember, i f the sl ow reacti on i s preceded by a fast one, the fast one wi l l establ i sh
equi l i bri um. The rate constant of the forward reacti on (k
1
) i s equal to the rate constant of the
reverse reacti on (k
21
). I f we use the l ogi c of the previ ous exampl e, then the sl ow reacti on wi l l
determi ne the rate for the overal l reacti on. However, i f we wri te the rate l aw for thi s reacti on,
we run i nto a probl em. The rate l aw for the second step i s:
Rate 5 k
2
[I ][I ][H
2
] or Rate 5 k
2
[I ]
2
[H
2
]
The probl em i s that the reacti on i ntermedi ate i s present i n the rate l aw. Because these are so
unstabl e, they are i nappropri ate for rate l aws. The way to get around thi s i s to express the
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i ntermedi ate i n terms of the i ni ti al reactant, I
2
. Thi s can be done usi ng our assumpti on about
the equi l i bri um that i s establ i shed i n the fi rst step. I n thi s equi l i bri um, we can say that:
Rate 5 k
1
[I
2
] 5 k
21
[I ]
2
I f we rearrange thi s a bi t, we can fi nd a sui tabl e substi tute for the [I ]
2
porti on i n the rate l aw:
@I #
2
5
k
1
k
21
@I
2
#
I f we substi tute thi s i nto the ori gi nal rate l aw, we end up wi th:
Rate I H
2 2
[ ][ ]
k
k
k
2
1
1
I f i t can be shown that k
2
k
1
k
21
i s equal to k, thi s i s a reasonabl e reacti on mechani sm
(experi mental evi dence does support thi s assumpti on).
You Try It!
The fol l owi ng reacti on
2NO(g) 1 O
2
(g) 2NO(g)
i s bel i eved to proceed by the mechani sm shown bel ow:
NO 1 O
2
k
1
k
1
NO
3
(fast)
NO
3
1 NO
k
2
NO
2
1 NO
2
(sl ow)
Wri te a rate l aw for thi s reacti on that i s consi stent wi th the mechani sm:
Answer: Rate 5
k
k
k
2
1
1
[NO]
2
[O
2
]
THE EFFECT OF CATALYSTS ON REACTION RATE
Catal ysts are substances that change the rate of a reacti on wi thout bei ng consumed. They
hel p the reacti on to occur at a faster rate. I ntroductory courses often work wi th the
decomposi ti on of hydrogen peroxi de as an exampl e of a reacti on affected by a catal yst. The
decomposi ti on, shown bel ow, occurs very sl owl y under normal condi ti ons:
2H
2
O
2
(aq) 2H
2
O(l) 1 O
2
(g)
I f you spri nkl e a l i ttl e bi t of manganese di oxi de i nto the hydrogen peroxi de, the reacti on
begi ns to proceed qui te rapi dl y. When the reacti on i s compl ete, the manganese di oxi de can be
recovered i ntact. I n bi ol ogy cl asses, the same reacti on can be performed usi ng an enzyme
(an organi c catal yst that i s produced i n l i vi ng organi sms) extracted from beef l i ver.
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The i mportant effect of a catal yst i s to hel p a reacti on occur more qui ckl y than i t coul d
wi thout the catal yst. The way that a catal yst accompl i shes thi s i s to l ower the acti vati on
energy of the reacti on. I n Fi gure 16.8, noti ce the decreased hei ght of the curve, i ndi cati ng the
l owered acti vati on energy.
There are three di fferent forms of catal ysi s. The fi rst i s homogeneous catal ysi s, i n whi ch
the catal yst i s i n the same phase as the reactants. The decomposi ti on of hydrogen peroxi de
can al so be performed usi ng a homogeneous catal yst l i ke HBr. The bromi ne i ons catal yze the
decomposi ti on. The second type of catal ysi s i s shown wi th the use of manganese di oxi de as a
catal yst i n the hydrogen peroxi de decomposi ti on. Thi s type i s known as heterogeneous
catal ysi s because the catal yst i s i n a di fferent phase than the reactants (maki ng a
heterogeneous mi xture). The fi nal type i s bi ol ogi cal , and catal ysi s i s done wi th enzymes.
Qui te often catal ysts wi l l hel p bend, stretch, or ori ent mol ecul es so that they can react
more easi l y.
Reaction progress
Catalyzed reaction
E
n
e
r
g
y
Uncatalyzed reaction
Figure16.8
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EXERCISES: KINETICS
Multiple Choice
1. I f a reacti on, 2A 1 3B products, i s
fi rst order for A and second order for
B, the rate l aw for the overal l
reacti on wi l l be wri tten as Rate 5
______________.
(A) k[A][B]
(B) k[A][B]
2
(C) k[A]
2
[B]
2
(D) k[A]
2
[B]
3
(E) k[A]
2
[B]
2. The rate l aw for the reacti on 2A 1 B
C was found to be Rate 5
k[A][B]
2
. I f the concentrati on of B i s
tri pl ed, what wi l l happen to the rate
of the reacti on?
(A) I t wi l l stay the same.
(B) I t wi l l i ncrease by two ti mes.
(C) I t wi l l i ncrease by three ti mes.
(D) I t wi l l i ncrease by si x ti mes.
(E) I t wi l l i ncrease by ni ne ti mes.
THE DATA TABLE BELOW IS TO BE USED FOR
QUESTION 3.
Experi ment
I ni ti al
[NO
2
] m
I ni ti al
Reacti on
Rate M s
21
1 0.010 7.1 3 10
25
2 0.020 28 3 10
25
M s
3. Ni trogen di oxi de decomposes accord-
i ng to the fol l owi ng reacti on:
2NO
2
(g) 2NO(g) 1 O
2
(g)
For the i ni ti al rate data gi ven above,
what i s the val ue of k i n the rate l aw?
(A) 0.010 M
(B) 7.1 3 10
23
s
21
(C) 3.5 3 10
23
s
21
(D) 0.71 M
21
s
21
(E) 4
2H
2
O
2
(l) 2H
2
O(l) 1 O
2
(g)
4. Hydrogen peroxi de decomposes
accordi ng to the reacti on above,
whi ch i s fi rst order for H
2
O
2
and has
a hal f-l i fe 18.0 mi nutes. I f an H
2
O
2
sol uti on that was i ni ti al l y 0.80 M i s
al l owed to decompose for 72 mi nutes,
what wi l l the concentrati on be at
that ti me?
(A) 0.80 M
(B) 0.40 M
(C) 0.20 M
(D) 0.10 M
(E) 0.05 M
5. Whi ch of the fol l owi ng woul d produce
a l i near graph for the fol l owi ng
reacti on?
A product(s)
(A) mol A vs. ti me i f the reacti on i s
fi rst order for A
(B)
1
A [ ]
vs. ti me i f the reacti on i s
fi rst order for A
(C)
1
2
A [ ]
vs. ti me i f the reacti on i s
second order for A
(D) l n [A] vs. ti me i f the reacti on i s
fi rst order for A
(E) l n [A] vs. ti me i f the reacti on i s
second order for A
Rate 5 k[HCrO
4
2
][HSO
3
2
]
2
[H
1
]
6. I n the reacti on above, what i s the
order of the reacti on wi th respect
to H
1
?
(A) 0
(B) 1
(C) 2
(D) 3
(E) 4
e
x
e
r
c
i
s
e
s
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Rate 5 k[NO]
2
[Br
2
]
7. What i s the order for the overal l
reacti on shown above?
(A) Zero order
(B) Fi rst order
(C) Second order
(D) Thi rd order
(E) Not enough i nformati on
8. Whi ch of the graphs bel ow represents
an exothermi c reacti on?
(A)
Reaction progress
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
(B)
Reaction progress
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
(C)
Reaction progress
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
(D)
Reaction progress
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
(E)
Reaction progress
P
o
t
e
n
t
i
a
l

e
n
e
r
g
y
9. A catal yst does not affect whi ch of
the fol l owi ng?
I . Acti vati on energy
I I . Reacti on rate
I I I . Potenti al energi es reactants or
products
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I I and I I I
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2A 1 B products
10. The rate l aw for the reacti on above i s
Rate 5 k[A]
2
. What effect woul d
addi ng addi ti onal B have? (Assume
no change i n temperature or vol ume.)
(A) Both the val ue of k and the
reacti on rate woul d decrease.
(B) Both the val ue of k and the
reacti on rate woul d i ncrease.
(C) The val ue of k woul d remai n
constant, but the rate woul d
decrease.
(D) The val ue of k woul d remai n
constant, but the rate woul d
i ncrease.
(E) Nei ther the val ue of k nor the
reacti on rate woul d change.
Step 1: NO(g) 1 Cl
2
(g) NOCl
2
(g)
(fast equi l i bri um)
Step 2: NO(g) 1 NOCl
2
(g) 2NOCl (g)
(sl ow)
ni sm shown above?
(A) Rate 5 k[NO][Cl
2
]
(B) Rate 5 k[NO]
2
2
]
(D) Rate 5 k[NO]
2
[Cl ]
(E) Rate 5 k[NO]
2
[Cl ][NOCl
2
]
12. The reacti on mechani sm for the
chl ori nati on of tri chl oromethane i s
shown bel ow:
Cl
2
(g)
k
1
k
1
2Cl (g) (fast)
Cl (g) 1 CHCl
3
(g)
k
2
HCl (g) 1
CCl
3
(g) (sl ow)
Cl (g) 1 CCl
3
(g)
k
3
CCl
4
(g) (fast)
Whi ch of the fol l owi ng represents an
i ntermedi ate i n the reacti on?
(A) CHCl
3
(B) Cl
(C) Cl
2
(D) CCl
4
(E) HCl
e
x
e
r
c
i
s
e
s
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Free Response
QUESTION 1
A hypotheti cal reacti on takes pl ace accordi ng to the fol l owi ng equati on:
2A 1 B 3C 1 2D
The fol l owi ng rate data were obtai ned from three di fferent experi ments, al l of whi ch were
performed at the same temperature:
Experiment Initial [A]
m
Initial [B]
n
Initial rate M s
21
1 0.10 0.10 0.10
2 0.20 0.10 0.40
3 0.20 0.20 0.40
(A) Determi ne the rate l aw for the reacti on.
(B) Cal cul ate the rate constant, k.
(C) Cal cul ate the rate of the reacti on when [A] 5 0.30 M and [B] 5 0.30 M.
QUESTION 2
The proposed mechani sm for the reacti on i n thi s questi on i s shown bel ow:
Step 1: 2NO(g)
k
1
k
1
N
2
O
2
(g) (fast)
Step 2: N
2
O
2
(g) 1 H
2
(g)
k
2
H
2
O
2
(g) 1 N
2
(g) (sl ow)
Step 3: H
2
(g) 1 H
2
O
2
(g)
k
1
k
1
2H
2
O (fast)
(A) Wri te the bal anced equati on for thi s reacti on.
(B) I denti fy the rate-determi ni ng step.
(C) Wri te a rate l aw that i s most consi stent wi th thi s mechani sm.
(D) Based on your rate l aw, determi ne the effect of doubl i ng the concentrati on
of NO (whi l e mai ntai ni ng constant amounts of al l other reactants) on the
reacti on rate.
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Multiple Choice
1. B
2. E
3. D
4. E
5. D
6. B
7. D
8. A
9. C
10. E
11. D
12. B
1. The correct answer is (B). The order tel l s you the exponent to pl ace next to the
concentrati on. Because A i s fi rst order, an understood 1 i s next to [A]. B i s second order,
so [B] wi l l be squared.
2. The correct answer is (E). Because the rate l aw has the concentrati on of B squared,
the effect of tri pl i ng B wi l l i ncrease the rate by (3)
2
5 9.
3. The correct answer is (D). Fi rst, you must determi ne what the rate l aw shoul d be.
Thi s i s a bi mol ecul ar reacti on wi th a si ngl e reactant. Therefore, the rate l aw shoul d be
Rate 5 k[NO
2
]
2
. Another way to sol ve thi s i s to use the experi mental data to determi ne
the order of the reacti on for NO
2
. Thi s techni que begi ns wi th the assumpti on that
Rate 5 k[NO
2
]m. You need to sol ve for m. You can set up an equati on to sol ve for m:
Rate 2
Rate 1
5
28 3 10
25
7.1 3 10
25
5 k~0.020!
m
k~0.010!
m
4 5 2m m5 2
Once you have the rate l aw, you just substi tute the numbers from one of the
experi ments and sol ve for k:
Rate 5 k[NO
2
]
2
k 5
Rate
NO
0.71 M s
2
1 1
[ ]
( )
2
5
2
7 1 10
0 010
.
.
4. The correct answer is (E). Probabl y the easi est way to sol ve thi s i s wi thout an
equati on. I f the hal f l i fe i s 18 mi nutes, then 72 mi nutes makes 4 hal f-l i ves. I f the
sampl e 0.80 cuts i n hal f four ti mes, i t becomes 0.800.400.200.100.05 M.
We al so had an equati on i n Chapter 4 that can be rearranged to sol ve for H
2
O
2
(i nstead
of N, whi ch i s i n the equati on):
[H
2
O
2
] 5 [H
2
O]
t
5 0(
1
2
)
4
[H
2
O
2
] 5 (0.8) (
1
2
)
4
5 0.05 M
5. The correct answer is (D). Thi s i s a fi rst-order reacti on wi th a si ngl e reactant. A
graph of the concentrati on pl otted agai nst ti me woul d produce a curve. By pl otti ng the
natural l ogari thm of the concentrati on agai nst the ti me, you can produce a strai ght
l i ne. Thi s i s characteri sti c of a fi rst-order reacti on. A si mi l ar transformati on i s al so
accompl i shed by taki ng the base 10 l ogari thm of the concentrati on.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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6. Thecorrect answer is(B). The order of the reacti on wi th respect to H
1
i s determi ned
by l ooki ng at the exponent next to the [H
1
]. Si nce there i s none wri tten, thi s means i t
i s an understood 1, whi ch represents fi rst order.
7. The correct answer is (D). Si mpl y add the exponents for each concentrati on:
(2 1 1) 5 3
8. The correct answer is (A). I n an exothermi c reacti on, the potenti al energy of the
products wi l l be l ower than that of the reactants. The energy di fference i s due to the
l oss of energy as heat. The onl y graph that shows a decrease i n the energy of the
products i s choi ce (A). The other most common type of pl ot i s choi ce (B), whi ch
represents an endothermi c reacti on.
9. The correct answer is (C). A catal yst does l ower the acti vati on energy and the
reacti on rate. However, the i ni ti al potenti al energy of the reactants and the fi nal
potenti al energi es of the products are the same wi th or wi thout catal ysi s.
10. The correct answer is (E). Because choi ce (B) i s not part of the rate l aw, i ts
concentrati on does not affect the rate or rate constant for the reacti on (as l ong as some
i s present).
11. The correct answer is (D). I n thi s reacti on, the rate-determi ni ng step i s the second
step. The rate l aw shoul d be wri tten from thi s step. However, when wri ti ng the
rate l aw:
Rate 5 k[NO][NOCl
2
]
you enter the concentrati on of an i ntermedi ate, whi ch i s i ncorrect. You must rewri te the
rate l aw i n terms of the reactants. Therefore, you need to create an equal i ty based on
the i ni ti al equi l i bri um, whi ch wi l l al l ow you to substi tute the reactants i nto the
expressi on:
NO(g) 1 Cl
2
(g)
k
1
k
1
NOCl
2
(g)
Rate 5 k
1
[NO][Cl
2
]
Rate 5 k
21
[NOCl
2
]
k
1
[NO][Cl
2
] 5 k
21
[NOCl
2
]
k
k
1
1
[NO][Cl
2
]5 [NOCl
2
]
Thi s can now be substi tuted i nto the rate l aw:
Rate 5 k
2
[NO][NOCl
2
]
Rate 5 k
2
k
k
1
1
[NO][NO][Cl
2
]
whi ch can now be rearranged. Duri ng the rearrangement, i t i s assumed that k
2
k
k
1
1
i s
equi val ent to the experi mental rate l aw constant, k:
Rate 5 k[NO]
2
[Cl ]
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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12. Thecorrect answer is(B). The easi est way to determi ne the i ntermedi ates i s to wri te
one equati on wi th al l of the reactants on one si de and al l of the products on the other
si de. For thi s reacti on, the fol l owi ng equati on resul ts:
Cl
2
(g) 1 Cl (g) 1 CHCl
3
(g) 1 Cl (g) 1 CCl
3
(g) 2Cl (g) 1 HCl (g) 1 CCl
3
(g) 1 CCl
4
(g)
Al l substances that are on both si des of the arrow can be cancel ed:
Cl
2
(g) 1 CHCl
3
(g) HCl (g) 1 CCl
4
(g)
The i ntermedi ates are those substances that appear i n the l onger, fi rst equati on but not
i n the bal anced equati on. Al though CCl
3
i s al so an i ntermedi ate, i t i s not one of the
choi ces i n the questi on.
Free Response
QUESTION 1
(A) The fi rst questi on can be done i n your head, but you may be asked to show your
work, so i t i s useful to be abl e to sol ve the probl em both ways. The qui ck
i nspecti on method i s to l ook at what happens to the rate when onl y one substance
changes. For exampl e, i n experi ment 2 the concentrati on of A doubl es whi l e the
concentrati on of B stays the same. The reacti on rate i ncreases by 4, whi ch
i ndi cates the reacti on i s second order for A. I n experi ment 3, the concentrati on of
B doubl es whi l e A remai ns constant. Thi s change produces no change i n reacti on
rate, meani ng that the reacti on i s zero order for B. By i nspecti on, the rate
equati on becomes Rate 5 k[A]
2
. Usi ng rates equati ons, you can al so determi ne
the rate l aw. Thi s requi res sol vi ng for the vari abl es mand n i n the equati on:
Rate 5 k[A]
m
[B]
n
To sol ve for m, we need to choose two experi ments where B i s constant. Thi s
al l ows us to cancel n and i sol ate m:
Rate 2
Rate 1
0.40 M s
0.10 M s

[ ] [ ]
[ ]
1
1
0 20 0 10
0 10 0
k
k
m n
m
. .
. ..10
[ ]
n
4 5 2
m
2 5 m
The same i s repeated for n:
Rate 3
Rate 2
0.40 M s
0.10 M s

[ ] [ ]
[ ]
1
1
0 20 0 20
0 20 0
k
k
m n
m
. .
. ..10
[ ]
n
1 5 2
n
n 5 0
Usi ng equati ons, we sti l l get Rate 5 k[A]
2
[B]
0
or Rate 5 k[A]
2
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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(B) To cal cul ate the rate l aw, we just need to substi tute some data i nto the equati on.
I t doesnt matter whi ch experi ment we use:
Rate 5 k[A]
2
0.10 M s
21
5 k(0.10 M)
2
k 5
0.10 M s
21
~0.01 M!
2
5 10 M
21
s
21
(C) Now that you have cal cul ated k, you can substi tute the val ues of A and B i nto the
rate equati on:
Rate 5 k[A]
2
5 (10 M
21
s
21
)(0.30 M)
2
5 0.90 M s
21
QUESTION 2
(A) To wri te the bal anced equati on, we need to wri te al l reactants and products and
cancel l i ke substances:
2NO(g) 1 N
2
O
2
(g) 1 H
2
(g) 1 H
2
(g) 1 H
2
O
2
(g) N
2
O
2
(g) 1 H
2
O
2
(g) 1 N
2
(g) 1
2H
2
O
After cancel i ng al l substances that appear on both si des of the arrow, the
equati on becomes:
2NO(g) 1 2H
2
(g) N
2
(g) 1 2H
2
O
(B) The rate-determi ni ng step i s the sl ow one, step 2.
(C) The rate l aw that i s most consi stent wi th thi s mechani sm must be determi ned
from step 2, the rate-determi ni ng step. From thi s step, we obtai n the rate l aw:
Rate 5 k
2
[N
2
O
2
][H
2
]
Unfortunatel y, we cant use thi s expressi on because i t contai ns an i ntermedi ate.
We need to fi nd a sui tabl e repl acement for N
2
O
2
. I n thi s case, we can obtai n i t
from the equi l i bri um i on, step 1. By usi ng the equi l i bri um, we can sol ve for N
2
O
2
i n terms of one of the reactants, NO.
For the forward reacti on: Rate 5 k
1
[NO]
2
For the reverse reacti on: Rate 5 k
21
[N
2
O
2
]
The two reacti ons have the same rate, so they are equal to each other. You can set
up the equal i ty and then rewri te the expressi on i n terms of [N
2
O
2
]:
k
1
[NO]
2
5 k
21
[N
2
O
2
]
[N
2
O
2
] 5
k
1
k
21
[NO]
2
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www.petersons.com
Thi s can be pl aced i nto the rate equati on i nstead of N
2
O
2
:
Rate 5 k
2
[N
2
O
2
][H
2
]
Rate 5 k
2
k
k
1
1
[NO]
2
[H
2
]
I f k
2
k
k
1
1
i s assumed to be equi val ent to the overal l rate constant, k, the
expressi on can then become:
Rate 5 k[NO]
2
[H
2
]
(D) Because the reacti on i s second order for NO, doubl i ng the concentrati on of NO
wi l l i ncrease the rate of reacti on four ti mes (2
2
5 4).
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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SUMMING IT UP
The rate at whi ch a reacti on occurs i s known as the reacti on rate. Thi s rate i s typi cal l y
determi ned by measuri ng the amount of one substance (ei ther a reactant or product) over
ti me. The reacti on stoi chi ometry can then be used to determi ne the other substances that
were not measured.
The rate of a reacti on i s someti mes affected by the concentrati on of a reactant. The degree
to whi ch the reacti on i s affected depends on the rate l aw for the reacti on.
The rate l aw i s an equati on that rel ates the concentrati on of the reactants to the rate of
the reacti on. The rate l aw can onl y be determi ned experi mental l y and i s not affected by
changes i n concentrati on.
The reacti on order determi nes the exact numeri cal rel ati onshi p between the reactants
and the reacti on rate. There are ti mes when the concentrati on of a reactant does not
affect the reacti on rate. Such reactants are descri bed as zero-order for the reacti on (as
l ong as they are present, i t does not matter how much there i s).
Fi rst-order reacti ons onl y depend on the concentrati on of a si ngl e substance. Qui te often
they are decomposi ti on reacti ons that fol l ow the form of a nucl ear decay.
Temperature has a defi ni te effect on reacti on rate, but the reasons for the changes are not
compl etel y understood. The two theori es that descri be thi s rel ati onshi p are the col l i si on
theory and the transi ti on-state model .
Col l i si on theory proposes that i ncreases i n temperature i ncrease reacti on rates by
i ncreasi ng the number of col l i si ons that occur between parti cl es and by i ncreasi ng the
ki neti c energy that parti cl es possess when they col l i de.
Transi ti on-state theory focuses on the rates at whi ch parti cl es form and are formed from
acti vated compl exes.
Cruci al to both theori es i s the concept of acti vati on energy, whi ch i s the amount of energy
that i s requi red to cause substances to react.
Catal ysts are substances that i ncrease the reacti on rate wi thout bei ng consumed i n the
process. They work by decreasi ng the acti vati on energy for a reacti on.
Reacti on mechani sms are proposed steps that occur duri ng a chemi cal reacti on. By
compari ng proposed reacti on mechani sms wi th experi mental rate data, you can
determi ne the rate l aw of a reacti on.
I n reacti on mechani sms of more than one step, the sl owest step, known as the
rate-determi ni ng step, wi l l determi ne the rate l aw and the rate of the reacti on.
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www.petersons.com
Thermodynamics
OVERVIEW
The first law of thermodynamics
Enthalpy
Thermochemical equations
Hesss law
Spontaneity
Entropy
The second law of thermodynamics
Gibbs free energy
Summing it up
One aspect of chemi cal behavi or that we have not l ooked at i n much detai l i s
the rel ati onshi p among the energi es of reactants, products, and reacti ons.
Near the end of Chapter 16, you read about acti vati on energy and how
reactants must meet or exceed that threshol d val ue before a reacti on can
occur. I n thi s chapter, we wi l l l ook more cl osel y at the energy i nteracti ons
between chemi cal reacti ons and the surroundi ng envi ronment. Al though these
i nteracti ons can be qui te compl ex, there are some basi c patterns that you can
l earn that wi l l al l ow you to make accurate predi cti ons about chemi cal
behavi ors.
I n thi s chapter, there i s some termi nol ogy that must be cl ear before we begi n.
The fi rst term i s the word system. The uni verse i s a very l arge pl ace and i t
woul d be i mpossi bl eand a bi t ri di cul ousto descri be al l energy changes i n
terms of the uni verse. I f we are descri bi ng a chemi cal reacti on that i s
occurri ng i n a beaker, i t i s useful to be abl e to restri ct our attenti on to the
acti vi ti es wi thi n the beaker wi thout havi ng to qual i fy our comments by
i ncl udi ng everythi ng outsi de the beaker. I f the beaker contai ns a si l ver ni trate
sol uti on reacti ng wi th a zi nc stri p, the beaker, the sol uti on, and the zi nc make
up al l that we are real l y i nterested i n. Thi s speci fi c pl ace or porti on of the
uni verse that we are setti ng asi de for observati on i s the system. Everythi ng
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
1
7
411
el se i s consi dered the surroundi ngs. Thi s parti cul ar system represents an open system
because i t i s open to the rest of the atmosphere. As such, the contents of the system are free
to i nteract wi th the surroundi ngs, and vi ce-versa. The most common of these i nteracti ons i s
the pressure exerted by the atmosphere on the system. Open systems exi st at atmospheri c
pressure and are affected by the temperature of the surroundi ngs. Cl osed systems are
physi cal l y i sol ated from the surroundi ngs. A stoppered test tube or a seal ed fl ask represent
cl osed systems. Most of the l ab work that you do as part of the AP course takes pl ace i n an
open system.
The next term that i s used or i mpl i ed throughout thi s chapter i s state functi on. A state
functi on i s a property of a system that i s onl y rel ated to i ts current condi ti onsi t i s not
concerned wi th how i t got to be at those condi ti ons. An exampl e woul d be a beaker of water at
50 C. The beaker of water possesses a certai n temperature, vol ume, and energy under these
condi ti ons. I t does not matter i f i t was once fi l l ed wi th i ce and reached 50C by bei ng warmed
or i f i t was once boi l i ng and reached 50C by bei ng cool ed. The state functi ons, among whi ch
are pressure, vol ume, temperature, energy, and enthal py, si mpl y descri be the substance as i t
i s at a parti cul ar moment.
THE FIRST LAW OF THERMODYNAMICS
The fi rst l aw of thermodynami cs i s one of the most fundamental premi ses i n sci ence. Al so
known as the l aw of conservati on of energy, i t states that energy can nei ther be created nor
destroyedi t i s conserved. An i mportant thi ng to remember i s that thi s appl i es to the
uni verse, not a parti cul ar system. Energy can be l ost or gai ned by a system, but the l aw of
conservati on of energy tel l s us that i t doesnt just appear or di sappear. I t i s transferred from
one object to another i n any number of forms. Any system, therefore, wi l l gai n and l ose energy
from the surroundi ng envi ronment.
The energy of a system consi sts of the energi es of al l components i n the system at al l l evel s,
i ncl udi ng the atomi c l evel . There are too many energy-rel ated factors to consi der i n a system,
so the energy of a system cant be measured di rectl y. We can, however, measure changes i n the
energy, whi ch wi l l gi ve us an i ndi rect l ook at the i ni ti al and fi nal energi es. The energy change
i n the system i s defi ned as DE, whi ch i s cal cul ated usi ng Equati on 17.1:
DE 5 E
fi nal
2 E
i ni ti al
(I n future probl ems, we wi l l use the symbol s f and i to represent fi nal and i ni ti al .)
Energy must be defi ned as havi ng a di recti on as wel l as an amount. Thi s wi l l be true for al l of
the measurements we di scuss i n thi s chapter. Di recti on i s necessary to understand whether
energy i s bei ng gai ned or l ost by the system. A posi ti ve change i n energy, DE, i ndi cates energy
i s gai ned by the system, whi l e a negati ve DE shows an energy l oss. Energy exchanges wi th
the envi ronment are defi ned i n terms of heat, q, and work, w. The energy of a system wi l l
i ncrease as heat i s added and wi l l decrease as heat i s l ost. Li kewi se, work done on a system
wi l l i ncrease i ts energy, whi l e work done by a system wi l l decrease i ts energy. The
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(Equati on 17.1)
www.petersons.com
rel ati onshi p between energy, heat, and work can be summari zed i n Equati on 17.2, shown
bel ow:
DE 5 q 1 w
Li ke E, q and w have si gns associ ated wi th thei r di recti ons. The val ue of q i s posi ti ve when
heat i s bei ng added to the system and negati ve when heat i s bei ng l ost. The val ue of w i s
posi ti ve when work i s done on the system and negati ve when work i s bei ng done by the
system. The si gn of DE wi l l depend on the si gns of q and w.
ENTHALPY
Because the systems that you are worki ng wi th are under fai rl y standard condi ti ons, you can
i gnore the effects of work on the system. Thi s means that the changes i n energy wi l l be
rel ated to heat. The heat that i s gai ned or l ost by a system i s defi ned as the enthal py of the
system. Enthal py i s a state functi on and i s defi ned by the symbol H. Li ke energy, enthal py
cant be measured di rectl y. I t i s understood i n terms of changes i n enthal py, DH. The change
i n enthal py, DH, at constant pressure, can be defi ned as Equati on 17.3:
DH 5 H
f
2 H
i
5 q
p
where q
p
i s the heat associ ated wi th constant pressure. When pressure changes, work has to
be consi dered, whi ch makes thi ngs a bi t more compl i cated. You are not responsi bl e for
knowi ng about thi s speci al si tuati on. The si gn of DH al so rel ates to the di recti on of heat
transfer. A posi ti ve val ue of DH i ndi cates that the system has gai ned heat from the
surroundi ngs. We have previ ousl y descri bed thi s as bei ng an endothermi c process. A
negati ve val ue of DH i ndi cates the system has l ost heat to the surroundi ngs, whi ch i s an
exothermi c process.
THERMOCHEMICAL EQUATIONS
A thermochemi cal equati on must be bal anced, i ncl ude al l states of each reactant and
product, and l i st the enthal py for the reacti on. An exampl e of such a reacti on i s shown bel ow:
N
2
(g) 1 3H
2
(g) 2NH
3
(g) DH 5 291.8 kJ
There are reasons for the speci fi c cri teri a i n the desi gn of thi s equati on. The states of matter
must be speci fi ed because, as you may recal l , a certai n amount of heat may be requi red or l ost
by reactants and/or products i f they change state i n the course of a reacti on. Second, the
equati on must be bal anced because enthal py val ues for equati ons vary accordi ng to the
number of mol es of a substance. That i s, the val ue of DH changes proporti onal l y to the
coeffi ci ents i n a bal anced equati on. I f you combi ne twi ce the amount of reactants, the
enthal py wi l l be twi ce as great. Thi s al so al l ows you to pl ace fracti onal coeffi ci ents i n front of
substances to si mpl i fy probl ems.
A fi nal assumpti on of thermochemi cal equati ons i s that when you reverse the di recti on of a
chemi cal reacti on, you onl y change the si gn of the enthal py. For exampl e, the synthesi s of
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(Equati on 17.2)
(Equati on 17.3)
Chapter 17: Thermodynamics 413
www.petersons.com
ammoni a i s an exothermi c process that rel eases 91.8 kJ of heat. I f you reverse the di recti on to
show the decomposi ti on of ammoni a, the reacti on becomes endothermi c:
2NH
3
(g) N
2
(g) 1 3H
2
(g) DH 5 191.8 kJ
Sample: The compl ete combusti on of butane gas, C
4
H
10
, i n oxygen gas, O
2
, produces CO
2
and H
2
O. I t i s a hi ghl y exothermi c process rel easi ng 2845 kJ of heat per mol e of
butane. Wri te the bal anced thermochemi cal equati on, usi ng al l whol e-number
coeffi ci ents. Al so, determi ne the enthal py change i n burni ng 50.0 g of butane gas.
Answer: 2C
4
H
10
(g) 1 13O
2
(g) 8CO
2
(g) 1 10H
2
O(g) DH 5 25690 kJ
The enthal py has to be negati ve because the heat i s gi ven off i n the reacti on. The
quanti ty has to be doubl ed because the ori gi nal val ue i s for one mol e of butane.
Many ti mes, fracti onal coeffi ci ents are used to si mpl i fy the equati ons. For exampl e,
the same reacti on can be rewri tten as:
C
4
H
10
(g) 1
13
2
O
2
(g) 4CO
2
(g) 1 5H
2
O(g) DH 5 22845 kJ
For the second part of thi s questi on, you know that the enthal py change for one
mol e of butane i s 22845 kJ. Al l you need to do i s determi ne what fracti on of a mol e
50.0 g i s and reduce the enthal py by that amount:
50.0 g 3
1 mol
58.14 g
5 0.86 mol
The enthal py for 50.0 g i s 0.86 3 22845 kJ 5 22450 kJ
Measuring the Heat of Reaction
Enthal py changes, l i ke the ones weve just fi ni shed l ooki ng at, can be determi ned experi men-
tal l y. We have descri bed enthal pi es i n terms of energy i nteracti ons between a system and the
surroundi ngs. Enthal py changes can be experi mental l y determi ned by measuri ng the effects
that a substance has on i ts surroundi ngs as wel l as the effects of the surroundi ngs on the
substance. I n thi s secti on, we wi l l l ook at how these changes are measured.
Thermochemi cal measurements are based on the rel ati onshi ps between heat and tempera-
ture. The measurement that rel ates to the two i s heat capaci ty, defi ned as the amount of
heat that i s requi red to rai se the temperature of a substance 1C. (The amount of substance
i s someti mes expressed i n mol es or i n grams.) The heat capaci ty of a mol e of a substance i s
known as the mol ar heat capaci ty, whi l e the heat capaci ty for gram val ues of a substance
are known as speci fi c heat capaci ti es. The speci fi c heat of a substance i s the amount of
heat requi red to rai se 1 gram of the substance 1C. The formul a that i s used to cal cul ate
speci fi c heat i s Equati on 17.4:
q 5 msDT
where qi s the heat requi red, mi s the number of grams of the substance, s i s the speci fi c heat,
and DT i s the di fference between the fi nal temperature and the i ni ti al temperature. I f you
exami ne the equati on, you wi l l see that i f you add equal amounts of heat to equi val ent masses
of di fferent materi al s, the change i n temperature wi l l be i nversel y rel ated to the speci fi c heat.
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(Equati on 17.4)
www.petersons.com
I f a substance has a smal l speci fi c heat, i t wi l l onl y take a smal l amount of heat to produce a
l arge change i n temperature. Li kewi se, a substance wi th a l arge speci fi c heat requi res a l arge
amount of heat to produce a si mi l ar change i n temperature. Water has one of the hi ghest
speci fi c heats at 4.18 J/gC; copper, by compari son, i s 0.384 J/gC. To hel p you vi sual i ze thi s
concept, i magi ne a cup of water si tti ng i n the mi dday sun on a hot summer day. Next to i t,
pi cture an equi val ent mass of copper. Now i magi ne pi cki ng up the pi ece of copper or sti cki ng
your fi nger i n the water. The copper wi l l be much hotter because the addi ti on of about the same
amount of heat produced a much l arger temperature change (due to the l ower speci fi c heat).
The typi cal way to measure the heat rel eased duri ng a reacti on i s to measure the temperature
change of the surroundi ngs. Thi s can be accompl i shed by usi ng a devi ce known as a
cal ori meter. The purpose of a cal ori meter i s to create a cl osed system i n whi ch to perform the
reacti on. The cl osed system al l ows the heat to be transferred enti rel y from the reactants to
the surroundi ngs wi thout i nterference from the outsi de envi ronment. Any devi ce that
i nsul ates the reacti on from the outsi de envi ronment can serve as a cal ori meter. The most
basi c type consi sts of a Styrofoam coffee cup, whi l e more sophi sti cated cal ori meters are used
for more accurate work.
The premi se behi nd the functi on of the cal ori meter i s that any heat rel eased duri ng a
chemi cal reacti on wi l l be l ost to the surroundi ngs. Thi s gai n of heat by the surroundi ngs
produces a temperature change i n the surroundi ngs. We can use the i ncrease i n temperature
as a way to detect the enthal py of the reacti on. To hel p you understand the concept of thi s
process, wel l consi der a very si mpl e exampl e.
Consi der a coffee-cup cal ori meter fi l l ed wi th 250 g of di sti l l ed water at room temperature
(25C). Now, l ets say you take a 5.00 g pi ece of i ron that has been heated to 100C by pl aci ng
i t i n a contai ner of boi l i ng water for an extended peri od of ti me. I f you pl ace the i ron i nto the
room temperature water, you can probabl y i magi ne that the temperature of the i ron wi l l cool
down whi l e the temperature of the water wi l l i ncrease. The i ncrease i n the waters
temperature and decrease i n the i rons temperature are di rectl y rel ated to the transfer of heat
from the i ron to the water. The two wi l l not stop changi ng temperature unti l they have both
reached the same temperature. I f the fi nal temperature of the water i s 25.2C, what i s the
speci fi c heat of the i ron? The speci fi c heat of water i s 4.18 J/gC.
The heat l ost by the i ron wi l l equal the heat gai ned by the water, so we can use the speci fi c
heat equati on to sol ve the probl em:
q
m
5 m
m
s
m
DT
m
q
H
2
O
5 m
H
2
O
s
H
2
O
DT
H
2
O
Si nce q
m
5 q
H
2
O
we can make these two equati ons equal to each other and sol ve them:
m
m
s
m
DT
m
5 m
H
2
O
s
H
2
O
DT
H
2
O
(5.0 g)(s
m
)(25.2C 2 100C) 5 (250 g)(4.18 J/gC)(25.2C 2 25.0C)
s
m
5
209 J
374 gC
5 0.559 J/gC
I n thi s second type of sampl e, the enthal py of a reacti on can be determi ned from the heat of
the reacti on, whi ch wi l l take pl ace at constant atmospheri c pressure.
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NOTE
Sometimes the
variable c is used
in place of s in
heat capacity
equations.
www.petersons.com
Sample: I n thi s probl em, 50.0 mL of 0.100 M AgNO
3
and 50.0 mL of 0.100 M HCl are mi xed
together. The sol i d si l ver chl ori de wi l l form accordi ng to the reacti on shown bel ow:
Ag
1
(aq) 1 Cl
2
(aq) AgCl (s)
The i ni ti al temperature of the sol uti on was 25.0C, and the fi nal temperature was
25.8C. Determi ne the enthal py, i n kJ mol
21
, for the formati on of si l ver chl ori de.
The vol ume of the fi nal sol uti on was 100 mL, and i t had a densi ty of 1.00 g/mL. The
speci fi c heat of water i s 4.18 J/gC.
Answer: The temperature change of the sol uti on i s determi ned by the amount of heat l ost i n
the reacti on. Usi ng the formul a for speci fi c heat, we can determi ne the heat gai ned
by the sol uti on. The mass of the sol uti on must be cal cul ated from the densi ty:
100 mL
1.00 g
1 mL
100 g
q 5 msDT
q 5 (100 g)(4.18 J/gC)(25.8C 2 25.0C) 5 334.4 J
Thi s number represents the amount of heat gai ned by the water. The probl em i s
aski ng for the enthal py i n kJ mol
21
. To convert to thi s answer, we need to
determi ne the mol ar quanti ti es of each substance:
50 mL of 0.100 M AgNO
3
5 0.050 L 3
0.100 mol
1 L
5 5 3 10
23
mol AgNO
3
50 mL of 0.100 M HCl 5 0.050 L 3
0.100 mol
1 L
5 5 3 10
23
mol HCl
These two wi l l combi ne to produce 5 3 10
23
mol AgCl . Therefore, we can convert the heat
gi ven i n J to kJ/mol usi ng the fol l owi ng procedure:
334.4 J 1 kJ/1000 J
5 10 mol AgCl
66.9 kJ mol
1
( )( )
3
Because the formati on of si l ver chl ori de i s exothermi c (i t caused a temperature
i ncrease i n the sol uti on), the si gn must be changed to negati ve q 5 DH 5
266.9 kJ mol
21
You Try It!
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.
Answer: q 5 192 kJ
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www.petersons.com
HESSS LAW
Hesss l aw i s an extremel y useful pri nci pl e that hel ps us to determi ne the enthal pi es of
reacti on for nearl y any combi nati on of materi al s. I t states that for reacti ons that occur i n
di fferent steps, the enthal py of reacti on i s equal to the sum of the enthal pi es for each step.
Hesss l aw wi l l al l ow us to cal cul ate the enthal py of reacti on by usi ng i nformati on about each
reactant. I n an exampl e, l ets consi der the compl ete combusti on of ethanol , C
2
H
5
OH, whi ch i s
shown i n the equati on bel ow:
C
2
H
5
OH(l) 1 3O
2
(g) 2CO
2
(g) 1 3H
2
O(l)
I f we want to determi ne the heat of reacti on, where do we even begi n? The easi est pl ace i s to
l ook at a measurement known as the standard enthal py of formati on, DH
f
. Thi s i s based
on two di fferent uni ts, the enthal py of formati on, DH
f
, whi ch represents the enthal py
change that occurs when a compound i s formed from i ts consti tuent el ements, and the
standard enthal py of reacti on, DH, whi ch i s the enthal py for a reacti on when al l
reactants and products are i n thei r standard state (the state they exi st i n at 25C and 1 atm).
The standard enthal py of formati on i s 1 mol e of a compound from i ts consti tuent el ements i n
thei r standard states. Enthal pi es of formati on can be found i n many di fferent reference books.
Lets take a l ook at how we can use enthal pi es of formati on to determi ne the enthal py of
reacti on for the combusti on of ethanol .
There are four di fferent substances i n the equati on: ethanol , oxygen, carbon di oxi de, and
water. We can use the heats of formati on for each of these four substances to determi ne the
heat of reacti on for the combusti on. An i mportant thi ng to remember i s that the heats of
formati on represent the energi es of formati on of a substance. For ethanol , the equati on and
subsequent heat of formati on i s:
2C(graphi te) 1 3H
2
(g) 1
1
2
O
2
(g) C
2
H
5
OH(l) DH
f
5 2277.7 kJ
I n the combusti on reacti on, however, ethanol i s bei ng broken apart, not put together. Earl i er
i n the chapter we l earned an easy way around thi s. Al l we have to do i s turn the reacti on
around i n the other di recti on and reverse the si gn of the enthal py. Therefore, by swi tchi ng the
di recti on we obtai n the equati on:
C
2
H
5
OH(l) 2C(graphi te) 1 3H
2
(g) 1
1
2
O
2
(g) DH
f
5 1277.7 kJ
A second consi derati on i s the other reactant oxygen, O
2
. The enthal py of formati on for any
el ement i n i ts most stabl e state i s zero. Therefore, we can di sregard any el ements i n thei r
most stabl e standard state.
The fi nal consi derati on i s that heats of formati on are l i sted for quanti ti es of one mol e. I n the
bal anced equati on for thi s reacti on, not al l substances are present i n quanti ti es of one mol e.
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www.petersons.com
As a resul t, the enthal pi es of formati on wi l l have to be mul ti pl i ed to account for the
di fferences. Usi ng Hesss l aw, we can now combi ne the heats of formati on for the three
substances i nto one l arge equati on:
C
2
H
5
OH(l) 2C(s) 1 3H
2
(g) 1 O
2
(g) DH
1
5 2DH
f
[C
2
H
5
OH(l)]
1 2C(s) 1 2O
2
(g) 2CO
2
(g) DH
2
5 2DH
f
[CO
2
(g)]
1 3H
2
(g) 1
3
2
O
2
(g) 3H
2
O(l) DH
2
5 3DH
f
[H
2
O(l)]
C
2
H
5
OH(l) 1 3O
2
(g) 2CO
2
(g) 1 3H
2
O(l) DH
rxn
5 DH
1
1 DH
2
1 DH
3
We can substi tute the val ues from a tabl e of standard enthal pi es of formati on to determi ne
the heat of reacti on:
DH
rxn
5 DH
1
1 DH
2
1 DH
3
5
2DH
f
[C
2
H
5
OH(l)] 1 2DH
f
[CO
2
(g)] 1 3DH
f
[H
2
O(l)] 5
2(2277.7 kJ) 1 2(2393.5 kJ) 1 3(2282.8 kJ) 5 21357.7 kJ
You Try It!
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) 220.0
H
2
O(l) 2285.8
SO
2
(g) 2296.8
Answer: 21125.2 kJ
The general equati on that descri bes thi s process i s Equati on 17.5:
DH
rxn
5 SnDH
f
(products) 2 SmDH
f
(reactants)
where n and mrepresent the stoi chi ometri c coeffi ci ents from the bal anced equati on.
SPONTANEITY
I n the next porti on of the chapter we are goi ng to consi der factors that determi ne the
spontanei ty of events. I n the chemi cal context, the term spontaneous refers to events that
wi l l occur on thei r own, i n a parti cul ar di recti on, and wi th no addi ti onal energy requi rement.
I f a hot pi ece of metal i s pl aced on a tabl e, the metal wi l l sl owl y cool off and i ts surroundi ngs
wi l l warm up. When the pi ece of metal has cool ed compl etel y, i t wi l l be the same temperature
as the surroundi ngs. Reachi ng thi s temperature was a spontaneous occurrence, but the pi ece
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(Equati on 17.5)
www.petersons.com
of metal wi l l not spontaneousl y get hot agai n. I t can be made to get hot agai n, but thi s
requi res that work be done on i t (energy must be added). Chemi cal reacti ons can occur
spontaneousl y as wel l . Previ ousl y we l ooked at the addi ti on of l ead (I I ) ni trate sol uti on to
potassi um i odi de sol uti on. When the two are mi xed, the yel l ow preci pi tate, l ead (I I ) i odi de,
forms wi thout anythi ng extra bei ng done to the mi xture. The reacti on occurs spontaneousl y.
I t does not reverse i tsel f and become two cl ear sol uti ons of potassi um i odi de and l ead (I I )
ni trate agai n.
Chemi cal reacti ons, l i ke the metathesi s reacti on that produces l ead (I I ) i odi de, can occur
spontaneousl y, just l i ke physi cal processes. I t was once bel i eved that onl y exothermi c
processes occurred spontaneousl y; however, i t has been shown that many endothermi c
reacti ons can occur spontaneousl y as wel l . Another factor that must be consi dered when
determi ni ng the spontanei ty of a reacti on i s entropy.
ENTROPY
Entropy descri bes the randomness or di sorder of a system. When a system becomes more
di sordered, i ts entropy i ncreases. For exampl e, when water evaporates, i t changes from a
l i qui d state, i n whi ch the parti cl es are rel ati vel y cl ose together and whose moti on i s somewhat
restri cted, to a gaseous state, i n whi ch the parti cl es are far apart and moti on i s compl etel y
random. The arrangements of the parti cl es have become more random, whi ch means that the
entropy has i ncreased. I ncreases i n entropy resul t i n posi ti ve entropy val ues; decreases i n
entropy resul t i n negati ve changes. Entropy remai ns constant, at zero, for some processes
that are consi dered reversi bl e processes. Reversi bl e processes are at equi l i bri um and do not
move spontaneousl y i n any parti cul ar di recti on. An exampl e woul d be the equi l i bri um of
water at the mel ti ng poi nt, 0C. At thi s temperature, water can ei ther freeze and become sol i d
or mel t and become l i qui d. Nei ther process i s favored over the other. The water mol ecul es that
joi n together i n the sol i d state can just as easi l y fal l apart and become l i qui d agai n. I f thi s
equi l i bri um mi xture i s pl aced i n a 25C room, the process wi l l spontaneousl y proceed i n the
l i qui d di recti on, and mel ti ng wi l l occur. The process i s no l onger reversi bl e, and the water wi l l
never freeze.
THE SECOND LAW OF THERMODYNAMICS
The second l aw of thermodynami cs states that for al l spontaneous processes the entropy of
the uni verse wi l l al ways i ncrease. Thi s i s often mi sunderstood to mean that the entropy of al l
parts of the system wi l l i ncrease. For exampl e, i f a smal l contai ner of water i s pl aced i nto a
freezer, i t wi l l spontaneousl y freeze. Al though the entropy of the water i n the contai ner
decreased, a number of processes had to occur for that change to take pl ace. The processes
that occurred i n the freezer that al l owed the water to freeze (such as the movement of the
compressor, the evaporati on and condensati on of the refri gerant, and the warmi ng of the ai r
around the contai ner), al l combi ne to produce a net i ncrease i n the entropy of the uni verse.
At the mol ecul ar l evel , entropy i s often descri bed i n terms of the moti on of parti cl es wi thi n a
system. The moti on can i nvol ve the enti re parti cl e movi ng about (transl ati onal moti on), the
vi brati ng of atoms wi thi n a mol ecul e (vi brati onal moti on), or the rotati on of enti re mol ecul es
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of atoms wi thi n a mol ecul e (rotati onal moti on). I ncreases i n moti on are associ ated wi th hi gher
entropy val ues. The thi rd l aw of thermodynami cs states that the entropy of a pure sol i d at
absol ute zero i s zero.
There are a few general trends about entropy that you shoul d become fami l i ar wi th. The AP
test wi l l occasi onal l y ask you to pi ck, from a l i st, the substances or reacti ons that have the
hi ghest entropy. The general processes that are associ ated wi th i ncreases i n entropy i ncl ude
When a sol i d mel ts (more moti on i s possi bl e)
When a sol i d di ssol ves i n sol uti on (sol ute breaks apart and can move about more
freel y)
When a sol i d or l i qui d becomes a gas (more moti on)
When a gaseous chemi cal reacti on produces more mol ecul es (more randoml y movi ng
parti cl es)
When the temperature of a substance i ncreases (more moti on)
Calculating Entropy Changes
Li ke enthal py, entropy cant be measured di rectl y. I t i s possi bl e to measure changes i n the
enthal py of a system, whi ch al l ows you to better understand the entropy of a system under
speci fi c condi ti ons. The entropy val ues for one mol e of a substance are known as standard
mol ar entropi es, S. The entropy change i n a chemi cal reacti on can be cal cul ated usi ng
the equati on:
DS 5 SnDS(products) 2 SmDS(reactants)
Sample: Cal cul ate the entropy change for the reacti on shown bel ow (assume that the
reacti on occurs at 25C):
2SO
2
(g) 1 O
2
(g) 2SO
3
(g)
The standard mol ar entropy val ue for the substances i n the reacti on are SO
2
(g) 5
248.1 J K
21
; SO
3
(g) 5 256.7 J K
21
; O
2
(g) 5 205.0 J K
21
.
Answer: You need to begi n wi th Equati on 17.6:
DS 5 SnDS(products) 2 SmDS(reactants)
DS
rxn
5 2DS(SO
3
) 2 [2DS(SO
2
) 1 DS(O
2
)]
DS
rxn
5 2 (256.7 J K
21
) 2 [2(248.1 J K
21
) 1 (205.0 J K
21
)]
DS
rxn
5 513.4 J K
21
2 [496.2 J K
21
1 205.0 J K
21
]
DS
rxn
5 513.4 J K
21
2 701.2 J K
21
5 2187.8 J K
21
The negati ve val ue tel l s you that thi s i s a decrease i n entropy, whi ch i s predi cted because thi s
i s a gaseous reacti on i n whi ch the number of mol es of parti cl es decreases from 3 to 2.
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(Equati on 17.6)
www.petersons.com
You Try It!
Cal cul ate the entropy change, DS, for the reacti on shown bel ow:
2H
2
(g) 1 O
2
(g) H
2
O(l)
The standard mol ar entropy val ues are H
2
(g) 5 130.6 J K
21
; O
2
(g) 5 205.0 J K
21
;
H
2
O(l) 5 69.9 J K
21
Answer: 2326.4 J K
21
GIBBS FREE ENERGY
Gi bbs free energy, al so known as free energy, provi des a way to predi ct the spontanei ty of a
reacti on usi ng a combi nati on of the enthal py and entropy of a reacti on. Free energy i s
defi ned as
G 5 H 2 TS
where T i s the absol ute temperature. I f temperature i s constant, the free energy change, DG,
for a reacti on i s determi ned by the fol l owi ng Equati on 17.7:
DG 5 DH 2 TDS
The val ue of DG wi l l tel l us i f the reacti on i s spontaneous. There are three possi bl e val ues
for DG:
DG , 0 The forward reacti on i s spontaneous.
DG 5 0 The reacti on i s at equi l i bri um.
DG . 0 The forward reacti on i s nonspontaneous, but the reverse reacti on i s
spontaneous.
Si nce we al ready have tabl es of standard enthal pi es and standard entropi es, we can
substi tute these val ues i nto the free energy equati on and determi ne the standard free
energi es of formati on for substances. The standard free energi es of formati on tel l you i f a
substance wi l l form spontaneousl y i f the consti tuent atoms are combi ned. The formul a to
determi ne the standard free energy change for a reacti on i s the same as Equati on 17.8 for the
enthal py change (except Gs are substi tuted for the Hs):
DG 5 SnDG
f
(products) 2 SmDG
f
(reactants)
Sample: Cal cul ate the standard free energy change for the compl ete combusti on of methane,
CH
4
, at 25C.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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(Equati on 17.7)
(Equati on 17.8)
www.petersons.com
Answer: CH
4
(g) 1 2O
2
(g) CO
2
(g) 1 2H
2
O(l)
The standard free energi es, DG, for the reactants and products are CH
4
(g) 5 250.8
kJ mol
21
1 2O
2
(g) 5 0 (free energi es for al l el ements i n thei r most stabl e form are
zero) CO
2
(g) 5 2394.4 kJ mol
21
2H
2
O(l) 5 2237.2 kJ mol
21
:
DG 5 SnDG
f
(products) 2 SmDG
f
(reactants)
DG 5 [DG
f
(CO
2
) 1 2DG
f
(H
2
O)] 2 [DG
f
(CH
4
) 1 2DG
f
(O
2
)]
DG 5 [(2394.4 kJ) 1 2(2237.2 kJ)] 2 [(250.8 kJ) 1 2(0)]
DG5 (2868.8 kJ) 2 (250.8 kJ) 5 2818.0 kJ
Thi s reacti on i s spontaneous.
You Try It!
Cal cul ate DG for the reacti on of al umi num wi th i ron (I I I ) oxi de:
2Al (s) 1 Fe
2
O
3
(s) Al
2
O
3
(s) 1 2Fe(s)
The standard free energi es, DG, for the reactants and products are: Al (s) 5 0;
Fe
2
O
3
(s) 5 2740.98 kJ mol
21
; Al
2
O
3
(s) 5 21576.5 kJ mol
21
; Fe(s) 5 0
Answer: 2835.5 kJ
Once you begi n to get a feel for the enthal py and entropy concepts, youl l probabl y l earn to
eyebal l a reacti on and tel l whether or not i t wi l l proceed spontaneousl y. There are some
patterns that you can study to hel p you remember the di fferent possi bl e rel ati onshi ps
between enthal py, entropy, and free energy. You can l earn these conceptual l y or from a
mathemati cal perspecti ve. Al l of the rel ati onshi ps are based on Equati on 17.7:
DG 5 DH 2 TDS
There are two condi ti ons that al ways produce the same resul t, whi l e two wi l l vary accordi ng
to temperature. I f a reacti on i s exothermi c, the potenti al energy of the reactants i s greater
than the potenti al energy of the products (whi ch means the products are more stabl e). I f
entropy i s posi ti ve, the reacti on i s creati ng more di sorder. Both of these condi ti ons are
favorabl e, so i f a reacti on has both a negati ve enthal py (exothermi c) and a posi ti ve entropy
(more di sordered) i t wi l l al ways be spontaneous (have a negati ve free energy). The opposi te i s
al so true: i f a reacti on i s endothermi c (posi ti ve enthal py) and has a negati ve entropy
(becomi ng more ordered), the free energy wi l l al ways be posi ti ve (the reacti on wi l l not be
spontaneous).
Both of these i deas can be understood mathemati cal l y from Equati on 17.7. I f DH i s negati ve
and DS i s posi ti ve, the val ue of DG wi l l stay negati ve (a negati ve mi nus a posi ti ve becomes
more negati ve). I f DH i s posi ti ve and DS i s negati ve, DG has to be posi ti ve (a posi ti ve mi nus
a negati ve becomes more posi ti ve).
The other two condi ti ons are dependent on temperature. For exampl e, assume the reacti on i s
exothermi c (DH wi l l have a negati ve val ue). I f the expressi on TDS becomes suffi ci entl y
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
negati ve, DG wi l l have a posi ti ve val ue. I n order for the expressi on to become more negati ve,
DS must be negati ve, and T must be l arge. So, for the condi ti on where a reacti on i s exothermi c
and i s becomi ng more ordered, the reacti on wi l l tend to be spontaneous at l ower temperatures
but nonspontaneous at hi gher temperatures. For the opposi te condi ti on, the opposi te i s true.
I f a reacti on i s endothermi c, DH wi l l be posi ti ve. I f TDS i s posi ti ve and smal l , the free energy
wi l l remai n posi ti ve (and the reacti on nonspontaneous), but as TDS becomes posi ti ve and
l arger, the free energy may become negati ve (and the reacti on spontaneous). These
rel ati onshi ps are summari zed i n Tabl e 17.1.
Sample: Predi ct the effect of i ncreasi ng temperature on the spontanei ty of the reacti on
bel ow:
2N
2
O
5
(g) 4NO
2
(g) 1 O
2
(g)
Answer: Thi s i s a reacti on that takes pl ace i n the gaseous state. There are 2 mol es of gas
parti cl es on the l eft si de of the equati on and 5 mol es of gas parti cl es on the ri ght
si de. The val ue of DS wi l l therefore be posi ti ve. As a resul t, the expressi on 2TDS
i s negati ve and becomes i ncreasi ngl y l arger as the temperature i ncreases. At
hi gher temperatures, thi s reacti on has a better chance of bei ng spontaneous. I f the
reacti on i s exothermi c, the reacti on wi l l be spontaneous regardl ess of temperature.
You Try It!
Predi ct the effect of i ncreasi ng temperature on the spontanei ty of the reacti on bel ow:
N
2
(g) 1 3H
2
(g) 2NH
3
(g)
Answer: Because DS i s negati ve, the term 2TDS i s posi ti ve. As the temperature
i ncreases, 2TDS gets more posi ti ve maki ng the reacti on l ess spontaneous. I f
the reacti on i s endothermi c, i t wi l l not be spontaneous at any temperatures;
i f the reacti on i s exothermi c, i t can be spontaneous at l ower temperatures.
TABLE 17.1
DH DS DG
2 1 Al ways negati ve (spontaneous)
1 2 Al ways posi ti ve (nonspontaneous)
2 2 Negati ve (spontaneous) at l ow temperature, but
posi ti ve (nonspontaneous) at hi gher temperatures
1 1 Posi ti ve (nonspontaneous) at l ow temperatures,
but negati ve (spontaneous) at hi gher temperatures
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Free Energy at Nonstandard Conditions
When the reacti on condi ti ons are not standard, a new expressi on al l ows us to cal cul ate the
free energy. Equati on, 17.9, i s shown bel ow:
DG 5 DG 1 RT l n Q
where R i s the i deal gas constant (8.314 J mol
21
K
21
), T i s the absol ute temperature, and Q i s
the reacti on quoti ent. I f you recal l , when a reacti on i s at equi l i bri um, Q 5 K (the equi l i bri um
constant) and DG 5 0. As a resul t, when a reacti on i s at equi l i bri um, Equati on 17.9 can be
changed to Equati on 17.10:
DG 5 2RT l n K
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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(Equati on 17.9)
(Equati on 17.10)
www.petersons.com
EXERCISES: THERMODYNAMICS
Multiple Choice
1. When a system experi ences the
fol l owi ng two condi ti ons, the DE i s
al ways negati ve.
(A) Absorbs heat and does work
(B) Absorbs heat and has work
done on i t
(C) Rel eases heat and does work
(D) Rel eases heat and has work
done on i t
(E) Because energy i s al ways
conserved, DE i s al ways 0.
2. The speci fi c heat of l ead metal , Pb, i s
0.127 J/gC. How many joul es of heat
woul d be requi red to rai se the
temperature of a 5.00 g sampl e from
25C to 35C?
(A) 2.5 3 10
23
(B) 0.127
(C) 6.4
(D) 16.1
(E) 390
CH
4
(g) 1 2O
2
(g) CO
2
(g) 1 2H
2
O(g)
3. For the compl ete combusti on of
methane gas, CH
4
, represented
above, DH i s 2 802 kJ. What i s the
val ue of DH i f the combusti on
produced l i qui d water H
2
O(l), rather
than water vapor H
2
O(g)? (DH for
the phase change H
2
O(g) H
2
O(l)
i s 244 kJ mol
21
.)
(A) 2714 kJ
(B) 2758 kJ
(C) 2802 kJ
(D) 2846 kJ
(E) 2890 kJ
Substance DH
f
(kJ mol
21
)
NO(g) 90.37
O
2
(g) 0
NO
2
(g) 33.84
4. Use the i nformati on shown above to
determi ne the standard enthal py
change for the formati on of ni trogen
di oxi de shown i n the reacti on bel ow:
2NO(g) 1 O
2
(g) 2NO
2
(g)
(A) 2113.06
(B) 256.53
(C) 56.53
(D) 90.37
(E) 124.21
C
2
H
4
(g) 1 6F
2
(g) 2CF
4
(g) 1 4HF(g)
5. For the equati on shown above, whi ch
materi al i n the reacti on has a
DH
f
5 0?
(A) C
2
H
4
(B) F
2
(C) CF
4
(D) HF
(E) None; al l substances have
nonzero val ues for DH
f
.
6. For whi ch of the fol l owi ng processes
woul d DS have a negati ve val ue?
I . CaCO
3
(s) CaO(s) 1 CO
2
(g)
I I . H
1
(aq) 1 Cl
2
(aq) HCl (s)
I I I . N
2
(g) 1 3H
2
(g) 2NH
3
(g)
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I I and I I I
e
x
e
r
c
i
s
e
s
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7. When sol i d ammoni um ni trate i s
pl aced i nto a fl ask of room tempera-
ture water and swi rl ed, the sol i d
di ssol ves and the fl ask gets noti ce-
abl y col der. What concl usi ons can you
make about the val ues of DH and DS
for thi s process?
(A) DH i s negati ve and DS i s
negati ve.
(B) DH i s negati ve and DS i s
posi ti ve.
(C) DH i s posi ti ve and DS i s
negati ve.
(D) DH i s posi ti ve and DS i s
posi ti ve.
(E) Not enough i nformati on i s
provi ded to make a val i d
concl usi on.
8. 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)
9. A reacti on i s spontaneous onl y at
hi gh temperatures. The si gns of DH
and DS must be
(A) DH 5 1, DS 5 1
(B) DH 5 1, DS 5 2
(C) DH 5 2, DS 5 1
(D) DH 5 2, DS 5 2
(E) You cant answer thi s wi thout
knowi ng the free energy.
Substance DS (J mol
21
K
21
)
N
2
(g) 191.5
H
2
(g) 130.6
NH
3
(g) 192.5
10. Based on the i nformati on above,
what i s the DS for the reacti on
shown bel ow?
N
2
(g) 1 3H
2
(g) 2NH
3
(g)
(A) 2129.6 J K
21
(B) 2198.3 J K
21
(C) 192.5 J K
21
(D) 585.3 J K
21
(E) 968.3 J K
21
N
2
1 O
2
N
2
O
11. The reacti on i ndi cated above i s
thermodynami cal l y nonspontaneous
at 298 K, but becomes spontaneous
at hi gher temperatures. Whi ch of the
fol l owi ng i s true at 298 K?
DG DH DS
(A) 1 1 1
(B) 2 2 2
(C) 2 2 1
(D) 2 1 2
(E) 1 1 2
12. I f the free energy, DG, for a reacti on
i s negati ve, what must the val ue of
the equi l i bri um constant, K, be for
that reacti on?
(A) K . 1
(B) K , 1
(C) K 5 1
(D) K 5 0
(E) K and DG are not rel ated.
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Free Response
QUESTION 1
Acetyl ene gas, C
2
H
2
, i s used i n gas wel di ng procedures and i s a very i mportant commerci al gas.
Use the data bel ow to answer the fol l owi ng questi ons about the combusti on of acetyl ene gas:
Substance DH
f
(kJ mol
21
) S (J mol
21
K
21
)
C
2
H
2
(g) 227 200.9
O
2
(g) 0 205.0
CO
2
(g) 2393.5 213.7
H
2
O(l) 2285.8 69.9
Use the data above to answer the questi ons that fol l ow. Assume al l reacti ons occur at 25C.
(A) Wri te a compl ete bal anced chemi cal equati on for the combusti on of acetyl ene,
C
2
H
2
. Assume that CO
2
(g) and H
2
O(l) are the onl y products.
(B) Cal cul ate the standard enthal py change, DH, for the combusti on of acetyl ene.
(C) Cal cul ate the standard entropy change, DS, for the combusti on of acetyl ene gas.
(D) Determi ne the val ue of DG for the reacti on.
(E) I f 1 mol of C
2
H
2
i s burned and al l of the evol ved heat i s used to heat a 6.00 kg of
pure water, what wi l l the temperature change of the water be? The speci fi c heat
of water i s 4.18 J g
21
K
21
.
QUESTION 2
(A) An i ce cube i s pl aced i n a fl ask at room temperature and al l owed to si t unti l the
temperature of the water i n the fl ask has reached room temperature. Descri be
the changes i n enthal py, entropy free energy, and temperature that occur duri ng
the ti me i nterval .
(B) 40.0 g of sodi um hydroxi de pel l ets are added to 500 mL of water, and most of i t
di ssol ves very qui ckl y. The temperature of the system i ncreases. Descri be the
changes i n enthal py, entropy, and free energy duri ng thi s process.
(C) Commerci al i nstant i ce packs are avai l abl e that contai n a mi xture of ammoni um
ni trate and water separated by a barri er. When the i ce pack i s twi sted, the
barri er breaks and the two substances mi x. The temperature rapi dl y decreases
as the ammoni um ni trate di ssol ves i n the water. Descri be the changes i n
enthal py, entropy, and free energy duri ng thi s process.
e
x
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Multiple Choice
1. C
2. C
3. E
4. A
5. B
6. D
7. D
8. D
9. A
10. B
11. A
12. A
1. Thecorrect answer is(C). DE i s determi ned by the sum of the heat and work (q 1 w).
The system l oses energy when i t rel eases heat or does work. When the system gai ns
heat or has work done on i t, i t gai ns energy. Losses of energy are shown as negati ve
energy val ues and gai ns are expressed usi ng posi ti ve val ues. The onl y way to guarantee
the DE wi l l be negati ve i s to rel ease heat and do work.
2. The correct answer is (C). I n thi s probl em you need to use Equati on 17.4:
q 5 msDT
You wi l l need to sol ve for q by substi tuti ng the gi ven i nformati on:
q 5 (5.00 g)(0.127 J/gC
21
)(35C 2 25C) 5 6.4 J
3. Thecorrect answer is (E). I n thi s probl em the enthal py of reacti on has al ready been
determi ned. The onl y step, therefore, i s to determi ne the effect of the addi ti onal heat
l oss of 44 kJ mol
21
as the water condenses. For each mol e of gaseous water vapor, an
addi ti onal 44 kJ of heat wi l l be l ost. Because the bal anced equati on shows two mol es of
water vapor, the total rel eased duri ng condensati on i s 88 kJ. Therefore, the total heat
l oss i n the reacti on wi l l be 2802 kJ 1 (288 kJ) 5 2890 kJ.
4. The correct answer is (A). Thi s questi on requi res the use of Equati on 17.5:
DH
rxn
5 SnDH
f
(products) 2 SmDH
f
(reactants)
DH
rxn
5 [(2)(33.84 kJ] 2 [(2)(90.37 kJ) 1 0] 5 2113.06 kJ
5. The correct answer is (B). Al l el ements i n thei r most stabl e form have a DH
f
5 0
6. The correct answer is (D). A negati ve val ue for DS means that a substance i s
decreasi ng i n entropy, or becomi ng more organi zed. I n I , a sol i d i s formi ng a sol i d and a
gas. The conversi on from sol i d or l i qui d to gas al ways i ncreases entropy. I n I I , i ons i n
sol uti on are much more free to move randoml y about than i ons packed i n a sol i d
crystal l i ne l atti ce. Therefore I I experi ences a decrease i n entropy. I n I I I , the reacti on
reduces the number of gas parti cl es, whi ch decreases the entropy. Both I I and I I I
decrease the entropy, maki ng i t more negati ve.
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7. Thecorrect answer is (D). There are two di fferent events that need to be consi dered
herethe enthal py and entropy. As far as the enthal py goes, the decrease i n
temperature i ndi cates an endothermi c process (heat i s bei ng removed from the
surroundi ngs to energi ze the process). Endothermi c processes have posi ti ve val ues for
DH. The next consi derati on i s the entropy. The sol i d i s di ssol vi ng i n the water, whi ch
means that the di ssol ved i ons have much more freedom or rotati on than thei r
crystal l i zed counterparts. Therefore, the di ssol vi ng i ncreases the entropy of the
ammoni um ni trate, maki ng DS more posi ti ve.
8. Thecorrect answer is (D). One of the major thi ngs to l ook for on a questi on l i ke thi s
i s the number of reactants and product parti cl es and thei r states. The l argest entropy
changes wi l l be associ ated wi th transformati ons from sol i ds or l i qui ds to gases. I n the
event that several choi ces l i sts gases as reactants and/or products, l ook for the number
of mol es of each. An i ncrease i n the number of mol es of gas i ncreases the entropy, whi l e
a decrease i n the number of mol es si gnal s a decrease i n the entropy.
9. The correct answer is (A). There are two ways to work thi s probl em. The fi rst i s to
memori ze the di fferent possi bl e combi nati ons of DH and DS and the correspondi ng
val ues of DG. There i s so much materi al that has to be memori zed al ready that thi s may
not be the best approach. The more effi ci ent approach i s to use the equati on
DG 5 DH 2 TDS. By substi tuti ng vari ous val ues i nto the equati on, you can
determi ne the si gn of DG (remember, negati ve i ndi cates spontaneous, whi l e posi ti ve i s
nonspontaneous). At hi gh temperatures, the val ue of TDS becomes l arge enough to
make DG negati ve.
10. The correct answer is (B). To cal cul ate DS, you need to use Equati on 17.6 and the
gi ven val ues:
DS
rxn
5 SnDS(products) 2 SmDS(reactants)
DS 5 [(2)(192.5 J K
21
)] 2 [(1)(191.5 J K
21
) 1 (3)(130.6 J K
21
)] 5 2198.3 J K
21
11. The correct answer is (A). Thi s i s just a vari ati on of questi on 9. The reacti on has a
posi ti ve enthal py and entropy at al l temperatures (just l i ke questi on 9). What wi l l vary
accordi ng to the temperature i s the free energy. Because the probl em tel l s you that the
reacti on i s nonspontaneous at 298, i t has to have a posi ti ve val ue (si nce a negati ve free
energy i ndi cates a spontaneous reacti on).
12. The correct answer is (A). There are two ways to do thi s one. One sol uti on i s more
mathemati cal and i nvol ves the use of Equati on 17.10, DG 5 2RT l n K. DG can onl y be
negati ve i f l n K i s a posi ti ve val ue. Any val ue l ess than 1 produces a negati ve natural
l ogari thm, and a val ue of 1 produces a natural l og of 0. Therefore, onl y when K . 1 can
you have a negati ve DG. The other way to sol ve thi s i s to use the conceptual i dea that a
spontaneous reacti on wi l l favor the products. Therefore, K i s greater than 1 for a
spontaneous reacti on.
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Free Response
QUESTION 1
(A) 2C
2
H
2
(g) 1 5O
2
(g) 4CO
2
(g) 1 2H
2
O(l)
(B) 2600.0 kJ. You need to use Equati on 17.5 to sol ve part (B). To si mpl i fy thi ngs, we
wi l l sol ve the equati on for the combusti on of 1 mol e of acetyl ene. Thi s can be
accompl i shed usi ng the bal anced equati on:
C
2
H
2
(g) 1
5
2
O
2
(g) 2CO
2
(g) 1 H
2
O(l)
DH
rxn
5 SnDH
f
(products) 2 SmDH
f
(reactants)
DH 5 @~2!~2393.5 kJ! 1 ~1!~2285.8 kJ!# 2 @~1!~227 kJ! 1 0#
5 ~21072.8 kJ! 2 ~227 kJ! 5 21300.0 kJ
Because thi s i s determi ned for 1 mol e of acetyl ene, thi s can al so be wri tten 1300
kJ mol
21
.
(C) To cal cul ate the standard entropy change, use Equati on 17.6:
DS
rxn
5 SnDS(products) 2 SmDS(reactants)
DS 5 DH
5 @~2!~213.7 J K
21
! 1 ~1!~69.9 J K
21
!# 2 @~1!~200.9 J K
21
! 1 ~5/2!~205.0 J K
21
!#
5 ~497.3 J K
21
! 2 ~713.8 J K
21
!
5 2216.5 J K
21
You have to remember that el ements have zero val ues for DH and DG, but not
for DS.
(D) To sol ve for DG, you need to use Equati on 17.7:
DG 5 DH 2 TDS
DG 5 21300 kJ 2 ~298 K!~ 2216.5 J K
21
!~1 kJ / 10
3
J!
5 21300 kJ 1 64.4 kJ 5 21236 kJ
From the answer, you know that the reacti on i s not spontaneous at room
temperature. Some l ogi c wi l l hel p you to val i date thi s. Most gases requi re that
you add energy (e.g., a spark, a match) before they wi l l react wi th oxygen.
(E) Thi s i s a speci fi c heat probl em. The fi rst thi ng that you need to do i s determi ne
the amount of heat that wi l l be generated from the combusti on of 1 mol of C
2
H
2
.
Because no heat i s l ost i n the heati ng of the water, you can assume that the heat
l ost by the acetyl ene wi l l be equal to the heat gai ned by the water. Thi s heat wi l l
be used to determi ne the temperature i ncrease of the water:
DH 5 (1 mol C
2
H
2
)(21300.0 kJ mol
21
) 5 21300 kJ
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Thi s amount of heat wi l l be the heat, q, used i n Equati on 17.4. However, because
the heat l ost by the acetyl ene wi l l equal the heat gai ned by the water, the val ue
of q wi l l need to be changed to posi ti ve i n Equati on 17.4:
q 5 msDT
1.30 3 10
6
J 5 (6000 g H
2
O)( 4.18 J g
21
K
21
)DT
DT 5 51.8 K 5 51.8C (si nce a change of 1 K 5 1C, DT wi l l produce the same
val ue for K orC).
QUESTION 2
(A) The i ce cube wi l l not mel t unl ess heat i s added. Therefore, DH i s posi ti ve,
denoti ng an endothermi c process. Li qui d water has more freedom of movement
and therefore wi l l possess a greater entropy, so DS wi l l be posi ti ve. Thi s process
occurs spontaneousl y, so DG must be negati ve. The temperature i ncreases duri ng
thi s transformati on.
(B) The amounts are real l y meani ngl ess i n thi s probl em. The key pi eces of
i nformati on are the words dissolved and that the temperatureincreases. Because
the temperature of the system i ncreases, the di ssol vi ng must be an exothermi c
process, meani ng that DH , 0. The sodi um hydroxi de di ssol ves i n sol uti on,
meani ng that the crystal l i ne l atti ce breaks apart i nto sol vated i ons. Thi s i s a
much l ess orderl y formati on, whi ch means the entropy has i ncreased. Therefore,
DS . 0 i n thi s process. Because the di ssol vi ng occurs spontaneousl y, DG must be
negati ve.
(C) Because the temperature decreases, the process i s endothermi c. Therefore,
DH . 0. The ammoni um ni trate di ssol ves i n the water so the entropy i ncreases
(DS . 0). The process occurs spontaneousl y, whi ch means that DG must be
negati ve.
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SUMMING IT UP
A system i s a term used to descri be a di screte regi on of space that i s set off i n some way
from the surroundi ngs. Open systems can exchange matter and/or energy wi th the
surroundi ngs; cl osed systems can onl y exchange energy.
A state functi on i s any property of a system that i s onl y rel ated to i ts physi cal state at any
parti cul ar ti me. Some exampl es of state functi ons are P, V, T, E, H, S, and G.
The fi rst l aw of thermodynami cs i s the same as the l aw of conservati on of energy, whi ch
states that matter i s nei ther created nor destroyed i n the uni verse.
The energy of a system i s determi ned by the amount of heat put i nto or l ost from a system
and the amount of work ei ther done on or by the system.
Enthal py i s a measure of the heat gai ned or l ost by a system. When no work i s done on or
by a system, energy and enthal py are equal .
A thermochemi cal equati on shows a bal anced chemi cal equati on and the enthal py of the
reacti on.
Endothermi c reacti ons, whi ch requi re the addi ti on of heat, have a posi ti ve enthal py val ue.
Exothermi c reacti ons, whi ch gi ve off heat, have a negati ve enthal py val ue.
The heat capaci ty of an object i s the amount of heat needed to rai se the temperature by
1C. Someti mes the uni ts are descri bed as the energy requi red to rai se the temperature
by 1 K. Understand that a di fference of 1 Kel vi n i s the same as a di fference of 1C.
The speci fi c heat of a substance descri bes the energy requi red to rai se the temperature of
1 gram of a substance by 1 K (or 1C).
A cal ori meter i s a devi ce that i nsul ates a reacti on from the external envi ronment. I t can
be used to measure heats of reacti on.
Hesss l aw i s a useful techni que that al l ows us to determi ne the heat of reacti on for an
unknown reacti on through mani pul ati on.
Standard uni ts appl y to systems that are at standard (normal ) condi ti ons. Standard
condi ti ons i ncl ude such condi ti ons as 25C (room temperature) and 1 atm (atmospheri c
pressure at sea l evel ).
Spontaneous events occur on thei r own wi thout any addi ti onal energy requi rements than
are present i n the surroundi ngs.
Entropy i s a measure of the di sorder of a system. A posi ti ve val ue of entropy, S, refers to
an i ncrease i n entropy, whi l e a negati ve val ue of S descri bes a decrease i n entropy.
The second l aw of thermodynami cs states that the entropy of the uni verse i s al ways
i ncreasi ng. Even i f a parti cul ar system i s decreasi ng i n entropy, i t can onl y do so at the
expense of the surroundi ngs (whi ch must be i ncreasi ng i n entropy).
Gi bbs free energy descri bes the spontanei ty of chemi cal reacti ons i n terms of enthal py,
entropy, and temperature. Negati ve val ues si gni fy a spontaneous reacti on, whi l e posi ti ve
val ues are nonspontaneous. A free energy of zero denotes equi l i bri um condi ti ons.
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Electrochemistry
OVERVIEW
Oxidation and reduction
Voltaic cells
The relationship between emf and free energy
The Nernst equation
Electrolysis
Faradays laws
Summing it up
You had a bri ef i ntroducti on to the topi c of el ectrochemi stry i n Chapter 11
when you revi ewed the oxi dati on-reducti on process i n whi ch reacti ons occur
by the transfer of el ectrons. One of the procedures you l ooked at was the
hal f-reacti on method of bal anci ng redox equati ons. I n thi s chapter, we wi l l be
l ooki ng at the oxi dati on and reducti on process i n even more depth.
OXIDATION AND REDUCTION
Oxi dati on and reducti on reacti ons, al so known as redox reacti ons, i nvol ve
the transfer of el ectrons from one substance that i s bei ng oxi di zed (l osi ng
el ectrons) to another that i s bei ng reduced (gai ni ng el ectrons). A very common
exampl e of a redox reacti on, one that you may very wel l have done i n the l ab,
i s the reacti on that occurs when you pl ace cl ean, i ron nai l s i nto a copper
sul fate sol uti on. I n thi s reacti on, shown bel ow, i ron i s oxi di zed and copper
i s reduced:
Fe(s) 1 Cu
21
(aq) Cu(s) 1 Fe
21
(aq)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
1
8
433
Two el ectrons are removed from i ron by the copper i on. The i ron, now an i on, moves i nto the
sol uti on, whi l e copper, now a sol i d, forms on the surface of the nai l . Thi s process can be
summari zed usi ng redox hal f-reacti ons (Chapter 11), such as the one shown here:
Oxi dati on: Fe Fe
21
1 2e
2
Reducti on: Cu
21
1 2e
2
Cu
The hal f-reacti on shows the transfer of the el ectrons that occurs i n the reacti on.
VOLTAIC CELLS
A vol tai c cel l (al so known as a gal vani c cel l ) i s a devi ce that al l ows for the transfer of
el ectrons (i n a redox reacti on) to be compl eted i n a separate pathway from the reacti on
mi xtures. I n a vol tai c cel l , the two hal f-reacti ons are physi cal l y separated from each other by
pl aci ng them i nto two separate reacti on vessel s. The el ectrons are transferred from one vessel
to the other by a connecti ng wi re (see Fi gure 18.1). I n vol tai c cel l s, the reacti ons i n each vessel
must be spontaneous. I n fi gure 18.1, i n the reacti on on the l eft, a zi nc stri p i s pl aced i n a zi nc
sul fate sol uti on, where zi nc from the stri p repl aces zi nc i n sol uti on (Zn Zn
21
1 2e
2
). I n the
reacti on vessel on the l eft, the zi nc stri p wi l l l ose mass over ti me. El ectrons create an el ectri c
potenti al di fference across the wi re, whi ch i s al so known as a vol tage. The vol tage across the
wi re wi l l al l ow el ectrons to be forced from the zi nc stri p, across the wi re, to the copper stri p.
However, an el ectri c current cannot be establ i shed unti l the ci rcui t i s compl eted.
The ci rcui t can be compl eted i n a coupl e of di fference ways, but i n Fi gure 18.1, the ci rcui t i s
compl eted by the use of a sal t bri dge. The sal t bri dge i s an i nverted U-tube i nto whi ch a gel
that contai ns a di ssol ved sal t i s pl aced. The gel i s needed so the sal t sol uti on wont run i nto
the reacti on vessel s. I n Fi gure 18.1, the ani on i n the sal t bri dge i s l abel ed as A
2
and the
cati on as C
1
. The sal t bri dge al l ows i ons to pass from one vessel to the other so that the
Figure18.1
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reacti on can proceed. The posi ti ve i ons (Zn
21
, Cu
21
, and C
1
) move toward the copper stri p,
whi l e the negati ve i ons (SO
4
22
, A
2
) move toward the zi nc stri p.
The force that al l ows a current to travel through wi re i s vol tage. An el ectri cal current can
fl ow when there i s a di fference i n el ectri cal potenti al (vol tage) from one l ocati on to another
(thi s i s created by a potenti al energy whose ori gi ns are el ectrostati c forces between charged
parti cl es). There i s a fai rl y good anal ogy that can hel p you understand the i dea of el ectri c
potenti al and the fl ow of el ectrons. I f you were to turn on a water spi got on whi ch a cl osed-up
garden hose had been pl aced, the hose woul d fi l l up, but no water woul d fl ow. At thi s poi nt,
there i s a water pressure that has bui l t up i nsi de the hose, but because there i s nowhere for
the water to exi t, the pressure stays bui l t up i n the hose. The pressure at one end of the hose
i s no di fferent from the pressure at the other end of the hose, and as a resul t, nothi ng
happens. I f you unpl ug the end of the garden hose, suddenl y there i s a di fference i n pressure
between the ends. Thi s di fference al l ows the water to fl ow from the end where the pressure i s
hi ghest to the end where i t i s l owest. El ectrons wi l l move from an area of hi gh el ectri cal
potenti al (vol tage) to an area of l ow el ectri cal potenti al . Movi ng el ectrons al l ow current
to fl ow.
Another i mportant part of the water anal ogy i s that the water that i ni ti al l y comes out of the
hose i s not the water that i s comi ng out of the spi got. I nstead, i t i s water that i s bei ng pushed
out of the end of the hose by the pressure exerted by the water at the spi got-end of the hose.
I n a si mi l ar fashi on, the el ectrons that are enteri ng the copper stri p are not the el ectrons that
were l eavi ng the zi nc stri p. The el ectrons i n the zi nc stri p create a pressure (vol tage) that
forces el ectrons i n the wi re to move onto the copper stri p.
I t i s easy to thi nk that the el ectrons that are bei ng created i n the zi nc vessel are the same
el ectrons that are reduci ng copper i n the copper vessel , but thi s i s not the case. The el ectrons
i n the zi nc vessel are hel pi ng to create the vol tage that wi l l al l ow el ectrons i n the wi re and/or
copper stri p to reduce the copper i ons. Another concept that may seem strange to you i s the
i dea of current. Current i s actual l y sai d to move i n the di recti on opposi te the fl ow of el ectrons.
The current i n thi s ci rcui t i s actual l y movi ng from the copper vessel to the zi nc vessel . On the
AP Chemi stry Test, you do not need to know any of these detai l s. What you are accountabl e
for i s understandi ng the basi c worki ngs of a vol tai c cel l , what vol tage i s, and the nature of the
reacti ons that are occurri ng on the vessel s. The more compl i cated i deas of current and
movements of el ectrons are more thoroughl y di scussed i n physi cs cl asses.
There are several terms you shoul d be fami l i ar wi th for vol tai c cel l s. Fi rst, the vol tage that i s
i mpressed across the ci rcui t (that i s, the di fference i n el ectri cal potenti al between the zi nc
stri p and the copper stri p) i s known as the cel l vol tage, whi ch i s al so occasi onal l y cal l ed the
cel l potenti al or the el ectromoti ve force, EMF. The copper el ectrode, because i t becomes
negati vel y charged and attracts cati ons, i s known as the cathode. The zi nc el ectrode becomes
posi ti vel y charged and i s known as the anode. You are expected to know whi ch part of the
reacti on takes pl ace at the cathode and whi ch part takes pl ace at the anode. These can
someti mes be di ffi cul t to remember, so a si mpl e mnemoni c devi ce can hel p you di sti ngui sh
between the two. Oxi dati on occurs at the Anode (note how each term starts wi th a vowel ), and
Reducti on occurs at the Cathode (note how each term starts wi th a consonant).
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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NOTE
In an electric
circuit, the current
actually flows in
the opposite
direction of the
electrons, but this
is a distinction
you are not
expected to
know.
Chapter 18: Electrochemistry 435
www.petersons.com
To summari ze vol tai c cel l s, l ets revi ew the components that create the cel l . Fi rst, you need
two hal f-cel l s, each of whi ch contai ns an el ectrode i mmersed i n an el ectrol yti c sol uti on
(typi cal l y contai ni ng the cati on of the metal i n the el ectrode). A spontaneous reacti on must
occur between the el ectrode and the sol uti on. A wi re connects the two el ectrodes and wi l l
al l ow the external fl ow of el ectrons from the anode to the cathode. I n Fi gure 18.1, a vol tmeter
i s shown as part of the ci rcui t between the two el ectrodes. Thi s i s not a necessary part of the
ci rcui ti t i s si mpl y there to measure the vol tage across the ci rcui t. The sal t bri dge compl etes
the el ectri c ci rcui t and al l ows the fl ow of cati ons and ani ons between the two hal f-reacti ons.
Someti mes a porous di sc i s used i n pl ace of a sal t bri dge. The dri vi ng force for the current i s
the di fference i n potenti al energi es between the two hal f-cel l s.
Cell Potentials and the Reduction Potential
The vol tage (or el ectri cal potenti al ) across the ci rcui t i s descri bed as the cel l vol tage and
defi ned by the symbol E
cel l
. When the hal f-cel l s contai n 1 M sol uti ons at 25C and 1 atm
pressure, the cel l vol tage i s cal l ed the standard cel l vol tageor standard emf and i s l abel ed
as E
cel l
. The cel l vol tage i s determi ned by the di fference between the two el ectrode potenti al s.
The cel l vol tage i s determi ned accordi ng to Equati on 18.1 bel ow:
E
cel l
5 E
ox
1 E
red
The subscri pt ox i s short for oxi dati on potenti al , whi ch i s the abi l i ty of the anode to produce
el ectrons (through the oxi dati on hal f-reacti on), and the subscri pt red i s short for reducti on
potenti al , whi ch i s the abi l i ty of the reducti on hal f-reacti on to gai n el ectrons at the cathode.
You have probabl y worked wi th tabl es of standard reducti on potenti al s before. These tabl es
provi de the reducti on potenti al s of vari ous substances. I t descri bes an oxi di zed speci ess
abi l i ty to gai n el ectrons i n a reducti on hal f-reacti on (l i ke copper i n the vol tai c cel l exampl e).
Accordi ng to thi s defi ni ti on, we can use a val ue from the tabl e to represent the E
red
i n the
expressi on above, but how do you fi nd the E
ox
?
Very conveni entl y, the oxi dati on potenti al i s the reverse of the reducti on potenti al . For
exampl e, consi der the oxi dati on of zi nc i n our previ ous exampl e:
Zn Zn
21
1 2e
2
I n i ts reducti on, the zi nc i on wi l l need to gai n 2 el ectrons, maki ng the reducti on of zi nc exactl y
opposi te the oxi dati on:
Zn
21
1 2e
2
Zn
Because oxi dati on i s si mpl y the opposi te of reducti on, i t i s onl y necessary to create a tabl e of
one of the val ues. By conventi on, the reducti on potenti al i s used i n tabl es, and the val ues are
typi cal l y gi ven for the standard reducti on potenti al , E, al so wri tten E
red
, i n uni ts of vol ts, V.
Because oxi dati on takes pl ace at the anode, thi s i s the val ue that wi l l need to be reversed
(si nce oxi dati on potenti al 5 2reducti on potenti al ). Therefore, we can rearrange Equati on 18.1
so we can use val ues from the reducti on potenti al tabl es i n Equati on 18.2:
E
cel l
5 E
cathode
2 E
anode
From a conceptual perspecti ve, the si ze of the reducti on potenti al hel ps to i l l ustrate a
substances tendency to be reduced. A l arge (more posi ti ve) val ue for the reducti on potenti al
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(Equati on 18.1)
(Equati on 18.2)
www.petersons.com
i ndi cates that a speci es wi l l be more easi l y reduced (the oxi di zed speci es wi l l gai n el ectrons).
The more posi ti ve the val ue, the more l i kel y the substance wi l l gai n el ectrons. I f you
remember back, thi s means that the substance wi l l have to take those el ectrons from another
substance. Therefore, the more l i kel y a substance i s to gai n el ectrons, the more l i kel y i t i s to
take them from another substance. The term to descri be a substance that removes the
el ectrons from another (oxi di zes i t) i s an oxi di zi ng agent.
Large negati ve val ues i ndi cate that the substance i s more easi l y oxi di zed (wi l l l ose el ectrons).
Because thi s oxi dati on wi l l requi re another substance to be reduced, the oxi di zed substance i s
known as a reduci ng agent. The substances wi th the most negati ve reducti on potenti al s are
the best reduci ng agents. Li thi um i s the most easi l y oxi di zed substance (and therefore the
best reduci ng agent), and fl uori ne i s the most di ffi cul t substance to oxi di ze (and as a resul t i s
the best oxi di zi ng agent). Thi s i s consi stent wi th what you l earned about the el ectronegati vi ty
and i oni zati on energy val ues for these substances (Chapters 4 and 6).
Sample: Whi ch i s the better oxi di zi ng agent, Cl
2
(aq) or Fe
31
(aq)? Whi ch i s the better
reduci ng agent, Al (s) or Cu(s)?
Answer: The better oxi di zi ng agent wi l l be the substance that i s the easi est to reduce (has
more posi ti ve reducti on potenti al ). To determi ne the reducti on potenti al of these
two speci es, you need to l ocate the hal f-reacti on that shows each as the reactant.
Chapter 1 has a tabl e of standard reducti on potenti al s that you can use for thi s
questi on. The val ues for Cl
2
and Fe
31
are:
Cl
2
(g) 1 2e
2
2Cl
2
1.36 V
Fe
31
(aq) 1 3e
2
Fe 0.77 V
Si nce Cl
2
has the l arger (more posi ti ve) val ue, i t i s the better oxi di zi ng agent.
On the second questi on, the better reduci ng agent i s the substance that i s more
easi l y oxi di zed (thereby reduci ng the other substance i t comes i nto contact wi th).
Therefore, the better reduci ng agents wi l l have the more negati ve reducti on
potenti al s. I f we consul t the tabl e, we fi nd that:
Al
31
(aq) 1 3e
2
Al 21.66 V
Cu
21
(aq) 1 2e
2
Cu 0.34 V
Cu
21
was chosen because i t i s the more common form of copper i on i n sol uti on.
Regardl ess of whi ch copper had been chosen, however, al umi num i s cl earl y more
negati ve and therefore a better reduci ng agent.
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www.petersons.com
You Try It!
1. Between Zn
21
(aq) and Pb
21
(aq), whi ch i s the better oxi di zi ng agent?
2. Between Ag(s) and Au(s), whi ch i s the better reduci ng agent?
Answers:
1. Pb
21
(aq)
2. Ag(s)
Sample: A vol tai c cel l i s created wi th two hal f-cel l s. I n the fi rst hal f-cel l , a copper el ectrode
i s pl aced i n a 1.0 M Cu(NO
3
)
2
sol uti on. I n the second hal f-cel l , a ti n el ectrode i s
pl aced i n a sol uti on of 1.0 M Sn(NO
3
)
2
. A sal t bri dge i s pl aced between the two
hal f-cel l s to compl ete the ci rcui t. Assume ti n i s the anode. Cal cul ate the cel l vol tage
of the vol tai c cel l .
Answer: To sol ve thi s, we need to use Equati on 18.2, al ong wi th the reducti on potenti al s of
the two materi al s:
E
cel l
5 E
cathode
2 E
anode
We are tol d that ti n i s the anode, so we can set up the equati on so that:
E
cel l
5 E
Cu
2 E
Sn
Looki ng up the reducti on potenti al s, we determi ne that:
Cu
21
(aq) 1 2e
2
Cu 0.34 V
Sn
21
(aq) 1 2e
2
Sn 20.14 V
Substi tuti ng these val ues i nto Equati on 18.2, we determi ne that:
E
cel l
5 0.34 2 (20.14) 5 0.48 V
Summary of Voltaic Cells
The di fference between the cathode and anode represents the di fference i n potenti al energi es.
Because oxi dati on occurs at the anode and reducti on occurs at the cathode, the substance i n
the cel l that i s hi gher (more posi ti ve) on the chart of reducti on potenti al s wi l l be the cathode.
Thats how you can determi ne the anode and cathode i f you are not gi ven that i nformati on.
I f a vol tai c cel l i s to run spontaneousl y, the reducti on potenti al at the cathode must be hi gher
(more posi ti ve) than the reducti on potenti al at the anode. Thi s wi l l al l ow the reacti on at the
anode to proceed as an oxi dati on (rather than a reducti on). The greater the di fference i n
potenti al s between the cathode and anode, the greater the cel l vol tage. E or E wi l l be posi ti ve
for spontaneous processes and negati ve for nonspontaneous ones.
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You Try It!
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.)
Answer: 1.10 V
The Activity Series of Metals
I f you recal l , i n Chapter 11 we descri bed the acti vi ty seri es for metal s. Thi s l i st hel ps predi ct
the behavi or of metal s i n chemi cal reacti ons (parti cul arl y repl acement reacti ons). Based upon
the acti vi ty seri es of metal s, i f a materi al i s hi gher than another on the l i st, i t can repl ace the
metal bel ow i t. What that real l y means i s that the metal bel ow i t exi sts as a cati on, and the
other metal i s gi vi ng i t el ectrons or reduci ng i t. Therefore, i f a metal i s a better reduci ng agent
than another, i t wi l l repl ace the other substance (by reduci ng i ts cati on). Therefore, i f we
consi der pl aci ng a magnesi um stri p i n a sol uti on of ni ckel (I I ) ni trate, we woul d expect the
reacti on to proceed as:
Mg(s) 1 Ni (NO
3
)
2
(aq) Mg(NO
3
)
2
(aq) 1 Ni (s)
Or, more si mpl y put:
Mg(s) 1 Ni
21
(aq) Mg
21
(aq) 1 Ni (s)
I f you wanted to determi ne the standard emf for thi s reacti on, i t wi l l be cal cul ated as:
E
cel l
5 E
cathode
2 E
anode
5 E
Ni
2 E
Mg
5 20.25 V 2 (22.37 V) 5 2.12 V
THE RELATIONSHIP BETWEEN EMF AND FREE ENERGY
I n Chapter 17, we showed the rel ati onshi p between free energy and the spontanei ty of a
reacti on. I f you recal l , a negati ve val ue for DG i ndi cated a spontaneous reacti on. I n the l ast
secti on, we saw that a posi ti ve cel l vol tage, or emf, i ndi cates a spontaneous process. The free
energy and emf can be rel ated i n Equati on 18.3, whi ch states
DG 5 2nFE
(where n i s the number of mol es of el ectrons transferred and F i s Faradays constant, 96,500
J V
21
mol
21
e
2
).
Because n and F are both posi ti ve, a posi ti ve cel l emf (spontaneous reacti on) wi l l produce a
negati ve DG (spontaneous reacti on). On the AP test, the symbol for Faradays constant i s
wri tten as 7.
Sample: Cal cul ate the standard free-energy change for the reacti on shown bel ow:
Zn(s) 1 2Ag
1
(aq) Zn
21
(aq) 1 2Ag(s)
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(Equati on 18.3)
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Answer: To sol ve the probl em we need to know the val ues for n and E. Lets begi n by l ooki ng
at E. Zi nc i s the anode i n thi s reacti on, and si l ver i s the cathode. You can tel l thi s i n
two ways: the fi rst i s that the reducti on potenti al for si l ver i s more posi ti ve than
zi nc, and second because si l ver i s bei ng reduced i n the reacti on. Knowi ng thi s, we
can use Equati on 18.2 to determi ne E:
E
cel l
5 E
cathode
2 E
anode
5 E
Ag
2 E
Zn
5 0.80 V 2 (20.76 V) 5 1.56 V
We al ready know that thi s wi l l occur spontaneousl y because of the posi ti ve val ue
for E. I n the reacti on, two el ectrons are transferred from Zn to 2Ag
1
, whi ch i s
evi dent from the hal f reacti ons shown bel ow:
Zn(s) Zn
21
(aq) 1 2e
2
(s)
2Ag
1
(aq) 1 2e
2
2Ag(s)
Because the val ue of n i s 2, we are ready to substi tute our data i nto Equati on 18.3:
DG 5 2nFE
DG 5 2(2)(1.56 V)(96,500 J V
21
mol
21
e
2
) 5 23.01310
5
J. Because free energi es
are gi ven i n kJ mol
21
, we can convert our answer to ki l ojoul es:
23.01 3 10
5
J 5 2301 kJ
You Try It!
Cal cul ate the standard free-energy change for the reacti on shown bel ow:
Cu
21
(aq) 1 Fe(s) Cu(s) 1 Fe
21
(aq)
Answer: 2151 kJ
THE NERNST EQUATION
I n the exampl es used so far, we have onl y consi dered cases where the concentrati on of the
sol uti ons i n each hal f-cel l was 1.0 M. However, the concentrati on of the reactants and
products i n the hal f-cel l s does affect the emf. We just fi ni shed showi ng how free energy and
emf are rel ated. I n the l ast chapter, we saw how the concentrati ons of reactants and products
affect the free energy i n Equati on 18.9:
DG 5 DG 1 RT l n Q
By combi ni ng thi s equati on wi th Equati on 18.3, DG 5 2nFE, we come up wi th a new
expressi on:
2nFE 5 2(nFE) 1 RT l n Q
I f thi s equati on i s rearranged to sol ve for E, i t becomes the Nernst equati on (Equati on 18.4):
E 5 E 2
RT
nF
l n Q
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(Equati on 18.4)
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Thi s expressi on can al so be wri tten usi ng the base 10 l ogari thm as opposed to the natural
l ogari thm. I n thi s form, Equati on 18.5 reads:
E 5 E 2
2 303 . RT
nF
Q log
Because R and F are constants, the expressi on can be si mpl i fi ed i f the reacti on takes pl ace at
standard temperature (remember, you have to use the absol ute temperature i n thi s
expressi on, so standard temperature i s 298 K). The si mpl i fi cati on i s shown bel ow:
2 303 . RT
nF n e
( )
( )
( )
2.303 8.31 J mol K 298 K
96, 500 J V mol
1 1
1 1
5
0 0592 .
n
I f thi s i s substi tuted i nto equati on 19.5, at standard temperature, the equati on becomes
Equati on 18.6:
E 5 E 2
0 0592 .
n
l og Q *
I n the You Try I t! from the vol tai c cel l s secti on, you l ooked at the reacti on bel ow:
Zn(s) 1 Cu
21
(aq) Zn
21
(aq) 1 Cu(s)
(where each sol uti on began at 1.0 M concentrati on).
I n that probl em, the emf was cal cul ated at 1.10 V. Lets use the Nernst equati on to determi ne
what woul d happen i f we used a concentrati on of 0.1 M Cu
21
sol uti on i nstead of 1.0 M.
To start wi th, the reacti on quoti ent, Q, wi l l onl y contai n the concentrati ons of the i ons, si nce
the neutral atoms are both i n the sol i d state. Therefore, Q wi l l be:
Q 5
[Zn
21
]
[Cu
21
]
5
1.0 M
0.10 M
Substi tuti ng thi s i nto the si mpl i fi ed Nernst equati on, Equati on 18.6, we obtai n:
E 5 E 2
0.0592
n
l og Q 5 1.10 V 2
0.0592 V
2
l og
S
1.0 M
0.10 M
D
E 5 1.10 V 2 [(0.0296 V)(1)] 5 1.07 V
ELECTROLYSIS
So far, weve focused our attenti on on vol tai c cel l s, whi ch rel y on spontaneous chemi cal
reacti ons to dri ve them. I n thi s secti on, we wi l l l ook more cl osel y at a di fferent type of
cel l one that requi res el ectri cal energy from an external source to al l ow a nonspontaneous
reacti on to occur. Thi s new type of reacti on i s known as el ectrol ysi s, and i t takes pl ace i n an
el ectrol yti c cel l .
* I f you actual l y try to perform the cal cul ati on shown, you wi l l obtai n
0.0591
n
, rather than
0.0592
n
. The
actual val ue i s obtai ned usi ng the non-rounded val ues for each number
~2.303!~8.314!~298.15!
~96485!
5 0.0592.
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(Equati on 18.5)
(Equati on 18.6)
www.petersons.com
An el ectrol yti c cel l i s si mi l ar to a vol tai c cel l , but there are some sl i ght di fferences. One of the
fi rst di fferences i s the source of el ectrons. I n the vol tai c cel l , the source of the el ectrons i s the
spontaneous oxi dati on that occurs at the anode. Because no spontaneous reacti ons occur i n an
el ectrol yti c cel l , the source of el ectrons i s a DC (di rect current) power suppl y. The power
suppl y forces el ectrons to the cathode rather than the potenti al of the hal f-reacti ons. The
cathode i n an el ectrol yti c cel l acqui res a negati ve charge (whi ch i s opposi te from a vol tai c cel l )
because el ectrons are bei ng forced onto i t, whi l e the anode takes on a posi ti ve charge (whi ch
i s opposi te from a vol tai c cel l ) because el ectrons are bei ng removed from i t by the
power suppl y.
The el ectrodes i n an el ectrol yti c cel l are pl aced i n a contai ner wi th ei ther a sol uti on or a
mol ten sal t. The i mportant feature i s that there are i ons avai l abl e to i nteract at the
el ectrodes. Even though the si gns on the el ectrodes are reversed, the same process occurs at
each. Oxi dati on sti l l occurs at the anode as the ani on i n the cel l i s attracted to i t and wi l l l ose
i ts el ectron(s) there. For exampl e, i n a cel l contai ni ng mol ten sodi um chl ori de, the Cl
2
i ons
wi l l be attracted to the ani on and be oxi di zed at the el ectrode. The neutral chl ori ne atoms wi l l
react to form chl ori ne gas, whi ch bubbl es out of the cel l . The sodi um i ons wi l l be attracted to
the cathode, where they wi l l be reduced. As the el ectrons are added to the sodi um i ons, the
sodi um wi l l begi n to pl ate out on the el ectrode. That i s, the metal begi ns to form on the
el ectrode. I n thi s parti cul ar exampl e, an aqueous sol uti on of sodi um chl ori de woul d not form
sodi um and chl ori ne because the water woul d be attracted to the el ectrodes before the
two i ons.
Because the reacti on i n an el ectrol yti c cel l i s nonspontaneous, a certai n amount of vol tage
must be appl i ed across the ci rcui t to cause the reacti on to occur. The mi ni mum vol tage
requi red to force the reacti on i s determi ned usi ng Equati on 18.2. For exampl e, i f an
el ectrol yti c cel l contai ns mol ten MgCl
2
, we can determi ne the mi ni mum emf for the cel l . To
begi n, we need the hal f-reacti ons and reducti on potenti al s of each substance:
Cathode: Mg
21
(l) 1 2e
2
Mg(s) E
red
5 22.37
Anode: 2Cl
2
(l) Cl
2
(g) 1 2e
2
E
red
5 1.36
These val ues are then used to determi ne the mi ni mum emf:
E
cel l
5 E
cathode
2 E
anode
5 E
Mg
2 E
Cl
5 22.37 V 2 1.36 V 5 23.73 V
You Try It!
What i s the mi ni mum emf requi red for the el ectrol yti c cel l contai ni ng mol ten KCl ?
Answer: 24.28 V
Special Considerations for Aqueous Solutions
I n the l ast secti on, we l ooked at an el ectrol yti c cel l contai ni ng mol ten NaCl . Very hi gh
temperatures are needed to mel t sodi um chl ori de, so you mi ght ask, Why cant we just
di ssol ve i t i n water and do the same thi ng? Before answeri ng that questi on, you may wi sh to
consi der a procedure that you may have seen demonstrated for you (or even performed) i n an
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i ntroductory cl assthe el ectrol ysi s of water. Water can al so be separated i nto hydrogen and
oxygen gas at the el ectrodes of an el ectrol yti c cel l . The questi on must now be reconsi dered: I f
you di ssol ve sal t i n water and pl ace i t i n an el ectrol yti c cel l , whi ch of the fol l owi ng wi l l col l ect
at the el ectrodes: sodi um and chl ori ne or hydrogen and oxygen?
The fi rst step to answeri ng thi s questi on i s to determi ne from whi ch el ectrode the hydrogen
and oxygen wi l l be l i berated. The cathode wi l l attract the hydrogen i ons (whi ch are posi ti vel y
charged), whi l e oxygen i s created at the anode. The next consi derati on must be whi ch
substance wi l l react at each el ectrode.
At the cathode, two di fferent reacti ons are possi bl e:
2H
2
O(l) 1 2e
2
H
2
(g) 1 2OH
2
(aq) E
red
5 20.83 V
Na
1
(aq) 1 e
2
Na(s) E
red
5 22.71 V
Earl i er, we sai d that the more posi ti ve the reducti on potenti al , the more l i kel y the reducti on
woul d be. Si nce the fi rst val ue i s more posi ti ve, hydrogen gas, H
2
, i s more l i kel y to be
produced at the cathode. Now l ets take a l ook at the anode to see whi ch i s more l i kel y to be
oxi di zed there:
2Cl
2
(aq) Cl
2
(g) 1 2e
2
E
red
5 1.36 V
2H
2
O(l) 4H
1
(aq) 1 O
2
(g) 1 4e
2
E
red
5 1.23 V
The oxi dati on of water i s sl i ghtl y favored at the anode, but the val ues are qui te cl ose to each
other. I f any extra vol tage i s appl i ed, i t i s l i kel y that chl ori ne gas wi l l form at the anode. The
di fference between sodi um and hydrogen, however, i s so l arge that sodi um wi l l not be
produced. The onl y way to produce the pure sodi um i s i n an el ectrol yti c cel l wi th mol ten
sodi um chl ori de (or some other si mi l ar sal t).
You Try It!
I f aqueous MgCl
2
i s pl aced i n an el ectrol yti c cel l , what wi l l the products be?
Answer: Cathode: H
2
(g); Anode: O
2
(g), or Cl
2
(g)
Purification of Metals by Electrolysis
I n the secti on on vol tai c cel l s, we saw that the anode l ost mass over ti me (as the metal s were
oxi di zed and went i nto sol uti on), whi l e the cathode gai ned mass over ti me (as the cati ons were
reduced and pl ated on the surface). The vol tai c cel l , however, requi res spontaneous reacti ons
i n each hal f-cel l , whi ch l i mi ts the types of el ectrodes that can be used. I n an el ectrol yti c cel l ,
because we are addi ng el ectri c current to the cathode and the anode, we can force
nonspontaneous reacti ons to occur. I n some cases, thi s al l ows us to use el ectrol ysi s for
purposes other than separati ng a mol ten compound or aqueous sol uti on. One of the more
common al ternate uses i s the puri fi cati on of di fferent metal s.
When el ectrol ysi s i s used to puri fy a metal , l i ke copper, the el ectrol yti c cel l i s set up wi th a
pure cathode and an i mpure anode. When current i s appl i ed to the cel l , the i mpure anode wi l l
begi n to break apart as: a) copper i ons are oxi di zed and enter sol uti on, b) other reacti ve i ons
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are oxi di zed and enter sol uti on, or c) other nonreacti ve i ons si mpl y fal l off the decomposi ng
anode to the bottom of the reacti on vessel . The copper i ons wi l l pl ate out on the pure copper
cathode, thus creati ng a l arger, pure copper cathode.
A si mi l ar techni que i s used to perform el ectropl ati ng. Thi s techni que al l ows a thi n coat of
metal to be pl ated on the surface of another to i mprove appearance, resi st corrosi on, or, i n the
case of jewel ry, save money on preci ous metal s. I n thi s techni que, the metal to be pl ated i s
made a cathode i n an el ectrol yti c cel l wi th a mol ten metal or metal l i c sal ts.
FARADAYS LAWS
I n the 1830s, Mi chael Faraday determi ned what are now known as Faradays l aws. They have
been revi sed to be consi stent wi th modern atomi c theory (whi ch was i n i ts i nfancy i n hi s day).
Faradays l aws are as fol l ows:
I f the same quanti ty of el ectri ci ty i s passed through a cel l , i t wi l l al ways l ead to the
same amount of chemi cal change for a gi ven reacti on. The wei ght of an el ement that
i s deposi ted or l i berated at an el ectrode i s proporti onal to the amount of el ectri ci ty
that i s passed through.
96,500 coul ombs of el ectri ci ty are requi red to deposi t or l i berate 1 mol e of a
substance that gai ns or l oses 1 el ectron duri ng the cel l reacti on. For every n
el ectrons i nvol ved i n a reacti on, 96,500 n coul ombs of el ectri ci ty are requi red to
l i berate a mol e of product.
The quanti ty 96,500 coul ombs (96,485 i s the number actual l y used, but the AP test and many
texts round i t to 96,500) was i ntroduced earl i er i n the chapter as Faradays constant, where
i ts uni ts were gi ven as J V
21
mol
21
e
2
. The ori gi ns of thi s uni t may hel p you understand i t
more cl earl y. I n Faradays l aws, he uses an amount requi red to deposi t or l i berate one mol e of
a substance that gai ns or l oses one el ectron duri ng the reacti on. That i s equi val ent to sayi ng
one mol e of el ectrons are deposi ted or l i berated. Robert Mi l l i kan l ater determi ned that the
charge of a si ngl e el ectron i s 1.60217733 3 10
219
coul ombs (coul omb i s the SI uni t of charge).
I t was al so l ater l earned that one mol e of anythi ng i s 6.0221367 3 10
23
parti cl es. I f you
rel ease one mol e of el ectrons, that woul d be 6.0221367 3 10
23
el ectrons. I f the charge on each
el ectron i s 1.60217733 3 10
219
coul ombs, then the total amount of charge bel ongi ng to one
mol e of el ectrons i s (6.0221367 3 10
23
)(1.60217733 310
219
C) 5 96,485 coul ombs. Therefore,
part two of Faradays l aw says that 96,500 coul ombs equal a charge of one mol e of el ectrons.
Because a vol t i s defi ned as one joul e per coul omb, the expressi on 1 C 5 1 J V
21
i s substi tuted
i nto Faradays constant for coul ombs. Therefore, 96,500 i s not some magi c numberi ts just
the charge of one mol e of el ectrons! To make thi ngs easi er, thi s quanti ty of charge i s often
referred to as a si ngl e uni t, the Faraday, 7. 1 faraday of charge 5 96,500 coul ombs.
Quantitative Treatment of Faradays Laws
A fai rl y common type of questi on on the AP test wi l l ask you to determi ne how much metal
can be col l ected on the cathode (pl ated out) for a certai n amount of charge added. Thi s i s a
di rect appl i cati on of Faradays l aws, and wel l exami ne thi s type of probl em i n thi s secti on.
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The conceptual treatment of thi s topi c i s rather si mpl e. I n the previ ous secti ons, we l ooked at
the number of el ectrons that are requi red to compl ete an el ectrol yti c process. Thi s was
accompl i shed through the stoi chi ometry of the hal f-reacti ons. For i nstance, i n the
hal f-reacti on:
Cu
21
(l) 1 2e
2
Cu(s)
you can see that for each mol e of copper i ons that i s reduced at the cathode, two mol es of
el ectrons are requi red. That means two faradays of charge are requi red to compl ete
thi s process. I f we were tal ki ng about a substance l i ke sodi um, onl y one faraday woul d
be requi red:
Na
1
(l) 1 e
2
Na(s)
Thats al l there i s to i t. Probl ems are made more di ffi cul t by gi vi ng you i nformati on such as
l engths of ti me or fracti ons of faradays or by aski ng for quanti ti es i n grams i nstead of mol es.
Each of these permutati ons just adds another l ayer of conversi on i nto the probl em, but you
shoul d al ways keep i n mi nd Faradays l aws as a means of doi ng a qui ck check on your work.
One of the fi rst thi ngs you need to know i s the rel ati onshi p between current and el ectri cal
charge. El ectri c current i s a measurement of the rate of charge fl ow. I t measures the amount
of charge that passes a gi ven poi nt i n a gi ven amount of ti me. The SI uni t of current i s the
ampere, abbrevi ated A, and i s commonl y shortened to the word amp. One ampere i s
descri bed by the fl ow of one coul omb of charge per second. The formul a for current i s seen i n
Equati on 18.7:
I 5
q
t
(where I i s the symbol for current, and q i s the symbol for charge).
I f uni ts are substi tuted i nto the expressi on, the formul a becomes:
Amperes 5
Coulombs
second
or A 5
C
s
Thi s equati on can be rearranged as necessary. We can demonstrate how these i deas are used
i n a sampl e probl em.
Sample: 10.0 amperes of current i s passed through an el ectrol yti c cel l fi l l ed wi th mol ten
l i thi um chl ori de, Li Cl , for 500 s. How many grams of l i thi um are col l ected at
the cathode?
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(Equati on 18.7)
www.petersons.com
Answer: Remember, for every 9.65 3 10
4
coul ombs of charge, one mol e of el ectrons can be
used to reduce l i thi um at the cathode. Because the l i thi um i on onl y needs one
el ectron, we wi l l onl y need 9.65 3 10
4
coul ombs per mol e of l i thi um. We just need to
fi gure out how many coul ombs of charge have been appl i ed. Thi s wi l l tel l us what
fracti on of a mol e we can reduce, whi ch we can easi l y convert to grams. Thi s
process can be summari zed i nto four basi c steps:
Determi ne the amount of charge, i n coul ombs, that pass through the cel l .
Usi ng Faradays constant, determi ne the number of mol es of el ectrons
that i s equi val ent to 5000 C.
Usi ng a hal f-reacti on, determi ne the number of mol es of the substance
that can be reduced by the mol es of el ectrons from number 2.
Convert the mol es of the substance to grams.
Usi ng our four steps, we can begi n to sol ve the probl em:
Determi ne the amount of charge, i n coul ombs, that pass through the cel l . I n
thi s probl em, you are tol d that 10 amperes pass through i n 500 s. Thi s i s a
total of 5000 C. Thi s can be shown mathemati cal l y usi ng Equati on 18.7:
q 5 I t 5 (10 A)(500 s) 5 5000 C
Usi ng Faradays constant, determi ne the number of mol es of el ectrons
that i s equi val ent to 5000 C:
5000 C 3
1 mol e
C
. 9 65 10
4
5 0.051813 mol e
2
(extra di gi ts to mi ni mi ze roundi ng errors)
Usi ng a hal f-reacti on, determi ne the number of mol es of the substance
that can be reduced by 0.051813 mol es of el ectrons:
Li
1
(l) 1 e
2
Li (s)
0.051813 mol e
2
3
1 mol Li
1 mol e
5 0.051813 mol Li i ons can be reduced.

Convert 0.051813 mol es to grams of l i thi um.
0.051813 mol Li 3
6.941 g Li
1 mol Li
5 0.360 g Li
You Try It!
I f 3.0 A of current i s passed through an el ectrol yti c cel l contai ni ng a concentrated
CuSO
4
sol uti on for 2.0 hours, how many grams of copper metal can be col l ected at
the cathode?
Answer: 7.1 g Cu
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www.petersons.com
A si mi l ar vari ati on requi res that you determi ne how l ong i t wi l l take to pl ate out a certai n
quanti ty of a substance. The process i s very si mi l ar, except that i t i s worked i n reverse. Wel l
exami ne thi s type of probl em i n the next sampl e.
Sample: 2.65 g of si l ver are col l ected at the cathode i n an el ectrol yti c cel l fi l l ed wi th aqueous
si l ver ni trate. How l ong di d i t take to col l ect thi s much si l ver i f a constant current
of 0.25 A was appl i ed?
Answer: The procedure i s very si mi l ar to the previ ous probl em. I n thi s probl em, you al ready
know how many grams of si l ver were col l ected. By worki ng backward, you can
determi ne how many mol es of si l ver thi s i s. From the hal f-reacti on, you can
determi ne how many mol es of el ectrons woul d have been requi red to reduce the
si l ver at the cathode. Faradays constant can be used to convert the number of
mol es of el ectrons to coul ombs, amps, or seconds.
The fi rst step i s to determi ne the number of mol es i n 2.65 g of si l ver:
2.65 g Ag 3
1 mol Ag
g Ag 107 87 .
5 0.02457 mol Ag
We can use the hal f-reacti on to determi ne the number of el ectrons requi red to
reduce 0.02457 mol Ag:
Ag
1
(aq) 1 e
2
Ag(s)
0.02457 mol Ag 3
1 mol
1 mol Ag
1
e
5 0.02457 mol e
2
Next, we use Faradays constant to convert the mol es of el ectrons to coul ombs:
0.02457 mol e
2
3
9.65 10 C
1 mol
4
1
e
5 2371.0 C
I n thi s step, we wi l l use Equati on 18.7 to determi ne the ti me:
I 5
q
t
, rearranged to sol ve for t i s t 5
q
I
t 5
2371.0 C
0.25 A
5 9484 s or 158 mi n
You Try It!
How l ong does 4.00 A have to be appl i ed to an el ectrol yti c cel l contai ni ng aqueous
si l ver ni trate to col l ect 9.5 g of si l ver at the cathode?
Answer: 2.13 s or 35.5 mi n
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EXERCISES: ELECTROCHEMISTRY
Multiple Choice
1. Whi ch of the fol l owi ng wi l l be the
best oxi di zi ng agent?
(A) Cl
2
(B) Fe
(C) Na
(D) Na
1
(E) F
2
2. A pi ece of copper metal i s pl aced i nto
sol uti ons contai ni ng each of the
fol l owi ng three cati ons. Whi ch i on
wi l l be reduced by the copper metal ?
I . Sn
21
I I . Zn
21
I I I . Ag
1
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
3. When mol ten CaCl
2
i s el ectrol yzed,
the cal ci um metal col l ects at the
__________charged el ectrode, whi ch
i s cal l ed the __________, and the
chl ori ne i s gi ven off at the __________
charged el ectrode, whi ch i s known as
the __________.
(A) posi ti vel y; anode; negati vel y;
cathode
(B) posi ti vel y; cathode; negati vel y;
anode
(C) negati vel y; anode; posi ti vel y;
cathode
(D) negati vel y; cathode; posi ti vel y;
anode
(E) posi ti vel y; el ectrol yte;
negati vel y; emf
4. I f 0.500 A of current i s appl i ed for
1.50 h to an el ectrol yti c cel l contai n-
i ng mol ten l i thi um chl ori de, how
many grams of l i thi um woul d be
deposi ted on the cathode?
(A) 0.388 g
(B) 0.194 g
(C) 0.097 g
(D) 0.050 g
(E) 5.4 3 10
25
g
5. The reducti on of 3.00 mol es of Ca
21
to Ca woul d requi re how many
coul ombs?
(A) 6.22 3 10
25
C
(B) 3.22 3 10
4
C
(C) 1.61 3 10
4
C
(D) 2.90 3 10
5
C
(E) 5.79 3 10
5
C
6. A vol tai c cel l i s created wi th one
hal f-cel l consi sti ng of a copper
el ectrode i mmersed i n 1.0 M CuSO
4
sol uti on and the other hal f-cel l
consi sti ng of a l ead el ectrode i m-
mersed i n a 1.0 M Pb(NO
3
)
2
sol uti on.
Each hal f-cel l i s mai ntai ned at 25C.
What i s the cel l potenti al , i n vol ts?
(A) 0.47 V
(B) 0.21 V
(C) 20.21 V
(D) 20.47 V
(E) 2.5 V
Ag
1
(aq) 1 Fe
21
(aq) Ag(s) 1 Fe
31
(aq)
7. For the reacti on above, what i s the
equi l i bri um constant at 25C?
(A) 1.0
(B) 1.6
(C) 3.2
(D) 6.4
(E) 10
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8. I f a current of 15.0 A i s appl i ed to a
sol uti on of Cr
31
i ons, how l ong wi l l i t
take to pl ate out 1.86 g of chromi um
metal ?
(A) 3.83 mi nutes
(B) 5.7 mi nutes
(C) 11.5 mi nutes
(D) 35.0 mi nutes
(E) 690.0 mi nutes
9. A vol tai c cel l i s set up wi th two
hal f-cel l s. I n the fi rst hal f-cel l , a
si l ver el ectrode i s pl aced i n an
aqueous sol uti on contai ni ng
Ag
1
i ons. I n the second hal f-cel l , a
ni ckel el ectrode i s pl aced i n an
aqueous sol uti on contai ni ng
Ni
21
i ons. The si l ver el ectrode i s the
________and has a ________charge.
(A) cathode; posi ti ve
(B) cathode; negati ve
(C) anode; posi ti ve
(D) anode; negati ve
(E) sal t bri dge; posi ti ve and
negati ve
10. 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)
Fe
31
(aq) 1 Ag(s) Fe
21
(aq) 1
Ag
1
(aq)
11. What i s the standard free energy
change (DG) for the reacti on shown
above?
(A) 22.5 kJ
(B) 2.9 kJ
(C) 8.7 kJ
(D) 10 kJ
(E) 29 kJ
12. An el ectrol yti c cel l contai ns mol ten
CuBr
2
. What i s the mi ni mum vol tage
that must be appl i ed to begi n
el ectrol ysi s?
(A) 0.17 V
(B) 0.34 V
(C) 0.73 V
(D) 1.07 V
(E) 1.41 V
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www.petersons.com
Free Response
QUESTION 1
A vol tai c cel l i s created usi ng a zi nc el ectrode i mmersed i n a 1.0 M sol uti on of Zn
21
i ons and
a si l ver el ectrode i mmersed i n a sol uti on of 1.0 M Ag
1
i ons. The two el ectrodes are connected
wi th a wi re, and a sal t bri dge i s pl aced between the two hal f-cel l s. The temperature of the
cel l s i s 25C.
(A) Wri te the bal anced hal f-reacti ons that are occurri ng at the cathode and the
anode.
(B) Cal cul ate the standard cel l vol tage for the cel l .
(C) Cal cul ate DG for the cel l .
(D) How wi l l the vol tage be affected i f 2.5 g of KCl i s added to each hal f-cel l ? Justi fy
your response.
QUESTION 2
An el ectrol yti c cel l contai ns mol ten NaCl .
(A) Gas i s seen bubbl i ng at one of the el ectrodes. I s thi s the cathode or anode?
Expl ai n.
(B) I f a current of 0.5 A i s appl i ed to the cel l for 30 mi nutes, how many grams of
sodi um metal wi l l be col l ected?
(C) I f the current i s rai sed to 5.0 A, how l ong wi l l i t have to be appl i ed to produce 10.0
g of sodi um metal ?
(D) I f the mol ten NaCl i s repl aced by an 1.0 M aqueous sodi um chl ori de sol uti on, how
much sodi um can be col l ected i f a current of 1.0 A i s appl i ed for 1.0 hour?
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Multiple Choice
1. A
2. C
3. D
4. B
5. E
6. A
7. C
8. C
9. A
10. E
11. B
12. C
1. The correct answer is (A). An oxi di zi ng agent i s a substance that oxi di zes another
substance (by removi ng el ectrons). Therefore, i t must be a substance that has a strong
attracti on for el ectrons. One way to thi nk of thi s i s to consi der the most el ectronegati ve
substance. The fl uori de i on has been thrown i n as a di stracter, but because i t i s an i on,
i t al ready has the nobl e gas confi gurati on. Chl ori ne i s the most el ectronegati ve
substance l eft. Another way to thi nk of thi s i s by l ooki ng at the chart of standard
reducti on potenti al s. The substances cl osest to the top are the best reduci ng agents
whi l e those at the bottom are the best oxi di zi ng agents.
2. The correct answer is (C). You can answer thi s by l ooki ng at the tabl e of standard
reducti on potenti al s. Si l ver i s the onl y substance that i s bel ow copper.
3. Thecorrect answer is (D). Mol ten CaCl
2
consi sts of Ca
21
and Cl
2
i ons. Cal ci um i ons
wi l l be attracted to the negati vel y charged el ectrode. I n an el ectrol yti c cel l , the
negati vel y charged el ectrode that attracts cati ons i s known as the cathode. Ani ons are
attracted to the posi ti ve anode.
4. The correct answer is (B). You need to use Equati on 18.7 for thi s probl em. I n the
equati on:
I 5
q
t
0.500 A 5
q
~1.50 h!~60 mi n/h!~60 s/mi n!
q 5 2700 C
Usi ng Faradays l aws, we can convert thi s to mol es of el ectrons:
2700 C 3
1 mol
9.65 10 C
1
4
e
5 0.0280 mol e
2
Because each mol e of l i thi um i ons requi res one mol e of el ectrons:
Li
1
(l) 1 e
2
Li (s)
0.0280 mol e
2
3
1 mol Li
1 mol
1
e
5 0.0280 mol Li
Fi nal l y, convert the mol es to grams:
0.0280 mol Li 3
6.941 g
1 mol Li
5 0.194 g
a
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5. The correct answer is (E). I n thi s probl em, you si mpl y need to determi ne how many
mol es of el ectrons wi l l be needed to accompl i sh thi s, and then convert thi s to coul ombs
(usi ng Faradays constant).
Each mol e of Ca
21
i ons requi res 2 e
2
, as can be seen i n the hal f-reacti on:
Ca
21
1 2e
2
Ca
Therefore, 3.00 mol es of Ca
21
wi l l requi re 6.00 mol es of el ectrons. When thi s i s
converted to coul ombs, the resul t yi el ds the fol l owi ng answer:
6.00 mol e
2
3
9.65 10 C
1 mol
4
1
e
5 5.79 10
5
C
6. Thecorrect answer is (A). Because each sol uti on i s present at 1.0 M concentrati ons,
we can use Equati on 18.2. Fi rst, we need to determi ne whi ch el ectrode i s the cathode
and whi ch i s the anode. The substance wi th the most negati ve reducti on potenti al wi l l
be the anode and the most posi ti ve reducti on potenti al wi l l be the cathode. Lead has a
reducti on potenti al of 20.13, whi l e copper has a val ue of 0.34. Therefore, l ead wi l l be
the anode and copper wi l l be the cathode. By l ooki ng at the hal f-reacti ons, we see that
the anode can suppl y the cathode wi th al l necessary el ectrons:
Anode: Pb
21
(aq) 1 2e
2
Pb(s) E 5 20.13 V
Cathode: Cu
21
(aq) 1 2e
2
Cu(s) E 5 0.34 V
Substi tuti ng these val ues i nto Equati on 17.2, we obtai n:
E
cel l
5 E
cathode
2 E
anode
E 5 0.34 V 2 (20.13 V) 5 0.47 V
7. The correct answer is (C). When sol vi ng probl ems that requi re the equi l i bri um
constant, you need to use the Nernst equati on:
E 5 E 2
0 0592 .
n
l og Q
We can rearrange the equati on to determi ne the equi l i bri um constant (when Q 5 K).
Under the new equati on:
E 5
0.0592 V
n
l og K
To sol ve for K, we wi l l need to know E. We can obtai n thi s from the hal f-reacti ons.
I n the equati on, si l ver i s bei ng reduced and i ron i s bei ng oxi di zed. The hal f-reacti ons
woul d be set up as fol l ows:
Oxi dati on: Fe
21
(aq) Fe
31
(aq) 1 e
2
Because thi s i s an oxi dati on, we wi l l need to reverse the equati on to use the val ue of the
reducti on potenti al :
Fe
31
(aq) 1 e
2
Fe
21
(aq) E 5 0.77 V
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The oxi dati on wi l l have a val ue of 20.77 V:
Reducti on: Ag
1
(aq) 1 e
2
Ag(s) E 5 0.80
E
cel l
5 E
ox
1 E
red
5 20.77 V 1 0.80 V 5 0.03 V
Thi s val ue can be substi tuted i nto our equati on, al ong wi th a val ue of n 5 1 (because
onl y one mol e of el ectrons i s transferred):
E 5
0.0592 V
n
l og K
0.03 V 5
0.0592 V
1
l og K
l og K 5 0.5068
K 5 10
0.5068
5 3.21
8. Thecorrect answer is (C). Fi rst, we need to determi ne how many mol es of chromi um
are i n 1.86 g of chromi um. Once we know thi s, we can determi ne the number of mol es
of el ectrons that were requi red to reduce that number of mol es, whi ch wi l l al l ow us to
sol ve the rest of the probl em:
1.86 g Cr 3
1 mol Cr
52.00 g Cr
5 0.035769 mol (extra di gi ts to avoi d error)
The hal f-reacti on tel l s us that each mol e of chromi um i ons requi res 3 el ectrons:
Cr
31
(aq) 1 3e
2
Cr(s)
Therefore, we need to use Faradays constant to determi ne the amount of charge
requi red to reduce thi s quanti ty of chromi um i ons:
0.035769 mol Cr
31
i ons 3
3 mol
1 mol Cr
9.65 10 C
1 mol
4
e
e
_
,
_
,
3
5 10355.13 C
To fi ni sh the cal cul ati on, use Equati on 18.7 to sol ve for t:
I 5
q
t
t
q
I

10355.13 C
15.0 A
5 690.3 s
Converti ng to mi nutes, we fi nd that:
690.3 s
1 min
60 s
5 11.5 mi n
9. The correct answer is (A). I n a vol tai c cel l , the substance wi th the most posi ti ve
reducti on potenti al wi l l be the cathode. Ag
1
has a val ue of 0.80 V, and Ni
21
has a val ue
of 20.25 V. That woul d make the si l ver el ectrode the cathode. I n a vol tai c cel l , the
cathode al ways has a posi ti ve charge.
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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10. The correct answer is (E). By exami ni ng Equati on 18.6, wi th the vari abl e
substi tuted i n
E 5 E 2
0 0592 .
n
l og Q 5 1.10 V 2
0.0592 V
2
l og
Zn
Cu
2
2
+
+
[ ]
[ ]
we see that the onl y way to have a val ue greater than 1.10 V i s i f
0.0592 V
2
l og
Zn
Cu
2
2
+
+
[ ]
[ ]
produces a negati ve val ue. Thi s can onl y happen when the [Zn
21
] i s l ess than the
[Cu
21
]. Thi s i s onl y true for choi ce (E).
11. The correct answer is (B). Equati ons 18.2 and 18.3 wi l l be needed to sol ve thi s
probl em. Fi rst, the val ue of E must be determi ned. I t can then be used i n Equati on 18.3.
The fi rst step, therefore, i s to cal cul ate E:
E
cel l
5 E
ox
1 E
red
By usi ng the same procedures as i n probl em 7, we fi nd that:
E
cel l
5 2E
Ag
1 E
Fe
5 2(0.80 V) 1 (0.77 V) 5 20.03 V
We can now substi tute thi s val ue i nto Equati on 18.3:
DG 5 2nFE 5 2(1 mol e
2
)(96,500 J V
21
mol
21
e
2
)(20.03 V) 5 2895 J
DG 5 2.9 kJ
12. The correct answer is (C). I n an el ectrol yti c cel l , the reacti ons are nonspontaneous
and wi l l onl y occur i f a certai n amount of vol tage i s appl i ed. Thi s can be cal cul ated
usi ng the equati on
E
cel l
5 E
cathode
2 E
anode
whi ch for thi s cel l wi l l be
E
cel l
5 E
Cu
2 E
Br
5 0.34 V 2 (1.07) 5 20.73 V
Therefore, the cel l requi res 0.73 V to begi n el ectrol ysi s.
Free Response
QUESTION 1
(A) The cathode and anode can be determi ned by the reducti on potenti al s of each
substance. The substance wi th the most posi ti ve reducti on potenti al wi l l be the
cathode. Therefore, i n thi s reacti on, Ag i s the cathode and Zn i s the anode. The
hal f reacti ons, therefore, wi l l be as fol l ows:
Oxi dati on: Zn(s) Zn
21
(aq) 1 2e
2
Reducti on: 2Ag
1
(aq) 1 2e
2
2Ag(s)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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(B) The standard cel l vol tage for the cel l wi l l be:
E
cel l
5 E
cathode
2 E
anode
5 (0.80 V 2 (20.76)) 5 1.56 V
(C) To sol ve for DG, we wi l l use Equati on 18.3:
DG 5 2nFE
where n wi l l equal 2 because 2 mol es of el ectrons are needed to reduce the si l ver:
DG 5 2(2 mol e
2
)(96,500 J V
21
mol
21
e
2
)(1.56 V) 5 2301 kJ
(D) I n the zi nc cel l , the addi ti on of KCl wi l l have no effect, but i n the si l ver cel l , the
addi ti on of KCl wi l l cause the formati on of the preci pi tate AgCl (s). Thi s wi l l
decrease the amount of avai l abl e Ag
1
and therefore decrease the vol tage.
QUESTION 2
(A) The bubbl i ng gas must be chl ori ne gas. Therefore, the reacti on that must be
occurri ng at the el ectrode i s:
2Cl
2
Cl
2
(g) 1 2e
2
Si nce thi s i s an oxi dati on, i t must be the anode. I n el ectrol yti c cel l s, the anode i s
posi ti vel y charged and wi l l therefore attract ani ons.
(B) I f 0.5 A i s appl i ed for 30 mi nutes, i t means the total charge appl i ed i s:
q 5 I t
q 5 (0.5 A)(30 mi n)(60 s/1 mi n) 5 900 C
Thi s val ue can be used to determi ne the number of mol es of el ectrons that wi l l be
suppl i ed:
900 C 3
1 mol
9.65 10 C
1
4
e
5 9.33 3 10
23
e
2
Because the reducti on of each mol e of sodi um i ons requi res one mol e of el ectrons,
the number of mol es of sodi um i ons wi l l al so equal 9.33 3 10
23
. I f thi s i s
converted to grams, the total amount of sodi um equal s:
9.33 3 10
23
mol Na 3
22.99 g Na
1 mol Na
5 0.214 g Na
(C) Thi s probl em must be sol ved i n the reverse order of Part (B). The 10.0 g of Na
must be converted to mol es of el ectrons, and then to coul ombs. The charge can
then be used to sol ve for t:
10.0 g Na 3
1 mol Na
22.99 g Na
5 0.435 mol Na
Each mol e of sodi um atoms was generated wi th one mol e of el ectrons, so the
amount of el ectrons requi red i s al so equal to 0.435 e
2
. Thi s can be converted to
coul ombs usi ng Faradays constant:
0.435 mol e
2
3
9.65 10 C
1 mol
4
1
e
5 41977.5 C
a
n
s
w
e
r
s
e
x
e
r
c
i
s
e
s
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Thi s val ue i s then used to determi ne t:
t
q
I

41977.5 C
5.0 A
5 8395.5 s 5 140 mi n
(D) I n aqueous sodi um chl ori de, sodi um i s no l onger col l ected at the cathode. Because
hydrogen i s much more readi l y reduced than hydrogen, hydrogen gas wi l l col l ect
at the cathode. Therefore, no sodi um wi l l be col l ected.
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SUMMING IT UP
Hal f-reacti ons are a way to show the transfer of el ectrons that occurs duri ng
oxi dati on-reducti on (redox) reacti ons.
A vol tai c, or gal vani c, cel l al l ows the oxi dati on and reducti on of substances to be
physi cal l y separated. Thi s i s accompl i shed by al l owi ng the el ectrons to pass from one
l ocati on to the other by way of an external path (such as a wi re). The ci rcui t i n a vol tai c
cel l must be compl eted usi ng a sal t bri dge or another porous barri er that al l ows for the
transfer of ani ons between the two hal f-cel l s.
A vol tage i s created when there i s a di fference i n el ectri cal potenti al energy between two
l ocati ons. A vol tage al l ows current to fl ow from one l ocati on to another.
I n a vol tai c cel l , oxi dati on takes pl ace at the anode and reducti on occurs at the cathode.
The anode i s posi ti vel y charged, whi l e the cathode i s negati vel y charged.
The standard reducti on potenti al s of the two hal f-cel l s can be used to determi ne the cel l
vol tage (al so known as cel l potenti al or emf).
An oxi di zi ng agent i s a substance that removes el ectrons from another substance, whi l e a
reduci ng agent adds el ectrons. Materi al s that are good oxi di zi ng agents have the most
posi ti ve reducti on potenti al s, whi l e good reduci ng agents have the most negati ve
reducti on potenti al s.
Vol tai c cel l s can onl y be created when each hal f-cel l contai ns a reacti on that occurs
spontaneousl y. Because of thi s, cel l vol tage and free energy can be rel ated (usi ng
Equati on 18.3).
The Nernst equati on (Equati on 18.4) can be used to rel ate the cel l potenti al to the
concentrati on of the sol uti ons i n each hal f-cel l .
El ectrol yti c cel l s can be created to separate materi al s. Unl i ke the reacti ons i n vol tai c
cel l s, the reacti ons i n el ectrol yti c cel l s are nonspontaneous. I n an el ectrol yti c cel l , a
vol tage i s appl i ed usi ng a power suppl y.
I n an el ectrol yti c cel l , the anode i s posi ti vel y charged and the cathode i s negati vel y charged.
When aqueous sol uti ons are pl aced i n el ectrol yti c cel l s, the col l ecti on of the sol ute at the
cathode and anode may be affected by the presence of hydrogen and hydroxi de i ons i n the
sol uti on.
Faradays l aws can be used to determi ne the amount of a substance that can be col l ected
at an el ectrode. I n addi ti on, Faradays l aws can determi ne the amount of current that
must be suppl i ed to an el ectrol yti c cel l .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Organic Chemistry
OVERVIEW
Alkanes
Isomers
Unsaturated hydrocarbons
Functional groups
Summing it up
Thi s topi c wi l l be treated di fferentl y from the others i n the book. The mai n
reason i s that the AP test has al most no questi ons that deal stri ctl y wi th the
topi c. I n many of the previ ous chapters, organi c compounds have been
di scussed among the i norgani c compounds (e.g., aci d-base equi l i bri a, chemi cal
bondi ng, i ntermol ecul ar forces), but no speci fi c knowl edge i s needed to
di sti ngui sh the organi c compounds from the i norgani c compounds. The onl y
topi cs uni que to organi c chemi stry that are covered on the AP test are
nomencl ature and structure. There are usual l y onl y one or two mul ti pl e-
choi ce questi ons devoted to thi s topi c, so i t i s unnecessary to have
end-of-chapter questi ons and practi ce essays.
The structures and nomencl ature of organi c chemi stry are al l based on the
carbon and hydrogen skel eton, known as a hydrocarbon. Di fferent
arrangements of carbon and hydrogen atoms, as wel l as the addi ti on of other
atoms or groups of atoms, al l ow a wi de di versi ty i n the number and types of
organi c compounds. I n thi s chapter, we wi l l proceed from the most basi c
hydrocarbons to more compl ex arrangements.
ALKANES
The al kanes are the most basi c type of hydrocarbon compound, contai ni ng
onl y carbon and hydrogen. Al l bonds i n al kane mol ecul es are si ngl e, coval ent
bonds. Carbon atoms can form four bonds i n any combi nati on (i .e., four si ngl e
bonds, one doubl e bond and two si ngl e bonds). Al kanes, al so known as
saturated hydrocarbons, contai n al l si ngl e bonds. Each carbon atom i s bonded
to at l east one other carbon atom, and the remai ni ng bonds are al l si ngl e
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c
h
a
p
t
e
r
1
9
459
bonds wi th hydrogen. The smal l est al kane i s methane, CH
4
, whi ch i s composed of one carbon
atom bonded wi th si ngl e bonds to four hydrogen atoms.
When an al kane contai ns two or more carbon atoms, the carbon atoms wi l l begi n bondi ng to
each other. The resul ti ng structures are known as hydrocarbon chai ns because of the way the
carbon atoms l i nk together. There are two types of hydrocarbon chai ns that can
formstrai ght-chai n and branched-chai n hydrocarbons. I n a strai ght chai n, the carbon
atoms at the end of the mol ecul e are bonded to one carbon and three hydrocarbons (shown as
a 2CH
3
group). The central carbon atoms are bonded to two carbon atoms and two hydrogen
atoms (2CH
2
2). The empi ri cal formul a for al l al kanes i s C
n
H
2n 1 2
. The names of al l al kanes
end i n ane. Some exampl es are the ethane mol ecul e, C
2
H
6
, and propane, C
3
H
8
. Tabl e 19.1
shows the names of the al kanes wi th up to 10 carbon atoms.
There are several di fferent ways to descri be organi c compounds. Fi gure 19.1 shows two of the
most basi c types of formul as, both mol ecul ar and structural , that are used to descri be organi c
compounds.
Branched-Chain Hydrocarbons
So far, we have just l ooked at hydrocarbons that are strai ght chai ns. There are many
compounds where central carbon atoms are bonded to three or four carbon atoms or other
non-hydrogen atoms. For branched-chai n hydrocarbons, there are speci al procedures for
nami ng compounds. To start wi th, we wi l l onl y consi der saturated hydrocarbons. Once you
understand some of the basi c rul es of nomencl ature, we can begi n to l ook at unsaturated
hydrocarbons and atoms other than carbon and hydrogen.
I n branched-chai n hydrocarbons, the branches occur when a carbon atom repl aces a hydrogen
atom bonded to a central carbon atom. I f a carbon atom repl aces hydrogen on ei ther of the end
carbon atoms, the chai n si mpl y i ncreases i n l ength by one rather than branchi ng. Al kyl
TABLE 19.1
Molecular Formula Structural Formula Name
CH
4
CH
4
Methane
C
2
H
6
CH
3
CH
3
Ethane
C
3
H
8
CH
3
CH
2
CH
3
Propane
C
4
H
10
CH
3
(CH
2
)
2
CH
3
Butane
C
5
H
12
CH
3
(CH
2
)
3
CH
3
Pentane
C
6
H
14
CH
3
(CH
2
)
4
CH
3
Hexane
C
7
H
16
CH
3
(CH
2
)
5
CH
3
Heptane
C
8
H
18
CH
3
(CH
2
)
6
CH
3
Octane
C
9
H
20
CH
3
(CH
2
)
7
CH
3
Nonane
C
10
H
22
CH
3
(CH
2
)
8
CH
3
Decane
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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groups are al kanes that are mi ssi ng a hydrogen atom and can therefore bond to another
substance. For exampl e, when the mol ecul e methane, CH
4
, l oses one hydrogen atom, i t
becomes CH
3
2, known as a methyl group. Note the ane endi ng of the al kane i s repl aced wi th
a yl endi ng i n the al kyl group. The methyl group can bond to a carbon i n another
hydrocarbon chai n. Ethane, C
2
H
6
, becomes an ethyl group when i t l oses a hydrogen atom.
One di ffi cul ty that branches present i s the possi bi l i ty of the formati on of i somers, mol ecul es
that have the same mol ecul ar formul a but di fferent structures. I n Fi gure 19.2, note how the
mol ecul es butane and 2-methyl propane have the same mol ecul ar formul as but di fferent
structures and properti es:
For exampl e, butane has a boi l i ng poi nt of 20.5C, whi l e 2-methyl propanes boi l i ng poi nt i s
211.7C. Onl y hydrocarbon chai ns wi th at l east four carbon atoms are capabl e of formi ng a
branch. Because there must be a way to di sti ngui sh i somers, the nomencl ature must take
these i nto account. The fol l owi ng are general rul es for nami ng branched-chai n al kanes:
Locate the l ongest, strai ght hydrocarbon chai n i n the mol ecul e. Thi s i s the mai n
part of the name of the mol ecul e. The names of any branches wi l l be added onto thi s.
Numbers are assi gned to each carbon atom begi nni ng wi th the carbon atom cl osest
to the substi tuent, shown i n Fi gure 19.3:
C C H
H H
C C
H H
H H H H
H
Lewis structure
Structural Diagram
C
H H
H
C
C
H
H
H H H H
H
C
Figure19.1
n-butane
CH
3
CH
2
CH
2
CH
3
CH
3
CHCH
3
CH
3
2-methylpropane
Figure19.2
CH
3 2 2
CH
3
CH
3
1 2
(not 4-methylpentane)
CH
3
CH
2
CHCH
2
CH
2
CH
3
CH
3
3-methylhexane
(not 4-methylhexane)
Figure19.3
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Chapter 19: Organic Chemistry 461
www.petersons.com
I f more than one group i s attached, a Greek prefi x i s used to desi gnate the number
of groups. Each group wi l l sti l l be assi gned a number. The numbers shoul d be
fol l owed by a hyphen and the name of the mol ecul e, shown i n Fi gure 19.4:
When two or more groups are attached, the l ongest chai n i s numbered so that the
seri es of numbers for al l groups i s l owest. Each number shoul d be separated by a
comma, and the l ast number shoul d be fol l owed by a hyphen, shown i n Fi gure 19.5:
When more than one type of substi tuent i s present, they are l i sted i n al phabeti cal
order, wi th numbers desi gnati ng the l ocati on of each group, shown i n Fi gure 19.6:
Sample: Name the mol ecul e shown bel ow:
CH
3
CH
2
CH
2
CHCHCH
3
CH
3
CH
3
Answer: Step 1: The l ongest chai n i s si x carbon atoms l ong, maki ng i t a hexane mol ecul e. I t
coul d start from ei ther the carbon on the far ri ght or the one above the rest of the
2,2-dimethylpentane
(not 2-dimethylpentane)
CH
3
CCH
2
CH
2
CH
3
CH
3
CH
3
CH
3
CH
3
2,2,4,4-tetramethylpentane
CH
3
C
CH
3
CH
3
CCH
3
CH
2
Figure19.4
2,3-dimethylpentane
(not 3,4-dimethylpentane)
CH
3
CH
2
CHCHCH
3
CH
3
CH
3
CH
3
CHCH
2
CH
2
CHCHCH
2
CH
3
CH
3
CH
3
CH
3
2,5,6-trimethyloctane
(not 3,4,7-trimethyloctane)
Figure19.5
CH
3
CHCHCH
2
CH
2
CH
3
CH
3
CH
2
CH
3
3-ethyl-2 methylhexane
Figure19.6
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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mol ecul e. Because i t i s easi er to work i n a strai ght l i ne, we wi l l count from one to
si x, movi ng from ri ght to l eft.
Steps 2and 3: The two groups are methyl groups and are attached at carbons 2 and
3. The numbers must go from ri ght to l eft si nce goi ng from l eft to ri ght woul d resul t
i n the l arger numbers 4 and 5. The prefi x di wi l l be used si nce there are two
methyl groups attached. Step 4 i s not necessary because the two substi tuent groups
are the same.
The name i s 2,3-di methyl hexane.
You Try It!
Name the mol ecul e shown bel ow:
CH
3
CHCHCHCH
3
CH
3
CH
3
CH
3
Answer: 2,3,4-tri methyl pentane
Sample: Draw a structural formul a for 2,2,3-tri methyl pentane.
Answer: Fi rst you need to draw a 5-carbon chai n si nce the mol ecul e i s cal l ed pentane. Onto
the 5-carbon chai n, you need to attach 3 methyl groups (you know thi s from the
prefi x tri ). The l ocati ons of each of the three methyl groups are two on carbon 2
and one on carbon 3. The mol ecul e wi l l l ook l i ke:
You Try It!
Draw a structural formul a for 3-ethyl -2-methyl pentane:
CH
3
CH
2
CHCHCH
3
CH
3
CH
2
CH
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Cycloalkanes
I n addi ti on to branched chai ns, al kanes can al so form ri ngs. The two termi nal carbons bond
together to compl ete a ri ng. The nomencl ature i s very si mi l ar except the prefi x cycl o i s added
before the name of the al kane. For i nstance, when the two termi nal carbon atoms i n hexane
connect together, a si x-si ded ri ng i s formed, cal l ed cycl ohexane. A fi ve-si ded ri ng woul d be
cal l ed cycl opentane. Each of these mol ecul es i s shown i n Fi gure 19.7:
ISOMERS
I n the previ ous secti on, we menti oned that di fferent mol ecul es, i somers, can have the same
mol ecul ar formul a but have a di fferent structure. We saw that butane, C
4
H
10
, has two
i somersbutane (al so known as n-butane) and 2-methyl propane. As mol ecul es get l onger,
more and more i somers become possi bl e. I n the fi rst sampl e, we wi l l consi der the number of
i somers of pentane.
Sample: Determi ne the number of i somers of pentane, and draw each i somers structure.
Answer: The number of possi bl e i somers begi ns to i ncrease dramati cal l y wi th the addi ti on of
more carbon atoms. Whi l e C
5
has onl y three i somers, C
10
has 75. To answer thi s
questi on, the fi rst thi ng we wi l l need to do i s draw the strai ght chai n. The fi rst
i somer i s the strai ght chai n, cal l ed n-pentane, shown i n Fi gure 19.8:
After that, smal l groups of atoms shoul d be removed from the end of the mol ecul e
and pl aced at other l ocati ons. You shoul d begi n by removi ng a methyl group from
the end of the mol ecul e and pl aci ng i t somewhere i n the mi ddl e. I f a methyl group
i s pl aced at carbon 2, the compound now becomes 2-methyl butane, as shown i n
Fi gure 19.9:
CCH
22
H CH H
2
H CH H
22
H CH
2
H CH
2
CCH
22
H CHH
22
H CHH
22
H CH
2
H CH
2
CCH
22
Cyclohexane Cyclopentane
Figure19.7
CH
3
CH
2
CH
2
CH
2
CH
3
n-pentane
Figure19.8
CH
3
CH
2
CHCH
3
CH
3
2-methylbutane
Figure19.9
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Note that i f you move the methyl group to carbon 3, the carbon atoms woul d have
to be numbered from the opposi te end, maki ng i t i n posi ti on 2 agai n. Thi s woul d not
change i ts structure. So, the next thi ng to do i s try to bri ng another methyl group
from the other end of the mol ecul e. Doi ng so produces 2,2-di methyl propane, the
thi rd C
5
H
12
i somer, shown i n Fi gure 19.10:
You Try It!
Draw and name the 5 i somers of C
6
H
14
.
Answer:
2,2-dimethylbutane
CH
3
CH
2
CCH
3
CH
3
CH
3
2,3-dimethylbutane
CH
3
CHCHCH
3
CH
3
CH
3
2-methylpentane
CH
3
CH
2
CH
2
CHCH
3
CH
3
n-hexane
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
3-methylpentane
CH
3
CH
2
CHCH
2
CH
3
CH
3
UNSATURATED HYDROCARBONS
Alkenes
Al kenes are hydrocarbons contai ni ng at l east one doubl e bond. For al kenes wi th onl y one
doubl e bond, the empi ri cal formul a i s C
n
H
2n
. The names for al l al kenes end wi th ene. The
nami ng system on al kenes i s the same as al kanes, wi th the excepti on of the ene endi ng. For
exampl e, the two-carbon al kane, C
2
H
6
, i s cal l ed ethane, whi l e the two-carbon al kene, C
2
H
4
, i s
cal l ed ethene.
For al kenes l onger than 3 carbons, the doubl e bond can be i n di fferent pl aces i n the mol ecul e.
Wri ti ng a number before the name of the al kene i denti fi es the l ocati on of the bond. The
number represents the bond number i n the mol ecul e, rather than the carbon number. The
bond between carbons 1 and 2 i s l abel ed 1, the bond between carbons 2 and 3 i s l abel ed 2,
and so on. I f more than one doubl e bond i s found, a prefi x i s used to show how many are
CH
3
CHCH
3
CH
3
CH
3
2,2-dimethylpropane
Figure19.10
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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present and numbers are gi ven to each one. Fi gure 19.11 shows two di fferent possi bl e
structures of pentenes.
I n addi ti on to the l ocati ons of the doubl e bonds, another di fference of al kenes i s the mol ecul es
i nabi l i ty to rotate at the doubl e bond. Wi th al kanes, when substi tuent groups attach to a
carbon, the mol ecul e can rotate around the C-C bonds i n response to el ectron-el ectron
repul si ons. Because the doubl e bond i n the al kene i s composed of both si gma and pi bonds, the
mol ecul e cant rotate around the doubl e bond (see Chapter 6). What thi s means for al kenes i s
that the mol ecul e can have di fferent structural ori entati ons around the doubl e bond. These
di fferent ori entati ons al l ow a new ki nd of i someri sm, known as geometri cal i someri sm.
When the non-hydrogen parts of the mol ecul e are on the same si de of the mol ecul e, the term
cis i s pl aced i n front of the name. When the non-hydrogen parts are pl aced on opposi te si des
of the mol ecul e, the term trans i s pl aced i n front of the name. I n the previ ous secti on, you
saw that the al kane butane has onl y two i somers. Because of geometri cal i someri sm, butene
has four i somers, shown i n Fi gure 19.12.
Sample: Name the compound shown bel ow:
CH
3
H CH
3
C
CH
3
CCH
C
H H
Answer: Fi rst, noti ce that the l ongest carbon chai n i s 5 carbons l ong, maki ng thi s pentene.
I n numberi ng the chai n, the numberi ng shoul d start so that the doubl e bond i s
gi ven the l owest possi bl e number. I n thi s case, that means numberi ng ri ght to l eft,
whi ch pl aces the bond at posi ti on 2. The next thi ng to do i s i denti fy the substi tuent
group on the chai n. A methyl group i s l ocated on carbon 4. Fi nal l y, the posi ti on of
the groups al ong the doubl e bond pl aces the non-hydrogen groups on the same si de
1-pentene
CH
2
CH
2
CH
3
CH CH
2
1,3-pentadiene
CHCH
3
CH CH CH
2
Figure19.11
trans-2-butene cis-2-butene
1-butene 2-methylpropene
CC CC
H H CH
3
CHH
22
H
C
H CH
3
C CC
H CHH
33
H
H CH
3
H
H
CHH
33
C
H
H
CHH
33
CCH
33
C
Figure19.12
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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of the bond, maki ng thi s a cis confi gurati on. Putti ng al l of thi s i nformati on
together, we come up wi th the term:
cis-4-methyl -2-pentene
You Try It!
Name the mol ecul e shown bel ow:
CH
3
C
CH
2
CHCH
2
CH
3
H CH
3
CH
2
C
H
Answer: trans-6-methyl -3-octene
Alkynes
Al kynes are hydrocarbons contai ni ng at l east one tri pl e bond. The empi ri cal formul a for
al kynes i s C
n
H
2n22
, and the names end i n 2yne. For exampl e, the two carbon al kyne has the
formul a C
2
H
2
, and i s known as ethyne.
The nami ng system for al kynes i s the same as for al kenes, except that al kynes do not have
geometri cal i somers. The tri pl e bond onl y al l ows a si ngl e group to extend off of the carbon
atoms attached by a tri pl e bond, so no cis or trans i somers are possi bl e.
Sample: Name the compound shown bel ow:
CH
3
C CCH
3
Answer: The l ongest chai n i s 4 carbon atoms l ong, so i t wi l l be cal l ed butyne. The tri pl e bond
appears at posi ti on 2 i n the mol ecul e, so the name of thi s compound i s 2-butyne.
You Try It!
Name the compound shown bel ow:
CH
3
CH
3
CHC CCH
3
Answer: 4-methyl -2-pentyne
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Aromatic Hydrocarbons
Aromati c hydrocarbons are cycl i c, pl anar compounds contai ni ng del ocal i zed el ectrons. The
del ocal i zati on of the el ectrons i n the pi orbi tal s makes these very stabl e structures. The most
common aromati c hydrocarbon i s C
6
H
6
, benzene. The structure of benzene i s shown i n
Fi gure 19.13:
There are two i mportant thi ngs i n the di agrams. Fi rst, you see the shorthand notati on for
hydrocarbon chai ns, whi ch are bent l i nes. Each bend represents a C-C-C bond. Each poi nt i s
understood to represent C-H bonds. I n the case of the benzene ri ng, because there are doubl e
bonds present, each poi nt represents a CH groupi ng (as opposed to a CH
2
group for a
hydrocarbon chai n wi th al l si ngl e bonds). The second i mportant feature i s the representati on
of the resonance structures. Because the el ectrons i n the benzene ri ng are del ocal i zed, the
fi gure i s usual l y drawn wi th a ci rcl e i n the center, whi ch represents the del ocal i zati on of the
pi el ectrons i n the benzene ri ng.
Additions to Alkenes and Alkynes
The doubl e and tri pl e bonds i n hydrocarbon chai ns are very reacti ve. Hal ogens readi l y react
wi th the carbon atoms by formi ng bonds wi th the el ectrons i n the pi orbi tal s of the doubl e (or
tri pl e) bond.
FUNCTIONAL GROUPS
There are certai n reacti ve si tes i n organi c compounds known as functi onal groups. Functi onal
groups are speci fi c combi nati ons of atoms that undergo characteri sti c reacti ons regardl ess of
the mol ecul e i n whi ch they appear. Because the functi onal group determi nes the reacti vi ty of
organi c mol ecul es, mol ecul es are usual l y cl assi fi ed accordi ng to the functi onal group they
contai n. Tabl e 19.2 contai ns a l i st of the common functi onal groups.
Alcohols (R-OH)
The pol ar hydroxyl group (OH) present i n al cohol s makes al cohol s more sol ubl e i n pol ar
sol vents than other hydrocarbons and al so i ncreases the boi l i ng temperature of these
compounds (because of i ncreased hydrogen bondi ng). The boi l i ng temperatures of al cohol s are
much hi gher than the boi l i ng temperatures of the al kanes to whi ch they are attached.
When nami ng al cohol s, the endi ng of the hydrocarbon i s removed and the suffi x ol i s used
i nstead. For exampl e, when a hydroxyl group attaches to an ethane mol ecul e, CH
3
CH
3
, the
resul ti ng al cohol , CH
3
CH
2
OH, i s known as ethanol .
CCH
CCH
CCH H CH
H CH H CCH
Figure19.13
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Ethers (R-O-R)
Ethers are formed from condensati on reacti ons (resul t i n the formati on of water) between two
al cohol s. The mai n functi on of ethers i s thei r use as sol vents. Ethers are named by pl aci ng the
names of the two R groups (R and R) before the word ether. The R groups shoul d be l i sted i n
al phabeti cal order i f they are two di fferent groups.
Aldehydes (R-COH)
Al dehydes contai n a carbonyl group (C5O) to whi ch at l east one hydrogen atom i s attached.
The suffi x al i s pl aced on the end of the name of al dehydes. For exampl e, the mol ecul e
CH
3
CH
2
COH i s known as propanal . Al dehydes must have the carbonyl on the l ast carbon on
the chai n (i n order to have the hydrogen atom attached to the carbon). As a resul t, there i s no
need for the use of numbers to di sti ngui sh the posi ti on of the carbonyl group.
Ketones (R-CO-R)
Ketones have the carbonyl group attached to an i nteri or carbon atom of an organi c compound.
The carbonyl group gi ves the mol ecul ar pol ari ty, thus many ketones are used as sol vents. I n
the nami ng of ketones, you need to repl ace the endi ng of the mol ecul e wi th the suffi x one. A
number i s used to i ndi cate the posi ti on of the carbonyl group i n the mol ecul e.
TABLE 19.2
Functional
Group
Type of
Compound
Suffix/
Prefix Sample Name
CH
2
5CH
2
Al kene ene CH
2
5CH
2
Ethene
CH[CH Al kyne yne CH[CH Ethyne
R-X Hal oal kene Hal o CH
3
-Cl Chl oromethane
R-OH Al cohol ol CH
3
-OH Methanol
R-O-R Ether Ether CH
3
-O-CH
3
Di methyl ether
R-COH Al dehyde al CH
3
-COH Ethanal
R-CO-R8 Ketone one CH
3
-CO-CH
3
2-propanone
R-COOH Carboxyl i c
aci d
oi c
aci d
CH
3
CH
2
-COOH Propanoi c aci d
R-COO-R Ester oate CH
3
-COO-CH
2
CH
3
Ethyl ethanoate
R
3
N Ami ne ami ne CH
3
-NH
2
Methyl ami ne
(methanami ne)
R-CO-NR
2
Ami de ami de CH
3
CH
2
-CO-NH
2
Propanami de
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Carboxylic Acids (R-COOH)
The functi onal group i n these organi c aci ds i s the carboxyl group (COOH). These weak aci ds
are very common and di ssoci ate i n sol uti on to yi el d a negati vel y charged COO
2
group and a
H
1
i on. The nami ng system for carboxyl i c aci ds i s to use the name of the mol ecul e but to
repl ace the endi ng wi th oi c aci d.
Esters (R-COO-R)
Esters are formed from the condensati on reacti on of carboxyl i c aci d and an al cohol . I n thi s
reacti on, the hydrocarbon group l eft behi nd when the al cohol l ost the OH- group repl aces the
hydrogen of the carboxyl i c aci d. Esters are usual l y sweet-smel l i ng substances and are used i n
soap maki ng. When nami ng esters, the fi rst thi ng i s to use the name of the group deri ved from
the al cohol fol l owed by the name of the group deri ved from the aci d, endi ng wi th oate.
Amines (R
3
N)
Ami nes are organi c bases. I n the generi c formul a, R
3
N, the R groups can be hydrocarbon
groups or hydrogen atoms. The nami ng system uses the names of the hydrocarbon groups
fol l owed by the term amine, wri tten as a si ngl e word.
Amides (RCO-NR
2
)
Ami des are formed when ami nes undergo a condensati on reacti on wi th a carboxyl i c aci d.
Duri ng the process of protei n synthesi s, thi s condensati on reacti on i s responsi bl e for the
l i nkages between huge numbers of ami no aci ds (whi ch contai n an ami ne group and a
carboxyl i c aci d). When nami ng ami des, the root of the carboxyl i c aci d (mi nus the oi c aci d) i s
attached to the term amideto form a si ngl e word.
You Try It!
Name each of the fol l owi ng compounds, and i denti fy the functi onal group i n each:
1. 2. 3. 4.
O
CH
3
CCH
2
CH
3
O
CH
3
C OH
O
CH
3
CH
2
C H
O
CH
3
C O CH
3
CH
2
OH CH
3
O
CH
3
C NH
2
CH
3
CH
2
O CH
2
CH
3
5.
6. 7. 8. 9.
N
H
CH
3
CH
2
CH
2
H
H C
Cl
Cl
Cl
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www.petersons.com
Answers:
1. 2-Butanone; ketone
2. Ethanoi c aci d; carboxyl i c aci d
3. Ethanol ; al cohol
4. Methyl ethanoate; ester
5. Ethanami de; ami de
6. Propyl ami ne; ami ne
7. Di ethyl ether; ether
8. Tri chl oromethane; hal oal kane
9. Propanal ; al dehyde
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SUMMING IT UP
The basi c structural uni t for al l organi c compounds i s the hydrocarbon backbone,
consi sti ng of a carbon atom bonded to hydrogen atoms.
A carbon atom can form four bonds, whi ch can be any combi nati on of si ngl e, doubl e, or
tri pl e bonds.
Al kanes are hydrocarbon compounds that contai n al l si ngl e bonds. The basi c formul a for
al l al kanes i s C
n
H
2n 1 2
.
Al kanes can be ei ther strai ght-chai n or branched-chai n. I n strai ght-chai n hydrocarbons,
the carbon atoms on the end of the chai n bond to onl y a si ngl e carbon atom and carbon
atoms i n the mi ddl e of the chai n bond to onl y two carbon atoms, one on each si de. I n
branched-chai n hydrocarbons, the central carbon atoms bond to addi ti onal carbon atoms.
The branched-chai n structures al l ow more than one mol ecul e to have the same mol ecul ar
formul a, whi l e havi ng a di fferent mol ecul ar structure. Mol ecul es wi th these characteri s-
ti cs are known as i somers.
Hydrocarbons wi th si ngl e carbon-carbon bonds are known as saturated, whi l e those
contai ni ng doubl e or tri pl e bonds between carbon atoms are known as unsaturated.
Al kenes are unsaturated hydrocarbons that contai n at l east one carbon-carbon doubl e
bond.
Al kenes are not free to rotate around the doubl e bond. As a resul t, al kenes can form
i somers based on the types of substi tuent groups attached to them as wel l as the
ori entati on of the mol ecul e on ei ther si de of the doubl e bond. When i somers form because
of these di fferences i n ori entati on, they are known as geometri cal i somers.
Al kynes contai n tri pl e bonds. Al though they are al so not abl e to rotate about the tri pl e
bond, they dont form geometri cal i somers because the mol ecul e has 180 bond angl es at
ei ther end of the tri pl e bond.
Aromati c hydrocarbons are cycl i c compounds wi th del ocal i zed el ectrons. They are very
stabl e structures and are found as ei ther the root or the substi tuent i n many organi c
compounds.
Functi onal groups are speci al reacti ve si tes that are l ocated wi thi n organi c compounds
that gi ve them characteri sti c properti es. You shoul d be abl e to recogni ze and i denti fy each
of the functi onal groups l i sted i n Tabl e 19.2.
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www.petersons.com
P
ART IV
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
TWO PRACTICE TESTS
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PRACTICE TEST 2
PRACTICE TEST 3
ANSWER SHEET PRACTICE TEST 2
SECTION I
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
65.
jA jB jC jD jE
66.
jA jB jC jD jE
67.
jA jB jC jD jE
68.
jA jB jC jD jE
69.
jA jB jC jD jE
70.
jA jB jC jD jE
71.
jA jB jC jD jE
72.
jA jB jC jD jE
73.
jA jB jC jD jE
74.
jA jB jC jD jE
75.
jA jB jC jD jE
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a
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w
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s
h
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e
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Practice Test 2 475
www.petersons.com
Practice Test 2
SECTION I
TIM E1 HO UR AND 30 M INUTES
NO CALCULATORS MAY BE USED WITH SECTION I.
mol 5 mol e(s)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
p
r
a
c
t
i
c
e
t
e
s
t
2
GO ON TO THE NEXT PAGE

477
i mmedi atel y fol l owi ng i t. Sel ect the one l ettered choi ce that best fi ts each statement and
then fi l l i n the correspondi ng oval on the answer sheet. A choi ce may be used once, more
than once, or not at al l i n each set.
QUESTIONS 14 REFER TO THE ORBITAL
DIAGRAMS SHOWN BELOW:
(A)
(B)
(C)
(D)
(E)
1. Represents a nonreacti ve atom
2. Represents a vi ol ati on of the Paul i
excl usi on pri nci pl e
3. Represents a vi ol ati on of Hunds rul e
4. Represents an atom i n an exci ted
state
USE THESE ANSWERS FOR QUESTIONS 58.
(B) Resonance (del ocal i zati on)
(D) Hybri di zed orbi tal s
(E) Di spersi on forces
5. Expl ai ns why methane has a boi l i ng
poi nt of 161C and octane has a
boi l i ng poi nt of 125.6C
6. Expl ai ns why benzene, whi ch
mathemati cal l y shoul d have three
doubl e bonds and three si ngl e bonds,
actual l y has si x bonds of i denti cal
l ength
7. I s used to expl ai n the fact that the
four bonds i n methane are equi val ent
8. Expl ai ns why the boi l i ng poi nt of
hel i um i s 2269C and the boi l i ng
poi nt for xenon i s 2108C
QUESTIONS 911 REFER TO THE PHASE
DIAGRAM OF A PURE SUBSTANCE,
SHOWN BELOW:
(A) Freezi ng
(B) Mel ti ng
(C) Subl i mati on
(D) Condensati on
(E) Vapori zati on
40C to 60C at a pressure of 1.5
atm, whi ch process i s occurri ng?
20C to 60C at a pressure of 0.5
atm, whi ch process i s occurri ng?
11. I f the pressure i ncreases from 0.5
atm to 1.0 atm at 60C, whi ch
process i s occurri ng?
478 PART IV: Two Practice Tests
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Directions: Each of the questi ons or i ncompl ete statements bel ow i s fol l owed by fi ve
answers or compl eti ons. Sel ect the one that i s best i n each case and then fi l l i n the
correspondi ng oval on the answer sheet.
12. Whi ch of the fol l owi ng i s the safest
and most effecti ve procedure to treat
a base spi l l onto ski n?
(A) Dry the affected area wi th
paper towel s.
(B) Fl ush the area wi th a di l ute
sol uti on of HCl .
(C) Fl ush the affected area wi th
water and then wi th a di l ute
NaOH sol uti on.
(D) Fl ush the affected area wi th
NaHCO
3
sol uti on.
(E) Fl ush the affected area wi th
vi negar sol uti on.
13. Whi ch of the fol l owi ng has an opti cal
i somer?
(A)
CH
3
C
CH
3
CH
3
(B)
CH
3
CH
2
CCH
3
Br
CH
3
(C)
CH
3
CH
2
CH
2
C
CH
2
(D)
CH
3
CH
2
CCH
2
OH
NH
2
CH
3
(D)
CH
3
CH
2
CCH
2
OH
NH
2
CH
3
14. What was the key fi ndi ng i n Ruther-

fords famous gol d-foi l experi ment?
(A) El ectrons orbi t the nucl eus i n
concentri c ri ngs.
(B) Al l neutrons are l ocated i n a
central nucl eus.
(C) Most of the mass of an atom i s
l ocated i n a central , dense core.
(D) Atoms are composed of posi -
ti vel y and negati vel y charge
parti cl es.
(E) Al pha parti cl es are attracted to
a negati vel y charged pl ate.
15. Whi ch of the fol l owi ng reacti ons i s
possi bl e at the anode of a gal vani c
cel l ?
(A) Zn Zn
21
1 2e
2
(B) Zn
21
1 2e
2
Zn
(C) Ag
1
1 e
2
Ag
(D) Mg 1 Ag
1
Mg
21
1 Ag
(E) Pb
21
1 2I
2
PbI
2
16. What i s the fi nal concentrati on of
l ead i ons, [Pb
21
], i n sol uti on when
100 mL of 0.10 M PbCl
2
(aq) i s mi xed
wi th 100 mL of 0.050 M H
2
SO
4
(aq)?
(A) 0.005 M
(B) 0.012 M
(C) 0.025 M
(D) 0.250 M
(E) 0.10 M
p
r
a
c
t
i
c
e
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s
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Practice Test 2 479

www.petersons.com
N
2
(g) 1 3H
2
(g) 2NH
3
(g)
DH5 292 kJ
17. Whi ch of the fol l owi ng changes woul d
cause a decrease i n the equi l i bri um
constant, K
eq
, for the reacti on shown
above?
(A) Decrease the temperature
(B) I ncrease the temperature
(C) I ncrease the pressure of the
reacti on vessel by decreasi ng
the vol ume
(D) The addi ti on of ni trogen gas to
the reacti on vessel
(E) The addi ti on of argon gas to the
reacti on vessel
23
53
1
0
V e +
_______
18. I n the nucl ear equati on shown above,
what i s the mi ssi ng product?
(A)
21
49
Sc
(B)
22
53
Ti
(C)
23
55
V
(D)
22
51
Ti
(E)
24
53
Cr
19. I n a 1.0 L sampl e of 0.01 M potas-
si um sul fate, K
2
SO
4,
what i s the
mi ni mum number of mol es of cal ci um
chl ori de, CaCl
2
, that can be added to
the sol uti on before the preci pi tate
cal ci um sul fate forms? Assume that
the addi ti on of cal ci um chl ori de has a
negl i gi bl e effect on the total vol ume
of the sol uti on. K
sp
for CaSO
4
5
2.4 3 10
25
(A) 2.4 3 10
25
mol
(B) 1.2 3 10
25
mol
(C) 2.4 3 10
23
mol
(D) 1.2 3 10
23
mol
(E) 0.01 mol
20. Whi ch of the fol l owi ng combi nati ons
of quantum numbers (n, l, m
l
, m
s
) i s
NOT al l owed?
(A) 1, 1, 0,
1
2
(B) 3, 0, 0, 2
1
2
(C) 2, 1, 21,
1
2
(D) 4, 3, 22, 2
1
2
(E) 4, 2, 0,
1
2
21. What woul d happen to the average
ki neti c energy of the mol ecul es of a
gas sampl e i f the temperature of the
sampl e i ncreased from 20C to 40C?
(A) I t woul d doubl e.
(B) I t woul d i ncrease.
(C) I t woul d decrease.
(D) I t woul d become hal f i ts val ue.
(E) Two of the above.
22. As the bond order of a bond i n-
creases, i ts bond energy ______and
i ts bond l ength ______.
(A) i ncreases; i ncreases
(B) decreases; decreases
(C) i ncreases; decreases
(D) decreases; i ncreases
(E) i s unaffected; i ncreases
23. At normal atmospheri c pressure and
a temperature of 0C, whi ch phase(s)
of H
2
O can exi st?
(A) I ce and water
(B) I ce and water vapor
(C) Water onl y
(D) Water vapor onl y
(E) I ce onl y
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
24. Commerci al vi negar was ti trated
wi th NaOH sol uti on to determi ne the
content of aceti c aci d, HC
2
H
3
O
2
. For
20.0 mi l l i l i ters of the vi negar, 36.0
mi l l i l i ters of 0.500 M NaOH
sol uti on was requi red. What was the
concentrati on of aceti c aci d i n the
vi negar assumi ng no other aci d was
present?
(A) 1.80 M
(B) 0.900 M
(C) 0.750 M
(D) 0.450 M
(E) 0.028 M
25. Based on the data bel ow for a reacti on
i n whi ch A and B react to form C,
what i s the rate l aw for the reacti on?
[A]
(mol L
21
)
[B]
(mol L
21
)
I ni ti al Rate of
Formati on of
C (mol L
21
s
21
)
0.2 0.2 0.50
0.4 0.2 2.00
0.8 0.2 8.00
0.2 0.4 1.00
0.2 0.8 2.00
(A) Rate 5 k[A][B]
(B) Rate 5 k[A]
2
[B]
(C) Rate 5 k[A][B]
2
(D) Rate 5 k[A]
2
[B]
2
(E) Rate 5 k[A]
3
26. I n whi ch of the fol l owi ng reacti ons
does the H
2
PO
4
2
i on act as an aci d?
I . H
3
PO
4
1 H
2
O H
3
O
1
1
H
2
PO
4
2
I I . H
2
PO
4
2
1 H
2
O H
3
O
1
1
HPO
4
22
I I I . H
2
PO
4
2
1 OH
2
H
3
PO
4
1
O
22
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I and I I I
QUESTIONS 2728 REFER TO THE
FOLLOWING DIAGRAM:
I . A
I I . B
I I I . C
27. Whi ch wi l l be affected by the addi -
ti on of a catal yst?
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I I and I I I
28. The reacti on shown i n the graph i s a
___________reacti on.
(A) fi rst-order
(B) catal yzed
(C) endothermi c
(D) exothermi c
(E) pri mary
I oni zati on Energi es for
el ement X (kJ mol
21
)
Fi rst Second Thi rd Fourth Fi fth
801 2427 3660 25024 32827
29. The i oni zati on energi es for el ement X
are l i sted i n the tabl e above. On the
basi s of the data, whi ch of the fol l ow-
i ng i s el ement X most l i kel y to be?
(A) Li
(B) Be
(C) B
(D) C
(E) N
p
r
a
c
t
i
c
e
t
e
s
t
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Practice Test 2 481

www.petersons.com
30. When sol i d sodi um hydr oxi de,
NaOH(s), i s added to water at 25C, i t
di ssol ves and the temperature of the
sol uti on i ncreases. Whi ch of the fol l ow-
i ng i s true for the val ues of DH and DS
for the di ssol vi ng process?
DH DS
(A) 1 1
(B) 1 2
(C) 0 0
(D) 2 2
(E) 2 1
31. Copper i s el ectropl ated from CuSO
4
sol uti on. A constant current of 10.00
amps i s appl i ed by an external power
suppl y for exactl y 75.0 mi nutes. How
many grams of copper can be pl ated
out duri ng thi s ti me i nterval ? The
atomi c mass of copper i s 63.55.
(A) 3.67 3 10
23
g
(B) 0.247 g
(C) 7.4 g
(D) 14.8 g
(E) 29.6 g
QUESTION 32 REFERS TO THE FOLLOWING
STANDARD HEATS OF FORMATION, H
f
:
DH
f
P
4
O
10
(s) 5 23110 kJ mol
21
DH
f
H
2
O(l) 5 2286 kJ mol
21
DH
f
H
3
PO
4
(s) 5 21279 kJ mol
21
32. Gi ven the standard heats of forma-
ti on shown above, cal cul ate the
change i n enthal py for the fol l owi ng
process:
P
4
O
10
(s) 1 6 H
2
O(l) 4 H
3
PO
4
(s)
(A) 2290 kJ
(B) 21128 kJ
(C) 22117 kJ
(D) 23547 kJ
(E) 24675 kJ
33. 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 onl y
(C) I I I onl y
(D) I and I I
(E) I and I I I
34. The nucl i de
7
12
N i s unstabl e. What
type of radi oacti ve decay woul d be
expected?
(A) b
2
(B) b
1
(C) f
(D) a
(E)
0
1
n
35. What vol ume of 0.500 M NaOH i s
requi red to neutral i ze 25.0 mL of 1.2
M H
2
SO
4
? (Assume compl ete i oni za-
ti on of the aci d.)
(A) 60 mL
(B) 90 mL
(C) 100 mL
(D) 120 mL
(E) 180 mL
36. The organi c compound represented
above i s an exampl e of a(n)
(A) organi c aci d.
(B) al cohol .
(C) ether.
(D) al dehyde.
(E) ketone.
37. The pH of a 1.0 M sodi um acetate
sol uti on i s
(A) 7.0
(B) greater than 7.0
(C) l ess than 7.0
(D) 0
(E) i mpossi bl e to predi ct
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www.petersons.com
C
2
H
4
(g) 1 3O
2
(g) 2CO
2
(g) 1 2H
2
O(l)
38. When 200.0 g of ethyl ene (C
2
H
4
)
burns i n oxygen to gi ve carbon
di oxi de and water, how many grams
of CO
2
are formed?
(A) 200 g
(B) 255 g
(C) 314 g
(D) 400 g
(E) 628 g
QUESTION 39 REFERS TO THE FOLLOWING
PHASE DIAGRAM FOR A PURE SUBSTANCE:
39. The normal boi l i ng poi nt for the
substance represented i n the phase
di agram above i s
(A) 33C
(B) 35C
(C) 84C
(D) 50C
(E) 28C
40. Whi ch of the fol l owi ng sol i d sal ts
shoul d be more sol ubl e i n 1.0 M NH
3
than i n water?
(A) Na
2
CO
3
(B) KCl
(C) AgBr
(D) KNO
3
(E) NaBr
41. I n the graph bel ow, whi ch shows the
rel ati onshi p between concentrati on
and ti me, what type of reacti on i s
represented?
1
[
]
A
(A) Zero order
(B) Fi rst order
(C) Second order
(D) Thi rd order
(E) The graph does not represent
any type of reacti on.
42. What i s the mol ar sol ubi l i ty of
PbSO
4
i n water at 25C (K
sp
for
PbSO
4
i s 1.3 3 10
28
)?
(A) 1.1 3 10
24
M
(B) 2.2 3 10
24
M
(C) 5.1 3 10
25
M
(D) 1.3 3 10
28
M
(E) 1.3 3 10
26
M
43.
PV
nRT
wi l l be l ess than 1 for a real gas
where
(A) the gas mol ecul es are l arge
enough to occupy a l arge
amount of space.
(B) there i s a l arge sampl e of very
fast movi ng parti cl es.
(C) the gas mol ecul es have a very
smal l mol ar mass.
(D) the gas mol ecul es are attracted
to each other.
(E) the gas mol ecul es are repel l ed
from each other.
p
r
a
c
t
i
c
e
t
e
s
t
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Practice Test 2 483

www.petersons.com
2CO(g) 1 O
2
(g) 2CO
2
(g)
DH 5 2514.2 kJ
44. I n the above reacti on, whi ch factors
wi l l cause the equi l i bri um to shi ft to
the ri ght?
I . An i ncrease i n vol ume
I I . An i ncrease i n temperature
I I I . Removal of CO
2
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I I and I I I
45. I f the temperature of a sol uti on
changes, whi ch measure of concen-
trati on wi l l change?
(A) Mass percent
(B) Mol e fracti on
(C) Mol al i ty
(D) Mol ari ty
(E) None of these measures wi l l
change.
46. The pH of a 0.100 M sol uti on of an
aqueous weak aci d (HA) i s 4.00. The
K
a
for the weak aci d i s
(A) 1.0 3 10
24
(B) 4.0 3 10
24
(C) 1.0 3 10
27
(D) 1.0 3 10
28
(E) 4.0 3 10
28
47. Equal numbers of mol es of the gases
Cl
2
, NO
2
, and CH
4
are pl aced i nto an
evacuated vessel equi pped wi th a
val ve. The val ve has a very smal l
hol e, si mi l ar to the si ze of a pi nhol e.
I f the val ve i s opened for a bri ef
peri od of ti me and then cl osed, whi ch
wi l l be true of the parti al pressures
of the gases remai ni ng i n the fl ask?
(A) P
Cl
2
, P
NO
2
, P
CH
4
(B) P
NO
2
, P
CH
4
, P
Cl
2
(C) P
CH
4
, P
Cl
2
, P
NO
2
(D) P
NO
2
, P
Cl
2
, P
CH
4
(E) P
CH
4
, P
NO
2
, P
Cl
2
48. Li qui d A and l i qui d B form a sol uti on
that behaves i deal l y accordi ng to
Raoul ts l aw. The vapor pressures of
the pure substances A and B are 75
mm Hg and 25 mm Hg, respecti vel y.
Determi ne the vapor pressure over
the sol uti on i f 1.50 mol es of l i qui d A
i s added to 5.50 mol es of l i qui d B.
(A) 30.0 mm Hg
(B) 35.7 mm Hg
(C) 71.4 mm Hg
(D) 125 mm Hg
(E) 250 mm Hg
49. How many grams are i n a 6.94-mol
sampl e of sodi um hydroxi de?
(A) 40.0 g
(B) 278 g
(C) 169 g
(D) 131 g
(E) 34.2 g
2C(s) 1 O
2
(g) 2CO(g)
50. 1.2 mol of O
2
and 3.50 mol of sol i d C
are pl aced i n a 2.00 L evacuated
vessel at 25C. I f the carbon and
oxygen react compl etel y to form
CO(g), what wi l l the fi nal pressure
be i n the contai ner?
(A) 1.2 atm
(B) 14.7 atm
(C) 20.0 atm
(D) 29.4 atm
(E) 42.8 atm
51. An unknown substance i s pl aced i nto
a hot fl ame. The col or of the fl ame i s
a bri ght red. Whi ch of the fol l owi ng
substances i s most l i kel y to be the
unknown?
(A) Cu(NO
3
)
2
(B) NaCl
(C) KCl
(D) Li Cl
(E) Ba(NO
3
)
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
52. Vi tami n C i s composed of 40.9% C,
4.58% H, and 54.52% O by mass. I f
the mol ar mass of vi tami n C i s 176.1,
what i s the mol ecul ar formul a?
(A) C
2
H
3
O
2
(B) C
3
H
4
O
3
(C) C
4
H
6
O
4
(D) C
6
H
8
O
6
(E) C
4
H
10
O
3
53. A mol ecul e or an i on i s a Lewi s base
i f i t
(A) accepts a proton from water.
(B) accepts a pai r of el ectrons to
form a bond.
(C) donates a pai r of el ectrons to
form a bond.
(D) donates a proton to water.
(E) donates a hydroxi de i on i n
sol uti on.
2NO 1 O
2
2NO
2
54. I n an experi ment, the gases above
are al l owed to establ i sh equi l i bri um
at 25C. I f [NO] 5 [O
2
] 5 2.0 3 10
26
M, how woul d you set up the equa-
ti on to determi ne [NO
2
]?
(A) 4.0 3 10
13
5
NO
2.0 10 2.0 10
2
6 6
1
]
1
]

1
]

(B) 4.0 3 10
13
5
NO
2.0 10 2.0 10
2
6 6
1
]
1
]

1
]

2
2
(C) 4.0 3 10
13
5
NO
2.0 10
2
6
1
]
1
]
2
(D) 2.0 3 10
26
5
NO
4.0 10 4.0 10
2
13 13
1
]
1
]

1
]

2
2
(E) 4.0 3 10
13
5
2.0 10 2.0 10
NO
6 6
2

1
]

1
]
1
]
2
2
55. I f an open contai ner of sal t sol uti on
i s l eft out for an extended peri od of
ti me i n a room where temperature
and pressure are constant, the vapor
pressure of the sol uti on wi l l
(A) i ncrease over ti me.
(B) decrease over ti me.
(C) remai n constant at al l ti mes.
(D) be zero si nce the contai ner
i s open.
(E) i ncrease for a peri od of ti me
and then sharpl y decrease.
Ca(OH)
2
(aq) 1 2HNO
3
(aq)
Ca(NO
3
)
2
(aq) 1 2H
2
O(l)
56. I n the reacti on shown above, how
many grams of Ca(NO
3
)
2
can be
produced by reacti ng excess HNO
3
wi th 7.40 g of Ca(OH)
2
?
(A) 10.2 g
(B) 16.4 g
(C) 32.8 g
(D) 8.22 g
(E) 7.40 g
57. Whi ch of the fol l owi ng substances
woul d you expect to have the l owest
boi l i ng poi nt?
(A) Di amond
(B) Ammoni a, NH
3
(C) Sodi um acetate, NaC
2
H
3
O
2
(D) Gl yceri ne, C
3
H
5
(OH)
3
(E) Si l ver
58. Whi ch substance(s) l i sted bel ow
woul d form basi c sol uti ons?
I . NH
4
Cl
I I . K
2
CO
3
I I I . NaF
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I I and I I I
p
r
a
c
t
i
c
e
t
e
s
t
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Practice Test 2 485

www.petersons.com
59. 50.0 g of an unknown substance i s
heated to 98.0C and then pl aced i n
a cal ori meter contai ni ng 100.0 g of
water (c 5 4.18 J/gC) at 20.91C.
The fi nal temperature of the mi xture
i s 23.0C. Whi ch metal was used?
(A) Al umi num (c 5 0.90 J/gC)
(B) I ron (c 5 0.45 J/gC)
(C) Copper (c 5 0.38 J/gC)
(D) Lead (c 5 0.13 J/gC)
(E) Si l ver (c 5 0.23 J/gC)
C(s) 1 CO
2
(g) 2CO(g)
60. I n the reacti on shown above, the
val ue of K
p
i s 167.5 at a temperature
of 1273 K. I f the P
CO
2
at thi s tem-
perature i s 0.10 atm, what wi l l the
P
CO
be?
(A) 0.1 atm
(B) 4.1 atm
(C) 12.9 atm
(D) 16.7 atm
(E) 53.0 atm
61. 0.05 mol of sol i d HgCl
2
i s vapori zed i n
a 1.00 L evacuated fl ask at 680 K.
What i s the pressure i nsi de the fl ask?
(The val ue of the gas constant, R, i s
0.0821 L atm mol
21
K
21
.)
(A) 0.05 atm
(B) 1.00 atm
(C) 2.0 atm
(D) 2.8 atm
(E) 3.2 atm
62. The vol ume of di sti l l ed water that
shoul d be added to 10.0 mL of
12.0 M HCl (aq) i n order to prepare
a 1.00 M HCl (aq) sol uti on i s approxi -
matel y
(A) 50.0 mL
(B) 60.0 mL
(C) 100 mL
(D) 110 mL
(E) 120 mL
63. I f G . 0 for a reacti on, whi ch of the
fol l owi ng statements about the
equi l i bri um constant, K, i s true?
(A) K 5 0
(B) K . 1
(C) K , 1
(D) K 5 1
(E) K 5 G
64. How many of the fol l owi ng mol ecul es
have al l of thei r atoms i n the same
pl ane?
CH
2
CH
2
F
2
O H
2
CO NH
3
CO
2
BeCl
2
H
2
O
2
(A) 3
(B) 4
(C) 5
(D) 6
(E) 7
65. What i s the coeffi ci ent for water
when the equati on bel ow i s bal anced?
__As(OH)
3
(s) 1 __H
2
SO
4
(aq)
__As
2
(SO
4
)
3
(aq) 1 __H
2
O(l)
(A) 1
(B) 2
(C) 4
(D) 6
(E) 12
66. I n a vol tai c cel l , one hal f-cel l contai ns
a cobal t el ectr ode i mmer sed i n a
1.0 M Co
21
sol uti on. I n the other hal f-
cel l , a l ead el ectrode i s i mmersed i n a
1.0 M Pb
21
sol uti on. The val ue for E
i s 0.15 V i n thi s cel l . I n a si mi l ar vol -
tai c cel l , a cobal t el ectrode i s i mmersed
i n a 0.0010 M Co
21
sol uti on and a l ead
el ectrode i s i mmersed i n a 0.10 M Pb
21
sol uti on. Whi ch statement bel ow accu-
ratel y descri bes the second vol tai c cel l ?
Co
21
1 2e
2
Co E 5 2 0.28 V
Pb
21
1 2e
2
Pb E 5 2 0.13 V
(A) The cel l wi l l have a l ower E.
(B) The cel l wi l l have a hi gher E.
(C) The cel l wi l l have an i denti cal
E, si nce E i s unaffected by
concentrati on.
(D) Cobal t wi l l become the cathode.
(E) The cathode wi l l di ssol ve.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
REFER TO THE DATA BELOW TO ANSWER
QUESTION 67:
C
2
H
6
(g) C
2
H
4
(g) 1 H
2
(g)
H 5 137 kJ
S 5 120 J K
21
67. Based on the data above, the reacti on
wi l l be
(A) spontaneous at al l temperatures.
(B) spontaneous at hi gh
temperatures.
(C) spontaneous onl y at l ow
temperatures.
(D) nonspontaneous at al l
temperatures.
(E) nonspontaneous at hi gh
temperatures.
a di pol e moment?
(A) BCl
3
(B) CO
2
(C) PCl
3
(D) Cl
2
(E) N
2
69. Whi ch of the fol l owi ng sol uti ons has
the l owest freezi ng poi nt?
(A) 0.10 m C
6
H
12
O
6
, gl ucose
(B) 0.10 m CoI
2
(C) 0.10 m ZnSO
4
(D) 0.10 m NaI
(E) 0.10 m Al I
3
70. What i s the pH of a sol uti on pre-
pared by mi xi ng 50 mL of 0.125 M
KOH wi th 0.050 L of 0.125 M HCl ?
(A) 4.0
(B) 5.7
(C) 6.3
(D) 7.0
(E) 8.1
71. What vol ume of 18.0 M sul furi c aci d
must be used to prepare 15.5 L of
0.195 M H
2
SO
4
?
(A) 168 mL
(B) 0.336 L
(C) 92.3 mL
(D) 226 mL
(E) 125 mL
72. A l arge, ol d car bumper i s goi ng to be
chrome pl ated. Thi s can be accom-
pl i shed usi ng an el ectrol yti c cel l
where the bumper wi l l act as a
cathode i n an aci di c di chromate,
Cr
2
O
7
22
, sol uti on. I f the current i s
20.0 amperes, how l ong wi l l i t take to
deposi t 100 grams of Cr(s) onto the
bumper? The atomi c mass of Cr i s
52.00; 1 faraday 5 96,500 coul ombs.
(A) 15.5 h
(B) 1.29 days
(C) 309 mi n
(D) 76.3 s
(E) 5.3 days
73. The correct name for the compound
[Co(NH
3
)
6
]Cl
3
i s
(A) cobal t (I I I ) hexammi ne chl ori de.
(B) hexammi necobal t chl ori de (I I I ).
(C) hexammi necobal t (I I I ) chl ori de.
(D) hexammi necobal t tri chl ori de.
(E) hexammi necobal t (VI ) chl ori de.
74. Cal cul ate the pH of a sol uti on that i s
0.2 M i n aceti c aci d (K
a
5 1.8 3 10
25
)
and 0.2 M i n sodi um acetate.
(A) 4.7
(B) 9.3
(C) 7.0
(D) 5.4
(E) 8.6
75. Whi ch of the fol l owi ng sol uti ons
woul d be orange?
(A) KMnO
4
(B) Ni (NO
3
)
2
(C) CuCl
2
(D) K
2
Cr
2
O
7
(E) Na
2
CrO
4
S T O P
End of secti on I . I f you have any ti me l eft, go over your work i n thi s
secti on onl y. Do not work i n any other secti on of the test.
p
r
a
c
t
i
c
e
t
e
s
t
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Practice Test 2 487
www.petersons.com
SECTION II REFERENCE INFORMATION
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www.petersons.com
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
2 Hg(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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Practice Test 2 489
www.petersons.com
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
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
1l 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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
THERMOCHEMISTRY/KINETICS
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 22.303 RT l og K
5 2n7E
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
m5 mass
8
m s
21
234
J s
223
J K
21
23
parti cl es mol
21
219
coul omb
21
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Practice Test 2 491
www.petersons.com
CONSTANTS
K
a
(weak aci d)
K
b
(weak base)
K
w
(water)
K
p
(gas pressure)
K
c
T 5 temperature
n 5 mol es
m5 mass
q 5 heat
C
p
P 5 pressure
V 5 vol ume
T 5 temperature
D 5 densi ty
m5 mass
v 5 vel oci ty
u
rms
M 5 mol ar mass
K
f
K
b
t 5 ti me (seconds)
21
K
21
5 0.0821 L atm mol
21
K
21
21
K
21
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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
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
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
OXIDATION-REDUCTION/ELECTROCHEMISTRY
Q 5
@C#
c
@D#
d
@A#
a
@B#
b
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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Practice Test 2 493
www.petersons.com
SECTION II
TIM E95 M INUTES
Part A
TIM E55 M INUTES
YOU MAY USE YOUR CALCULATOR FOR PART A.
Directions: CLEARLY SHOW THE METHOD USED AND STEPS I NVOLVED I N
ARRI VI NG AT YOUR ANSWERS. I t i s to your advantage to do thi s because you may
earn parti al credi t i f you do, and you wi l l recei ve l i ttl e or no credi t i f you do not.
Attenti on shoul d be pai d to si gni fi cant fi gures.
Answer questi on 1 bel ow. The Secti on I I wei ghti ng for thi s questi on i s 20 percent. Wri te
al l of your answers i n the space provi ded fol l owi ng each questi on.
1. The sol ubi l i ty of cal ci um oxal ate, CaC
2
O
4
, i s 6.1 3 10
23
g per l i ter at 25C.
(a) Determi ne the mol ar sol ubi l i ty of CaC
2
O
4
at 25C.
(b) Wri te a bal anced equati on for the sol ubi l i ty equi l i bri um.
(c) Wri te the expressi on for the sol ubi l i ty product constant, K
sp
, and cal cul ate
i ts val ue.
(d) I f CaC
2
O
4
i s pl aced i n a 0.10 M CaCl
2
sol uti on, how wi l l thi s affect the mol ar
sol ubi l i ty? Expl ai n, and show cal cul ati ons to support your answer.
(e) I f 50.0 mL of 0.0025 M CaCl
2
i s added to 50.0 mL of 1.0 3 10
25
M Na
2
C
2
O
4
, wi l l
any cal ci um oxal ate preci pi tate?
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
Directions: Answer questi ons 2 and 3. The Secti on I I wei ght for these questi ons i s
40 percent.
2. I
2
(g) 1 Br
2
(g) 2I Br(g)
0.0015 mol each of I
2
and Br
2
were pl aced i nto an evacuated 5.0 L vessel at 150C.
The contents are al l owed to come to equi l i bri um at thi s temperature, and the
equi l i bri um constant K
c
i s measured at 1.2 3 10
2
.
(a) Wri te the equi l i bri um expressi on, K
c
, for thi s reacti on.
(b) Cal cul ate the equi l i bri um composi ti on of the mi xture at 150C.
(c) Cal cul ate the val ue of K
p
at thi s same temperature.
(d) What effect woul d addi ng 0.05 mol of I
2
have on the mi xture at equi l i bri um?
Expl ai n.
3. 2SO
2
(g) 1 O
2
(g) 2SO
3
(g)
Substance DH
f
(kJ mol
21
) S (J K
21
mol )
SO
2
(g) 2297 248
SO
3
(g) 2396 257
O
2
(g) 0 205
The reacti on, shown above, i s carri ed out at 25C and 1 atm pressure.
(a) Cal cul ate the val ue of the standard enthal py change, DH.
(b) Cal cul ate the val ue of the standard entropy change, DS.
(c) Cal cul ate the val ue of the standard free energy change, DG.
(d) Di scuss whether at thi s temperature the reacti on i s
(i) endothermi c or exothermi c.
(ii) i ncreasi ng or decreasi ng i n entropy.
(iii) spontaneous or nonspontaneous.
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Practice Test 2 495

www.petersons.com
Part B
TIM E40 M INUTES
YOU MAY NOT USE CALCULATORS WITH PART B.
Directions: Answer questi on 4 bel ow. The Secti on I I score wei ghti ng for thi s questi on
i s 10 percent.
4. Wri te the formul as to show the reactants and products for the three equati ons
wri tten bel ow. Assume that each reacti on occurs. Al so assume that al l sol uti ons are
aqueous unl ess otherwi se stated. I f substances are extensi vel y i oni zed i n sol uti on, be
sure to represent them as such. Omi t formul as for i ons or mol ecul es that are
unchanged duri ng the reacti on. Equati ons must be bal anced. Answer the questi on
regardi ng each reacti on.
(a) Sol i d ammoni um carbonate i s heated.
Question: Descri be the change i n moi st l i tmus paper hel d over the reacti on vessel as
the reacti on proceeds.
(b) A stri p of copper i s submerged i n di l ute ni tri c aci d.
Question: Descri be the changes i n col or of the reacti on wi th ti me.
(c) Ethanol i s compl etel y burned i n ai r.
Question: When one mol ecul e of ethanol i s compl etel y combusted, how many
mol ecul es of products are formed?
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www.petersons.com
Directions: For the remai nder of the test, your responses wi l l be graded accordi ng to
thei r accuracy and rel evancy. Your responses shoul d be wel l organi zed and presented i n
a cl ear, conci se manner. Bri ef, speci fi c answers are preferabl e to l onger, general
responses. You may use any exampl es or equati ons i f they are appropri ate.
Answer questi ons 5 and 6. The wei ghti ng of these two questi ons i n Secti on I I i s
30 percent (15 percent each).
5. 2SO
3
(g) 2SO
2
(g) 1 O
2
(g)
DH 5 197 kJ
For the reacti on shown above, descri be the changes that wi l l occur to the number of
mol es of SO
3
under the fol l owi ng condi ti ons:
(a) Addi ti onal oxygen i s added to the reacti on vessel .
(b) The pressure i n the reacti on vessel i s decreased by i ncreasi ng i ts vol ume.
(c) The pressure i s i ncreased by the addi ti on of hel i um gas.
(d) The temperature i s i ncreased.
(e) Oxygen gas i s removed.
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Practice Test 2 497

www.petersons.com
6. A student performed a ti trati on of a weak, monoproti c aci d, HA, wi th a sodi um
hydroxi de, NaOH, sol uti on.
(a) On the graph that i s provi ded, sketch an approxi mate representati on of the
ti trati on curve for the experi ment. On the curve, l abel the equi val ence poi nt:
p
H
Vol ume of NaOH (mL)
(b) Di scuss at l east two ways i n whi ch the sketch i n (a) di ffers from the pl ot that
woul d resul t from the ti trati on of a strong, monoproti c, l i ke HCl .
(c) The student has a choi ce between the two i ndi cators: methyl red (pH range
4.86.0) or phenol phthal ei n (pH range 5 8.210.0). Whi ch shoul d she choose?
Justi fy your response.
(d) Whi l e the student was performi ng her fi rst tri al , she di spensed 50.0 mL of ti trant
(base) from her buret (the maxi mum), but her anal yte (aci d) sti l l had not changed
col or. What i s the most l i kel y source of her error? (Assume that she di d put an
i ndi cator i n the anal yte.)
S T O P
End of Secti on I I . I f you have any ti me l eft, go over your work i n thi s
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Section I
1. C
2. A
3. B
4. D
5. E
6. B
7. D
8. E
9. B
10. C
11. D
12. E
13. D
14. C
15. A
16. C
17. B
18. E
19. C
20. A
21. B
22. C
23. A
24. B
25. B
26. B
27. E
28. D
29. C
30. E
31. D
32. A
33. A
34. B
35. D
36. D
37. B
38. E
39. C
40. C
41. C
42. A
43. D
44. C
45. D
46. C
47. E
48. B
49. B
50. D
51. D
52. D
53. C
54. B
55. B
56. B
57. B
58. E
59. E
60. B
61. D
62. D
63. C
64. C
65. D
66. B
67. B
68. C
69. E
70. D
71. A
72. A
73. C
74. A
75. D
1. The correct answer is (C). The orbi tal di agram i n choi ce (C) shows fi l l ed s and p
subl evel s, whi ch are characteri sti c of the nonreacti ve nobl e gases.
2. The correct answer is (A). I n choi ce (A), two el ectrons i n the same orbi tal have l i ke
spi ns, whi ch i s not al l owed by the Paul i Excl usi on Pri nci pl e (they must have opposi te
spi ns).
3. The correct answer is (B). The second el ectron i n the p orbi tal shoul d go i nto a
di fferent orbi tal . Accordi ng to Hunds rul e, al l orbi tal s shoul d fi l l wi th a si ngl e el ectron
(each havi ng l i ke spi ns) pri or to a second el ectron enteri ng any orbi tal .
4. Thecorrect answer is (D). The onl y way a si ngl e el ectron coul d be i n an orbi tal that
i s of hi gher energy than an unoccupi ed orbi tal i s i f i t i s exci ted.
5. The correct answer is (E). Octane i s a much l arger mol ecul e al l owi ng for a greater
number of i nteracti ons between the mol ecul es. Thi s attracti ve force i s suffi ci ent to al l ow
octane to remai n i n the l i qui d state at hi gher temperatures.
6. Thecorrect answer is (B). The i denti cal bond l engths i n each carbon-carbon bond i n
the benzene ri ng shows that al l bonds are i denti cal . Thi s contradi cts the model that
woul d show three doubl e bonds and three si ngl e bonds. I f that model were correct, the
doubl e bonds woul d be shorter than the si ngl e bonds. The l ogi cal concl usi on i s that the
el ectrons del ocal i ze and spread around the enti re ri ng so that al l are shared equal l y.
7. The correct answer is (D). Accordi ng to el ectron confi gurati on of carbon, the carbon
atom shoul d have two el ectrons i n the 2s orbi tal and one i n each of the two 2p orbi tal s.
The four carbon-hydrogen bonds i n methane shoul d be di fferent because of the di fferent
orbi tal s, yet experi mental evi dence shows them to be the same. The sol uti on i s that one
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Practice Test 2 499
www.petersons.com
of the 2s el ectrons i s rai sed to a p orbi tal , and the resul t i s the formati on of four
i denti cal hybri di zed sp
3
orbi tal s.
8. The correct answer is (E). Si nce He and Xe are both si ngl e atoms, the onl y
i ntermol ecul ar forces that can act between them are di spersi on forces. Because xenon i s
a much l arger atom, i t has a l arger el ectron densi ty that can l ead to a greater
fl uctuati on i n charge di stri buti on, causi ng l arger di spersi on forces.
9. The correct answer is (B). Fol l owi ng the chart, the transi ti on from 40 to 60 degrees
at the constant pressure of 1.5 atm moves from sol i d to l i qui d, whi ch i s i ndi cati ve of
mel ti ng.
10. The correct answer is (C). At the l ow pressure l i sted i n the probl em, the change i n
temperature moves the substance from the sol i d state to the gaseous state, otherwi se
known as subl i mati on.
11. The correct answer is (D). Thi s process vari es the pressure whi l e mai ntai ni ng
constant temperature. Thi s causes a change from a gas to a l i qui d, otherwi se known as
condensati on.
12. Thecorrect answer is(E).A base spi l l shoul d be treated wi th l arge amounts of water.
Al though water wi l l di l ute the base, a weak aci d wi l l more qui ckl y neutral i ze the base
and shoul d, therefore, be used. I f a strong aci d i s used, i t coul d qui ckl y neutral i ze the
base, but i f too much i s used, the effects coul d be as harmful , or more harmful , than the
base. A weak aci d wont be harmful i f too much i s used.
13. Thecorrect answer is(D). Opti cal i somers are non-superi mposabl e mi rror i mages. I n
choi ce (D), al l four groups are di fferent and the mol ecul ar structure does not al l ow for
the mi rror i mages to be superi mposed.
14. The correct answer is (C). The unexpected and si gni fi cant fi ndi ng i n Rutherfords
gol d foi l experi ment was that the al pha parti cl es were defl ected as they passed
through the foi l . Had Thomsons model of the atom been correct, i t was predi cted that
the al pha parti cl e shoul d pass through unhi ndered. Thi s fi ndi ng l ed hi m to concl ude
that there must be a very dense, posi ti vel y charged (repel s the posi ti vel y charged al pha
parti cl e) core, whi ch i s now known as the nucl eus. Al though choi ce (B) menti ons the
nucl eus, i t al so menti ons neutrons, whi ch werent di scovered unti l much l ater.
15. The correct answer is (A). The anode i n a gal vani c (vol tai c) cel l i s where oxi dati on
occurs. Choi ce (A) i s the onl y exampl e of an oxi dati on that coul d occur i n a hal f-cel l
(Zi nc i s l osi ng el ectrons).
16. The correct answer is (C). I n thi s probl em, you hopeful l y recogni zed that l ead and
sul fate wi l l form a preci pi tate. What that means i s that when the two substances
combi ne, the preci pi tate wi l l fal l out of sol uti on, l eavi ng behi nd a certai n amount of l ead
i ons. Sol vi ng the probl em requi res you to determi ne the quanti ty of preci pi tate that can
form (from the stoi chi ometri c rati os) and then see i f there i s any l ead l eft over.
Step 1: Determi ne how much l ead i s present i n 100 mL of PbCl
2
:
0.100 L 3 0.1 M PbCl
2
5 0.01 mol PbCl
2
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www.petersons.com
Step 2: Use the stoi chi ometri c rati os to determi ne how much PbCl
2
i s requi red to
compl etel y react wi th H
2
SO
4
:
0.1 L 3 0.050 M H
2
SO
4
5 5 3 10
23
mol H
2
SO
4
I f an equati on i s wri tten to show the formati on of the preci pi tate
Pb
21
(aq) 1 SO
4
22
(aq) PbSO
4
(s)
you can see that onl y one mol e of l ead i ons i s requi red for each mol e of sul fate. As a
resul t, 0.005 mol of PbCl
2
wi l l react wi th the 0.005 mol H
2
SO
4
to yi el d 0.005 mol PbSO
4
.
That l eaves 0.005 mol Pb
21
i ons l eft over.
Because the probl em i s aski ng for the concentrati on of Pb
21
, you need to di vi de the
number of mol es by the vol ume, i n thi s case 200 mL. Therefore, the sol uti on wi l l be:
0.005 mol PbSO
0.200 L
4
5 0.025 M
17. The correct answer is (B). Because the reacti on i s exothermi c, an i ncrease i n
temperature wi l l cause the equi l i bri um to shi ft to the l eft, reduci ng the val ue of K
eq
. Al l
of the other changes wi l l cause a shi ft to the ri ght (whi ch i ncreases the val ue of K
eq
).
18. The correct answer is (E). I n the beta decay shown, vanadi um253 wi l l convert a
neutron to a proton and a beta parti cl e. The proton wi l l i ncrease the atomi c number by
1, whi l e mai ntai ni ng a constant mass number. The new el ement, therefore, i s
chromi um253.
19. The correct answer is (C). To sol ve thi s, you need to use the K
sp
expressi on for
CaSO
4
:
K
sp
5 [Ca
21
][SO
4
22
]
From the gi ven i nformati on i n the probl em we can cal cul ate the concentrati on of sul fate
i on i n sol uti on. Once that has been determi ned, you can use the gi ven K
sp
to sol ve for
[Ca
21
]:
0.01 M K
2
SO
4
3 1.0 L 5 0.01 mol K
2
SO
4
0.01 mol K
2
SO
4
3
1 mol SO
1 mol K SO
4
2
2 4
5 0.01 mol SO
4
22
0.01 mol SO
1.0 L sol n
4
2
5 0.01 M SO
4
22
K
sp
5 [Ca
21
][SO
4
22
]
2.4 3 10
25
5 [Ca
21
] (0.01 M SO
4
22
)
[Ca
21
] 5 2.4 3 10
23
M
I n 1.0 L of sol uti on, thi s amounts to 2.4 3 10
23
mol Ca
21
, whi ch can be found i n
2.4 3 10
23
mol CaCl
2
(si nce each mol e of CaCl
2
yi el ds one mol e of Ca
21
).
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Practice Test 2 501
www.petersons.com
20. Thecorrect answer is (A). The val ues for the l quantum number can onl y go as hi gh
as n21, meani ng l cant have a val ue of 1 when n 5 1. An l val ue of 1 corresponds to a
p orbi tal , whi ch i s not found i n the fi rst energy l evel .
21. The correct answer is (B). Be careful not to fal l for questi ons l i ke thi s one. The
temperature gi ves the i ni ti al i mpressi on that i t has doubl ed. Doubl i ng the temperature
wi l l cause pressure and ki neti c energy to doubl e. However, careful observati on wi l l
show that the absol ute temperature i s not doubl i ng. The absol ute temperature i s onl y
changi ng from 293 K to 313 K. Therefore, the average ki neti c energy wi l l i ncrease, but
i t wont doubl e.
22. The correct answer is (C). Bond order i s the number of pai rs of el ectrons shared
between two atoms. I ncreasi ng the number of pai rs of el ectrons bei ng shared between
atoms wi l l i ncrease the attracti ve force between the two atoms, whi ch wi l l cause a
correspondi ng i ncrease i n the amount of energy requi red to break apart the atoms. Thi s
has the effect of pul l i ng the atoms cl oser together (decreasi ng the bond l ength).
23. The correct answer is (A). Under normal atmospheri c pressure, water can exi st as
onl y l i qui d or sol i d at 0C. I f the pressure i s mani pul ated, water can al so exi st as a gas,
but that i s not requi red i n thi s probl em.
24. The correct answer is (B). From a conceptual perspecti ve, remember that to
neutral i ze an aci d you must add enough strong base so that al l of the hydrogen
(hydroni um) i ons i n the aci d combi ne wi th the hydroxi de i ons of the base to form water.
Therefore, i f you determi ne the number of mol es of hydroxi de i ons you add to the
mi xture duri ng the ti trati on, thi s shoul d equal the number of mol es of aci d when the
sol uti on i s neutral .
The number of mol es of base requi red for the neutral i zati on was:
0.036 L 3 0.500
mol
L
5 0.018 mol NaOH
Because aceti c aci d i s monoproti c, thi s i s how many mol es of aceti c aci d must be present
i n the 20 mL sampl e. To determi ne the mol ari ty of the sampl e, we can use the mol ari ty
equati on:
M 5
0.018 mol
0.020 L
5 0.900 M
25. The correct answer is (B). I n each of the fi rst three measurements, when the
concentrati on of A i s doubl ed whi l e B i s hel d constant, the i ni ti al rate i ncreases by four
ti mes (2
2
). Thi s l eads to the [A]
2
expressi on. I n the l ast two pi eces of data, the
concentrati on of B i s doubl ed whi l e A i s hel d constant. Thi s causes a doubl i ng i n the
i ni ti al rate, meani ng the reacti on i s fi rst order for B.
26. The correct answer is (B). I n equati on I I , H
2
PO
4
2
donates a proton, maki ng i t an
aci d. I n equati ons I and I I I , i t i s recei vi ng a proton, maki ng i t a base.
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www.petersons.com
27. The correct answer is (E). One of the more i mportant thi ngs to remember about
catal ysts i s that they do not reduce the energy change between reactants and products
(l abel ed A i n the di agram). A catal yst hel ps to provi de a pathway wi th reduced
acti vati on energy. Thi s wi l l l ower the hei ghts of B and C on the chart.
28. The correct answer is (D). The reacti on i s exothermi c because the energy of the
products i s l ower than the energy of the reactants. Thi s l oss of energy i s i n the form of
heat.
29. The correct answer is (C). There i s an enormous gap between the thi rd and fourth
energy l evel s, meani ng that the thi rd el ectron was si gni fi cantl y easi er to remove than
the fourth. Thi s i s characteri sti c of an el ement i n group 3 because the fourth el ectron
needs to come from a l ower energy l evel . I n addi ti on, the removal of the three previ ous
el ectrons l eaves the nucl eus wi th extra protons, l eadi ng to a very hi gh effecti ve nucl ear
charge on the fourth el ectron. Fi nal l y, the fi rst three el ectrons are more shi el ded than
the fourth el ectron si nce they are i n a hi gher energy l evel .
30. The correct answer is (E). Di ssol vi ng i ncreases the entropy of a substance because
the parti cl es are movi ng farther apart, and hence have more freedom of random moti on.
An i ncrease i n temperature i s i ndi cati ve of an exothermi c process. Hence, H wi l l be
negati ve and S wi l l be posi ti ve.
31. Thecorrect answer is (D). I n thi s probl em you need to determi ne how many mol es of
el ectrons are produced. From thi s you can determi ne how many mol es of copper can be
reduced at the cathode:
10 A 3
1C
1A s

s
1 mi n
_
,
_
,
75
60
mi n 5 4.50 3 10
4
C
4.50 3 10
4
C 3
1 mol
9500
e
5 0.4663 mol e
2
0.4663 mol e
2
3
1 mol Cu
2 mol
63.55 g
1 mol Cu e
_
,
_
,
5 14.8 g Cu
32. The correct answer is (A). I n order to determi ne the enthal py change for the
reacti on, you need to use Hesss l aw:
DH
rxn
5 SnDH
f
(products) 2 SmDH
f
(reactants)
DH
f
P
4
O
10
(s) 5 23110 kJ mol
21
DH
f
H
2
O(l) 5 2286 kJ mol
21
DH
f
H
3
PO
4
(s) 5 21279 kJ mol
21
The sol uti on i s obtai ned by substi tuti ng the gi ven val ues i nto the equati on:
5 4~H
3
PO
4
! 2 @P
4
O
10
1 6~H
2
O!#
5 4~21279! 2@23110 1 6~2286!# 5 2290 kJ
a
n
s
w
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Practice Test 2 503
www.petersons.com
33. Thecorrect answer is (A). I n the acetyl ene mol ecul e, one el ectron i n the 2s orbi tal of
carbon i s promoted to the unoccupi ed 2p orbi tal . The 2s and one of the 2p orbi tal s
hybri di ze to form two sp hybri d orbi tal s, whi ch wi l l form the C2H bond and the s C2C
bond. The two p bonds between the C atoms are formed by the two unhybri di zed
p orbi tal s from each carbon.
34. Thecorrect answer is (B). The most obvi ous feature to note about the i sotope shown
i s that the number of neutrons i s l ess than the number of protons. The most l i kel y
decay, therefore, i s one that wi l l i ncrease the number of neutrons and decrease the
number of protons. I n a posi tron emi ssi on, a proton i s converted to a neutron and a
posi tron. Thi s has the effect of decreasi ng the atomi c number by one whi l e mai ntai ni ng
the same mass number. I n thi s case, ni trogen213 becomes carbon213, whi ch now has
more neutrons than protons.
35. The correct answer is (D). Thi s probl em i s another neutral i zati on probl em, but thi s
ti me the aci d i s a di proti c aci d. As a resul t, each mol e of H
2
SO
4
wi l l yi el d two mol es of
hydrogen i ons. The cal cul ati on i s as fol l ows:
Mol es of H
2
SO
4
i n 25 mL of 1.2 M H
2
SO
4
0.025 L 3 1.2
mol
L
5 0.03 mol H
2
SO
4
Therefore, there wi l l be 0.06 mol H
1
. To neutral i ze thi s wi l l requi re 0.06 mol OH
2
. To
fi ni sh the probl em:
0.06 mol
X L
5 0.5 M X 5 0.120 L or 120 mL
36. The correct answer is (D). The key to i denti fyi ng an al dehyde i s the carbonyl group
on the l ast carbon atom.
37. The correct answer is (B). Thi s i s a sal t produced from the cati on of a strong base
and the ani on of a weak aci d. Sodi um therefore, i s a very weak aci d, but acetate i s a
strong base. Remember, the conjugate base of a weak aci d i s strong. The acetate i on wi l l
hydrol yze to form hydroxi de i ons.
38. The correct answer is (E). Thi s i s a mass-to-mass conversi on. The sol uti on i s as
fol l ows:
C
2
H
4
(g) 1 3O
2
(g) 2CO
2
(g) 1 2H
2
O(l)
200.0 g C
2
H
4
3
1 mol C H
28.01 g
2 mol CO
1 mol C H
2 4 2
2 4
_
,
_
,
3
44.01 g CO
1 mol CO
2
2
_
,
5 628 g
39. The correct answer is (C). The normal boi l i ng poi nt i s determi ned by the
temperature where the l i qui d-gas l i ne (on the phase di agram) i s crossed by the 1.0 atm
mark.
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40. The correct answer is (C). The sol ubi l i ty equi l i bri um of AgBr i s shown bel ow:
AgBr(s) Ag
1
(aq) 1 Br
2
(aq)
I n the presence of NH
3
, the si l ver i on, Ag
1
, forms the compl ex i on Ag(NH
3
)
21
. When
thi s i on forms, i t removes si l ver i ons from the sol uti on, thus dri vi ng the equi l i bri um
reacti on to the ri ght.
41. The correct answer is (C). Thi s i s one you shoul d probabl y commi t to memory.
Fi rst-order reacti ons can be transformed to strai ght-l i ne graphs i f the natural l og of the
concentrati on of the reactant i s pl otted agai nst ti me. Second-order reacti ons, l i ke the
one represented i n the graph for thi s questi on, are transformed to strai ght-l i ne graphs
by pl otti ng the reci procal of the concentrati on.
42. The correct answer is (A). I n thi s questi on, you just need to set up the equi l i bri um
expressi on for l ead (I I ) sul fate, whi ch i s:
K
sp
5 [Pb
21
][SO
4
22
]
By determi ni ng the concentrati ons of l ead and sul fate at equi l i bri um, we can tel l how
much of i t i s sol ubl e:
Let x 5 [Pb
21
] 5 [SO
4
22
]
K
sp
5 x
2
1.3 3 10
28
5 x
2
1 3 10
8
.

5 x 5 1.1 3 10
24
M
43. The correct answer is (D). The attracti ons between gas parti cl es wi l l cause them to
exert l ess force on the wal l s of the contai ner, thereby exerti ng l ess pressure. Thi s wi l l
decrease the val ue of the numerator of the fracti on, thereby maki ng the resul t l ess
than 1.
44. Thecorrect answer is (C). I n the reacti on shown, an i ncrease i n vol ume wi l l cause a
decrease i n pressure. Thi s favors the reacti on to the l eft because there are more mol es
of gas. Because the reacti on i s exothermi c, an i ncrease i n temperature wi l l al so dri ve
the reacti on to the l eft. Removi ng CO
2
wi l l cause the reacti on to shi ft ri ght to repl ace
the removed gas. Therefore, choi ce (C) i s the onl y possi bl e answer.
45. The correct answer is (D). Choi ces (A), (B), and (C) are al l based on wei ghts, whi ch
do not change wi th changes i n temperature. Mol ari ty, on the other hand, i s a
concentrati on uni t compari ng mass per uni t of vol ume. Because vol ume i s affected by
changes i n temperature, mol ari ty wi l l be affected by temperature i ncrease.
a
n
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p
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Practice Test 2 505
www.petersons.com
46. The correct answer is (C). I n order to sol ve for the K
a
, you wi l l need to use the
expressi on taken from the di ssoci ati on of HA:
HA H
1
1 A
2
K
a
H A
HA
1
]

1
]
[ ]
+
47. The correct answer is (E). I n thi s probl em, you need to remember that l i ghter gases
effuse more qui ckl y than heavi er gases. That means that CH
4
wi l l effuse most qui ckl y,
fol l owed by NO
2
, and fi nal l y Cl
2
. That means that after the ti me peri od, more CH
4
wi l l
have effused than NO
2
. Cl
2
wi l l have effused the l east, so i t wi l l be the most pl enti ful i n
the fl ask. Si nce parti al pressures are proporti onal to mol e fracti ons, the most pl enti ful
gas wi l l al so exert the greatest parti al pressure.
48. The correct answer is (B). The total pressure can be determi ned usi ng the equati on
bel ow:
P
total
5 P
A
1 P
B
5 X
A
P
A
1 X
B
P
B
P
total
5
1.50 mol
7.0 mol
_
,
(75 mm Hg) 1
5.50 mol
7.0 mol
_
,
(25 mm Hg) 5 35.7 mm Hg

49. The correct answer is (B). Thi s i s a standard mol e-to-gram conversi on usi ng the
mol ar mass of the substance:
6.94 mol NaOH 3
40.0 g NaOH
1 mol NaOH
5 278 g
50. The correct answer is (D). There are a few thi ngs to l ook out for i n thi s probl em.
Fi rst, the temperature i s gi ven i n degrees Cel si us (so i t must be converted). The second
i s the stoi chi ometry. The bal anced equati on states that two mol es of carbon are needed
for each mol e of oxygen. I n the probl em, the amount of carbon gi ven i s an excess si nce
the 1.20 mol of O
2
wi l l onl y requi re 2.40 mol of C. I t i s very i mportant, then, to not use
the 3.50 mol val ue i n the cal cul ati on. The number of mol es of CO that are produced wi l l
be twi ce that of the oxygen that i s used. Because 1.2 mol es of oxygen are consumed, 2.4
mol of CO wi l l be produced. Wi th thi s out of the way, we can use the i deal gas l aw to
sol ve for P:
P
nRT
V
5
( . ) ( 2 4 298
1 1
mol CO) (0.0821 L atm mol K K)
2.00 L

5 29.4 atm
51. The correct answer is (D). Li thi um sal ts burn bri ght red i n fl ame tests. Stronti um
does al so, but i t i s not l i sted as a choi ce.
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www.petersons.com
52. The correct answer is (D). Fi rst, the percentages shoul d be used to determi ne the
empi ri cal formul a of vi tami n C. The empi ri cal formul a can then be compared to the
mol ecul ar formul a, and any adjustments can be made at that ti me.
Because percents are gi ven i nstead of mol es or grams, assume a 100 g sampl e to
si mpl i fy the probl em:
40.9 g C 3
1 mol C
12.011 g C
5 3.41 mol C
4.58 g H 3
1 mol H
1.01 g H
5 4.53 mol H
54.52 g O 3
1 mol O
16.00 g O
5 3.41 mol O
I n the next step, each i s to be di vi ded by the smal l est number of mol es (3.41):
C 5
3 41
3 41
.
.
5 1.00
H 5
4 53
3 41
.
.
5 1.33
O 5
3 41
3 41
.
.
5 1.00
I n order to make thi s work, you wi l l need to mul ti pl y every val ue by 3. Therefore, the
empi ri cal formul a for the compound wi l l be:
C
3
H
4
O
3
The formul a wei ght for thi s compound i s 88.1 g. Because thi s i s exactl y one hal f of the
mol ecul ar wei ght, the subscri pts for al l substances i n the empi ri cal formul a must be
mul ti pl i ed by 2:
C
6
H
8
O
6
5 vi tami n C (ascorbi c aci d)
53. The correct answer is (C). Thi s i s si mpl y the defi ni ti on of Lewi s aci ds and bases.
Lewi s aci ds accept a pai r of el ectrons whi l e Lewi s bases donate a pai r of el ectrons.
54. Thecorrect answer is(B). Thi s i s a matter of rememberi ng the proper procedures for
wri ti ng an equi l i bri um constant. I n the expressi on, the product(s) i s the numerator and
the reactant(s) i s the denomi nator. The coeffi ci ents for each shoul d become exponents.
Therefore, i n the reacti on shown, the equi l i bri um expressi on shoul d be:
K

1
]
1
]

1
]
NO
NO O
2
2
2
2
Choi ce (B) represents thi s wi th the gi ven i nformati on substi tuted i n.
a
n
s
w
e
r
s
p
r
a
c
t
i
c
e
t
e
s
t
2
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Practice Test 2 507
www.petersons.com
55. The correct answer is (B). As the sal t sol uti on si ts out, water wi l l conti nue to
evaporate whi l e the amount of sol ute wi l l remai n constant. As a resul t, the
concentrati on of the sol uti on conti nues to i ncrease over ti me. Thi s causes the vapor
pressure to decrease over ti me.
56. The correct answer is (B). A mass-to-mass conversi on. The sol uti on i s as fol l ows:
Ca(OH)
2
(aq) 1 2HNO
3
(aq) Ca(NO
3
)
2
(aq) 1 2H
2
O(l)
7.40 g Ca(OH)
2
1 mol Ca(OH)
74.1 g
2
_
,
3
1 mol Ca(NO )
1 mol Ca(OH)
164.1 g Ca
3 2
2
_
,
((NO )
1 mol Ca(NO )
3 2
3 2
_
,
5 16.4 g
57. The correct answer is (B). NH
3
has the weakest i ntermol ecul ar forces of the other
mol ecul es. Di amond exi sts i n a coval ent network bond, sodi um acetate i s an i oni c
compound, and gl yceri ne contai ns several C2O and O2H bonds (whi ch al l ow hydrogen
bondi ng). Si l ver has metal l i c bonds whi l e ammoni a, NH
3
, i s onl y hel d together by fai rl y
weak hydrogen bonds (the N2H bond i s not very pol ar).
58. The correct answer is (E). NH
4
Cl i s a sal t formed from a weak base (NH
3
) and a
strong aci d (HCl ). I t wi l l hydrol yze to form an aci di c sol uti on. The other two substances,
NaF and K
2
CO
3
, are sal ts of strong bases and weak aci ds. As a resul t, the conjugates,
F
2
and CO
3
2
, wi l l hydrol yze to form basi c sol uti ons.
59. The correct answer is (E). Thi s probl em requi res the use of the formul a for
determi ni ng the speci fi c heat of a substance. You al so have to remember that the
amount of heat l ost by the object as i t cool s wi l l be the same as the amount of heat
gai ned by the water. Fi rst, we can determi ne the amount of heat gai ned by the water:
q 5 mC
p
DT 5 (100.0 g)(4.18 J/gC)(2.09C) 5 873.6 J
Knowi ng thi s, we can assume that i t i s the same as the amount of heat that was l ost by
the unknown metal . We can determi ne the speci fi c heat of the metal usi ng the
formul a bel ow:
C
q
m T
p

873 6 . J
(50.0 g)(75 C)
5 0.23 J/gC
60. Thecorrect answer is (B). An i mportant consi derati on when you set thi s probl em up
i s to remember that C i s a sol i d and shoul d not be entered i nto the equi l i bri um constant
expressi on. As a resul t, the expressi on for K
p
shoul d be wri tten as:
K
p
5 K
p
5
~P
co
!
2
~P
co
2
!
The other i mportant thi ng to remember i s to square the val ue of P
CO
because of the
coeffi ci ent i t has i n the bal anced equati on. Substi tuti ng the val ue of K and the val ue of
P
CO
2
i nto the equati on, we fi nd that:
167 5
0 10
2
.
( )
.
P
CO
atm
P
CO
16 75 4 1 . .
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61. The correct answer is (D). Thi s probl em requi res the use of the i deal gas equati on,
PV 5 nRT. You are gi ven al l but P, so the probl em can be set up as:
P
nRT
V

(0.05 mol )(0.0821 L atm mol K )(680 K)
1.00 L

1 1
2.8 8 atm
62. Thecorrect answer is (D). Thi s i s a di l uti on probl em. I n order to sol ve i t, you need to
use a modi fi ed versi on of the mol ari ty equati on. You know the mol ari ty and the vol ume
of the ori gi nal sol uti on, whi ch means you can determi ne the number of mol es of HCl i n
the ori gi nal 10.0 mL. Thi s i s done usi ng the cal cul ati on:
0.010 L 3 12.0
mol
L
5 0.12 mol HCl
You need to add enough water so that the TOTAL vol ume (the 10 mL you started wi th
pl us what you added) i s suffi ci ent to create a mol ari ty of 1.00 M:
V
f
3 1.00
mol
L
5 0.12 mol HCl
V
f
5 0.120 L, meani ng that 110 mL must be added to the 10 mL you started wi th to gi ve
a new vol ume of 120 mL (0.120 L). The shortcut formul a that can be used to sol ve thi s
type of probl em i s:
M
1
V
1
5 M
2
V
2
Where the subscri pts 1 and 2 represent the i ni ti al and fi nal states.
63. The correct answer is (C). To determi ne the correct answer, you need to use the
rel ati onshi p:
DG 5 2RT l n K or DG 5 22.303 RT l og K
For thi s step, you need to recal l that the when K i s greater than 1, l og K (or l n K) i s
posi ti ve, and therefore DG i s negati ve. When K i s l ess than 1, l og K (l n K) i s negati ve,
and DG i s posi ti ve. So, when K i s l ess than 1, the val ue of DG wi l l be posi ti ve.
64. The correct answer is (C). Of the seven choi ces, three are very easy to i denti fythe
mol ecul es wi th onl y three atoms i n them. A mol ecul e wi th three atoms must exi st i n a
si ngl e pl ane. The next are a bi t tri cki er. Ethyl ene (ethene), because of the pi bond
between the carbon atoms, i s l ocked i nto a ri gi d structure that i s i n a si ngl e pl ane. I n
the remai ni ng structures, the l one pai r el ectrons i n ammoni a, NH
3
, push the hydrogen
atoms i nto a pyrami dal geometry. The C5O doubl e bond i n formal dehyde (methanal )
l ocks the mol ecul e i n a pl anar confi gurati on. The hydrogen peroxi de mol ecul e i s the
most di ffi cul t to i denti fy. I t forms a rather strange structure known as a skew-chai n,
whi ch i s not pl anar but rather bends i nto two pl anes. So, there are fi ve di fferent
mol ecul es among the choi ces that have al l atoms i n the same pl ane.
a
n
s
w
e
r
s
p
r
a
c
t
i
c
e
t
e
s
t
2
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Practice Test 2 509
www.petersons.com
65. The correct answer is (D). The bal anced equati on, whi ch bal anced rather easi l y i f
you start wi th the pol yatomi c i on sul fate, i s:
2 As(OH)
3
(s) 1 3H
2
SO
4
(aq) As
2
(SO
4
)
3
(aq) 1 6H
2
O(l)
66. The correct answer is (B). Thi s probl em requi res the use of the Nernst equati on (or
at l east i ts appl i cati on). However, before you can sol ve the equati on, you need to know
whi ch el ectrode i s the cathode and whi ch i s the anode. Remember, the substance wi th
the most negati ve reducti on potenti al i s the most easi l y oxi di zed, maki ng i t the anode.
I n thi s probl em, l ead i s the anode and cobal t the cathode. The emf of the second cel l can
be determi ned by:
E 5 E 2
0.0592
n
l og Q
5 0.15 V 2
S
0.0592
2
D
3 l og
S
0.001
0.10
D
5 0.21 V
You wont have a cal cul ator to fi gure thi s out, but wi th a l i ttl e l ogi c you can sti l l get the
answer. Remember that the l ogari thm of a number l ess than 1 wi l l be negati ve.
Therefore, i n the equati on, you wi l l be subtracti ng a negati ve number (whi ch i s the
same as addi ng a posi ti ve). Thi s wi l l produce a resul t that i s l arger than the ori gi nal
vol tage, whi ch, i n thi s case, i s al l the answer requi res you to know.
67. The correct answer is (B). For thi s probl em, refer to the equati on:
DG5 DH 2 TDS
A negati ve G i ndi cates a spontaneous reacti on. I f you substi tute the val ues of DH and
DS i n the equati on
DG5 1.37 3 10
3
J 2 T(120 J K
21
)
you can see that DG can onl y be negati ve when T i s a l arge val ue.
68. The correct answer is (C). Bond di pol es can be treated as vector quanti ti es or
quanti ti es wi th both a magni tude and a di recti on. Symmetri c mol ecul es, such as CO
2
and BCl
3
, have vectors that cancel each other out (as do the equal and opposi te
attracti ons between the di atomi c Cl
2
). Onl y PCl
3
, wi th i ts tri gonal pyrami dal shape,
di spl ays a net force or di pol e moment.
69. Thecorrect answer is (E). I n thi s probl em, you have to consi der the vant Hoff factor
for each sol ute. Thi s i s because as the number of i ons i n sol uti on i ncreases, the freezi ng
poi nt of the sol uti on wi l l decrease. Therefore, the sol ute that di ssoci ates i nto the l argest
number of i ons wi l l produce the l argest freezi ng poi nt depressi on. I n thi s probl em, Al I
3
produces four i ons, more than any other choi ce.
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70. Thecorrect answer is(D). I f youre thi nki ng qui ckl y, you wi l l real i ze the si mpl i ci ty of
thi s probl em. Fi rst of al l , 0.050 L i s the same thi ng as 50 mL. Because of thi s, you have
equal vol umes of sol uti ons wi th i denti cal mol ari ti es. That means the number of mol es of
hydrogen i ons i n the aci di c sol uti on wi l l equal the number of mol es of hydroxi de i ons i n
the basi c sol uti on. As a resul t, the two sol uti ons wi l l compl etel y neutral i ze one another,
resul ti ng i n a sol uti on wi th pH 7.0. No cal cul ati on i s necessary.
71. The correct answer is (A). Thi s probl em can be sol ved by determi ng the vol ume
where the number of mol es wi l l be equal i n the two sol uti ons. Thi s i s accompl i shed
usi ng the equati on:
M
1
V
1
5 M
2
V
2
(18.0 M)(V
1
) 5 (15.5 L)(0.195 M)
V
1
5 0.168 L 5 168 mL
72. The correct answer is (A). To sol ve thi s probl em we need to determi ne how many
mol es of el ectrons wi l l be requi red to produce 100.0 g of chromi um atoms (from the
reducti on of chromi um i ons). Once we know thi s, we can determi ne how l ong the 20.0 A
current needs to fl ow:
100.0 g Cr 3
1 mol
52.00 g
5 1.923 mol Cr
The oxi dati on state of the chromi um i ons i n the di chromate i ons i s 16, so si x mol es of
el ectrons wi l l be requi red to reduce 1 mol e of Cr
61
i ons:
1.923 mol Cr 3
6 mol
1 mol Cr
e
5 11.54 mol e
2
11.54 mol e
2
3
96500 C
1 mol e
5 1.114 3 10
6
C
5.567 3 10
5
C 3
1
1
1
20
A s
C A

_
,
_
,
5 5.570 3 10
4
s
5.570 3 10
4
s 3
1 min
60 s
1 hr
60 min
_
,
_
,
5 15.5 hr
73. Thecorrect answer is(C). I f you remember the name of the l i gand (NH
3
i n thi s case)
comes fi rst preceded by a prefi x i ndi cati ng the number of ti mes the l i gand occurs. Thi s
i s fol l owed by the name of the metal i on, whose charge i s i ndi cated by a Roman
numeral . Fi nal l y, the name of the ani on i s l i sted.
a
n
s
w
e
r
s
p
r
a
c
t
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c
e
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e
s
t
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Practice Test 2 511
www.petersons.com
74. Thecorrect answer is (A). Thi s probl em i s an exampl e of the common-i on effect. The
weak aceti c aci d i oni zes i n water accordi ng to the fol l owi ng equati on:
HC
2
H
3
O
2
H
1
1 C
2
H
3
O
2
2
Because thi s i s i n equi l i bri um, i t wi l l be di sturbed by the presence of the acetate i on,
donated by the sodi um acetate. Sodi um wi l l not affect the equi l i bri um. The next step i s
to set up an equi l i bri um tabl e, taki ng i nto account the i ni ti al presence of acetate i on.
HC
2
H
3
O
2
H
1
C
2
H
3
O
2
2
Start 0.20 0 0.20
D 2x 1x 1x
Fi ni sh 0.20 2 x x 0.20 1 x
The expressi on for K
a
, then becomes:
K
a
5
[H
1
][C
2
H
3
O
2
2
]
[HC
2
H
3
O
2
]
5
~x!~0.20 1 x!
~0.20 2 x!
I t must be assumed that x i s very smal l rel ati ve to 0.20 (we can check thi s l ater), so we
can rewri te the expressi on as:
K
a
5 1.8 3 10
25
5
x ( )( )
( )
0 20
0 20
.
.
5 x
1.8 3 10
25
5 x
Our assumpti on about x bei ng much smal l er than 0.20 i s supported, so we can sol ve the
probl em:
[H1] 5 1.8 3 10
25
M
pH 5 2l og [1.8 3 10
25
] 5 4.7
You wont be abl e to use a cal cul ator on the mul ti pl e-choi ce questi ons, but your
fami l i ari ty wi th l ogari thms can hel p you here. You shoul d know that the 2l og (1.0 3
10
25
) i s 5. Concentrati ons hi gher than thi s wi l l produce a pH l ower than 5.0 and
concentrati ons l ower than thi s wi l l produce a pH hi gher than 5.0. Si nce 1.8 3 10
25
.
1.0 3 10
25
, you can rul e out the other possi bl e answer, choi ce (D), whi ch i s 5.4.
75. The correct answer is (D). Onl y experi ence wi th these chemi cal s, ei ther through
actual l ab experi ence or demonstrati ons, wi l l hel p you answer questi ons l i ke these. The
di chromate i on has a characteri sti c orange col or. Na
2
CrO
4
i s yel l ow, KmnO
4
i s purpl e,
Ni (NO
3
)
2
i s green, and CuCl
2
i s bl ue-green.
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Section II
1. (a) I f 6.1 3 10
23
g CaC
2
O
4
can be di ssol ved per l i ter of sol uti on, then determi ni ng
the mol ar sol ubi l i ty of the substance si mpl y requi res that you convert thi s val ue
to the number of mol es per l i ter:
6.1 3 10
23
g CaC
2
O
4
3
1 mol CaC O
128.1 g CaC O
2 4
2 4
5 4.8 3 10
25
mol per l i ter.
(b) The sol ubi l i ty equi l i bri um i s based on the fol l owi ng equati on:
CaC
2
O
4
(s) Ca
21
(aq) 1 C
2
O
4
22
(aq)
(c) K
sp
can be cal cul ated based on the fol l owi ng
K
sp
5 [Ca
21
][C
2
O
4
22
]
where the concentrati ons used i n the equati on wi l l be obtai ned from (A). Whi l e
thi s step i s probabl y one that you can do i n your head, wel l go through i t just to
make sure you are fol l owi ng the correct procedure. The next step i s to set up an
equi l i bri um tabl e:
CaC
2
O
4
Ca
21
C
2
O
4
22
Start 0 0
D 14.8 3 10
25
14.8 3 10
25
Fi ni sh 4.8 3 10
25
4.8 3 10
25
K
sp
5 @Ca
21
#@ C
2
O
4
22
#
5~4.8310
25
!~4.8310
25
!
52.3310
29
(d) I n thi s probl em, cal ci um oxal ate i s bei ng pl aced i nto a sol uti on that contai ns a
common i on. Any cal cul ati ons rel ated to sol ubi l i ty wi l l have to take thi s i nto
account. I n thi s case, the equi l i bri um concentrati ons of the substances wi l l be
affected by the i ni ti al presence of cal ci um i ons i n sol uti on (the cal ci um from
cal ci um chl ori de wi l l suppress the di ssol vi ng of some of the cal ci um oxal ate). To
determi ne the extent of thi s effect we must observe the sol ubi l i ty equi l i bri um
expressi on usi ng the modi fi ed concentrati on data:
CaC
2
O
4
Ca
21
C
2
O
4
22
Start 0.10 0
D 1x 1x
Fi ni sh 0.10 1 x x
a
n
s
w
e
r
s
p
r
a
c
t
i
c
e
t
e
s
t
2
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Practice Test 2 513
www.petersons.com
At thi s poi nt, we can use the val ue of K
sp
that was cal cul ated i n part (c) to set up
the expressi on that wi l l sol ve for x, the mol ar sol ubi l i ty:
K
sp
5 [Ca
21
][ C
2
O
4
22
]
2.3 3 10
29
5 (0.10 1 x)x
At thi s poi nt, we wi l l make the assumpti on that xi s qui te smal l compared to 0.10
and, as a resul t, wi l l not be i ncl uded i n that porti on of the cal cul ati on. Therefore:
2.3 3 10
29
5 0.10x
x 5 2.3 3 10
28
M
By compari son, thi s number i s much smal l er than the val ue for di ssol vi ng i n
pure substances. I n addi ti on, our assumpti on that x was much smal l er than 0.10
has been supported.
(e) Thi s probl em cal l s for the use of the i on product. I f we cal cul ate the i on product,
we can then compare i t to K
sp
for the substance. I f i t i s l ess than K
sp
,
preci pi tati on wi l l not occur. I f i t exceeds K
sp
, then preci pi tati on wi l l occur.
Because we are gi ven vol umes, we need to determi ne the concentrati ons i n the
fi nal mi xture. Thi s wi l l be accompl i shed by determi ni ng how many mol es are i n
the ori gi nal sol uti on and then usi ng the combi ned vol umes of the two sol uti ons to
cal cul ate the new concentrati on.
The number of mol es i n 50.0 mL of 0.0025 M CaCl
2
i s:
0.050 L 3
0.0025 mol CaCl
1 L CaCl
2
2
5 1.25 3 10
24
mol CaCl
2
Because the di ssoci ati on of CaCl
2
yi el ds one mol e of Ca
21
for every mol e of CaCl
2
,
we can say that we have 1.25 3 10
24
mol Ca
21
.
Next, we need to fi nd the number of mol es of oxal ate i ons:
0.050 L Na
2
C
2
O
4
3
1 10 Na C O
1L Na C O
5
2 2
2 2
mol .0
4
4

5 5.0 3 10
27
mol Na
2
C
2
O
4
Because each mol e of Na
2
C
2
O
4
yi el ds one mol e of C
2
O
4
22
i ons, we can say that we
have 5.0 3 10
7
mol C
2
O
4
22
i ons.
Before we can use these quanti ti es i n the i on product expressi on, we wi l l have to
convert them to mol ari ti es. We need to make sure we are usi ng the combi ned
vol ume of the two sol uti ons to determi ne the mol ari ty i n the fi nal mi xture:
[Ca
21
] 5
125 10
0.100 L
mol
4
5 1.25 3 10
23
M
[C
2
O
4
22
] 5
5 10
0.100 L
7
mol

5 5.0 3 10
26
M
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www.petersons.com
At thi s poi nt, we are ready to cal cul ate Q:
Q 5 @Ca
21
#@C
2
O
4
22
#
5 @1.25 3 10
23
M#@5.0 3 10
26
M# 5 6.25 3 10
29
Because Q . K
sp
, we expect that CaC
2
O
4
wi l l preci pi tate.
2. (a) The equi l i bri um expressi on, K
c
, can be wri tten as:
K
c
2
2 2
[I Br]
[I ][Br ]
(b) Thi s process wi l l requi re a few steps. I n the fi rst, we need to determi ne the
concentrati on of each substance when they were fi rst put i n the fl ask. Thi s i s
obtai ned by:
M 5
0.0015 mol
5.00 L
5 3.0 3 10
24
M
Once thi s i s known, we can set up an equi l i bri um cal cul ati on tabl e to determi ne
the concentrati ons of the substances at equi l i bri um:
I
2
Br
2
2I Br
Start 3.0 3 10
24
3.0 3 10
24
0
D 2x 2x 12x
Fi ni sh (3.0 3 10
24
) 2 x (3.0 3 10
24
) 2 x 2x
These val ues can now be pl aced i nto the equi l i bri um constant expressi on
from (a):
K
c
2
2 2
[I Br]
[I ][Br ]
1.2 3 10
2
5
2
3 0 10 3 0 10
2
4 4
x
x x
( )
( )( )

. .
To si mpl i fy what coul d be a rather messy probl em, we can take the square root of
each si de of the equati on:
=1.2 3 10
2
5
~2x!
2
~3.0 3 10
24
2 x! ~3.0 3 10
24
2 x!
10.95 5
~2x!
3.0 3 10
24
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Practice Test 2 515
www.petersons.com
We can now rearrange thi s equati on and sol ve for x:
( . )
.
.
. .
3 0 10
2
10 95
0 183
3 0 10 1 183
4
4
3

x
x
x
x
..
.
.
0 10
1 183
4
4
2 54 10

x M
Now that we know the val ue of x, we can substi tute i t back i nto the val ues shown
i n the equi l i bri um tabl e to sol ve the probl em:
[I
2
] 5 [Br
2
] 5 (3.0 3 10
24
2 2.54 3 10
24
) 5 4.6 3 10
25
[I Br] 5 2x 5 2(2.54 3 10
24
) 5 5.1 3 10
24
(c) To sol ve thi s probl em, you need to use the val ue for K
c
and the formul a:
K
p
5 K
c
(RT)Dn
For thi s reacti on, Dn 5 mol es products 2 mol es reactants 5 222 5 0. Si nce
Dn 5 0, then K
p
5 K
c
for thi s reacti on.
(d) I f 0.05 mol I
2
are added to the vessel , the equi l i bri um wi l l shi ft to the ri ght (the
formati on of 2I Br) to al l evi ate the stress.
3. (a) I n order to sol ve thi s probl em, you need to use the gi ven i nformati on i n thi s
formul a:
DH
rxn
5 SnDH
f
(products) 2 SmDH
f
(reactants)
Substi tuti ng the data, we get:
DH 5 2~SO
3
! 2 @2~SO
2
! 1 O
2
#
5 2 mol ~2396 kJ mol
21
! 2 @2 mol ~2297 kJ mol
21
! 1 0#
5 2792 kJ 1 594 kJ
5 2198 kJ
(b) For thi s probl em, you need to use the equati on bel ow:
DS 5 SnDS~products! 2 SnDS~reactants!
DS 5 2~SO
3
! 2 @2~SO
2
! 1 O
2
#
DS 5 2 mol ~257 J K
21
mol ! 2 @2 mol ~248 J K
21
mol ! 1 1 mol ~205 J K
21
mol !#
DS 5 514 J K
21
2 701 J K
21
5 2187 J K
21
(c) I n thi s porti on, you dont need to use the standard free energy val ues. You have
al ready cal cul ated entropy and enthal py, so the equati on to use i s:
DG 5 DH 2 TDS
DG 5 2198 kJ 2 F~298 K!~2187 J K
21
!
S
1 kJ
1000 J
D
G
5 2198 kJ 155.7 kJ
5 2142 kJ
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www.petersons.com
(d) (i) The reacti on i s exothermi c, whi ch you can tel l by the negati ve val ue of DH.
(ii) The reacti on i s decreasi ng i n entropy. Thi s i s consi stent wi th the fact that
you are starti ng wi th 3 mol es of gas and decreasi ng to 2 mol es of gas.
(iii) The process i s spontaneous, whi ch you can tel l by the negati ve val ue for DG.
4. (a) (NH
4
)
2
CO
3
H
2
O 1 CO
2
1 2NH
3
Thi s i s a decomposi ti on reacti on that i s very frequentl y referred to and/or
performed i n i ntroductory cl asses.
Answer: As NH
3
gas i s produced, moi st red l i tmus paper woul d turn bl ue.
(b) 3Cu 1 8H
1
1 2NO
3
2
3Cu
21
1 2NO 1 4H
2
O
Thi s i s a tri cky one. One of the key cl ues i n the probl em was the term dilutei n
reference to ni tri c aci d. Thi s outcome i s di fferent from the outcome wi th
concentrated ni tri c aci d. When concentrated aci d i s used, the ni trate i on i s
reduced to NO
2
, but wi th the di l ute aci d, i t i s reduced to NO. Hydrogen faci l i tates
i n the reacti on but does not form a gas (i t i s used to form water).
Answer: Sol uti on turns bl ue, and gas bubbl es form.
(c) C
2
H
5
OH 1 3O
2
2CO
2
1 3H
2
O
Thi s i s a typi cal combusti on reacti on. The reacti on shown i s a compl ete
combusti on reacti on, whi ch assumes an excess of O
2
.
Answer: 5 mol ecul es of product are formed from 1 mol ecul e of ethanol .
5. (a) Accordi ng to Le Chtel i ers Pri nci pl e, the addi ti on of oxygen gas wi l l force the
reacti on to the l eft; therefore, there wi l l be an i ncrease i n SO
3
.
(b) I f the pressure i s reduced by i ncreasi ng the vol ume, the reacti on wi l l shi ft to the
ri ght. Thi s wi l l create more gas parti cl es to compensate for the decrease i n
pressure. The shi ft to the ri ght wi l l cause a decrease i n SO
3
.
(c) The addi ti on of an i nert gas, l i ke hel i um, wi l l have no effect on the equi l i bri um
mi xture. Al though the i nert gas i ncreases the overal l pressure i n the contai ner, i t
does not affect the concentrati ons or parti al pressures of the i ndi vi dual gases. As
a resul t, the amount of SO
3
wi l l remai n constant.
(d) The reacti on i s endothermi c (as evi dent from the posi ti ve val ue of DH). Therefore,
i f the reacti on mi xture i s heated, the equi l i bri um wi l l shi ft to the ri ght,
decreasi ng the amount of SO
3
.
(e) I f oxygen gas i s removed, the equi l i bri um wi l l shi ft to the ri ght to create more.
Thi s wi l l cause a decrease i n the amount of SO
3
.
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Practice Test 2 517
www.petersons.com
6. (a)
(b) One of the bi ggest di fferences i s the steepness of the curve around the
equi val ence poi nt. Strong aci ds experi ence a very l arge i ncrease i n pH wi th a
rel ati vel y smal l addi ti on of base.
One other di fference i s the l ocati on of the equi val ence poi nt. For strong aci ds, the
equi val ence poi nt i s l ocated at 7.0, but for weaker aci ds, thi s equi val ence poi nt i s
at a hi gher pH.
(c) Strong aci d, strong base ti trati ons are much more forgi vi ng on your choi ce of
i ndi cator. The reason for thi s i s because of the l arge change i n pH wi th a
rel ati vel y smal l addi ti on of base near the equi val ence poi nt. The di fference i n
base vol ume requi red to change from pH 4 to pH 10 i s rel ati vel y smal l . Therefore,
a vari ety of i ndi cators can be used wi th reasonabl y smal l errors.
Wi th a weak aci d, strong base ti trati on l i ke thi s one, the si tuati on i s more cri ti cal
for two reasons. Fi rst, the pH changes a bi t more gradual l y than wi th strong aci d
ti trati ons. As a resul t, an i ndi cator l i ke methyl red wi l l change col or wel l before
the equi val ence poi nt i s reached.
The second reason the i ndi cator choi ce i s cri ti cal i s real l y an extensi on of the fi rst
reason. For weak aci ds, the pH at the equi val ence i s greater than 7.0. Because
the pH changes gradual l y and because the pH i s greater than 7, i t i s i mportant to
sel ect an i ndi cator, l i ke phenol phthal ei n, that wi l l change col or i n a range of pH
val ues between 8 and 10.
(d) The most l i kel y source of the error i s a probl em wi th the concentrati on of the
ti trant. I f the base i s too di l ute, the vol ume that must be added (to suppl y enough
hydroxi de i ons) must be i ncreasedso much so that i t can exceed the vol ume of
the buret. I t i s i mportant to perform some approxi mate cal cul ati ons pri or to a
ti trati on to assure that an adequate concentrati on of base i s used.
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www.petersons.com
ANSWER SHEET PRACTICE TEST 3
SECTION I
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
65.
jA jB jC jD jE
66.
jA jB jC jD jE
67.
jA jB jC jD jE
68.
jA jB jC jD jE
69.
jA jB jC jD jE
70.
jA jB jC jD jE
71.
jA jB jC jD jE
72.
jA jB jC jD jE
73.
jA jB jC jD jE
74.
jA jB jC jD jE
75.
jA jB jC jD jE
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Practice Test 3 519
www.petersons.com
Practice Test 3
SECTION I
TIM E1 HO UR AND 30 M INUTES
NO CALCULATORS MAY BE USED WITH SECTION I.
mol 5 mol e(s)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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3

521
i mmedi atel y fol l owi ng i t. Sel ect the one l ettered choi ce that best fi ts each statement and
then fi l l i n the correspondi ng oval on the answer sheet. A choi ce may be used once, more
than once, or not at al l i n each set.
QUESTIONS 13 REFER TO THE CHOICES
BELOW:
(A) Hei senberg uncertai nty
pri nci pl e
(B) Schrdi nger equati on
(C) Hunds rul e
(D) X-ray di ffracti on
(E) Photoel ectri c effect
1. Can be used to predi ct the paramag-
neti sm of certai n el ements
2. Predi cts that i t i s i mpossi bl e to know
si mul taneousl y both the l ocati on and
momentum of an el ectron
3. Predi cts the l ocati ons and ori enta-
ti ons of atomi c orbi tal s
USE THESE ANSWERS FOR QUESTIONS 46:
(A) Arrheni us aci d
(B) Brnsted-Lowry aci d
(C) Brnsted-Lowry base
(D) Lewi s aci d
(E) Lewi s base
4. BF
3
i n the reacti on: BF
3
1 F
2
BF
4
5. CN
2
i n the reacti on: Cu
21
(aq) 1
4CN
2
(aq) Cu(CN)
4
22
(aq)
6. H
2
O i n the reacti on: HC
2
H
3
O
2
(aq) 1
H
2
O(aq) C
2
H
3
O
2
2
(aq) 1 H
3
O
1
(aq)
QUESTIONS 79 REFER TO THE CHOICES
BELOW:
(A) N
(B) Cl
(C) Ne
(D) Mg
(E) Rb
7. Whi ch el ement i s the most el ectrone-
gati ve?
8. Whi ch el ement has the most possi bl e
oxi dati on states?
9. Whi ch el ement has the smal l est fi rst
i oni zati on energy?
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www.petersons.com
Directions: Each of the questi ons or i ncompl ete statements bel ow i s fol l owed by fi ve
answers or compl eti ons. Sel ect the one that i s best i n each case and then fi l l i n the
correspondi ng oval on the answer sheet.
10. About how many mi l l i l i ters of
6.0-mol ar HCl must be di l uted to
obtai n 1.0 l i ters of 2.5-mol ar HCl ?
(A) 130 mL
(B) 250 mL
(C) 400 mL
(D) 420 mL
(E) 840 mL
to be a sol i d at room temperature?
(A) Na
2
S
(B) HF
(C) NH
3
(D) N
2
(E) H
2
12. The K
sp
of Al (OH)
3
i s 2 3 10
232
. At
what pH wi l l a 0.2 M Al
31
sol uti on
begi n to show preci pi tati on of
Al (OH)
3
?
(A) 2l og
(B) 2l og
(C) 2l og
(D) 2l og
(E) 2l og
13. Whi ch of the fol l owi ng represents a
pai r of i sotopes of the same el ement?
Atomi c
Number
Mass
Number
(A) I 92 208
I I 92 211
(B) I 45 106
I I 92 206
(C) I 92 238
I I 89 235
(D) I 92 233
I I 89 233
(E) I 7 15
I I 8 16
14. The mel ti ng poi nt of MgS i s hi gher than
that of KCl . Whi ch of the fol l owi ng ob-
servati ons can expl ai n thi s?
I . Mg
21
has a greater posi ti ve
charge than K
1
I I . S
22
has a greater negati ve
charge than Cl
2
I I I . S
22
has a smal l er radi us
than Cl
2
(A) I I I onl y
(B) I I and I I I
(C) I and I I I
(D) I and I I
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Practice Test 3 523

www.petersons.com
15. Whi ch choi ce shows the correct
arrangement of the aci ds i n order of
i ncreasi ng aci d strength?
(A) HCl O
4
, HCl O
3
, HCl O
2
, HCl O
(B) HCl O
4
, HCl O, HCl O
3
, HCl O
2
(C) HCl O, HCl O
2
, HCl O
3
, HCl O
4
(D) HCl O
3
, HCl O, HCl O
4
, HCl O
2
(E) More i nformati on i s needed to
answer the questi on.
16. The hal f-l i fe of i s 28 years. How
l ong wi l l i t take for a gi ven sampl e of
to be 87.5% decomposed?
(A) 8.75 hal f-l i ves
(B) 3.5 years
(C) 84 years
(D) 24.5 years
(E) 2.2 3 10
4
years
17. Whi ch one of the fol l owi ng reacti ons
woul d have a posi ti ve val ue for
DS?
(A) Ba(OH)
2
(s) 1 CO
2
(g)
BaCO
3
(s) 1 H
2
O(l)
(B) N
2
(g) 1 3H
2
(g) 2NH
3
(g)
(C) 2SO
3
(g) 2SO
2
(g) 1 O
2
(g)
(D) AgNO
3
(aq) 1 HCl (aq)
AgCl (s) 1 HNO
3
(aq)
(E) 2NO
2
(g) N
2
O
4
(g)
18. I n the mol ecul e SF
6
, what i s the
hybri di zati on of S?
(A) sp
(B) sp
2
(C) sp
3
(D) dsp
3
(E) d
2
sp
3
19. Whi ch of the fol l owi ng speci es cannot
functi on as an oxi di zi ng agent?
(A) S(s)
(B) NO
3
2
(aq)
(C) Cr
2
O
7
22
(aq)
(D) I
2
(aq)
(E) MnO
4
2
(aq)
20. Whi ch of the fol l owi ng processes
must exi st i n equi l i bri um wi th the
evaporati on process when a measure-
ment of vapor pressure i s made?
(A) Fusi on
(B) Vapori zati on
(C) Subl i mati on
(D) Boi l i ng
(E) Condensati on
2CO
2
(g) 2CO(g) 1 O
2
(g)
DH 5 2514 kJ
21. The equi l i bri um constant wi l l be the
hi ghest when the reacti on above i s
carri ed out at
(A) l ow temperature and l ow
pressure.
(B) l ow temperature and hi gh
pressure.
(C) hi gh temperature and hi gh
pressure.
(D) hi gh temperature and l ow
pressure.
(E) any temperature or pressure;
nei ther affect the reacti on.
22. Whi ch of the fol l owi ng sol i d sal ts i s
more sol ubl e i n 1.0 M H
1
than i n
pure water?
(A) NaCl
(B) CaCO
3
(C) KCl
(D) AgCl
(E) KNO
3
23. Whi ch of the fol l owi ng i s a conjugate
aci d-base pai r?
(A) H
3
O
1
and OH
2
(B) HCl and OCl
2
(C) NH
4
1
/NH
3
(D) H
2
SO
4
/SO
4
22
(E) HCl O
4
and Cl O
4
2
24. Pl ace the el ements S, Cl , and F i n
order of i ncreasi ng atomi c radi us.
(A) S, Cl , F
(B) S, F, Cl
(C) F, Cl , S
(D) F, S, Cl
(E) Cl , F, S
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3H
2
(g) 1 N
2
(g) 2NH
3
(g)
25. I f 2.00 mol H
2
, 1.00 mol N
2
, and 2.00
mol NH
3
are pl aced i nto a 1.00 L
evacuated fl ask. How wi l l the
reacti on above proceed i f K
c
5 0.105
(A) The reacti on must proceed from
ri ght to l eft.
(B) The reacti on must proceed from
l eft to ri ght.
(C) The reacti on i s al ready at
equi l i bri um, so no net move-
ment wi l l occur.
(D) The reacti on cannot establ i sh
equi l i bri um at thi s tempera-
ture.
(E) The reacti on wi l l proceed from
l eft to ri ght unti l 2.23 mol NH
3
have been produced.
26. A gas sampl e i s heated from 223.0C
to 57.0C, and the vol ume i s i n-
creased from 2.00 L to 4.00 L. I f the
i ni ti al pressure i s 0.125 atm, whi ch
of the fol l owi ng cal cul ati ons wi l l yi el d
the correct fi nal pressure?
(A)
(B)
(C)
(D)
(E)
27. A 0.10-mol ar sol uti on of a weak
monoproti c aci d, HA, has a pH of
4.00. The i oni zati on constant of thi s
aci d i s
(A) 5.0 3 10
27
(B) 1.0 3 10
27
(C) 5.0 3 10
26
(D) 1.0 3 10
26
(E) 5.0 3 10
26
Rate 5 k[NO]
2
[Cl
2
]
28. What i s the order of the above reacti on
wi th respect to ni tri c oxi de, NO?
(A) 0
(B) 1
(C) 2
(D) 3
(E) 4
Mg 1 2H
2
O Mg(OH)
2
1 H
2
29. I n the reacti on above, what mass of
hydrogen can be produced by reac-
ti on of 4.73 g of magnesi um wi th
1.83 g of water?
(A) 0.103 g
(B) 0.0162 g
(C) 0.0485 g
(D) 0.219 g
(E) 3.20 g
30. H
2
S i s a gas at room temperature
whi l e H
2
O i s a l i qui d. What can
expl ai n thi s di fference?
(A) H
2
O i s amphoteri c.
(B) H
2
S i s fl ammabl e.
(C) H
2
O mol ecul es have smal l er
di pol e moments than H
2
S.
(D) H
2
S i s a heavi er mol ecul e.
(E) The greater el ectronegati vi ty of
O al l ows more hydrogen bondi ng.
31. A vol tai c cel l i s desi gned wi th a
copper el ectrode i mmersed i n 1.0 M
copper (I I ) sul fate sol uti on,
CuSO
4
(aq), and a l ead el ectrode
i mmersed i n 1.0 M l ead (I I ) ni trate
sol uti on, Pb(NO
3
)
2
(aq) at 25C. Gi ven
the standard reducti on potenti al s
shown bel ow, determi ne the potenti al
of the cel l i n vol ts:
Pb
21
1 2e
2
Pb E 5 20.13 V
Cu
21
1 2e
2
Cu E 5 10.34 V
(A) 0.47 V
(B) 0.92 V
(C) 0.22 V
(D) 0.58 V
(E) 0.17 V
p
r
a
c
t
i
c
e
t
e
s
t
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Practice Test 3 525

www.petersons.com
32. Whi ch of the fol l owi ng i s the l east
sol ubl e?
(A) CaSO
4
K
sp
5 9.1 10
26
(B) BaF
2
K
sp
5 1.0 10
26
(C) Ni CO
3
K
sp
5 6.6 10
214
(D) CaCrO
4
K
sp
5 7.1 10
24
(E) Sn(OH)
2
K
sp
5 1.4 10
228
33. Whi ch of the fol l owi ng has an
i ncompl ete octet i n i ts Lewi s struc-
ture?
(A) SO
2
(B) I Cl
(C) CO
2
(D) F
2
(E) NO
34. How many mi l l i l i ters of 0.20 M KOH
are needed to compl etel y neutral i ze
20 mL of 0.10 M H
3
PO
4
?
(A) 3.0 mL
(B) 10 mL
(C) 20 mL
(D) 30 mL
(E) 60 mL
35. I f undergoes a beta decay and
the product of thi s decay undergoes
another beta decay, whi ch nucl i de i s
produced?
(A)
(B)
(C)
(D)
(E)
Zn(s) 1 2HCl (aq) ZnCl
2
(aq) 1 H
2
(g)
36. I n the reacti on above, i f 32.7 g of Zn
are al l owed to react compl etel y wi th
an excess of HCl , how many l i ters of
hydrogen gas, H
2
, wi l l be produced?
(A) 5.6 L
(B) 11.2 L
(C) 22.4 L
(D) 33.6 L
(E) 44.8 L
37. Ni ckel i s el ectropl ated from a Ni SO
4
sol uti on. I f a constant current of
5.00 amp i s appl i ed to a Ni SO
4
sol uti on, how l ong wi l l i t take to
deposi t 100.0 g of Ni ?
(A) 1.22 s
(B) 57.2 s
(C) 62.9 mi n
(D) 18.3 h
(E) 2.41 days
38. An i ce cube mel ts at room tempera-
ture and atmospheri c pressure.
Whi ch statement bel ow correctl y
descri bes the thermodynami c proper-
ti es of thi s process?
DH DS DG
(A) 2 1 1
(B) 2 2 1
(C) 1 2 2
(D) 1 1 1
(E) 1 1 2
39. Whi ch of the i ons bel ow has the
l argest i oni c radi us?
(A) Li
(B) Be
(C) F
(D) Cl
(E) Br
40. The compound bel ow i s an exampl e
of whi ch of the fol l owi ng?
(A) Al dehyde
(B) Ester
(C) Ami ne
(D) Ketone
(E) Ether
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www.petersons.com
PCl
5
(g) PCl
3
(g) 1 Cl
2
(g)
41. I n the reacti on above, assume that
0.75 mol of PCl
5
i s pl aced i n a 1.0 L
reacti on vessel . At equi l i bri um, the
0.65 mol of PCl
5
i s present. What
i s K
c
?
(A) 65
(B) 6.5
(C) 0.10
(D) 0.15
(E) 0.015
42. Sol i d bari um ni trate, Ba(NO
3
)
2
, gradu-
al l y di ssol ved i n a 1.0 310
24
M Na
2
CO
3
sol uti on. At what Ba
21
concentrati on
wi l l a preci pi tate begi n to form? (K
sp
for BaCO
3
5 5.1 3 10
29
)
(A) 4.1 3 10
25
M
(B) 8.1 3 10
25
M
(C) 5.1 3 10
25
M
(D) 1.2 3 10
26
M
(E) 8.1 3 10
28
M
43. Whi ch of the fol l owi ng i s an i somer
of n-hexane?
(A) 2,3-di methyl butane
(B) 2-methyl butane
(C) 2,2-di methyl propane
(D) 2,3-di methyl pentane
(E) 3-ethyl -2-methyl pentane
44. A crystal of NaCl i s
(A) soft, l ow mel ti ng, and a good
(B) hard, hi gh mel ti ng, and a good
(C) soft, l ow mel ti ng, and a poor
(D) hard, hi gh mel ti ng, and a poor
(E) soft, hi gh mel ti ng, and a poor
45. A vol tai c cel l i s set up at standard
temperature wi th a zi nc el ectrode
pl aced i n a 0.5 M sol uti on of Zn
21
.
The other cel l contai ns a copper
el ectrode i mmersed i n a 0.5 M
sol uti on of Cu
21
. What wi l l happen
to the cel l emf i f the copper sol uti on
i s i ncreased i n concentrati on from
0.5 M to 5.0 M?
(A) emf wi l l i ncrease.
(B) emf wi l l decrease.
(C) emf wi l l experi ence a rapi d
decrease fol l owed by a steady
i ncrease.
(D) emf wi l l onl y change i f the zi nc
sol uti on i s changed.
(E) emf i s unaffected.
46. Several pi eces of mossy zi nc are
added to hydrochl ori c aci d i n a fi l ter
fl ask fi tted wi th a pi ece of rubber
tubi ng. The rubber tubi ng i s sub-
merged under water so that the gas
can be bubbl ed through the water
and col l ected i n a gas-col l ecti on tube.
After a certai n amount of hydrogen
gas had been col l ected, the pressure
i n the gas-col l ecti on tube i s 300 mm
Hg and the temperature i s 20.0C. I f
the vapor pressure of water at thi s
temperature i s 18 mm Hg, what i s
the pressure of the hydrogen gas?
(A) 318 mm Hg
(B) 282 mm Hg
(C) 320 mm Hg
(D) 300 mm Hg
(E) 18 mm Hg
47. General l y the vapor pressure of a
l i qui d i s rel ated to
I . the amount of l i qui d.
I I . temperature.
I I I . i ntermol ecul ar forces.
(A) I onl y
(B) I I onl y
(C) I I I onl y
(D) I and I I
(E) I I and I I I
p
r
a
c
t
i
c
e
t
e
s
t
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Practice Test 3 527

www.petersons.com
48. The mol ar sol ubi l i ty of BaCO
3
(K
sp
5
1.6 3 10
29
) i n 0.10 M BaCl
2
sol u-
ti on i s
(A) 1.6 3 10
210
(B) 4.0 3 10
25
(C) 7.4 3 10
24
(D) 0.10
(E) 1.6 3 10
28
49. Each of the fol l owi ng can act as both
a Brnsted aci d and a Brnsted base
EXCEPT
(A) HSO
4
2
(B) H
2
PO
4
2
(C) NH
4
1
(D) H
2
O
(E) HCO
3
2
50. Whi ch of the fol l owi ng vi ol ates the
octet rul e?
(A) NF
3
(B) I F
3
(C) PF
3
(D) SbF
3
(E) AsF
3
51. The mol al i ty of the magnesi um
sul fate i n a 1.0 M MgSO
4
sol uti on
can be determi ned usi ng the
(A) temperature of the sol uti on.
(B) K
sp
for MgSO
4.
(C) vol ume of the sol uti on.
(D) i on-product.
(E) densi ty of the sol uti on.
52. A l ab i nstructor i s prepari ng
5.00 l i ters of a 0.100-mol ar Pb(NO
3
)
2
(mol ecul ar wei ght 331) sol uti on. She
shoul d wei gh out
(A) 165.5 g of Pb(NO
3
)
2
and add
5.00 kg of H
2
O.
(B) 165.5 g of Pb(NO
3
)
2
and add
H
2
(C) 33.1 g of Pb(NO
3
)
2
and add H
2
O
unti l the sol uti on has a vol ume
of 5.00 l i ters.
(D) 331 g of Pb(NO
3
)
2
and add 5.00
l i ters of H
2
O.
(E) 165.5 g of Pb(NO
3
)
2
and add
5.00 l i ters of H
2
O.
53. 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 NaCl
(B) 0.10 M NH
4
NO
3
(C) 0.10 M NH
4
Cl
(D) 0.10 M HCl
(E) 0.10 M Na
2
SO
4
54. A 2.00-l i ter sampl e of argon gas at
77C and 720 mm Hg i s heated unti l
i t occupi es a vol ume of 4.00 l i ters.
Duri ng the expansi on, the pressure i s
constant. What i s the temperature of
the gas after i t has expanded?
(A) 154C
(B) 308C
(C) 427C
(D) 700C
(E) 720.C
55. 2NO N
2
O
2
(fast equi l i bri um)
N
2
O
2
1 H
2
k
2
N
2
O 1 H
2
O (sl ow)
N
2
O 1 H
2
k
3
N
2
1 H
2
O (fast)
Ni tri c oxi de, NO, can be reduced by
hydrogen gas to yi el d ni trogen gas
and water vapor. The decomposi ti on
i s bel i eved to occur accordi ng to the
reacti on mechani sm shown above.
The rate l aw for the reacti on that i s
consi stent wi th thi s mechani sm i s
gi ven by whi ch of the fol l owi ng?
(A) Rate 5 k[NO]
2
(B) Rate 5 k[NO]
2
[N
2
O
2
]
(C) Rate 5 k[N
2
O
2
][H
2
]
(D) Rate 5 k[NO]
2
[H
2
]
(E) Rate 5 k[N
2
O][H
2
]
56. The normal boi l i ng poi nt of l i qui d X
i s l ess than that of Y, whi ch i s l ess
than that of Z. Whi ch of the fol l owi ng
i s the correct order of i ncreasi ng
vapor pressure of the three l i qui ds
at STP?
(A) X, Y, Z
(B) Z, Y, X
(C) Y, X, Z
(D) X, Z, Y
(E) Y, Z, X
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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C(s) 1 H
2
O(g) CO(g) 1 H
2
(g)
DG 5 91.2 kJ
DS 5 135 J mol
21
K
21
57. What i s the val ue of DH for the
reacti on shown above at 25C?
(A) 40.3 kJ
(B) 226 kJ
(C) 91.3 kJ
(D) 131.4 kJ
(E) 25.7 kJ
58. I n the mol ecul e NaAsO
3
, what i s the
oxi dati on number of As?
(A) 1
(B) 2
(C) 3
(D) 4
(E) 5
59. A sol uti on contai ni ng 292 g of
Mg(NO
3
)
2
per l i ter (of sol uti on) has a
densi ty of 1.108 g/mL. The mol al i ty
of the sol uti on i s
(A) 2.00 m
(B) 2.41 m
(C) 5.50 m
(D) 6.39 m
(E) 11.08 m
I oni zati on Energi es for
Unknown El ement Q (kJ mol
21
)
Fi rst Second Thi rd
520 7298 11815
60. Whi ch el ement bel ow i s most l i kel y
to be el ement Q?
(A) Li
(B) Ca
(C) Al
(D) F
(E) Ba
61. Carbonated beverages get thei r fi zz
from carbon di oxi de that i s di ssol ved
i n water. Under whi ch condi ti ons i s i t
possi bl e to di ssol ve the most carbon
di oxi de i n water?
(A) Hi gh pressure, hi gh tempera-
ture
(B) Hi gh pressure, l ow temperature
(C) Low pressure, hi gh temperature
(D) Low pressure, l ow temperature
(E) A vacuum, hi gh temperature
62. Determi ne the mol ecul ar formul a of a
compound that contai ns 40.0 percent
C, 6.71 percent H, 53.29 percent O
and has a mol ecul ar mass of 60.05.
(A) C
2
H
4
O
2
(B) CH
2
O
(C) C
2
H
3
O
4
(D) C
2
H
2
O
4
(E) C
4
H
8
O
4
63. A gaseous mi xture contai ni ng 1.5 mol
Ne and 4.5 mol NO
2
has a total
pressure of 8.0 atm. What i s the
parti al pressure of NO
2
?
(A) 1.5 atm
(B) 2.7 atm
(C) 4.5 atm
(D) 6.0 atm
(E) 8.0 atm
64. I n the compound Mn
2
O
7
, what i s the
oxi dati on number of manganese?
(A) 12
(B) 13
(C) 15
(D) 17
(E) 18
Si (s) 1 2Cl
2
(g) Si Cl
4
(l)
65. I n the reacti on above, i f 3.84 mol Cl
2
react wi th an excess of Si , how many
mol es of Si Cl
4
wi l l be produced?
(A) 0.96 mol
(B) 1.92 mol
(C) 3.84 mol
(D) 4.00 mol
(E) 5.72 mol
p
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Practice Test 3 529

www.petersons.com
CO(g) 1 NO
2
(g) CO
2
(g) 1 NO(g)
66. For the reacti on represented above,
the experi mental rate l aw i s gi ven as
fol l ows:
Rate 5 k[NO
2
]
2
I f addi ti onal CO gas i s added to the
reacti on vessel , whi l e temperature
remai ns constant, whi ch of the
fol l owi ng i s true?
(A) Both the reacti on rate and
k i ncrease.
(B) Both the reacti on rate and
k decrease.
(C) Both the reacti on rate and
k remai n the same.
(D) The reacti on rate i ncreases but
k remai ns the same.
(E) The reacti on rate decreases but
k remai ns the same.
N
2
(g) 1 O
2
(g) 2NO
67. I n the formati on of NO (shown
above), what effect wi l l the addi ti on
of a catal yst have on the equi l i bri um
constant, K
eq
, for the reacti on?
Assume temperature and pressure
remai n constant.
(A) A catal yst wi l l i ncrease K
eq
.
(B) A catal yst wi l l decrease K
eq
.
(C) A catal yst wi l l have no effect
on K
eq
.
(D) A catal yst wi l l fi rst i ncrease
K
eq
, unti l the reacti on sl ows,
then K
eq
wi l l decrease.
(E) A catal yst wi l l cause a dramati c
i ncrease i n K
eq
.
68. Whi ch of the fol l owi ng i s predi cted to
have a square pl anar mol ecul ar
structure?
(A) TeBr
4
(B) BrF
3
(C) I F
5
(D) XeF
4
(E) SCl
2
69. Whi ch of the fol l owi ng pai rs woul d
make an effecti ve buffer sol uti on?
(A) HCl /NaCl
(B) KOH/K
2
SO
4
(C) HCl O
4
/NaCl O
4
(D) NaHCO
3
/Na
2
CO
3
(E) HCl /NH
4
Cl
70. A 100.0-g sampl e of water at 25.0C i s
mi xed wi th 100.0 g of a certai n metal
at 100.0C. After thermal equi l i bri um
i s establ i shed, the fi nal temperature
of the mi xture i s 30.0C. What i s the
speci fi c heat of the metal , assumi ng i t
i s constant over the temperature
range concerned? The speci fi c heat of
water i s 4.18 J/gC.
(A) 0.30 J/gC
(B) 0.60 J/gC
(C) 0.90 J/gC
(D) 0.030 J/gC
(E) 2.21 J/gC
...NH
3
(g) 1 ...O
2
(g) ...NO(g) 1 ...H
2
O
71. I f the equati on above i s bal anced, the
coeffi ci ent before the O
2
wi l l be
(A) 1
(B) 2
(C) 3
(D) 5
(E) 8
72. A sampl e of ni trogen gas i s pl aced
i nto a cl osed contai ner. The vol ume i s
hel d constant whi l e the temperature
i s i ncreased from 200 K to 400 K.
Gi ven these condi ti ons, whi ch of the
choi ces bel ow i s true?
(A) The densi ty of the gas doubl es.
(B) The pressure of the gas doubl es.
(C) The average vel oci ty of the gas
mol ecul es doubl es.
(D) The number of ni trogen gas
mol ecul es i ncreases.
(E) The potenti al energy of the gas
mol ecul es doubl es.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
2A 1 B C
73. The data bel ow corresponds to the
reacti on shown above.
Experi ment
I ni ti al
[A]
I ni ti al
[B]
I ni ti al
Rate
1 0.010 0.025 0.015
2 0.020 0.050 0.060
3 0.040 0.050 0.060
4 0.040 0.075 0.135
Whi ch rate l aw best descri bes
the data?
(A) Rate 5 k[B]
2
(B) Rate 5 k[A]
2
(C) Rate 5 k[A][B]
(D) Rate 5 k[A]
2
[B]
(E) Rate 5 k[A][B]
2
3Mg 1 N
2
Mg
3
N
2
74. I n the reacti on above, what mass of
magnesi um ni tri de can be made from
reacti on of 1.22 g of magnesi um wi th
excess ni trogen?
(A) 1.69 g
(B) 15.2 g
(C) 5.07 g
(D) 5.02 g
(E) 0.592 g
75. Whi ch of the fol l owi ng must be true
for a reacti on that proceeds sponta-
neousl y from i ni ti al standard state
condi ti ons?
(A) DG . 0 and K
eq
. 1
(B) DG . 0 and K
eq
, 1
(C) DG , 0 and K
eq
. 1
(D) DG , 0 and K
eq
, 1
(E) DG 5 0 and K
eq
5 1
S T O P
End of Secti on I . I f you have any ti me l eft, go over your work i n thi s
secti on onl y. do not work i n any other secti on of the test.
p
r
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Practice Test 3 531
www.petersons.com
SECTION II REFERENCE INFORMATION
56
Ba
137.33
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)
Une
(266)
Unh
(263)
88
Ra
226.02
Fr
(223)
55
Cs
132.91
38
Sr
87.62
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
107.87
Cd
112.41
49
In
114.82
Sn
118.71
51
Sb
121.75
Te
127.60
53
I
126.91
54
Xe
131.29
Rb
85.47
90
Th
232.04
91
231.04
92
U
238.03
93
237.05
94
(244)
95
(243)
96
(247)
97
(247)
98
(251)
99
(252)
100
(257)
101
(258)
102
(259)
58
Ce
140.12
59
140.91
60
144.24
61
(145)
62
150.4
63
151.97
64
157.25
65
158.93
66
162.50
67
164.93
68
167.26
69
168.93
70
173.04
103
(260)
71
Lu
174.97
20 21
44.96
22
Ti
23
V
24
Cr
52.00
25 26 27 28 29 30 31 32 33
As
34
78.96
35
Br
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
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
24.30
11
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
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www.petersons.com
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
2 Hg(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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Practice Test 3 533
www.petersons.com
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
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
1l 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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
THERMOCHEMISTRY/KINETICS
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 22.303 RT l og K
5 2n7E
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
m5 mass
8
m s
21
234
J s
223
J K
21
23
parti cl es mol
21
219
coul omb
21
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Practice Test 3 535
www.petersons.com
CONSTANTS
K
a
(weak aci d)
K
b
(weak base)
K
w
(water)
K
p
(gas pressure)
K
c
T 5 temperature
n 5 mol es
m5 mass
q 5 heat
C
p
P 5 pressure
V 5 vol ume
T 5 temperature
D 5 densi ty
m5 mass
v 5 vel oci ty
u
rms
M 5 mol ar mass
K
f
K
b
t 5 ti me (seconds)
21
K
21
5 0.0821 L atm mol
21
K
21
21
K
21
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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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www.petersons.com
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
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
OXIDATION-REDUCTION/ELECTROCHEMISTRY
Q 5
@C#
c
@D#
d
@A#
a
@B#
b
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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Practice Test 3 537
www.petersons.com
SECTION II
TO TAL TIM E95 M INUTES
Part A
TIM E55 M INUTES
YOU MAY USE YOUR CALCULATOR FOR PART A.
Directions: CLEARLY SHOW THE METHOD USED AND STEPS I NVOLVED I N
ARRI VI NG AT YOUR ANSWERS. I t i s to your advantage to do thi s because you may
earn parti al credi t i f you do and you wi l l recei ve l i ttl e or no credi t i f you do not. Attenti on
shoul d be pai d to si gni fi cant fi gures.
Answer questi on 1 bel ow. The Secti on I I wei ghti ng for thi s questi on i s 20 percent. Wri te
al l of your answers i n the space provi ded fol l owi ng each questi on.
1. I n water, propanoi c aci d, HC
3
H
5
O
2
, i s a weak aci d wi th an equi l i bri um constant, K
a
,
equal to 1.3 3 10
25
.
(a) Wri te the equi l i bri um expressi on, K
a
, for propanoi c aci d.
(b) Cal cul ate the pH of a 0.100 M sol uti on of propanoi c aci d.
(c) Cal cul ate the pH of a 0.100 M sol uti on of sodi um propanoate, NaC
3
H
5
O
2
.
(d) Cal cul ate the pH of a mi xture made by combi ni ng equal vol umes of 0.100 M
propanoi c aci d and 0.100 M sodi um propanoate.
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www.petersons.com
Directions: Answer questi ons 2 and 3. The Secti on I I wei ght for these questi ons i s
40 percent.
2. 2NO(g) 1 Cl
2
(g) 2NOCl (g)
Experi ment I ni ti al p
NO
(atm) I ni ti al p
Cl
2
(atm) I ni ti al Rate (atm s
21
)
1 0.50 0.50 5.0 3 10
23
2 1.00 1.00 4.0 3 10
22
3 0.50 1.00 1.0 3 10
22
4 0.75 1.25 ???
Use the rate data for the reacti on above to answer the fol l owi ng questi ons.
(a) Wri te the rate equati on based on the experi mental data.
(b) What i s the order of the reacti on for NO, Cl
2
, and overal l ? Justi fy each response.
(c) Cal cul ate the rate constant, k, for thi s reacti on.
(d) Determi ne the mi ssi ng i ni ti al rate i n experi ment 4.
3. An el ectrol yti c cel l contai ns mol ten ZnCl
2
. The zi nc chl ori de i s el ectrol yzed by
passi ng a current of 3.0 A through the cel l for a certai n l ength of ti me. Duri ng thi s
process, 24.5 g of Zn are deposi ted on the cathode.
(a) Wri te the chemi cal equati on for the reacti on at the cathode.
(b) Wri te the chemi cal equati on for the reacti on at the anode.
(c) How l ong does the process take?
(d) What wei ght of chl ori ne gas bubbl es are rel eased at the anode?
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Practice Test 3 539

www.petersons.com
Part B
TIM E40 M INUTES
YOU MAY NOT USE CALCULATORS WITH PART B.
Directions: Answer questi on 4 bel ow. The Secti on I I score wei ghti ng for thi s questi on
i s 10 percent.
4. Wri te the formul as to show the reactants and products for the three equati ons
wri tten bel ow. Assume that each reacti on occurs. Al so assume that al l sol uti ons are
aqueous unl ess otherwi se stated. I f substances are extensi vel y i oni zed i n sol uti on, be
sure to represent them as such. Omi t formul as for i ons or mol ecul es that are
unchanged duri ng the reacti on. Equati ons must be bal anced. Answer the questi on
regardi ng each reacti on.
(a) Sol i d potassi um chl orate i s heated i n the presence of manganese di oxi de as a
catal yst.
Questions: What i s the test for the gas produced i n thi s reacti on?
(b) A sol uti on of si l ver ni trate i s added to a sol uti on of potassi um chl ori de.
Question: What evi dence of a chemi cal change i s observed i n thi s reacti on? Be speci fi c.
(c) Sampl es of boron tri chl ori de gas and ammoni a gas are mi xed.
Question: Whi ch speci es acts as a Lewi s aci d i n thi s reacti on? Expl ai n.
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www.petersons.com
Directions: For the remai nder of the test, your responses wi l l be graded accordi ng to
thei r accuracy and rel evancy. Your responses shoul d be wel l organi zed and presented i n
a very cl ear, conci se manner. Bri ef, speci fi c answers are preferabl e to l onger, general
responses. You may use any exampl es or equati ons i f they are appropri ate.
Answer questi ons 5 and 6. The wei ghti ng of these two questi ons i n Secti on I I i s 30
percent (15 percent each).
5. You are to determi ne the mol ar mass of a vol ati l e l i qui d usi ng the vapor densi ty
method. Assume you have the fol l owi ng equi pment avai l abl e to you:
Hot water bath Accurate bal ance Thermometer
Barometer Al umi num foi l Strai ght pi n
Unknown l i qui d 125 mL Erl enmeyer fl ask Cl amp
Ri ng stand Graduated cyl i nder
(a) Descri be the procedures you woul d use to set up the equi pment and perform the
experi ment.
(b) Li st the measurements you woul d need to take.
(c) Show the setup of the cal cul ati on of the mol ecul ar mass (not necessary to
cal cul ate).
(d) Descri be the effects on the cal cul ated mol ecul ar mass i f the l i qui d was not
compl etel y vapori zed.
(e) Show the setup for the cal cul ati on of the percent error i f your resul ts were 130 g/mol
and the accepted val ue was 125.5 g/mol .
6. Expl ai n each of the fol l owi ng observati ons usi ng pri nci pl es of atomi c structure
and/or bondi ng.
(a) Rubi di um has a l ower 1
st
i oni zati on energy than sodi um.
(b) The i oni c radi us of P i s l arger than S.
(c) Magnesi um atoms (atomi c number 12) are l arger than chl ori ne atoms (atomi c
number 17).
(d) There i s a l arge i ncrease between the 2
nd
and 3
rd
i oni zati on energi es of magnesi um.
S T O P
End of Secti on I I . I f you have any ti me l eft, go over your work i n thi s
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Practice Test 3 541
www.petersons.com
Section I
1. C
2. A
3. B
4. D
5. E
6. C
7. B
8. A
9. E
10. D
11. A
12. A
13. A
14. D
15. C
16. C
17. C
18. E
19. D
20. E
21. A
22. B
23. C
24. C
25. A
26. C
27. B
28. C
29. A
30. E
31. A
32. E
33. E
34. D
35. C
36. B
37. D
38. E
39. E
40. B
41. E
42. C
43. A
44. D
45. A
46. B
47. E
48. E
49. C
50. B
51. E
52. B
53. E
54. C
55. D
56. B
57. D
58. E
59. B
60. A
61. B
62. A
63. D
64. D
65. B
66. C
67. C
68. D
69. D
70. A
71. D
72. B
73. A
74. A
75. C
1. The correct answer is (C). Paramagneti sm can be seen i n atoms wi th unpai red
el ectrons. Hunds rul e al l ows us to predi ct the pai ri ng of el ectrons i n atomi c orbi tal s,
and, therefore, the magneti c properti es of the atom.
2. The correct answer is (A). Thi s statement i s pretty much a paraphrase of
Hei senbergs pri nci pl e, whi ch eventual l y l ed to the quantum model of the atom, based
on probabi l i ti es of fi ndi ng el ectrons i n certai n regi ons.
3. The correct answer is (B). The Schrdi nger equati on al l ows us to narrow down the
pl aces most l i kel y to fi nd el ectrons i n an atom. These l ocati ons are a vari ety of orbi tal s.
4. The correct answer is (D). BF
3
, wi th i ts i ncompl ete octet, i s capabl e of accepti ng a
pai r of el ectrons from F
2
to form a coval ent bond. El ectron pai r acceptors are Lewi s
aci ds.
5. Thecorrect answer is (E). CN
2
i s donati ng a pai r of el ectrons i n the formati on of the
compl ex i on. El ectron pai r donors are Lewi s bases.
6. Thecorrect answer is(C). H
2
O accepts a proton from HC
2
H
3
O
2
. Proton acceptors are
Brnsted-Lowry bases. Water can act as a Brnsted-Lowry aci d or base, but i n thi s
reacti on i t i s a base.
7. The correct answer is (B). El ectronegati vi ty i s the measure of the strength of the
attracti on an atom has for the el ectrons of another atom i n a chemi cal bond. Atoms wi th
the hi ghest el ectronegati vi ti es are those wi th the l argest effecti ve nucl ear charge and
the smal l est amount of shi el di ng. Whi l e neon seems to match thi s descri pti on, i t i s
unabl e to form chemi cal bonds and therefore has no el ectronegati vi ty. The hal ogen
chl ori ne i s the next best candi date.
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www.petersons.com
8. The correct answer is (A). Thi s i s one of those you ei ther know i t, or you dont
questi ons. I f you stop to thi nk of the vari ety of mol ecul es ni trogen forms even wi th
oxygen, i t shoul d be apparent that no other mol ecul e i n the l i st has such a l arge vari ety
of oxi dati on states.
9. Thecorrect answer is (E). I oni zati on energy, the energy requi red to remove an outer
el ectron from an atom, vari es much the same as el ectronegati vi ty. As the amount of
shi el di ng i ncreases, the i oni zati on energy decreases (the shi el di ng weakens the
attracti on between the nucl eus and the outermost el ectrons). As the effecti ve nucl ear
charge i ncreases, the i oni zati on energy i ncreases (hi gher effecti ve nucl ear charge
means a stronger attracti on between the nucl eus and the el ectrons). Therefore, the
el ements wi th the smal l est i oni zati on energi es wi l l be those wi th the most shi el di ng
and the smal l est effecti ve nucl ear charges. Rubi di um, a group 1A el ement i n peri od 5 i s
the most sui tabl e candi date among the other choi ces.
10. Thecorrect answer is (D). I n thi s probl em, you know that i n the fi nal sol uti on, there
are 2.5 mol es of HCl present i n the 1.00 L of sol uti on. That means that there must have
al ways been 2.5 mol es of HCl present. To determi ne the vol ume of 6.0 M HCl that woul d
contai n 2.5 mol HCl , we need to use the mol ari ty equati on:
M 5
mol es sol ute
Li ters sol n
6.0 M 5
2.5 mol HCI
Li ters sol n
To sol ve for the vol ume, we can use the equati on:
V 5
2.5 mol
6.0 M
Sol vi ng for V, we obtai n 0.417 L. I n mi l l i l i ters thi s i s cl osest to 420 mL.
11. The correct answer is (A). Thi s questi on i s checki ng your abi l i ty to determi ne the
presence and strengths of i ntermol ecul ar forces. Two of the choi ces are el ements(D)
and (E)whi ch onl y exert di spersi on forces. They wi l l have very l ow boi l i ng
temperatures. The next two(B) and (C)experi ence hydrogen bondi ng, whi ch wi l l
general l y produce hi gher boi l i ng temperatures than di spersi on forces. Fi nal l y, the
correct choi ce, (A), i s an i oni c compound. I oni c bonds are much stronger than any of the
i ntermol ecul ar forces, so Na
2
S wi l l have the hi ghest mel ti ng/boi l i ng poi nt.
a
n
s
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Practice Test 3 543
www.petersons.com
12. The correct answer is (A). The mi ni mum amount of hydroxi de i on that must be
present to cause the preci pi tati on of Al (OH)
3
can be cal cul ated from the equi l i bri um
expressi on:
K
sp
5 2.0 3 10
232
5 [Al
31
][OH
2
]
3
5 (0.2)(x)
3
x
3
5
2.0 3 10
232
0.2
5 1.0 3 10
231
x 5 =
3
1.0 310
231
At thi s poi nt, you know that [OH
2
] 5 =
3
1.0 3 10
231
. I n order to cal cul ate the pH, you
need to determi ne the [H
1
], whi ch i s done wi th the cal cul ati on:
[H
1
]
21 3 10
214
[OH
2
]
5
S
21 3 10
214
=
3
1.0 3 10
231
D
Because pH 5 2l og [H
1
], we can say that the pH at whi ch preci pi tati on wi l l begi n i s:
pH 5 2l og
S
21 3 10
214
=
3
1.0 3 10
231
D
13. Thecorrect answer is(A). I sotopes of an el ement must have the same atomi c number
(number of protons), but a di fferent mass number (whi ch, for atoms wi th the same
atomi c number, means they have a di fferent number of neutrons). The onl y pai r that
has the same number of protons but di fferent numbers of neutrons i s choi ce (A).
14. Thecorrect answer is(D). Both substances are i oni c sol i ds. The di fference i n mel ti ng
poi nts wi l l be due to the di fferences i n l atti ce energi es. The total number of charges i n
the atom affects l atti ce energi es. Si nce choi ces I and I I both deal wi th these di fferences,
they are the correct expl anati ons. I I I descri bes i oni c radi us, whi ch does not determi ne
the l atti ce energy.
15. The correct answer is (C). The general trend for oxoaci ds i s that the greater the
number of oxygen atoms, the greater the strength of the aci d.
16. Thecorrect answer is (C). 87.5 percent decomposed i s the same thi ng as sayi ng that
stronti um290 has undergone three hal f-l i ves (50 percent decomposes i n the fi rst; hal f of
that, or 25 percent i n the second, and hal f of that agai n, 12.5 percent decomposes i n the
thi rd). Once that has been determi ned, the probl em can be sol ved by mul ti pl yi ng the
hal f-l i fe by the number of hal f-l i ves:
28 years
1 hal f-l i fe
3 3 hal f-l i ves 5 84 years
17. Thecorrect answer is (C). A posi ti ve val ue of S represents an i ncrease i n entropy. I n
choi ce (C), the number of mol es of gas parti cl es i ncreases from 2 mol to 3 mol , an overal l
i ncrease. Thi s wi l l create more di sorder, and hence an i ncrease i n entropy.
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www.petersons.com
18. Thecorrect answer is(E). There are two ways to approach thi s. The fi rst i s to si mpl y
have memori zed that when 6 el ectron pai rs are found around a central atom, the
hybri di zati on has to be d
2
sp
3
. The other way i s to consi der the orbi tal di agram of sul fur:
Unhybri di zed S atom

1s 2s 2p 3s 3p 3d
Hybri di zed S atom

1s 2s 2p

sp
3
d
2
3d
The sul fur atom, because i t has empty d orbi tal s, can promote one 3p and one 3s
el ectron to yi el d the 6 sp
3
d
2
(d
2
sp
3
) hybri di zed orbi tal s.
19. The correct answer is (D). Oxi di zi ng agents are substances that are capabl e of
oxi di zi ng other substances. Oxi dati on i s the l oss of el ectrons, whi ch means that an
oxi di zi ng agent takes el ectrons away from other atoms. Onl y el emental i odi ne, I
2
, acts
as an oxi di zi ng agent (I
2
1 2e
2
2I
2
).
20. Thecorrect answer is(E). Vapor pressure i s measured when the rates of evaporati on
and condensati on are i n equi l i bri um.
21. The correct answer is (A). The reacti on i s exothermi c, whi ch means that a decrease
i n temperature wi l l cause a shi ft to the ri ght. The ri ght si de of the equati on al so has
more mol es of gas parti cl es than the l eft si de. Thi s means that i n l ow-pressure
si tuati ons, the reacti on wi l l shi ft to the ri ght. Therefore, under l ow temperature and
pressure condi ti ons, the reacti on wi l l shi ft to the ri ght, rai si ng the val ue of K
eq
.
22. The correct answer is (B). The CO
3
22
i on wi l l form an equi l i bri um wi th H
1
as
shown bel ow:
CO
3
22
1 H
1
HCO
3
2
Usi ng Le Chtel i ers Pri nci pl e, we know that i f we remove CO
3
22
(by formi ng HCO
3
2
),
we wi l l dri ve the sol ubi l i ty equi l i bri um of CaCO
3
to the ri ght:
CaCO
3
Ca
21
1 CO
3
22
23. Thecorrect answer is (C). Conjugate aci d-base pai rs must be rel ated by the l oss and
subsequent gai n of a proton. Choi ce (C) i s the onl y choi ce i n whi ch the l oss of a si ngl e
proton yi el ds that conjugate.
24. Thecorrect answer is (C). Atomi c radi us decreases movi ng from l eft to ri ght across a
peri od, and i ncreases movi ng top to bottom down a group. Fl uori ne i s above chl ori ne, so
i t must be smal l er than chl ori ne. Chl ori ne i s to the ri ght of sul fur, meani ng that i t must
be smal l er than sul fur. Therefore, fl uori ne i s the smal l est atom, fol l owed by chl ori ne,
whi ch i s l arger, and sul fur, whi ch i s the l argest.
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Practice Test 3 545
www.petersons.com
25. Thecorrect answer is (A). I n thi s probl em, you wi l l be compari ng Q to K
c
. From your
compari son, you wi l l determi ne the di recti on of the reacti on. The cal cul ati on of Q wi l l
proceed as fol l ows:
Q 5
@NH
3
#
2
@H
2
#
3
@N
2
#
5
~2.00 M NH
3
!
2
~2.00 M H
2
!
3
~1.00 M N
2
!
5
4.00
8.00
5 0.5
The val ue of Q i s greater than K
c
, i ndi cati ng that there i s too much product at thi s
stage. To achi eve equi l i bri um (where K
c
5 0.105), the reacti on wi l l have to proceed
toward the l eft.
26. The correct answer is (C). Thi s i s a combi ned gas l aw probl em i nvol vi ng pressure,
vol ume, and temperature. One very i mportant thi ng to remember i s that i n al l gas l aw
probl ems, the temperature must be the absol ute temperature. Once that i s establ i shed,
the equati on must be set up to sol ve for the fi nal pressure:
I sol ati ng P
2
, you end up wi th the equati on:
27. The correct answer is (B). You must start thi s probl em by setti ng up the equati on
for K
a
:
K
a
5
I n order to sol ve for K
a
, we cant have any unknowns on the ri ght si de of the equati on.
Careful i nspecti on l ets us know that we dont. We know the pH of the sol uti on, whi ch
means that we know the hydrogen i on concentrati on. I n addi ti on, because i t i s a
monoproti c aci d, we know that the concentrati on of A
2
wi l l be equal to the hydrogen i on
concentrati on. We are gi ven the i ni ti al concentrati on of HA so we can use that to hel p
sol ve the probl em:
HA H
1
A
2
Start 0.10 0 0
D 2x 1x 1x
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www.petersons.com
Before substi tuti ng any numbers i nto the K
a
equati on, we can determi ne the hydrogen
i on concentrati on:
x 5 [H
1
] 5 10
2pH
5 10
24
Si nce [H
1
] 5 [A
2
] and assumi ng x i s smal l :
K
a
5
[H
1
][A
2
]
[HA]
5
~1 3 10
24
! ~1 3 10
24
0.10
5 1.0 3 10
27
28. The correct answer is (C). The superscri pt number next to the concentrati on of NO
([NO]
2
) i ndi cates the order of the reacti on. Si nce the superscri pt i s a 2, thi s i ndi cates
that the order wi th respect to NO i s second.
29. Thecorrect answer is (A). When you see two masses i n a stoi chi ometry probl em, you
shoul d be al erted that you are deal i ng wi th a l i mi ti ng reactant probl em. Thi s probl em
wi l l have two stagesthe fi rst i s to determi ne the l i mi ti ng reactant, and the second to
determi ne the mass of the hydrogen gas. Before we do anythi ng, we need to see the
bal anced equati on for the reacti on:
Mg(s) 1 2H
2
O(l) Mg(OH)
2
(aq) 1 H
2
(g)
Wi th thi s establ i shed, we can begi n to determi ne whi ch reactant i s the l i mi ti ng
reactant:
4.73 g Mg 3
1 mol Mg
24.30 g Mg
5 0.195 mol Mg
1.83 g H
2
O 3
1 mol H
2
O
18.02 g H
2
O
5 0.102 mol H
2
O
From the bal anced equati on we can see that we need two mol es of H
2
O for every one
mol e of Mg. I n the present amounts the rati os are nearl y reverse (there i s nearl y twi ce
as much magnesi um). Thi s means that water i s the l i mi ti ng reactant. Because of thi s,
we can now sol ve the probl em usi ng the number of mol es of water present as a
starti ng poi nt:
~0.102 mol H
2
O!
S
1 mol H
2
2 mol H
2
O
DS
2.02 g H
3
1 mol H
2
D
5 0.103 g
30. The correct answer is (E). O i s far more el ectronegati ve than S. As a resul t, the
bonds i n H
2
O are far more pol ar than those i n H
2
S. Thi s greater pol ari ty al l ows for
greater hydrogen bondi ng i n water, and subsequentl y a hi gher boi l i ng temperature.
31. The correct answer is (A). Fi rst thi ng you need to do i s determi ne whi ch materi al i s
the cathode and whi ch i s the anode. Remember that the anode i s al ways the materi al
wi th more negati ve reducti on potenti al . I n thi s case, l ead i s the anode and copper i s the
cathode. Once thi s has been establ i shed, you can determi ne the reducti on potenti al of
the cel l usi ng the formul a:
E
cel l
5 E
cathode
2 E
anode
5 0.34 V 2 (20.13 V) 5 0.47 V
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Practice Test 3 547
www.petersons.com
32. The correct answer is (E). I n thi s questi on you are real l y just showi ng that you can
i nterpret the sol ubi l i ty product constant expressi on, K
sp
. Si nce the val ue of K
sp
i s the
product of the concentrati ons of the ani on and cati on i n sol uti on, smal l er val ues of K
sp
i ndi cate smal l er concentrati ons of di ssoci ated i ons. Thi s means that l ess of the sol i d has
di ssol ved. Sn(OH)
2
has, by far, the smal l est val ue for K
sp
, and i s therefore the
l east sol ubl e.
33. Thecorrect answer is(E). Wi th a doubl e bond between N and O, oxygen has an octet;
however, ni trogen onl y possesses seven el ectrons. The octet rul e cant be sati sfi ed
for NO.
34. The correct answer is (D). The fi rst thi ng to noti ce here i s that H
3
PO
4
i s a pol yproti c
aci d. Each mol e wi l l yi el d three mol es of H
1
i ons. I n 0.020 L of 0.10 M sol uti on, there are
2.0 310
23
mol es of H
3
PO
4
. After compl ete di ssoci ati on, thi s wi l l yi el d 6.0 310
23
mol es of
H
1
i ons. I n order to neutral i ze thi s much H
1
, you wi l l need
6.0 3 10
23
mol es
0.20 M
5 0.03 L KOH,
or 30 mL.
35. Thecorrect answer is (C). Beta decay occurs when a neutron breaks down to form a
proton and a beta parti cl e (el ectron). Thi s wi l l cause the atomi c number to i ncrease by
one, and the mass number remai ns constant. I n the fi rst beta decay, l ead214
becomes bi smuth214. The second beta decay converts bi smuth214 to pol oni um214,
as shown bel ow:
82
214
Pb
83
214
Bi 1
21
0
e
83
214
Bi
84
214
Po 1
21
0
e
36. The correct answer is (B). Thi s i s a grams to l i ters stoi chi ometri c conversi on. The
conversi on factor of 22.4 L per mol e of gas wi l l be used i n the fi nal porti on:
32.7 g Zn 3 5 11.2 L H
2
37. Thecorrect answer is (D). To sol ve thi s, fi rst we need to determi ne how many mol es
of el ectrons wi l l be requi red to reduce the 100.0 g of Ni . Once we know that, we can use
the current to determi ne the ti me:
100.0 g Ni 3 5 1.704 mol Ni
The next step i s to determi ne how many mol es of el ectrons wi l l be requi red and then
how many coul ombs of charge:
1.704 mol Ni 3
2 mol e
2
1 mol Ni
5 3.408 mol e
2
3.408 mol e
2
3
96 500 C
1 mol e
2
5 3.289 3 10
5
C
Because charge 5 current 3 ti me, we can rearrange the equati on to sol ve for ti me:
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www.petersons.com
3.289 3 10
5
C
5.00 A
5 6.578 3 10
4
s
6.578 3 10
4
s 3 5 18.3 hr
38. Thecorrect answer is (E). You need to consi der the answers to three questi ons whi l e
worki ng through thi s one. Fi rst of al l , i f an i ce cube si ts out at room temperature, i s
heat requi red to mel t i t? I f so, the process i s endothermi c (and DH wi l l be posi ti ve). The
second questi on: I s the water more di sordered than the i ce? I f so, the process i ncreases
the entropy (whi ch wi l l be posi ti ve). The fi nal questi on: I s the process spontaneous? I f
so, the free energy i s negati ve.
39. The correct answer is (E). I oni c radi i are a l i ttl e more di ffi cul t to judge than atomi c
radi i because they vary wi thi n a peri od. There are certai n trends that you can
remember, however. For cati ons (mostl y we l ook at groups 1A, and 2A, and someti mes
3A), the i oni c radi us decreases from l eft to ri ght i n a peri od, and i ncreases goi ng top to
bottom. The reason for the decrease i n si ze goi ng across a peri od i s that the atom l oses
al l of i ts outer el ectrons. Because the atoms have not l ost thei r protons, the effecti ve
nucl ear charge i s rather hi gh on the remai ni ng el ectrons. For ani ons, the reverse i s
true. As the atoms gai n el ectrons, the i ons become l arger than the neutral atom because
the addi ti onal el ectrons are bei ng attracted by the same number of protons as the
neutral atom. I n thi s questi on, three of the atoms are i n the same peri od, and the other
two are i n the same group. Br has been chosen because i t i s the farthest down the l i st.
40. The correct answer is (B). Esters have the characteri sti c R-COOR structure si mi l ar
to thi s one.
41. The correct answer is (E). You need to set up an equi l i bri um tabl e to sol ve thi s
probl em. Because the reacti on takes pl ace i n a 1.0 L vessel , you can assume that the
number of mol es and the mol ari ty are equi val ent:
PCl
5
PCl
3
Cl
2
Start 0.75 0 0
D 20.10 10.10 10.10
Fi ni sh 0.65 0.10 0.10
The decrease i n PCl
5
can be assumed to be the same as the i ncrease i n the other two
gases si nce the stoi chi ometri c rati os of each i s 1:1. Now that you have the val ues for the
concentrati on of each substance, you can sol ve for K
c
:
K
c
5
[PCl
3
] [Cl
2
]
[PCl
5
]
5
~0.10! ~0.10!
~0.65!
5 0.015
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Practice Test 3 549
www.petersons.com
42. The correct answer is (C). I n thi s probl em, you wi l l need to use the K
sp
equati on for
bari um carbonate, substi tuti ng the gi ven val ue for K
sp
as wel l as the concentrati on of
carbonate i on i n the sodi um carbonate sol uti on. By usi ng these two val ues, you can
sol ve for the unknown concentrati on of bari um i ons. Because bari um ni trate wi l l onl y
rel ease one mol e of bari um i ons per mol e of bari um ni trate, the requi red concentrati on
of bari um i ons wi l l equal the requi red concentrati on of bari um ni trate:
K
sp
5 5.1 3 10
29
5 [Ba
21
][CO
3
22
] 5 (x)(1 3 10
24
)
x 5
5.1 3 10
29
1 3 10
24
5 5.1 3 10
25
43. The correct answer is (A). I somers have the same mol ecul ar formul as. An i somer of
n-hexane woul d need to have a formul a C
6
H
14
. Wi thout even drawi ng the structures,
you shoul d be abl e to determi ne that no choi ce other than (A) has si x carbons. A cl oser
i nspecti on of choi ce (A) shoul d l et you know that the mol ecul e does i n fact al so have the
formul a C
6
H
14
.
44. The correct answer is (D). Sodi um chl ori de i s a typi cal exampl e of an i oni c
compound, gi vi ng i t several uni que characteri sti cs. The mel ti ng poi nt i s hi gh, due to the
very strong el ectrostati c attracti ons bi ndi ng the i ons i nto a ri gi d crystal l i ne l atti ce.
Because of the ri gi di ty of the crystal l i ne l atti ce, i oni c sal ts are hard. One thi ng that i s
not menti oned i n the probl em, but i s worth rememberi ng, i s that i oni c sal ts al so tend to
be bri ttl e because of the vari ous pl anes that exi st wi thi n the crystal l i ne l atti ce (the
crystal can break al ong these pl anes). Fi nal l y, i oni c sal ts are poor conductors of
el ectri ci ty because the el ectrons are l ocal i zed about i ndi vi dual atoms. I n sol uti on, or i n
a mol ten state, when i ndi vi dual i ons are free to move about, i oni c compounds make
good conductors.
45. The correct answer is (A). Thi s questi on i s a conceptual appl i cati on of the Nernst
Equati on. The Nernst equati on i s used to determi ne the i mpact of di fferences i n
concentrati on on cel l emf. The equati on takes the form:
E 5 E 2
0.0592
n
l og Q
The val ue of Q depends on the concentrati on of the substances i n the reacti on. For thi s
reacti on, Q wi l l be set up as:
Q 5
@Zn
21
#
@Cu
21
#
5
0.50 M
5.0 M
5 0.1
A l i ttl e qui ck remi nder about l ogari thms here: the l ogari thm of a number l ess than 1 i s
negati ve. Numbers greater than 1 are posi ti ve. Therefore, you shoul d be abl e to see that
as the concentrati on of the substance at the anode becomes l ess than the concentrati on
of the substance at the cathode, the val ue of Q wi l l decrease. When the val ue of the
concentrati on of the substance at the anode i s greater than the concentrati on of the
substance at the cathode, the val ue of Q wi l l i ncrease.
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I f you l ook at the effect thi s has on the overal l equati on, when the val ue of l og Q i s
negati ve, the val ue of
0.0592
n
l og Q wi l l be added to the cel l vol tage. I n other words, i t
i ncreases over standard condi ti ons. When the val ue of l og Q i s posi ti ve, the val ue of
0.0592
n
l og Q wi l l be subtracted from the cel l vol tage. I n other words, i t decreases over
standard condi ti ons.
I n summary, when the concentrati on of the substance at the anode i s greater than the
concentrati on at the cathode, the cel l emf decreases. When the val ue of the
concentrati on at the anode i s l ower than the concentrati on at the cathode, cel l emf
i ncreases.
46. The correct answer is (B). What you need to remember i n thi s probl em i s that the
sum of the parti al pressures i n a system wi l l equal the total pressure. I n addi ti on, you
need to remember that when you col l ect a gas over a l i qui d, you need to take i nto
account the vapor pressure of the l i qui d as part of the total pressure. Therefore, of the
300 mm Hg total pressure, 18 mm Hg of that i s due to the vapor pressure of water at
thi s temperature. That l eaves the remai nder from hydrogen.
47. The correct answer is (E). An i ncreased temperature wi l l cause an i ncrease i n the
numbers of parti cl es that possess enough ki neti c energy to escape from the l i qui d to the
gaseous phase. I ntermol ecul ar forces are al so a key determi nant as to how much energy
a parti cl e must have to be abl e to escape from the l i qui d to the gaseous phase. The
amount of l i qui d, however, i s not a determi ni ng factor i n vapor pressure, as the
numbers of parti cl es that change phase are goi ng to be proporti onal to the i ncrease i n
sampl e si ze.
48. Thecorrect answer is(E). We can set up an equi l i bri um tabl e to determi ne the mol ar
sol ubi l i ty of BaCO
3
. Keep i n mi nd that there are 0.1 mol Ba
21
i ons al ready i n sol uti on
from the BaCl
2
:
BaCO
3
Ba
21
CO
3
22
Start 0.1 0
D 1x 1x
Fi ni sh 0.1 1 x x
At thi s poi nt, we wi l l assume that the val ue of x i s si gni fi cantl y smal l er than the val ue
0.1, whi ch means the equi l i bri um expressi on wi l l be:
K
sp
5 [Ba
21
][CO
3
22
]
1.6 3 10
29
5 ~0.1!~x!
1.6 3 10
28
5 x
Our assumpti on about x i s correct, so we can keep thi s answer.
49. Thecorrect answer is (C). Wi th the excepti on of choi ce (C), al l of the substances can
ei ther donate a proton, or accept one. NH
4
1
can onl y l ose an el ectron. I t cannot gai n
one, so i t i s onl y a Brnsted-Lowry aci d.
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Practice Test 3 551
www.petersons.com
50. The correct answer is (B). N, P, As, and Sb are al l group 5 el ements that can form
three si ngl e bonds wi th fl uori ne to yi el d an octet. I odi ne, a group 8 el ement, accordi ng
to the octet rul e, shoul d onl y be abl e to combi ne wi th one fl uori ne atom. Combi ni ng wi th
3 i s a vi ol ati on of the octet rul e.
51. The correct answer is (E). You shoul d be very cl ear on the di fferences between
mol ari ty and mol al i ty. Mol al i ty i s the measure of the number of mol es of sol ute
di ssol ved per ki l ogram of sol vent. The mol ari ty i s a measure of the mol es of sol ute
di ssol ved i n a gi ven vol ume of sol uti on. I f you know that a gi ven sol uti on has a mol ari ty
of 1.00, then you know there i s 1.00 mol es of sol vent per l i ter of sol uti on. Knowi ng the
densi ty wi l l al l ow you to determi ne the mass of a sol uti on. I f the mass of the sol ute i s
subtracted from the mass of the sol uti on, the resul t wi l l be the mass of the sol vent,
whi ch i s requi red for the determi nati on of mol al i ty.
52. The correct answer is (B). One i mportant factor to remember (and one of the most
frequentl y forgotten) i s that mol ari ty i s the measure of the number of mol es of sol ute
per l i ter of sol uti on. That means that the total vol ume of the sol uti on must equal 5.00 L
i n thi s probl em. I n order to prepare a 0.1 mol ar sol uti on, you must have 0.10 mol es per
l i ter of sol uti on.
I n thi s probl em you must be careful of the total vol ume. The mol ari ty, 0.10 M, tel l s us
that we shoul d be usi ng 0.10 mol es of sol vent per l i ter of sol uti on. I n thi s probl em, there
are 5.00 L of sol uti on, so we wi l l need to use 5 3 0.10 mol to get the correct answer,
whi ch i s shown bel ow:
S
0.10 mol Pb~NO
3
!
2
1.00 L
DS
331 g Pb ~NO
3
!
2
1 mol Pb ~NO
3
!
2
D
~5.00 L! 5 165.5 g Pb~NO
3
!
2
I f you add 165.5 g Pb(NO
3
)
2
to a contai ner (such as a vol umetri c fl ask) and add enough
water to equal 5.00 L, you are maki ng a 0.1 M sol uti on.
53. The correct answer is (E). Thi s questi on i s checki ng your knowl edge of col l i gati ve
properti es, more speci fi cal l y boi l i ng poi nt el evati on. When a nonvol ati l e sol ute i s
di ssol ved i n a sol vent, the vapor pressure of the sol uti on decreases rel ati ve to the pure
sol vent. Thi s decrease i n vapor pressure causes a correspondi ng i ncrease i n the boi l i ng
temperature. The more sol ute parti cl es that are present i n the sol vent, the hi gher the
boi l i ng poi nt el evati on. I n thi s questi on, the sol ute parti cl es are al l i oni c compounds,
and the concentrati ons are al l the same. The di fference between each sal t i s the number
of i ons that each wi l l form upon di ssoci ati on. The correct choi ce, Na
2
SO
4
, di ssoci ates
i nto three i ons (two Na
1
and one SO
4
22
), whi ch i s the l argest amount of any choi ce.
54. The correct answer is (C). There are two di stracters i mbedded i n the probl em. The
probl em i s real l y a Charl ess l aw probl em; however, because the pressure i s gi ven, i t
appears l i ke a combi ned gas l aws probl em. Because the pressure remai ns constant, i t i s
not requi red i n the equati on. I n addi ti on, the temperature i s gi ven i n degrees Cel si us
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www.petersons.com
rather than Kel vi n. Once you have i denti fi ed the potenti al pi tfal l s, you shoul d be abl e to
sol ve thi s probl em rather easi l y usi ng the Charl ess l aw equati on:
V
1
T
1
5
V
2
T
2
2.00 L
350 K
5
4.00 L
xK
2.00x 5 1400
x 5 700 K
x 5 700 2 273 5 427C
55. The correct answer is (D). The sol uti on of thi s probl em requi res a few steps. Fi rst,
the rate determi ni ng step i s the second step i n the reacti on mechani sm, so the rate l aw
can be set up as:
Rate 5 k
2
[N
2
O
2
][H
2
]
However, N
2
O
2
i s a reacti on i ntermedi ate, whi ch i s not al l owed i n the rate l aw. I n order
to sol ve the probl em, we wi l l have to use the fi rst step i n the mechani sm and fi nd a
sui tabl e substi tuti on for N
2
O
2
. I n the fi rst step, whi ch i s an equi l i bri um step, the rates
of the forward and reverse reacti ons are i denti cal . Therefore, we can set up an
expressi on such that k
1
5 k
21
. I n thi s expressi on, we obtai n the fol l owi ng equal i ty:
k
1
[NO]
2
5 k
21
[N
2
O
2
]
I f we rearrange thi s to set i t equal to [N
2
O
2
], we wi l l then have a sui tabl e expressi on to
substi tute i nto the rate l aw:
[N
2
O
2
] 5 [NO]
2
The new rate l aw expressi on becomes:
Rate 5 k
2
[NO]
2
[H
2
]
I f you repl ace the expressi on k
2
wi th k, the experi mental rate constant, the rate
l aw i s:
Rate 5 k[NO]
2
[H
2
]
56. The correct answer is (B). There are two l evel s of i nterpretati on that you can make
here. The fi rst concerns onl y the defi ni ti on of boi l i ng poi nt, whi ch states that a l i qui d
wi l l boi l when the vapor pressure equal s the atmospheri c pressure. What thi s means i s
that a substance wi th a l ow vapor pressure wi l l have to be heated to a hi gher
temperature to make the vapor pressure equal the atmospheri c pressure. Materi al s
wi th hi gher vapor pressures wont need to be heated as much to boi l .
The second way to i nterpret thi s i s through the ori gi ns of vapor pressure. Substances
that evaporate easi l y (are vol ati l e) have weaker i ntermol ecul ar forces than those that
do not evaporate easi l y. Substances wi th hi gher vapor pressures are substances wi th
weaker i ntermol ecul ar forces. Thi s means that they wi l l al so have l ower boi l i ng
temperatures.
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Practice Test 3 553
www.petersons.com
57. The correct answer is (D). Thi s probl em uses the free energy equati on:
DG 5 DH 2 TDS
To sol ve thi s probl em, we need to rearrange the equati on to sol ve for DH:
DH 5 DG 1 TDS
When the gi ven i nformati on i s substi tuted i n the equati on, you obtai n:
DH 5 91.2 kJ 1 (298 K)(135 J) 5 131.4 kJ
58. Thecorrect answer is (E). I n the NaAsO
3
mol ecul e, you can determi ne the oxi dati on
number of As by fi rst determi ni ng the charges on the cati on and ani on. Si nce sodi um
al ways has a charge of 1
1
, that means the AsO
3
must have a 1
2
charge. Oxygen, wi th
a 2
2
charge, contri butes 3(2
2
), or 6
2
charge. I n order to have a total charge of 1
2
,
arseni c must have an oxi dati ve of
1
5. Thi s can be shown mathemati cal l y as:
21 5 3(22) 1 5
59. The correct answer is (B). The fi rst thi ng that must be done i s to cal cul ate the
mol ari ty of the sol uti on. Thi s i s accompl i shed usi ng the grams of sol ute per l i ter data:
292 g Mg~NO
3
!
2
3
1 mol Mg~NO
3
!
2
148.32 g Mb~NO
3
!
2
5 1.969 mol Mg~NO
3
!
2
Next, we can use the densi ty of the sol uti on to determi ne the overal l mass of the
sol uti on:
Mass of sol uti on 5 densi ty 3 vol ume
5 1.108 g/mL 3 1.00 L 3 1000 mL/L
5 1108 g
Usi ng thi s mass of the sol uti on, we can subtract the mass of the Mg(NO
3
)
2
to determi ne
the mass of the sol vent (water):
Mass of sol uti on 2 mass of sol ute 5 mass of sol vent
1108 g 2 292 g Mg(NO
3
)
2
5 816 g H
2
O
5 0.816 kg H
2
O (kg i s the uni t of mol al i ty)
Fi nal l y, we can cal cul ate the mol al i ty:
Mol al i ty 5
mol es of sol ute
kb of sol vent
5
1.969 mol Mg~N
3
!
2
0.816 kg H
2
O
5 2.41 m
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60. Thecorrect answer is (A). Li has been chosen because of the l arge jump between the
fi rst and second i oni zati on energi es. Thi s means that the fi rst el ectron was rel ati vel y
much easi er to remove than the second. Thi s pattern i s consi stent wi th el ements i n
group 1A si nce the second el ectron must be removed from a l ower energy l evel , whi ch
has both l ess shi el di ng and a hi gher effecti ve nucl ear charge than the fi rst el ectron di d.
61. Thecorrect answer is(B). Gases are most sol ubl e i n l i qui ds at l ow temperature. Thi s
i s unl i ke most sol i ds, whi ch become l ess sol ubl e at l ower temperatures. I n addi ti on,
hi gh external pressures i ncrease the sol ubi l i ty of gases i n l i qui ds. For sol i ds, pressure
has a negl i gi bl e effect.
62. Thecorrect answer is (A). The fi rst step i s to determi ne the number of mol es of each
substance present. From thi s we can determi ne the empi ri cal formul a, and l ater the
mol ecul ar formul a. When gi ven percentages, you can assume a 100 g sampl e, whi ch
al l ows you to di rectl y convert each percentage di rectl y to an amount i n grams. The
number of mol es of each substance can be cal cul ated as shown bel ow:
40.0 g C 3 5 3.33 mol C
6.71 g H 3 5 6.64 mol H
53.29 g O 3 5 3.33 mol O
The next step i s to di vi de each number by the smal l est number of mol es:
C 5 5 1
H 5 5 1.99 2
O 5 5 1
These can be used as subscri pts i n the empi ri cal formul a:
CH
2
O
The formul a wei ght of the empi ri cal formul a can then be compared to the mol ecul ar
wei ght to determi ne i f any adjustment wi l l be necessary. The formul a wei ght of the
empi ri cal formul a i s:
CH
2
O 5 (1 3 12.011 g) 1 (2 3 1.01 g) 1 (1 3 16.00) 5 30.03 g
Si nce the mol ecul ar wei ght i s 60.5 g, that means that each subscri pt must be mul ti pl i ed
by two i n order to obtai n the mol ecul ar formul a:
C
2
H
4
O
2
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Practice Test 3 555
www.petersons.com
63. Thecorrect answer is (D). Thi s i s a parti al pressure probl em. To sol ve i t, you need to
use two equati ons (both from Chapter 8):
X
A
5
n
A
n
t
and P
A
5 P
t
X
A
We can determi ne the mol e fracti on of NO
2
usi ng the fi rst equati on. Next, knowi ng the
total pressure, we can substi tute the mol e fracti on i nto the second equati on (al ong wi th
the total pressure) to sol ve for the parti al pressure of NO
2
:
X
A
5
n
A
n
t
5
4.5 mol
6.0 mol
5 0.75
P
NO
2
5 P
t
X
A
5 (8.00 atm)(0.75) 5 6.0 atm
64. The correct answer is (D). When cal cul ati ng the oxi dati on numbers, the total
numbers must add up to the charge of the speci es (whether i t i s an i on, mol ecul e, or
formul a uni t). I n thi s case, for the formul a:
Mn
2
O
7
The oxi dati on state of oxygen i s 22, whi ch gi ves a total of 214. I n order to bal ance thi s
wi th two manganese atoms, the oxi dati on state on each must be 17.
65. The correct answer is (B). Thi s i s a mol e-to-mol e conversi on. I f you have a bal anced
equati on to start, you can sol ve these i n your head. The mol e rati os from the bal anced
equati on al l ow you to qui ckl y convert between mol es of substances. The rati o of Cl
2
to
Si Cl
4
i s 2 to 1. That means you wi l l produce onl y hal f as many mol es of Si Cl
4
, or 1.92
mol . You can al so sol ve the probl em usi ng a formul a, as shown bel ow:
3.84 mol Cl
2
3 5 1.92 mol Si Cl
4
66. Thecorrect answer is(C). The reacti on i s zero order for CO. You can tel l thi s because
the rate l aw does not contai n any i nformati on about i t. As a resul t, the rate of the
reacti on i s unaffected by the concentrati on of CO, provi ded that some i s present.
67. The correct answer is (C). An i mportant thi ng to remember about catal ysts i s that
they do not affect the equi l i bri um of a system. They affect onl y the rates at whi ch
equi l i bri um i s attai ned.
68. The correct answer is (D). A square pl anar confi gurati on i s achi eved when an atom
has si x el ectron pai rs, four of whi ch are bondi ng pai rs, and two of whi ch are l one pai rs.
Because Xe i s a nobl e gas, i t can form four si ngl e bonds whi l e sti l l mai ntai ni ng two l one
pai rs of el ectrons.
69. Thecorrect answer is (D). Effecti ve buffers consi st of weak aci ds and thei r conjugate
bases. Thi s pai ri ng consi sts of the weak aci d HCO
3
2
, and i ts conjugate, CO
3
22
.
70. Thecorrect answer is (A). Thi s probl em uses the equati on for speci fi c heat capaci ty:
q 5 mC
p
DT
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The l ogi c i s that the heat l ost by the metal as i t i s cool i ng i s transferred to the water.
Thi s heat transfer causes an i ncrease i n the waters temperature. Because the heat l ost
by the metal i s the same as the heat gai ned by the water, two equati ons can be set up
and made equal to one another. Thi s wi l l al l ow us to sol ve for the unknown, the speci fi c
heat of the metal .
For water:
q 5 mC
p
DT 5 (100.0 g)(4.18 J/gC)(5C) 5 2090 J
Thi s i s the same amount of heat l ost by the metal . Whi l e i t i s techni cal l y correct to
assi gn the metal a negati ve si gn (whi ch woul d come as a resul t of the decrease i n
temperature, and the subsequent negati ve val ue for q), the si gn has no i mpact on the
fi nal answer so we wi l l use posi ti ve val ues.
For the metal :
q 5 mC
p
DT
C
p
5
q
mDT
5
2090 J
~100.0 g!~70C!
5 0.30 J/gC
71. The correct answer is (D). The bal anced equati on i s shown bel ow:
4NH
3
(g) 1 5O
2
(g) 4NO(g) 1 6H
2
O
72. The correct answer is (B). The change from 200 K to 400 K shoul d stand out to you
as a doubl i ng of the absol ute temperature. Of al l the choi ces that are l i sted, pressure i s
the onl y one that i s di rectl y rel ated to temperature (i .e., when temperature doubl es,
pressure doubl es). The most tempti ng di stracter i s probabl y choi ce (C). Whi l e vel oci ty
does i ncrease wi th i ncreased temperature, you may remember from Chapter 8 that i t
does so accordi ng to the equati on:
u
rms
5
3RT
M
73. Thecorrect answer is (A). The best strategy to sol ve probl ems l i ke thi s i s to l ook for
patterns i n the experi mental data, parti cul arl y where the concentrati on of one reactant
remai ns constant whi l e the other changes. I n thi s reacti on, compari ng experi ments 1
and 2 doesnt provi de a cl ear pi cture of the rate l aw. The concentrati on of A and B each
doubl e, whi l e the i ni ti al rate i ncreases by four ti mes. Nothi ng cl ear can be concl uded
here, so check another.
Looki ng at experi ments 2 and 3, we see a cri ti cal pi ece of the puzzl e. The concentrati on
of A doubl es whi l e B remai ns constant, and the i ni ti al rate al so remai ns constant. Thi s
means that the reacti on order for A i s zero.
Goi ng back to the data from experi ments 1 and 2, we can now see that i f the reacti on i s
zero order for A, then i t must be second order for B (to account for the fourfol d i ncrease
i n the i ni ti al rate). We can confi rm thi s by compari ng experi ments 1 and 4. I n these
experi ments, the concentrati on of B tri pl es (we dont need to worry about what A i s
doi ng si nce i t i s zero order), and the i ni ti al rate i ncrease 3
2
ti mes, or 9 ti mes. The rate
l aw must be Rate 5 k[B]
2
.
a
n
s
w
e
r
s
p
r
a
c
t
i
c
e
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e
s
t
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Practice Test 3 557
www.petersons.com
74. Thecorrect answer is(A). Thi s i s a mass-to-mass stoi chi ometri c conversi on. The fi rst
step i n sol vi ng the probl em i s to determi ne the bal anced equati on for the reacti on. Thi s
wi l l be necessary to determi ne the mol e rati os i n the conversi on. The bal anced
equati on i s:
3Mg(s) 1 N
2
(g) Mg
3
N
2
(s)
At thi s poi nt, you can set up the conversi on from grams of Mg to grams of Mg
3
N
2
:
1.22 g Mg 3
S
1 mol Mg
24.30 g Mg
DS
1 mol Mg
3
N
2
3 mol Mg
D
3
S
100.92 g Mg
3
N
2
1 mol Mg
3
N
2
D
5 1.69 g
75. Thecorrect answer is (C). The fi rst thi ng to consi der i s the free energy. Reacti ons for
whi ch DG i s negati ve wi l l proceed spontaneousl y. Thi s rul es out three of the fi ve
choi ces. To determi ne the correct answer you need to use the rel ati onshi p:
DG 5 2RT l n K or DG 5 22.303 RT l og K
For thi s step, you need to recal l that when K i s greater than 1, l og K (or l n K) i s posi ti ve,
and therefore DG i s negati ve. When K i s l ess than 1, l og K (l n K) i s negati ve, and DG
i s posi ti ve. So, when K i s greater than 1 (and therefore DG i s negati ve), the reacti on
wi l l be spontaneous.
Section II
1. (a) Propanoi c aci d wi l l di ssoci ate and establ i sh the fol l owi ng equi l i bri um:
HC
3
H
5
O
2
H
1
1 C
3
H
5
O
2
2
The equi l i bri um constant expressi on, therefore, wi l l be:
K
a
5
[H
1
] [C
3
H
5
O
2
2
]
[HC
3
H
5
O
2
]
(b) To cal cul ate the pH, we need to determi ne the concentrati on of hydrogen i ons i n
the expressi on for K
a
i n part (a). We wi l l need to set up an equi l i bri um tabl e to
do thi s (assume x i s smal l ):
HC
3
H
5
O
2
H
1
C
3
H
5
O
2
2
Start 0.10 0 0
D 2x 1x 1x
K
a
5 1.3 3 10
25
5
[H
1
] [C
3
H
5
O
2
2
]
[HC
3
H
5
O
2
]
5
~x! ~x!
~0.10 2 x!
5
x
2
0.10
Rearrangi ng to sol ve for x we obtai n:
x 5 =1.3 3 10
26
5 1.1 3 10
23
M
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www.petersons.com
Si nce x i s equal to [H
1
]:
[H
1
] 5 x 5 1.1 3 10
23
M
Fi nal l y, we can sol ve for pH, usi ng the [H
1
]:
pH 5 2l og [H
1
] 5 2l og (1.1 3 10
23
) 5 2.96
(c) To sol ve thi s probl em requi res a few steps. Fi rst, you need to deci de whether the
sal t wi l l be aci di c or basi c i n sol uti on. Si nce i t i s the sal t of a strong base and a
weak aci d, i t wi l l be basi c i n sol uti on. The propanoate i on ~C
3
H
5
O
2
2
! wi l l
hydrol yze to yi el d HC
3
H
5
O
2
and OH2. Therefore, i t wi l l be basi c i n sol uti on.
Thus, i n order to cal cul ate the pH, we wi l l need to sol ve the equi l i bri um
expressi on for K
b
and use thi s val ue to cal cul ate the pH. The reacti on that wi l l
determi ne the pH i s:
C
3
H
5
O
2
2
1 H
2
O HC
3
H
5
O
2
1 OH
2
To sol ve for OH
2
(whi ch wi l l al l ow us to cal cul ate the pH), we need to establ i sh a
val ue for K
b
. Thi s can be done as shown bel ow:
K
b
5
K
w
K
a
5
1.0 3 10
214
1.3 3 10
25
5 7.7 3 10
210
Wi th thi s establ i shed, we can set up an equi l i bri um tabl e to cal cul ate the [OH
2
]:
C
3
H
5
O
2
2
HC
3
H
5
O
2
OH2
Start 0.10 0 0
D 2x 1x 1x
The next step i s to cal cul ate K
b
. Thi s wi l l al l ow us to determi ne the [OH
2
], whi ch
wi l l al l ow us to cal cul ate the pH:
K
b
5 7.7 3 10
210
5
[HC
3
H
5
O
2
] [OH
2
]
[C
3
H
5
O
2
2
]
5
~x! ~x!
~0.10 2 x!
Agai n, we wi l l assume that x i s si gni fi cantl y smal l er than 0.10. Therefore:
x
2
0.10
5 7.7 3 10
210
Sol vi ng for x, we obtai n:
x 5 =7.7 3 10
211
5 8.77 3 10
26
Therefore, [OH2] 5 x 5 8.77 3 10
26
M
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Practice Test 3 559
www.petersons.com
To cal cul ate the pH, there are a few di fferent strategi es we can use. We wi l l use
the techni que of determi ni ng the [H
1
] from the [OH
2
], and then use the normal
pH equati on:
@H
1
# 5
1.0 3 10
214
@OH
2
#
5
1.0 3 10
214
8.77 3 10
26
5 1.14 3 10
29
pH 5 2l og [H
1
] 5 2l og (1.14 3 10
29
) 5 8.94
(d) Thi s probl em wi l l be si mi l ar to part (a) except thi s ti me, you wi l l be starti ng wi th
an amount of propanoate i on. The fi rst thi ng to do i s to set up an equi l i bri um tabl e:
HC
3
H
5
O
2
H
1
C
3
H
5
O
2
2
Start 0.100 0 0.100
D 2x 1x 1x
Fi ni sh 0.100 2 x x 0.100 1 x
We can use the val ue and equati on for K
a
that was gi ven i n part (a):
K
a
5 1.3 3 10
25
5
[H
+
] [C
3
H
5
O
2
2
]
[HC
3
H
5
O
2
]
5
~x! ~0.100 1 x!
~0.100 2 x!
At thi s poi nt, we must make the assumpti on that x i s much l ess than 0.100.
Doi ng so al l ows us to rewri te the equati on as:
1.3 3 10
25
5
~x! ~0.100!
~0.100!
Sol vi ng for x, we obtai n:
x 5 [H
1
] 5 1.3 3 10
25
M
Fi nal l y, we can use the [H
1
] to sol ve for pH:
pH 5 2l og [H
1
] 5 2l og (1.3 3 10
25
) 5 4.89
2. (a) and (b) Rate 5 k(p
NO
)
2
(p
Cl
2
)
Looki ng at the data, the di fferences between experi ments 1 and 2 are not
suffi ci ent enough to make a judgment about the order si nce the parti al pressures
of each gas changes. However, from experi ments 1 and 3, the pressure of Cl
2
doubl es, whi l e the pressure of NO remai ns constant. Thi s doubl i ng of pressure
causes a doubl i ng of the rate, i ndi cati ng that the reacti on i s fi rst order for Cl
2
.
Compari son of experi ments 2 and 3 show that the concentrati on of NO decreases
by one hal f, whi l e the pressure of NO doubl es (from experi ment 3 to experi ment
2), the i ni ti al rate i ncrease by four ti mes. Thi s i ndi cates that the reacti on i s
second order for NO.
As a check, a compari son of experi ments 1 and 2 where each NO and Cl
2
doubl e
shoul d produce an ei ghtfol d i ncrease i n the i ni ti al rate, whi ch i t does.
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www.petersons.com
(c) To cal cul ate k, you just need to substi tute data i nto the rate l aw. I t doesnt matter
whi ch of the three experi ments you pi ck, they wi l l al l come out the same:
Rate 5 k(p
NO
)
2
(p
Cl
2
)
k 5
Rate
~ p
NO
!
2
~ p
Cl
2
!
5
5.0 3 10
23
atm s
21
~0.50 atm!
2
~0.50 atm!
5 4.0 3 10
22
atm
22
s
21
(d) Equi pped wi th the rate constant k from part (c), we can cal cul ate the mi ssi ng
rate i n experi ment 4:
Rate 5 k~ p
NO
!
2
~ p
Cl
2
!
5 ~4.0 3 10
22
atm
22
s
21
! ~0.75 atm!
2
~1.25 atm!
5 2.8 3 10
22
atm s
21
3. (a) At the anode, chl ori de i ons are oxi di zed to become chl ori ne gas, Cl
2
. Thi s wi l l
proceed accordi ng to the hal f-reacti on:
2Cl
2
Cl
2
(g) 1 2e
2
(b) At the cathode, zi nc i ons wi l l be reduced to zi nc metal :
Zn
21
1 2e
2
Zn(s)
(c) To determi ne the ti me requi red for the reacti on, you need to consi der the amount
of zi nc deposi ted at the cathode and the amount of current passed through the
cel l . From the amount of zi nc deposi ted, you can determi ne how many mol es of
el ectrons wi l l be requi red to al l ow thi s reducti on. You can then determi ne how
much current wi l l have to pass through the cel l to produce thi s many el ectrons:
24.5 g Zn 3
1 mol Zn
65.39 g Zn
5 0.3747 mol Zn
Because each zi nc i on requi res 2e
2
, the number of el ectrons requi red by the zi nc
wi l l be:
0.3747 mol Zn 3
2 mol e
2
1 mol Zn
5 0.7494 mol e
2
Usi ng Faradays constant, we can determi ne that the number of Coul ombs
requi red wi l l be:
0.7494 mol e
2
3
96,500 C
1 mol e
2
5 72,317 C
To determi ne how l ong a current of 3.0 A wi l l have to be appl i ed to produce thi s
amount of charge, you need to use the equati on:
Charge 5 current 3 ti me
The uni ts of whi ch are:
Coul ombs 5 Amps 3 second
Thi s can be rearranged to sol ve for the ti me:
Coul ombs
Amps
5 seconds
a
n
s
w
e
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s
p
r
a
c
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i
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e
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s
t
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Practice Test 3 561
www.petersons.com
Substi tuti ng our data, we obtai n:
72,317 C
3.0 A
5 24,106 seconds, or 402 mi nutes, or 6.7 hours.
(d) The amount of chl ori ne l i berated at the anode i s sol ved i n the same way, but the
reverse di recti on. The fi rst steps of the probl em can be ski pped because we
al ready know how l ong the current i s appl i ed, how much charge i s produced
duri ng thi s ti me, and how many el ectrons wi l l be avai l abl e at the anode for
oxi di zi ng the chl ori de i ons. We can pi ck up the probl em at that poi nt:
0.7494 mol e
2
3
1 mol Cl
2
2 mol e
2
5 0.3747 mol Cl
2
Thi s can now be converted to grams:
0.3747 mol Cl
2
3
70.91 g
1 mol Cl
2
5 26.57 g Cl
2
4. (a) 2KCl O
3
MnO
2
2KCl 1 3O
2
Thi s decomposi ti on of potassi um chl orate i s a fai rl y common way to generate
oxygen gas i n the l aboratory. The catal yst, wri tten above the arrow, greatl y
faci l i tates thi s process.
Answer: Pl ace a gl owi ng spl i nt i nto the reacti on vessel , and the spl i nt shoul d
burst i nto fl ame.
(b) Ag
1
1 Cl
2
AgCl
Thi s i s a metathesi s reacti on where the reacti on i s dri ven by the formati on of the
i nsol ubl e sal t, si l ver chl ori de.
Answer: A whi te preci pi tate of si l ver chl ori de i s formed.
(c) BCl
3
1 NH
3
Cl
3
BNH
3
One thi ng to l ook out for whenever you see ammoni a i s i ts behavi or as a Lewi s
base and i ts abi l i ty to form compl exes. I n thi s probl em, you are al so gi ven boron
tri chl ori de, whi ch i s frequentl y ci ted as bei ng an exampl e of a mol ecul e where the
central atom has an i ncompl ete octet. Al though boron tri chl ori de i s stabl e, i t
readi l y reacts wi th ammoni a.
Answer: BCl
3
acts as a Lewi s aci d i n the reacti on, because i t accepts the
non-bonded pai r of el ectrons of the ni trogen atom i n NH
3
.
5. (a) Your procedures may vary somewhat, but they shoul d be si mi l ar to those l i sted here.
Start heati ng the water bath so i t wi l l be hot when needed.
Ti ghtl y cover the mouth of the Erl enmeyer fl ask wi th a smal l square pi ece of
al umi num foi l .
Poke a smal l hol e i n the mouth of the fl ask wi th the strai ght pi n.
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www.petersons.com
Wei gh the empty fl ask (wi th the foi l on i t).
Remove the cap and pl ace a 2-mL sampl e of the unknown l i qui d i nto the fl ask
and repl ace the foi l .
Usi ng the cl amp and ri ng stand; i mmerse the fl ask i nto the water bath and heat.
When no more l i qui d i s vi si bl e and no more condensate can be seen l eavi ng the
pi nhol e, heat for about 30 more seconds and then remove the fl ask from
the water bath. Record the temperature of the water bath just pri or to removi ng
the fl ask.
Al l ow the fl ask to cool to room temperature.
Dry the fl ask thoroughl y, and rewei gh.
Fi l l the fl ask wi th water and empty i nto a graduated cyl i nder (to determi ne the
vol ume of the fl ask).
Use the barometer to measure the barometri c pressure.
(b) You wi l l need to record the fol l owi ng measurements:
1. Mass of the fl ask and foi l (empty).
2. Mass of the fl ask, foi l , and condensed vapor.
3. Vol ume of the fl ask.
4. Barometri c pressure.
5. Temperature of the boi l i ng water bath.
(c) Mol ecul ar mass 5
mRT
PV
Where m i s mass. R must contai n uni ts consi stent wi th al l other uni ts i n the
cal cul ati on. The most cruci al i s the uni t of pressure, whi ch wi l l be determi ned by
the uni ts on the barometer. As an exampl e, the val ue of the i deal gas constant
mi ght be 62.4 mm Hg L mol K, where atmospheres have been converted to
mm Hg.
The uni ts of measure wi l l set up as fol l ows (i f mm Hg i s used):
Mol ecul ar mass 5
~g! ~mm Hg L mol
21
K
21
! ~K!
~mm Hg! ~L!
The resul ti ng uni ts i n the cal cul ati on wi l l be g/mol , the desi red uni ts.
(d) I f the l i qui d was not compl etel y vapori zed, the val ue of mi n the equati on i n part
(c) woul d be too hi gh. Thi s wi l l cause the mol ar mass to be too hi gh.
(e) Experi mental error i s al ways cal cul ated the same way:
your val ue 2 theoreti cal val ue
theoreti cal val ue
3 100%
130 2 125.5
125.5
3 100%5 error
a
n
s
w
e
r
s
p
r
a
c
t
i
c
e
t
e
s
t
3
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Practice Test 3 563
www.petersons.com
6. (a) I oni zati on energy i s determi ned by two mai n factors. The fi rst i s the amount of
nucl ear shi el di ng between the nucl eus and the outermost el ectrons i n an atom.
The more shi el di ng, the more the attracti on i s affected, and therefore the weaker
the attracti ve force. Thi s means that as the amount of shi el di ng i ncreases, the
i oni zati on energy decreases. Shi el di ng i ncreases as you move down a group,
meani ng the group trend for i oni zati on energy i s that the i oni zati on energy for an
atom decreases as you move down a group. The second mai n trend i s the peri odi c
trend, whi ch i s determi ned by the effecti ve nucl ear charge acti ng on the
outermost el ectrons. As you move from l eft to ri ght across a peri od, the effecti ve
nucl ear charge i ncreases. Thi s i s because the number of protons i n the nucl eus i s
i ncreasi ng, whi l e the shi el di ng i s remai ni ng constant. As a resul t, the attracti ve
force between the nucl eus and the outermost el ectrons i ncreases as you move l eft
to ri ght across a peri od. The peri odi c trend i s that i oni zati on energy i ncreases
from l eft to ri ght. For thi s questi on, rubi di um has a hi gher fi rst i oni zati on energy
than sodi um because i t i s farther down a group. I t therefore has more shi el di ng
and a weaker attracti on on the outermost el ectrons.
(b) Both phosphorus and sul fur form negati ve i ons. Phosphorus wi l l gai n three
el ectrons when i t i oni zes, whi l e sul fur wi l l onl y gai n two. Negati ve i ons are l arger
than the el ement because when an atom gai ns el ectrons, the number of el ectrons
exceeds the number of protons. As a resul t, there i s a reduced overal l attracti on
for each el ectron, whi ch causes the i on to become l arger. The more el ectrons that
an atom gai ns, the l arger the di fference between the number of protons i n the
nucl eus and the number of val ence el ectrons.
Because phosphorus wi l l gai n three el ectrons compared to sul furs two, i t wi l l
form a l arger i on.
(c) Thi s i s an exampl e of a peri odi c trend for the atomi c radi us. A common
mi sconcepti on i s to thi nk that because an atom has a l arger atomi c number, i t
wi l l natural l y have a greater atomi c si ze. Thi s i s i ncorrect. As you move down a
group, atoms wi th l arger atomi c numbers have l arger atomi c radi i . However,
movi ng across a peri od, the i ncreasi ng effecti ve nucl ear charge causes a greater
attracti on between the nucl eus and the val ence el ectrons. As a resul t, the atoms
get smal l er as you move l eft to ri ght across a peri od.
(d) The magnesi um atom has two val ence el ectrons. Each one of these el ectrons can
be removed wi th a rel ati vel y smal l amount of energy. However, once those outer
el ectrons are removed from the 3s orbi tal s, the 2p orbi tal s contai n the outermost
el ectrons. These el ectrons i n the 2p orbi tal s are i soel ectroni c to the nobl e gases
and very stabl e. I n addi ti on, an atom l i ke magnesi um has two addi ti onal
protons provi di ng an even greater effecti ve nucl ear charge. As a resul t, there
wi l l be a tremendous di fference between the i oni zati on energi es for the 2
nd
and
3
rd
el ectrons.
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APPENDIX
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
COLLEGE-BY-COLLEGE GUIDE TO AP CREDIT
AND PLACEMENT
College-by-College
Guide to AP Credit
and Placement
For the past two decades, nati onal and i nternati onal parti ci pati on i n the AP
Program has grown steadi l y. Col l eges and uni versi ti es routi nel y award credi t
for AP test scores of 3, 4, or 5, dependi ng on the test taken. The fol l owi ng chart
i ndi cates the score requi red for AP credi t, how many credi ts are granted, what
courses are wai ved based on those credi ts, and other pol i cy sti pul ati ons at
more than 400 sel ecti ve col l eges and uni versi ti es.
Use thi s chart to di scover just how val uabl e a good score on the AP Chemi stry
Test can be!
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
a
p
p
e
n
d
i
x
567
School Name R
e
q
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e
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S
c
o
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C
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e
d
i
t
s
G
r
a
n
t
e
d
Course
Waived Stipulations
Agnes Scott Col l ege (GA) 45 3 CHE 101 Student may submi t
appl i cati on for l ab credi t. I f
l ab credi t i s gi ven, then the
natural sci ence di stri buti onal
standard i s met.
Al bany Col l ege of Pharmacy
of Uni on Uni versi ty (NY)
45
Al bertson Col l ege of
I daho (I D)
35
Al bi on Col l ege (MI ) 4 CHEM 121
Al bri ght Col l ege (PA) 45
Al l egheny Col l ege (PA) 45
Al ma Col l ege (MI ) 4 CHM 115
Ameri can Uni versi ty (DC) 45 8 CHEM
110G &
CHEM
210G
Asbury Col l ege (KY) 3 4 CHE 121
4 8 CHE 121
& 122
Auburn Uni versi ty (AL) 4 4 CHEM
1030 &
1031
5 8 CHEM
1030, 1031,
1040 &
1041
Augustana Col l ege (I L) 34 3 CH 121
5 6 CH 122
Augustana Col l ege (SD) 45
Austi n Col l ege (TX) 45 CHEM 111
Azusa Paci fi c
Uni versi ty (CA)
3 4 CHEM 151
45 4 CHEM 151
& 152
Babson Col l ege (MA) 45
Bal dwi n-Wal l ace
Col l ege (OH)
35 4 CHM 111
& 111L
Bard Col l ege (NY) 5
568 APPENDIX
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c
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C
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s
G
r
a
n
t
e
d
Course
Waived Stipulations
Barnard Col l ege (NY) 45 3 CHEM BC
1002
Bates Col l ege (ME) 45 CHEM
107A &
CHEM
108A
Bayl or Uni versi ty (TX) 3 CHEM
13001100
4 CHEM
13001100
or 1301
5 CHEM
1301 &
1302
Bel mont Uni versi ty (TN) 3 PHY 1010
4 CEM 1610
5 CEM 1610
& CEM
1620
Bel oi t Col l ege (WI ) 45 4 Credi t wi l l be granted once a
student matri cul ates to
Bel oi t Col l ege and provi des
offi ci al score reports to the
Regi strars Offi ce.
Benedi cti ne Uni versi ty (I L) 4 6 CHEM 113
& CHEM
123
Bentl ey Col l ege (MA) 45 Hi gh school graduates who
have taken the AP test may
be awarded credi t for scores
of 4 or 5 on any subject test.
Berea Col l ege (KY) 35
Bernard M. Baruch Col l ege
of the Ci ty Uni versi ty of
New York (NY)
45
Bi rmi ngham-Southern
Col l ege (AL)
4 CH 121 &
122
Boston Col l ege (MA) 4
Boston Uni versi ty (MA) 45 CH 101 &
CH 102
Bowdoi n Col l ege (ME) 45 CHEM 101
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College-by-College Guide to AP Credit and Placement 569
www.petersons.com
School Name R
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c
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C
r
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s
G
r
a
n
t
e
d
Course
Waived Stipulations
Bradl ey Uni versi ty (I L) 3 3 CHM 100
4 3 CHM 110
4 1 CHM 111
5 3 CHM 110
& CHM
112
5 1 CHM 111
Brandei s Uni versi ty (MA) 45 CHEM
11a,b,18a,b
Bri gham Young
Uni versi ty (UT)
3 6 CHEM 101
4 6 CHEM 105
5 7 CHEM 105
& CHEM
106
Brown Uni versi ty (RI )
Bryan Col l ege (TN) 35
Bryn Mawr Col l ege (PA) 4
Bucknel l Uni versi ty (PA) 45 CHEM 201
& CHEM
221
No l ab credi t.
Butl er Uni versi ty (I N) 4 5 CH 105 Take CH 106 or 107, earn at
l east an A- and recei ve 5
hours for CH 105.
5 5 CH 105 Take CH106 or 107, earn at
l east a C and recei ve 5 hours
for CH 105.
Cal vi n Col l ege (MI ) 3 4 Student does not recei ve
credi t for Chemi stry 103, but
i s i nvi ted to wri te an
exempti on/credi t
exami nati on for Chemi stry
103 or for Chemi stry 103
104.
4 4 CHEM 103 Student recei ves col l ege
credi t for Chemi stry 103 and
i s i nvi ted to wri te an
exempti on/credi t
exami nati on for Chemi stry
104.
570 APPENDIX
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G
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a
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t
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d
Course
Waived Stipulations
Cal vi n Col l egecontinued 5 4 CHEM 103
& CHEM
104
Cani si us Col l ege (NY) 3 8 Free
el ecti ve
45 8 CHEM 111
& CHEM
112 (l abs
wai ved)
Carl eton Col l ege (MN) 3 CHEM 123
or CHEM
128
45 6 CHEM 230 6 credi ts granted that count
toward a chemi stry major
and pl acement i s awarded
i nto Chemi stry 230
(Equi l i bri um and Anal ysi s).
Carnegi e Mel l on
Uni versi ty (PA)
45
Carrol l Col l ege (MT) 35
Carson-Newman
Col l ege (TN)
45
Case Western Reserve
Uni versi ty (OH)
45 8 CHEM
105, 106,
and CHEM
113
Students pl anni ng to major
i n an engi neeri ng di sci pl i ne
wi l l recei ve 8 credi t hrs. of
chemi stry credi t and wi l l
sati sfy the CHEM 111
requi rement, but must
regi ster for ENGR 145.
Cedarvi l l e Uni versi ty (OH) 3 5 CHEM
1000
4 4 CHEM
1110 or
CHEM
1050
5 4 CHEM
1110
Central Col l ege (I A) 35
Centre Col l ege (KY) 45
Chapman Uni versi ty (CA) 4 4 SCI -
100.CHEM
&
WAI VER-
SCI 100
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G
r
a
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t
e
d
Course
Waived Stipulations
Chri stendom Col l ege (VA) 45
Chri sti an Brothers
Uni versi ty (TN)
45
Cl aremont McKenna
Col l ege (CA)
45 Wi l l wai ve one of the two
general educati on
requi rements i f students
recei ve one or more scores of
4 or 5.
Cl arkson Uni versi ty (NY) 4 CM 131
5 CM 131 &
CM 132
Cl ark Uni versi ty (MA) 45
Cl emson Uni versi ty (SC) 35 8 CH 101 &
CH 102 or
CH 112
Coe Col l ege (I A) 45
Col by Col l ege (ME) 45
Col gate Uni versi ty (NY) 45
Col l ege of Charl eston (SC) 3 4
or
8
CHEM 111
& 111L/
CHEM 112
& 112L
3 5 CHEM 111 & 111L; 4 or
5 5 CHEM 111, 111L, 112,
and 112L.
The Col l ege of New
Jersey (NJ)
45 CHE 201
& CHE
202
Col l ege of Sai nt
Benedi ct (MN)
3 CHEM 123
4 4 CHEM 123
5 8 CHEM 123
& CHEM
234
The Col l ege of St.
Schol asti ca (MN)
4 4 CHM 1110
5 8 CHM 1110
& CHM
1120
Col l ege of the Atl anti c (ME) 45
Col l ege of the Hol y
Cross (MA)
45
The Col l ege of Wi l l i am and
Mary (VA)
4 4 CHEM
103151
572 APPENDIX
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Course
Waived Stipulations
The Col l ege of Wi l l i am and
Marycontinued
5 8 CHEM
103151 &
308354
The Col l ege of Wooster (OH) 45
Col orado Chri sti an
Uni versi ty (CO)
35
The Col orado Col l ege (CO) 4 CH 107
5 CH 107 &
CH 108
Col orado School of
Mi nes (CO)
4 4 Chemi stry
I
5 8 Chemi stry
I &
Chemi stry
I I & l ab
Col orado State
Uni versi ty (CO)
3 5 C CC 107,
C CC 108
45 9 C CC 111,
C CC 112,
C 113, C
114
Col umbi a Col l ege (NY) 45 3 Requi res compl eti on of
CHEM C2407 wi th a grade
of C or better.
45 6 Requi res compl eti on of
CHEM C3045C3046 wi th a
grade of C or better.
Col umbi a Uni versi ty, The Fu
Foundati on School of
Engi neeri ng and Appl i ed
Sci ence (NY)
45 6 Requi res begi nni ng wi th and
compl eti on of CHEM C3045
and CHEM C3046 wi th a
grade of C or better.
(Students must consul t wi th
department for speci fi c
requi rements.)
Concordi a Col l ege (MN) 3 Chemi stry
111A
4 Chemi stry
127A
5 Chem
127A &
128
Connecti cut Col l ege (CT) 45
Converse Col l ege (SC) 34 4
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Course
Waived Stipulations
Converse Col l egecontinued 5 8
Cooper Uni on for the
Advancement of Sci ence and
Art (NY)
45 3 CH 110
Cornel l Col l ege (I A) 45
Cornel l Uni versi ty (NY) 5 4 CHEM
206, 207 or
211
Department determi nes
pl acement on basi s of
student/advi sor meeti ng
pri or to regi strati on and/or
exam gi ven duri ng fal l
ori entati on. Students who
take 215 wi l l al so recei ve 4
AP credi ts.
Cornerstone Uni versi ty (MI ) 45 8 CHM 121
& CHM
122
Covenant Col l ege (GA) 4 8 CHE 121
& CHE
122
Crei ghton Uni versi ty (NE) 4 34 CHM 203
& CHM
204
CHM 204 wi l l be awarded
onl y upon department
approval of l ab notebooks.
5 68 CHM
203/204 &
CHM
205/206
Credi t for 204 and 206 wi l l
be awarded onl y upon
department approval of l ab
notebooks.
Dartmouth Col l ege (NH) 5 CHEM 5
Davi dson Col l ege (NC) 45 CHE 115
Deni son Uni versi ty (OH) 45 CHEM 199
DePauw Uni versi ty (I N) 45 4 CHEM 156
& CHEM
170
CHEM 170 (1/4 course
credi t).
Di cki nson Col l ege (PA) 3 Credi t for 141 gi ven upon
successful compl eti on of 241.
45 CHEM 141
Domi ni can Uni versi ty (I L) 35 4 CHEM 120
Drake Uni versi ty (I A) 4 8 CHEM 1,2,
3, 4
Drew Uni versi ty (NJ) 45 4
Drexel Uni versi ty (PA) 45
Drury Uni versi ty (MO) 3 4 CHEM 107
574 APPENDIX
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Course
Waived Stipulations
Drury Uni versi tycontinued 45 8 CHEM 107
& CHEM
108
Duke Uni versi ty (NC) 45 CHEM 19
Duquesne Uni versi ty (PA) 4 5 CHEM 121
5 10 CHEM 121
& CHEM
122
Earl ham Col l ege (I N) 5 6
El i zabethtown Col l ege (PA) 3 4 CH 101
45 8 CH 101 &
CH 105
El mi ra Col l ege (NY) 3 4 CHE 1510
45 8 Regi strar and Chemi stry
facul ty wi l l determi ne
pl acement.
El on Uni versi ty (NC) 45 4 CHM 111
& CHM
113
Embry-Ri ddl e Aeronauti cal
Uni versi ty (AZ)
35
Emerson Col l ege (MA) 35
Emory Uni versi ty (GA) 45 4
Erski ne Col l ege (SC) 45
Eugene Lang Col l ege The
New School for Li beral
Arts (NY)
45
Fai rfi el d Uni versi ty (CT) 45 4 CH 11
Fl ori da I nsti tute of
Technol ogy (FL)
4 4 General
Chemi stry
I
5 8 General
Chemi stry
I & I I
Fl ori da I nternati onal
Uni versi ty (FL)
3 CHM 1020
& 1020L
4 4 CHM 1045
& 1045L
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Course
Waived Stipulations
Fl ori da I nternati onal
Uni versi tycontinued
5 8 CHM 1045,
1045L
&CHM
1046,
1046L
Fl ori da State Uni versi ty (FL) 3 4 CHM 1020
& CHM
1020L
4 4 CHM 1045
& CHM
1045L
5 9 CHM 1045,
CHM
1045L,
CHM 1046,
& CHM
1046L
Fordham Uni versi ty (NY) 35 Currentl y, a grade of 3 wi l l
be accepted as el ecti ve
credi t. However, grades of 4
or 5 may be appl i ed towards
the core curri cul um.
Franci scan Uni versi ty of
Steubenvi l l e (OH)
45
Frankl i n and Marshal l
Col l ege (PA)
45 CHM 111
& CHM
112
Furman Uni versi ty (SC) 4 CHEM 11
5 CHEM 11
& CHEM
12
George Fox Uni versi ty (OR) 3 3 CHEM 110
45 8 CHEM 211
& CHEM
212
Georgetown Col l ege (KY) 35 36
Georgetown Uni versi ty (DC) 4 3
5 3 CHEM 001
The George Washi ngton
Uni versi ty (DC)
45 8 CHEM 11
& CHEM
12
Georgi a I nsti tute of
Technol ogy (GA)
5 4 CHEM
1310
576 APPENDIX
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Course
Waived Stipulations
Georgi a State
Uni versi ty (GA)
35
Gettysburg Col l ege (PA) 45 4
Gonzaga Uni versi ty (WA) 4 4 CHEM 105
& CHEM
105L
5 8 CHEM
105/105L
& CHEM
170/170L
Gordon Col l ege (MA) 45
Goshen Col l ege (I N) 35 3 Gen Ed
Physi cal
Sci ence
Goucher Col l ege (MD) 45
Gri nnel l Col l ege (I A) 45 4
Grove Ci ty Col l ege (PA) 45
Gustavus Adol phus
Col l ege (MN)
45
Hami l ton Col l ege (NY) 45 4 Students havi ng obtai ned a 4
or 5 wi l l recei ve 1 credi t
upon compl eti on of CHEM
125 and/or 190 wi th a
mi ni mum grade of a C- i n
the course(s).
Haml i ne Uni versi ty (MN) 35 El ecti ve
Credi t
Hampshi re Col l ege (MA) 35
Hanover Col l ege (I N) 35
Hardi ng Uni versi ty (AR) 4 8 CHEM 121
& CHEM
122
Harvard Uni versi ty (MA) 5 CHEM 57 Pl acement i n CHEM 17 or
CHEM 20.
Harvey Mudd Col l ege (CA) 5 Before advanced pl acement
can be awarded, a student
must take the HMC
chemi stry pl acement exams
and di scuss the resul ts wi th
a chemi stry facul ty member.
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Waived Stipulations
Haverford Col l ege (PA) 45 The regi strar wi l l award one
course credi t for an AP score
of 5 and one-hal f course
credi t for a score of 4. No
credi t i s awarded for scores
under 4.
Hendri x Col l ege (AR) 45 Credi t for CHEM 100
(Concepts of Chemi stry) may
be earned or, upon
compl eti on of CHEM 120
(General Chemi stry I I ) wi th
a grade of C or better,
credi t for CHEM 110
(General Chemi stry I ) may
be earned.
Hi l l sdal e Col l ege (MI ) 3 4 SCI 101
45 8 CHM 101
& CHM
102
Hi ram Col l ege (OH) 45
Hobart and Wi l l i am Smi th
Col l eges (NY)
45
Hope Col l ege (MI ) 45
Houghton Col l ege (NY) 4 4 Lab sci ence
not Gen-
eral Chem-
i stry I
5 4 General
Chemi stry
I l l i noi s Col l ege (I L) 45
I l l i noi s I nsti tute of
Technol ogy (I L)
45 8 CHEM 124
& CHEM
125
I l l i noi s Wesl eyan
Uni versi ty (I L)
45 Credi t wi l l be granted and
recorded by I WU onl y after
the successful compl eti on of
four course uni ts of study i n
resi dence.
I owa State Uni versi ty of
Sci ence and Technol ogy (I A)
35
I thaca Col l ege (NY) 3 6 CHEM
3041
578 APPENDIX
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Waived Stipulations
I thaca Col l egecontinued 4 8 CHEM
3041 &
CHEM
304121
5 8 CHEM
3041 &
CHEM
304121 &
CHEM
304122
James Madi son
Uni versi ty (VA)
3 4 GSCI 101
& GSCI
104
4 8 CHEM
131,
CHEM
131L,
CHEM 132
& CHEM
132L
CHEM 131, CHEM 131L,
CHEM 132 & CHEM 132L
or CHEM 120 & 120L for
non majors.
4 6 CHEM 131
& CHEM
132 for
majors
John Brown Uni versi ty (AR) 3 CHM 1124
45 CHM 1124
& CHM
1134
John Carrol l Uni versi ty (OH) 4 5 CH 141 &
CH 143
5 10 CH
141CH
144
The Johns Hopki ns
Uni versi ty (MD)
45 6 CHEM 30,
101 & 102
or CHEM
30, 105 &
106
Juni ata Col l ege (PA) 45
Kal amazoo Col l ege (MI ) 45
Kenyon Col l ege (OH) 45 CHEM 121
or 122 and
124
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Course
Waived Stipulations
Ketteri ng Uni versi ty (MI ) 45 4 CHEM-
135/136 or
CHEM-
137/138
Knox Col l ege (I L) 35 CHEM 101
& CHEM
102
Lafayette Col l ege (PA) 45 CHEM 121
& CHEM
122
Lake Forest Col l ege (I L) 45
Lawrence Technol ogi cal
Uni versi ty (MI )
4 34 CHM 1213
or CHM
1154 or
CHM 3144
or Nat Sci
El ecti
5 39 CHM 1213
& CHM
1223
Lawrence Uni versi ty (WI ) 45
Lebanon Val l ey Col l ege (PA) 3 4 CHM 100
45 8 CHM
111/112/
113/114
Lehi gh Uni versi ty (PA) 4 5 CHM 95 &
CHM 97
Students may appl y to the
department for a speci al
exami nati on that, i f
compl eted successful l y, wi l l
resul t i n an addi ti onal three
credi t hours for CHM 31.
5 8 CHM 95,
CHM 97 &
CHM 31
LeTourneau Uni versi ty (TX) 3 3 CHEM
1113
Credi t for l aboratori es i n the
natural sci ences coul d be
awarded on demonstrated
mastery of equi val ent col l ege
l evel l aboratory experi ences.
45 6 CHEM
1113 &
CHEM
1123
Credi t for l aboratori es i n the
natural sci ences coul d be
awarded on demonstrated
mastery of equi val ent col l ege
l evel l aboratory experi ences.
580 APPENDIX
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Waived Stipulations
Lewi s & Cl ark Col l ege (OR) 4 Student may peti ti on for
pl acement i nto Chemi stry
120.
5 CHEM 110 Pl acement i nto Chemi stry
120 or 210.
Li nfi el d Col l ege (OR) 45
Li pscomb Uni versi ty (TN) 3 8 CM 1113 &
CM 1211
45 8 CM 1113,
CM 1211,
CM 1123,
& CM 1221
Loui si ana State Uni versi ty
and Agri cul tural and
Mechani cal Col l ege (LA)
3 6 CHEM
1201 &
CHEM
1202
45 6 CHEM
1421 &
CHEM
1422
Loyol a Col l ege i n
Maryl and (MD)
45
Loyol a Marymount
Uni versi ty (CA)
45 8 CHEM
110, 111,
112, & 113
Loyol a Uni versi ty
Chi cago (I L)
45 8 CHEM 105
& CHEM
106
Loyol a Uni versi ty New
Orl eans (LA)
45 3 CHEM
T122
Luther Col l ege (I A) 45 4
Lycomi ng Col l ege (PA) 4 4 CHEM 110
5 8 CHEM 110
& CHEM
111
Lyon Col l ege (AR) 45
Mari st Col l ege (NY) 45 10 CHEM
111L, 112L,
113L, 114L
For non-sci ence majors.
45 Sci ence majors must contact
Bi ol ogy Department.
Marl boro Col l ege (VT) 45 8
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Waived Stipulations
Marquette Uni versi ty (WI ) 3 4 CHEM 1
45 8 CHEM 1 &
CHEM 2
Maryvi l l e Col l ege (TN) 35
Maryvi l l e Uni versi ty of Sai nt
Loui s (MO)
35
Massachusetts I nsti tute of
Technol ogy (MA)
0 0 No credi t i s gi ven for the
Col l ege Board AP Chemi stry
test. To recei ve credi t for 12
uni ts of 5.111, Pri nci pl es of
Chemi cal Sci ence, you must
pass the Advanced
Pl acement (Advanced
Standi ng) test admi ni stered
duri ng freshman ori entati on.
The Masters Col l ege and
Semi nary (CA)
45
McDani el Col l ege (MD) 45 Students may recei ve
advanced pl acement pl us up
to 8 hours credi t.
McGi l l Uni versi ty (QC) 45 8 CHEM 110
& CHEM
120
McKendree Col l ege (I L) 35 3 None
Mercer Uni versi ty (GA) 35
Messi ah Col l ege (PA) 3 3 CHE 102
or CHE
110
4 4 CHE 105
5 8 CHE 105
& CHE
106
Mi ami Uni versi ty (OH) 45 10 CHM 141,
142, 144, &
145
Mi chi gan State
Uni versi ty (MI )
3 5 CHM 141
& CHM
161 or I SP
200-l evel
course
582 APPENDIX
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Waived Stipulations
Mi chi gan State Uni versi ty
continued
45 8 CHM 151,
152, & 161
or I SP
200-l evel
course
Mi chi gan Technol ogi cal
Uni versi ty (MI )
3 5 CH 1110 &
CH 1111
45 9 CH 1110,
1111 &
1120
Mi ddl ebury Col l ege (VT) 45 CHEM
0103
Pl acement i n CHEM 0107
recommended.
Mi l l i gan Col l ege (TN) 35 8 CHEM 170
& CHEM
171
Mi l l saps Col l ege (MS) 45 4 CHEM
1213 &
CHEM
1223
Mi l l s Col l ege (CA) 45
Mi ssi ssi ppi Col l ege (MS) 35 8 CHE 101
& CHE
102
Mi ssouri State
Uni versi ty (MO)
3 4 CHM 160
4 7 CHM 160
& CHM
170
5 9 CHM 160,
170, & 175
Credi t may be awarded for a
score of 3 on these
exami nati ons. Students must
present thei r exami nati on
bookl et to the appropri ate
department head for revi ew.
Moravi an Col l ege (PA) 35 Acceptance condi ti onal upon
departmental approval .
Departments reserve the
ri ght to veri fy test resul ts
and to make suppl emental
assi gnments.
Morehouse Col l ege (GA) 45
Mount Hol yoke Col l ege (MA) 45 4
Muhl enberg Col l ege (PA) 35
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Waived Stipulations
Murray State
Uni versi ty (KY)
3 4 CHE 101
45 4 CHE 105
New Col l ege of Fl ori da (FL) 45
New Jersey I nsti tute of
Technol ogy (NJ)
4 3 CHEM 125
5 7 CHEM
124, 125 &
126
New Mexi co I nsti tute of
Mi ni ng and Technol ogy (NM)
34 3 CHEM 121 Student shoul d consul t the
department chai r concerni ng
l aboratory credi ts.
5 6 CHEM 121
& CHEM
122
Student shoul d consul t the
department chai r concerni ng
l aboratory credi ts.
New York Uni versi ty (NY) 45 8 V25.0101
0102
North Carol i na State
Uni versi ty (NC)
3 4 CH 101 &
CH 102
45 8 CH 101,
CH 102,
CH 201,
CH 202
North Central Col l ege (I L) 3 Pl acement i n CHM 205 or
210. 7.00 hours for CHM 142
and chemi stry el ecti ve i f
student earns a B- or hi gher
i n CHM 205 or 210.
45 4 CHM 142 Pl acement i n CHM 205 or
210. Ful fi l l s al l sci ence.
Northwestern Col l ege (I A) 45 4 CHE 111
Northwestern Col l ege (MN) 3 4 CHE 1021
45 8 CHE 1021
& CHE
1022
Northwestern Uni versi ty (I L) 34 CHEM 101
5 CHEM
101, 102
and 103
Occi dental Col l ege (CA) 45
Ogl ethorpe Uni versi ty (GA) 3 4 GEN 101
584 APPENDIX
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Course
Waived Stipulations
Ogl ethorpe Uni versi ty
continued
45 4 CHM 101
Ohi o Northern
Uni versi ty (OH)
34 4 CHEM 100 For a score of 5, a student
wi l l get 10 semester hours
and CHEM 100 or CHEM
171 or CHEM 181 or CHEM
225 wi l l be wai ved.
The Ohi o State
Uni versi ty (OH)
3 5 CHEM 121
45 10 CHEM 121
& CHEM
122
Ohi o Wesl eyan
Uni versi ty (OH)
Okl ahoma Ci ty
Uni versi ty (OK)
45 4 CHEM
1014
For non majors.
Okl ahoma State
Uni versi ty (OK)
3 5 CHEM
1215
45 9 CHEM
1314 &
CHEM
1515
Paci fi c Lutheran
Uni versi ty (WA)
45 4 CHEM 120
Paci fi c Uni versi ty (OR) 45 3
Peabody Conservatory of
Musi c of The Johns Hopki ns
Uni versi ty (MD)
45
The Pennsyl vani a State
Uni versi ty Uni versi ty Park
Campus (PA)
4 4 CHEM 012
& CHEM
014
5 8 CHEM
012, 013,
014, & 015
Pepperdi ne Uni versi ty (CA) 35 4 Laboratory
Sci ence GE
Requi rement
Pi tzer Col l ege (CA) 45
Poi nt Loma Nazarene
Uni versi ty (CA)
3 3
45 6
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Course
Waived Stipulations
Pol ytechni c Uni versi ty,
Brookl yn Campus (NY)
45 4 CH 1004
Pomona Col l ege (CA) 45 One course credi t for a score
of 4 or 5, after the student
has successful l y taken
CHEM51 wi th a grade of C-
or better.
Presbyteri an Col l ege (SC) 4 4 CHEM 101
& CHEM
101L
CHEM 102 & CHEM 102L
wi th a 70 on departmental
exam.
Pri nceton Uni versi ty (NJ) 4 CHEM 201
& CHEM
207
5 CHEM
201/207 &
CHEM 202
Provi dence Col l ege (RI ) 45
Purdue Uni versi ty (I N) 3 3 CHM 111
45 8 CHM 115
& CHM
116
Queens Uni versi ty at
Ki ngston (ON)
45 CHEM 112
Qui ncy Uni versi ty (I L) 45
Qui nni pi ac Uni versi ty (CT) 45 8 CH 110 &
CH 111
Randol ph-Macon Womans
Col l ege (VA)
45
Reed Col l ege (OR) 45
Renssel aer Pol ytechni c
I nsti tute (NY)
4 4 Students who achi eve a
grade of 4 wi l l recei ve 4
credi ts for CHEM 1200
(Chemi stry I I ) i f they obtai n
a grade of A i n CHEM 1100
(Chemi stry I ) or CHEM 1300
(Chemi cal Pri nci pl es for
Engi neers).
5 8 CHEM
1100 or
CHEM
1300 &
CHEM
1200
586 APPENDIX
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Course
Waived Stipulations
Rhodes Col l ege (TN) 45 6 CHEM 111
& CHEM
112
Ri ce Uni versi ty (TX) 45 8 CHEM 121
& CHEM
122
Rochester I nsti tute of
Technol ogy (NY)
35 For non chemi stry majors:
1011201, 205, or, 1011208,
1011273, 277 or, 1011211,
212 and 1011205, 206 or,
1011215, 216 and 1011205,
206 or, 1011241, 242, 245,
246 or, 1011271, 205,
1011273, 277
45 For chemi stry majors:
1010-251, 252
Rol l i ns Col l ege (FL) 45 4
Rose-Hul man I nsti tute of
Technol ogy (I N)
4 Honors
Chem
el i gi bl e
5 12 CHEM 111,
113, & 115
Rutgers, The State
Uni versi ty of New Jersey,
Newark (NJ)
45
Rutgers, The State
Uni versi ty of New Jersey,
New
Brunswi ck/Pi scataway (NJ)
45
Sai nt Franci s
Uni versi ty (PA)
3 CHEM 101
& 102 or
CHEM 103
& 104
Score of 3 recei ves a wai ver
from both Chemi stry 101
and Chemi stry 102 or from
both Chemi stry 103 and
Chemi stry 104.
45 CHEM 101
& 102 or
CHEM 103
& 104
Score of 4 or 5 recei ves
credi t for both Chemi stry
101 and Chemi stry 102 or
for both Chemi stry 103 and
Chemi stry 104.
Sai nt Johns Uni versi ty (MN) 3 0 CHEM 123
4 4 CHEM 123
5 8 CHEM 123
& CHEM
234
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Course
Waived Stipulations
Sai nt Josephs
Uni versi ty (PA)
45 3 CHM 1031
St. Lawrence
Uni versi ty (NY)
45 CHEM 103
Sai nt Loui s Uni versi ty (MO) 5 8 CH A 161
& CH A
162
Sai nt Marys Col l ege (I N) 3 8 CHEM 101
& CHEM
102
45 8 CHEM 101
& 102 or
CHEM 121
& 122
Sai nt Marys Col l ege of
Cal i forni a (CA)
34 CHEM 8 &
CHEM 9
5 CHEM 8,
9, 10, & 11
St. Marys Col l ege of
Maryl and (MD)
45
St. Norbert Col l ege (WI ) 35
St. Ol af Col l ege (MN) 5 No LAB credi t awarded.
Sal em Col l ege (NC) 3 CHEM 110
45 CHEM 110
&
CHEM120
Samford Uni versi ty (AL) 4 4 CHEM 203
5 8 CHEM 203
& CHEM
204
San Di ego State
Uni versi ty (CA)
35 6 CHEM 200
& CHEM
201
Santa Cl ara Uni versi ty (CA) 45 5 CHEM 11
Sarah Lawrence
Col l ege (NY)
45
Scri pps Col l ege (CA) 45
Seattl e Paci fi c
Uni versi ty (WA)
4 5 CHM 1211
588 APPENDIX
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Course
Waived Stipulations
Seattl e Paci fi c Uni versi ty
continued
5 5 CHM 1211
& CHM
1212
Seattl e Uni versi ty (WA) 35 4 CHEM 121 Each student must consul t
wi th chemi stry chai rperson
for eval uati on of l aboratory
experi ence. An addi ti onal
credi t may be granted for
l ab, ful fi l l i ng uni versi ty core,
or CHEM 131 l ab wi l l be
requi red.
Sewanee: The Uni versi ty of
the South (TN)
45 4
Si ena Col l ege (NY) 45
Si mpson Col l ege (I A) 35
Ski dmore Col l ege (NY) 45
Smi th Col l ege (MA) 45
Southern Methodi st
Uni versi ty (TX)
45 8 CHEM
1403 &
CHEM
1404
Southwest Bapti st
Uni versi ty (MO)
3 4 CHE 1104
45 5 CHE 1115
Southwestern
Uni versi ty (TX)
45 34
Stanford Uni versi ty (CA) 45 4 CHEM 33
or above
State Uni versi ty of New York
at Bi nghamton (NY)
3 4 CHEM 101
4 4 CHEM 111
5 8 CHEM 107
& CHEM
108
at Buffal o (NY)
35
Col l ege at Geneseo (NY)
3 7 CHEM
1TR
4 7 CHEM 116
& 117 or
CHEM 118
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Course
Waived Stipulations
Col l ege at Geneseo
continued
5 7 CHEM 120
& 121 or
CHEM 122
Col l ege of Envi ronmental
Sci ence and Forestry (NY)
45
Stetson Uni versi ty (FL) 3 4 CY 101
45 8 CY 101 &
CY 102
Stevens I nsti tute of
Technol ogy (NJ)
45 8 CH 115,
116, 117 &
118
Stonehi l l Col l ege (MA) 45 4 General
Chemi stry
I
Stony Brook Uni versi ty,
State Uni versi ty of New
York (NY)
3 3 None
45 8 CHE 131
& CHE
132
(wai ver of
CHE 133,
134)
Susquehanna
Uni versi ty (PA)
45 I n excepti onal cases, the
department may al so
recommend credi t for scores
of 3.
Swarthmore Col l ege (PA) 45 No AP/I B credi t i f you take
Chem 001 or Chem 010. I f
conti nui ng i n Chem, take
Chem 010H.
Sweet Bri ar Col l ege (VA) 45
Syracuse Uni versi ty (NY) 45 4 CHE 106
& CHE
107
Tabor Col l ege (KS) 2 4 CH 111
35 8 CH 111 &
CH 112
Tayl or Uni versi ty (I N) 3 5 CHE 201
4 8
or
10
CHE 201
& 202 or
CHE 211
590 APPENDIX
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Course
Waived Stipulations
Tayl or Uni versi tycontinued 5 8
or
10
CHE 201
& 202 or
CHE 211 &
212
Tennessee Technol ogi cal
Uni versi ty (TN)
4 4
or
8
CHEM
1110 or
CHEM
1010 &
1020
Students may submi t the
exam essay porti on for
departmental eval uati on for
possi bl e credi t i n CHEM
1120.
5 8 CHEM
1110 and
1120 or
CHEM
1010 and
1020
Texas A&M Uni versi ty (TX) 3 4 CHEM 101
45 8 CHEM 101
& CHEM
102
Texas Chri sti an
Uni versi ty (TX)
3 3 10163
45 8 10113,
10123,
10122
Texas Tech Uni versi ty (TX) 3 8 CHEM
1305, 1306
& 1105,
1106
45 8 CHEM
1307, 1308
& 1107,
1108
Transyl vani a
Uni versi ty (KY)
45
Tri ni ty Col l ege (CT) 45 Students who have secured
an advanced pl acement
grade i n Chemi stry of 4 or 5
may recei ve one course
credi t. (Thi s course credi t
may not be counted toward
the chemi stry major.)
Tri ni ty Uni versi ty (TX) 45 3 CHEM
1318
Truman State
Uni versi ty (MO)
3 4 CHEM 100
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Course
Waived Stipulations
Truman State Uni versi ty
continued
45 5 CHEM 120
Tufts Uni versi ty (MA) 5 Pl acement i nto Chemi stry 31
or 51; accel erati on credi t of
two courses.
Tul ane Uni versi ty (LA) 4 4 CHEM 107
& CHEM
117
5 8 CHEM 107
& 117 &
CHEM 108
& 118
Uni on Col l ege (NE) 35
Uni on Col l ege (NY) 45
Uni on Uni versi ty (TN) 35 4 CHE 105
or CHE
111
The Uni versi ty of Al abama
i n Huntsvi l l e (AL)
35 8 CH 121,
125, 123, &
126
The Uni versi ty of
Ari zona (AZ)
3 4 CHEM
103A &
CHEM
104A
45 8 CHEM
103A,
103B,
104A, &
104B
Uni versi ty of Arkansas (AR) 4 CHEM
1103/1101L
& CHEM
1123/1121L
5 CHEM
1103/1101L
& CHEM
1123H/
1121M
Uni versi ty of Cal i forni a,
Berkel ey (CA)
35 Consul t the Career Center
regardi ng the use of tests for
admi ssi on to professi onal
school s.
Davi s (CA)
34 8 Chemi stry
10
592 APPENDIX
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Course
Waived Stipulations
Davi scontinued
5 8 Chemi stry
2A
Al though Chemi stry 2A may
be taken for ful l credi t,
students are strongl y
encouraged to enrol l i n the
2HA, 2HB, 2HC sequence.
I rvi ne (CA)
3 8 El ecti ve
credi t onl y
45 8 Chemi stry 1A pl us 4 uni ts of
el ecti ve credi t. (Chemi stry
1A/1LA pl us 3 uni ts of
el ecti ve credi t for Chemi stry
and Engi neeri ng majors.)
Uni versi ty of Cal i forni a, Los
Angel es (CA)
35
Ri versi de (CA)
35 8 CHEM
001W &
el ecti ve
Santa Barbara (CA)
35 8 Natural
Sci ence 1B
Santa Cruz (CA)
35 8 Sati sfi es
one I N
Uni versi ty of Central
Arkansas (AR)
4 CHEM
1450
5 CHEM
1450 &
CHEM
1451
Uni versi ty of Central
Fl ori da (FL)
3 CHM 1020
& 1020L
4 CHM
2045C or
CHM 2045
& CHM
2045L
5 CHM
2045C and
CHM 2046
& 2046L
Uni versi ty of Chi cago (I L) 4 2 quarters
10000-l evel
PHSC
Students who regi ster for
ei ther chemi stry or physi cs
forego AP credi t for 10000-
l evel PHSC.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Waived Stipulations
Uni versi ty of Chi cago
continued
5 General
Chemi stry
I , I I , I I I
Uni versi ty of Col orado at
Boul der (CO)
4 5 CHEM
1111
5 10 CHEM
1111 &
CHEM
1131
Uni versi ty of
Connecti cut (CT)
45 8 CHEM
127Q &
CHEM
128Q
Uni versi ty of Dal l as (TX) 35 68 CHE 1303,
1103, 1304,
& 1104
Uni versi ty of Dayton (OH) 45 3 Students wi th a score of 5
may be el i gi bl e for addi ti onal
credi t.
Uni versi ty of Del aware (DE) 35 48 CHEM
101102 or
CHEM 105
or CHEM
103104or
111112
Uni versi ty of Denver (CO) 3 4
4 8
5 12 NATS 4/8
El ecti ve
Uni versi ty of Evansvi l l e (I N) 45
Uni versi ty of Fl ori da (FL) 3 4 CHM 1020
& CHM
0301L
The 0301 course number has
no UF course equi val ent;
these courses provi de
General Educati on credi t but
may not count toward the
major.
4 4 CHM 2045
& CHM
2045L
5 8 CHM
2045/2045L
& CHM
2046/2046L
594 APPENDIX
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Course
Waived Stipulations
Uni versi ty of Georgi a (GA) 3 4 CHEM
1110 &
CHEM
1110L
4 4 CHEM
1211 &
CHEM
1211L
5 8 CHEM
1211/1211L
& CHEM
1212/1212L
Uni versi ty of I l l i noi s at
Chi cago (I L)
45 10 CHEM 112
& CHEM
114
Permi ssi on to enrol l i n
Chemi stry 222.
Uni versi ty of I l l i noi s at
UrbanaChampai gn (I L)
45 6 CHEM 102
& CHEM
104
The Uni versi ty of I owa (I A) 34 3 El ecti ve
hours
May be appl i ed toward
General Educati on Program:
natural sci ences (non l ab
hours)
5 6 3 semester hours may be
appl i ed toward General
Educati on Program: natural
sci ences (non l ab) hours and
3 used as el ecti ve hours or
al l 6 may be used as el ecti ve
hours.
Uni versi ty of Kansas (KS) 34 5 CHEM 184
5 10 CHEM 184
& CHEM
188
Uni versi ty of Kentucky (KY) 35 6 CHE 105
& CHE
107
3 credi t hours each for CHE
105 and CHE 107 wi th grade
of CR.
Uni versi ty of Maryl and,
Bal ti more County (MD)
45 4 CHEM 101
Col l ege Park (MD)
4 4 CHEM 131
& CHEM
132
CHEM ful fi l l s a major
requi rement i n al l Li fe
Sci ences; i t al so ful fi l l s a
CORE-Lab (Physi cal ) Sci ence
requi rement.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Course
Waived Stipulations
Col l ege Parkcontinued
5 6 CHEM
131/132 &
CHEM 271
CHEM ful fi l l s a major
requi rement i n al l Li fe
Sci ences; i t al so ful fi l l s a
CORE-Lab (Physi cal ) Sci ence
requi rement.
Uni versi ty of Mary
Washi ngton (VA)
3 4 CHEM
0105
4 4 CHEM
0111
5 8 CHEM
0111 &
CHEM
0112
Uni versi ty of Mi ami (FL) 4 4 CHM 111
& CHM
113
5 8 CHM 111,
112, 113, &
114
Uni versi ty of Mi chi gan (MI ) 3 5 CHEM
125/126 &
CHEM 130
3 hours for Chemi stry 130
and 2 hours for Chemi stry
125(1)/126(1) i f pl aced i nto
Chem 210, 211 by taki ng
pl acement test duri ng
ori entati on. For Col l ege of
Li terature, Sci ence, & the
Arts.
3 0 CHEM
125/126 &
CHEM 130
No credi t i f not pl aced i nto
Chem 210 and 211 by taki ng
pl acement test duri ng
ori entati on. For Col l ege of
Li terature, Sci ence, & the
Arts.
4 3 CHEM 130 For Col l ege of Engi neeri ng
45 5 CHEM
125/126 &
CHEM 130
Al l students wi th an AP
score of 4 or 5 are el i gi bl e to
el ect Chem 210 and 211. For
Col l ege of Li terature,
Sci ence, & the Arts.
5 5 CHEM
125/126 &
CHEM 130
For Col l ege of Engi neeri ng.
Uni versi ty of Mi chi gan
Dearborn (MI )
35 CHEM 144
or CHEM
134
596 APPENDIX
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Waived Stipulations
Uni versi ty of Mi nnesota,
Morri s (MN)
3 4 CHEM
1101
45 8 CHEM
1101 &
CHEM
1102
Uni versi ty of Mi nnesota,
Twi n Ci ti es Campus (MN)
35 8 CHEM
1021 &
CHEM
1022
Ful fi l l s physi cal sci ence/l ab
requi rement. Does not ful fi l l
envi ronmental theme.
Uni versi ty of Mi ssouri
Col umbi a (MO)
3 5 CHEM
1310 &
CHEM
1320
45 8 CHEM
1310, 1320,
1330
Kansas Ci ty (MO)
35 10 CHEM 211
& 211L &
212R &
212LR
Rol l a (MO)
3 4 CHEM 1
4 5 CHEM 1 &
CHEM 2
5 5 CHEM 5
Uni versi ty of Nebraska
Li ncol n (NE)
35 8 CHEM 109
& CHEM
110
The Uni versi ty of North
Carol i na at Ashevi l l e (NC)
3 3 CHEM 132
45 4 CHEM 144
Carol i na at Chapel Hi l l (NC)
3 4 CHEM 101
&
CHEM101L
5 8 CHEM
101, 101L,
102,102L
Carol i na Wi l mi ngton (NC)
3 4 CHEM 101
1 Lab
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Course
Waived Stipulations
Carol i na Wi l mi ngton
continued
45 8 CHEM 101
1 Lab &
CHEM 102
1 Lab
Uni versi ty of North
Fl ori da (FL)
3 4 CHEM
1020C
4 4 CHEM
2045C
5 8 CHEM
2045C &
CHEM
2046C
Uni versi ty of Notre
Dame (I N)
4 3 CHEM
10101
5 8 CHEM
10117 &
CHEM
10118
Uni versi ty of Okl ahoma (OK) 45 CHEM
1315 &
CHEM
1415
Uni versi ty of
Pennsyl vani a (PA)
5 CHEM 091 No AP credi t i s gi ven for
l aboratory work.
Uni versi ty of Pi ttsburgh (PA) 34 4 CHEM
0110
5 8 CHEM
0110 &
CHEM
0120
Uni versi ty of Puget
Sound (WA)
45 CHM 110
& CHM
111
Uni versi ty of Redl ands (CA) 35
Uni versi ty of Rhode
I sl and (RI )
35 8 CHEM
101/102 &
CHEM
112/114
Uni versi ty of Ri chmond (VA) 45 4 CHEM 141
Uni versi ty of Rochester (NY) 45 4 CHM 131 El i gi bl e to appl y for CHM
171Q (Organi c Chemi stry).
Pl acement i n CHM 132 i n
the spri ng. Students taki ng
131 wi l l forfei t AP credi t.
598 APPENDIX
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Course
Waived Stipulations
Uni versi ty of St.
Thomas (MN)
35 CHEM 100 A score of 3 or hi gher may 5
CHEM 100, dependi ng on
l aboratory experi ence, at the
di screti on of the chai r of the
department.
45 CHEM 111 A score of 4 or hi gher may 5
CHEM 111, dependi ng on
l aboratory experi ence, at the
di screti on of the chai r of the
department.
Uni versi ty of St.
Thomas (TX)
35 CHEM
1341 &
CHEM
1342
Uni versi ty of San Di ego (CA) 35
The Uni versi ty of
Scranton (PA)
45 36
Uni versi ty of South
Carol i na (SC)
3 CHM 111
& CHM
111L
45 CHM
111/111L &
CHM112/
112L
Uni versi ty of Southern
Cal i forni a (CA)
35 4
The Uni versi ty of Tennessee
at Chattanooga (TN)
3 4 CHEM 121
& CHEM
123
45 8 CHEM
121, 123,
122, & 124
The Uni versi ty of Texas at
Austi n (TX)
4 CH 301,
302, CR
5 CH 301,
302, A
The Uni versi ty of Texas at
Dal l as (TX)
3 3 SCH free
el ecti ves
4 CHEM
1311 1
Lab
5 CHEM
1311/1312
1 Lab
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Course
Waived Stipulations
Uni versi ty of the Paci fi c (CA) 45 5 CHEM 25
Uni versi ty of the Sci ences i n
Phi l adel phi a (PA)
45
Uni versi ty of Tul sa (OK) 45 6 CHEM
1013 &
CHEM
1023
Uni versi ty of Utah (UT) 35 8 1 Sci ence
I E
Pl acement by Department.
Uni versi ty of Vi rgi ni a (VA) 45 6 CHEM 141
& CHEM
142
No l aboratory credi t gi ven.
Uni versi ty of
Washi ngton (WA)
4 10 CHEM 142
& CHEM
152
5 16 CHEM
142, 152 &
162
General chemi stry for
sci ence and engi neeri ng
majors. Counts toward
Natural Worl d general
educati on requi rement for
graduati on. CHEM 142 al so
sati sfi es Quanti tati ve and
Symbol i c Reasoni ng
graduati on requi rement.
Uni versi ty of Wi sconsi nLa
Crosse (WI )
3 4 El ecti ve
credi t
45 5 CHEM 103
Uni versi ty of Wi sconsi n
Madi son (WI )
3 3 Chemi stry
El ecti ves
45 3 CHEM 103
Uni versi ty of Wi sconsi n
Ri ver Fal l s (WI )
35 5 CHEM 121 Students who i ntend to
conti nue i n Chemi stry
shoul d take CHEM 122 i n
the fi rst semester at UWRF.
Ursi nus Col l ege (PA) 45
Val parai so Uni versi ty (I N) 3 4 CHEM 121
45 8 CHEM 121
& CHEM
122
Vanderbi l t Uni versi ty (TN) 4 Permi ts entry i nto
Chemi stry 218a.
600 APPENDIX
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Course
Waived Stipulations
Vanderbi l t Uni versi ty
continued
5 8 CHEM
102a, 102b,
& CHEM
104a, 104b
Vassar Col l ege (NY) 45
Vi l l anova Uni versi ty (PA) 5
Vi rgi ni a Mi l i tary
I nsti tute (VA)
35 8 CH 137 &
CH 138
w/l abs
Chemi stry majors must take
fi rst-year chemi stry; al l
others wi l l recei ve credi t
dependi ng upon score and
curri cul um.
Vi rgi ni a Pol ytechni c
I nsti tute and State
Uni versi ty (VA)
45 8 CHEM
1035, 1045,
1036, &
1046
Wabash Col l ege (I N) 45 Advanced Pl acement credi ts
earned i n Bi ol ogy, Chemi stry,
or Physi cs wi l l NOT ful fi l l
the col l ege l aboratory sci ence
di stri buti on requi rement.
Wagner Col l ege (NY) 45
Wake Forest Uni versi ty (NC) 45 4 CHM 111
& CHM
111L
Wartburg Col l ege (I A) 3 CH 113 Wi th recommendati on to
audi t CH 113.
45 CH 113 Wi th no recommendati on to
audi t.
Washi ngton & Jefferson
Col l ege (PA)
45
Washi ngton and Lee
Uni versi ty (VA)
4 4 CHEM 100
5 7 CHEM 100
& CHEM
15CN
Washi ngton Col l ege (MD) 45 8 CHE 101
& CHE
102
Washi ngton Uni versi ty i n St.
Loui s (MO)
4 6 El ecti ve
credi t
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Waived Stipulations
Washi ngton Uni versi ty i n St.
Loui scontinued
5 10 CHEM
111A,
112A, 151,
& 152
Students are permi tted to
pl ace i nto Chem 251.
However, students who
i ntend to major i n chemi stry
may fi nd i t useful to take the
enti re general chemi stry
sequence i n preparati on for
advanced coursework.
Wel l esl ey Col l ege (MA) 45 CHEM 105
& 205 or
CHEM 120
Wel l s Col l ege (NY) 45
Wesl eyan Col l ege (GA) 45
Wesl eyan Uni versi ty (CT) 4 Students can recei ve 1.00
credi t by ei ther: a)
compl eti ng CHEM 144 wi th
a mi ni mum grade of B, or b)
compl eti ng a ful l year of
Organi c Chemi stry (251 &
252) wi th a mi ni mum grade
of B.
5 Students can recei ve 2.00
credi ts by compl eti ng a ful l
year of Organi c Chemi stry
(251 & 252) wi th a mi ni mum
grade of B. No credi t wi l l be
granted i f a student
compl etes any of the
fol l owi ng courses: CHEM
141, 142, 143, or 144.
Western Washi ngton
Uni versi ty (WA)
35 10 CHEM 121
& CHEM
122
Westmi nster Col l ege (UT) 3 8 CHEM
100T
45 8 CHEM 111
& CHEM
112
Westmont Col l ege (CA) 45
Wheaton Col l ege (I L) 35 4
Wheaton Col l ege (MA) 45
602 APPENDIX
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Course
Waived Stipulations
Whi tman Col l ege (WA) 45 3 CHEM 125 AP credi t does not cover
chemi stry l aboratory courses.
Students must have
compl eted and passed
Chemi stry 135, or an
equi val ent col l ege chemi stry
course, i n order to enrol l i n
Chemi stry 136.
Whi tworth Col l ege (WA) 34 4 CH 161 I n Chemi stry, documentati on
of l ab experi ence requi red for
4th credi t.
5 8 CH 161 &
CH 281
I n Chemi stry, documentati on
of l ab experi ence requi red for
4th credi t.
Wi l l amette Uni versi ty (OR) 45 CHEM 115 These course credi ts do not
sati sfy Mode of I nqui ry
general requi rements.
Wi l l i am Jewel l Col l ege (MO) 45 4 CHE 121
Wi l l i ams Col l ege (MA) 35 Dept.
Assi gns
Pl acement and major course
credi t depend on department
exam resul ts and
consul tati on wi th the
department.
Wi nona State
Uni versi ty (MN)
35
Wi ttenberg Uni versi ty (OH) 45
Wofford Col l ege (SC) 45 8 CHEM 123
& CHEM
124
Chemi stry majors must
val i date thi s score by
passi ng a test admi ni stered
by the chemi stry
department.
Worcester Pol ytechni c
I nsti tute (MA)
45 Students who pass the
advanced pl acement test i n
Bi ol ogy, Chemi stry, or
Physi cs B wi th a 4 or 5 wi l l
be awarded 1/3 uni t of
advanced pl acement credi t.
Thi s credi t wi l l show on the
transcri pt as L.
Xavi er Uni versi ty (OH) 3 3 CHEM 160 Those taki ng CHEM 161
(l ab) must audi t CHEM 160.
4 7 CHEM 160
& CHEM
161 &
CHEM 162
Those taki ng CHEM 163
(l ab) must audi t CHEM 162.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Course
Waived Stipulations
Xavi er
Uni versi tycontinued
5 9 CHEM
160/161 &
CHEM
162/163
Yal e Uni versi ty (CT) 5
604 APPENDIX
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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NOTES
NOTES
NOTES
NOTES
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You Try It!

100 PART III: AP Chemistry Review

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

1.5 atm 0.5 liters

5 0.865 mol PbI

5 0.418 mol PbI

5 0.051813 mol Li i ons can be reduced.

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14. What was the key fi ndi ng i n Ruther-

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(25 mm Hg) 5 35.7 mm Hg

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