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"Frontmatter". In: Physical Chemistry of Macromolecules (Second Edition)
PHYSICAL CHEMISTRY OF
MACROMOLECULES
Second Edition
PHYSICAL CHEMISTRY
OF MACROMOLECULES
Basic Principles and Issues
Second Edition
S. F. SUN
St. John’s University
Jamaica, New York
A Wiley-Interscience Publication
JOHN WILEY & SONS, INC.
263032677.001.png
Copyright # 2004 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
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Library of Congress Cataloging-in-Publication Data:
Sun, S. F., 1922-
Physical chemistry of macromolecules : basic principles and issues / S. F. Sun.–2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN 0-471-28138-7 (acid-free paper)
1. Macromolecules. 2. Chemistry, Physical organic. I. Title.
QD381.8.S86 2004
547 0 .7045–dc22
2003063993
Printed in the United States of America.
10987654321
CONTENTS
Preface to the Second Edition
xv
Preface to the First Edition
xix
1 Introduction
1
1.1 Colloids, 1
1.2 Macromolecules, 3
1.2.1 Synthetic Polymers, 4
1.2.2 Biological Polymers, 7
1.3 Macromolecular Science, 17
References, 17
2 Syntheses of Macromolecular Compounds
19
2.1 Radical Polymerization, 19
2.1.1 Complications, 21
2.1.2 Methods of Free-Radical Polymerization, 23
2.1.3 Some Well-Known Overall Reactions of
Addition Polymers, 23
2.2 Ionic Polymerization, 25
2.2.1 Anionic Polymerization, 25
2.2.2 Cationic Polymerization, 27
2.2.3 Living Polymers, 27
2.3 Coordination Polymerization, 30
2.4 Stepwise Polymerization, 32
v
vi
CONTENTS
2.5 Kinetics of the Syntheses of Polymers, 33
2.5.1 Condensation Reactions, 34
2.5.2 Chain Reactions, 35
2.6 Polypeptide Synthesis, 40
2.6.1 Synthesis of Insulin, 43
2.6.2 Synthesis of Ribonucleus, 48
2.7 DNA Synthesis, 48
References, 50
Problems, 50
3 Distribution of Molecular Weight
52
3.1 Review of Mathematical Statistics, 53
3.1.1 Binomial Distribution, 53
3.1.2 Poisson Distribution, 54
3.1.3 Gaussian Distribution, 55
3.2 One-Parameter Equation, 56
3.2.1 Condensation Polymers, 57
3.2.2 Addition Polymers, 58
3.3 Two-Parameter Equations, 59
3.3.1 Normal Distribution, 59
3.3.2 Logarithm Normal Distribution, 60
3.4 Types of Molecular Weight, 61
3.5 Experimental Methods for Determining Molecular
Weight and Molecular Weight Distribution, 64
References, 65
Problems, 65
4 Macromolecular Thermodynamics
67
4.1 Review of Thermodynamics, 68
4.2 S of Mixing: Flory Theory, 71
4.3 H of Mixing, 75
4.3.1 Cohesive Energy Density, 76
4.3.2 Contact Energy (First-Neighbor Interaction or
Energy Due to Contact), 79
4.4 G of Mixing, 81
4.5 Partial Molar Quantities, 81
4.5.1 Partial Specific Volume, 82
4.5.2 Chemical Potential, 83
4.6 Thermodynamics of Dilute Polymer Solutions, 84
4.6.1 Vapor Pressure, 87
4.6.2 Phase Equilibrium, 89
Appendix: Thermodynamics and Critical Phenomena, 91
References, 92
Problems, 93

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