Fundamentals of General, Organic, and Biological Chemistry

993 Pages·2012·48.97 MB·English

by  John E. McMurry, Carl A. Hoeger, Virginia E. Peterson, David S. Ballantine

Fundamentals of General, Organic, and Biological
Chemistry
Seventh
Edition
John McMurry
Cornell University
David S. Ballantine
Northern Illinois University
Carl A. Hoeger
University of California, San Diego
Virginia E. Peterson
University of Missouri, Columbia
Boston Columbus Indianapolis New York San Francisco Upper Saddle River
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Delhi Mexico City São Paulo Sydney Hong Kong Seoul Singapore Taipei Tokyo

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. A professor 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 numer-
ous 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 Wash-
ington, DC, he joined the faculty in the Department of Chemistry and
Biochemistry of Northern Illinois University, where he has been a pro-
fessor since 1989. He was awarded the Excellence in Undergraduate
Teaching Award in 1998 and has been departmental Director of Undergraduate Studies
since 2008. In addition, he is the coordinator for the Introductory and General Chem-
istry programs and is responsible for supervision of the laboratory teaching assistants.
Carl A. Hoeger received 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 antago-
nists. During this time he also taught general, organic, and biochemistry
at San Diego City College, Palomar College, and Miramar College. He joined the teach-
ing faculty at University of California, 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; his current project involves the use of videopodcasts as
adjuncts to live lectures. In 2004, he won the Paul and Barbara Saltman Distinguished
Teaching Award from UCSD. He is deeply involved with the General Chemistry pro-
gram at UCSD and also shares partial responsibility for the training and guidance of
teaching assistants in the Chemistry and Biochemistry departments.
Virginia E. Peterson received her B.S. in Chemistry in 1967 from the
University of Washington in Seattle and her Ph.D. in Biochemistry 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 Professor Emerita. When she retired
in 2011 she had been the Director of Undergraduate Advising for the department
for 8 years and had taught both senior capstone classes and biochemistry classes for
nonscience majors. Although retired, Dr. Peterson continues to advise undergraduates
and teach classes. Awards include both the college-level and the university-wide Excel-
lence in Teaching Award and, in 2006, the University’s 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
Brief Contents
Features  xi 16
Aldehydes and Ketones  484
Preface  xii
17
Carboxylic Acids and Their Derivatives  514
1
Matter and Measurements  2
18
Amino Acids and Proteins  548
2
Atoms and the Periodic Table  44
19
Enzymes and Vitamins  586
3
Ionic Compounds  72
20
The Generation of Biochemical Energy  622
4
Molecular Compounds  98
21
Carbohydrates  656
5
Classification and Balancing of Chemical
22
Carbohydrate Metabolism  692
Reactions  132
23
6 Lipids  720
Chemical Reactions: Mole and Mass
Relationships  158
24
Lipid Metabolism  752
7
Chemical Reactions: Energy, Rates,
25
Nucleic Acids and Protein Synthesis  774
and Equilibrium  178
26
8 Genomics  804
Gases, Liquids, and Solids  212
27
9 Protein and Amino Acid Metabolism  824
Solutions  252
28
10 Chemical Messengers: Hormones,
Acids and Bases  290
Neurotransmitters, and Drugs  842
11
Nuclear Chemistry  328
29
Body Fluids  870
12
Introduction to Organic Chemistry:
Alkanes  356
Appendices  A-1
13
Alkenes, Alkynes, and Aromatic
Compounds  394 Glossary  A-6
Answers to Selected Problems  A-13
14
Some Compounds with Oxygen, Sulfur,
or a Halogen  432 Photo Credits  C-1
15 Index  I-1
Amines  460
iv
Contents
Features  xi
Preface xii
1
Matter and Measurements 2
1.1 Chemistry: The Central Science 3
1.2 States of Matter 5
1.3 Classification of Matter 6
CHEMISTRY IN ACTION: Aspirin—A Case Study 8
1.4 Chemical Elements and Symbols 9
1.5 Elements and the Periodic Table 11
1.6 Chemical Reactions: An Example of Chemical
Change 14
1.7 Physical Quantities 14
CHEMISTRY IN ACTION: Mercury and Mercury
Poisoning 15
1.8 Measuring Mass, Length, and Volume 17
1.9 Measurement and Significant Figures 19
1.10 Scientific Notation 21
1.11 Rounding Off Numbers 23 3.5 Ions and the Octet Rule 79
1.12 Problem Solving: Unit Conversions and Estimating 3.6 Ions of Some Common Elements 80
Answers 25 3.7 Naming Ions 82
1.13 Temperature, Heat, and Energy 29 CHEMISTRY IN ACTION: Salt 83
CHEMISTRY IN ACTION: Temperature–Sensitive Materials 31 3.8 Polyatomic Ions 85
1.14 Density and Specific Gravity 33 CHEMISTRY IN ACTION: Biologically Important
CHEMISTRY IN ACTION: A Measurement Example: Ions 86
Obesity and Body Fat 35 3.9 Formulas of Ionic Compounds 86
3.10 Naming Ionic Compounds 89
2 3.11 H+ and OH- Ions: An Introduction to Acids
Atoms and the Periodic Table 44
and Bases 91
2.1 Atomic Theory 45
CHEMISTRY IN ACTION: Osteoporosis 93
CHEMISTRY IN ACTION: Are Atoms Real? 48
4
2.2 Elements and Atomic Number 48
Molecular Compounds 98
2.3 Isotopes and Atomic Weight 50
2.4 The Periodic Table 52 4.1 Covalent Bonds 99
2.5 Some Characteristics of Different Groups 54 4.2 Covalent Bonds and the Periodic Table 101
4.3 Multiple Covalent Bonds 104
CHEMISTRY IN ACTION: The Origin of Chemical Elements 56 4.4 Coordinate Covalent Bonds 106
2.6 Electronic Structure of Atoms 56 4.5 Characteristics of Molecular Compounds 107
2.7 Electron Configurations 59 4.6 Molecular Formulas and Lewis Structures 108
2.8 Electron Configurations and the Periodic Table 62 4.7 Drawing Lewis Structures 108
2.9 Electron-Dot Symbols 65
CHEMISTRY IN ACTION: CO and NO: Pollutants or
CHEMISTRY IN ACTION: Atoms and Light 66
Miracle Molecules? 113
3 4.8 The Shapes of Molecules 114
Ionic Compounds 72 CHEMISTRY IN ACTION: VERY Big Molecules 118
3.1 Ions 73 4.9 Polar Covalent Bonds and Electronegativity 119
3.2 Periodic Properties and Ion Formation 75 4.10 Polar Molecules 121
3.3 Ionic Bonds 77 4.11 Naming Binary Molecular Compounds 123
3.4 Some Properties of Ionic Compounds 77 CHEMISTRY IN ACTION: Damascenone by Any Other
CHEMISTRY IN ACTION: Ionic Liquids 78 Name Would Smell as Sweet 125
v
vi CONTENTS
5 7.5 How Do Chemical Reactions Occur? Reaction
Classification and Balancing of Chemical
Rates 190
Reactions 132 7.6 Effects of Temperature, Concentration, and Catalysts
5.1 Chemical Equations 133 on Reaction Rates 192
5.2 Balancing Chemical Equations 135 CHEMISTRY IN ACTION: Regulation of Body
5.3 Classes of Chemical Reactions 138 Temperature 195
5.4 Precipitation Reactions and Solubility Guidelines 139 7.7 Reversible Reactions and Chemical
CHEMISTRYINACTION:Gout and Kidney Stones: Equilibrium 195
Problems in Solubility 140 7.8 Equilibrium Equations and Equilibrium
5.5 Acids, Bases, and Neutralization Reactions 141 Constants 196
5.6 Redox Reactions 142 7.9 Le Châtelier’s Principle: The Effect of Changing
Conditions on Equilibria 200
CHEMISTRYINACTION:Batteries 147
5.7 Recognizing Redox Reactions 148 CHEMISTRY IN ACTION: Coupled Reactions 204
5.8 Net Ionic Equations 150
8
Gases, Liquids, and Solids 212
6
Chemical Reactions:Mole and Mass 8.1 States of Matter and Their Changes 213
Relationships 158 8.2 Intermolecular Forces 216
8.3 Gases and the Kinetic–Molecular Theory 220
6.1 The Mole and Avogadro’s Number 159
8.4 Pressure 221
6.2 Gram–Mole Conversions 163
CHEMISTRY IN ACTION: Greenhouse Gases and Global
CHEMISTRYINACTION:Did Ben Franklin Have
Warming 224
Avogadro’s N umber? A Ballpark Calculation 164
8.5 Boyle’s Law: The Relation between Volume and
6.3 Mole Relationships and Chemical Equations 165
Pressure 225
6.4 Mass Relationships and Chemical Equations 167
6.5 Limiting Reagent and Percent Yield 169 CHEMISTRY IN ACTION: Blood Pressure 228
8.6 Charles’s Law: The Relation between Volume and
CHEMISTRYINACTION:Anemia—A Limiting Reagent
Temperature 228
Problem? 172
8.7 Gay-Lussac’s Law: The Relation between Pressure
7 and Temperature 230
Chemical Reactions:Energy,Rates, 8.8 The Combined Gas Law 231
and Equilibrium 178 8.9 Avogadro’s Law: The Relation between Volume and
Molar Amount 232
7.1 Energy and Chemical Bonds 179 8.10 The Ideal Gas Law 233
7.2 Heat Changes during Chemical Reactions 180 8.11 Partial Pressure and Dalton’s Law 236
7.3 Exothermic and Endothermic Reactions 181 8.12 Liquids 237
CHEMISTRYINACTION:Energy from Food 185 8.13 Water: A Unique Liquid 239
7.4 Why Do Chemical Reactions Occur? Free 8.14 Solids 240
Energy 186 8.15 Changes of State 242
CHEMISTRY IN ACTION: CO as an Environmentally
2
Friendly Solvent 245
9
Solutions 252
9.1 Mixtures and Solutions 253
9.2 The Solution Process 255
9.3 Solid Hydrates 257
9.4 Solubility 258
9.5 The Effect of Temperature on Solubility 258
9.6 The Effect of Pressure on Solubility: Henry’s Law 260
9.7 Units of Concentration 262
CHEMISTRY IN ACTION: Breathing and Oxygen
Transport 263
9.8 Dilution 270
9.9 Ions in Solution: Electrolytes 272
9.10 Electrolytes in Body Fluids: Equivalents and
Milliequivalents 273
CONTENTS vii
11.7 Ionizing Radiation 341
11.8 Detecting Radiation 343
11.9 Measuring Radiation 344
CHEMISTRY IN ACTION: Irradiated Food 345
11.10 Artificial Transmutation 347
CHEMISTRY IN ACTION: Body Imaging 348
11.11 Nuclear Fission and Nuclear Fusion 349
12
Introduction to Organic Chemistry:
Alkanes 356
12.1 The Nature of Organic Molecules 357
12.2 Families of Organic Molecules: Functional
Groups 359
12.3 The Structure of Organic Molecules: Alkanes and
Their Isomers 364
12.4 Drawing Organic Structures 367
12.5 The Shapes of Organic Molecules 372
9.11 Properties of Solutions 275
12.6 Naming Alkanes 374
CHEMISTRY IN ACTION: Electrolytes, Fluid Replacement, 12.7 Properties of Alkanes 380
and Sports Drinks 276 12.8 Reactions of Alkanes 381
9.12 Osmosis and Osmotic Pressure 279
MASTERING REACTIONS: Organic Chemistry and the
9.13 Dialysis 283
Curved Arrow Formalism 382
CHEMISTRY IN ACTION: Timed-Release Medications 284 12.9 Cycloalkanes 383
10 CHEMISTRY IN ACTION: Surprising Uses of Petroleum 385
Acids and Bases 290 12.10 Drawing and Naming Cycloalkanes 386
10.1 Acids and Bases in Aqueous Solution 291
13
10.2 Some Common Acids and Bases 292
Alkenes, Alkynes, and Aromatic
10.3 The Brønsted–Lowry Definition of Acids and
Compounds 394
Bases 293
10.4 Acid and Base Strength 296 13.1 Alkenes and Alkynes 395
13.2 Naming Alkenes and Alkynes 396
CHEMISTRY IN ACTION: GERD—Too Much Acid or Not
13.3 The Structure of Alkenes: Cis–Trans
Enough? 299
10.5 Acid Dissociation Constants 301 Isomerism 399
10.6 Water as Both an Acid and a Base 302 13.4 Properties of Alkenes and Alkynes 402
10.7 Measuring Acidity in Aqueous Solution: pH 303 13.5 Types of Organic Reactions 403
10.8 Working with pH 306 CHEMISTRY IN ACTION: The Chemistry of Vision and
10.9 Laboratory Determination of Acidity 308 Color 406
10.10 Buffer Solutions 308 13.6 Reactions of Alkenes and Alkynes 407
CHEMISTRY IN ACTION: Buffers in the Body: Acidosis and MASTERING REACTIONS: How Addition Reactions
Alkalosis 312 Occur 414
10.11 Acid and Base Equivalents 313 13.7 Alkene Polymers 415
10.12 Some Common Acid–Base Reactions 316 13.8 Aromatic Compounds and the Structure of
10.13 Titration 317 Benzene 418
CHEMISTRY IN ACTION: Acid Rain 320 CHEMISTRY IN ACTION: Polycyclic Aromatic Hydrocar-
10.14 Acidity and Basicity of Salt Solutions 321 bons and Cancer 420
13.9 Naming Aromatic Compounds 421
11
Nuclear Chemistry 328 13.10 Reactions of Aromatic Compounds 424
11.1 Nuclear Reactions 329 14
11.2 The Discovery and Nature of Radioactivity 330 Some Compounds with Oxygen, Sulfur,
11.3 Stable and Unstable Isotopes 331 or a Halogen 432
11.4 Nuclear Decay 332 14.1 Alcohols, Phenols, and Ethers 433
11.5 Radioactive Half-Life 337 14.2 Some Common Alcohols 434
CHEMISTRY IN ACTION: Medical Uses of Radioactivity 338 14.3 Naming Alcohols 436
11.6 Radioactive Decay Series 340 14.4 Properties of Alcohols 439
viii CONTENTS
14.5 Reactions of Alcohols 440
MASTERING REACTIONS: How Eliminations Occur 441
CHEMISTRY IN ACTION: Ethyl Alcohol as a Drug and a
Poison 446
14.6 Phenols 447
14.7 Acidity of Alcohols and Phenols 448
CHEMISTRY IN ACTION: Phenols as Antioxidants 449
14.8 Ethers 450
14.9 Thiols and Disulfides 452
CHEMISTRY IN ACTION: Inhaled Anesthetics 453
14.10 Halogen-Containing Compounds 454
15
Amines 460
15.1 Amines 461 18
CHEMISTRY IN ACTION: Knowing What You Work With: Amino Acids and Proteins 548
Material Safety Data Sheets 465 18.1 An Introduction to Biochemistry 549
15.2 Properties of Amines 467 18.2 Protein Structure and Function: An Overview 551
15.3 Heterocyclic Nitrogen Compounds 469 18.3 Amino Acids 552
15.4 Basicity of Amines 471 18.4 Acid–Base Properties of Amino Acids 555
CHEMISTRY IN ACTION: Organic Compounds in Body 18.5 Handedness 556
Fluids and the “Solubility Switch” 473 18.6 Molecular Handedness and Amino Acids 557
15.5 Amine Salts 474 18.7 Primary Protein Structure 560
15.6 Amines in Plants: Alkaloids 476 CHEMISTRY IN ACTION: Proteins in the Diet 564
CHEMISTRY IN ACTION: Toxicology 478 18.8 Shape-Determining Interactions in Proteins 565
CHEMISTRY IN ACTION: Protein Analysis by
16
Electrophoresis 568
Aldehydes and Ketones 484
18.9 Secondary Protein Structure 569
16.1 The Carbonyl Group 485
18.10 Tertiary Protein Structure 572
16.2 Naming Aldehydes and Ketones 488
18.11 Quaternary Protein Structure 573
CHEMISTRY IN ACTION: Chemical Warfare among the
CHEMISTRY IN ACTION: Collagen—A Tale of Two
Insects 489
Diseases 576
16.3 Properties of Aldehydes and Ketones 490
18.12 Chemical Properties of Proteins 577
16.4 Some Common Aldehydes and Ketones 492
16.5 Oxidation of Aldehydes 494 CHEMISTRY IN ACTION: Prions: Proteins That Cause
16.6 Reduction of Aldehydes and Ketones 496 Disease 579
19
CHEMISTRY IN ACTION: How Toxic Is Toxic? 499 Enzymes and Vitamins 586
16.7 Addition of Alcohols: Hemiacetals and Acetals 500 19.1 Catalysis by Enzymes 587
MASTERING REACTIONS: Carbonyl Additions 506 19.2 Enzyme Cofactors 589
19.3 Enzyme Classification 590
17
Carboxylic Acids and Their Derivatives 514 19.4 How Enzymes Work 594
17.1 Carboxylic Acids and Their Derivatives: Properties CHEMISTRY IN ACTION: Extremozymes—Enzymes from
the Edge 595
and Names 515
17.2 Some Common Carboxylic Acids 525 19.5 Effect of Concentration on Enzyme Activity 598
17.3 Acidity of Carboxylic Acids 526 19.6 Effect of Temperature and pH on Enzyme Activity 599
CHEMISTRY IN ACTION: Acids for the Skin 528 CHEMISTRY IN ACTION: Enzymes in Medical Diagnosis 601
17.4 Reactions of Carboxylic Acids: Ester and Amide 19.7 Enzyme Regulation: Feedback and Allosteric
Formation 528 Control 602
17.5 Aspirin and Other Over-the-Counter Carboxylic 19.8 Enzyme Regulation: Inhibition 604
Acid Derivatives 532 CHEMISTRY IN ACTION: Enzyme Inhibitors as Drugs 607
17.6 Hydrolysis of Esters and Amides 534 19.9 Enzyme Regulation: Covalent Modification and
17.7 Polyamides and Polyesters 537 Genetic Control 608
CHEMISTRY IN ACTION: Kevlar: A Life-Saving 19.10 Vitamins and Minerals 610
Polymer 538 CHEMISTRY IN ACTION: Vitamins, Minerals, and Food
17.8 Phosphoric Acid Derivatives 540 Labels 615
CONTENTS ix
20 21.8 Variations on the Carbohydrate Theme 680
The Generation of Biochemical Energy 622 21.9 Some Important Polysaccharides 682
20.1 Energy and Life 623 CHEMISTRY IN ACTION: Cell Walls: Rigid Defense
20.2 Energy and Biochemical Reactions 624 Systems 685
CHEMISTRYINACTION:Life without Sunlight 627
20.3 Cells and Their Structure 628 22
20.4 An Overview of Metabolism and Energy Carbohydrate Metabolism 692
Production 629 22.1 Digestion of Carbohydrates 693
20.5 Strategies of Metabolism: ATP and Energy 22.2 Glucose Metabolism: An Overview 694
Transfer 632 22.3 Glycolysis 696
20.6 Strategies of Metabolism: Metabolic Pathways and 22.4 Entry of Other Sugars into Glycolysis 700
Coupled Reactions 634
CHEMISTRY IN ACTION: Tooth Decay 701
CHEMISTRYINACTION:Basal Metabolism 636 22.5 The Fate of Pyruvate 701
20.7 Strategies of Metabolism: Oxidized and Reduced
CHEMISTRY IN ACTION: Microbial Fermentations: Ancient
Coenzymes 637
and Modern 703
20.8 The Citric Acid Cycle 639
22.6 Energy Output in Complete Catabolism
20.9 The Electron-Transport Chain and ATP
of Glucose 704
Production 643
22.7 Regulation of Glucose Metabolism and Energy
20.10 Harmful Oxygen By-Products and Antioxidant
Production 705
Vitamins 647
22.8 Metabolism in Fasting and Starvation 706
CHEMISTRYINACTION:Plants and Photosynthesis 649 22.9 Metabolism in Diabetes Mellitus 707
21 CHEMISTRY IN ACTION: Diagnosis and Monitoring
Carbohydrates 656 of Diabetes 709
21.1 An Introduction to Carbohydrates 657 22.10 Glycogen Metabolism: Glycogenesis and
21.2 Handedness of Carbohydrates 659 Glycogenolysis 710
21.3 The d and l Families of Sugars: Drawing Sugar CHEMISTRY IN ACTION: The Biochemistry of Running 712
Molecules 661 22.11 Gluconeogenesis: Glucose from
CHEMISTRY IN ACTION: Chirality and Drugs 663 Noncarbohydrates 713
21.4 Structure of Glucose and Other
Monosaccharides 664 23
21.5 Some Important Monosaccharides 669 Lipids 720
CHEMISTRY IN ACTION: Cell-Surface Carbohydrates and 23.1 Structure and Classification of Lipids 721
Blood Type 672 23.2 Fatty Acids and Their Esters 724
21.6 Reactions of Monosaccharides 673 23.3 Properties of Fats and Oils 727
21.7 Disaccharides 676 CHEMISTRY IN ACTION: Lipids in the Diet 728
CHEMISTRY IN ACTION: Carbohydrates and Fiber in the 23.4 Chemical Reactions of Triacylglycerols 730
Diet 679 CHEMISTRY IN ACTION: Detergents 731
23.5 Phospholipids and Glycolipids 733
23.6 Sterols 738
CHEMISTRY IN ACTION: Butter and Its Substitutes 740
23.7 Structure of Cell Membranes 741
23.8 Transport Across Cell Membranes 743
23.9 Eicosanoids: Prostaglandins and Leukotrienes 745
24
Lipid Metabolism 752
24.1 Digestion of Triacylglycerols 753
24.2 Lipoproteins for Lipid Transport 755
CHEMISTRY IN ACTION: Lipids and Atherosclerosis 757
24.3 Triacylglycerol Metabolism: An Overview 758
CHEMISTRY IN ACTION: Fat Storage: A Good Thing or
Not? 760
24.4 Storage and Mobilization of Triacylglycerols 761