Robert J. Ouellette THE OHIO STATE UNIVERSITY

Introduction to

General, Organic, and Biological

Chemistry

THIRD EDITION

MACMILLAN PUBLISHING COMPANY NEW YORK

Maxwell Macmillan, Inc. TORONTO

1 Chemistry l

1.1 Why Am I Studying Chemistry? 2 1.2 What Is Science? 2 1.3 How Do We Do Science? 3 1.4 What Is Chemistry? 6 1.5 Where Do We Go from Here? 12

ESSAY

What Happened to the Dinosaurs? 5

Summary 13 / Exercises 13

2 Measurements 15

2.1 What Is a Measurement? 16 2.2 How Reliable Are Measurements? 16 2.3 Significant Figures Give the Uncertainty in Measurements 17 2.4 Expressing Large and Small Numbers 19 2.5 Using Units In Problem Solving 20 2.6 The Metrie System 21 2.7 Temperature Units 26

ix

x Contents

ESSAYS

Are We the Center of the Universe? 23 International Units (IU) and the U.S. RDA 26 Hyperthermia and Hypothermia 29

Summary 29 / Exercises 30

3 Properties of Matter 32

3.1 Matter Exists in Three States 33 3.2 Density of Matter 34 3.3 Energy Is an Extensive Property 37 3.4 Physical and Chemical Properties 40 3.5 Mass Is Conserved in Chemical Reactions 41 3.6 Energy Is Conserved in Chemical Reactions 44 3.7 Mixtures and Pure Substances 44 3.8 Elements 46 3.9 The Composition of Compounds 50

ESSAYS

Specific Gravity as a Diagnostic Tool 37 It Is Calories That We Worry About 38 How Do You Stay Cool? 43 Your Body, Your Elements 49

Summary 51 / Exercises 51

4 Atoms, Molecules, and Ions 54

4.1 What Is the Smallest Unit of Matter? 55 4.2 The Atom Is Very Small 56 4.3 Atoms Contain Subatomic Particles 57 4.4 Atomic Number, Mass Number, and Isotopes 58 4.5 Molecules and Molecular Formulas 61 4.6 Ions 63 4.7 Ionic Compounds 66

ESSAYS

Calcium Ions and Your Diet 63 Phosphate Supplements Soil for Agriculture 67

Summary 70 / Exercises 70

5 Calculations with Chemical Formulas 73

5.1 Matter—Submicroscopic and Macroscopic Views 74 5.2 Atomic Weights 74 5.3 Molecular and Formula Weights of Compounds 75

Contents xi

5.4 Percent Composition 76 5.5 Avogadro's Number and the Mole 77 5.6 Calculations Using Moles 81 5.7 Empirical Formula and Molecular Formula 84

ESSAYS

How Big 1s Avogadro's Number? 81 Products from the Earth, Sea, and Air 83

Summary 88 / Exercises 88

6 Chemical Equations and Reactions 91

6.1 Chemical Equations Represent Chemical Reactions 92 6.2 Symbols in Equations 92 6.3 Balancing Equations 93 6.4 Stoichiometry and the Balanced Equation 98 6.5 Solving Stoichiometry Problems 100 6.6 Types of Chemical Reactions 101 6.7 Combination Reactions 102 6.8 Decomposition Reactions 103 6.9 Single-Replacement Reactions 103 6.10 Double-Replacement Reactions 104 6.11 Neutralization Reactions 107 6.12 Oxidation-Reduction Reactions 108

ESSAYS

What Makes a Rocket Fly? 97 Sulfuric Acid—A World Class Chemical 107 Preventing Corrosion, an Unwanted Oxidation 113

Summary 114 / Exercises 114

7 The Periodic Table and Atomic Structure 119

7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9

ESSAYS

Atmospheric Atomic Tests Had to Be Stopped 123 Lighting Our Way with Excited Atoms 126 Silicon Affects Your Life-style 140

Summary 144 / Exercises 144

Organizing the Elements 120 Mendeleev's Classification of Elements 121 The Modern Periodic Table 124 Where Are the Electrons in the Atom? 125 Shells, Subshells, and Orbitals 127 Electron Configuration 131 Electron-Dot Symbols 136 The Periodic Table and Electron Configuration 136 Uses of the Periodic Table 139

xii Contents

8 Chemical Bonds 148

8.1 Bonds and Structure 149 8.2 Types of Bonds 149 8.3 Ionic Bonds 150 8.4 Covalent Bonds 153 8.5 Drawing Lewis Structures 155 8.6 Polar Covalent Bonds 157 8.7 Coordinate Covalent Bonds 159 8.8 Resonance Structures 160 8.9 Molecular Geometry 161 8.10 Polarity of Molecules 165

ESSAYS

Ion Radius Affects Cell Composition and Enzyme Reactions 152 Coordinate Covalent Bonds and Respiration 160

Summary 166 / Exercises 167

9 Gases, Liquids, and Solids 170

9.1 The Organization of Matter 171 9.2 Pressure 173 9.3 The Gas Laws 176 9.4 Avogadro's Hypothesis and the Ideal Gas Law 183 9.5 Dalton's Law of Partial Pressures 184 9.6 Liquids 186 9.7 Solids 190 9.8 Le Chätelier's Principle and Changes of State 191 9.9 Types of Intermolecular Forces 192

ESSAYS

Blood Pressure 173 Breathing and Boyle's Law 1 78 Water—A Common but Very Unusual Compound 195

Summary 196 / Exercises 197

10 Solutions 201

10.1 Solutions—Around Us and in Us 202 10.2 Solvents and Solutes 202 10.3 Concentration Teils Us the Amount of Solute in Solution 204 10.4 Percent Concentration 204 10.5 Molarity 207 10.6 Dilution of Solutions 208 10.7 Electrolytes and Nonelectrolytes 209

Contents xiii

10.8 10.9 10.10 10.11 10.12

ESSAYS

Hot Packs and Cold Packs 203 Gas Solubility and the Bends 212 Solubility of Vitamins 214 Osmosis Is a Way to Kill Bacteria 220

Summary 220 / Exercises 221

11 Reaction Rates and Equilibrium 223

11.1 Reactions—An Overview 224 11.2 Energy and Chemical Reactions 224 11.3 Why Do Reactions Occur? 226 11.4 Kinetics 230 11.5 Activation Energy 234 11.6 Chemical Equilibrium 238 11.7 Chemical Equilibrium and Le Chätelier's Principle 241

ESSAYS

Explosions and Entropy 228 The Effect of Temperature on Organisms 233 Catalysts in Living Systems 234

Summary 244 / Exercises 244

12 Acid-Base Equilibria 247

12.1 General Properties of Acids and Bases 248 12.2 Acids and Bases Are Chemical Opposites 249 12.3 Reactions of Acids and Bases 252 12.4 Conjugate Acids and Conjugate Bases 253 12.5 Self-ionization of Water 254 12.6 Strengths of Acids and Bases 257 12.7 The pH Scale 260 . 12.8 Hydrolysis of Salts 264 12.9 Buffers 266 12.10 Buffers in the Body 267 12.11 Titration 269

ESSAYS

Antacids 252 Acid and Tooth Decay 262 Acids and Bases in Agriculture 266

The Formation of a Solution 210 Factors That Control Solubility 211 Colligative Properties 214 Osmosis 216 Osmosis and Cells 219

Summary 272 / Exercises 273

Contents

13 Nuclear Chemistry 216

13.1 Radiosotopes and Nuclear Chemistry 277 13.2 Radioactivity 278 13.3 Units of Radiation 279 13.4 Balancing Nuclear Equations 280 13.5 Half-lives 282 13.6 Biological Effects of Radiation 284 13.7 Use of Radioisotopes in Diagnosis 287 13.8 Use of Radioisotopes in Therapy 290 13.9 Nuclear Transmutations 291 13.10 Fission and Fusion Reactions 292

ESSAYS

The Radon Problem 286 Positron Emission Tomography 289

Summary 295 / Exercises 295

14 Introäuction to Organic Chemistry 298

14.1 Organic Compounds 299 14.2 Orbitals and Molecular Shapes 301 14.3 Structural Formulas 303 14.4 Structural Models 306 14.5 Functional Groups 308 14.6 Isomers 310 14.7 Organic Reactions and Mechanisms 313 14.8 Acid—Base Reactions in Organic Chemistry 315 14.9 Oxidation-Reduction Reactions 316

ESSAY

Organic Compounds in Daily Life 300

Summary 317 / Exercises 318

IS Saturated Hydrocarbons 322

15.1 Classes of Hydrocarbons 323 15.2 Alkanes 323 15.3 Nomenclature of Alkanes 325 15.4 Physical Properties of Alkanes 330 15.5 Oxidation of Alkanes 332 15.6 Halogenation of Alkanes 333 15.7 The Mechanism of Chlorination of Alkanes 334 15.8 Cycloalkanes 336

Contents xv

ESSAYS

What Are Octane Numbers? 332 Freons, Radicals, and the Ozone Layer 335

Summary 340 / Exercises 341

16 Unsaturated Hydrocarbons 345

16.1 Types of Unsaturated Hydrocarbons 346 16.2 Geometrie Isomerism 348 16.3 Nomenclature of Alkenes 350 16.4 Oxidation and Reduction of Alkenes 352 16.5 Addition Reactions of Alkenes 353 16.6 Polymerization of Alkenes 357 16.7 Alkynes 358 16.8 Aromatic Hydrocarbons 360 16.9 Nomenclature of Aromatic Hydrocarbons 362 16.10 Polycyclic and Heterocyclic Aromatic Hydrocarbons

ESSAYS

Geometrie Isomers and the Sex Life of Moths 349 Hydrogenation of Oils 352

Summary 365 / Exercises 366

11 Alcohols, Phenols, and Ethers

17.1 Compounds of Oxygen 371 17.2 Common Alcohols and Phenols 372 17.3 Nomenclature and Classification of Alcohols 375 17.4 Hydrogen Bonding in Alcohols 377 17.5 Acid-Base Reactions 379 17.6 Substitution Reactions 380 17.7 Dehydration of Alcohols 382 17.8 Oxidation of Alcohols 384 17.9 Ethers 386 17.10 Sulfur Compounds 388

ESSAYS

Ethanol—An Antidote for Methanol Poisoning 386 Anesthetics 387

Summary 389 / Exercises 389

18 Aldehydes and Ketones 393

18.1 The Carbonyl Group 394 18.2 Nomenclature of Aldehydes and Ketones 395

364

370

xvi Contents

18.3 Physical Properties of Aldehydes and Ketones 397 18.4 Oxidation of Carbonyl Compounds 399 18.5 Reduction of Carbonyl Compounds 401 18.6 Carbonyl Compounds Undergo Addition Reactions 402 18.7 Addition of Oxygen Compounds 403 18.8 Addition of Nitrogen Compounds 406 18.9 Reactivity of the a Carbon Atom 408 18.10 The Aldol Condensation 410

ESSAYS

Benedict's Test and Diabetes 400 Exercise—Aerobic and Anaerobic 401 Isomerism, Addition Reactions, and Vision 407

Summary 411 / Exercises 411

19 Carboxylic Acids and Esters 415

19.1 Carboxylic Acids and Derivatives 416 19.2 Nomenclature of Carboxylic Acids 395 19.3 Physical Properties of Carboxylic Acids 397 19.4 Acidity of Carboxylic Acids 420 19.5 Salts of Carboxylic Acids 422 19.6 Esters 423 19.7 Hydrolysis and Saponification of Esters 427 19.8 Nucleophilic Acyl Substitution 430 19.9 Esters and Anhydrides of Phosphoric Acid 432 19.10 The Claisen Condensation 433

ESSAYS

Polyesters 424 Esters as Food Additives 426 Soaps and Detergents 428 Thioesters Are Nature's Active Acyl Compounds 431

Summary 435 / Exercises 435

20 Amines and Amides 439

20.1 Organic Nitrogen Compounds 440 20.2 Amines 441 20.3 Nomenclature of Amines 443 20.4 Physical Properties of Amines 444 20.5 Basicity of Amines 446 20.6 Reaction of Amines with Nitrous Acid 449 20.7 Amides 451 20.8 Formation of Amides 454 20.9 Hydrolysis of Amides 456

ESSAYS

Designer Drugs 440

Contents xvii

Adrenaline and Amphetamines 448 Barbiturates 452 Bullet-Resistant and Flame-Resistant Polymers 455

Summary 457 / Exercises 458

21 Biochemistry

21.1 What Is Biochemistry? 463 21.2 Composition of Biochemicals 463 21.3 Biochemical Reactions 466 21.4 The Cell and Chemical Reactions 468 21.5 Configuration of Biochemicals 471 21.6 Enantiomers Are Optically Active 475 21.7 Perspective Representations of Enantiomers 476 21.8 Multiple Chiral Centers 479 21.9 How Are Stereoisomers Formed? 482

ESSAYS

Biochemistry, Food, and You 467 Chirality and Odor 479

Summary 482 / Exercises 483

22 Carbohydrates

22.1 Carbohydrates—Sources of Energy 487 22.2 Classification of Carbohydrates 487 22.3 Configuration of Monosaccharides 489 22.4 Glucose—A Key Compound 492 22.5 Hemiacetals and Hemiketals 495 22.6 Glycosides 499 22.7 Oxidation of Carbohydrates 500 22.8 Disaccharides 502 22.9 Polysaccharides 507

ESSAYS

Blood Glucose 494 Lactose Intolerance 504 Sweeteners 505

Summary 509 / Exercises 509

23 Lipids 513

23.1 Classification of Lipids 514 23.2 Terpenes 515 23.3 Steroids 516

462

486

xviii Contents

23.4 Waxes 520 23.5 Fatty Acids 521 23.6 Triglycerides 523 23.7 Phosphoglycerides 526 23.8 Sphingophospholipids 528 23.9 Glycosphingolipids 529 23.10 Biological Membranes 530

ESSAYS

Anabolic Steroids 518 Whale Oil 520 Prostaglandins 523 Triglycerides Store Energy 524

Summary 532 / Exercises 533

24 Amino Acids and Proteins 536

24.\ Proteins—An Overview 537 24.2 Amino Acids 538 24.3 Acid-Base Properties of Amino Acids 540 24.4 Isolectric Point 543 24.5 Peptides 544 24.6 Structure of Peptides 546 24.7 Bonding in Proteins 546 24.8 Structure of Proteins 549 24.9 Hydrolysis of Proteins 553 24.10 Denaturation of Proteins 555 24.11 Classification of Proteins 557

ESSAYS

Cholesterol and Lipoproteins 537 Complete Proteins in the Diet 554

Summary 558 / Exercises 559

25 Nucleic Acids 561

25.1 Genes Contain Nucleic Acids 562 25.2 Nucleic Acids Are Polymers 562 25.3 Polynucleotides 566 25.4 The Flow of Genetic Information 570 25.5 DNA Replicates Itself 570 25.6 DNA Produces Several Types of RNA 572 25.7 The Genetic Code 575 25.8 Protein Synthesis and Translation 576 25.9 Gene Mutations and Genetic Disease 580 25.10 Recombinant DNA and Genetic Engineering 582 25.11 Viruses 583

Contents xix

ESSAYS

Nucleosides in Medicine 565 Exons and Introns 574 How Do Antibiotics Work? 578 A Gene Defect May Cause Osteoarthritis 581 AIDS Is a Retrovirus Disease 584

Summary 584 / Exercises 585

26 Enzymes 587

26.1 Biological Catalysts 588 26.2 Classification of Enzymes 589 26.3 Models of Enzyme Action 592 26.4 Active Sites 594 26.5 Cofactors 594 26.6 Kinetics of Enzyme Reactions 596 26.7 Enzyme Inhibition 599 26.8 Regulatory Enzymes 602 26.9 Zymogens 604

ESSAYS

Muscle Relaxants 589 Sulfa Drugs as Competitive Inhibitors 600 Mercury and Lead Poisoning 603

Summary 605 / Exercises 606

21 Biochemical Energy 608

21A Free Energy Controls Biochemical Reactions 609 27.2 Metabolie Reactions and ATP 612 27.3 Coupling of Phosphorylation 616 27.4 Substrate Level Phosphorylation 616 27.5 Oxidation and Reduction 618 27.6 Cellular Respiration 620 27.7 Citric Acid Cycle 621 27.8 Food and Energy 624 27.9 The Mitochondria 625 27.10 Regulation of Metabolie Reactions 627

ESSAY

Effect of Barbiturates on the Citric Acid Cycle 624

Summary 628 / Exercises 629

Contents

28 Metabolism of Carbohydrates 631

28.1 Digestion of Carbohydrates 632 28.2 Glycolysis 634 28.3 Pyruvic Acid—A Key Compound 640 28.4 The ATP Profit from Glucose 642 28.5 Gluconeogenesis 645 28.6 The Pentose Phosphate Pathway 647 28.7 Glycogenolysis and Glycogenesis 648 28.8 Regulation of Carbohydrate Metabolism 651

ESSAYS

The Marathon and Carbohydrate Loading 634 Alcohol Fermentation 644 Glycogen Storage Diseases 650

Summary 651 / Exercises 652

29 Metabolism of Triglycerides 654

29.1 Fats and Energy 655 29.2 Catabolic Reactions of Triglycerides 656 29.3 Catabolism of Unsaturated Fatty Acids 662 29.4 Ketone Bodies 663 29.5 Biosynthesis of Fatty Acids 664

ESSAYS

Wouldn't You Rather Be Fat? 661 Essential Fatty Acids 667

Summary 668 / Exercises 668

30 Metabolism of Proteins 670

30.1 Digestion of Proteins 671 30.2 Deamination of Amino Acids in Catabolism 673 30.3 The Urea Cycle 675 30.4 The Fate of the Carbon Skeleton 678 30.5 Decarboxylation of Amino Acids 679 30.6 Biosynthesis of Amino Acids 681

ESSAYS

Transaminases Are Monitored in Medical Diagnosis 673 Hyperammonemia 676 Phenylketonuria 679 Histamine and Antihistamines 680

Summary 682 / Exercises 682

Contents xxi

Appendix A Scientific Notation and Significant Figur es A*l

Appendix B Glossary A*5

Appendix C Answers to Problems A»21

Appendix D Answers to Odd-Numbered Exercises A»25

Index M