You are on page 1of 53

Chemistry The Central Science 13th

Edition Theodore E. Brown


Visit to download the full and correct content document:
https://textbookfull.com/product/chemistry-the-central-science-13th-edition-theodore-e
-brown-2/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Chemistry The Central Science 13th Edition Theodore E.


Brown

https://textbookfull.com/product/chemistry-the-central-
science-13th-edition-theodore-e-brown-2/

Chemistry The Central Science 14th Edition in SI Units


Theodore L. Brown

https://textbookfull.com/product/chemistry-the-central-
science-14th-edition-in-si-units-theodore-l-brown/

Chemistry 2nd Edition Catrin Brown

https://textbookfull.com/product/chemistry-2nd-edition-catrin-
brown/

Chemistry 13th Edition Raymond Chang

https://textbookfull.com/product/chemistry-13th-edition-raymond-
chang/
Organic chemistry William Henry Brown

https://textbookfull.com/product/organic-chemistry-william-henry-
brown/

Human Universals Donald E. Brown

https://textbookfull.com/product/human-universals-donald-e-brown/

Organic Chemistry 8th Edition William H. Brown

https://textbookfull.com/product/organic-chemistry-8th-edition-
william-h-brown/

Strength Training 2nd Edition Lee E. Brown

https://textbookfull.com/product/strength-training-2nd-edition-
lee-e-brown/

Personal finance. 13th Edition E Thomas Garman

https://textbookfull.com/product/personal-finance-13th-edition-e-
thomas-garman/
Chemistry
T h e C e n T r a l S C i e n C e 13 Th ediTion
Chemistry
T h e C e n T r a l S C i e n C e 13 Th ediTion

Theodore L. Brown
University of illinois at Urbana-Champaign

H. Eugene LeMay, Jr.


University of Nevada, reno

Bruce E. Bursten
University of tennessee, Knoxville

Catherine J. Murphy
University of illinois at Urbana-Champaign

Patrick M. Woodward
the Ohio state University

Matthew W. Stoltzfus
the Ohio state University

Boston Columbus indianapolis new York San Francisco Upper Saddle river
amsterdam Cape Town dubai london Madrid Milan Munich Paris Montréal Toronto
delhi Mexico City São Paulo Sydney hong Kong Seoul Singapore Taipei Tokyo
Editor in Chief, Chemistry: Adam Jaworski
Senior Acquisitions Editor: Terry Haugen
Acquisitions Editor: Chris Hess, Ph.D.
Executive Marketing Manager: Jonathan Cottrell
Associate Team Lead, Program Management, Chemistry and Geoscience: Jessica Moro
Editorial Assistant: Lisa Tarabokjia/Caitlin Falco
Marketing Assistant: Nicola Houston
Director of Development: Jennifer Hart
Development Editor, Text: Carol Pritchard-Martinez
Team Lead, Project Management, Chemistry and Geosciences: Gina M. Cheselka
Project Manager: Beth Sweeten
Full-Service Project Management/Composition: Greg Johnson, PreMediaGlobal
Operations Specialist: Christy Hall
Illustrator: Precision Graphics
Art Director: Mark Ong
Interior / Cover Designer: Tamara Newnam
Image Lead: Maya Melenchuk
Photo Researcher: Kerri Wilson, PreMediaGlobal
Text Permissions Manager: Alison Bruckner
Text Permission Researcher: Jacqueline Bates, GEX Publishing Services
Senior Content Producer: Kristin Mayo
Production Supervisor, Media: Shannon Kong
Electrostatic Potential Maps: Richard Johnson, Chemistry Department, University of New Hampshire
Cover Image Credit: “Metal-Organic Frameworks” by Omar M. Yaghi, University of California, Berkeley

Credits and acknowledgments borrowed from other sources and reproduced, with permission, in this textbook appear on the
appropriate page within the text or on pp. P-1–P-2.

Copyright © 2015, 2012, 2009, 2006, 2003, 2000, 1997, 1994, 1991, 1988, 1985, 1981, 1977 Pearson Education, Inc. All rights
reserved. Manufactured in the United States of America. This publication is protected by Copyright, and permission should be
obtained from the publisher prior to any prohibited reproduction, storage in a retrieval system, or transmission in any form or by
any means, electronic, mechanical, photocopying, recording, or likewise. To obtain permission(s) to use material from this work,
please submit a written request to Pearson Education, Inc., Permissions Department, 1 Lake Street, Department 1G, Upper Saddle
River, NJ 07458.

Many of the designations used by manufacturers and sellers to distinguish their products are claimed as trademarks. Where those
designations appear in this book, and the publisher was aware of a trademark claim, the designations have been printed in initial
caps or all caps.

Library of Congress Cataloging-In Publication Data


Brown, Theodore L. (Theodore Lawrence), 1928- author.
Chemistry the central science.—Thirteenth edition / Theodore L. Brown, University of Illinois at Urbana-Chanmpaign,
H. Euguene LeMay, Jr., University of Nevada, Reno, Bruce E. Bursten, University of Tennessee, Knoxville,
Catherine J. Murphy, University of Illinois at Urbana-Chanmpaign, Patrick M. Woodward, The Ohio State University,
Matthew W. Stoltzfus, The Ohio State University.
pages cm
Includes index.
ISBN-13: 978-0-321-91041-7
ISBN-10: 0-321-91041-9
1. Chemistry--Textbooks. I. Title.
QD31.3.B765 2014
540—dc23 2013036724

1 2 3 4 5 6 7 8 9 10—CRK— 17 16 15 14

Student Edition: 0-321-91041-9 / 978-0-321-91041-7


www.pearsonhighered.com Instructor’s Resource Copy: 0-321-96239-7 / 978-0-321-96239-3
To our students,
whose enthusiasm and curiosity
have often inspired us,
and whose questions and suggestions
have sometimes taught us.
ontents
Preface xx

1 Introduction: Matter and Measurement 2


2 Atoms, Molecules, and Ions 40
3 Chemical Reactions and Reaction Stoichiometry 80
4 Reactions in Aqueous Solution 122
5 Thermochemistry 164
6 Electronic Structure of Atoms 212
7 Periodic Properties of the Elements 256
8 Basic Concepts of Chemical Bonding 298
9 Molecular Geometry and Bonding Theories 342
10 Gases 398
11 Liquids and Intermolecular Forces 442
12 Solids and Modern Materials 480
13 Properties of Solutions 530
14 Chemical Kinetics 574
15 Chemical Equilibrium 628
16 Acid–Base Equilibria 670
17 Additional Aspects of Aqueous Equilibria 724
18 Chemistry of the Environment 774
19 Chemical Thermodynamics 812
20 Electrochemistry 856
21 Nuclear Chemistry 908
22 Chemistry of the Nonmetals 952
23 Transition Metals and Coordination Chemistry 996
24 The Chemistry of Life: Organic and Biological Chemistry 1040
APPENdICES
A Mathematical Operations 1092
B Properties of Water 1099
C Thermodynamic Quantities for Selected Substances at
298.15 K (25 °C) 1100
D Aqueous Equilibrium Constants 1103
E Standard Reduction Potentials at 25 °C 1105
Answers to Selected Exercises A-1
Answers to Give It Some Thought A-31
Answers to Go Figure A-38
Answers to Selected Practice Exercises A-44
Glossary G-1
Photo/Art Credits P-1
Index I-1
vi
ontents
Preface xx

2 Atoms, Molecules,
1 Introduction: Matter and Ions 40
and Measurement 2 2.1 The Atomic Theory of Matter 42
2.2 The discovery of Atomic Structure 43
1.1 The Study of Chemistry 2
Cathode Rays and Electrons 43
The Atomic and Molecular Perspective of Radioactivity 45 The Nuclear Model of the
Chemistry 4 Why Study Chemistry? 5 Atom 46
1.2 Classifications of Matter 6 2.3 The Modern View of Atomic Structure 47
States of Matter 7 Pure Substances 7 Atomic Numbers, Mass Numbers, and
Elements 7 Compounds 8 Mixtures 10 Isotopes 49
1.3 Properties of Matter 11 2.4 Atomic Weights 50
Physical and Chemical Changes 12 The Atomic Mass Scale 50 Atomic Weight 51
Separation of Mixtures 13
2.5 The Periodic Table 52
1.4 Units of Measurement 14
2.6 Molecules and Molecular
SI Units 15 Length and Mass 17
Compounds 56
Temperature 17 derived SI Units 19
Volume 19 density 19 Molecules and Chemical Formulas 56
Molecular and Empirical Formulas 56
1.5 Uncertainty in Measurement 22 Picturing Molecules 57
Precision and Accuracy 22 Significant
2.7 Ions and Ionic Compounds 58
Figures 22 Significant Figures in
Calculations 22 Predicting Ionic Charges 59 Ionic
Compounds 60
1.6 dimensional Analysis 27
2.8 Naming Inorganic Compounds 62
Using Two or More Conversion Factors 28
Conversions Involving Volume 29 Names and Formulas of Ionic Compounds 62
Names and Formulas of Acids 67 Names and
Chapter Summary and Key Terms 32
Formulas of Binary Molecular Compounds 68
Learning Outcomes 32
Key Equations 32 Exercises 32 Additional 2.9 Some Simple Organic Compounds 69
Exercises 37 Alkanes 69 Some derivatives of Alkanes 70
Chemistry Put to Work Chemistry and the Chapter Summary and Key Terms 72
Chemical Industry 6 Learning Outcomes 72 Key
Equations 73 Exercises 73
A Closer Look The Scientific Method 14
Additional Exercises 78
Chemistry Put to Work Chemistry in
the News 20 A Closer Look Basic Forces 49
Strategies in Chemistry Estimating Answers 28 A Closer Look The Mass Spectrometer 52
Strategies in Chemistry The Importance of A Closer Look What Are Coins Made Of? 54
Practice 31 Chemistry and Life Elements Required by Living
Strategies in Chemistry The Features of This Organisms 61
Book 32 Strategies in Chemistry How to Take a Test 71

vii
viii Contents

Electrolytes and Nonelectrolytes 124 How


Compounds dissolve in Water 125 Strong
and Weak Electrolytes 126
4.2 Precipitation Reactions 128

3
Solubility Guidelines for Ionic

Chemical Reactions Compounds 129 Exchange (Metathesis)


Reactions 130 Ionic Equations and Spectator
and Reaction Ions 131
4.3 Acids, Bases, and Neutralization
Stoichiometry 80 Reactions 132
3.1 Chemical Equations 82 Acids 132 Bases 133 Strong and Weak
Acids and Bases 133 Identifying Strong
Balancing Equations 82 Indicating the States
and Weak Electrolytes 135 Neutralization
of Reactants and Products 85
Reactions and Salts 135 Neutralization
3.2 Simple Patterns of Chemical Reactivity 86 Reactions with Gas Formation 138
Combination and decomposition
4.4 Oxidation–Reduction Reactions 138
Reactions 86 Combustion Reactions 89
Oxidation and Reduction 138 Oxidation
3.3 Formula Weights 89 Numbers 140 Oxidation of Metals by Acids
Formula and Molecular Weights 90 and Salts 142 The Activity Series 143
Percentage Composition from Chemical
4.5 Concentrations of Solutions 146
Formulas 91
Molarity 146 Expressing the Concentration
3.4 Avogadro’s Number and the Mole 91 of an Electrolyte 147 Interconverting Molarity,
Molar Mass 93 Interconverting Masses Moles, and Volume 148 dilution 149
and Moles 95 Interconverting Masses and
4.6 Solution Stoichiometry and Chemical
Numbers of Particles 96
Analysis 151
3.5 Empirical Formulas from Analyses 98 Titrations 152
Molecular Formulas from Empirical
Chapter Summary and Key Terms 155
Formulas 100 Combustion Analysis 101
Learning Outcomes 156 Key
3.6 Quantitative Information from Balanced Equations 156 Exercises 156
Equations 103 Additional Exercises 161 Integrative
Exercises 161 design an
3.7 Limiting Reactants 106
Experiment 163
Theoretical and Percent Yields 109
Chemistry Put to Work Antacids 139
Chapter Summary and Key Terms 111
Learning Outcomes 111 Key Equations 112 Strategies in Chemistry Analyzing Chemical
Exercises 112 Additional Exercises 118 Reactions 146
Integrative Exercises 120 design an
Experiment 120
Strategies in Chemistry Problem Solving 92
Chemistry and Life Glucose Monitoring 95
Strategies in Chemistry Design an
Experiment 110
5 Thermochemistry 164
5.1 Energy 166
Kinetic Energy and Potential Energy 166
Units of Energy 168 System and

4
Surroundings 169 Transferring Energy: Work
and Heat 169
Reactions in Aqueous 5.2 The First Law of Thermodynamics 170
Solution 122 Internal Energy 171 Relating ∆E to Heat and
Work 172 Endothermic and Exothermic
4.1 General Properties of Aqueous Processes 173 State Functions 174
Solutions 124
Contents ix

5.3 Enthalpy 175 Orbitals and Quantum Numbers 228


Pressure–Volume Work 175 Enthalpy 6.6 Representations of Orbitals 230
Change 177 The s Orbitals 230 The p Orbitals 233
5.4 Enthalpies of Reaction 179 The d and f Orbitals 233

5.5 Calorimetry 181 6.7 Many-Electron Atoms 234


Heat Capacity and Specific Heat 181 Orbitals and Their Energies 234 Electron Spin
Constant-Pressure Calorimetry 183 and the Pauli Exclusion Principle 235
Bomb Calorimetry (Constant-Volume 6.8 Electron Configurations 237
Calorimetry) 185 Hund’s Rule 237 Condensed Electron
5.6 Hess’s Law 187 Configurations 239 Transition
Metals 240 The Lanthanides and
5.7 Enthalpies of Formation 189 Actinides 240
Using Enthalpies of Formation to Calculate
6.9 
Electron Configurations and the
Enthalpies of Reaction 192
Periodic Table 241
5.8 Foods and Fuels 194 Anomalous Electron Configurations 245
Foods 194 Fuels 197 Other Energy Chapter Summary and Key Terms 246
Sources 198 Learning Outcomes 247 Key Equations 247
Chapter Summary and Key Terms 200 Exercises 248 Additional Exercises 252
Learning Outcomes 201 Key Equations 202 Integrative Exercises 255 Design an
Exercises 202 Additional Exercises 209 Experiment 255
Integrative Exercises 210 Design an A Closer Look Measurement and the Uncertainty
Experiment 211 Principle 225
A Closer Look Energy, Enthalpy, and P–V A Closer Look Thought Experiments and
Work 178 Schrödinger’s Cat 227
Strategies in Chemistry Using Enthalpy as a A Closer Look Probability Density and Radial
Guide 181 Probability Functions 232
Chemistry and Life The Regulation of Body Chemistry and Life Nuclear Spin and Magnetic
Temperature 186 Resonance Imaging 236

Chemistry Put to Work The Scientific and


Political Challenges of Biofuels 198

7 Periodic Properties of
6  lectronic Structure of
E
the Elements
7.1 Development of the Periodic
256

Atoms 212 Table 258


6.1 The Wave Nature of Light 214 7.2 Effective Nuclear Charge 259
6.2 Quantized Energy and Photons 216 7.3 Sizes of Atoms and Ions 262
Hot Objects and the Quantization of Energy 216 Periodic Trends in Atomic Radii 264 Periodic
The Photoelectric Effect and Photons 217 Trends in Ionic Radii 265

6.3 Line Spectra and the Bohr Model 219 7.4 Ionization Energy 268
Variations in Successive Ionization
Line Spectra 219 Bohr’s Model 220
Energies 268 Periodic Trends in First
The Energy States of the Hydrogen Atom 221
Ionization Energies 268 Electron
Limitations of the Bohr Model 223
Configurations of Ions 271
6.4 The Wave Behavior of Matter 223
7.5 Electron Affinity 272
The Uncertainty Principle 225
7.6 Metals, Nonmetals, and
6.5 
Quantum Mechanics and Atomic Metalloids 273
Orbitals 226 Metals 274 Nonmetals 276 Metalloids 277
x Contents

7.7 
Trends for Group 1A and Group 2A Bond Enthalpies and the Enthalpies of
Metals 278 Reactions 327 Bond Enthalpy and Bond
Length 329
Group 1A: The Alkali Metals 278 Group 2A:
The Alkaline Earth Metals 281 Chapter Summary and Key Terms 332
Learning Outcomes 333 Key Equations 333
7.8 Trends for Selected Nonmetals 282 Exercises 333 Additional Exercises 338
Hydrogen 282 Group 6A: The Oxygen Integrative Exercises 340 Design an
Group 283 Group 7A: The Halogens 284 Experiment 341
Group 8A: The Noble Gases 286 A Closer Look Calculation of Lattice Energies: The
Chapter Summary and Key Terms 288 Born–Haber Cycle 304
Learning Outcomes 289 Key Equations 289 A Closer Look Oxidation Numbers, Formal Charges,
Exercises 289 Additional Exercises 294
and Actual Partial Charges 319
Integrative Exercises 296 Design an
Experiment 297 Chemistry Put to Work Explosives and Alfred
Nobel 330
A Closer Look Effective Nuclear Charge 261
Chemistry Put to Work Ionic Size and
Lithium-Ion Batteries 267
Chemistry and Life The Improbable Development
of Lithium Drugs 281

9 Molecular Geometry
and Bonding
Theories 342
8 Basic Concepts of 9.1 Molecular Shapes 344
Chemical Bonding 298 9.2 The Vsepr Model 347
Effect of Nonbonding Electrons and Multiple
8.1 Lewis Symbols and the Octet Rule 300 Bonds on Bond Angles 351 Molecules with
The Octet Rule 300 Expanded Valence Shells 352 Shapes of
8.2 Ionic Bonding 301 Larger Molecules 355
Energetics of Ionic Bond Formation 302 9.3 
Molecular Shape and Molecular
Electron Configurations of Ions of the s- and Polarity 356
p-Block Elements 305 Transition Metal 9.4 Covalent Bonding and Orbital Overlap 358
Ions 306
9.5 Hybrid Orbitals 359
8.3 Covalent Bonding 306 sp Hybrid Orbitals 360 sp2 and sp3 Hybrid
Lewis Structures 307 Multiple Bonds 308 Orbitals 361 Hypervalent Molecules 362
8.4 Bond Polarity and Electronegativity 309 Hybrid Orbital Summary 364
Electronegativity 309 Electronegativity and 9.6 Multiple Bonds 365
Bond Polarity 310 Dipole Moments 311 Resonance Structures, Delocalization, and p
Differentiating Ionic and Covalent Bonding 314 Bonding 368 General Conclusions about s
8.5 Drawing Lewis Structures 315 and p Bonding 372
Formal Charge and Alternative Lewis 9.7 Molecular Orbitals 373
Structures 317 Molecular Orbitals of the Hydrogen
8.6 Resonance Structures 320 Molecule 373 Bond Order 375
Resonance in Benzene 322 9.8 Period 2 Diatomic Molecules 376
8.7 Exceptions to the Octet Rule 322 Molecular Orbitals for Li 2 and Be 2 377
Odd Number of Electrons 323 Less Than an Molecular Orbitals from 2p Atomic
Octet of Valence Electrons 323 More Than an Orbitals 377 Electron Configurations for B 2
Octet of Valence Electrons 324 through Ne 2 381 Electron Configurations
and Molecular Properties 383 Heteronuclear
8.8 
Strengths and Lengths of Covalent Bonds 325
Diatomic Molecules 384
Contents xi

Chapter Summary and Key Terms 386 Exercises 432 Additional Exercises 438
Learning Outcomes 387 Key Equations 388 Integrative Exercises 440 Design an
Exercises 388 Additional Exercises 393 Experiment 441
Integrative Exercises 396 Design an Strategies in Chemistry Calculations Involving
Experiment 397
Many Variables 410
Chemistry and Life The Chemistry of Vision 372
A Closer Look The Ideal-Gas Equation 421
A Closer Look Phases in Atomic and Molecular
Chemistry Put to Work Gas Separations 425
Orbitals 379
Chemistry Put to Work Orbitals and Energy 385

10 Gases 11 Liquids and


398 Intermolecular
10.1 Characteristics of Gases 400 Forces 442
10.2 Pressure 401
11.1 
A Molecular Comparison of Gases,
Atmospheric Pressure and the Barometer 401
Liquids, and Solids 444
10.3 The Gas Laws 404
11.2 Intermolecular Forces 446
The Pressure–Volume Relationship: Boyle’s
Dispersion Forces 447 Dipole–Dipole
Law 404 The Temperature–Volume
Forces 448 Hydrogen Bonding 449
Relationship: Charles’s Law 406 The
Ion–Dipole Forces 452 Comparing
Quantity–Volume Relationship: Avogadro’s
Intermolecular Forces 452
Law 406
11.3 Select Properties of Liquids 455
10.4 The Ideal-Gas Equation 408
Viscosity 455 Surface Tension 456 Capillary
Relating the Ideal-Gas Equation and the Gas
Action 456
Laws 410
11.4 Phase Changes 457
10.5 
Further Applications of the Ideal-Gas
Energy Changes Accompanying Phase
Equation 412
Changes 457 Heating Curves 459 Critical
Gas Densities and Molar Mass 413 Volumes
Temperature and Pressure 460
of Gases in Chemical Reactions 414
11.5 Vapor Pressure 461
10.6 Gas Mixtures and Partial
Volatility, Vapor Pressure, and
Pressures 415
Temperature 462 Vapor Pressure and Boiling
Partial Pressures and Mole Fractions 417 Point 463
10.7 The Kinetic-Molecular Theory of 11.6 Phase Diagrams 464
Gases 418
The Phase Diagrams of H 2O and CO2 465
Distributions of Molecular Speed 419
Application of Kinetic-Molecular Theory to the 11.7 Liquid Crystals 467
Gas Laws 420 Types of Liquid Crystals 467
10.8 Molecular Effusion and Diffusion 421 Chapter Summary and Key Terms 470
Learning Outcomes 471 Exercises 471
Graham’s Law of Effusion 423 Diffusion and
Additional Exercises 477 Integrative
Mean Free Path 424
Exercises 478 Design an
10.9 Real Gases: Deviations from Ideal Experiment 479
Behavior 426 Chemistry Put to Work Ionic
The van der Waals Equation 428 Liquids 454
Chapter Summary and Key Terms 431 A Closer Look The Clausius–Clapeyron
Learning Outcomes 431 Key Equations 432 Equation 463
xii Contents

12 Solids and Modern 13 Properties of


Materials 480 Solutions 530
12.1 Classification of Solids 480 13.1 The Solution Process 530
12.2 Structures of Solids 482 The Natural Tendency toward Mixing 532
Crystalline and Amorphous Solids 482 Unit The Effect of Intermolecular Forces on Solution
Cells and Crystal Lattices 483 Filling the Unit Formation 532 Energetics of Solution
Cell 485 Formation 533 Solution Formation and
Chemical Reactions 535
12.3 Metallic Solids 486
The Structures of Metallic Solids 487 Close
13.2 Saturated Solutions and Solubility 536
Packing 488 Alloys 491 13.3 Factors Affecting Solubility 538
12.4 Metallic Bonding 494 Solute–Solvent Interactions 538 Pressure
Effects 541 Temperature Effects 543
Electron-Sea Model 494 Molecular–Orbital
Model 495 13.4 Expressing Solution Concentration 544
12.5 Ionic Solids 498 Mass Percentage, ppm, and ppb 544 Mole
Fraction, Molarity, and Molality 545
Structures of Ionic Solids 498
Converting Concentration Units 547
12.6 Molecular Solids 502
13.5 Colligative Properties 548
12.7 Covalent-Network Solids 503
Vapor-Pressure Lowering 548 Boiling-Point
Semiconductors 504 Semiconductor Elevation 551 Freezing-Point Depression 552
Doping 506 Osmosis 554 Determination of Molar Mass
12.8 Polymers 507 from Colligative Properties 557
Making Polymers 509 Structure and Physical 13.6 Colloids 559
Properties of Polymers 511 Hydrophilic and Hydrophobic Colloids 560
12.9 Nanomaterials 514 Colloidal Motion in Liquids 562
Semiconductors on the Nanoscale 514 Metals Chapter Summary and Key Terms 564
on the Nanoscale 515 Carbons on the Learning Outcomes 565 Key Equations 565
Nanoscale 516 Exercises 566 Additional Exercises 571
Chapter Summary and Key Terms 519 Integrative Exercises 572 Design an
Learning Outcomes 520 Key Equation 520 Experiment 573
Exercises 521 Additional Exercises 527 Chemistry and Life Fat-Soluble and Water-Soluble
Integrative Exercises 528 Design an Vitamins 539
Experiment 529 Chemistry and Life Blood Gases and Deep-Sea
A Closer Look X-ray Diffraction 486 Diving 544
Chemistry Put to Work Alloys of Gold 494 A Closer Look Ideal Solutions with Two or More
Chemistry Put to Work Solid-State Volatile Components 550
Lighting 508 A Closer Look The Van’t Hoff Factor 558
Chemistry Put to Work Recycling Chemistry and Life Sickle-Cell Anemia 562
Plastics 511
Contents xiii

14 Chemical Kinetics 574 15 Chemical


14.1 Factors that Affect Reaction Rates 576 Equilibrium 628
14.2 Reaction Rates 577 15.1 The Concept of Equilibrium 630
Change of Rate with Time 579 Instantaneous
15.2 The Equilibrium Constant 632
Rate 579 Reaction Rates and
Stoichiometry 580 Evaluating Kc 634 Equilibrium Constants
in Terms of Pressure, Kp 635 Equilibrium
14.3 Concentration and Rate Laws 581 Constants and Units 636
Reaction Orders: The Exponents in the
15.3 
Understanding and Working with
Rate Law 584 Magnitudes and Units of
Rate Constants 585 Using Initial Rates to
Equilibrium Constants 637
Determine Rate Laws 586 The Magnitude of Equilibrium Constants 637
The Direction of the Chemical Equation
14.4 
The Change of Concentration with
and K 639 Relating Chemical Equation
Time 587 Stoichiometry and Equilibrium Constants 639
First-Order Reactions 587 Second-Order
15.4 Heterogeneous Equilibria 641
Reactions 589 Zero-Order Reactions 591
Half-Life 591 15.5 Calculating Equilibrium Constants 644
14.5 Temperature and Rate 593 15.6 Applications of Equilibrium Constants 646
The Collision Model 593 The Orientation Predicting the Direction of Reaction 646
Factor 594 Activation Energy 594 The Calculating Equilibrium Concentrations 648
Arrhenius Equation 596 Determining the 15.7 Le Châtelier’s Principle 650
Activation Energy 597 Change in Reactant or Product
14.6 Reaction Mechanisms 599 Concentration 651 Effects of Volume and
Elementary Reactions 599 Multistep Pressure Changes 652 Effect of Temperature
Mechanisms 600 Rate Laws for Elementary Changes 654 The Effect of Catalysts 657
Reactions 601 The Rate-Determining Step Chapter Summary and Key Terms 660
for a Multistep Mechanism 602 Mechanisms Learning Outcomes 660 Key Equations 661
with a Slow Initial Step 603 Mechanisms Exercises 661 Additional Exercises 666
with a Fast Initial Step 604 Integrative Exercises 668 Design an
Experiment 669
14.7 Catalysis 606
Homogeneous Catalysis 607 Heterogeneous Chemistry Put to Work The Haber Process 633
Catalysis 608 Enzymes 609 Chemistry Put to Work Controlling Nitric Oxide
Emissions 659
Chapter Summary and Key Terms 614
Learning Outcomes 614 Key Equations 615
Exercises 615 Additional Exercises 624
Integrative Exercises 626 Design an
Experiment 627
A Closer Look Using Spectroscopic Methods to

16 Acid–Base Equilibria
Measure Reaction Rates: Beer’s Law 582
Chemistry Put to Work Methyl Bromide in the
Atmosphere 592
670
Chemistry Put to Work Catalytic Converters 610 16.1 Acids and Bases: A Brief Review 672
Chemistry and Life Nitrogen Fixation and 16.2 BrØnsted–Lowry Acids and Bases 673
Nitrogenase 612
xiv Contents

The H + Ion in Water 673 Proton-Transfer 17.3 Acid–Base Titrations 738


Reactions 673 Conjugate Acid–Base Pairs 674 Strong Acid–Strong Base Titrations 738 Weak
Relative Strengths of Acids and Bases 676 Acid–Strong Base Titrations 740 Titrating
16.3 The Autoionization of Water 678 with an Acid–Base Indicator 744 Titrations of
The Ion Product of Water 679 Polyprotic Acids 746
16.4 The pH Scale 680 17.4 Solubility Equilibria 748
pOH and Other “p” Scales 682 Measuring The Solubility-Product Constant, Ksp 748
pH 683 Solubility and Ksp 749
16.5 Strong Acids and Bases 684 17.5 Factors That Affect Solubility 751
Strong Acids 684 Strong Bases 685 Common-Ion Effect 751 Solubility and
pH 753 Formation of Complex Ions 756
16.6 Weak Acids 686
Amphoterism 758
Calculating Ka from pH 688 Percent
Ionization 689 Using Ka to Calculate pH 690 17.6 Precipitation and Separation of Ions 759
Polyprotic Acids 694 Selective Precipitation of Ions 760
16.7 Weak Bases 696 17.7 
Qualitative Analysis for Metallic
Types of Weak Bases 698 Elements 762
16.8 Relationship between Ka and Kb 699 Chapter Summary and Key Terms 765
Learning Outcomes 765 Key Equations 766
16.9 Acid–Base Properties of Salt Solutions 702 Exercises 766 Additional Exercises 771
An Anion’s Ability to React with Water 702 Integrative Exercises 772 Design an
A Cation’s Ability to React with Water 702 Experiment 773
Combined Effect of Cation and Anion in Chemistry and Life Blood as a Buffered
Solution 704 Solution 737
16.10 
Acid–Base Behavior and Chemical A Closer Look Limitations of Solubility
Structure 705 Products 751
Factors That Affect Acid Strength 705 Binary Chemistry and Life Ocean Acidification 753
Acids 706 Oxyacids 707 Carboxylic Chemistry and Life Tooth Decay and
Acids 709
Fluoridation 755
16.11 Lewis Acids and Bases 710
Chapter Summary and Key Terms 713
Learning Outcomes 714 Key Equations 714
Exercises 715 Additional Exercises 720
Integrative Exercises 722 Design an

18 Chemistry of the
Experiment 723
Chemistry Put to Work Amines and Amine
Hydrochlorides 701
Chemistry and Life The Amphiprotic Behavior of
Amino Acids 709
Environment 774
18.1 Earth’s Atmosphere 776
Composition of the Atmosphere 776
Photochemical Reactions in the
Atmosphere 778 Ozone in the
Stratosphere 780

17 Additional Aspects of
18.2 
Human Activities and Earth’s
Atmosphere 782
The Ozone Layer and Its Depletion 782 Sulfur
Aqueous Equilibria 724 Compounds and Acid Rain 784 Nitrogen
Oxides and Photochemical Smog 786
17.1 The Common-Ion Effect 726 Greenhouse Gases: Water Vapor, Carbon
17.2 Buffers 729 Dioxide, and Climate 787
Composition and Action of Buffers 729 18.3 Earth’s Water 791
Calculating the pH of a Buffer 731 Buffer The Global Water Cycle 791 Salt Water:
Capacity and pH Range 734 Addition of Earth’s Oceans and Seas 792 Freshwater and
Strong Acids or Bases to Buffers 735 Groundwater 792
Contents xv

18.4 Human Activities and Water Quality 794 Learning Outcomes 844 Key Equations 845
Exercises 845 Additional Exercises 851
Dissolved Oxygen and Water Quality 794
Integrative Exercises 853 Design an
Water Purification: Desalination 795 Water
Experiment 855
Purification: Municipal Treatment 796
A Closer Look The Entropy Change When a Gas
18.5 Green Chemistry 798
Expands Isothermally 820
Supercritical Solvents 800 Greener Reagents
Chemistry and Life Entropy and Human
and Processes 800
Society 828
Chapter Summary and Key Terms 803
A Closer Look What’s “Free” about Free Energy? 836
Learning Outcomes 803 Exercises 804
Additional Exercises 808 Integrative Chemistry and Life Driving Nonspontaneous
Exercises 809 Design an Experiment 811 Reactions: Coupling Reactions 842
A Closer Look Other Greenhouse Gases 790
A Closer Look The Ogallala Aquifer—A Shrinking
Resource 794
A Closer Look Fracking and Water Quality 797

20 Electrochemistry 856
20.1 
Oxidation States and Oxidation–Reduction

19 Chemical
Reactions 858
20.2 Balancing Redox Equations 860
Half-Reactions 860 Balancing Equations by
Thermodynamics 812 the Method of Half-Reactions 860 Balancing
Equations for Reactions Occurring in Basic
19.1 Spontaneous Processes 814 Solution 863
Seeking a Criterion for Spontaneity 816 20.3 Voltaic Cells 865
Reversible and Irreversible Processes 816
20.4 
Cell Potentials Under Standard
19.2 
Entropy and the Second Law of
Conditions 868
Thermodynamics 818
Standard Reduction Potentials 869 Strengths
The Relationship between Entropy and of Oxidizing and Reducing Agents 874
Heat 818 ∆S for Phase Changes 819 The
Second Law of Thermodynamics 820
20.5 Free Energy and Redox Reactions 876
Emf, Free Energy, and the Equilibrium
19.3 
The Molecular Interpretation of
Constant 877
Entropy and the Third Law of
Thermodynamics 821 20.6 
Cell Potentials Under Nonstandard
Conditions 880
Expansion of a Gas at the Molecular Level 821
Boltzmann’s Equation and Microstates 823 The Nernst Equation 880 Concentration
Molecular Motions and Energy 824 Making Cells 882
Qualitative Predictions about ∆S 825 The 20.7 Batteries and Fuel Cells 886
Third Law of Thermodynamics 827 Lead–Acid Battery 886 Alkaline Battery 887
19.4 
Entropy Changes in Chemical Nickel–Cadmium and Nickel–Metal Hydride
Reactions 828 Batteries 887 Lithium-Ion Batteries 887
Hydrogen Fuel Cells 889
Entropy Changes in the Surroundings 830
19.5 Gibbs Free Energy 831 20.8 Corrosion 891
Corrosion of Iron (Rusting) 891 Preventing
Standard Free Energy of Formation 834
Corrosion of Iron 892
19.6 Free Energy and Temperature 836
20.9 Electrolysis 893
19.7 
Free Energy and the Equilibrium
Quantitative Aspects of Electrolysis 894
Constant 838
Chapter Summary and Key Terms 897
Free Energy under Nonstandard
Learning Outcomes 898 Key Equations 899
Conditions 838 Relationship between ∆G° Exercises 899 Additional Exercises 905
and K 840 Integrative Exercises 907 Design an
Chapter Summary and Key Terms 844 Experiment 907
xvi Contents

A Closer Look Electrical Work 879


Chemistry and Life Heartbeats and
Electrocardiography 884
Chemistry Put to Work Batteries for Hybrid and
Electric Vehicles 889
Chemistry Put to Work Electrometallurgy of
Aluminum 895
22 Chemistry of the
Nonmetals 952
22.1 
Periodic Trends and Chemical
Reactions 952
Chemical Reactions 955
22.2 Hydrogen 956

21 Nuclear Chemistry 908


Isotopes of Hydrogen 956 Properties of
Hydrogen 957 Production of Hydrogen 958
Uses of Hydrogen 959 Binary Hydrogen
21.1 Radioactivity and Nuclear Equations 910 Compounds 959
Nuclear Equations 911 Types of Radioactive 22.3 Group 8A: The Noble Gases 960
Decay 912 Noble-Gas Compounds 961
21.2 Patterns of Nuclear Stability 914 22.4 Group 7A: The Halogens 962
Neutron-to-Proton Ratio 914 Radioactive Properties and Production of the Halogens 962
Decay Chains 916 Further Observations 916 Uses of the Halogens 964 The Hydrogen
21.3 Nuclear Transmutations 918 Halides 964 Interhalogen Compounds 965
Oxyacids and Oxyanions 966
Accelerating Charged Particles 918 Reactions
Involving Neutrons 919 Transuranium 22.5 Oxygen 966
Elements 920 Properties of Oxygen 967 Production of
21.4 Rates of Radioactive Decay 920 Oxygen 967 Uses of Oxygen 967
Ozone 967 Oxides 968 Peroxides and
Radiometric Dating 921 Calculations Based
Superoxides 969
on Half-Life 923
21.5 Detection of Radioactivity 926 22.6 
The Other Group 6A Elements: S, Se, Te,
and Po 970
Radiotracers 927
General Characteristics of the Group 6A
21.6 
Energy Changes in Nuclear Reactions 929
Elements 970 Occurrence and Production
Nuclear Binding Energies 930 of S, Se, and Te 970 Properties and Uses of
21.7 Nuclear Power: Fission 932 Sulfur, Selenium, and Tellurium 971
Nuclear Reactors 934 Nuclear Waste 936 Sulfides 971 Oxides, Oxyacids, and
Oxyanions of Sulfur 971
21.8 Nuclear Power: Fusion 937
21.9 
Radiation in the Environment and Living 22.7 Nitrogen 973
Systems 938 Properties of Nitrogen 973 Production and
Uses of Nitrogen 973 Hydrogen Compounds
Radiation Doses 940 Radon 942
of Nitrogen 973 Oxides and Oxyacids of
Chapter Summary and Key Terms 944 Nitrogen 975
Learning Outcomes 945 Key Equations 945
Exercises 946 Additional Exercises 949 22.8 
The Other Group 5A Elements: P, As, Sb,
Integrative Exercises 951 Design an and Bi 977
Experiment 951 General Characteristics of the Group 5A
Chemistry and Life Medical Applications of Elements 977 Occurrence, Isolation, and
Radiotracers 928 Properties of Phosphorus 977 Phosphorus
A Closer Look The Dawning of the Nuclear Halides 978 Oxy Compounds of
Phosphorus 978
Age 934
A Closer Look Nuclear Synthesis of the 22.9 Carbon 980
Elements 939 Elemental Forms of Carbon 980 Oxides
of Carbon 981 Carbonic Acid and
Chemistry and Life Radiation Therapy 943
Carbonates 983 Carbides 983
Contents xvii

22.10 
The Other Group 4A Elements: Si, Ge, Sn, Electron Configurations in Octahedral
and Pb 984 Complexes 1024 Tetrahedral and Square-
Planar Complexes 1026
General Characteristics of the Group 4A
Elements 984 Occurrence and Preparation of Chapter Summary and Key Terms 1030
Silicon 984 Silicates 985 Glass 986 Learning Outcomes 1031 Exercises 1031
Silicones 987 Additional Exercises 1035 Integrative
Exercises 1037 Design an Experiment 1039
22.11 Boron 987
A Closer Look Entropy and the Chelate
Chapter Summary and Key Terms 989
Learning Outcomes 990 Exercises 990 Effect 1010
Additional Exercises 994 Integrative Chemistry and Life The Battle for Iron in Living
Exercises 994 Design an Experiment 995 Systems 1011
A Closer Look The Hydrogen Economy 958 A Closer Look Charge-Transfer Color 1028
Chemistry and Life Nitroglycerin, Nitric Oxide,
and Heart Disease 976
Chemistry and Life Arsenic in
Drinking Water 980
Chemistry Put to Work Carbon Fibers and
Composites 982

24 The Chemistry of Life:


Organic and Biological
Chemistry 1040
23 Transition Metals 24.1 
General Characteristics of Organic
Molecules 1042
and Coordination The Structures of Organic Molecules 1042
The Stabilities of Organic Substances 1043
Chemistry 996 Solubility and Acid–Base Properties of Organic
Substances 1042
23.1 The Transition Metals 998
24.2 Introduction to Hydrocarbons 1044
Physical Properties 998
Structures of Alkanes 1045 Structural
Electron Configurations and Oxidation Isomers 1045 Nomenclature of Alkanes 1046
States 999 Magnetism 1001 Cycloalkanes 1049 Reactions of
23.2 Transition-Metal Complexes 1002 Alkanes 1049
The Development of Coordination Chemistry: 24.3 Alkenes, Alkynes, and Aromatic
Werner’s Theory 1003 The Metal–Ligand Hydrocarbons 1050
Bond 1005 Charges, Coordination Numbers,
Alkenes 1051 Alkynes 1053 Addition
and Geometries 1006
Reactions of Alkenes and Alkynes 1054
23.3 
Common Ligands in Coordination Aromatic Hydrocarbons 1056 Stabilization of
Chemistry 1007 p Electrons by Delocalization 1056
Metals and Chelates in Living Systems 1009 Substitution Reactions 1057
23.4 
Nomenclature and Isomerism in 24.4 Organic Functional Groups 1058
Coordination Chemistry 1012 Alcohols 1058 Ethers 1061 Aldehydes
Isomerism 1014 Structural Isomerism 1014 and Ketones 1061 Carboxylic Acids and
Stereoisomerism 1015 Esters 1062 Amines and Amides 1066
23.5 
Color and Magnetism in Coordination 24.5 
Chirality in Organic
Chemistry 1019 Chemistry 1067
Color 1019 Magnetism of Coordination 24.6 Introduction to Biochemistry 1067
Compounds 1021 24.7 Proteins 1068
23.6 Crystal-Field Theory 1021 Amino Acids 1068 Polypeptides and
Proteins 1070 Protein Structure 1071
xviii Contents

24.8 Carbohydrates 1073 C Thermodynamic Quantities


Disaccharides 1074 Polysaccharides 1075 for Selected Substances AT 298.15 K
24.9 Lipids 1076 (25 °C) 1100
Fats 1076 Phospholipids 1077 D
Aqueous Equilibrium Constants 1103
24.10 Nucleic Acids 1077
E Standard Reduction Potentials at
Chapter Summary and Key Terms 1082
Learning Outcomes 1083 Exercises 1083 25 °C 1105
Additional Exercises 1089
Answers to Selected Exercises A-1

Integrative Exercises 1090

Design an Experiment 1091 Answers to Give It Some Thought A-31
Chemistry Put to Work Gasoline 1050
A Closer Look Mechanism of Addition Answers to Go Figure A-38
Reactions 1055
Answers to Selected Practice Exercises A-44
Strategies in Chemistry What Now? 1081
Glossary G-1
Appendices
Photo/Art Credits P-1
A Mathematical Operations 1092
B Properties of Water 1099 Index I-1
Chemical Applications and Essays
The Ogallala Aquifer—A Shrinking Resource 794
Chemistry Put to Work
Fracking and Water Quality 797
Chemistry and the Chemical Industry 6 The Entropy Change When a Gas Expands Isothermally 820
Chemistry in the News 20 What’s “Free” about Free Energy? 836
Antacids 139 Electrical Work 879
The Scientific and Political Challenges of Biofuels 198 The Dawning of the Nuclear Age 934
Ionic Size and Lithium-Ion Batteries 267 Nuclear Synthesis of the Elements 939
Explosives and Alfred Nobel 330 The Hydrogen Economy 958
Orbitals and Energy 385 Entropy and the Chelate Effect 1010
Gas Separations 425 Charge-Transfer Color 1028
Ionic Liquids 454 Mechanism of Addition Reactions 1055
Alloys of Gold 494
Solid-State Lighting 508
Recycling Plastics 511 Chemistry and Life
Methyl Bromide in the Atmosphere 592 Elements Required by Living Organisms 61
Catalytic Converters 610 Glucose Monitoring 95
The Haber Process 633 The Regulation of Body Temperature 186
Controlling Nitric Oxide Emissions 659 Nuclear Spin and Magnetic Resonance Imaging 236
Amines and Amine Hydrochlorides 701 The Improbable Development of Lithium Drugs 281
Batteries for Hybrid and Electric Vehicles 889 The Chemistry of Vision 372
Electrometallurgy of Aluminum 895 Fat-Soluble and Water-Soluble Vitamins 539
Carbon Fibers and Composites 982 Blood Gases and Deep-Sea Diving 544
Gasoline 1050 Sickle-Cell Anemia 562
Nitrogen Fixation and Nitrogenase 612
The Amphiprotic Behavior of Amino Acids 709
Blood as a Buffered Solution 737
A Closer Look Ocean Acidification 753
The Scientific Method 14 Tooth Decay and Fluoridation 755
Basic Forces 49 Entropy and Human Society 828
The Mass Spectrometer 52 Driving Nonspontaneous Reactions: Coupling Reactions 842
What Are Coins Made Of? 54 Heartbeats and Electrocardiography 884
Energy, Enthalpy, and P–V Work 178 Medical Applications of Radiotracers 928
Measurement and the Uncertainty Principle 225 Radiation Therapy 943
Thought Experiments and Schrödinger’s Cat 226 Nitroglycerin, Nitric Oxide, and Heart Disease 976
Probability Density and Radial Probability Functions 232 Arsenic in Drinking Water 980
Effective Nuclear Charge 261 The Battle for Iron in Living Systems 1011
Calculation of Lattice Energies: The Born–Haber Cycle 304
Oxidation Numbers, Formal Charges, and Actual Partial
Strategies in Chemistry
Charges 319
Phases in Atomic and Molecular Orbitals 379 Estimating Answers 28
The Ideal-Gas Equation 421 The Importance of Practice 31
The Clausius–Clapeyron Equation 463 The Features of This Book 32
X-ray Diffraction 486 How to Take a Test 71
Ideal Solutions with Two or More Volatile Components 550 Problem Solving 92
The Van’t Hoff Factor 558 Design an Experiment 110
Using Spectroscopic Methods to Measure Reaction Rates: Analyzing Chemical Reactions 146
Beer’s Law 582 Using Enthalpy as a Guide 181
Limitations of Solubility Products 751 Calculations Involving Many Variables 410
Other Greenhouse Gases 790 What Now? 1081

xix
Preface
To the Instructor As authors, we want this text to be a central, indispensa-
ble learning tool for students. Whether as a physical book or in
electronic form, it can be carried everywhere and used at any
time. It is the one place students can go to obtain the informa-
Philosophy tion outside of the classroom needed for learning, skill develop-
We authors of Chemistry: The Central Science are delighted and ment, reference, and test preparation. The text, more effectively
honored that you have chosen us as your instructional partners for than any other instrument, provides the depth of coverage and
your general chemistry class. We have all been active researchers coherent background in modern chemistry that students need
who appreciate both the learning and the discovery aspects of the to serve their professional interests and, as appropriate, to pre-
chemical sciences. We have also all taught general chemistry many pare for more advanced chemistry courses.
times. Our varied, wide-ranging experiences have formed the basis If the text is to be effective in supporting your role as in-
of the close collaborations we have enjoyed as coauthors. In writing structor, it must be addressed to the students. We have done
our book, our focus is on the students: we try to ensure that the text our best to keep our writing clear and interesting and the book
is not only accurate and up-to-date but also clear and readable. We attractive and well illustrated. The book has numerous in-text
strive to convey the breadth of chemistry and the excitement that study aids for students, including carefully placed descrip-
scientists experience in making new discoveries that contribute to tions of problem-solving strategies. We hope that our cumula-
our understanding of the physical world. We want the student to tive experiences as teachers is evident in our pacing, choice of
appreciate that chemistry is not a body of specialized knowledge examples, and the kinds of study aids and motivational tools
that is separate from most aspects of modern life, but central to any we have employed. We believe students are more enthusiastic
attempt to address a host of societal concerns, including renewable about learning chemistry when they see its importance relative
energy, environmental sustainability, and improved human health. to their own goals and interests; therefore, we have highlighted
Publishing the thirteenth edition of this text bespeaks an many important applications of chemistry in everyday life. We
exceptionally long record of successful textbook writing. We are hope you make use of this material.
appreciative of the loyalty and support the book has received It is our philosophy, as authors, that the text and all the sup-
over the years, and mindful of our obligation to justify each new plementary materials provided to support its use must work in
edition. We begin our approach to each new edition with an in- concert with you, the instructor. A textbook is only as useful to
tensive author retreat, in which we ask ourselves the deep ques- students as the instructor permits it to be. This book is replete
tions that we must answer before we can move forward. What with features that can help students learn and that can guide
justifies yet another edition? What is changing in the world not them as they acquire both conceptual understanding and prob-
only of chemistry, but with respect to science education and the lem-solving skills. There is a great deal here for the students to
qualities of the students we serve? The answer lies only partly use, too much for all of it to be absorbed by any one student.
in the changing face of chemistry itself. The introduction of You will be the guide to the best use of the book. Only with your
many new technologies has changed the landscape in the teach- active help will the students be able to utilize most effectively
ing of sciences at all levels. The use of the Internet in accessing all that the text and its supplements offer. Students care about
information and presenting learning materials has markedly grades, of course, and with encouragement they will also be-
changed the role of the textbook as one element among many come interested in the subject matter and care about learning.
tools for student learning. Our challenge as authors is to main- Please consider emphasizing features of the book that can en-
tain the text as the primary source of chemical knowledge and hance student appreciation of chemistry, such as the Chemistry
practice, while at the same time integrating it with the new ave- Put to Work and Chemistry and Life boxes that show how chem-
nues for learning made possible by technology and the Internet. istry impacts modern life and its relationship to health and life
This edition incorporates links to a number of those new meth- processes. Learn to use, and urge students to use, the rich online
odologies, including use of the Internet, computer-based class- resources available. Emphasize conceptual understanding and
room tools, such as Learning Catalytics™, a cloud-based active place less emphasis on simple manipulative, algorithmic prob-
learning analytics and assessment system, and web-based tools, lem solving.
particularly MasteringChemistry®, which is continually evolv-
ing to provide more effective means of testing and evaluating What Is New in This Edition?
student performance, while giving the student immediate and
helpful feedback. In past versions, MasteringChemistry® pro- A great many changes have been made in producing this thir-
vided feedback only on a question level. Now with Knewton- teenth edition. We have continued to improve upon the art
enhanced adaptive follow-up assignments, and Dynamic Study program, and new features connected with the art have been
Modules, MasteringChemistry® continually adapts to each stu- introduced. Many figures in the book have undergone modifi-
dent, offering a personalized learning experience. cation, and dozens of new figures have been introduced.

xx
Preface xxi

A systematic effort has been made to place explanatory la- in some of the existing questions and addition of new ones.
bels directly into figures to guide the student. New designs have The answers to all the GIST items are provided in the back
been employed to more closely integrate photographic materi- of the text.
als into figures that convey chemical principles. • New end-of-chapter exercises have been added, and many
We have continued to explore means for more clearly and of those carried over from the twelfth edition have been
directly addressing the issue of concept learning. It is well es- significantly revised. Analysis of student responses to the
tablished that conceptual misunderstandings, which impede twelfth edition questions in MasteringChemistry® helped
student learning in many areas, are difficult to correct. We have us identify and revise or create new questions, prompt-
looked for ways to identify and correct misconceptions via the ing improvements and eliminations of some questions.
worked examples in the book, and in the accompanying prac- Additionally, analysis of usage of MasteringChemistry®
tice exercises. Among the more important changes made in the has enhanced our understanding of the ways in which in-
new edition, with this in mind, are: structors and students have used the end-of-chapter and
• A major new feature of this edition is the addition of a MasteringChemistry® materials. This, in turn, has led to
second Practice Exercise to accompany each Sample Ex- additional improvements to the content within the text
ercise within the chapters. The majority of new Practice and in the MasteringChemistry® item library. At the end of
Exercises are of the multiple-choice variety, which enable each chapter, we list the Learning Outcomes that students
feedback via MasteringChemistry®. The correct answers should be able to perform after studying each section.
to select Practice Exercises are given in an appendix, and End-of-chapter exercises, both in the text and in Master-
guidance for correcting wrong answers is provided in Mas- ingChemistry® offer ample opportunities for students to
teringChemistry®. The new Practice Exercise feature adds assess mastery of learning outcomes. We trust the Learning
to the aids provided to students for mastering the concepts Outcomes will help you organize your lectures and tests as
advanced in the text and rectifying conceptual misunder- the course proceeds.
standings. The enlarged practice exercise materials also
further cement the relationship of the text to the online
learning materials. At the same time, they offer a new sup- Organization and Contents
portive learning experience for all students, regardless of
whether the MasteringChemistry® program is used. The first five chapters give a largely macroscopic, phenomeno-
logical view of chemistry. The basic concepts introduced—such
• A second major innovation in this edition is the Design
as nomenclature, stoichiometry, and thermochemistry—provide
An Experiment feature, which appears as a final exercise
necessary background for many of the laboratory experiments
in all chapters beginning with Chapter 3, as well as in
usually performed in general chemistry. We believe that an early
MasteringChemistry®. The Design an Experiment exercise is
introduction to thermochemistry is desirable because so much
a departure from the usual kinds of end-of-chapter exer-
of our understanding of chemical processes is based on consid-
cises in that it is inquiry based, open ended, and tries to
erations of energy changes. Thermochemistry is also important
stimulate the student to “think like a scientist.” Each exer-
when we come to a discussion of bond enthalpies. We believe we
cise presents the student with a scenario in which vari-
have produced an effective, balanced approach to teaching ther-
ous unknowns require investigation. The student is called
modynamics in general chemistry, as well as providing students
upon to ponder how experiments might be set up to pro-
with an introduction to some of the global issues involving en-
vide answers to particular questions about a system, and/
ergy production and consumption. It is no easy matter to walk
or test plausible hypotheses that might account for a set of
the narrow pathway between—on the one hand—trying to teach
observations. The aim of the Design an Experiment exer-
too much at too high a level and—on the other hand—resorting
cises is to foster critical thinking. We hope that they will
to oversimplifications. As with the book as a whole, the emphasis
be effective in active learning environments, which include
has been on imparting conceptual understanding, as opposed to
classroom-based work and discussions, but they are also
presenting equations into which students are supposed to plug
suitable for individual student work. There is no one right
numbers.
way to solve these exercises, but we authors offer some
The next four chapters (Chapters 6–9) deal with elec-
ideas in an online Instructor’s Resource Manual, which
tronic structure and bonding. We have largely retained our
will include results from class testing and analysis of stu-
presentation of atomic orbitals. For more advanced students,
dent responses.
Closer Look boxes in Chapters 6 and 9 highlight radial prob-
• The Go Figure exercises introduced in the twelfth edition ability functions and the phases of orbitals. Our approach of
proved to be a popular innovation, and we have expanded placing this latter discussion in a Closer Look box in Chapter
on its use. This feature poses a question that students can 9 enables those who wish to cover this topic to do so, while
answer by examining the figure. These questions encour- others may wish to bypass it. In treating this topic and others
age students to actually study the figure and understand its in Chapters 7 and 9, we have materially enhanced the accom-
primary message. Answers to the Go Figure questions are panying figures to more effectively bring home their central
provided in the back of the text. messages.
• The popular Give It Some Thought (GIST) questions em- In Chapters 10–13, the focus of the text changes to the
bedded in the text have been expanded by improvements next level of the organization of matter: examining the states of
xxii Preface

­ atter. Chapters 10 and 11 deal with gases, liquids, and inter-


m Science has traditionally been valued for its clarity of writing,
molecular forces, as in earlier editions. Chapter 12 is devoted its scientific accuracy and currency, its strong end-of-chapter
to solids, presenting an enlarged and more contemporary view exercises, and its consistency in level of coverage. In making
of the solid state as well as of modern materials. The chapter changes, we have made sure not to compromise these charac-
provides an opportunity to show how abstract chemical bond- teristics, and we have also continued to employ an open, clean
ing concepts impact real-world applications. The modular design in the layout of the book.
organization of the chapter allows you to tailor your coverage to The art program for this thirteenth edition has continued
focus on materials (semiconductors, polymers, nanomaterials, the trajectory set in the twelfth edition: to make greater and
and so forth) that are most relevant to your students and your more effective use of the figures as learning tools, by drawing
own interests. Chapter 13 treats the formation and properties the reader more directly into the figure. The art itself has con-
of solutions in much the same manner as the previous edition. tinued to evolve, with modifications of many figures and addi-
The next several chapters examine the factors that determine tions or replacements that teach more effectively. The Go Figure
the speed and extent of chemical reactions: kinetics (Chapter 14), feature has been expanded greatly to include a larger number
equilibria (Chapters 15–17), thermodynamics (Chapter 19), and of figures. In the same vein, we have added to the Give it Some
electrochemistry (Chapter 20). Also in this section is a chapter Thought feature, which stimulates more thoughtful reading of
on environmental chemistry (Chapter 18), in which the concepts the text and fosters critical thinking.
developed in preceding chapters are applied to a discussion of the We provide a valuable overview of each chapter under the
atmosphere and hydrosphere. This chapter has increasingly come What’s Ahead banner. Concept links ( ) continue to provide
to be focused on green chemistry and the impacts of human activi- easy-to-see cross-references to pertinent material covered ear-
ties on Earth’s water and atmosphere. lier in the text. The essays titled Strategies in Chemistry, which
After a discussion of nuclear chemistry (Chapter 21), the provide advice to students on problem solving and “thinking
book ends with three survey chapters. Chapter 22 deals with like a chemist,” continue to be an important feature. For exam-
nonmetals, Chapter 23 with the chemistry of transition metals, ple, the new Strategies in Chemistry essay at the end of Chapter 3
including coordination compounds, and Chapter 24 with the introduces the new Design an Experiment feature and provides
chemistry of organic compounds and elementary biochemical a worked out example as guidance.
themes. These final four chapters are developed in a parallel We have continued to emphasize conceptual exercises in
fashion and can be covered in any order. the end-of-chapter exercise materials. The well-received Visu-
Our chapter sequence provides a fairly standard organ- alizing Concepts exercise category has been continued in this
ization, but we recognize that not everyone teaches all the edition. These exercises are designed to facilitate concept un-
topics in the order we have chosen. We have therefore made derstanding through use of models, graphs, and other visual
sure that instructors can make common changes in teaching materials. They precede the regular end-of-chapter exercises
sequence with no loss in student comprehension. In particu- and are identified in each case with the relevant chapter section
lar, many instructors prefer to introduce gases (Chapter 10) number. A generous selection of Integrative Exercises, which
after stoichiometry (Chapter 3) rather than with states of give students the opportunity to solve problems that integrate
matter. The chapter on gases has been written to permit this concepts from the present chapter with those of previous chap-
change with no disruption in the flow of material. It is also ters, is included at the end of each chapter. The importance
possible to treat balancing redox equations (Sections 20.1 of integrative problem solving is highlighted by the Sample
and 20.2) earlier, after the introduction of redox reactions Integrative Exercise, which ends each chapter beginning with
in Section 4.4. Finally, some instructors like to cover organic Chapter 4. In general, we have included more conceptual end-
chemistry (Chapter 24) right after bonding (Chapters 8 and of-chapter exercises and have made sure that there is a good
9). This, too, is a largely seamless move. representation of somewhat more difficult exercises to provide
We have brought students into greater contact with de- a better mix in terms of topic and level of difficulty. Many of the
scriptive organic and inorganic chemistry by integrating exam- exercises have been restructured to facilitate their use in Mas-
ples throughout the text. You will find pertinent and relevant teringChemistry®. We have made extensive use of the metadata
examples of “real” chemistry woven into all the chapters to il- from student use of MasteringChemistry® to analyze end-of-
lustrate principles and applications. Some chapters, of course, chapter exercises and make appropriate changes, as well as to
more directly address the “descriptive” properties of elements develop Learning Outcomes for each chapter.
and their compounds, especially Chapters 4, 7, 11, 18, and New essays in our well-received Chemistry Put to Work
22–24. We also incorporate descriptive organic and inorganic and Chemistry and Life series emphasize world events, scientific
chemistry in the end-of-chapter exercises. discoveries, and medical breakthroughs that bear on topics de-
veloped in each chapter. We maintain our focus on the positive
aspects of chemistry without neglecting the problems that can
Changes in This Edition arise in an increasingly technological world. Our goal is to help
The What is New in This Edition section on pp. xx–xxi details students appreciate the real-world perspective of chemistry and
changes made throughout the new edition. Beyond a mere list- the ways in which chemistry affects their lives.
ing, however, it is worth dwelling on the general goals we set It is perhaps a natural tendency for chemistry text-
forth in formulating this new edition. Chemistry: The Central books to grow in length with succeeding editions, but it is
Preface xxiii

one that we have resisted. There are, nonetheless, many new of intermolecular attractions. Chapter 12 includes the latest up-
items in this edition, mostly ones that replace other material dates to materials chemistry, including plastic electronics. New
­considered less pertinent. Here is a list of several significant material on the diffusion and mean free path of colloids in solu-
changes in content: tion is added to Chapter 13, making a connection to the diffu-
In Chapter 1, the Closer Look box on the scientific method sion of gas molecules from Chapter 10.
has been rewritten. The Chemistry Put to Work box, dealing In Chapter 14, ten new Go Figure exercises have been
with Chemistry in the News, has been completely rewritten, with added to reinforce many of the concepts presented as figures
items that describe diverse ways in which chemistry intersects and graphs in the chapter. The Design an Experiment exercise in
with the affairs of modern society. The Chapter Summary and the chapter connects strongly to the Closer Look box on Beer’s
Learning Outcomes sections at the end of the chapter have been Law, which is often the basis for spectrometric kinetics experi-
rewritten for ease of use by both instructor and student, in this ments performed in the general chemistry laboratory.
and all chapters in the text. Similarly, the exercises have been The presentation in Chapter 16 was made more closely tied
thoroughly vetted, modified where this was called for and re- to that in Chapter 15, especially through the use of more initial/
placed or added to, here and in all succeeding chapters. change/equilibrium (ICE) charts. The number of conceptual
In Chapter 3, graphic elements highlighting the correct ap- end-of-chapter exercises, including Visualizing Concepts fea-
proach to problem solving have been added to Sample Exercises tures, was increased significantly.
on calculating an empirical formula from mass percent of the Chapter 17 offers improved clarity on how to make buff-
elements present, combustion analysis, and calculating a theo- ers, and when the Henderson–Hasselbalch equation may not
retical yield. be accurate. Chapter 18 has been extensively updated to reflect
Chapter 5 now presents a more explicit discussion of com- changes in this rapidly evolving area of chemistry. Two Closer
bined units of measurement, an improved introduction to en- Look boxes have been added; one dealing with the shrinking
thalpy, and more consistent use of color in art. level of water in the Ogallala aquifer and a second with the po-
Changes in Chapter 6 include a significant revision of the tential environmental consequences of hydraulic fracking. In
discussion of the energy levels of the hydrogen atom, including Chapter 20, the description of Li-ion batteries has been signifi-
greater clarity on absorption versus emission processes. There cantly expanded to reflect the growing importance of these bat-
is also a new Closer Look box on Thought Experiments and teries, and a new Chemistry Put to Work box on batteries for
Schrödinger’s Cat, which gives students a brief glimpse of some hybrid and electric vehicles has been added.
of the philosophical issues in quantum mechanics and also con- Chapter 21 was updated to reflect some of the current is-
nects to the 2012 Nobel Prize in Physics. sues in nuclear chemistry and more commonly used nomencla-
In Chapter 7, the emphasis on conceptual thinking was en- ture for forms of radiation are now used. Chapter 22 includes an
hanced in several ways: the section on effective nuclear charge improved discussion of silicates.
was significantly revised to include a classroom-tested analogy, In Chapter 23, the section on crystal-field theory (Section
the number of Go Figure features was increased substantially, 23.6) has undergone considerable revision. The description of
and new end-of-chapter exercises emphasize critical thinking how the d-orbital energies of a metal ion split in a tetrahedral
and understanding concepts. In addition, the Chemistry Put to crystal field has been expanded to put it on par with our treat-
Work box on lithium-ion batteries was updated and revised to ment of the octahedral geometry, and a new Sample Exercise
include discussion of current issues in using these batteries. Fi- that effectively integrates the links between color, magnetism,
nally, the values of ionic radii were revised to be consistent with and the spectrochemical series has been added. Chapter 24’s
a recent research study of the best values for these radii. coverage of organic chemistry and biochemistry now includes
In Chapter 9, which is one of the most challenging for oxidation–reduction reactions that organic chemists find
students, we continue to refine our presentation based on our most relevant.
classroom experience. Twelve new Go Figure exercises will stim-
ulate more student thought in a chapter with a large amount
of graphic material. The discussion of molecular geometry was
made more conceptually oriented. The section on delocalized To the Student
bonding was completely revised to provide what we believe will
be a better introduction that students will find useful in organic Chemistry: The Central Science, Thirteenth Edition, has been writ-
chemistry. The Closer Look box on phases in orbitals was re- ten to introduce you to modern chemistry. As authors, we have, in
vamped with improved artwork. We also increased the number effect, been engaged by your instructor to help you learn chemistry.
of end-of-chapter exercises, especially in the area of molecular Based on the comments of students and instructors who have used
orbital theory. The Design an Experiment feature in this chapter this book in its previous editions, we believe that we have done
gives the students the opportunity to explore color and conju- that job well. Of course, we expect the text to continue to evolve
gated π systems. through future editions. We invite you to write to tell us what you
Chapter 10 contains a new Sample Exercise that walks the like about the book so that we will know where we have helped you
student through the calculations that are needed to understand most. Also, we would like to learn of any shortcomings so that we
Torricelli’s barometer. Chapter 11 includes an improved defini- might further improve the book in subsequent editions. Our ad-
tion of hydrogen bonding and updated data for the strengths dresses are given at the end of the Preface.
xxiv Preface

Advice for Learning and a feeling for the scope of topics. Try to avoid thinking that you
must learn and understand everything right away.
Studying Chemistry You need to do a certain amount of preparation before
Learning chemistry requires both the assimilation of many con- lecture. More than ever, instructors are using the lecture pe-
cepts and the development of analytical skills. In this text, we riod not simply as a one-way channel of communication from
have provided you with numerous tools to help you succeed in teacher to student. Rather, they expect students to come to class
both tasks. If you are going to succeed in your chemistry course, ready to work on problem solving and critical thinking. Com-
you will have to develop good study habits. Science courses, and ing to class unprepared is not a good idea for any lecture envi-
chemistry in particular, make different demands on your learn- ronment, but it certainly is not an option for an active learning
ing skills than do other types of courses. We offer the following classroom if you aim to do well in the course.
tips for success in your study of chemistry: After lecture, carefully read the topics covered in class.
Don’t fall behind! As the course moves along, new top- As you read, pay attention to the concepts presented and to the
ics will build on material already presented. If you don’t keep application of these concepts in the Sample Exercises. Once you
up in your reading and problem solving, you will find it much think you understand a Sample Exercise, test your understand-
harder to follow the lectures and discussions on current topics. ing by working the accompanying Practice Exercise.
Experienced teachers know that students who read the relevant Learn the language of chemistry. As you study chemis-
sections of the text before coming to a class learn more from the try, you will encounter many new words. It is important to pay
class and retain greater recall. “Cramming” just before an exam attention to these words and to know their meanings or the
has been shown to be an ineffective way to study any subject, entities to which they refer. Knowing how to identify chemi-
chemistry included. So now you know. How important to you, cal substances from their names is an important skill; it can
in this competitive world, is a good grade in chemistry? help you avoid painful mistakes on examinations. For example,
Focus your study. The amount of information you will “chlorine” and “chloride” refer to very different things.
be expected to learn can sometimes seem overwhelming. It is Attempt the assigned end-of-chapter exercises. Work-
essential to recognize those concepts and skills that are par- ing the exercises selected by your instructor provides necessary
ticularly important. Pay attention to what your instructor is practice in recalling and using the essential ideas of the chapter.
emphasizing. As you work through the Sample Exercises and You cannot learn merely by observing; you must be a partici-
homework assignments, try to see what general principles and pant. In particular, try to resist checking the Student Solutions
skills they employ. Use the What’s Ahead feature at the begin- Manual (if you have one) until you have made a sincere effort
ning of each chapter to help orient yourself to what is important to solve the exercise yourself. If you get stuck on an exercise,
in each chapter. A single reading of a chapter will simply not be however, get help from your instructor, your teaching assistant,
enough for successful learning of chapter concepts and prob- or another student. Spending more than 20 minutes on a single
lem-solving skills. You will need to go over assigned materials exercise is rarely effective unless you know that it is particularly
more than once. Don’t skip the Give It Some Thought and Go challenging.
Figure features, Sample Exercises, and Practice Exercises. They Learn to think like a scientist. This book is written by sci-
are your guides to whether you are learning the material. They entists who love chemistry. We encourage you to develop your
are also good preparation for test-taking. The Learning Out- critical thinking skills by taking advantage of new features in
comes and Key Equations at the end of the chapter should help this edition, such as exercises that focus on conceptual learning,
you focus your study. and the Design an Experiment exercises.
Keep good lecture notes. Your lecture notes will provide Use online resources. Some things are more easily learned
you with a clear and concise record of what your instructor by discovery, and others are best shown in three dimensions.
regards as the most important material to learn. Using your If your instructor has included MasteringChemistry® with your
lecture notes in conjunction with this text is the best way to de- book, take advantage of the unique tools it provides to get the
termine which material to study. most out of your time in chemistry.
Skim topics in the text before they are covered in lecture. The bottom line is to work hard, study effectively, and use
Reviewing a topic before lecture will make it easier for you to the tools available to you, including this textbook. We want
take good notes. First read the What’s Ahead points and the to help you learn more about the world of chemistry and why
end-of-chapter Summary; then quickly read through the chap- chemistry is the central science. If you really learn chemistry,
ter, skipping Sample Exercises and supplemental sections. Pay- you can be the life of the party, impress your friends and par-
ing attention to the titles of sections and subsections gives you ents, and … well, also pass the course with a good grade.
Preface xxv

Acknowledgments
The production of a textbook is a team effort requiring the in- dents both here and abroad. Colleagues have also helped im-
volvement of many people besides the authors who contributed mensely by reviewing our materials, sharing their insights, and
hard work and talent to bring this edition to life. Although their providing suggestions for improvements. On this edition, we
names don’t appear on the cover of the book, their creativity, were particularly blessed with an exceptional group of accuracy
time, and support have been instrumental in all stages of its de- checkers who read through our materials looking for both tech-
velopment and production. nical inaccuracies and typographical errors.
Each of us has benefited greatly from discussions with
colleagues and from correspondence with instructors and stu-

Thirteenth Edition Reviewers Charity Lovett Seattle University


Yiyan Bai Houston Community College Michael Lufaso University of North Florida
Ron Briggs Arizona State University Diane Miller Marquette University
Scott Bunge Kent State University Gregory Robinson University of Georgia
Jason Coym University of South Alabama Melissa Schultz The College of Wooster
Ted Clark The Ohio State University Mark Schraf West Virginia University
Michael Denniston Georgia Perimeter College Richard Spinney The Ohio State University
Patrick Donoghue Appalachian State University Troy Wood SUNY Buffalo
Luther Giddings Salt Lake Community College Kimberly Woznack California University of Pennsylvania
Jeffrey Kovac University of Tennessee Edward Zovinka Saint Francis University

Thirteenth Edition Accuracy Reviewers Pamela Marks Arizona State University


Luther Giddings Salt Lake Community College Lee Pedersen University of North Carolina
Jesudoss Kingston Iowa State University Troy Wood SUNY Buffalo
Michael Lufaso University of North Florida

Thirteenth Edition Focus Group Participants Andy Jorgensen University of Toledo


Tracy Birdwhistle Xavier University David Katz Pima Community College
Cheryl Frech University of Central Oklahoma Sarah Schmidtke The College of Wooster
Bridget Gourley DePauw University Linda Schultz Tarleton State University
Etta Gravely North Carolina A&T State University Bob Shelton Austin Peay State University
Thomas J. Greenbowe Iowa State University Stephen Sieck Grinnell College
Jason Hofstein Siena College Mark Thomson Ferris State University

MasteringChemistry® Summit Participants Gary Michels Creighton University


Phil Bennett Santa Fe Community College Bob Pribush Butler University
Jo Blackburn Richland College Al Rives Wake Forest University
John Bookstaver St. Charles Community College Joel Russell Oakland University
David Carter Angelo State University Greg Szulczewski University of Alabama, Tuscaloosa
Doug Cody Nassau Community College Matt Tarr University of New Orleans
Tom Dowd Harper College Dennis Taylor Clemson University
Palmer Graves Florida International University Harold Trimm Broome Community College
Margie Haak Oregon State University Emanuel Waddell University of Alabama, Huntsville
Brad Herrick Colorado School of Mines Kurt Winklemann Florida Institute of Technology
Jeff Jenson University of Findlay Klaus Woelk University of Missouri, Rolla
Jeff McVey Texas State University at San Marcos Steve Wood Brigham Young University

Reviewers of Previous Editions of Chemistry: John Arnold University of California


The Central Science Socorro Arteaga El Paso Community College
Margaret Asirvatham University of Colorado
S.K. Airee University of Tennessee
Todd L. Austell University of North Carolina, Chapel Hill
John J. Alexander University of Cincinnati
Melita Balch University of Illinois at Chicago
Robert Allendoerfer SUNY Buffalo
Rosemary Bartoszek-Loza The Ohio State University
Patricia Amateis Virginia Polytechnic Institute and State
University Rebecca Barlag Ohio University
Sandra Anderson University of Wisconsin Hafed Bascal University of Findlay
xxvi Preface

Boyd Beck Snow College Paul A. Flowers University of North Carolina at Pembroke
Kelly Beefus Anoka-Ramsey Community College Michelle Fossum Laney College
Amy Beilstein Centre College Roger Frampton Tidewater Community College
Donald Bellew University of New Mexico Joe Franek University of Minnesota
Victor Berner New Mexico Junior College David Frank California State University
Narayan Bhat University of Texas, Pan American Cheryl B. Frech University of Central Oklahoma
Merrill Blackman United States Military Academy Ewa Fredette Moraine Valley College
Salah M. Blaih Kent State University Kenneth A. French Blinn College
James A. Boiani SUNY Geneseo Karen Frindell Santa Rosa Junior College
Leon Borowski Diablo Valley College John I. Gelder Oklahoma State University
Simon Bott University of Houston Robert Gellert Glendale Community College
Kevin L. Bray Washington State University Paul Gilletti Mesa Community College
Daeg Scott Brenner Clark University Peter Gold Pennsylvania State University
Gregory Alan Brewer Catholic University of America Eric Goll Brookdale Community College
Karen Brewer Virginia Polytechnic Institute and State James Gordon Central Methodist College
University John Gorden Auburn University
Edward Brown Lee University Thomas J. Greenbowe Iowa State University
Gary Buckley Cameron University Michael Greenlief University of Missouri
Carmela Byrnes Texas A&M University Eric P. Grimsrud Montana State University
B. Edward Cain Rochester Institute of Technology John Hagadorn University of Colorado
Kim Calvo University of Akron Randy Hall Louisiana State University
Donald L. Campbell University of Wisconsin John M. Halpin New York University
Gene O. Carlisle Texas A&M University Marie Hankins University of Southern Indiana
Elaine Carter Los Angeles City College Robert M. Hanson St. Olaf College
Robert Carter University of Massachusetts at Boston Daniel Haworth Marquette University
Harbor Michael Hay Pennsylvania State University
Ann Cartwright San Jacinto Central College Inna Hefley Blinn College
David L. Cedeño Illinois State University David Henderson Trinity College
Dana Chatellier University of Delaware Paul Higgs Barry University
Stanton Ching Connecticut College Carl A. Hoeger University of California, San Diego
Paul Chirik Cornell University Gary G. Hoffman Florida International University
Tom Clayton Knox College Deborah Hokien Marywood University
William Cleaver University of Vermont Robin Horner Fayetteville Tech Community College
Beverly Clement Blinn College Roger K. House Moraine Valley College
Robert D. Cloney Fordham University Michael O. Hurst Georgia Southern University
John Collins Broward Community College William Jensen South Dakota State University
Edward Werner Cook Tunxis Community Technical College Janet Johannessen County College of Morris
Elzbieta Cook Louisiana State University Milton D. Johnston, Jr. University of South Florida
Enriqueta Cortez South Texas College Andrew Jones Southern Alberta Institute of Technology
Thomas Edgar Crumm Indiana University of Pennsylvania Booker Juma Fayetteville State University
Dwaine Davis Forsyth Tech Community College Ismail Kady East Tennessee State University
Ramón López de la Vega Florida International University Siam Kahmis University of Pittsburgh
Nancy De Luca University of Massachusetts, Lowell North Steven Keller University of Missouri
Campus John W. Kenney Eastern New Mexico University
Angel de Dios Georgetown University Neil Kestner Louisiana State University
John M. DeKorte Glendale Community College Carl Hoeger University of California at San Diego
Daniel Domin Tennessee State University Leslie Kinsland University of Louisiana
James Donaldson University of Toronto Jesudoss Kingston Iowa State University
Bill Donovan University of Akron Louis J. Kirschenbaum University of Rhode Island
Stephen Drucker University of Wisconsin-Eau Claire Donald Kleinfelter University of Tennessee, Knoxville
Ronald Duchovic Indiana University–Purdue University at Fort Daniela Kohen Carleton University
Wayne David Kort George Mason University
Robert Dunn University of Kansas George P. Kreishman University of Cincinnati
David Easter Southwest Texas State University Paul Kreiss Anne Arundel Community College
Joseph Ellison United States Military Academy Manickham Krishnamurthy Howard University
George O. Evans II East Carolina University Sergiy Kryatov Tufts University
James M. Farrar University of Rochester Brian D. Kybett University of Regina
Debra Feakes Texas State University at San Marcos William R. Lammela Nazareth College
Gregory M. Ferrence Illinois State University John T. Landrum Florida International University
Clark L. Fields University of Northern Colorado Richard Langley Stephen F. Austin State University
Jennifer Firestine Lindenwood University N. Dale Ledford University of South Alabama
Jan M. Fleischner College of New Jersey Ernestine Lee Utah State University
Preface xxvii

David Lehmpuhl University of Southern Colorado John Reissner University of North Carolina
Robley J. Light Florida State University Helen Richter University of Akron
Donald E. Linn, Jr. Indiana University–Purdue University Thomas Ridgway University of Cincinnati
Indianapolis Mark G. Rockley Oklahoma State University
David Lippmann Southwest Texas State Lenore Rodicio Miami Dade College
Patrick Lloyd Kingsborough Community College Amy L. Rogers College of Charleston
Encarnacion Lopez Miami Dade College, Wolfson Jimmy R. Rogers University of Texas at Arlington
Arthur Low Tarleton State University Kathryn Rowberg Purdue University at Calumet
Gary L. Lyon Louisiana State University Steven Rowley Middlesex Community College
Preston J. MacDougall Middle Tennessee State University James E. Russo Whitman College
Jeffrey Madura Duquesne University Theodore Sakano Rockland Community College
Larry Manno Triton College Michael J. Sanger University of Northern Iowa
Asoka Marasinghe Moorhead State University Jerry L. Sarquis Miami University
Earl L. Mark ITT Technical Institute James P. Schneider Portland Community College
Pamela Marks Arizona State University Mark Schraf West Virginia University
Albert H. Martin Moravian College Gray Scrimgeour University of Toronto
Przemyslaw Maslak Pennsylvania State University Paula Secondo Western Connecticut State University
Hilary L. Maybaum ThinkQuest, Inc. Michael Seymour Hope College
Armin Mayr El Paso Community College Kathy Thrush Shaginaw Villanova University
Marcus T. McEllistrem University of Wisconsin Susan M. Shih College of DuPage
Craig McLauchlan Illinois State University David Shinn University of Hawaii at Hilo
Jeff McVey Texas State University at San Marcos Lewis Silverman University of Missouri at Columbia
William A. Meena Valley College Vince Sollimo Burlington Community College
Joseph Merola Virginia Polytechnic Institute and State David Soriano University of Pittsburgh-Bradford
University Eugene Stevens Binghamton University
Stephen Mezyk California State University Matthew Stoltzfus The Ohio State University
Eric Miller San Juan College James Symes Cosumnes River College
Gordon Miller Iowa State University Iwao Teraoka Polytechnic University
Shelley Minteer Saint Louis University Domenic J. Tiani University of North Carolina,
Massoud (Matt) Miri Rochester Institute of Technology Chapel Hill
Mohammad Moharerrzadeh Bowie State University Edmund Tisko University of Nebraska at Omaha
Tracy Morkin Emory University Richard S. Treptow Chicago State University
Barbara Mowery York College Michael Tubergen Kent State University
Kathleen E. Murphy Daemen College Claudia Turro The Ohio State University
Kathy Nabona Austin Community College James Tyrell Southern Illinois University
Robert Nelson Georgia Southern University Michael J. Van Stipdonk Wichita State University
Al Nichols Jacksonville State University Philip Verhalen Panola College
Ross Nord Eastern Michigan University Ann Verner University of Toronto at Scarborough
Jessica Orvis Georgia Southern University Edward Vickner Gloucester County Community College
Mark Ott Jackson Community College John Vincent University of Alabama
Jason Overby College of Charleston Maria Vogt Bloomfield College
Robert H. Paine Rochester Institute of Technology Tony Wallner Barry University
Robert T. Paine University of New Mexico Lichang Wang Southern Illinois University
Sandra Patrick Malaspina University College Thomas R. Webb Auburn University
Mary Jane Patterson Brazosport College Clyde Webster University of California at Riverside
Tammi Pavelec Lindenwood University Karen Weichelman University of Louisiana-Lafayette
Albert Payton Broward Community College Paul G. Wenthold Purdue University
Christopher J. Peeples University of Tulsa Laurence Werbelow New Mexico Institute of Mining and
Kim Percell Cape Fear Community College Technology
Gita Perkins Estrella Mountain Community College Wayne Wesolowski University Of Arizona
Richard Perkins University of Louisiana Sarah West University of Notre Dame
Nancy Peterson North Central College Linda M. Wilkes University at Southern Colorado
Robert C. Pfaff Saint Joseph’s College Charles A. Wilkie Marquette University
John Pfeffer Highline Community College Darren L. Williams West Texas A&M University
Lou Pignolet University of Minnesota Troy Wood SUNY Buffalo
Bernard Powell University of Texas Thao Yang University of Wisconsin
Jeffrey A. Rahn Eastern Washington University David Zax Cornell University
Steve Rathbone Blinn College Dr. Susan M. Zirpoli Slippery Rock University
Scott Reeve Arkansas State University
xxviii Preface

We would also like to express our gratitude to our many team e­ specially in keeping us on task in terms of consistency and stu-
members at Pearson whose hard work, imagination, and com- dent understanding; Donna, our copy editor, for her keen eye;
mitment have contributed so greatly to the final form of this Beth Sweeten, our project manager, and Gina C ­ heselka, who
edition: Terry Haugen, our senior editor, who has brought en- managed the complex responsibilities of bringing the design,
ergy and imagination to this edition as he has to earlier ones; photos, artwork, and writing together with efficiency and good
Chris Hess, our chemistry editor, for many fresh ideas and his cheer. The Pearson team is a first-class operation.
unflagging enthusiasm, continuous encouragement, and sup- There are many others who also deserve special recogni-
port; Jennifer Hart, Director of Development, who has brought tion, including the following: Greg Johnson, our production
her experience and insight to oversight of the entire project; editor, who skillfully kept the process moving and us authors on
­Jessica Moro, our project editor, who very effectively coordinat- track; Kerri Wilson, our photo researcher, who was so effective
ed the scheduling and tracked the multidimensional deadlines in finding photos to bring chemistry to life for students; and
that come with a project of this magnitude; Jonathan ­Cottrell Roxy Wilson (University of Illinois), who so ably coordinated
our marketing manager, for his energy, enthusiasm, and crea- the difficult job of working out solutions to the end-of-chapter
tive promotion of our text; Carol Pritchard-Martinez, our exercises. Finally, we wish to thank our families and friends for
­development editor, whose depth of experience, good judgment, their love, support, encouragement, and patience as we brought
and careful attention to detail were invaluable to this revision, this thirteenth edition to completion.

Theodore L. Brown H. Eugene LeMay, Jr. Bruce E. Bursten Catherine J. Murphy Patrick M. Woodward Matthew W. Stoltzfus
Department of Chemistry Department of Chemistry Department of Chemistry Department of Chemistry Department of Chemistry Department of Chemistry
University of Illinois at University of Nevada University of Tennessee University of Illinois at and Biochemistry and Biochemistry
Urbana-Champaign Reno, NV 89557 Knoxville, TN 37996 Urbana-Champaign The Ohio State University The Ohio State University
Urbana, IL 61801 lemay@unr.edu bbursten@utk.edu Urbana, IL 61801 Columbus, OH 43210 Columbus, OH 43210
tlbrown@illinois.edu or murphycj@illinois.edu. woodward@chemistry. stoltzfus.5@osu.edu
tlbrown1@earthlink.net ohio-state.edu
Another random document with
no related content on Scribd:
In the more severe cases with already existing impaction of the
colon, purgatives and copious injections will be demanded as advised
under that disease.
In dogs the first object is the unloading of the rectum and colon
and this usually demands direct mechanical intervention. (See
Intestinal Indigestion with Constipation.) In case of hypertrophied
prostate this may be rendered somewhat difficult, yet with a free use
of oily, soapy or mucilaginous injections it can usually be
accomplished.
The further treatment is on the same line as for the soliped. An
abundance of exercise in the open air is a prime essential, together
with a free access to fresh water. House dogs must be taken out for
urination and defecation at regular times that are not too far apart.
The food must be of a laxative nature. At first fresh whey or
buttermilk only may be allowed, but as some action of the bowels is
obtained well salted beef tea, pulped or scraped red muscle seasoned
with salt, or milk treated in the same way is permissible. If the
bowels fail to respond when the dog is taken out at the regular times
an injection of cold water may be given. Sulphate of eserine (⅕ gr.)
may be given daily by the mouth or hypodermically, or castor oil (½
to 1 oz.) may be administered at one dose to be followed by careful
dietary and hygienic measures. Or sweet oil, calomel and jalap,
podophyllin, or colocynth may be substituted. When the bowels have
been freely opened a daily morning dose of a drop of the fluid extract
of belladonna and ½ gr. of nux vomica will often materially improve
the peristalsis. Active manipulation of the abdomen may be
employed, or, if available, a current of electricity through the torpid
bowels for 10 or 15 minutes daily.
CONSTIPATION IN BIRDS.
Causes: Matted feathers, impacted cloaca, arrest of eggs, debility, catarrh,
parasites, nervous disorder. Symptoms: swelling of anus, pendent abdomen,
waddling gait, straining without effect. Treatment: remove obstruction by
mechanical means, cut off matted feathers, egg matter may demand laparotomy,
castor oil, tincture of rhubarb, enemata, green food, ensilage, roots, onions.
In birds torpid and obstructed bowels may come from the effects
of a previous diarrhœa, which has led to the matting together of the
feathers over the anus at once obstructing defecation and rendering
it painful. It may result in and be aggravated by a slow accumulation
of indigestible matters in the intestine or cloaca (pebbles, feathers,
etc.), and the arrest of eggs in the oviduct, pressing upon and
obstructing the bowel. In a recent case the author removed 18 ozs. of
impacted egg matter from the oviduct of a hen, which when divested
of this load weighed barely 2 lbs. Debility of the general system and
particularly of the walls of the bowels, and its various causes (old
age, exhausting disease, intestinal catarrh, parasites, nervous
diseases, etc.) retard defecation and favor impaction as in the
mammal.
The symptoms may be; hard dry droppings, matting of the
feathers over the anus with feculent matters, a firm swelling
surrounding the sphincter, a pendent condition of the abdomen
which when manipulated is felt to be firm and resistant, ruffling of
the feathers, drooping of the head, wings and tail, walking sluggishly
with legs half bent and a waddling gait, and ineffectual attempts to
defecate.
Treatment. As in dogs remove the obstructing mass by mechanical
means. Matted feathers may be clipped off, and feculent
accumulations may be dislodged by the aid of the finger, or in small
birds of a blunt prob. This may be favored by manipulation through
the abdominal walls, and the injection of soapy or oily enemata.
Accumulations of impacted egg matter may be similarly removed, or,
failing this, by an incision made through the abdominal walls and
oviduct. As a purgative give one or two teaspoonfuls castor oil
according to the size of the hen, or a few drops to a small cage bird.
For the latter Friedberger and Fröhner advise a few drops of tincture
of rhubarb in the drinking water. Injections of warm or cold
soapsuds or water may be continued as symptoms demand. Green
food, ensilage, roots, worms, snails and insects are indicated to
correct the tendency to costiveness and may be continued until the
bowels have acquired their proper tone. A moderate allowance of
onions is often of great value.
HAIR BALLS IN THE INTESTINES—HORSE.
EGAGROPILES.
Seat, colon, cæcum; hair of oat seed, clover leaf, vine tendrils, hair of horse,
nucleus, calcic admixture, straw, in horses on dry food, with depraved appetite, or
with skin disease. Symptoms: none, or torpid bowels, colics, recurring,
fermentations, tympany, obstruction, rupture, peritonitis, rectal exploration.
Lesions: impacted ball, with excess of liquid and gas in front, rupture, ragged
bloody edges. Treatment: extraction, enemata, eserine, barium chloride.
Hair balls, received the name of egagropiles because of their
discovery in the alimentary canal of the wild goat, but they are found
in various forms in all the domestic animals. In horses they occupy
the cæcum and colon and are most frequently composed of the fine
vegetable hairs that surround the grain of the oat, or the leaf of
clover, of the woody tendrils of vines, and of the hairs of themselves
and their fellows taken in at the period of moulting. They sometimes
contain a nucleus of leather or other foreign body which has been
swallowed but in many cases no such object can be found, the hair
having become rolled and felted by the vermicular movements of the
stomach and intestines. An admixture of mucus assists materially in
the felting, and calcareous and magnesian salts may make up the
greater part of the mass, rendering it virtually a calculus. They may
further have a large admixture of straw and vegetable fibres of larger
size than oat or clover hairs. They are most frequent in horses kept
on dry food, (sweepings of oatmeal mills) and at hard work, and
which show depraved appetite and lick each other. Omnibus horses
suffer more than army horses. Skin diseases, by encouraging licking,
contribute to their production.
Symptoms. In the great majority of cases hair balls do not
seriously incommode the horse. They do not attain a large size, and
being light do not drag injuriously on the intestine and mesentery.
They do, however, retard the movement of the ingesta, and when
grown to a considerable size they may block the intestine, more
particularly the pelvic flexure, the floating colon or rectum. Under
such conditions they produce colics which may be slight, transient,
and recurrent, or severe and even fatal, having all the characteristics
of complete obstruction from other causes. Fermentations,
tympanies, and straining without defecation are common features.
When the obstruction takes place in the pelvic flexure, the floating
colon or rectum, it may often be detected by rectal exploration. When
complete obstruction occurs all the violent symptoms of that
condition are present, and these may pass into those of rupture
(Peuch, Leblanc, Neyraud), and shock or peritonitis. If the animal
has passed hair balls even months before, the colics may with
considerable confidence be attributed to other balls of the same kind.
Lesions. In case of death there are the usual lesions of gaseous
indigestion, with or without enteritis, but with the accumulation of a
great quantity of liquid contents, above the ball, which is felt as a
firm body impacted in the gut. In other cases the distended bowel
has given way and the liquid contents and often the hair ball as well
are found free in the abdominal cavity. In such a case the edges of the
laceration are covered with blood clots and thickened with
inflammatory exudation, and there is more or less peritonitis.
Treatment. Relief may sometimes be obtained by the extraction of
a hair ball lodged in the rectum or adjacent part of the floating colon.
In other cases abundant soapy or oily enemata, and the employment
of eserine or barium chloride subcutem are indicated.
HAIR AND BRISTLE BALLS IN DOG AND
PIG.
From licking in skin disease. Symptoms: of obstruction. Treatment:
manipulation, enemata, oil, antispasmodics, eserine, barium chloride, laparotomy,
diet in convalescence.
The hair balls of dogs come mainly from licking themselves when
affected with skin diseases or parasites. In pigs they are mostly
attributed to depraved appetite.
The hair balls of the dog are small, open in texture, and easily
disintegrated, having little mucus and no earthy salts in their
composition.
The bristle balls of pigs take the form of straight or curved rods of
firm consistency, but without earthy salts. The projecting ends of the
bristles render them particularly irritating.
The symptoms are those of obstruction of the bowels, and the
treatment consists in efforts to dislodge them. If situated near the
anus they may sometimes be reached with the finger, or copious oily
injections may facilitate their passage. Manipulations through the
abdominal walls may be helpful in the dog. Oleaginous laxatives and
antispasmodics may be tried, or these failing, eserine or barium
chloride. As a last resort laparotomy may be performed, the ball
abstracted and the intestine and abdominal wall carefully sutured
(Siedamgrotzky). In such a case the diet should be restricted for a
week to beef soups, buttermilk, and well boiled gruels, especially
flaxseed.
INTESTINAL CALCULI. ENTEROLITHS.
BEZOARS.

Earthy basis, nucleus, stratification, in cæcum or colon, multiple, size, number


up to 1000. Composition, phosphates of lime, magnesia, and ammonia, silica,
mucus, epithelium, organic matter. Ammonio-magnesian tend to crystalline form,
common phosphate of lime to smooth forms. Concretions. Source in food.
Ammonia from bacteridian fermentation, action of colloids, varied nuclei, rapid
growth. Lesions: catarrh, dilation, obstruction, rupture, peritonitis. Symptoms:
intermittent colics with obstruction, tympany, bowel distension, liquid and
gaseous, before obstruction. Diagnosis: by hand in rectum, hard obstruction with
distension in front. Treatment: purgative dangerous, but exceptionally successful,
extraction, oleaginous enemata, laparotomy.

Horse. Intestinal calculi have an earthy basis (ammonio-


magnesian phosphate, or oxalate of lime, and more or less silica)
glued together by mucus and having a central nucleus usually of
some foreign body, (a particle of sand, pebble, morsel of hair, lead,
cloth, nail, coin, blood clot, or inspissated mucus) around which the
earthy salts have been deposited layer after layer. They are usually
formed in the cæcum or double colon and may be multiple and
moulded upon each other, so that they become discoid, angular or
otherwise altered from the globular shape. The worn, flattened
surface in such cases shows concentric rings representing the layers
as deposited in succession.
The size of the masses may be from a pea or smaller, up to calculi
of six inches in diameter.
In number there may be a single calculus or there may be an
indefinite quantity. Zundel counted 400 in a single colon, and Gurlt
1,000.
Composition. They are usually composed of phosphate of lime and
of magnesia, of ammonio-magnesian phosphate, with a little silica,
mucus, epithelium, and organic matters from the ingesta. Traces of
sodium chloride, and iron oxide may also be present.
The phosphates of lime, magnesia, and of ammonia and magnesia
usually constitute the main part of the calculus. Fürstenberg found
specimens in which the ammonio-magnesian phosphate amounted
to 72 to 94 per cent.
The calculi containing an excess of ammonio-magnesian
phosphate tend to assume a crystalline or coralline form which
causes them to be specially irritating to the mucosa. When broken
they show a radiated structure from the centre to the circumference
in addition to the concentric rings. These are usually of a yellowish
brown or a gray color and have a specific gravity of 1694 to 1706.
Calculi in which the common phosphate of lime abounds are likely
to be smooth on the surface and on section show the concentric rings
more distinctly and the radiating lines less so. The brownish calculi
of this variety are much more compact, and harder than the
crystalline or mulberry calculi, and have a higher specific gravity—
(1823).
Bluish calculi with a smooth glistening surface and lower specific
gravity—1681—, have been found of small size and in great numbers
in the colon (1000 in the colon, Gurlt).
In some calculi there is a large admixture of alimentary matters,
and a low specific gravity (1605 to 1674). These were designated as
pseudo calculi, by Fürstenberg.
In still other cases a calculous looking mass, when broken into, is
found to be composed of a mass of dried alimentary matter enclosed
in a thin layer of lime salts. These have a low specific gravity (1446 to
1566) and have been named concretions by Fürstenberg.
Causes. As a large proportion of the calculus is phosphate of lime
or ammonio-magnesian phosphate, we must look for the source of
these in the food and then at the conditions which determine their
precipitation.
The percentage of ash and of phosphoric acid in the common foods
of horses may be seen in the following table:
Ash. PO5 in the Ash. PO5 in the entire food.
Per cent. Per cent. Per cent.
Wheat bran 7.3 50 3.65
Wheat grain 3.0 46.38 1.3914
Oats grain 2.50 26.5 0.6625
Barley grain 3.10 39.9 1.2276
Bean grain 3.10 31.6 0.9864
Pea grain 2.75 34.8 0.957
Tare grain 3.00 36.2 1.086
Indian corn grain 1.5
Rye grain 1.6 39.9 1.0384

The source of the magnesia may be found to a large extent in the


grains represented in the following table:

Ash. Mg. in Ash.


Per cent. Per cent.
Oat, grain 2.50 7.3
Barley, grain 3.10 8.5
Rye, grain 1.6 2.4
Wheat, grain 2.12 9.98
Wheat, bran 7.3 11.2
Bean 3.1 6.6
Pea 2.7 5.6

The amount of magnesia in each of these grains is amply sufficient


to furnish the material for the constant growth of a calculus. Wheat
bran is preëminent in the amount of its magnesia and therefore
wheat bran has been charged with predisposing to calculi. In the
perisperm as a whole, Fürstenberg found 1 per cent. of phosphate of
magnesia, and in coarse bran not less than 2.5 per cent.
The ammonia which is essential to the precipitation of the
phosphate of magnesia in the form of the compound salt (ammonio-
magnesian) can be found wherever proteids are in process of septic
fermentation. The slightest failure to peptonize every particle of such
proteids, implies septic change and the evolution of ammonia, which
on coming in contact with magnesia phosphate instantly precipitates
the insoluble salt.
This fully agrees with the doctrine of the formation of urinary
calculi through the agency of bacteria, since the ammonia is
essentially a fermentation or bacterial product.
It may also be noted that the experiments of Rainey and Ord
showed that in the presence of colloids (mucus, epithelium, pus,
blood) the earthy salts are precipitated as minute globular bodies
which by further accretions become calculi. In the absence of colloids
the salts tend to precipitate in angular crystalline forms, so that the
mulberry and coralline calculi may possibly have been precipitated in
the absence of such bodies. From the solvent quality of ammonia,
however, the contents may easily pass from a fermenting liquid
containing colloids to a non-fermenting and noncolloid mixture.
The presence of a solid body which may act as a nucleus is an
essential element, and the condition of the food or drink will often
supply this. It has been noticed that army horses in the field, feeding
from the ground and taking in sand and pebbles, are unusually liable
to intestinal calculus. Horses which lick earth in connection with
acidity of the stomach or other dyspepsia are specially subject to it.
Horses watered from shallow streams with sandy bottoms, where
they take in sand with the water, have been similarly affected.
Millers’ horses, in the days of old process milling, suffered not alone
because of the abundance of oat hairs in the feed but also on account
of the grit from the millstones. Hay and other fodders that have lain
on the ground and which contain earth and sand furnish other
sources of such nuclei. Shingle nails and other small nails, pins,
needles, coins, etc., which have mixed with the feed are common
causes of trouble, and indeed any foreign body may become the
centre and starting point of a calculus.
Catarrhal affections and other lesions of the mucosa, which furnish
excess of mucus, beside pus, lymph and even blood as nuclei, are
invoked as starting points of the calculi, but however true this may
be in particular cases, irritation and catarrh appear to be much more
frequently the result than the cause of the calculus.
Attempts have been made to estimate the time taken in the
formation of a calculus by allowing a ring for each feed and
successive deposit therefrom (Fürstenberg, Colin). Thus a calculus of
14 pounds with 720 layers, it was estimated could be formed in one
year at two feeds per day. More definite evidence was found in the
case of Pastore in which a coin with the mint mark of 1847 was found
as the nucleus of a calculus the size of the fist in 1848.
Lesions. Formed in the most spacious parts of the colon and
cæcum, calculi usually rest there for a length of time without visible
injury, and it is only when they are moved onward and get arrested at
a narrow part of the gut (pelvic flexure, floating colon, rectum) that
they cause appreciable trouble. Yet it is claimed that by their weight
they drag upon the yielding walls of the bowel, causing dilatation and
attenuation, weakening the peristalsis and predisposing to rupture.
The compression of the vessels also tends to anæmia and atrophy. In
the case of rough crystalline calculi the mucosa is subjected to
attrition, irritation, and inflammation. The more serious and urgent
trouble is that of obstruction of the narrower portions of the colon
and rectum, which may be absolute and persistent, leading to
rupture and death or a fatal inflammation on the one hand, or may
end in recovery on the other, in connection with a displacement
onward or backward of the calculus as the result of peristalsis or
anti-peristalsis.
Symptoms. These are intermittent colics, each reaching a climax
and followed by a sudden recovery as the calculus is displaced into a
more spacious part of the colon. A significant feature is the complete
obstruction, fæces being passed for a short time at first and then
suddenly and absolutely stopped. Coincident with this are tympany,
violent colics, straining, rolling, sitting on the haunches,
perspirations, anxious countenance, and all the symptoms of
obstruction.
Diagnosis is never quite certain unless the practitioner with his
oiled hand in the rectum can detect a hard stony mass obstructing
the pelvic flexure of the double colon with a tense elastic distended
bowel immediately in front of it, or a similar hard obstruction of the
terminal part of the floating colon with a similar distension in front
of it. The pelvic flexure may usually be felt below and to the right at
the entrance to the pelvis, and the floating colon above, under the
right, or more commonly the left kidney. Calculi in the more spacious
parts of the double colon or in the cæcum are inaccessible to
manipulation. The feed (bran, ground feed) will be suggestive, as will
the occupation of the proprietor (miller, baker).
Treatment. This is rather a hopeless undertaking. No effective
solvent of the calculus can be given, and purgatives usually increase
the danger by increasing the peristalsis and dangerously distending
the bowel above the point of obstruction. It is true that this is
sometimes followed by a temporary recovery the calculus being
loosened and falling back into the dilated portion of the bowel. Less
frequently the increase in the peristalsis forces on a moderately sized
calculus to complete expulsion. It is a desperate though sometimes
successful resort. A more rational course of treatment is the dilation
of the bowel back of the obstruction by copious mucilaginous, soapy
or oleaginous enemata. Trasbot suggests CO2 produced by injecting
sodium bicarbonate and tartaric acid. This may be seconded by the
hypodermic injection of barium chloride or of atropia. When the
calculus is lodged in the floating colon or rectum it may be possible
to reach it with the hand and extract it at once. The last resort, is by
laparotomy for the removal of the calculus. One such successful case
is on record in which Filizet removed a calculus as large as an
infant’s head. In other cases the horses failed to survive. Desperate as
the resort may be it is not to be neglected in a case of undoubted
calculus, solidly impacted and of such a size that its passage is
impossible. A fatal result is imminent, and even if the present attack
should pass off it can only be looked on in the light of an
intermission, so that there is practically nothing to lose in case the
result should prove fatal. Anæsthesia and rigid antiseptic measures
should of course be adopted.
FOREIGN BODIES IN THE INTESTINES OF
SOLIPEDS.
Sand, pebbles, earth, lime, nails, pins, needles, coins, shot, cloth, leather, rubber,
sponge, tooth, bone, wood, twine. Symptoms: as in intestinal indigestion or calculi,
or sand or pebbles in fæces; peritonitis, phlegmon. Lesions: congestion, catarrh,
ulceration, abscess, needles may travel to other organs. Treatment: laxative,
enemata, or as for calculi.
All sorts of foreign bodies are taken in with food and water and
find their way to the intestines. Sand from drinking from shallow
streams with sandy bottoms, from browsing on sandy pastures where
the vegetation is easily torn up, or from feeding grain from sandy
earth will sometimes load the intestines to an extraordinary extent so
that such horses will pass sand for some weeks after leaving the
locality. Small stones and gravel are taken in in the same way or from
the habit of eating earth or licking crumbling lime walls. Nails, pins,
needles, coins, shot, pieces of cloth, leather, caouchouc, sponge, and
even a molar tooth and a piece of a dorsal vertebra have been thus
taken. Recently the author saw a small twig of hard wood transfixing
the pylorus and duodenum with fatal effect. In another case were
balls of binding twine which had been taken in with the fodder on
which it had been used.
The symptoms are usually those of intestinal indigestion or calculi.
In some cases, however, they are peculiar, thus there may be a
constant passage of sand, there may be indications of peritonitis, or
there may form a phlegmonous swelling of the abdominal walls in
the abscess of which the foreign body is found.
Lesions. Pechoux found 56 lbs. of a brownish earth in the cæcum
and colon. Congestion and ulceration of the intestines are common,
with occasionally abscess. All the lesions that attend on or follow
obstruction may be met with. Boullon saw a remarkable case of the
ingestion of needles in which these bodies were found in the small
intestine, liver, pancreas, diaphragm, kidney and lung.
Treatment varies with the character of the bodies ingested, sand
and gravel may be passed on by a laxative diet and even by the use of
mild laxatives. Bernard gave 10 quarts of water and 4 oz. Glauber
salts every hour for eight days, and the same amount by enema. For
the larger solid bodies which obstruct the intestines the treatment is
the same as for calculus. For sharp pointed bodies causing abscess
and fistulæ, we must follow the indications, ever aiming at the
discovery of the whereabouts of the offending object and its removal.
FOREIGN BODIES IN THE INTESTINES OF
RUMINANTS.
Foreign bodies are usually arrested in the rumen of cattle and
unless sharp, pointed or rough so as to cause mechanical trouble or
caustic so as to act chemically, rarely do much harm. The most
extraordinary objects that have found their way into the intestine are
snakes. Gherardi claims that he found in the intestines a snake of 25
inches long; Jager found one of 21 inches in length, in an advanced
state of decomposition, in the rectum of a calf. It is supposed that
both had been taken in with the food. In each case there was
obstruction of the intestine with severe colicy symptoms.
FOREIGN BODIES IN THE INTESTINES OF
CARNIVORA.

Small bodies, especially playthings, feathers, hair, bristles, bones of prey.


Lesions: congestion, inflammation, hemorrhage, ulceration, perforation,
invagination. Symptoms: colic, vomiting, tucked up belly, straining, palpitation,
rabiform symptoms, cough, convulsions. Course: emaciation, prostration, death in
five days or two weeks according to seat of obstruction. Treatment: Oleaginous
injections, laparotomy.

Causes. The dog is especially liable to this form of trouble, in


consequence of his habit of carrying objects in his mouth and of
playing with different objects especially the playthings of children.
Marbles, pebbles, spinning-tops, corks, coins, nuts, peach stones,
pieces of rubber, cloth or leather, bits of wood, sponge, needles, pins,
potato, bone, cord, hair, bristles, feathers, wire, and a number of
other objects. Some of them like feathers, hair, and bones are
swallowed with food, and when that has been digested, they are
either vomited or failing in this, are passed on into the intestine.
Lately the author made a post mortem of a house dog with over 24
inches of the jejunum virtually blocked with fragments gnawed from
a caouchouc ball and pieces of twine.
Cats also swallow a variety of objects. Benjamin and Megnin
record three cases of intestinal obstruction by the crystal drops of
shades.
Lesions. When the lumen of the intestine is blocked with a round
solid body like a marble or peach stone there occur active congestion,
inflammation, blood stasis and hemorrhage, with in many cases
necrosis, ulceration and perforation. Similar lesions occur from cord.
In a recent case of impaction with gnawed fragments of caouchouc
and cord, the 24 inches of the bowel implicated were the seat of
extended patches of necrosis and of deep, and even perforating
ulcers on the lesser curvature of the intestine, evidently caused by
the tension of the stretched cord on the shorter attached border of
the gut. Cadeac says the lesions from cord are always at the point of
attachment of the mesentery, whereas those coming from round or
cubical solid bodies are mainly on the greater curvature. Mathis
found at the pylorus a piece of net from which a cord extended
through the small intestine and ended in a ravelled mass near the
ileo-cæcal valve. The dragging of the cord on the intestine often
causes invagination at one or several points.
Symptoms. There may be slight colic, dullness, a disposition to lie
curled up in some secluded place, loss or caprice of appetite,
vomiting, tucked up abdomen, arching of the back, straining, and
unless the bowels are distended with gas, the obstruction can usually
be felt by the two hands applied on opposite sides of the abdomen.
The matters vomited are at first alimentary, then bilious and in the
advanced stages always feculent.
The French veterinarians assure us that rabiform symptoms are
very common as the result of obstruction of the intestines with
foreign bodies. The indications are signs of fury without the barking
which characterizes genuine rabies. The patient becomes wicked,
cross and excitable, sometimes dull and morose, and snappish, his
eyes glittering and his mouth frothy. He has alternate paroxysms of
fury and torpor, at one time flying at and biting any living thing he
meets, or tearing some object to pieces, and at another hiding away
in secluded and dark corners. Massenat saw two dogs supposed to be
affected by rabies, but which recovered promptly after having
vomited the foreign bodies which they had swallowed. In a country
where rabies is so prevalent as in France, it would be interesting to
see the results of inoculation with some of the most pronounced of
these rabiform cases.
Beside the rabiform symptoms cough and epileptic seizures
occasionally result from the foreign bodies.
Course. Termination. Unless relief is obtained by vomiting or
purging, appetite ceases altogether, emaciation advances rapidly, the
animal becomes dull and stupid, being evidently poisoned by the
absorbed toxins, and death may ensue in four or five days if the
obstruction is near the stomach, or in one or two weeks if in the large
intestines.
Treatment. The general treatment advised for the horse is
applicable to the carnivora. Purgatives are always dangerous as
threatening the overdistension and rupture of the bowel above the
obstruction. Oleaginous and mucilaginous injections with
manipulations are more promising if the obstruction is in the colon
or rectum.
In many cases laparotomy is the only hopeful resort. Felizet and
Degive have been quite successful in removing corks in this way, and
Fröhner advises the operation to be performed under opium
narcosis, and with antiseptic precautions. Make an incision of 1¾
inch near the umbilicus and parallel to the linea alba, extract the
blocked loop of intestine, ligature it in front of the foreign body and
behind it, incise, remove the offending mass and carefully close by
sutures, bringing the muscular and serous coats in accurate
opposition. Remove the ligatures, disinfect, return the bowel into the
abdomen, close the abdominal wound with sutures and apply an
antiseptic bandage.
If such cases are to be operated on it is important that it be done
early, before the occurrence of necrosis, ulceration, perforation, or
general infection.
RUPTURE OF THE INTESTINE. SOLIPEDS.
Causes: overdistensions in front of obstructions, softening, friability, necrosis,
suppuration or ulceration, Duodenum from worms or perforation by pointed
bodies, exudate in verminous embolism, petechial fever. Jejunum and ileum, by
disease of walls, ulcers, abscesses, neoplasms, caustics in umbilical hernia,
clamping of hernia. Cæcum, falls, blows, kicks, blows of horn, tusk, stump, calculi,
abscesses, cauterizing of hernia. Colon, external traumas, calculi, worms,
verminous thrombosis, neoplasms, abscesses, overdistensions, violent straining,
arsenic. Symptoms: follow accident, signs of obstruction, no rumbling, tympany,
stiffness, great prostration, fever. Death in short time.
Causes. Ruptures occur as we have already seen from
overdistensions of the bowel in front of some obstruction, by ingesta,
concretions, calculi, foreign bodies, etc., and this may take place in
the most healthy organs. In other cases, however, there has been
some pathological process at work rendering the intestinal wall soft,
friable, necrotic, suppurative or ulcerative, by which its substance is
attenuated or its consistency or cohesion reduced.
Duodenum. Lacerations of the duodenum are often connected
with obstruction by tumors or the ravages of worms. These latter are
mostly the ascaris megalocephala, accumulated in mass, and
sometimes engaged in pouches outside the walls of the gut. In other
cases, the walls of the intestine have been perforated by hard woody
stalks of straw or hay (Mollereau) or of still more woody plants as in
a case observed by the author, and in which the pylorus was
perforated. Sometimes the exudate or blood extravasation attending
on petechial fever, or verminous embolism will pave the way for the
rupture. Perforations by pieces of wire (Schmidt) or other metallic
bodies are also observed. Adhesive peritonitis has also rendered the
walls friable and predisposed to rupture.
Jejunum and Ileum. Lesions are most frequent toward the
termination of the ileum and resulting from obstructions of the
bowel or the weakening of the walls by disease, or both. Ulcerations,
abscess of the closed follicles opening into the peritoneum, and
neoplasms of various kinds are to be especially noted among the
causes. The impaction of the cæcum, blocking the ileo-cæcal valve is
also among the observed factors. Other instances have been traced to
deep cauterization of an umbilical hernia, the enclosed loop of small
intestine becoming inflamed and perforated. The author has
observed one instance from clamping of a hernia in which the
contained intestine was adherent to the hernial sac.
Cæcum. From its position on the lower part of the abdomen and
from its habitual plenitude with food or water, this organ is
especially exposed to direct mechanical injuries and ruptures. A
sudden fall, more especially if the umbilical region strikes on a stone
or other projecting solid body, kicks with heavy boots or with the feet
of other animals, blows with a cow’s horn or a boar’s tusks, and
violent contact with stumps, poles and other objects may be the
occasion of the rupture. These are usually found near the base of the
viscus and across its longitudinal direction.
Inflammations, connected with punctures, calculi, parasites, etc.,
may render the walls so friable that they give way under slight strain
or injury. Abscesses have been found in the walls of the viscus
leading to perforation, and extension of inflammation from an
umbilicus cauterized for hernia has determined adhesion and
perforation.
Colon. The loaded colon is even more liable to mechanical injury
than the cæcum. Occupying as it does the more lateral parts of the
abdominal floor, it is even more exposed to kicks and blows, and
extending as it does back toward the inguinal regions, it is especially
in the way of blows of horns so often delivered in this region. From
the solid nature of its contents the presence of calculi, the presence
of blood sucking worms, and its implication in the congestions and
extravasations of verminous thrombosis, this organ is especially
liable to degenerations and inflammations which render its walls
particularly friable. Neoplasms of various kinds, cancerous,
tubercular, etc., have been found on its walls as occasions of rupture.
Abscesses of strangles have ruptured into the viscus. Overdistensions
in front of an obstruction in the pelvic flexure, floating colon or
rectum are the most frequent causes of rupture. Again, cases have
been seen as the result of violent exertions, as during straining in
dystokia. It has been a complication of phrenic hernia, of volvulus of
the double colon, and of ulceration caused by the prolonged
ingestion of arsenic. In severe impaction the necrosis of the intestinal

You might also like