dennis tonnn

General, Organic, and Biochemistry

General, Organic, and Biochemistry

Third Edition

Katherine J. DennistonTowson University

Joseph J. ToppingTowson University

Robert L. CaretSan Jos State University

Boston Burr Ridge, IL Dubuque, IA Madison, WI New York San Francisco St. LouisBangkok Bogot Caracas Lisbon London Madrid

Mexico City Milan New Delhi Seoul Singapore Sydney Taipei Toronto

GENERAL, ORGANIC, AND BIOCHEMISTRYTHIRD EDITION

Published by McGraw-Hill, an imprint of The McGraw-Hill Companies, Inc., 1221 Avenue of theAmericas, New York, NY 10020. Copyright 2001, 1997 by The McGraw-Hill Companies, Inc.All rights reserved. No part of this publication may be reproduced or distributed in any form orby any means, or stored in a database or retrieval system, without the prior written consent ofThe McGraw-Hill Companies, Inc., including, but not limited to, in any network or other electronicstorage or transmission, or broadcast for distance learning.

Some ancillaries, including electronic and print components, may not be available to customersoutside the United States.

This book is printed on acid-free paper.

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ISBN 0072317841ISBN 0071180737 (ISE)

Vice president and editor-in-chief: Kevin T. KanePublisher: James M. SmithSponsoring editor: Kent A. PetersonDevelopmental editor: Shirley R. OberbroecklingEditorial assistant: Jennifer L. BensinkSenior marketing manager: Martin J. LangeSenior marketing assistant: Tami PetscheSenior project manager: Marilyn M. SulzerProduction supervisor: Sandy LudovissyDesign manager: Stuart D. PatersonCover/interior designer: Elise LansdonCover image: FPG InternationalSenior photo research coordinator: Lori HancockPhoto research: Feldman and AssociatesSenior supplement coordinator: Brenda A. ErnzenCompositor: GACIndianapolisTypeface: 10/12 PalatinoPrinter: Von Hoffman Press, Inc.

The credits section for this book begins on page 823 and is considered an extension of the copyrightpage.

Library of Congress Cataloging-in-Publication Data

Denniston, K. J. (Katherine J.)General, organic, and biochemistry / Katherine J. Denniston, Joseph J. Topping,

Robert L. Caret. 3rd ed.p. ; cm.

Rev. ed. of : Principles & applications of organic & biological chemistry / Robert L.Caret, Katherine J. Denniston, Joseph J. Topping. 2nd ed. 1997.

Includes index.ISBN 00723178411. Chemistry, Organic. 2. Biochemistry. I. Topping, Joseph J. II. Caret, Robert L.,

1947 . III. Caret, Robert L., 1947 Principles & applications of organic & biologicalchemistry. IV. Title.

[DNLM: 1. Chemistry. 2. Biochemistry. 3. Chemistry, Organic. QD 33 D411g 2001]QD253 . C27 2001547dc21 99088202

CIP

INTERNATIONAL EDITION ISBN 0071180737Copyright 2001. Exclusive rights by The McGraw-Hill Companies, Inc., for manufacture and export. This book cannot be re-exported from the country to which it is sold by McGraw-Hill.The International Edition is not available in North America.

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vBrief Contents

Preface xx

General Chemistry

1 Chemistry Methods and Measurement 12 The Composition and Structure

of the Atom 33

3 Elements, Atoms, Ions, and the Periodic Table 57

4 Structure and Properties of Ionic andCovalent Compounds 81

5 Calculations and the Chemical Equation 1176 States of Matter: Gases, Liquids, and

Solids 149

7 Reactions and Solutions 1758 Chemical and Physical Change: Energy, Rate,

and Equilibrium 205

9 Charge-Transfer Reactions: Acids and Basesand Oxidation-Reduction 237

10 The Nucleus, Radioactivity, and NuclearMedicine 269

Organic Chemistry

11 An Introduction to Organic Chemistry: TheSaturated Hydrocarbons 295

12 The Unsaturated Hydrocarbons: Alkenes,Alkynes, and Aromatics 323

13 Alcohols, Phenols, Thiols, and Ethers 35514 Aldehydes and Ketones 38315 Carboxylic Acids and Carboxylic Acid

Derivatives 407

16 Amines and Amides 439

Biochemistry

17 Carbohydrates 46718 Lipids and Their Functions in Biochemical

Systems 495

19 Protein Structure and Function 53320 Enzymes 56521 Carbohydrate Metabolism 59922 Aerobic Respiration and Energy

Production 635

23 Fatty Acid Metabolism 66524 Introduction to Molecular Genetics 691

Appendixes 729

Glossary 769

Answers to Selected Problems 785

Credits 821

Index 823

Preface xx

General Chemistry

1 Chemistry: Methods andMeasurement 1

CHEMISTRY CONNECTION:Chance Favors the PreparedMind 2

1.1 The Discovery Process 3Chemistry 3Major Areas of

Chemistry 3The Scientific Method 3

A HUMAN PERSPECTIVE:The Scientific Method 4

Models in Chemistry 5Science and Technology 6

1.2 Data, Results, and Units 61.3 Measurement in Chemistry 7

English and Metric Units 7Unit Conversion: English and Metric Systems 9Conversion of Units within the Same System 9Conversion of Units from One System to

Another 111.4 Error, Accuracy, Precision, and Uncertainty 131.5 Significant Figures and Scientific Notation 14

Significant Figures 14Recognition of Significant Figures 15Scientific Notation 16Significant Figures in Calculation of Results 17Rounding Off Numbers 19

1.6 Experimental Quantities 20Mass 20Length 21Volume 21Time 22

Temperature 22Energy 23Concentration 24Density and Specific Gravity 24

A HUMAN PERSPECTIVE:Food Calories 25

A CLINICAL PERSPECTIVE:Diagnosis Based on Waste 28

Summary 28Key Terms 29Questions and Problems 30Critical Thinking Problems 31

2 The Compositionand Structure ofthe Atom 33

CHEMISTRY CONNECTION:Curiosity, Science, and Medicine 34

2.1 Matter and Properties 34Matter and Physical Properties 34Matter and Chemical Properties 35Intensive and Extensive Properties 36Classification of Matter 37

2.2 Matter and Structure 39Atomic Structure 39Isotopes 41Ions 44

2.3 Development of the Atomic Theory 44Daltons Theory 44Subatomic Particles: Electrons, Protons, and

Neutrons 45The Nucleus 46Light and Atomic Structure 47The Bohr Atom 49

2.4 Modern Atomic Theory 50

Contents

A HUMAN PERSPECTIVE:Atomic Spectra and the Fourth of July 51

AN ENVIRONMENTAL PERSPECTIVE:Electromagnetic Radiation and Its Effects on OurEveryday Lives 52


3 Elements,Atoms, Ions,and the PeriodicTable 57

CHEMISTRY CONNECTION:Managing Mountainsof Information 58

3.1 The Periodic Law and the Periodic Table 58Numbering Groups in the Periodic Table 60Periods and Groups 61Metals and Nonmetals 61Atomic Number and Atomic Mass 61

A MEDICAL PERSPECTIVE:Copper Deficiency and Wilsons Disease 62

3.2 Electron Arrangement and the Periodic Table 63Valence Electrons 63The Quantum Mechanical Atom 66Energy Levels and Sublevels 66Electron Configuration and the Aufbau

Principle 68Abbreviated Electron Configurations 70

3.3 The Octet Rule 71Ion Formation and the Octet Rule 71

A CLINICAL PERSPECTIVE:Dietary Calcium 73

3.4 Trends in the Periodic Table 73Atomic Size 74Ion Size 74Ionization Energy 74Electron Affinity 76


4 Structure andProperties of Ionic andCovalentCompounds 81

CHEMISTRY CONNECTION:Magnets and Migration 82

4.1 Chemical Bonding 82Lewis Symbols 83Principal Types of Chemical

Bonds: Ionic and Covalent 83Polar Covalent Bonding and Electronegativity 85

4.2 Naming Compounds and Writing Formulas ofCompounds 86Ionic Compounds 87Covalent Compounds 92

4.3 Properties of Ionic and Covalent Compounds 94Physical State 94Melting and Boiling Points 94Structure of Compounds in the Solid State 94

A HUMAN PERSPECTIVE:How the Elements Came into Being 95

Solutions of Ionic and Covalent Compounds 954.4 Drawing Lewis Structures of Molecules and

Polyatomic Ions 95Lewis Structures of Molecules 95

A CLINICAL PERSPECTIVE:Blood Pressure and the Sodium Ion/Potassium IonRatio 96

Lewis Structures of Polyatomic Ions 99Lewis Structure, Stability, Multiple Bonds, and

Bond Energies 102Lewis Structures and Resonance 103Lewis Structures and Exceptions to the Octet

Rule 104Lewis Structures and Molecular Geometry; VSEPR

Theory 106Lewis Structures and Polarity 110

4.5 Properties Based on Molecular Geometry 112Solubility 112Boiling Points of Liquids and Melting Points of

Solids 113Summary 114Key Terms 115Questions and Problems 115Critical Thinking Problems 116

viii Contents

5 Calculationsand theChemicalEquation 117

CHEMISTRY CONNECTION:The Chemistry ofAutomobile Air Bags 118

5.1 The Mole Concept and Atoms 119The Mole and Avogadros Number 119Calculating Atoms, Moles, and Mass 120

5.2 Compounds 123The Chemical Formula 123

5.3 The Mole Concept Applied to Compounds 1245.4 The Chemical Equation and the Information It

Conveys 126A Recipe for Chemical Change 126Features of a Chemical Equation 127The Experimental Basis of a Chemical

Equation 1275.5 Balancing Chemical Equations 1285.6 The Extent of Chemical Reactions 132

A CLINICAL PERSPECTIVE:Carbon Monoxide Poisoning: A Case of CombiningRatios 133

5.7 Calculations Using the Chemical Equation 133General Principles 133Use of Conversion Factors 134The Limiting Reactant Problem 140Theoretical and Percent Yield 141

A MEDICAL PERSPECTIVE:Pharmaceutical Chemistry: The PracticalSignificance of Percent Yield 144


6 States ofMatter: Gases,Liquids, andSolids 149

CHEMISTRY CONNECTION:The Demise of theHindenburg 150

6.1 The Gaseous State 151Ideal Gas Concept 151Measurement of Gases 151Boyles Law 152Charless Law 154

A CLINICAL PERSPECTIVE:Autoclaves and the Gas Laws 156

Combined Gas Law 156Avogadros Law 158Molar Volume of a Gas 159Gas Densities 159The Ideal Gas Law 160Daltons Law of Partial Pressures 162Kinetic Molecular Theory of Gases 162

AN ENVIRONMENTAL PERSPECTIVE:The Greenhouse Effect and Global Warming 163

Ideal Gases Versus Real Gases 1646.2 The Liquid State 164

Compressibility 165Viscosity 165Surface Tension 165

A CLINICAL PERSPECTIVE:Blood Gases and Respiration 166

Vapor Pressure of a Liquid 166Van der Waals Forces 167Hydrogen Bonding 167

6.3 The Solid State 169Properties of Solids 169Types of Crystalline Solids 169


7 Reactions andSolutions 175

CHEMISTRY CONNECTION:Seeing a Thought 176

7.1 Writing Chemical Reactions 177Combination Reactions 177Decomposition

Reactions 177Replacement Reactions 177

Contents ix

7.2 Types of Chemical Reactions 178Precipitation Reactions 178Reactions with Oxygen 180AcidBase Reactions 180Oxidation-Reduction Reactions 180

7.3 Properties of Solutions 181General Properties of Liquid Solutions 181Solutions and Colloids 182Degree of Solubility 183Solubility and Equilibrium 183Solubility of Gases: Henrys Law 183

7.4 Concentration of Solutions: Percentage 184Weight/Volume Percent 184

A HUMAN PERSPECTIVE:Scuba Diving: Nitrogen and the Bends 185

Weight/Weight Percent 1867.5 Concentration of Solutions: Moles and

Equivalents 187Molarity 187Dilution 188Representation of Concentration of Ions in

Solution 1907.6 Concentration-Dependent Solution

Properties 191Vapor Pressure Lowering 191Freezing Point Depression and Boiling Point

Elevation 192Osmotic Pressure 193

7.7 Water as a Solvent 1967.8 Electrolytes in Body Fluids 197

A HUMAN PERSPECTIVE:An Extraordinary Molecule 198

A CLINICAL PERSPECTIVE:Hemodialysis 200


8 Chemical and PhysicalChange: Energy, Rate,and Equilibrium 205

CHEMISTRY CONNECTION:The Cost of Energy? More ThanYou Imagine 206

8.1 Thermodynamics 206The Chemical Reaction and

Energy 207Exothermic and Endothermic Reactions 207

Enthalpy 208Spontaneous and Nonspontaneous Reactions 209Entropy 209Free Energy 210

A HUMAN PERSPECTIVE:Triboluminescence: Sparks in the Dark with Candy 211

8.2 Experimental Determination of Energy Changein Reactions 212

8.3 Kinetics 215The Chemical Reaction 216Activation Energy and the Activated

Complex 216Factors That Affect Reaction Rate 217

A CLINICAL PERSPECTIVE:Hot and Cold Packs 218

Mathematical Representation of Reaction Rate 221

8.4 Equilibrium 223Rate and Reversibility of Reactions 223Physical Equilibrium 223Chemical Equilibrium 225The Generalized Equilibrium-Constant Expression

for a Chemical Reaction 226LeChateliers Principle 230


9 Charge-TransferReactions: Acidsand Bases andOxidationReduction 237

CHEMISTRY CONNECTION:Drug Delivery 238

9.1 Acids and Bases 239Arrhenius Theory of Acids and Bases 239BrnstedLowry Theory of Acids and Bases 239Conjugate Acids and Bases 240

9.2 Solutions of Acids and Bases 244Strengths of Acids and Bases 244The Dissociation of Water 243The pH Scale 244The Importance of pH and pH Control 249

9.3 Reactions between Acids and Bases 249Neutralization 249

AN ENVIRONMENTAL PERSPECTIVE:Acid Rain 252

x Contents

Polyprotic Substances 2529.4 AcidBase Buffers 254

The Buffer Process 254Addition of Base (OH) to a Buffer Solution 254Addition of Acid (H3O

) to a Buffer Solution 255Preparation of a Buffer Solution 255

A CLINICAL PERSPECTIVE:Control of Blood pH 258

9.5 OxidationReduction Processes 258Oxidation and Reduction 258

A CLINICAL PERSPECTIVE:Oxidizing Agents for Chemical Control of Microbes 259

Applications of Oxidation and Reduction 260A CLINICAL PERSPECTIVE:

Electrochemical Reactions in the Statue of Libertyand in Dental Fillings 261

Biological Processes 262Voltaic Cells 262

A MEDICAL PERSPECTIVE:Turning the Human Body into a Battery 264

Electrolysis 265Summary 266Key Terms 266Questions and Problems 267Critical Thinking Problems 268

10 The Nucleus,Radioactivity, andNuclear Medicine 269

CHEMISTRY CONNECTION:An Extraordinary Woman inScience 270

10.1 Natural Radioactivity 271Alpha Particles 271Beta Particles 272Gamma Rays 272Properties of Alpha, Beta, and Gamma

Radiation 27210.2 Writing a Balanced Nuclear Equation 273

Alpha Decay 273Beta Decay 274Gamma Production 274Predicting Products of Nuclear Decay 274

10.3 Properties of Radioisotopes 275Nuclear Structure and Stability 275Half-Life 276

10.4 Nuclear Power 277Energy Production 277Nuclear Fission 278

Nuclear Fusion 278Breeder Reactors 280

10.5 Radiocarbon Dating 280AN ENVIRONMENTAL PERSPECTIVE:

Nuclear Waste Disposal 281

10.6 Medical Applications of Radioactivity 282Cancer Therapy Using Radiation 282Nuclear Medicine 282Making Isotopes for Medical Applications 284

10.7 Biological Effects of Radiation 285A CLINICAL PERSPECTIVE:

Magnetic Resonance Imaging 286

Radiation Exposure and Safety 28610.8 Detection and Measurement of Radiation 288

Nuclear Imaging 288Computer Imaging 288The Geiger Counter 289Film Badges 289

10.9 Units of Radiation Measurement 289The Curie 290The Roentgen 290The Rad 290The Rem 290

AN ENVIRONMENTAL PERSPECTIVE:Radon and Indoor Air Pollution 291


Organic Chemistry

11 An Introduction toOrganic Chemistry: The SaturatedHydrocarbons 295

CHEMISTRY CONNECTION:The Origin of OrganicCompounds 296

11.1 The Chemistry of Carbon 297Important Differences between Organic and

Inorganic Compounds 298Families of Organic Compounds 299

11.2 Alkanes 300Structure and Physical Properties 300Alkyl Groups 302Nomenclature 304

Contents xi

Constitutional Isomers 307AN ENVIRONMENTAL PERSPECTIVE:

Oil-Eating Bacteria 309

11.3 Cycloalkanes 309cis-trans Isomerism in Cycloalkanes 311

11.4 Conformations of Alkanes and Cycloalkanes 313

11.5 Reactions of Alkanes and Cycloalkanes 314Combustion 314

A MEDICAL PERSPECTIVE:Polyhalogenated Hydrocarbons Used as Anesthetics 315

Halogenation 315Summary of Reactions 317Summary 317Key Terms 317Questions and Problems 318Critical Thinking Problems 321

12 The UnsaturatedHydrocarbons:Alkenes,Alkynes, andAromatics 323

CHEMISTRY CONNECTION:A Cautionary Tale: DDT and Biological Magnification 324

12.1 Alkenes and Alkynes: Structure and PhysicalProperties 325

12.2 Alkenes and Alkynes: Nomenclature 32612.3 Geometric Isomers: A Consequence of

Unsaturation 32912.4 Reactions Involving Alkenes 332

Hydrogenation: Addition of H2 to an Alkene 332Halogenation: Addition of X2 to an Alkene 334Hydration: Addition of H2O to an Alkene 336Hydrohalogenation: Addition of HX to an

Alkene 337Oxidation Reactions 339Addition Polymers of Alkenes 339

A HUMAN PERSPECTIVE:Life without Polymers? 340

12.5 Aromatic Hydrocarbons 342Structure and Properties 342Nomenclature 343

A HUMAN PERSPECTIVE:Aromatic Compounds and Carcinogenesis 346

Reactions Involving Benzene 346

12.6 Heterocyclic Aromatic Compounds 347Summary of Reactions 348Summary 349Key Terms 350Questions and Problems 350Critical Thinking Problems 352

13 Alcohols,Phenols, Thiols,and Ethers 355

CHEMISTRY CONNECTION:Fetal AlcoholSyndrome 356

13.1 Alcohols: Structure and Physical Properties 357

13.2 Alcohols: Nomenclature 358I.U.P.A.C. Names 358Common Names 359

13.3 Medically Important Alcohols 36013.4 Classification of Alcohols 36113.5 Reactions Involving Alcohols 363

Preparation of Alcohols 363Dehydration of Alcohols 366Oxidation Reactions 368

13.6 Oxidation and Reduction in Living Systems 370

A HUMAN PERSPECTIVE:Alcohol Consumption and the Breathalyzer Test 371

A CLINICAL PERSPECTIVE:Multistep Organic Synthesis 372

13.7 Phenols 37313.8 Ethers 37413.9 Thiols 376Summary of Reactions 378Summary 379Key Terms 379Questions and Problems 379Critical Thinking Problems 382

14 Aldehydes andKetones 383

CHEMISTRY CONNECTION:Genetic Complexity fromSimple Molecules 384

14.1 Structure and PhysicalProperties 385

xii Contents

14.2 I.U.P.A.C. Nomenclature and Common Names 386Naming Aldehydes 386Naming Ketones 389

14.3 Important Aldehydes and Ketones 39014.4 Reactions Involving Aldehydes and

Ketones 391Preparation of Aldehydes and Ketones 391

A CLINICAL PERSPECTIVE:Aldehydes in Medicine 392

Oxidation Reactions 393Reduction Reactions 395Addition Reactions 396KetoEnol Tautomers 398Aldol Condensation 399

A HUMAN PERSPECTIVE:The Chemistry of Vision 401

Summary of Reactions 402Summary 403Key Terms 404Questions and Problems 404Critical Thinking Problems 406

15 Carboxylic Acids andCarboxylic AcidDerivatives 407

CHEMISTRY CONNECTION:Wake Up, Sleeping Gene 408

15.1 Carboxylic Acids 409Structure and Physical

Properties 409Nomenclature 410Some Important Carboxylic Acids 414Reactions Involving Carboxylic Acids 415

AN ENVIRONMENTAL PERSPECTIVE:Garbage Bags from Potato Peels 416

15.2 Esters 418Structure and Physical Properties 418Nomenclature 419Reactions Involving Esters 419

15.3 Acid Chlorides and Acid Anhydrides 424Acid Chlorides 424Acid Anhydrides 426

15.4 Natures High-Energy Compounds:Phosphoesters and Thioesters 429

A HUMAN PERSPECTIVE:Carboxylic Acid Derivatives of Special Interest 430

Summary of Reactions 433


16 Amines and Amides 439

CHEMISTRY CONNECTION:The Nicotine Patch 440

16.1 Amines 441Structure and Physical

Properties 441Nomenclature 445

A CLINICAL PERSPECTIVE:Medically Important Amines 447

Reactions Involving Amines 448A MEDICAL PERSPECTIVE:

Secondary Amines and Cancer 451

Quaternary Ammonium Salts 45216.2 Heterocyclic Amines 45216.3 Amides 454A HUMAN PERSPECTIVE:

Amines and the Central Nervous System 455

Structure and Physical Properties 456Nomenclature 456Reactions Involving Amides 456

A CLINICAL PERSPECTIVE:Medically Important Amides 457

16.4 A Preview of Amino Acids, Proteins, and ProteinSynthesis 460

Summary of Reactions 461Summary 462Key Terms 462Questions and Problems 462Critical Thinking Problems 465

Biochemistry

17 Carbohydrates467

CHEMISTRY CONNECTION:Chemistry Throughthe Looking Glass 468

A HUMAN PERSPECTIVE:Tooth Decay and Simple Sugars 470

Contents xiii

17.1 Types of Carbohydrates 47117.2 Monosaccharides 471

Nomenclature 471Stereoisomers 472Some Important Monosaccharides 473Reducing Sugars 480

17.3 Disaccharides 481Maltose 482Lactose 482Sucrose 483

A HUMAN PERSPECTIVE:Blood Transfusions and the Blood Group Antigens484

17.4 Polysaccharides 485Starch 485Glycogen 487Cellulose 487

A CLINICAL PERSPECTIVE:The Bacterial Cell Wall 488

A MEDICAL PERSPECTIVE:Monosaccharide Derivatives andHeteropolysaccharides of Medical Interest 490


18 Lipids and TheirFunctions inBiochemical Systems 495

CHEMISTRY CONNECTION:Life-Saving Lipids 496

18.1 Biological Functions ofLipids 496

18.2 Fatty Acids 498Structure and Properties 498Chemical Reactions of Fatty Acids 501Eicosanoids: Prostaglandins, Leukotrienes, and

Thromboxanes 50318.3 Glycerides 505

Neutral Glycerides 505Phosphoglycerides 507

18.4 Nonglyceride Lipids 509Sphingolipids 509

A CLINICAL PERSPECTIVE:Disorders of Sphingolipid Metabolism 510

Steroids 512

A HUMAN PERSPECTIVE:Anabolic Steroids and Athletics 513

A CLINICAL PERSPECTIVE:Steroids and the Treatment of Heart Disease 515

Waxes 51618.5 Complex Lipids 51618.6 The Structure of Biological Membranes 519

Fluid Mosaic Structure of Biological Membranes 519

Membrane Transport 522A CLINICAL PERSPECTIVE:

Antibiotics That Destroy Membrane Integrity 524

Energy Requirements for Transport 528Summary 529Key Terms 529Questions and Problems 530Critical Thinking Problems 531

19 ProteinStructure andFunction 533

CHEMISTRY CONNECTION:AngiogenesisInhibitors: Proteinsthat Inhibit TumorGrowth 534

19.1 Cellular Functions of Proteins 53519.2 The -Amino Acids 53519.3 The Peptide Bond 539A HUMAN PERSPECTIVE:

The Opium Poppy and Peptide Synthesis in theBrain 542

19.4 The Primary Structure of Proteins 54319.5 The Secondary Structure of Proteins 544

-Helix 544-Pleated Sheet 546

19.6 The Tertiary Structure of Proteins 546A HUMAN PERSPECTIVE:

Collagen: A ProteinThat Makes Us Strong 548

19.7 The Quaternary Structure of Proteins 54919.8 An Overview of Protein Structure and

Function 55119.9 Myoglobin and Hemoglobin 552

Myoglobin and Oxygen Storage 552Hemoglobin and Oxygen Transport 552

xiv Contents

A MEDICAL PERSPECTIVE:Immunoglobulins: Proteins That Defend the Body 554

Oxygen Transport from Mother to Fetus 556Sickle Cell Anemia 557

19.10 Denaturation of Proteins 55719.11 Dietary Protein and Protein Digestion 560Summary 562Key Terms 563Questions and Problems 563Critical Thinking Problems 564

20 Enzymes 565CHEMISTRY CONNECTION:

Super Hot Enzymesand the Origin ofLife 566

20.1 Nomenclature andClassification 567Nomenclature of Enzymes 567Classification of Enzymes 568

20.2 The Effect of Enzymes on the Activation Energyof a Reaction 571

20.3 The Effect of Substrate Concentration onEnzyme-Catalyzed Reactions 572

20.4 The EnzymeSubstrate Complex 57320.5 Specificity of the EnzymeSubstrate

Complex 57420.6 The Transition State and Product

Formation 575A CLINICAL PERSPECTIVE:

The AIDS Test 576

20.7 Cofactors and Coenzymes 57920.8 Environmental Effects 581

Effect of pH 581Effect of Temperature 583

20.9 Regulation of Enzyme Activity 584Allosteric Enzymes 584Feedback Inhibition 586Zymogens 586

20.10 Inhibition of Enzyme Activity 587Irreversible Inhibitors 587Reversible, Competitive Inhibitors 587

A CLINICAL PERSPECTIVE:Enzymes, Nerve Transmission, and Nerve Agents 588

Reversible, Noncompetitive Inhibitors 590

20.11 Proteolytic Enzymes 590A CLINICAL PERSPECTIVE:

Enzymes, Isoenzymes, and Myocardial Infarction 592

20.12 Uses of Enzymes in Medicine 594Summary 595Key Terms 596Questions and Problems 597Critical Thinking Problems 598

21 CarbohydrateMetabolism 599

CHEMISTRY CONNECTION:The Man Who Got Tipsy fromEating Pasta 600

21.1 ATP: The Cellular EnergyCurrency 601

21.2 Overview of CatabolicProcesses 604Stage I: Hydrolysis of Dietary Macromolecules

into Small Subunits 604Stage II: Conversion of Monomers into a Form

That Can Be Completely Oxidized 606Stage III: The Complete Oxidation of Nutrients

and the Production of ATP 60721.3 Glycolysis 608

An Overview 608Reactions of Glycolysis 609Regulation of Glycolysis 615

21.4 Fermentations 616Lactate Fermentation 616Alcohol Fermentation 617

21.5 The Pentose Phosphate Pathway 61821.6 Gluconeogenesis: The Synthesis of Glucose 61921.7 Glycogen Synthesis and Degradation 621

The Structure of Glycogen 621Glycogenolysis: Glycogen Degradation 621Glycogenesis: Glycogen Synthesis 624

A HUMAN PERSPECTIVE:Fermentations: The Good, the Bad, and the Ugly 626

Compatibility of Glycogenesis and Glycogenolysis 628

A HUMAN PERSPECTIVE:Glycogen Storage Diseases 630

Summary 631Key Terms 631

Contents xv

Questions and Problems 631Critical Thinking Problems 632

22 AerobicRespirationand EnergyProduction 635

CHEMISTRY CONNECTION:Mitochondria fromMom 636

22.1 The Mitochondria 637Structure and Function 637Origin of the Mitochondria 637

A HUMAN PERSPECTIVE:Exercise and Energy Metabolism 638

22.2 Conversion of Pyruvate to Acetyl CoA 63822.3 An Overview of Aerobic Respiration 64122.4 The Citric Acid Cycle (The Krebs Cycle) 642

Reactions of the Citric Acid Cycle 64222.5 Control of the Citric Acid Cycle 64522.6 Oxidative Phosphorylation 646

Electron Transport Systems and the Hydrogen Ion Gradient 646

ATP Synthase and the Production of ATP 647Summary of the Energy Yield 648

A HUMAN PERSPECTIVE:Brown Fat: The Fat That Makes You Thin? 650

22.7 The Degradation of Amino Acids 652Removal of -Amino Groups:

Transamination 652Removal of -Amino Groups: Oxidative

Deamination 654The Fate of Amino Acid Carbon Skeletons 654

22.8 The Urea Cycle 656Reactions of the Urea Cycle 656

22.9 Overview of Anabolism: The Citric Acid Cycle asa Source of Biosynthetic Intermediates 659


23 Fatty AcidMetabolism 665

CHEMISTRY CONNECTION:Obesity: A GeneticDisorder? 666

23.1 Lipid Metabolism in Animals 667Digestion and Absorption of Dietary

Triglycerides 667Lipid Storage 668

23.2 Fatty Acid Degradation 670An Overview of Fatty Acid Degradation 670

A HUMAN PERSPECTIVE:Losing Those Unwanted Pounds of Adipose Tissue 672

The Reactions of -Oxidation 67423.3 Ketone Bodies 677

Ketosis 677Ketogenesis 678

A CLINICAL PERSPECTIVE:Diabetes Mellitus and Ketone Bodies 680

23.4 Fatty Acid Synthesis 682A Comparison of Fatty Acid Synthesis and

Degradation 68223.5 The Regulation of Lipid and Carbohydrate

Metabolism 684The Liver 684Adipose Tissue 685Muscle Tissue 685The Brain 686

23.6 The Effects of Insulin and Glucagon on Cellular Metabolism 686


24 Introductionto Molecular Genetics 691

CHEMISTRY CONNECTION:Molecular Genetics andDetection of Human GeneticDisease 692

24.1 The Structure of theNucleotide 693Chemical Composition of DNA and RNA 693Nucleotide Structure 693

24.2 The Structure of DNA and RNA 696DNA Structure: The Double Helix 696

A CLINICAL PERSPECTIVE:Fooling the AIDS Virus with Look-AlikeNucleotides 698

RNA Structure 69924.3 DNA Replication 700

xvi Contents

24.4 Information Flow in Biological Systems 701Classes of RNA Molecules 702Transcription 703Post-transcriptional Processing of RNA 705

24.5 The Genetic Code 70724.6 Protein Synthesis 708

The Role of Transfer RNA 709The Process of Translation 711

24.7 Mutation, Ultraviolet Light, and DNARepair 713The Nature of Mutations 713The Results of Mutations 713Mutagens and Carcinogens 714Ultraviolet Light Damage and DNA Repair 714

A CLINICAL PERSPECTIVE:The Ames Test for Carcinogens 715

Consequences of Defects in DNA Repair 71624.8 Recombinant DNA 716

Tools Used in the Study of DNA 716

A HUMAN PERSPECTIVE:DNA Fingerprinting 720

Genetic Engineering 72124.9 Polymerase Chain Reaction 723A MEDICAL PERSPECTIVE:

1-Antitrypsin and Familial Emphysema 724


Appendixes 729

Glossary 769

Answers to Selected Problems 785

Credits 821

Index 823

Contents xvii

xviii

Chemistry Connection

Chance Favors the Prepared Mind 2

Curiosity, Science, and Medicine 34

Managing Mountains of Information 58

Magnets and Migration 82

The Chemistry of Automobile Air Bags 118

The Demise of the Hindenburg 150

Seeing a Thought 176

The Cost of Energy? More Than You Imagine 206

Drug Delivery 238

An Extraordinary Woman in Science 270

The Origin of Organic Compounds 296

A Cautionary Tale: DDT and BiologicalMagnification 324

Fetal Alcohol Syndrome 356

Genetic Complexity from Simple Molecules 384

Wake Up, Sleeping Gene 408

The Nicotine Patch 440

Chemistry Through the Looking Glass 468

Life-Saving Lipids 496

Angiogenesis Inhibitors: Proteins that Inhibit Tumor Growth 534

Super Hot Enzymes and the Origin of Life 566

The Man Who Got Tipsy from Eating Pasta 600

Mitochondria from Mom 636

Obesity: A Genetic Disorder? 666

Molecular Genetics and Detection of Human Genetic Disease 692

A Human Perspective

The Scientific Method 4

Food Calories 25

Atomic Spectra and the Fourth of July 51

How the Elements Came into Being 95

Scuba Diving: Nitrogen and the Bends 185

An Extraordinary Molecule 198

Triboluminescence: Sparks in the Dark with Candy 211

Life without Polymers? 340

Aromatic Compounds and Carcinogenesis 346

Alcohol Consumption and the Breathalyzer Test 371

The Chemistry of Vision 401

Carboxylic Acid Derivatives of Special Interest 430

Amines and the Central Nervous System 455

Tooth Decay and Simple Sugars 470

Blood Transfusions and the Blood Group Antigens 484

Anabolic Steroids and Athletics 513

The Opium Poppy and Peptide Synthesis in the Brain 542

Collagen: A Protein That Makes Us Strong 548

Fermentations: The Good, the Bad, and the Ugly 626

Glycogen Storage Diseases 630

Exercise and Energy Metabolism 638

Brown Fat: The Fat That Makes You Thin? 650

Chemistry Connections and Perspectives

Losing Those Unwanted Pounds of Adipose Tissue 672

DNA Fingerprinting 720

A Clinical Perspective

Diagnosis Based on Waste 28

Dietary Calcium 73

Blood Pressure and the Sodium Ion/Potassium Ion Ratio 96

Carbon Monoxide Poisoning: A Case of Combining Ratios 133

Autoclaves and the Gas Laws 156

Blood Gases and Respiration 166

Hemodialysis 200

Hot and Cold Packs 218

Control of Blood pH 258

Oxidizing Agents for Chemical Control of Microbes 259

Electrochemical Reactions on the Statue of Liberty and in Dental Fillings 261

Magnetic Resonance Imaging 286

Multistep Organic Synthesis 372

Aldehydes in Medicine 392

Medically Important Amines 447

Medically Important Amides 457

The Bacterial Cell Wall 488

Disorders of Sphingolipid Metabolism 510

Steroids and the Treatment of Heart Disease 515

Antibiotics That Destroy Membrane Integrity 524

The AIDS Test 576

Enzymes, Nerve Transmission, and Nerve Agents 588

Enzymes, Isoenzymes, and Myocardial Infarction 592

Diabetes Mellitus and Ketone Bodies 680

Fooling the AIDS Virus with Look-AlikeNucleotides 698

The Ames Test for Carcinogens 715

A Medical Perspective

Copper Deficiency and Wilsons Disease 62

Pharmaceutical Chemistry: The Practical Significance of Percent Yield 144

Turning the Human Body into a Battery 264

Polyhalogenated Hydrocarbons Used as Anesthetics 315

Secondary Amines and Cancer 451

Monosaccharide Derivatives andHeteropolysaccharides of Medical Interest 490

Immunoglobulins: Proteins That Defend the Body 554

1-Antitrypsin and Familial Emphysema 724

An Environmental Perspective

Electromagnetic Radiation and Its Effects on Our Everyday Life 52

The Greenhouse Effect and Global Warming 163

Acid Rain 252

Nuclear Waste Disposal 281

Radon and Indoor Air Pollution 291

Oil-Eating Bacteria 309

Garbage Bags from Potato Peels 416

Chemistry Connections and Perspectives xix

xx

Ours is an age when an understanding of chemistry has be-come an increasingly important aspect of medicine. Thethird edition of General, Organic, and Biochemistry has beendesigned to help undergraduate health-related majors andstudents of all majors understand key concepts and appre-ciate the significant connections between chemistry, health,disease, and the treatment of disease. This text strikes abalance between theoretical and practical chemistry, whileemphasizing material that is unique to health-related stud-ies. It is written at a level intended for students whose pro-fessional goals do not include a mastery of chemistry, butfor whom an understanding of the principles of chemistryand their practical ramifications is a necessity.

Key Changes to the Third EditionIn the preparation of the third edition, we have beenguided by the collective wisdom of reviewers who repre-sent the diversity of higher education experiences, includ-ing two-year and four-year colleges and universities. Overfifty different reviewers participated in the review process.We also received very valuable comments from a focusgroup of faculty who regularly teach this material.

New OrganizationRecognizing that courses based on this textbook are orga-nized in a variety of formats within both quarter and se-mester systems, we have reorganized the chapter sequenceinto three sections: inorganic chemistry (Chapters 110),organic chemistry (Chapters 1116), and biochemistry(Chapters 1724). The new organization will allow tremen-dous latitude in usage. The course may be taught in a tra-ditional sense, following the new chapter order, withineither the semester or quarter system. If you prefer the or-ganization in the second edition, you may continue toteach using the different teaching order without affectingyour students understanding of the material. Many usersof the second edition choose to integrate traditional organicand biochemistry and we have constructed the chapters toallow for alternate order of coverage. Frequent use of cross-referencing and reviewing of material discussed earlier inthe book support this needed flexibility.

Clear PresentationTodays students have numerous demands on their time.Many students are nontraditional students, working fulltime, who have families. Students need to be able to iden-tify important concepts quickly and easily. Each section ofthe book was reviewed with the goal of becoming moreconcise while retaining the intellectual rigor of a collegetextbook. Some of the ways we have accomplished thisgoal include:

New design facilitates access to information andengages student interest.Key terms are bolded and are immediately defined.In-chapter examples provide stepwise guidance toproblem-solving strategies.New tables were created allowing easier access toinformation.More headings allow students to find importantmaterial faster.

Key Features of the Third EditionEngaging ApplicationsWe believe that there are a variety of factors in a text thatcan promote student learning and facilitate teaching. It isimportant to engage the interest of the student, especiallywhen the subject may appear difficult and does not seemdirectly related to the students career goals. We have in-cluded a diverse array of applications to accomplish ourgoals.

Perspectives: We have added eleven new Clinical,Medical, and Human Perspectives throughout thebook. A list of Chemistry Connections andPerspectives is provided on page xviii. These providenew and updated applications of chemistry to engagethe students interest and help them understandchemistry in the context of their daily lives.

Learning goal icons : These icons help to alertthe student to the important concepts covered in thetext. An icon is placed next to the textual material thatsupports the learning goal.

1

Preface

xxiii

This text has a complete support package for instructorsand students. Several print and media supplements havebeen prepared to accompany the text and make learning asmeaningful and up-to-date as possible.

For the Instructor:

1. Instructors Manual: The Instructors Manualcontains the printed test item file and solutions to theeven-numbered problems. Written by the authors, thisancillary also contains suggestions for organizinglectures, additional Perspectives, and a list of eachchapters key problems and concepts.

2. Transparencies: A set of 100 transparencies isavailable to help the instructor coordinate the lecturewith key illustrations from the text.

3. Computerized Test Bank: This computerizedclassroom management system/service includes adatabase of test questions, reproducible student self-quizzes, and a grade-recording program. Disks areavailable for IBM and Macintosh computers, andrequire no programming experience.

4. Laboratory Resource Guide: This helpful prep guidecontains the hints that the authors have learned overthe years to ensure students success.

5. Book-Specific Website: A book-specific website isavailable to students and instructors using this text.The website will offer quizzes, key definitions, andinteresting links for the students. The instructor willfind a downloadable version of the Test Bank, thetransparencies in a PowerPoint Presentation, theInstructors Manual, and Solutions Manual. Alsoavailable for the instructor is PageOut, which allowsthe instructor to create his or her own personal coursewebsite. The address for the book-specific website ishttp://www.mhhe.com/physsci/chemistry/denniston.

For the Students:

1. Student Study Guide/Solutions Manual: A separateStudent Study Guide/Solutions Manual is available.It contains the answers and complete solutions for theodd-numbered problems. It also offers students a

variety of exercises and keys for testing theircomprehension of basic, as well as difficult, concepts.

2. Laboratory Manual: Written by Charles H.Henrickson, Larry C. Byrd, and Norman W. Hunter,all of Western Kentucky University, Experiments inGeneral, Organic, and Biochemistry, carefully and safelyguides students through the process of scientificinquiry. The manual features self-containedexperiments that can easily be reorganized to suitindividual course needs.

3. Is Your Math Ready for Chemistry? Developed byWalter Gleason of Bridgewater State College, thisunique booklet provides a diagnostic test thatmeasures the students math ability. Part II of thebooklet provides helpful hints in the math skillsneeded to successfully complete a chemistry course.

4. Problem Solving Guide to General Chemistry:Written by Ronald DeLorenzo of Middle GeorgiaCollege, this exceptional supplement provides thestudent with over 2500 problems and questions. Theguide holds the students interest by integrating thesolution of chemistry problems with real-lifeapplications, analogies, and anecdotes.

5. Schaums Outline of General, Organic, andBiological Chemistry: Written by George Odian andIra Blei, this supplement provides students with over1400 solved problems with complete solutions. It alsoteaches effective problem-solving techniques.

6. How to Study Science: Written by Fred Drewes ofSuffolk County Community College, this excellentworkbook offers students helpful suggestions formeeting the considerable challenges of a sciencecourse. It offers tips on how to take notes and how toovercome science anxiety. The books unique designhelps to stir critical thinking skills, while facilitatingcareful note taking on the part of the student.

7. Book-Specific Website: A book-specific website isavailable to students and instructors using this text.The website will offer quizzes, key definitions, andinteresting links for the students. The address for thebook-specific website is http://www.mhhe.com/physsci/chemistry/denniston.

Supplementary MaterialsSupplements

xxv

We are grateful to our families, whose patience and sup-port made it possible for us to undertake this project. Weare grateful to our colleagues at McGraw-Hill, especiallyJim Smith, publisher, and Kent Peterson, sponsoring editor,for their support of our book. We would like to thankShirley Oberbroeckling, developmental editor, for herguidance during the reviewing and writing process. Wealso would like to express our appreciation to MarilynSulzer, project manager, for her skilled assistance through-out production.

A revision cannot move forward without the feedbackof professors teaching the course. The reviewers have ourgratitude and assurance that their comments received seri-ous consideration.

The following professors provided reviews, partici-pated in a focus group, or gave valuable advice for thepreparation of the third edition:

Hugh Akers, Lamar UniversityCatherine A. Anderson, San Antonio CollegeA. G. Andrewes, Saginaw Valley State UniversityMark A. Benvenuto, University of Detroit-MercyWarren L. Bosch, Elgin Community CollegeJames R. Braun, Clayton College and State UniversityPhilip A. Brown, Barton CollegeTeresa L. Brown, Rochester Community CollegeScott Carr, Trinity Christian CollegeBernadette Corbett, Metropolitan Community CollegeWayne B. Counts, Georgia Southwestern State UniversityRobert P. Dixon, Southern Illinois UniversityWes Fritz, College of DuPageEdwin J. Geels, Dordt CollegeDeepa Godambe, William Rainey Harper CollegeJudith M. Iriarte-Gross, Middle Tennessee State UniversityT. G. Jackson, University of South AlabamaPaul G. Johnson, Duquesne UniversityWarren Johnson, University of Wisconsin-Green BayJames F. Kirby, Quinnipiac CollegeRoscoe E. Lancaster, Golden West College Richard H. Langley, Stephen F. Austin State UniversityJulie E. Larson, Bemidji State UniversityK. W. Loach, Plattsburgh State UniversityRalph Martinez, Humboldt State UniversityJohn Mazzella, William Paterson University

Lawrence McGahey, College of St. ScholasticaCleon McKnight, Hinds Community CollegeMelvin Merken, Worcester State CollegeRobert Midden, Bowling Green State UniversityDavid Millsap, South Plains CollegeEllen M. Mitchell, Bridgewater CollegeJay Mueller, Green River Community CollegeLynda P. Nelson, Westark CollegeRichard E. Parent, Housatonic Community Technical CollegeChetna Patel, Aurora UniversityJeffrey A. Rahn, Eastern Washington UniversityB. R. Ramachandran, Indiana State UniversityJohn W. Reasoner, Western Kentucky UniversityRill Ann Reuter, Winona State UniversityTerry Salerno, Minnesota State University-MankatoKaren Sanchez, Florida Community College at JacksonvilleSarah Selfe, University of WashingtonKevin R. Siebenlist, Marquette UniversitySteven M. Socal, Southern Utah UniversityGordon Sproul, University of South Carolina-BeaufortPratibha Varma-Nelson, Saint Xavier UniversityRobert T. Wang, Salem State UniversitySteven Weitstock, Indiana University Catherine Woytowicz, Loyola UniversityJesse Yeh, South Plains CollegeEdward P. Zovinka, St. Francis College

The following professors provided reviews and othervaluable advice for the previous editions:

Raymond D. Baechler, Russell Sage CollegeSatinder Bains, Arkansas State University-Beebe Sister Marjorie Baird, O.P., West Virginia Northern

Community CollegeRonald Bost, North Central Texas CollegeFred Brohn, Oakland Community CollegeSister Helen Burke, Chestnut Hill CollegeSharmaine S. Cady, East Stroudsburg UniversityRobert C. Costello, University of South Carolina-SumterMarianne Crocker, Ozarks Technical Community CollegePeter DiMaria, Delaware State UniversityRonald Dunsdon, Iowa Central Community CollegeDonald R. Evers, Iowa Central Community CollegePatrick Flash, Kent State University-Ashtabula

Acknowledgements

xxvii

Clear Approach to Solving ProblemsBecause problem solving is most efficientlylearned by a combination of studying examplesand practicing, problems with step-by-stepsolutions are provided wherever appropriate.Examples are followed by a question requiringthe student to integrate the newly learnedmaterial.

The General, Organic, and Biochemistry Learning System is easy to follow, and will allow thestudent to excel in this course. The materials are presented in such a way that the student willeffectively learn and retain the important information.

The General, Organic, and Biochemistry Learning System

1328

382 13 Alcohols, Phenols, Thiols, and Ethers

d. ?

13.56 We have seen that alcohols are capable of hydrogen bond-ing to each other. Hydrogen bonding is also possible be-tween alcohol molecules and water molecules or betweenalcohol molecules and ether molecules. Ether molecules donot hydrogen bond to each other, however. Explain.

Thiols13.57 Cystine is an amino acid formed from the oxidation of two

cysteine molecules to form a disulfide bond. The molecularformula of cystine is C6H12O4N2S2. Draw the structural for-mula of cystine. (Hint: For the structure of cysteine, see Fig-ure 19.11.)

13.58 Explain the way in which British Anti-Lewisite acts as anantidote for mercury poisoning.

13.59 Give the I.U.P.A.C. name for each of the following thiols.(Hint: Use the rules for alcohol nomenclature and the suffix-thiol.)a. CH3CH2CH2SHb. CH3CHCH2CH3A

SHc. CH2CH3

ACH3CCH3A

SHd.

13.60 Give the I.U.P.A.C. name for each of the following thiols.(Hint: Use the rules for alcohol nomenclature and the suffix-thiol.)a. CH2CHCH3A A

SH SHb.

c. CH3CHCH2CH2CH3ASH

d. CH3CH2CH2CH2CH2CH2CH2SH

1. You are provided with two solvents: water (H2O) and hexane(CH3CH2CH2CH2CH2CH3). You are also provided with twobiological molecules whose structures are shown here:

Predict which biological molecule would be more soluble inwater and which would be more soluble in hexane. Defendyour prediction. Design a careful experiment to test yourhypothesis.

Consider the digestion of dietary molecules in the diges-tive tract. Which of the above two biological moleculeswould be more easily digested under the conditions presentin the digestive tract?

2. Cholesterol is an alcohol and a steroid (Section 18.4). Dietsthat contain large amounts of cholesterol have been linked toheart disease and atherosclerosis, hardening of the arteries.The narrowing of the artery, caused by plaque buildup, isvery apparent. Cholesterol is directly involved in thisbuildup. Describe the various functional groups and princi-pal structural features of the cholesterol molecule. Wouldyou use a polar or nonpolar solvent to dissolve cholesterol?Explain your reasoning.

Cholesterol

3. An unknown compound A is known to be an alcohol withthe molecular formula C4H10O. When dehydrated, com-pound A gave only one alkene product, C4H8, compound B.Compound A could not be oxidized. What are the identitiesof compound A and compound B?

4. Sulfides are the sulfur analogs of ethers, that is, ethers inwhich oxygen has been substituted by a sulfur atom. Theyare named in an analogous manner to the ethers with theterm sulfide replacing ether. For example, CH3SCH3 is di-methyl sulfide. Draw the sulfides that correspond to the fol-lowing ethers and name them:a. diethyl ether c. dibutyl etherb. methyl propyl ether d. ethyl phenyl ether

5. Dimethyl sulfoxide (DMSO) has been used by many sportsenthusiasts as a linament for sore joints; it acts as an anti-inflammatory agent and a mild analgesic (pain killer). How-ever, it is no longer recommended for this purpose because itcarries toxic impurities into the blood. DMSO is a sulfoxideit contains the SPO functional group. DMSO is preparedfrom dimethyl sulfide by mild oxidation, and it has themolecular formula C2H6SO. Draw the structure of DMSO.

CH3%

DHO

H

CH3%

CH3G

CH3A

CH3D

HOCOOOCOCH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3


H

O

A

B


OB

OB

HA

COHA

HOCOOHA

HOCOOHA

HOCOOHA

HOOCOHA

OB

CH2OH

Critical Thinking Problems

OSH

OSHHSO

CH2OH2

10.3 Properties of Radioisotopes 275

EXAMPLE 10.1Predicting the Products of Radioactive Decay

Determine the identity of the unknown product of the alpha decay of cali-fornium-245:

Cm He X

Solution

Step 1. The mass number of the californium isotope is 245. Therefore thesum of the mass numbers of the products must also be 245, and Xmust have a mass number of 241.

Step 2. Likewise, the charge on the left is 96, and the charge on the rightmust also be 96. The sum of the unknown nuclear charge plus thecharge of the alpha particle (2) must equal 96.

Step 3. The unknown charge must be 94, because [94 (2) 96]. The un-known is

X

Referring to the periodic table, we find that the element that has atomic num-ber 94 is plutonium; therefore X Pu.

Complete each of the following nuclear equations:

a. Kr X eb. X He Rn

Complete each of the following nuclear equations:

a. U X eb. B Li X73

115

01

23992

Q u e s t i o n 10.4

22286

42

01

8536

Q u e s t i o n 10.3

24194

24194

42

24596

A variety of questions and problems thatrange in level of difficulty help studentsmeasure their mastery of the chapter material.The odd-numbered questions are answered inthe back of the text.

At the end of the chapter, the student willfind several problems that require thought-provoking answers dealing with daily life andthe health care sciences.

Dynamic VisualsMany of the equations andreactions are color coded to helpthe student understand thechemical changes that occur incomplex reactions. The student caneasily recognize the chemicalgroups being added or removed ina reaction by the color coding.Green background illustrates animportant equation or key reaction;yellow background illustratesenergy in the general andbiochemistry sections and revealsthe parent chain of a compound inthe organic section; red and bluelettering distinguish two or morecompounds that appear similar.

The art program has beensignificantly updated with the useof molecular art and drawings. Thestudents will gain a betterperspective and understanding of amolecule with a Spartan computer-generated model.

xxviii

119

11.2 Alkanes 303

Carbon atoms are classified according to the number of other carbon atoms towhich they are attached. A primary carbon (1) is directly bonded to one other car-bon. A secondary carbon (2) is bonded to two other carbon atoms; a tertiary car-bon (3) is bonded to three other carbon atoms, and a quaternary carbon to four.

Alkyl groups are classified according to the number of carbons attached to thecarbon atom that joins the alkyl group to a molecule.

COC OA

A

H

HPrimary

alkyl group

COCOA

A

C

HSecondary alkyl group

COCOA

A

C

CTertiary

alkyl group

Figure 11.3The tetrahedral carbon atom: (a) a tetra-hedron; (b) the tetrahedral carbon drawnwith dashes and wedges; (c) the stickdrawing of the tetrahedral carbon atom;(d) drawing of a ball-and-stick model ofmethane.(a) (b) (c) (d)

A

G^; HC

HH

H

HC

HH

H

Figure 11.2(a) Drawing and (b) ball-and-stick modelof ethane. All the carbon atoms have atetrahedral arrangement, and all bondangles are approximately 109.5.(c) Drawing and (d) ball-and-stick modelof a more complex alkane, butane.

C CC

H H$C

CH

i

H H$C

H

&@

i

HH&@

HH

CH

109.5i&@

iH

$CC

H H

HH

(a) (b)

(c) (d)

Table 11.4 Names and Formulas of the First Five Continuous-ChainAlkyl Groups

Alkyl Group Structure Name

CH3 MethylCH3CH2 EthylCH3CH2CH2 PropylCH3CH2CH2CH2 ButylCH3CH2CH2CH2CH2 Pentyl

20 1 Chemistry: Methods and Measurement

1.6 Experimental QuantitiesThus far we have discussed the scientific method and its role in acquiring data andconverting the data to obtain the results of the experiment. We have seen that suchdata must be reported in the proper units with the appropriate number of signifi-cant figures. The quantities that are most often determined include mass, length,volume, time, temperature, and energy. Now lets look at each of these quantitiesin more detail.

MassMass describes the quantity of matter in an object. The terms weight and mass, incommon usage, are often considered synonymous. They are not, in fact. Weight isthe force of gravity on an object:

Weight mass acceleration due to gravity

When gravity is constant, mass and weight are directly proportional. But gravityis not constant; it varies as a function of the distance from the center of the earth.Therefore weight cannot be used for scientific measurement because the weight ofan object may vary from one place on the earth to the next.

Mass, on the other hand, is independent of gravity; it is a result of a compari-son of an unknown mass with a known mass called a standard mass. Balances areinstruments used to measure the mass of materials

Learning Goal

9

812

The Chemical ReactionConsider the exothermic reaction that we discussed in Section 8.1:

CH4(g) 2O2(g) CO2(g) 2H2O(l)

For the reaction to proceed, CH and OO bonds must be broken, and CO and HO bonds must be formed. Sufficient energy must be available to causethe bonds to break if the reaction is to take place. This energy is provided by thecollision of molecules. If sufficient energy is available at the temperature of the re-action, one or more bonds will break, and the atoms will recombine in a lower en-ergy arrangement, in this case as carbon dioxide and water. A collision producingproduct molecules is termed an effective collision. Only effective collisions lead tochemical reaction.

Activation Energy and the Activated ComplexThe minimum amount of energy required to produce a chemical reaction is calledthe activation energy for the reaction.

211 kcal

Learning Goal

5

11.2 Alkanes 307

Now add the substituents. In this example a bromine atom is bonded to carbon-1,and a methyl group is bonded to carbon-4:

Finally, add the correct number of hydrogen atoms so that each carbon has fourcovalent bonds:

As a final check of your accuracy, use the I.U.P.A.C. system to name the compoundthat you have just drawn, and compare the name with that in the original problem.

The molecular formula and condensed formula can be written from the struc

HOCOCOCOCOCOCOHA

A

A

A

A

A A

A

A

A

A

1 2 3 4 5 6

Br H H H H H

HOCOHAH

H H H H H

OCOCOCOCOCOCOA

A

A

A

A

A A

A

A

A

A

1 2 3 4 5 6

Br

HOCOHAH

EXAMPLE 9.10Calculating the pH of a Buffer SolutionCalculate the pH of a buffer solution similar to that described in Example 9.9except that the acid concentration is doubled, while the salt concentration re-mains the same.

Solution

Acetic acid is the acid; [acid] 2.00 101 M (remember, the acid concentra-tion is twice that of Example 9.9; 2 [1.00 101] 2.00 101 M

Sodium acetate is the salt; [salt] 1.00 101 MThe equilibrium is

CH3COOH(aq) H2O(l) H3O(aq) CH3COO

(aq)acid salt

and the hydronium ion concentration,

[H3O]

Substituting the values given in the problem

[H3O]

[H3O] 3.50 105

and because

pH log [H3O]

pH log 3.50 105

4.456

The pH of the buffer solution is 4.456.

A comparison of the two solutions described in Examples 9 9 and 9 10 demon-

[2.00 101]1.75 105

[1.00 101]

[acid]Ka[salt]

xxix

Health/Life Related ApplicationsThere are four different Perspective boxes in thetext. Chemistry Connections provides anintroductory scenario for the chapter, MedicalPerspective and Clinical Perspective demonstrateuse of the chapter material in an allied health field,Environmental Perspective demonstrates chapterconcepts in ecological problems, and HumanPerspective demonstrates how important chemistryis in our day to day lives.

Clear PresentationEach chapter begins with an outline thatintroduces students to the topics to bepresented. This outline also provides theinstructor with a quick topic summary toorganize lecture material.

A list of learning goals, based on the majorconcepts covered in the chapter, enablesstudents to preview the material and becomeaware of the topics they are expected to master.

This icon is found within the chapterswherever the associated learning goal is firstpresented, allowing the student to focusattention on the major concepts.

528

144 5 Calculations and the Chemical Equation

In recent years the major pharmaceutical industries have in-troduced a wide variety of new drugs targeted to cure or alle-viate the symptoms of a host of diseases that afflict humanity.

The vast majority of these drugs are synthetic; they aremade in a laboratory or by an industrial process. These sub-stances are complex molecules that are patiently designed andconstructed from relatively simple molecules in a series ofchemical reactions. A series of ten to twenty steps, or sequen-tial reactions, is not unusual to put together a final product thathas the proper structure, geometry, and reactivity for efficacyagainst a particular disease.

Although a great deal of research occurs to ensure that eachof these steps in the overall process is efficient (having a largepercent yield), the overall process is still very inefficient (lowpercent yield). This inefficiency, and the research needed tominimize it, at least in part determines the cost and availabilityof both prescription and over-the-counter preparations.

Consider a hypothetical five-step sequential synthesis. Ifeach step has a percent yield of 80% our initial impressionmight be that this synthesis is quite efficient. However, oncloser inspection we find quite the contrary to be true.

The overall yield of the five-step reaction is the product ofthe decimal fraction of the percent yield of each of the sequen-tial reactions. So, if the decimal fraction corresponding to 80%is 0.80:

0.80 0.80 0.80 0.80 0.80 0.33

Converting the decimal fraction to percentage:

0.33 100% 33% yield

Many reactions are considerably less than 80% efficient, espe-cially those that are used to prepare large molecules with com-plex arrangements of atoms. Imagine a more realistic scenarioin which one step is only 20% efficient (a 20% yield) and theother four steps are 50%, 60%, 70%, and 80% efficient. Repeat-

ing the calculation with these numbers (after conversion to adecimal fraction):

0.20 0.50 0.60 0.70 0.80 0.0336

Converting the decimal fraction to a percentage:

0.0336 100% 3.36% yield

a very inefficient process.If we apply this logic to a fifteen- or twenty-step synthesis

we gain some appreciation of the difficulty of producing mod-ern pharmaceutical products. Add to this the challenge of pre-dicting the most appropriate molecular structure that will havethe desired biological effect and be relatively free of side effects.All these considerations give new meaning to the term wonderdrug that has been attached to some of the more successful syn-thetic products.

We will study some of the elementary steps essential to thesynthesis of a wide range of pharmaceutical compounds inlater chapters, beginning with Chapter 11.

Pharmaceutical Chemistry: The Practical Significance of Percent Yield

5.1 The Mole Concept and AtomsAtoms are exceedingly small, yet their masses have beenexperimentally determined for each of the elements. Theunit of measurement for these determinations is theatomic mass unit, abbreviated amu:

1 amu 1.661 1024 g

The periodic table provides atomic masses in atomicmass units.

A more practical unit for defining a collection ofatoms is the mole:

1 mol of atoms 6.022 1023 atoms of an element

This number is often referred to as Avogadros number.The mole and the atomic mass unit are related. The

atomic mass of a given element corresponds to the aver-age mass of a single atom in atomic mass units and themass of a mole of atoms in grams. One mole of atoms ofany element contains the same number, Avogadrosnumber, of atoms.

Summary

68

156 6 States of Matter: Gases, Liquids, and Solids

A sample of nitrogen gas has a volume of 3.00 L at 25C. What volume will it oc-cupy at each of the following temperatures if the pressure and number of molesare constant?a. 546 K b. 0.00C c. 373 K

The behavior of a hot-air balloon is a commonplace consequence of Charlesslaw. The balloon rises because air expands when heated (Figure 6.4). The volumeof the balloon is fixed because the balloon is made of an inelastic material; as a re-sult, when the air expands some of the air must be forced out. Hence the density ofthe remaining air is less (less mass contained in the same volume), and the balloonrises. Turning down the heat reverses the process, and the balloon descends.

Boyles law describes the inverse proportional relationship between volumeand pressure; Charless law shows the direct proportional relationship betweenvolume and temperature.

Combined Gas LawOften, a sample of gas (a fixed number of moles of gas) undergoes change involv-ing volume, pressure, and temperature simultaneously. It would be useful to haveone equation that describes such processes.

Q u e s t i o n 6.6

Jacques Charles and Joseph Gay-Lussac were eighteenth-century chemists and physicists. They were also balloon enthu-siasts. It is clear that their hobby and their scientific pursuitswere intertwined. Charless law is actually attributed to thework of both men. The observation that the pressure and tem-perature of a gas are directly proportional

P T

follows directly from Charless law and Boyles law. The equality

P k T

is often termed Gay-Lussacs law. You can readily verify this pro-portionality by observing the fate of a balloon when it is heatedor cooled (try putting an inflated balloon in the refrigerator, re-move it, and allow it to return to room temperature).

A very practical application of Gay-Lussacs law is the au-toclave, a piece of equipment commonly found in hospital, clin-ical, and biological laboratories. It is designed and used tosterilize laboratory materials such as glassware, surgical instru-ments, and so forth. It uses steam at high temperatures andpressures and takes advantage of the exceptionally high heatcapacity (energy storage capability) of steam.

The autoclave kills microorganisms by using the heat en-ergy in steam. However, steam has a temperature of 100C atnormal atmospheric pressure; this temperature is too low (in-sufficient energy) to kill all harmful bacteria. Gay-Lussacs lawpredicts that, at a constant volume (the volume of the auto-

clave), if the steam is heated further, both the pressure and tem-perature of the steam will increase. At the maximum safe oper-ating pressure of the autoclave, temperatures may reach asmuch as 150C; when maintained for a sufficient interval, thistemperature is sufficiently high to kill most microorganisms.

Autoclaves and the Gas Laws

Figure 6.4Charless law predicts that the volume of airin the balloon will increase when heated.We assume that the volume of the balloonis fixed; consequently, some air will bepushed out. The air remaining in the bal-loon is less dense (same volume, less mass)and the balloon will rise. When the heateris turned off the air cools, the densityincreases, and the balloon returns to earth.

Chemical and PhysicalChange: Energy, Rate,and Equilibrium8

A rapid, exothermicchemical reaction

OutlineCHEMISTRY CONNECTION:

The Cost of Energy? More Than YouImagine

8.1 ThermodynamicsThe Chemical Reaction and

EnergyExothermic and Endothermic

ReactionsEnthalpySpontaneous and Nonsponta-

neous ReactionsEntropyFree Energy

A HUMAN PERSPECTIVE:Triboluminescence: Sparks in the Darkwith Candy

8.2 Experimental Determinationof Energy Change inReactions

8.3 KineticsThe Chemical ReactionActivation Energy and the

Activated ComplexFactors That Affect Reaction

RateA CLINICAL PERSPECTIVE:

Hot and Cold PacksMathematical Representation

of Reaction Rate8.4 Equilibrium

Rate and Reversibility ofReactions

Physical EquilibriumChemical EquilibriumThe Generalized Equilibrium-

Constant Expression for aChemical Reaction

LeChateliers PrincipleSummaryKey TermsQuestions and ProblemsCritical Thinking Problems

Correlate the terms endothermic andexothermic with heat flow betweena system and its surroundings.

State the meaning of the termsenthalpy, entropy, and free energyand know their implications.

Describe experiments that yieldthermochemical information andcalculate fuel values based onexperimental data.

Describe the concept of reactionrate and the role of kinetics inchemical and physical change.

Describe the importance ofactivation energy and the activatedcomplex in determining reactionrate.

Predict the way reactant structure,concentration, temperature, andcatalysis affect the rate of achemical reaction.

Write rate equations for elementaryprocedures.

Recognize and describe equilibriumsituations.

Write equilibrium-constantexpressions and use theseexpressions to calculate equilibriumconstants.

Use LeChateliers principle topredict changes in equilibriumposition.

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3

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Learning Goals

205

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At the end of each chapter is asummary designed to help studentsmore easily identify important conceptsand help them review for quizzes andtests.

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Because k2 is a constant, we may equate them, resulting in

and use this expression to solve some practical problems.Consider a gas occupying a volume of 10.0 L at 273 K. The ratio V/T is a con-

stant, k2. Doubling the temperature, to 546 K, increases the volume to 20.0 L asshown here:

Vf 20.0 L

Tripling the temperature, to 819 K, increases the volume by a factor of 3:

Vf 30.0 L

These relationships are illustrated in Figure 6.3.

Vf819 K

10.0 L273 K

Vf546 K

10.0 L273 K

VfTf

ViTi

Appendix A contains a review of themathematics used here.

1325

Questions and Problems 379

13.1 Alcohols: Structure and PhysicalProperties

Alcohols are characterized by the hydroxyl group (OH)and have the general formula ROH. They are very po-lar, owing to the polar hydroxyl group, and are able toform intermolecular hydrogen bonds. Because of hydro-gen bonding between alcohol molecules, they havehigher boiling points than hydrocarbons of comparablemolecular weight. The smaller alcohols are very watersoluble.

13.2 Alcohols: NomenclatureIn the I.U.P.A.C. system, alcohols are named by deter-mining the parent compound and replacing the -e endingwith -ol. The chain is numbered to give the hydroxylgroup the lowest possible number. Common names arederived from the alkyl group corresponding to the par-ent compound.

13.3 Medically Important AlcoholsMethanol is a toxic alcohol that is used as a solvent.Ethanol is the alcohol consumed in beer, wine, and dis-tilled liquors. Isopropanol is used as a disinfectant. Eth-ylene glycol (1,2-ethanediol) is used as antifreeze, andglycerol (1,2,3-propanetriol) is used in cosmetics andpharmaceuticals.

13.4 Classification of AlcoholsAlcohols may be classified as primary, secondary, or ter-tiary, depending on the number of alkyl groups attachedto the carbinol carbon, the carbon bearing the hydroxylgroup. A primary alcohol has a single alkyl groupbonded to the carbinol carbon. Secondary and tertiary al-cohols have two and three alkyl groups, respectively.

13.5 Reactions Involving AlcoholsAlcohols can be prepared by the hydration of alkenes. Al-cohols can undergo dehydration to yield alkenes. Primaryand secondary alcohols undergo oxidation reactions toyield aldehydes and ketones, respectively. Tertiary alco-hols do not undergo oxidation.

13.6 Oxidation and Reduction in LivingSystems

In organic and biological systems oxidation involves thegain of oxygen or loss of hydrogen. Reduction involvesthe loss of oxygen or gain of hydrogen. Nicotinamideadenine dinucleotide, NAD, is a coenzyme involved inmany biological oxidation and reduction reactions.

13.7 PhenolsPhenols are compounds in which the hydroxyl group isattached to a benzene ring; they have the general for-mula ArOH. Many phenols are important as antisep-tics and disinfectants.

13.8 EthersEthers are characterized by the ROR functionalgroup. Ethers are generally nonreactive but are extremelyflammable. Diethyl ether was the first general anestheticused in medical practice. It has since been replaced bypenthrane and enthrane, which are less flammable.

13.9 ThiolsThiols are characterized by the sulfhydryl group (SH).The amino acid cysteine is a thiol that is extremely im-portant for maintaining the correct shapes of proteins.Coenzyme A is a thiol that serves as a carrier of acetylgroups in biochemical reactions.

Alcohols: Structure and Physical Properties13.11 Arrange the following compounds in order of increasing

boiling point, beginning with the lowest:a. CH3CH2CH2CH2CH3 b. CH3CHCH2CHCH3A A

OH OHc. CH3CHCH2CH2CH3 d. CH3CH2CH2OCH2CH3A

OH13.12 Why do alcohols have higher boiling points than alkanes?

Why are small alcohols readily soluble in water whereaslarge alcohols are much less soluble?

13.13 Which member of each of the following pairs is more solu-ble in water?a. CH3CH2OH or CH3CH2CH2CH2OHb. CH3CH2CH2CH2CH3 or CH3CH2CH2CH2OOHc. or CH3CHCH3A

OH

OHA

Questions and Problems

Key Terms

Summary

alcohol (13.1)carbinol carbon (13.4)dehydration (13.5)disulfide (13.9)elimination reaction

(13.5)ether (13.8)fermentation (13.3)hydration (13.5)hydroxyl group (13.1)

oxidation (13.6)phenol (13.7)primary (1) alcohol

(13.4)reduction (13.6)secondary (2) alcohol

(13.4)tertiary (3) alcohol (13.4)thiol (13.9)Zaitsevs rule (13.5)

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Chapter 2 The Composition and Structure of the Atom 22.1 Matter and Properties2.2 Matter and Structure2.3 Development of the Atomic Theory2.4 Modern Atomic Theory

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