Fundamentals of general, organic, and biological chemistry

992 Pages·2010·113.232 MB·English

by  John McMurry, et al

A01_MCMU4501_06_SE_FM.QXD 1/16/09 12:30 AM Page i
Fundamentals
of General, Organic,
and Biological Chemistry
SIXTH EDITION
John McMurry
Cornell University
Mary Castellion
Norwalk,Connecticut
David S. Ballantine
Northern Illinois University
Carl A. Hoeger
University of California,San Diego
Virginia E. Peterson
University of Missouri,Columbia
Prentice Hall
New York Boston San Francisco
London Toronto Sydney Tokyo Singapore Madrid
Mexico City Munich Paris Cape Town Hong Kong Montreal
A01_MCMU4501_06_SE_FM.QXD 1/16/09 9:51 PM Page ii
Library of Congress Cataloging-in-Publication Data
Fundamentals of general, organic, and biological chemistry/John McMurry... [et al.]. 6th ed.
p. cm.
Rev. ed. of: Fundamentals of general, organic, and biological chemistry/John McMurry,
Mary E. Castellion, David S. Ballantine. 5th ed. ©2007.
Includes index.
ISBN 0-13-605450-1
1. Chemistry Textbooks. I. McMurry, John.
QD31.3.M355 2010
540 dc22
2008054670
Editor in Chief, Science: Nicole Folchetti Senior Operations Supervisor: Alan Fischer
Acquisitions Editor: Dawn Giovanniello Composition/Full Service: Macmillan Publishing
Assistant Editor: Laurie Varites Solutions
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Managing Editor, Chemistry and Geosciences: Photo Researcher: Eric Schrader
Gina M. Cheselka Cover Photo: David Fleetham/Alamy
Project Manager: Wendy Perez Other image credits appear in the backmatter
© 2010, 2007, 2003, 1999, 1996, 1992 Pearson Education, Inc.
Pearson Prentice Hall
Pearson Education, Inc.
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All rights reserved. No part of this book may be reproduced, in any form or by any means, without permission in writing from the
publisher.
Pearson Prentice Hall is a trademark of Pearson Education, Inc.
Printed in the United States of America.
10 9 8 7 6 5 4 3 2 1
ISBN-10: 0-13-605450-1
ISBN-13: 978-0-13-605450-4
A01_MCMU4501_06_SE_FM.QXD 1/8/09 5:55 PM Page iii
About the Authors
John McMurry, educated at Harvard and Columbia, has taught
approximately 17,000 students in general and organic chemistry over
a 30-year period. AProfessor of Chemistry at Cornell University since
1980, Dr. McMurry previously spent 13 years on the faculty at the
University of California at Santa Cruz. He has received numerous
awards, including the Alfred P. Sloan Fellowship (1969 71), the
National Institute of Health Career Development Award (1975 80),
the Alexander von Humboldt Senior Scientist Award (1986 87), and the Max Planck
Research Award (1991).
David S. Ballantine received his B.S. in Chemistry in 1977 from
the College of William and Mary in Williamsburg, VA, and his Ph.D.
in Chemistry in 1983 from the University of Maryland at College
Park. After several years as a researcher at the Naval Research Labs in
Washington, DC, he joined the faculty in the Department of Chemistry
and Biochemistry of Northern Illinois University, where he has been a
professor for the past twenty years. He was awarded theExcellence in
Undergraduate Teaching Award in 1998 and was recently named the departmental
Director of Undergraduate Studies. In addition, he is the faculty advisor to the NIU
Chemistry Club, an American Chemical Society Student Affiliate program.
Carl A.Hoegerreceived his B.S. in Chemistry from San Diego State
University and his Ph.D. in Organic Chemistry from the University of
Wisconsin, Madison in 1983. After a postdoctoral stint at the Univer-
sity of California, Riverside, he joined the Peptide Biology Laboratory
at the Salk Institute in 1985 where he ran the NIH Peptide Facility
while doing basic research in the development of peptide agonists
and antagonists. During this time he also taught general, organic, and
biochemistry at San Diego City College, Palomar College, and Miramar College.
He joined the teaching faculty at University of Califiornia, San Diego in 1998.
Dr.Hoeger has been teaching chemistry to undergraduates for over 20 years, where
he continues to explore the use of technology in the classroom. In 2004 he won the
Paul and Barbara Saltman Distinguished Teaching Award from UCSD. He is
currently the General Chemistry coordinator at UCSD, where he is also responsible
for the training and guidance of over 100 teaching assistants in the Chemistry and
Biochemistry departments.
Virginia E.Petersonreceived her B.S. in Chemistry in 1967 from
the University of Washington in Seattle, and her Ph.D. in Bio-
chemistry in 1980 from the University of Maryland at College Park.
Between her undergraduate and graduate years she worked in lipid,
diabetes, and heart disease research at Stanford University. Following
her Ph.D. she took a position in the Biochemistry Department at the
University of Missouri in Columbia and is now an Associate Professor.
Currently she is the Director of Undergraduate Advising for the department and
teaches both senior capstone classes and biochemistry classes for nonscience
majors. Awards include both the college level and the university-wide Excellence in
Teaching Award and, in 2006, the Universitys Outstanding Advisor Award and the
State of Missouri Outstanding University Advisor Award. Dr. Peterson believes in
public service and in 2003 received the Silver Beaver Award for service from the
Boy Scouts of America.
iii
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Brief Contents
Applications xiii 17
Carboxylic Acids and Their
Preface xv Derivatives 516
A Students Guide to Using This Text xxiv 18
Amino Acids and Proteins 552
1
Matter and Life 2
19
Enzymes and Vitamins 592
2
Measurements in Chemistry 18
20
Chemical Messengers: Hormones,
3
Atoms and the Periodic Table 48 Neurotransmitters, and Drugs 628
4 21
Ionic Compounds 78 The Generation of Biochemical
5 Energy 658
Molecular Compounds 106
22
6 Carbohydrates 692
Chemical Reactions: Classification
23
and Mass Relationships 142 Carbohydrate Metabolism 728
7 24
Chemical Reactions: Energy, Rates, Lipids 756
and Equilibrium 182
25
Lipid Metabolism 786
8
Gases, Liquids, and Solids 214
26
Nucleic Acids and Protein
9
Solutions 254 Synthesis 808
10 27
Acids and Bases 292 Genomics 840
11 28
Nuclear Chemistry 332 Protein and Amino Acid
12 Metabolism 860
Introduction to Organic Chemistry:
29
Alkanes 360 Body Fluids 878
13
Alkenes, Alkynes, and Aromatic Appendices A-1
Compounds 396
Glossary A-6
14
Some Compounds with Oxygen,
Answers to Selected Problems A-13
Sulfur, or a Halogen 434
Photo Credits A-49
15
Amines 464
Index A-51
16
Aldehydes and Ketones 488
iv
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Contents
Applications xiii
Preface xv
A Students Guide to Using This Text xxiv
1
Matter and Life
2
1.1 Chemistry: The Central Science 3
1.2 States of Matter 5
1.3 Classification of Matter 6
1.4 An Example of a Chemical Reaction 8
1.5 Chemical Elements and Symbols 8
Application:Aspirin A Case Study 9
1.6 Elements and the Periodic Table 11
Application:Mercury and Mercury Poisoning 14
3.5 Some Characteristics of Different Groups 59
2
Application:The Origin of Chemical
Measurements in Chemistry
18
Elements 61
2.1 Physical Quantities 19 3.6 Electronic Structure of Atoms 61
2.2 Measuring Mass 21 3.7 Electron Configurations 64
2.3 Measuring Length and Volume 22 3.8 Electron Configurations and the
2.4 Measurement and Significant Figures 24 Periodic Table 68
2.5 Scientific Notation 26 3.9 Electron-Dot Symbols 71
Application:Powers of 10 28 Application:Atoms and Light 72
2.6 Rounding Off Numbers 29
4
2.7 Problem Solving: Converting a Quantity from One
Ionic Compounds
78
Unit to Another 31
2.8 Problem Solving: Estimating Answers 33 4.1 Ions 79
2.9 Measuring Temperature 35 4.2 Periodic Properties and Ion Formation 81
Application:Temperature-Sensitive 4.3 Ionic Bonds 83
Materials 36 4.4 Some Properties of Ionic Compounds 84
2.10 Energy and Heat 38 4.5 Ions and the Octet Rule 84
2.11 Density 39 Application:Minerals and Gems 85
Application:Obesity and Body Fat 41 4.6 Ions of Some Common Elements 87
2.12 Specific Gravity 42 Application:Salt 89
4.7 Naming Ions 90
3
4.8 Polyatomic Ions 91
Atoms and the Periodic Table
48
Application:Biologically Important Ions 92
3.1 Atomic Theory 49 4.9 Formulas of Ionic Compounds 93
Application:Are Atoms Real? 52 4.10 Naming Ionic Compounds 95
3.2 Elements and Atomic Number 53 4.11 H*and OH+Ions: An Introduction to Acids
3.3 Isotopes and Atomic Weight 54 and Bases 98
3.4 The Periodic Table 57 Application:Osteoporosis 100
v
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vi Contents
Application:Anemia A Limiting Reagent
Problem? 162
6.9 Precipitation Reactions and Solubility
Guidelines 163
Application:Gout and Kidney Stones:
Problems in Solubility 165
6.10 Acids, Bases, and Neutralization
Reactions 165
6.11 Redox Reactions 166
Application:Batteries 171
6.12 Recognizing Redox Reactions 172
6.13 Net Ionic Equations 174
7
Chemical Reactions: Energy, Rates,
and Equilibrium
182
7.1 Energy and Chemical Bonds 183
5
Molecular Compounds 7.2 Heat Changes during Chemical Reactions 183
106
7.3 Exothermic and Endothermic Reactions 184
5.1 Covalent Bonds 107
7.4 Why Do Chemical Reactions Occur?
5.2 Covalent Bonds and the Periodic Table 110 Free Energy 188
5.3 Multiple Covalent Bonds 113 Application:Energy from Food 189
5.4 Coordinate Covalent Bonds 115 7.5 How Do Chemical Reactions Occur? Reaction
Application:CO and NO:Pollutants or Miracle Rates 193
Molecules? 116 7.6 Effects of Temperature, Concentration,
5.5 Molecular Formulas and Lewis Structures 117 andCatalysts on Reaction Rates 195
5.6 Drawing Lewis Structures 117 7.7 Reversible Reactions and Chemical
5.7 The Shapes of Molecules 122 Equilibrium 198
Application:VERY Big Molecules 127 Application:Regulation of Body Temperature 198
5.8 Polar Covalent Bonds and Electronegativity 128 7.8 Equilibrium Equations and Equilibrium
Constants 200
5.9 Polar Molecules 130
7.9 Le Châteliers Principle: The Effect of Changing
5.10 Naming Binary Molecular Compounds 132
Conditions on Equilibria 203
5.11 Characteristics of Molecular Compounds 134
Application:Nitrogen Fixation 207
Application:Damascenone by Any Other Name
Would Smell as Sweet 135
8
Gases, Liquids, and Solids
214
6
Chemical Reactions: Classification 8.1 States of Matter and Their Changes 215
and Mass Relationships 8.2 Gases and the Kinetic Molecular Theory 218
142
8.3 Pressure 218
6.1 Chemical Equations 143
8.4 Boyles Law: The Relation between Volume
6.2 Balancing Chemical Equations 145 andPressure 222
6.3 Avogadros Number and the Mole 148 Application:Blood Pressure 223
6.4 Gram Mole Conversions 152 8.5 Charless Law: The Relation between Volume
Application:Did Ben Franklin Have Avogadros andTemperature 225
Number? A Ballpark Calculation 153 8.6 Gay-Lussacs Law: The Relation between Pressure
6.5 Mole Relationships and Chemical Equations 155 and Temperature 226
6.6 Mass Relationships and Chemical 8.7 The Combined Gas Law 228
Equations 156 8.8 Avogadros Law: The Relation between Volume
6.7 Limiting Reagent and Percent Yield 159 and Molar Amount 229
6.8 Classes of Chemical Reactions 161 8.9 The Ideal Gas Law 231
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8.10 Partial Pressure and Daltons Law 233 10.11 Buffer Solutions 312
8.11 Intermolecular Forces 235 10.12 Buffers in the Body 315
Application:Greenhouse Gases and Global Application:Buffers in the Body:Acidosis
Warming 236 andAlkalosis 317
8.12 Liquids 240 10.13 Acid and Base Equivalents 318
8.13 Water: A Unique Liquid 242 10.14 Some Common Acid Base Reactions 320
8.14 Solids 243 10.15 Titration 321
8.15 Changes of State 244 Application:Acid Rain 324
Application:Biomaterials for Joint 10.16 Acidity and Basicity of Salt Solutions 325
Replacement 246
Application:CO as an Environmentally Friendly 11
2 Nuclear Chemistry
Solvent 248 332
11.1 Nuclear Reactions 333
9 11.2 The Discovery and Nature of Radioactivity 334
Solutions
254
11.3 Stable and Unstable Isotopes 335
9.1 Mixtures and Solutions 255 11.4 Nuclear Decay 336
9.2 The Solution Process 257 11.5 Radioactive Half-Life 341
9.3 Solid Hydrates 259 Application:Medical Uses of Radioactivity 342
9.4 Solubility 260 11.6 Radioactive Decay Series 344
9.5 The Effect of Temperature on Solubility 261 11.7 Ionizing Radiation 345
9.6 The Effect of Pressure on Solubility: 11.8 Detecting Radiation 347
Henrys Law 262 11.9 Measuring Radiation 348
9.7 Units of Concentration 265 Application:Irradiated Food 349
Application:Breathing and Oxygen Transport 266 11.10 Artificial Transmutation 350
9.8 Dilution 273 Application:Body Imaging 352
9.9 Ions in Solution: Electrolytes 275 11.11 Nuclear Fission and Nuclear Fusion 352
9.10 Electrolytes in Body Fluids: Equivalents Application:Archaeological Radiocarbon
andMilliequivalents 276 Dating 355
9.11 Properties of Solutions 278
Application:Electrolytes,Fluid Replacement, 12
Introduction to Organic Chemistry:
andSports Drinks 279
9.12 Osmosis and Osmotic Pressure 282 Alkanes 360
9.13 Dialysis 285
12.1 The Nature of Organic Molecules 361
Application:Timed-Release Medications 286
12.2 Families of Organic Molecules: Functional
Groups 363
10
Acids and Bases
292
10.1 Acids and Bases in Aqueous Solution 293
10.2 Some Common Acids and Bases 294
10.3 The Brønsted Lowry Definition of Acids
andBases 295
10.4 Water as Both an Acid and a Base 298
10.5 Acid and Base Strength 299
Application:GERD Too Much Acid or Not
Enough? 302
10.6 Acid Dissociation Constants 303
10.7 Dissociation of Water 304
10.8 Measuring Acidity in Aqueous Solution: pH 306
10.9 Working with pH 308
10.10 Laboratory Determination of Acidity 310
Application:pH of Body Fluids 311
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viii Contents
12.3 The Structure of Organic Molecules: 13.10 Naming Aromatic Compounds 423
Alkanes and Their Isomers 368 13.11 Reactions of Aromatic Compounds 426
12.4 Drawing Organic Structures 370 Application:Why We See Color 428
12.5 The Shapes of Organic Molecules 376
12.6 Naming Alkanes 378 14
Some Compounds with Oxygen,
Application:Displaying Molecular
Shapes 379 Sulfur, or a Halogen
434
12.7 Properties of Alkanes 385
14.1 Alcohols, Phenols, and Ethers 435
12.8 Reactions of Alkanes 386
14.2 Some Common Alcohols 437
12.9 Cycloalkanes 387
14.3 Naming Alcohols 438
Application:Petroleum 388
14.4 Properties of Alcohols 441
12.10 Drawing and Naming Cycloalkanes 389
14.5 Reactions of Alcohols 442
Application:Ethyl Alcohol as a Drug and
13
Alkenes, Alkynes, and Aromatic a Poison 447
14.6 Phenols 448
Compounds
396
14.7 Acidity of Alcohols and Phenols 449
13.1 Alkenes and Alkynes 397 Application:Phenols as Antioxidants 450
13.2 Naming Alkenes and Alkynes 398 14.8 Ethers 451
13.3 The Structure of Alkenes: Cis Trans 14.9 Thiols and Disulfides 453
Isomerism 401
Application:Inhaled Anesthetics 454
13.4 Properties of Alkenes and Alkynes 405
14.10 Halogen-Containing Compounds 455
13.5 Types of Organic Reactions 405
Application:Chlorofluorocarbons and the Ozone
Application:The Chemistry of Vision 406 Hole 457
13.6 Reactions of Alkenes and Alkynes 409
13.7 How Alkene Addition Reactions Occur 415 15
Amines
13.8 Alkene Polymers 416 464
Application:Polymer Applications Currency 420 15.1 Amines 465
13.9 Aromatic Compounds and the Structure Application:Chemical Information 468
ofBenzene 420
15.2 Properties of Amines 471
Application:Polycyclic Aromatic Hydrocarbons
15.3 Heterocyclic Nitrogen Compounds 473
and Cancer 422
Application:NO:A Small Molecule with Big
Responsibilities 475
15.4 Basicity of Amines 476
Application:Organic Compounds in Body Fluids
and the Solubility Switch 478
15.5 Amine Salts 479
15.6 Amines in Plants: Alkaloids 481
Application:Toxicology 482
16
Aldehydes and Ketones
488
16.1 The Carbonyl Group 489
16.2 Naming Aldehydes and Ketones 492
Application:Chemical Warfare among the
Insects 493
16.3 Properties of Aldehydes and Ketones 494
Application:Vanilla:Which Kind Is Best? 496
16.4 Some Common Aldehydes and Ketones 497
16.5 Oxidation of Aldehydes 499
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Contents ix
16.6 Reduction of Aldehydes and Ketones 500
Application:How Toxic Is Toxic? 503
16.7 Addition of Alcohols: Hemiacetals and
Acetals 504
17
Carboxylic Acids and Their
Derivatives
516
17.1 Carboxylic Acids and Their Derivatives: Properties
and Names 517
17.2 Some Common Carboxylic Acids 527
17.3 Acidity of Carboxylic Acids 528
Application:Acids for the Skin 530
Application:Acid Salts as Food Additives 531
17.4 Reactions of Carboxylic Acids: Ester and Amide
Formation 532
17.5 Aspirin and Other Over-the-Counter Carboxylic
Acid Derivatives 535 19.3 Enzyme Classification 596
17.6 Hydrolysis of Esters and Amides 538 Application:Biocatalysis:Industrial
17.7 Polyamides and Polyesters 541 Biochemistry 600
Application:Kevlar:A Life-Saving Polymer 542 19.4 How Enzymes Work 600
17.8 Phosphoric Acid Derivatives 543 19.5 Effect of Concentration on Enzyme Activity 603
19.6 Effect of Temperature and pH on Enzyme
18 Activity 604
Amino Acids and Proteins
552 19.7 Enzyme Regulation: Feedback and Allosteric
Control 606
18.1 An Introduction to Biochemistry 553
Application:Extremozymes Enzymes from the
18.2 Protein Structure and Function:
Edge 607
An Overview 555
Application:Enzymes in Medical Diagnosis 608
18.3 Amino Acids 556
19.8 Enzyme Regulation: Inhibition 610
18.4 Acid Base Properties of Amino Acids 559
Application:Enzyme Inhibitors as Drugs 613
Application:Nutrition in Health and Disease 560
19.9 Enzyme Regulation: Covalent Modification and
18.5 Handedness 561
Genetic Control 614
18.6 Molecular Handedness and Amino Acids 562
19.10 Vitamins 615
18.7 Primary Protein Structure 565
Application:Vitamins,Minerals,and Food
Application:Proteins in the Diet 569
Labels 621
18.8 Shape-Determining Interactions in Proteins 570
Application:Protein Analysis by
20
Electrophoresis 573 Chemical Messengers: Hormones,
18.9 Secondary Protein Structure 574
Neurotransmitters, and Drugs
628
18.10 Tertiary Protein Structure 576
18.11 Quaternary Protein Structure 579 20.1 Messenger Molecules 629
Application:Collagen A Tale of Two Diseases 581 20.2 Hormones and the Endocrine System 630
18.12 Chemical Properties of Proteins 583 Application:Homeostasis 631
Application:Prions:Proteins that Cause 20.3 How Hormones Work: Epinephrine and
Disease 584 Fight-or-Flight 634
20.4 Amino Acid Derivatives and Polypeptides as
19 Hormones 636
Enzymes and Vitamins
592
20.5 Steroid Hormones 638
19.1 Catalysis by Enzymes 593 Application:Plant Hormones 641
19.2 Enzyme Cofactors 595 20.6 Neurotransmitters 641
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21.10 Harmful Oxygen By-Products and Antioxidant
Vitamins 685
Application:Plants and Photosynthesis 686
22
Carbohydrates
692
22.1 An Introduction to Carbohydrates 693
22.2 Handedness of Carbohydrates 695
22.3 The Dand LFamilies of Sugars: Drawing Sugar
Molecules 697
Application:Chirality and Drugs 699
22.4 Structure of Glucose and Other
Monosaccharides 700
Application:Carbohydrates in the Diet 704
22.5 Some Important Monosaccharides 705
22.6 Reactions of Monosaccharides 709
22.7 Disaccharides 711
Application:Cell Walls:Rigid Defense
Systems 714
22.8 Variations on the Carbohydrate Theme 715
22.9 Some Important Polysaccharides 717
20.7 How Neurotransmitters Work: Acetylcholine,
ItsAgonists and Antagonists 643 Application:Cell-Surface Carbohydrates and
Blood Type 720
20.8 Histamine and Antihistamines 646
Application:Dietary Fiber 722
Application:And from This Little Frog ... 647
20.9 Serotonin, Norepinephrine, and Dopamine 648
23
20.10 Neuropeptides and Pain Relief 650 Carbohydrate Metabolism 728
20.11 Drug Discovery and Drug Design 651
23.1 Digestion of Carbohydrates 729
23.2 Glucose Metabolism: An Overview 730
21
The Generation of Biochemical 23.3 Glycolysis 732
23.4 Entry of Other Sugars into Glycolysis 736
Energy
658
Application:Tooth Decay 737
21.1 Energy and Life 659 23.5 The Fate of Pyruvate 738
21.2 Energy and Biochemical Reactions 660 23.6 Energy Output in Complete Catabolism of
Application:Life without Sunlight 663 Glucose 740
21.3 Cells and Their Structure 664 Application:Microbial Fermentations:Ancient and
21.4 An Overview of Metabolism and Energy Modern 741
Production 666 23.7 Regulation of Glucose Metabolism and Energy
21.5 Strategies of Metabolism: ATP and Energy Production 741
Transfer 669 23.8 Metabolism in Fasting and Starvation 742
21.6 Strategies of Metabolism: Metabolic Pathways 23.9 Metabolism in Diabetes Mellitus 744
and Coupled Reactions 671 Application:Diagnosis and Monitoring
Application:Basal Metabolism 673 of Diabetes 744
21.7 Strategies of Metabolism: Oxidized and Reduced 23.10 Glycogen Metabolism: Glycogenesis and
Coenzymes 674 Glycogenolysis 746
21.8 The Citric Acid Cycle 677 Application:The Biochemistry of Running 748
21.9 The Electron-Transport Chain and ATP 23.11 Gluconeogenesis: Glucose from
Production 680 Noncarbohydrates 749
Application:Energy Undone:Blockers and Application:Polysaccharides What Are They
Uncouplers of Oxidative Phosphorylation 683 Good For? 751