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Organic Chemistry 7th Edition Francis A. Carey Digital
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Author(s): Francis A. Carey
ISBN(s): 9780073047874, 0073047872
Edition: 7th
File Details: PDF, 29.98 MB
Year: 2008
Language: english
 M cGraw-Hill offers various tools and technology to
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Solutions Manual CPS eInstruction

ISBN-13: 978-0-07-304788-1 • ISBN-10: 0-07-304788-0 The Classroom Performance System’s
(CPS) eInstruction brings interactivity
Written by Robert C. Atkins (James Madison University)
into the classroom or lecture hall. It is
and Francis A. Carey, the Solutions Manual provides
a wireless response system that gives
step-by-step solutions to guide students through the Apago PDF Enhancer
the instructor and students immediate
reasoning behind solving each problem in the text. There
feedback from the entire class. The
is also a self-test at the end of each chapter designed to
wireless response pads are essentially remotes that are
assess the student’s mastery of the material.
easy to use and engage students. CPS allows instructors
to motivate student preparation, promote interactivity
and active learning, and receive immediate feedback to
assess student understanding. Questions covering the
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in the CPS eInstruction software are available on the
Organic Chemistry ARIS™ site.

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car47872_fm_i-xxxii 11/24/06 23:09 Page i
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S e v e n t h E d i t i o n

Francis A. Carey
University of Virginia
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Boston Burr Ridge, IL Dubuque, IA New York San Francisco St. Louis
Bangkok Bogotá Caracas Kuala Lumpur Lisbon London Madrid Mexico City
Milan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei Toronto
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ORGANIC CHEMISTRY, SEVENTH EDITION

Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the
Americas, New York, NY 10020. Copyright © 2008 by The McGraw-Hill Companies, Inc. All rights reserved.
No part of this publication may be reproduced or distributed in any form or by any means, or stored in a
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but not limited to, in any network or other electronic storage or transmission, or broadcast for distance
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Some ancillaries, including electronic and print components, may not be available to customers outside the
United States.

E This book is printed on recycled, acid-free paper containing 10% postconsumer waste.

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ISBN 978–0–07–304787–4
MHID 0–07–304787–2

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The credits section for this book begins on page C-1 and is considered an extension of the copyright page.

Library of Congress Cataloging-in-Publication Data

Carey, Francis A., 1937-

Organic chemistry / Francis A. Carey.—7th ed.
p. cm.
Includes index.
ISBN 978-0-07-304787-4—ISBN 0-07-304787-2 (hard copy : alk. paper)
1. Chemistry, Organic. I. Title.
QD251.3.C37 2008
547—dc22
2006031901

www.mhhe.com
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This edition is dedicated to my colleague and friend Bob Atkins, who is not only the
lead author of our Solutions Manual but who also has contributed generously of his
time, knowledge, and common sense throughout the seven editions of this text.

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About the Cover

Chemists are increasingly concerned with prepar-

ing compounds designed to have particular prop-
erties. The compound featured on the cover is the
creation of Dr. Dirk Guldi of the University of
Erlangen (Germany) and Dr. Maurizio Prato of the
University of Trieste (Italy).
The cylindrical object is a form of carbon
known as a nanotube.* About 1 percent of the car-
bons of this nanotube are linked to molecules of
the organometallic “sandwich” compound fer-
rocene.† On irradiation with visible light, ferrocene
transfers an electron to the nanotube, generating a
charge-separated species. Thus, nanotubes that bear
appropriate attached groups hold promise as mate-
rials suitable for devices, such as solar cells, that
are capable of converting sunlight to electricity.

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*For more about carbon nanotubes, see pages 432–433.

†
For more about ferrocene, see page 600.

iv
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About the Author

Francis A. Carey, a native of Philadelphia, was educated at Drexel University (B.S. in

chemistry, 1959) and Penn State (Ph.D., 1963). Following postdoctoral work at Harvard
and military service, he served on the faculty of the University of Virginia from 1966
until retiring as Professor Emeritus in 2000.
In addition to this text, Professor Carey is coauthor (with Robert C. Atkins) of
Organic Chemistry: A Brief Course and (with Richard J. Sundberg) of Advanced Organic
Chemistry, a two-volume treatment designed for graduate students and advanced under-
graduates.
Frank and his wife Jill, who is a teacher/director of a preschool and a church organist,
are the parents of Andy, Bob, and Bill and the grandparents of Riyad and Ava.

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Brief Contents

List of Important Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxxi

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1 Structure Determines Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . 58
3 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers . . . . . . . . . . . . 102
4 Alcohols and Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5 Structure and Preparation of Alkenes: Elimination Reactions . . . . . . . . . . . . . . . . . . . 182
6 Addition Reactions of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
7 Stereochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
8 Nucleophilic Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
9 Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
10 Conjugation in Alkadienes and Allylic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
11 Arenes and Aromaticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
12 Reactions of Arenes: Electrophilic Aromatic Substitution . . . . . . . . . . . . . . . . . . . . . . 470
13 Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
14
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Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
15 Alcohols, Diols, and Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
16 Ethers, Epoxides, and Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
17 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group . . . . . . . . . . . . . . 700
18 Enols and Enolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 752
19 Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
20 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution . . . . . . . . . . . . . . . . . . . . . 825
21 Ester Enolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 880
22 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
23 Aryl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 964
24 Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 990
25 Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1022
26 Lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
27 Amino Acids, Peptides, and Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1106
28 Nucleosides, Nucleotides, and Nucleic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1162
29 Synthetic Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1200

Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G-1
Credits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C-1
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-1

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Contents

List of Important Features xix

Preface xxv
Acknowledgments xxxi

I N T R O D U C T I O N 2
The Origins of Organic Chemistry 2
Berzelius, Wöhler, and Vitalism 2
The Structural Theory 4
Electronic Theories of Structure and Reactivity 4
The Influence of Organic Chemistry 5
Computers and Organic Chemistry 5
Challenges and Opportunities 5
Where Did the Carbon Come From? 7

C H A P T E R 1
Structure Determines Properties 8
1.1 Atoms, Electrons, and Orbitals 9
1.2 Ionic Bonds 12
1.3 Covalent Bonds, Lewis Structures, and the Octet Rule 14
1.4 Double Bonds and Triple Bonds 16
1.5 Polar Covalent Bonds and Electronegativity 16
Electrostatic Potential Maps 19 Apago PDF Enhancer
1.6 Structural Formulas of Organic Molecules 19
1.7 Formal Charge 22
1.8 Resonance 24
1.9 The Shapes of Some Simple Molecules 29
Molecular Modeling 30
1.10 Molecular Dipole Moments 32
1.11 Curved Arrows and Chemical Reactions 33
1.12 Acids and Bases: The Arrhenius View 35
1.13 Acids and Bases: The Brønsted–Lowry View 36
1.14 What Happened to pKb? 40
1.15 How Structure Affects Acid Strength 41
1.16 Acid–Base Equilibria 45
1.17 Lewis Acids and Lewis Bases 48
1.18 Summary 49
Problems 52
Descriptive Passage and Interpretive Problems 1: Amide Lewis Structures 57

C H A P T E R 2
Alkanes and Cycloalkanes: Introduction to Hydrocarbons 58
2.1 Classes of Hydrocarbons 59
2.2 Electron Waves and Chemical Bonds 60
2.3 Bonding in H2: The Valence Bond Model 61
2.4 Bonding in H2: The Molecular Orbital Model 63
2.5 Introduction to Alkanes: Methane, Ethane, and Propane 64
Methane and the Biosphere 65
2.6 sp3 Hybridization and Bonding in Methane 66
2.7 Bonding in Ethane 68
2.8 Isomeric Alkanes: The Butanes 68
2.9 Higher n-Alkanes 68
2.10 The C5H12 Isomers 69
2.11 IUPAC Nomenclature of Unbranched Alkanes 71
What’s In a Name? Organic Nomenclature 72

vii
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viii CONTENTS

2.12 Applying the IUPAC Rules: The Names of the C6H14 Isomers 73
2.13 Alkyl Groups 74
2.14 IUPAC Names of Highly Branched Alkanes 76
2.15 Cycloalkane Nomenclature 77
2.16 Sources of Alkanes and Cycloalkanes 78
2.17 Physical Properties of Alkanes and Cycloalkanes 80
2.18 Chemical Properties: Combustion of Alkanes 82
2.19 Oxidation–Reduction in Organic Chemistry 85
Thermochemistry 86
2.20 sp2 Hybridization and Bonding in Ethylene 89
2.21 sp Hybridization and Bonding in Acetylene 91
2.22 Which Theory of Chemical Bonding Is Best? 92
2.23 Summary 93
Problems 97
Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes 100

C H A P T E R 3
Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 102
3.1 Conformational Analysis of Ethane 104
3.2 Conformational Analysis of Butane 107
Molecular Mechanics Applied to Alkanes and Cycloalkanes 109
3.3 Conformations of Higher Alkanes 110
3.4 The Shapes of Cycloalkanes: Planar or Nonplanar? 110
3.5 Small Rings: Cyclopropane and Cyclobutane 111
3.6 Cyclopentane 112
3.7 Conformations of Cyclohexane 112
3.8 Axial and Equatorial Bonds in Cyclohexane 113
3.9 Conformational Inversion (Ring Flipping) in Cyclohexane 115
3.10 Conformational Analysis of Monosubstituted Cyclohexanes 116
3.11 Disubstituted Cycloalkanes: cis–trans Stereoisomers 119
Enthalpy, Free Energy, and Equilibrium Constant 120
3.12
3.13
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Conformational Analysis of Disubstituted Cyclohexanes 121
Medium and Large Rings 125
3.14 Polycyclic Ring Systems 125
3.15 Heterocyclic Compounds 128
3.16 Summary 129
Problems 132
Descriptive Passage and Interpretive Problems 3: Cyclic Forms
of Carbohydrates 137

C H A P T E R 4
Alcohols and Alkyl Halides 138
4.1 Functional Groups 139
4.2 IUPAC Nomenclature of Alkyl Halides 141
4.3 IUPAC Nomenclature of Alcohols 142
4.4 Classes of Alcohols and Alkyl Halides 142
4.5 Bonding in Alcohols and Alkyl Halides 143
4.6 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces 144
4.7 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides 148
4.8 Mechanism of the Reaction of Alcohols with Hydrogen Halides 149
4.9 Potential Energy Diagrams for Multistep Reactions: The SN1 Mechanism 154
4.10 Structure, Bonding, and Stability of Carbocations 155
4.11 Effect of Alcohol Structure on Reaction Rate 158
4.12 Reaction of Methyl and Primary Alcohols with Hydrogen Halides:
The SN2 Mechanism 159
4.13 Other Methods for Converting Alcohols to Alkyl Halides 160
4.14 Halogenation of Alkanes 161
4.15 Chlorination of Methane 162
4.16 Structure and Stability of Free Radicals 162
4.17 Mechanism of Methane Chlorination 167
4.18 Halogenation of Higher Alkanes 168
From Bond Enthalpies to Heats of Reaction 169
4.19 Summary 173
Problems 176
Descriptive Passage and Interpretive Problems 4: More About Potential
Energy Diagrams 180
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CONTENTS ix

C H A P T E R 5
Structure and Preparation of Alkenes: Elimination Reactions 182
5.1 Alkene Nomenclature 183
5.2 Structure and Bonding in Alkenes 185
Ethylene 186
5.3 Isomerism in Alkenes 187
5.4 Naming Stereoisomeric Alkenes by the E–Z Notational System 188
5.5 Physical Properties of Alkenes 189
5.6 Relative Stabilities of Alkenes 191
5.7 Cycloalkenes 195
5.8 Preparation of Alkenes: Elimination Reactions 196
5.9 Dehydration of Alcohols 197
5.10 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule 198
5.11 Stereoselectivity in Alcohol Dehydration 199
5.12 The E1 and E2 Mechanisms of Alcohol Dehydration 200
5.13 Rearrangements in Alcohol Dehydration 202
5.14 Dehydrohalogenation of Alkyl Halides 205
5.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides 207
5.16 Anti Elimination in E2 Reactions: Stereoelectronic Effects 209
5.17 Isotope Effects and the E2 Mechanism 210
5.18 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides 211
5.19 Summary 213
Problems 217
Descriptive Passage and Interpretive Problems 5: A Mechanistic Preview of Addition Reactions 222

C H A P T E R 6
Addition Reactions of Alkenes 224
6.1 Hydrogenation of Alkenes 225
6.2 Heats of Hydrogenation 226
6.3 Stereochemistry of Alkene Hydrogenation 229
6.4 Electrophilic Addition of Hydrogen Halides to Alkenes 229
6.5 Apago PDF Enhancer
Regioselectivity of Hydrogen Halide Addition: Markovnikov’s Rule 231
6.6 Mechanistic Basis for Markovnikov’s Rule 233
Rules, Laws, Theories, and the Scientific Method 235
6.7 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes 235
6.8 Free-Radical Addition of Hydrogen Bromide to Alkenes 236
6.9 Addition of Sulfuric Acid to Alkenes 239
6.10 Acid-Catalyzed Hydration of Alkenes 241
6.11 Thermodynamics of Addition–Elimination Equilibria 243
6.12 Hydroboration–Oxidation of Alkenes 246
6.13 Stereochemistry of Hydroboration–Oxidation 248
6.14 Mechanism of Hydroboration–Oxidation 248
6.15 Addition of Halogens to Alkenes 251
6.16 Stereochemistry of Halogen Addition 251
6.17 Mechanism of Halogen Addition to Alkenes: Halonium Ions 252
6.18 Conversion of Alkenes to Vicinal Halohydrins 254
6.19 Epoxidation of Alkenes 255
6.20 Ozonolysis of Alkenes 257
6.21 Introduction to Organic Chemical Synthesis 259
6.22 Reactions of Alkenes with Alkenes: Polymerization 260
Ethylene and Propene: The Most Important Industrial Organic Chemicals 265
6.23 Summary 266
Problems 269
Descriptive Passage and Interpretive Problems 6: Some Unusual Electrophilic Additions 274

C H A P T E R 7
Stereochemistry 276
7.1 Molecular Chirality: Enantiomers 277
7.2 The Chirality Center 279
7.3 Symmetry in Achiral Structures 281
7.4 Optical Activity 282
7.5 Absolute and Relative Configuration 284
7.6 The Cahn–Ingold–Prelog R–S Notational System 285
7.7 Fischer Projections 288
7.8 Properties of Enantiomers 290
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x CONTENTS

Chiral Drugs 291

7.9 Reactions That Create a Chirality Center 292
7.10 Chiral Molecules with Two Chirality Centers 295
7.11 Achiral Molecules with Two Chirality Centers 297
7.12 Molecules with Multiple Chirality Centers 299
Chirality of Disubstituted Cyclohexanes 300
7.13 Reactions That Produce Diastereomers 301
7.14 Resolution of Enantiomers 303
7.15 Stereoregular Polymers 305
7.16 Chirality Centers Other Than Carbon 306
7.17 Summary 307
Problems 310
Descriptive Passage and Interpretive Problems 7: Prochirality 316

C H A P T E R 8
Nucleophilic Substitution 318
8.1 Functional Group Transformation by Nucleophilic Substitution 319
8.2 Relative Reactivity of Halide Leaving Groups 322
8.3 The SN2 Mechanism of Nucleophilic Substitution 323
8.4 Steric Effects and SN2 Reaction Rates 326
8.5 Nucleophiles and Nucleophilicity 328
8.6 The SN1 Mechanism of Nucleophilic Substitution 330
Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides 331
8.7 Carbocation Stability and SN1 Reaction Rates 331
8.8 Stereochemistry of SN1 Reactions 334
8.9 Carbocation Rearrangements in SN1 Reactions 335
8.10 Effect of Solvent on the Rate of Nucleophilic Substitution 337
8.11 Substitution and Elimination as Competing Reactions 339
8.12 Nucleophilic Substitution of Alkyl Sulfonates 342
8.13 Looking Back: Reactions of Alcohols with Hydrogen Halides 344
8.14 Summary 346
Problems 347
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Descriptive Passage and Interpretive Problems 8: Nucleophilic Substitution 352

C H A P T E R 9
Alkynes 354
9.1 Sources of Alkynes 355
9.2 Nomenclature 357
9.3 Physical Properties of Alkynes 357
9.4 Structure and Bonding in Alkynes: sp Hybridization 357
9.5 Acidity of Acetylene and Terminal Alkynes 360
9.6 Preparation of Alkynes by Alkyation of Acetylene and Terminal Alkynes 361
9.7 Preparation of Alkynes by Elimination Reactions 363
9.8 Reactions of Alkynes 364
9.9 Hydrogenation of Alkynes 365
9.10 Metal–Ammonia Reduction of Alkynes 367
9.11 Addition of Hydrogen Halides to Alkynes 368
9.12 Hydration of Alkynes 370
9.13 Addition of Halogens to Alkynes 371
Some Things That Can Be Made from Acetylene . . . But Aren’t 372
9.14 Ozonolysis of Alkynes 372
9.15 Summary 373
Problems 376
Descriptive Passage and Interpretive Problems 9: Thinking Mechanistically About Alkynes 380

C H A P T E R 10
Conjugation in Alkadienes and Allylic Systems 382
10.1 The Allyl Group 383
10.2 Allylic Carbocations 384
10.3 SN1 Reactions of Allylic Halides 385
10.4 SN2 Reactions of Allylic Halides 388
10.5 Allylic Free Radicals 389
10.6 Allylic Halogenation 390
10.7 Allylic Anions 393
10.8 Classes of Dienes 394
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CONTENTS xi

10.9 Relative Stabilities of Dienes 395

10.10 Bonding in Conjugated Dienes 396
10.11 Bonding in Allenes 398
10.12 Preparation of Dienes 399
10.13 Addition of Hydrogen Halides to Conjugated Dienes 400
10.14 Halogen Addition to Dienes 403
10.15 The Diels–Alder Reaction 403
Diene Polymers 404
10.16 The  Molecular Orbitals of Ethylene and 1,3-Butadiene 407
10.17 A  Molecular Orbital Analysis of the Diels–Alder Reaction 408
10.18 Summary 410
Problems 413
Descriptive Passage and Interpretive Problems 10: Intramolecular and Retro Diels–Alder Reactions 417

C H A P T E R 11
Arenes and Aromaticity 420
11.1 Benzene 421
11.2 Kekulé and the Structure of Benzene 422
11.3 A Resonance Picture of Bonding in Benzene 424
11.4 The Stability of Benzene 424
11.5 An Orbital Hybridization View of Bonding in Benzene 426
11.6 The  Molecular Orbitals of Benzene 427
11.7 Substituted Derivatives of Benzene and Their Nomenclature 428
11.8 Polycyclic Aromatic Hydrocarbons 430
11.9 Physical Properties of Arenes 431
Carbon Clusters, Fullerenes, and Nanotubes 432
11.10 Reactions of Arenes: A Preview 432
11.11 The Birch Reduction 433
11.12 Free-Radical Halogenation of Alkylbenzenes 436
11.13 Oxidation of Alkylbenzenes 438
11.14 SN1 Reactions of Benzylic Halides 440
11.15 SN2 Reactions of Benzylic Halides 441
11.16
11.17
Preparation of Alkenylbenzenes 442
Addition Reactions of Alkenylbenzenes 443
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11.18 Polymerization of Styrene 445
11.19 Cyclobutadiene and Cyclooctatetraene 446
11.20 Hückel’s Rule 448
11.21 Annulenes 450
11.22 Aromatic Ions 452
11.23 Heterocyclic Aromatic Compounds 455
11.24 Heterocyclic Aromatic Compounds and Hückel’s Rule 457
11.25 Summary 459
Problems 462
Descriptive Passage and Interpretive Problems 11: The Hammett Equation 466

C H A P T E R 12
Reactions of Arenes: Electrophilic Aromatic Substitution 470
12.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene 471
12.2 Mechanistic Principles of Electrophilic Aromatic Substitution 472
12.3 Nitration of Benzene 474
12.4 Sulfonation of Benzene 476
12.5 Halogenation of Benzene 477
12.6 Friedel–Crafts Alkylation of Benzene 478
12.7 Friedel–Crafts Acylation of Benzene 481
12.8 Synthesis of Alkylbenzenes by Acylation–Reduction 483
12.9 Rate and Regioselectivity in Electrophilic Aromatic Substitution 484
12.10 Rate and Regioselectivity in the Nitration of Toluene 485
12.11 Rate and Regioselectivity in the Nitration of (Trifluoromethyl)benzene 488
12.12 Substituent Effects in Electrophilic Aromatic Substitution: Activating Substituents 490
12.13 Substituent Effects in Electrophilic Aromatic Substitution: Strongly Deactivating Substituents 493
12.14 Substituent Effects in Electrophilic Aromatic Substitution: Halogens 496
12.15 Multiple Substituent Effects 498
12.16 Regioselective Synthesis of Disubstituted Aromatic Compounds 499
12.17 Substitution in Naphthalene 502
12.18 Substitution in Heterocyclic Aromatic Compounds 502
12.19 Summary 504
Problems 507
Descriptive Passage and Interpretive Problems 12: Nucleophilic Aromatic Substitution 512
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xii CONTENTS

C H A P T E R 13
Spectroscopy 516
13.1 Principles of Molecular Spectroscopy: Electromagnetic Radiation 518
13.2 Principles of Molecular Spectroscopy: Quantized Energy States 519
13.3 Introduction to 1H NMR Spectroscopy 519
13.4 Nuclear Shielding and 1H Chemical Shifts 521
13.5 Effects of Molecular Structure on 1H Chemical Shifts 524
Ring Currents: Aromatic and Antiaromatic 529
13.6 Interpreting 1H NMR Spectra 530
13.7 Spin–Spin Splitting in 1H NMR Spectroscopy 532
13.8 Splitting Patterns: The Ethyl Group 534
13.9 Splitting Patterns: The Isopropyl Group 536
13.10 Splitting Patterns: Pairs of Doublets 536
13.11 Complex Splitting Patterns 538
1
13.12 H NMR Spectra of Alcohols 539
Magnetic Resonance Imaging (MRI) 540
13.13 NMR and Conformations 540
13
13.14 C NMR Spectroscopy 541
13
13.15 C Chemical Shifts 543
13
13.16 C NMR and Peak Intensities 545
13
13.17 C—1H Coupling 546
13
13.18 Using DEPT to Count Hydrogens Attached to C 546
13.19 2D NMR: COSY and HETCOR 547
13.20 Introduction to Infrared Spectroscopy 550
Spectra by the Thousands 551
13.21 Infrared Spectra 552
13.22 Characteristic Absorption Frequencies 554
13.23 Ultraviolet-Visible (UV-VIS) Spectroscopy 557
13.24 Mass Spectrometry 559
13.25 Molecular Formula as a Clue to Structure 563
Gas Chromatography, GC/MS, and MS/MS 564
13.26 Summary 566
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Problems 569
Descriptive Passage and Interpretive Problems 13: Calculating Aromatic 13
C Chemical Shifts 575

C H A P T E R 14
Organometallic Compounds 578
14.1 Organometallic Nomenclature 580
14.2 Carbon–Metal Bonds in Organometallic Compounds 580
14.3 Preparation of Organolithium Compounds 581
14.4 Preparation of Organomagnesium Compounds: Grignard Reagents 583
14.5 Organolithium and Organomagnesium Compounds as Brønsted Bases 584
14.6 Synthesis of Alcohols Using Grignard Reagents 586
14.7 Synthesis of Alcohols Using Organolithium Reagents 588
14.8 Synthesis of Acetylenic Alcohols 588
14.9 Retrosynthetic Analysis 589
14.10 Preparation of Tertiary Alcohols from Esters and Grignard Reagents 592
14.11 Alkane Synthesis Using Organocopper Reagents 593
14.12 An Organozinc Reagent for Cyclopropane Synthesis 595
14.13 Carbenes and Carbenoids 596
14.14 Transition-Metal Organometallic Compounds 599
An Organometallic Compound That Occurs Naturally: Coenzyme B12 601
14.15 Homogeneous Catalytic Hydrogenation 602
14.16 Olefin Metathesis 605
14.17 Ziegler–Natta Catalysis of Alkene Polymerization 607
14.18 Summary 610
Problems 613
Descriptive Passage and Interpretive Problems 14: Oxymercuration 617

C H A P T E R 15
Alcohols, Diols, and Thiols 620
15.1 Sources of Alcohols 621
15.2 Preparation of Alcohols by Reduction of Aldehydes and Ketones 622
15.3 Preparation of Alcohols by Reduction of Carboxylic Acids and Esters 628
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CONTENTS xiii

15.4 Preparation of Alcohols from Epoxides 629

15.5 Preparation of Diols 630
15.6 Reactions of Alcohols: A Review and a Preview 632
15.7 Conversion of Alcohols to Ethers 632
15.8 Esterification 635
15.9 Esters of Inorganic Acids 637
15.10 Oxidation of Alcohols 638
15.11 Biological Oxidation of Alcohols 640
Economic and Environmental Factors in Organic Synthesis 641
15.12 Oxidative Cleavage of Vicinal Diols 643
15.13 Thiols 644
15.14 Spectroscopic Analysis of Alcohols and Thiols 647
15.15 Summary 648
Problems 652
Descriptive Passage and Interpretive Problems 15: The Pinacol Rearrangement 658

C H A P T E R 16
Ethers, Epoxides, and Sulfides 662
16.1 Nomenclature of Ethers, Epoxides, and Sulfides 663
16.2 Structure and Bonding in Ethers and Epoxides 664
16.3 Physical Properties of Ethers 665
16.4 Crown Ethers 667
16.5 Preparation of Ethers 668
Polyether Antibiotics 669
16.6 The Williamson Ether Synthesis 670
16.7 Reactions of Ethers: A Review and a Preview 671
16.8 Acid-Catalyzed Cleavage of Ethers 672
16.9 Preparation of Epoxides: A Review and a Preview 674
16.10 Conversion of Vicinal Halohydrins to Epoxides 675
16.11 Reactions of Epoxides: A Review and a Preview 676
16.12 Nucleophilic Ring Opening of Epoxides 677
16.13 Apago PDF Enhancer
Acid-Catalyzed Ring Opening of Epoxides 679
16.14 Epoxides in Biological Processes 682
16.15 Preparation of Sulfides 682
16.16 Oxidation of Sulfides: Sulfoxides and Sulfones 683
16.17 Alkylation of Sulfides: Sulfonium Salts 684
16.18 Spectroscopic Analysis of Ethers, Epoxides, and Sulfides 685
16.19 Summary 688
Problems 692
Descriptive Passage and Interpretive Problems 16: Epoxide Rearrangements and the NIH Shift 697

C H A P T E R 17
Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 700
17.1 Nomenclature 701
17.2 Structure and Bonding: The Carbonyl Group 704
17.3 Physical Properties 706
17.4 Sources of Aldehydes and Ketones 707
17.5 Reactions of Aldehydes and Ketones: A Review and a Preview 710
17.6 Principles of Nucleophilic Addition: Hydration of Aldehydes and Ketones 711
17.7 Cyanohydrin Formation 715
17.8 Acetal Formation 718
17.9 Acetals as Protecting Groups 721
17.10 Reaction with Primary Amines: Imines 722
Imines in Biological Chemistry 725
17.11 Reaction with Secondary Amines: Enamines 727
17.12 The Wittig Reaction 728
17.13 Planning an Alkene Synthesis via the Wittig Reaction 730
17.14 Stereoselective Addition to Carbonyl Groups 732
17.15 Oxidation of Aldehydes 733
17.16 Baeyer–Villiger Oxidation of Ketones 734
17.17 Spectroscopic Analysis of Aldehydes and Ketones 736
17.18 Summary 738
Problems 742
Descriptive Passage and Interpretive Problems 17: Alcohols, Aldehydes, and Carbohydrates 749
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xiv CONTENTS

C H A P T E R 18
Enols and Enolates 752
18.1 The  Hydrogen and Its pKa 753
18.2 The Aldol Condensation 757
18.3 Mixed Aldol Condensations 761
18.4 Alkylation of Enolate Ions 763
18.5 Enolization and Enol Content 764
18.6 Stabilized Enols 766
18.7  Halogenation of Aldehydes and Ketones 768
18.8 Mechanism of  Halogenation of Aldehydes and Ketones 768
18.9 The Haloform Reaction 770
18.10 Some Chemical and Stereochemical Consequences of Enolization 772
The Haloform Reaction and the Biosynthesis of Trihalomethanes 773
18.11 Effects of Conjugation in ,-Unsaturated Aldehydes and Ketones 774
18.12 Conjugate Addition to ,-Unsaturated Carbonyl Compounds 775
18.13 Addition of Carbanions to ,-Unsaturated Ketones: The Michael Reaction 778
18.14 Conjugate Addition of Organocopper Reagents to ,-Unsaturated Carbonyl Compounds 778
18.15 Summary 779
Problems 782
Descriptive Passage and Interpretive Problems 18: Enolate Regiochemistry and Stereochemistry 787

C H A P T E R 19
Carboxylic Acids 790
19.1 Carboxylic Acid Nomenclature 791
19.2 Structure and Bonding 793
19.3 Physical Properties 794
19.4 Acidity of Carboxylic Acids 794
19.5 Salts of Carboxylic Acids 797
19.6 Substituents and Acid Strength 799
19.7 Ionization of Substituted Benzoic Acids 801
19.8
19.9
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Dicarboxylic Acids 802
Carbonic Acid 802
19.10 Sources of Carboxylic Acids 803
19.11 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents 806
19.12 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles 806
19.13 Reactions of Carboxylic Acids: A Review and a Preview 807
19.14 Mechanism of Acid-Catalyzed Esterification 808
19.15 Intramolecular Ester Formation: Lactones 811
19.16  Halogenation of Carboxylic Acids: The Hell–Volhard–Zelinsky Reaction 813
19.17 Decarboxylation of Malonic Acid and Related Compounds 815
19.18 Spectroscopic Analysis of Carboxylic Acids 817
19.19 Summary 818
Problems 821
Descriptive Passage and Interpretive Problems 19: Lactonization Methods 825

C H A P T E R 20
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 825
20.1 Nomenclature of Carboxylic Acid Derivatives 830
20.2 Structure and Reactivity of Carboxylic Acid Derivatives 831
20.3 General Mechanism for Nucleophilic Acyl Substitution 834
20.4 Nucleophilic Acyl Substitution in Acyl Chlorides 836
20.5 Nucleophilic Acyl Substitution in Acid Anhydrides 839
20.6 Sources of Esters 842
20.7 Physical Properties of Esters 842
20.8 Reactions of Esters: A Review and a Preview 844
20.9 Acid-Catalyzed Ester Hydrolysis 844
20.10 Ester Hydrolysis in Base: Saponification 848
20.11 Reaction of Esters with Ammonia and Amines 851
20.12 Amides 852
20.13 Hydrolysis of Amides 857
20.14 Lactams 861
-Lactam Antibiotics 861
20.15 Preparation of Nitriles 862
20.16 Hydrolysis of Nitriles 863
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CONTENTS xv

20.17 Addition of Grignard Reagents to Nitriles 864

20.18 Spectroscopic Analysis of Carboxylic Acid Derivatives 866
20.19 Summary 867
Problems 870
Descriptive Passage and Interpretive Problems 20: Thioesters 876

C H A P T E R 21
Ester Enolates 880
21.1 Ester  Hydrogens and Their pKa’s 881
21.2 The Claisen Condensation 883
21.3 Intramolecular Claisen Condensation: The Dieckmann Cyclization 886
21.4 Mixed Claisen Condensations 886
21.5 Acylation of Ketones with Esters 887
21.6 Ketone Synthesis via -Keto Esters 888
21.7 The Acetoacetic Ester Synthesis 889
21.8 The Malonic Ester Synthesis 892
21.9 Michael Additions of Stabilized Anions 894
21.10 Reactions of LDA-Generated Ester Enolates 895
21.11 Summary 897
Problems 899
Descriptive Passage and Interpretive Problems 21: The Enolate Chemistry of Dianions 903

C H A P T E R 22
Amines 908
22.1 Amine Nomenclature 909
22.2 Structure and Bonding 911
22.3 Physical Properties 913
22.4 Basicity of Amines 914
Amines as Natural Products 919
22.5
22.6
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Tetraalkylammonium Salts as Phase-Transfer Catalysts 921
Reactions That Lead to Amines: A Review and a Preview 922
22.7 Preparation of Amines by Alkylation of Ammonia 923
22.8 The Gabriel Synthesis of Primary Alkylamines 924
22.9 Preparation of Amines by Reduction 926
22.10 Reductive Amination 928
22.11 Reactions of Amines: A Review and a Preview 929
22.12 Reaction of Amines with Alkyl Halides 931
22.13 The Hofmann Elimination 931
22.14 Electrophilic Aromatic Substitution in Arylamines 932
22.15 Nitrosation of Alkylamines 935
22.16 Nitrosation of Arylamines 937
22.17 Synthetic Transformations of Aryl Diazonium Salts 938
22.18 Azo Coupling 942
From Dyes to Sulfa Drugs 943
22.19 Spectroscopic Analysis of Amines 944
22.20 Summary 947
Problems 953
Descriptive Passage and Interpretive Problems 22: Synthetic Applications of Enamines 960

C H A P T E R 23
Aryl Halides 964
23.1 Bonding in Aryl Halides 965
23.2 Sources of Aryl Halides 966
23.3 Physical Properties of Aryl Halides 966
23.4 Reactions of Aryl Halides: A Review and a Preview 966
23.5 Nucleophilic Substitution in Nitro-Substituted Aryl Halides 968
23.6 The Addition–Elimination Mechanism of Nucleophilic Aromatic Substitution 971
23.7 Related Nucleophilic Aromatic Substitution Reactions 973
23.8 The Elimination–Addition Mechanism of Nucleophilic Aromatic Substitution: Benzyne 974
23.9 Diels–Alder Reactions of Benzyne 978
23.10 m-Benzyne and p-Benzyne 979
23.11 Summary 980
Problems 982
Descriptive Passage and Interpretive Problems 23: The Heck Reaction 986
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xvi CONTENTS

C H A P T E R 24
Phenols 990
24.1 Nomenclature 991
24.2 Structure and Bonding 992
24.3 Physical Properties 993
24.4 Acidity of Phenols 994
24.5 Substituent Effects on the Acidity of Phenols 995
24.6 Sources of Phenols 996
24.7 Naturally Occurring Phenols 998
24.8 Reactions of Phenols: Electrophilic Aromatic Substitution 999
24.9 Acylation of Phenols 1001
24.10 Carboxylation of Phenols: Aspirin and the Kolbe–Schmitt Reaction 1002
24.11 Preparation of Aryl Ethers 1004
Agent Orange and Dioxin 1005
24.12 Cleavage of Aryl Ethers by Hydrogen Halides 1006
24.13 Claisen Rearrangement of Allyl Aryl Ethers 1006
24.14 Oxidation of Phenols: Quinones 1007
24.15 Spectroscopic Analysis of Phenols 1009
24.16 Summary 1010
Problems 1013
Descriptive Passage and Interpretive Problems 24: Directed Metalation of Aryl Ethers 1018

C H A P T E R 25
Carbohydrates 1022
25.1 Classification of Carbohydrates 1023
25.2 Fischer Projections and D–L Notation 1024
25.3 The Aldotetroses 1025
25.4 Aldopentoses and Aldohexoses 1026
25.5 A Mnemonic for Carbohydrate Configurations 1028
25.6 Cyclic Forms of Carbohydrates: Furanose Forms 1029
25.7 Cyclic Forms of Carbohydrates: Pyranose Forms 1032
25.8
25.9
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Mutarotation and the Anomeric Effect 1035
Ketoses 1037
25.10 Deoxy Sugars 1038
25.11 Amino Sugars 1039
25.12 Branched-Chain Carbohydrates 1040
25.13 Glycosides 1040
25.14 Disaccharides 1042
25.15 Polysaccharides 1044
How Sweet It Is! 1045
25.16 Reactions of Carbohydrates 1047
25.17 Reduction of Monosaccharides 1047
25.18 Oxidation of Monosaccharides 1047
25.19 Cyanohydrin Formation and Chain Extension 1049
25.20 Epimerization, Isomerization, and Retro-Aldol Cleavage 1050
25.21 Acylation and Alkylation of Hydroxyl Groups 1052
25.22 Periodic Acid Oxidation 1053
25.23 Summary 1054
Problems 1057
Descriptive Passage and Interpretive Problems 25: Emil Fischer and the Structure of (+)-Glucose 1061

C H A P T E R 26
Lipids 1064
26.1 Acetyl Coenzyme A 1066
26.2 Fats, Oils, and Fatty Acids 1067
26.3 Fatty Acid Biosynthesis 1070
26.4 Phospholipids 1073
26.5 Waxes 1075
26.6 Prostaglandins 1076
Nonsteroidal Antiinflammatory Drugs (NSAIDs) and COX-2 Inhibitors 1078
26.7 Terpenes: The Isoprene Rule 1079
26.8 Isopentenyl Diphosphate: The Biological Isoprene Unit 1082
26.9 Carbon–Carbon Bond Formation in Terpene Biosynthesis 1082
26.10 The Pathway from Acetate to Isopentenyl Diphosphate 1086
26.11 Steroids: Cholesterol 1087
26.12 Vitamin D 1090
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CONTENTS xvii

Good Cholesterol? Bad Cholesterol? What’s the Difference? 1091

26.13 Bile Acids 1092
26.14 Corticosteroids 1092
26.15 Sex Hormones 1093
26.16 Carotenoids 1093
Anabolic Steroids 1094
Crocuses Make Saffron from Carotenes 1095
26.17 Summary 1096
Problems 1098
Descriptive Passage and Interpretive Problems 26: Polyketides 1101

C H A P T E R 27
Amino Acids, Peptides, and Proteins 1106
27.1 Classification of Amino Acids 1108
27.2 Stereochemistry of Amino Acids 1113
27.3 Acid–Base Behavior of Amino Acids 1114
27.4 Synthesis of Amino Acids 1117
Electrophoresis 1117
27.5 Reactions of Amino Acids 1119
27.6 Some Biochemical Reactions of Amino Acids 1120
27.7 Peptides 1127
27.8 Introduction to Peptide Structure Determination 1130
27.9 Amino Acid Analysis 1130
27.10 Partial Hydrolysis of Peptides 1131
27.11 End Group Analysis 1132
27.12 Insulin 1133
27.13 The Edman Degradation and Automated Sequencing of Peptides 1134
Peptide Mapping and MALDI Mass Spectrometry 1136
27.14 The Strategy of Peptide Synthesis 1137
27.15 Amino Group Protection 1138
27.16 Carboxyl Group Protection 1140
27.17
27.18
Peptide Bond Formation 1141 Apago PDF Enhancer
Solid-Phase Peptide Synthesis: The Merrifield Method 1143
27.19 Secondary Structures of Peptides and Proteins 1145
27.20 Tertiary Structure of Polypeptides and Proteins 1148
27.21 Coenzymes 1152
Oh NO! It’s Inorganic! 1153
27.22 Protein Quaternary Structure: Hemoglobin 1153
27.23 Summary 1154
Problems 1156
Descriptive Passage and Interpretive Problems 27: Amino Acids in Enantioselective Synthesis 1159

C H A P T E R 28
Nucleosides, Nucleotides, and Nucleic Acids 1162
28.1 Pyrimidines and Purines 1163
28.2 Nucleosides 1166
28.3 Nucleotides 1167
28.4 Bioenergetics 1170
28.5 ATP and Bioenergetics 1170
28.6 Phosphodiesters, Oligonucleotides, and Polynucleotides 1172
28.7 Nucleic Acids 1173
28.8 Secondary Structure of DNA: The Double Helix 1174
“It Has Not Escaped Our Notice . . .” 1175
28.9 Tertiary Structure of DNA: Supercoils 1177
28.10 Replication of DNA 1178
28.11 Ribonucleic Acids 1180
28.12 Protein Biosynthesis 1183
RNA World 1184
28.13 AIDS 1184
28.14 DNA Sequencing 1185
28.15 The Human Genome Project 1187
28.16 DNA Profiling and the Polymerase Chain Reaction 1188
28.17 Summary 1191
Problems 1194
Descriptive Passage and Interpretive Problems 28: Oligonucleotide Synthesis 1195
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xviii CONTENTS

C H A P T E R 29
Synthetic Polymers 1200
29.1 Some Background 1201
29.2 Polymer Nomenclature 1202
29.3 Classification of Polymers: Reaction Type 1203
29.4 Classification of Polymers: Chain Growth and Step Growth 1204
29.5 Classification of Polymers: Structure 1205
29.6 Classification of Polymers: Properties 1207
29.7 Addition Polymers: A Review and a Preview 1209
29.8 Chain Branching in Free-Radical Polymerization 1211
29.9 Anionic Polymerization: Living Polymers 1214
29.10 Cationic Polymerization 1216
29.11 Polyamides 1217
29.12 Polyesters 1218
29.13 Polycarbonates 1219
29.14 Polyurethanes 1220
29.15 Copolymers 1221
29.16 Summary 1223
Problems 1225
Descriptive Passage and Interpretive Problems 29: Chemical Modification of Polymers 1227

Glossary G-1
Credits C-1
Index I-1

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car47872_fm_i-xxxii 11/15/06 18:32 Page xix
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List of Important Features

Mechanisms 10.4 Orbital Interactions in the Diels–Alder Reaction 409

11.1 The Birch Reduction 435
4.1 Formation of tert-Butyl Chloride from tert-Butyl
Alcohol and Hydrogen Chloride 150 11.2 Free-Radical Polymerization of Styrene 445
4.2 Formation of 1-Bromoheptane from 1-Heptanol and 12.1 Nitration of Benzene 475
Hydrogen Bromide 160 12.2 Sulfonation of Benzene 477
4.3 Free-Radical Chlorination of Methane 167 12.3 Bromination of Benzene 478
5.1 The E1 Mechanism for Acid-Catalyzed Dehydration 12.4 Friedel–Crafts Alkylation 479
of tert-Butyl Alcohol 200
12.5 Friedel–Crafts Acylation 482
5.2 Carbocation Rearrangement in Dehydration of
3,3-Dimethyl-2-butanol 202 14.1 Formation of a Lithium Dialkylcuprate (Gilman
Reagent) 594
5.3 Hydride Shift in Dehydration of 1-Butanol 205
14.2 Similarities Between the Mechanisms of Reaction
5.4 E2 Elimination of an Alkyl Halide 209 of an Alkene with Iodomethylzinc Iodide and a
5.5 The E1 Mechanism for Dehydrohalogenation of Peroxy Acid 597
2-Bromo-2-methylbutane in Ethanol 212 14.3 Formation of Dibromocarbene from
6.1 Hydrogenation of Alkenes 227 Tribromomethane 597
6.2 Electrophilic Addition of a Hydrogen Halide to an 14.4 Homogeneous Hydrogenation of Propene in the
Alkene 231 Presence of Wilkinson’s Catalyst 603
6.3
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14.5 Olefin Cross-Metathesis 606
Free-Radical Addition of Hydrogen Bromide to
1-Butene 238 14.6 Polymerization of Ethylene in the Presence of a
6.4 Addition of Sulfuric Acid to Propene 240 Ziegler–Natta Catalyst 609
6.5 Acid-Catalyzed Hydration of 2-Methylpropene 242 15.1 Sodium Borohydride Reduction of an Aldehyde or
6.6 Hydroboration of 1-Methylcyclopentene 249 Ketone 627

6.7 Oxidation of an Organoborane 250 15.2 Acid-Catalyzed Formation of Diethyl Ether from
Ethyl Alcohol 634
6.8 Electrophilic Addition of Bromine to Ethylene 253
15.3 Chromic Acid Oxidation of 2-Propanol 640
6.9 Formation of a Bromohydrin 254
15.4 Oxidation of Ethanol by NAD 642
6.10 Epoxidation of an Alkene 257
16.1 Cleavage of Ethers by Hydrogen Halides 673
6.11 Acid-Catalyzed Dimerization of 2-Methylpropene 262
16.2 Nucleophilic Ring Opening of an Epoxide 679
6.12 Free-Radical Polymerization of Ethylene 263
16.3 Acid-Catalyzed Ring Opening of Ethylene
8.1 The SN2 Mechanism of Nucleophilic Oxide 680
Substitution 323
16.4 Nucleophilic Substitution of Adenosine
8.2 The SN1 Mechanism of Nucleophilic Triphosphate (ATP) by Methionine 685
Substitution 332
17.1 Hydration of an Aldehyde or Ketone in Basic
8.3 Carbocation Rearrangement in the SN1 Hydrolysis Solution 714
of 2-Bromo-3-methylbutane 336
17.2 Hydration of an Aldehyde or Ketone in Acid
9.1 Sodium–Ammonia Reduction of an Alkyne 367 Solution 715
9.2 Conversion of an Enol to a Ketone 370 17.3 Cyanohydrin Formation 716
10.1 Hydrolysis of an Allylic Halide 387 17.4 Acetal Formation from Benzaldehyde and
10.2 Allylic Chlorination of Propene 391 Ethanol 719
10.3 Addition of Hydrogen Chloride to 17.5 Imine Formation from Benzaldehyde and
1,3-Cyclopentadiene 401 Methylamine 723
xix
Another Random Scribd Document
with Unrelated Content
 382 AVIGATION cated outside the landing area but not
more than 1,000 ft. outside the boundary of the field. Transmitter B
is located farther from the field at a distance of a mile to a mile and
a half from A. If an airplane flies over B headed for A, continuing his
flight, without changing his heading, should bring the airplane
directly over the landing area. The transmission from A and B are on
different frequencies. The transmitters at A and B are not especially
powerful. It is sufficient if signals can be picked up at a distance of
25 miles. The antenna for this transmission is non-directional; that
is, the signals are broadcast with equal intensity in all directions. At
each station, A and J5, is also a marker beacon. This beacon uses a
low-power ultra-high-frequency transmitter, the wave length of the
oscillator being 4 meters. A very short horizontal doublet antenna is
used, located one-quarter wavelength above the ground. This form
of antenna is very directional. The antenna is placed so that it is in
line with the approach to the field, i.e., along the fine AB. Then the
radiation is a fan-shaped wave in a plane through A or through B
perpendicular to the line AB. The procedure for utilizing the above-
described equipment is as foUows. The pilot, by making use of radio
beacon, radio compass, or dead reckoning, arrives within receiving
distance of station A. He then tunes in on B with his radio compass,
and flies directly towards it, setting his directional gyro on his
heading. He is then flying directly away from the field. After passing
over B, the pilot makes a gradual flat turn of 180°, using his
directional gyro to tell him when he has exactly reversed his
heading. Altitude should be gradually lost so that the altitude is
approximately 700 ft. above the ground when the airplane passes
the outer station B. The exact time of passing B is told by the signal
denoting passing the standing wave of the marker beacon. The
receiver of the radio compass is then tuned on A and the airplane
headed in that direction. In this, the pilot is aided by his directional
gyro which he had previously set on the reverse heading. In
proceeding from B to A the throttle is set back approximately at
1,000 r.p.m. and the plane is put in a steady glide at an airspeed
about 30 per cent above stalling speed. If this procedure has been
followed the plane should arrive at station A at an altitude of 200 ft.,
and continuing the steady glide the plane should pass over all
obstacles and reach the landing area properly.
 RADIO LANDINGS 383 As soon as the wheels touch the
ground, the pilot cuts the throttle, permitting the plane to come to
rest. The pilot knows when he is passing over station A either by the
" zone of silence " or from the signal from the marker beacon
located at A. If his altitude at that time is less than 200 ft., the pilot
merely opens the engine, putting the airplane in level flight for a
brief interval of time, and then permits the plane to settle into its
glide again. If the plane is higher than 200 ft. in passing over A, the
pilot may either momentarily glide more steeply before resuming his
normal glide or he may return to B and start his glide again at a
slightly steeper angle. The altitudes mentioned in this paragraph are
read from a sensitive altimeter set at correct ground barometer
reading from information radioed up to the pilot by the ground
operator. This method of landing without seeing the ground has
been tested by many hundred landings either in hooded cockpits or
in actual fog. No accidents have ever been reported in using this
method.
 CHAPTER XXI AEROSTATICS Introduction. Aerodynamics
treats of air in motion; aerostatics deals with air at rest. In aviation,
aerostatics deals with the problems of lighter-than-air craft. All
lighter-than-air craft are balloons, but present-day usage is to
employ the term balloon only for craft which has no motive power
and the term dirigible balloon or simply dirigible for a balloon
supphed with motive power. The term airship is synonymous with
dirigible; an airplane should not be called an airship. Balloons are
classified in two types, captive and free balloons. Captive balloons
are moored to the ground and are used for observing artillery fire,
etc. Captive balloons, if spherical in shape, have a strong tendency
to rotate, so that they are usually elongated in shape with
protuberances so designed that the balloon lies in the direction of
the wind. This shape is called a kiteballoon. Free balloons are usually
the so-called spherical shape. The upper part is a true hemisphere;
the lower half is hemispherical except that at the extreme lower part
the skin cones down to a long narrow tube called the appendix. In
the earlier forms a rope netting was arranged over the upper half of
the bag, the ends coming down just below the appendix where they
were fastened to a metal concentration-ring from which the basket
for passengers was hung. Because of the weight of the rope and the
criss-cross of the netting forming many tiny pockets to retain
rainwater, the netting arrangement was discarded for the suspension
band or " bellyband," a strip of fabric around the equator of the bag,
ropes from the concentration-ring being attached to this band. The
most modern method is to fasten each rope from the concentration-
ring to a piece of fabric, called a finger-patch, cemented to the bag
at the point where the curve of the suspension rope is just tangent
to the sphere of the envelope. A valve, normally held shut by
springs, is opened by pulling the 384
 INTRODUCTION 385 valve-rope which hangs down inside
the bag, coming through the appendix, the lower end being at the
basket. Dirigibles are classified according to their method of
construction as rigid, semi-rigid, and non-rigid. The rigid ones are
freValve ■Valve Netting Envelope Appendix Concentration Ring
Basket Free Balloon with Netting Suspension
 386 AEROSTATICS care of the transverse loads, the gas
being in a single large envelope. The non-rigid is a single rubberized-
cloth gas-tight bag containing the gas. Since, in non-rigid and semi-
rigid types, the pressure of the gas inside the bag is relied upon to
give the bag its shape, both these types are termed pressure
airships. Gases. Hot-air, coal-gas, hydrogen, and helium are the
principal gases used for lighter-than-air work. Heated aif is used
sometimes for parachute jumps at carnivals; as soon as the air cools
lift is lost. Coal-gas or ordinary illuminating gas is used sometimes
for free balloons, the hydrogen contained in these gases being
chiefly responsible for the lifting power. Hydrogen has been used for
more than a century and is best from the point of lift but has the
disadvantage that, if it mixes with air, it is highly inflammable and
explosive. Helium though furnishing less lift than hydrogen is
perfectly inert so that in its use there is not the fire hazard always
present with hydrogen. Previous to 1915, helium cost approximately
$2,000 per cubic foot. During the war the cost to the United States
government was reduced to $400 per 1,000 cu. ft. At present, owing
to improvements in the method of extraction from natural gas, the
cost is about $10 per 1,000 cu. ft. The cost of hydrogen is about $5
per l,000;'cu. ft. Under standard conditions of 59° F. temperature
and 29.92 in. of mercury pressure, the weight per cubic foot of the
gases important in aerostatics is as follows Air 0.07651 lb. 0^ ^
Hydrogen 0.00532 lb. \(S^ Helium 0.01056 lb. \o^ Average
illuminating gas 0.0323 lb. Laws of Aerostatics. Six physical laws find
application in aerostatic work. Full explanations are given in any
standard textbook on physics. Briefly these laws are as follows.
Archimedes' law: the buoyant or upward force exerted upon a body
immersed in a fluid is equal to the weight of the fluid displaced.
Boyle's law: at a constant temperature, the volume of a gas varies
inversely as the pressure. Charles' law : at a constant pressure, the
volume of a gas varies directly as the absolute temperature.
 LIFT 387 Dalton's law: the pressure of a mixture of several
gases in a given space is equal to the sum of the pressures which
each gas would exert by itself if confined in that space. Joule's law:
gases in expanding do no interior work. Pascal's law: the fluid
pressure due to external pressure on the walls of the containing
vessel is the same at all points throughout the fluid. Lift. A body
completely immersed in a fluid displaces its own volume of fluid. If
the weight of the fluid displaced equals the weight of the body, the
body is in equihbrium. If the weight of the fluid displaced is greater
than the weight of the body, the body rises. If the weight of the fluid
displaced is less than the weight of the body, the body falls. The
operation of a balloon and a submarine is somewhat similar in that
both are entirely submerged in a fluid. The submarine is entirely
sealed when under water, and the skin must be of sufficient strength
to withstand stresses due to difference in pressure between inside
and outside the hull. Balloons either are open to the air or have
other arrangements so that there will be little or no pressure
difference. Lift is obtained directly from Archimedes' principle. Unit
lift is the difference between the weight of a cubic foot of air and the
weight of a cubic foot of the gas. The gross lift or buoyancy of a
balloon or airship is expressed by the following equation: L = V{Ba -
A) L = gross Hft in pounds V = volume of gas in cubic feet Da =
weight of a cubic foot of air Dg = weight of a cubic foot of gas The
net lift or useful load is the difference between the gross lift and the
dead weight of the bag, ropes, basket, etc. From the laws of Boyle
and Charles, volume varies inversely as pressure and directly as
absolute temperature. If Pq is the standard pressure. To the
standard temperature, and Vo the standard volume, then Ti, the
volume when the pressure is Pi and the absolute temperature is Ti,
may be found by the following,
 388 AEROSTATICS The foregoing is true only if the gas is in
a perfectly elastic container. Example. A cloth bag contains 1,000
cubic feet of air, the temperature being 59° F. and the pressure
29.92 in. What is the volume if the pressure is increased to 40.0 in.
and the temperature decreased to 0°F.? Solution. i 0 -r 1 , ^^^460
29.92 = 1'^00 519X40:0 = 663 cu. ft. In practice the balloon bag is
made of rubberized cloth. If there is not sufficient volume of gas to
fill the bag, the cloth sides will fold in and the bag will be flabby.
When the volume of the gas is just equal to the cubical content the
bag will be fully inflated. Any further increase in volume of the gas
means that gas will escape through the appendix. If the appendix is
closed, a decrease in the air pressure outside or an increase of
temperature of the gas inside will cause the bag to burst. For this
reason, though the appendix is usually tied shut while the balloon is
being handled on the ground, the tie-off is broken as soon as the
balloon leaves the ground. Density varies inversely as volume, so
that if Do is the density under normal pressure Po and normal
absolute temperature To, the density Di under pressure Pi and
temperature Ti is found by the following relation : Di^To Pi Do Ti ^
Po Under normal conditions, the temperature of the gas inside the
envelope is the same as the temperature of the adjacent air. The
open appendix ensures that the pressure of the gas and air are the
same. Considering the pressure of the gas the same as the pressure
of the surrounding air and the temperature of the gas the same as
that of the air, the expression for lift under other than standard
conditions becomes
 ASCENSION OF A FREE BALLOON 389 L = gross lift in
pounds V = volume of bag in cubic feet ■Dflo = weight of a cubic
foot of air under standard con/ T P T P\ ditions L = V[Dao^^ - D,, ^
^ D,o = weight of a cubic foot of \ i 1 /^o J^i ^0/ gas under
standard con= V(B — n ^ — — ditions y yi^a, ^go) rp^ p^ p^ ^
Standard pressure Pi = actual pressure Tq = standard absolute
temperature Ti = actual absolute temperature Example. A 10,000-
cu.-ft. free balloon is filled with pure hydrogen. Air and gas are at a
temperature of 32° F. and a pressure of 28 in. What is the lift?
Solution. Lift = V{Dao- Dgo)~X^ = 10,000 (0.07651 - 0.00532) ^ X
2II2 = 703 lb. Problems 1. A 30,000-cu.-ft. free balloon is full of
pure hydrogen; air and gas are at a temperature of 80° F. and a
pressure of 26.3 in. What is the lift? 2. A 10,000-cu.-ft. free balloon
is full of pure helium; air and gas are at a temperature of 75° F. and
a pressure of 27.5 in. What is the lift? 3. A 20,000-cu.-ft. free balloon
is full of pure hydrogen; air and gas are at a temperature of —10° F.
and a pressure of 21.3 in. What is the lift? 4. A 20,000-cu.-ft. free
balloon is full of pure helium; air and gas are at a temperature of —
10° F. and a pressure of 21.3 in. What is the lift? 5. A 30,000-cu.-ft.
free balloon is full of pure hydrogen; air and gas are at a
temperature of 20° F. and a pressure of 23.7 in. What is the lift?
Ascension of a Free Balloon. When a free balloon, full of gas on the
ground, has lift greater than its weight, it rises, and because the
atmospheric pressure decreases with altitude, gas will expand and
tend to occupy greater volume. Since the fabric does not stretch, the
volume is fixed and gas is forced out of the
 390 AEROSTATICS appendix. As the altitude increases, the
density of the air decreases; but the density of the hfting gas
decreases at the same rate, so that the difference between the two
weight densities, which is the unit Hft, also decreases at the same
rate. The gross lift which is the constant volume multipHed by the
unit lift decreases. Ascension will continue until the gross lift just
equals the weight. If the bag is only partially inflated at the ground,
on rising, the atmospheric pressure being less, the gas will expand,
rounding out the bag more fully. There will be no loss of gas till the
bag is fully rounded out. The altitude where the bag is completely
full and where any further increase in altitude will cause gas to
escape is called the pressure height. A free balloon which is fully
inflated at the ground will start to lose lift immediately on leaving
the ground and there will be a continuous loss of lift as the balloon
rises. A free balloon which is partially inflated at the ground will have
a constant Hft until the pressure height is reached; above that
altitude, Hft will decrease with altitude. While inflating a balloon,
sufficient sandbags are placed in the basket or hung on the netting
to ensure that the balloon will not leave the ground. When ready to
start, the balloon is weighed-o£f. This process is the removing of
ballast until the total weight of the balloon just equals the total lift.
In this condition, a man standing on the ground can with practically
no exertion move the balloon up in the air a foot or so, where it will
stay in equihbrium. Adding a fraction of an ounce of sand will make
the balloon sink slowly to the ground. Tossing overboard a little
ballast will cause the balloon to rise slowly; heaving over a lot of
sand will cause the bag to rise swiftly. If the bag is fuUy inflated at
the ground, after weighing-off, weight equals Hft. If ballast is then
jettisoned, the weight is lessened. The balloon will rise. As it rises,
gas will escape, so that the Hft will decrease. At the start, the
accelerating force will be equal to the difference between the weight
and the lift; i.e., the force in pounds will equal the pounds of sand
put over. In ascending, since the difference between the weight of
the balloon and the lift will be less owing to the decreasing lift, the
upward accelerating force diminishes. At the height where the Hft
has decreased till it equals the weight, there will be no unbalanced
 ASCENSION OF A FREE BALLOON 391 upward accelerating
force and the balloon will be in equilibrium. To ascend further, more
ballast must be put overboard. The ascent to a high altitude can be
made by easy stages, by first dropping a little ballast, then a little
more, and a little more till the desired height is reached. A bag,
which is only partially inflated at the ground is weighedoff in the
same manner as a fully inflated bag. When a little ballast is dropped,
however, the balloon will immediately rise to its pressure height, the
upward accelerating force being constant to that altitude. On
reaching the pressure height gas will begin to escape, and with
decreasing lift, the difference between lift and weight will get
smaller, till equilibrium is reached. A partially inflated balloon will be
at pressure height when its volume has increased to equal the
capacity of the balloon. As the volume of a gas varies inversely with
density, the reciprocal of the ratio of the new volume to the old is
the ratio of new density to the old. Using Table I, interpolating if
necessary, the altitude may be found corresponding to this density.
If it is desired to ascend to some predetermined moderately high
altitude, there is no special merit in fully inflating the bag for gas will
start to escape immediately as the balloon rises. A partially inflated
balloon on reaching its pressure height is exactly in the same
condition as if it had been fully inflated on the ground. It should be
noticed that there is a difference in maneuvering. On the ground,
the fully inflated bag has more lift so that more ballast can be
carried. In ascending with the full bag, ballast is gradually dropped
so that, when the altitude is reached corresponding to the pressure
height of a partially inflated bag, the amount of ballast remaining in
each case would be the same. The bag which was fully inflated on
the ground can be brought up to any desired altitude slowly. A bag
only partially inflated on the ground will have a constant upward
accelerating force; therefore there will be a constantly increasing
upward velocity. Arriving at the pressure height, the balloon will have
considerable upward momentum, the product of its mass times its
velocity, and this momentum will tend to carry the balloon on
upward beyond its equilibrium point. At the equilibrium point, the lift
equals the weight. If momentum carries the balloon above its
pressure height, the gas having already expanded to fill the bag, gas
will be forced out and lift will decrease. Lift being less than
 392 AEROSTATICS the weight, there is a downward
accelerating force which acts first to decelerate the upward velocity,
and, when this has been reduced to zero, the downward force will
cause a downward velocity with ever-increasing speed. A skilful pilot
will time his actions so that, just when the balloon has reached its
highest point and is about to start on its downward plunge, just
enough ballast is thrown over so that the weight remaining equals
the then-existing lift. Example. A 10,000-cu.-ft. free balloon is
inflated with 8,000 cu. ft. of pure hydrogen at the ground,
temperature 59° F., pressure 29.92 in. What is lift at 5,000-ft.
altitude (temperature 45° F., pressure 24.8 in.)? At 10,000-ft.
altitude (temperature 15° F., pressure 21.1 in.)? What is the pressure
height? Solution. At ground L = 8,000 (0.07651 - 0.00532) = 570 lb.
Y At 5,000-ft. altitude: To determine if bag is full _8 000??^'x^
-8,U0U 24.8,^519 = 9,391 cu. ft. (volume at 5,000-ft. alt.) L =
9,391 (0.07651 - 0.00532) ^ X ^q^ = 570 lb. At 10,000-ft. altitude:
To determine if bag is full o r.r.^ 475 29.92 = 8,000X5^9X20=
10,951 cu. ft. = volume of original gas at 10,000-ft. altitude; i.e.,
951 cu. ft. has escaped. 519 21 1 ■ L = 10,000 (0.07651 - 0.00532)
^ X ^g^ - 549 lb. To find pressure height: Pi _ 8,000 Po ~ 10,000 =
0.8 From Table I by interpolation Pi/Po is 0.8 at 7,075-ft. altitude.
 DESCENT OF A FREE BALLOON 393 Problems (See Table I
for pressures and temperatures at altitude.) 1. A 10,000-cu.-ft. free
balloon is inflated at the ground with 7,000 cu. ft. of pure hydrogen
under standard atmospheric conditions. (a) What is the lift at the
ground? (6) What is the lift at 5,000-ft. altitude? 2. A 25,000-cu.-ft.
free balloon is inflated at the ground with 15,000 cu. ft. of pure
helium under standard atmospheric conditions. (a) What is the lift at
the ground? (6) What is the lift at 5,000-ft. altitude? (c) What is the
lift at 10,000-ft. altitude? 3. The total weight of a 20,000-cu.-ft.
balloon, including bag, basket, crew, instruments, and 300 lb.
ballast, but less gas, is 1,450 lb. The bag is filled with pure hydrogen
on a day when the temperature is 65° F. and the barometer is 29.6
in. (a) How much ballast must be dropped off in weighing-off, i.e.,
having weight just equal lift at the ground? (6) How much more
ballast must be dropped in order for the bag to be in equilibrium at
5,000-ft. altitude? 4. The balloon described in problem 3 is inflated
with only 18,000 cu. ft. of hydrogen under the same atmospheric
conditions as in 3. (a) How much ballast must be dropped in
weighing-off? (b) What is the pressure height? (c) How much more
ballast must be dropped in order to be in equilibrium at 5,000-ft.
altitude? Descent of a Free Balloon. In descending, the atmospheric
pressure increases. Any gas that has escaped from the appendix or
that has been valved is gone. When the balloon is in equilibrium, if
gas is valved, the lift becomes less than the weight, so that balloon
starts downward under an accelerating force which is the excess of
the weight over the lift. The effect of the increase in atmospheric
pressure while descending will be to decrease the volume of the gas
in the bag. The same weight of gas as at the beginning of the
descent will displace less and less volume of air, but the density of
the gas and air will increase as the volume decreases. The lift will
remain the same all the way down, and there will therefore be a
constant accelerating force downward which will cause ever-
increasing downward velocity. The only way to check descent will be
to introduce a decelerating force, that is, an upward force. This can
be accomplished only by making the weight less than lift, which is
done by dropping ballast. The upward excess of lift will decrease the
downward speed to zero and then cause an upward acceleration.
 394 AEROSTATICS If it is desired to descend to a definite
altitude and remain there in equilibrium, the pilot, after valving a
shght amount of gas to start descent, must drop ballast as he nears
the desired altitude. At the instant that his downward progress is
checked completely and before he starts to rise again, he must valve
just enough gas to gain equihbrium. The faster the balloon is
descending, the greater is the amount of ballast needed to check the
speed. A good pilot valves only a Uttle gas at a time, so that only a
little ballast must be sacrificed in maneuvering. In landing, the pilot
comes down towards the ground, and at the proper height, which he
has learned by experience, the pilot tosses over ballast so that his
downward speed is zero when he is just a few feet off the ground.
At that instant, he is pulling the ripcord, which entirely opens one
seam of the bag, completely emptying it of gas. Example. A 10,000-
cu.-ft. bag is full of hydrogen at 12,000-ft. altitude (temperature
16.2° F., pressure 19.03 in.) and is in equilibrium, (a) What is the
total weight of the bag including ballast? (6) If 100 *cu. ft. of gas is
valved, what is the loss of lift at this altitude? (c) At 7,000-ft.
altitude, what is the volume of the gas in the bag? (d) What is lift at
7,000-ft. altitude? (e) What ballast must be dropped at 7,000-ft.
altitude to secure equilibrium? Solviion. (a) Li2,ooo = 10,000
(0.07651 - 0.00532) ^^ X |^ = 494 lb. (6) L = 100 (0.07651 -
0.00532) ^^ X ^ = 5 1b. 19 03 494 (c) 77,000 = 9,900 X 23^0^ X
^ = 8,468 cu. ft. 23 09 519 ■ (d) L7,ooo = 8468 (0.07651 -
0.00532) ^^ X ^ = 489 lb. (e) Ballast to be dropped W — Ly.ooo =
5 Problems 1. A 30,000-cu.-ft. balloon is only partially inflated with
20,000 cu. ft. of pure hydrogen under standard atmospheric
conditions at the
 SUPERHEAT 395 ground, (a) What is the lift at the ground?
(b) What is the lift at 15,000-ft. altitude? (c) If balloon is in
equilibrium at 15,000-ft. altitude, what is excess weight after 150 cu.
ft. of gas are valved? (d) What is volume of bag after descending to
10,000-ft. altitude? (e) What is lift at 10,000-ft. altitude? 2. A
20,000-cu.-ft. balloon is filled with pure helium at the ground under
standard atmospheric conditions, (a) What is the lift at the ground?
(b) What weight of ballast must be tossed over to rise to 5,000-ft.
altitude; (c) to 10,000-ft. altitude? (d) If 200 cu. ft. of helium are
valved at 10,000-ft. altitude, what is the remaining lift? (e) When
balloon has descended to 5,000-ft. altitude, 200 cu. ft. additional of
helium are valved; what is the remaining lift? Superheat. The sun's
radiation consists not only of the long heat waves but also of the
shorter light and electric waves. It is the heat radiation that warms
the earth and to a smaller extent the atmosphere. Light radiation
may change into heat radiation in passing through surfaces. This
effect may be noticed in a tent which has the flaps down; the
confined air is at a higher temperature than the outside air because
the light in passing through the tent fabric is changed to heat. In
greenhouses there is no ventilation, and the air inside is hotter than
outside, as the result of light changing to heat in passing through
the glass. Naturally the foregoing is true only on sunny days. In free
balloons, the sun shining on the bag heats up the gas inside the bag
to a higher temperature than the surrounding air. This is called
superheat. Free balloons are suspended in air. If the air is moving,
the balloon travels with it. Air does not travel past the balloon; the
only heat lost is by direct conduction to the surrounding air. Kite
balloons are moored to the ground for observational purposes. In
perfectly still air, the same conditions apply as in a free balloon. If
any breeze is blowing, the air passing the balloon takes up heat, so
that any superheat is quickly lost, the temperature of the gas being
reduced to that of the surrounding air. Dirigibles in motion are
forcing their way through air, and this air acts to cool off any
superheat. Superheat give additional lift to a balloon. It is a false,
treacherous lift, since if the sun goes behind a cloud or the sun sets,
the additional lift is quickly lost.
 396 AEROSTATICS Black surfaces absorb heat and light;
shiny surfaces reflect heat and light. Balloons whose envelopes are
of dark material have been found to have in the center of the bag a
temperature 70° hotter than the outer air. With lighter-colored
surface the superheat will be less. The increase in temperature due
to superheat will cause the gas to expand. Below the pressure
height, this will increase the fullness of the bag; for a fully inflated
bag, superheat will force out gas; in either case, lift is increased. If a
balloon or airship is brought out of a hangar, the gas is presumably
at the same pressure and temperature as the atmosphere. If the
balloon is weighed-off immediately, the unit lift is due to the
difference in weight density of the air and gas at the same
temperature. Should the balloon stay on the ground with the sun
shining brightly, the gas will receive superheat and will expand. The
additional lift involves adding ballast to prevent the balloon or airship
from rising. The weight of ballast that must be added exactly
represents the additional lift due to superheat. When rising, the
balloon moves upward through the air, and this air passing the
envelope tends to cool it slightly. The additional Hft can be
calculated if the number of degrees of superheat is known. If the
balloon is initially inflated, the increased temperature will cause
expansion, reducing the density, the volume being the same. If the
balloon is only partially inflated, the expansion of the gas will cause
a greater displacement of the bag until the bag is fully inflated.
Further expansion will cause gas to escape. For the partially inflated
bag, gas expanding but not escaping will not change the weight of
the gas contained in the envelope; more air will be displaced,
however, so that the lift will be increased. It will be noted that, when
a fully inflated bag is superheated, the increase in lift is exactly equal
to the weight of the gas forced out of the bag by the expansion. The
finding of the increased lift from superheat is illustrated by the
following two examples. Example. An 8,000-cu-ft. balloon is fully
inflated with pure hydrogen under standard conditions. What is the
additional lift due to superheat of 40°?
 SUPERHEAT ' 397 Solution. Lift without superheat = 8,000
(0.07651 - 0.00532) = 569.5 lb. Weight of displaced air= 8,000 X
0.07651 = 612.1 lb. ^ 519 Weight of superheated gas = 8,000 X
0.00532 X ^ = 39.5 lb. Lift with superheat = 612.1 - 39.5 = 572.6
lb. Gain = 572.6 - 569.5 = 3.1 lb. Check. 559 Volume of superheated
gas = 8,000 X kTq = 8,616 cu. ft. Volume of escaping gas = 8,616
— 8,000 = 616 cu. ft. 519 Weight of escaping gas = 616 X 0.00532
X ^ = 3.1 lb. Example. A 10,000-cu.-ft. balloon is inflated with 8,000
cu. ft. of pure hydrogen under standard conditions. What is the
additional lift due to superheat of 40°? Solution, Lift without
superheat = 8,000 (0.07651 - 0.00532) = 569.5 lb. 559 Volume of
superheated gas = 8,000 X cTq = 8,616 cu. ft. Weight of displaced
air = 8,616 X 0.07651 = 659.2 lb. Weight of superheated gas =
8,000 X 0.00532 = 42.6 lb. Lift with superheat = 659.2 - 42.6 =
616.6 lb. Gain=47.11b. Problems 1. A 10,000-cu-ft. hydrogen-filled
balloon is brought out of the hangar. Both air and hydrogen are at
29.9 in. pressure and 45° F. temperature, (a) What is the lift? (b)
Owing to sun's rays, the hydrogen experiences 30° superheat; what
is then the lift?
 398 ' AEROSTATICS 2. On a cold day a 25,000-cu.-ft.
balloon is filled with pure hydrogen. Air and gas are at 30.1 in.
pressure and 18° F. temperature, (a) What is the lift? (6) If the
hydrogen is superheated 45° F., what is the lift? 3. A 10,000-cu.-ft.
balloon contains 7,000 cu. ft. of pure hydrogen. Air and gas are at
29.9 in. pressure and 70° F. temperature, (a) What is lift? (6) What
is lift if the hydrogen is superheated 35° F.? 4. A 10,000-cu.-ft.
balloon contains 9,000 cu. ft. of pure helium. Air and gas are at 29.9
in. pressure and 32° F. temperature, (a) What is lift? (b) What is the
lift if the helium is superheated 50° F.? 5. A 10,000-cu.-ft. balloon is
full of hydrogen at 75° F. temperature. Atmospheric pressure is 29.9
in. and atmospheric temperature is 40° F. (a) What is lift? (6) What
is the lift if the sun goes behind clouds and the gas loses all its
superheat? Purity. Any gas which remains inside a balloon for any
length of time contains impurities owing to air seeping in through
the appendix and mixing with the gas and to other causes. Although
the impurities may be dry air, water vapor, carbon dioxide, or other
substances, only a slight error is involved if all impurities are
considered as being dry air. The purity of a gas is defined as the
ratio of the volume of pure gas in the mixture to the total volume of
impure gas. Considering all impurities as being dry air, they merely
support themselves and furnish no lift. The impurities merely
subtract from the total volume of lifting gas. A volume of gas of x
per cent purity is x per cent of the volume of pure gas, giving lift,
and (100 — x) per cent of the volume of dry air giving no lift.
Example. A 10,000-cu.-ft. balloon is inflated with hydrogen of 95 per
cent purity under standard conditions. What is the lift? Solution. Gas
is 95 per cent pure hydrogen 5 per cent dry air Lift = 0.95 X 10,000
X (0.07651 - 0.00532) = 676.3 lb. Check. Weightof 9,500 cu. ft. of
pure hydrogen = 9,500 X 0.00532 = 50.5 lb. Weight of 500 cu. ft. of
dry air = 500 X 0.07651 = 38.3 lb. Weight of 10,000 cu. ft. of
impure gas = 88.8 lb. Weight of 10,000 cu. ft. of displaced air =
10,000 X 0.07651 = 765.1 lb. Difference in weight of displaced air
and gas = 676.3 lb.
 NON-RIGID AIRSHIP 399 Non-Rigid Airship. A non-rigid
airship is propelled through the air by one or more engines. To
reduce the drag resistance of this motion, the gas bag is made of
streamline shape. The rubberized cloth is tailored to the correct
shape, and the pressure inside the bag is relied upon to fill out the
bag properly. Use is made of two or more ballonets to preserve the
shape of the bag. Without ballonets, a non-rigid airship, which might
have been fully inflated on the ground, on ascending would need to
have gas valved to prevent bursting, on descending would be flabby.
In free balloons there is no special objection to flabbiness; but in
dirigibles, flabbiness will destroy the streamline contour of the
envelope. Partial inflation means that the nose will be cupped or
dished in, increasing the drag enormously. A ballonet is a bag or
compartment in the main gas bag that is formed by a diaphragm
made of the same kind of gas-tight rubberized cloth as the outer
skin. The ballonet compartment is to hold air, and it has a valve
opening to the atmosphere. The main gas bag is sealed to the outer
air except for a gas valve used only in emergency. During inflation
the ballonet is filled with air while the main bag is being filled with
gas. On rising, the expansion of the gas causes the flexible wall of
the ballonet chamber to collapse, expelling air. When the ballonet
wall has entirely flattened out against the skin of the envelope so
that all the air has been expelled, the non-rigid airship is at its
pressure height. On descending, air is introduced into the ballonet,
thus maintaining the rigidity of shape of the main envelope. To force
air into the ballonet a scoop hangs down from the ballonet with its
open end in the slipstream of the propeller. Sometimes a small
auxiliary blower is used to pump air into the ballonet. If the non-
rigid airship ever ascends above its pressure height, gas win have to
be valved, and on descending, even with full ballonets, the main
envelope will still be flabby. For this reason great care needs to be
exercised that pressure airships do not rise to too great altitudes.
The aerostatics of pressure airships does not vary much from that of
free balloons below the pressure height, bearing in mind that the air
in the ballonets contributes no lift. Superheat affects the operation
of an non-rigid airship in the following manner. Bringing the airship
out of the hangar into the
 400 AEROSTATICS bright sunshine, the pilot will notice
immediately by his pressure gage or manometer that the pressure
inside the gas chamber is increasing. The valve releasing air from
the ballonet must be opened at once to prevent the gas bag from
bursting. Each pound of air valved increases the lift by 1 lb. When
the airship starts to move forward, the superheat is reduced by the
air circulating past the outside of the envelope. The gas contracts,
air is forced into the ballonet, lift is reduced, and therefore ballast
must be discarded. The ballonet capacity is small compared with the
gas capacity of an airship. Because air is heavier than the gas, the
ballonets are always located on the lower side of the hull. In this
location the sun's rays do not shine on the ballonets but on the
upper side of the hull; any heating of the air would be by direct
conduction from the warm gas through the separating wall to the air.
Any heating of the air would add to the lift in the same way that lift
was obtained in the old-style hot-air balloons; ordinarily this
additional lift is so small that it is neglected. Example. A non-rigid
airship of 200,000 cu.-ft.-capacity is brought out of the hangar.
Atmospheric temperature is 50° F. and pressure is 30.2 in. Ballonets
have 40,000-cu.-ft. capacity. How much added lift will the dirigible
pick up if gas is superheated 30° F. before takeoff? Solution. Volume
of unsuperheated gas = 200,000 - 40,000 = 160,000 cu. ft. Original
lift = 160,000 (0.07651 -0.00532) ^x|^ = 11,7001b. 540 Volume of
superheated gas = 160,000 Xttk = 169,410 cu. ft. Volume of
displaced air = 169,410 - 160,000 = 9,410 cu. ft. 519 30 2 Weight of
displaced air = 9,410 X 0.07651 X ^ X 29^ = 738 lb. gain in lift
Check. Kin 3Q 2 Original lift = 160,000 (0.07651 -0.00532) ^Jq X
29^ = 11,700 lb.
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