Physical Chemistry of Macromolecules

Written by a chemical physicist specializing in macromolecular physics, this book brings to life the definitive work of celebrated scientists who combined multidisciplinary perspectives to pioneer the field of polymer science. The author relates firsthand the unique environment that fostered the experimental breakthroughs underlying some of todaya??s most widely accepted theories, mathematical principles, and models for characterizing macromolecules. Physical Chemistry of Macromolecules employs the unifying principles of physical chemistry to define the behavior, structure, and intermolecular properties of macromolecules in both solution and bulk states. The text explains the experimental techniques, such as light scattering, and results used to support current theories. Examining both equilibrium and transport properties, the book describes the properties of dilute, semi-dilute, and concentrated polymer solutions, including compressible fluids. It then covers amorphous liquids and glasses,and polymer networks. The final chapters discuss the properties of solutions containing stiff-chain molecules and polyelectrolytes. Topics also include the macromolecular nature of rubber elasticity, viscoelasticity, and the distribution of relaxation times associated with the glass transition. By explaining the experimental and mathematical basis for the theories and models used to define macromolecular behavior, Physical Chemistry of Macromoleculesdemonstrates how these techniques and models can be applied to analyze and predict the properties of new polymeric materials.

Introduction to macromolecules	p. 1
What is a macromolecule?	p. 1
The discovery of macromolecules	p. 2
The structure of macromolecules in solution	p. 3
The remarkable properties of pure bulk polymers	p. 6
Building new materials using macromolecules	p. 8
Suggestions for further reading	p. 10
Describing polymer structure	p. 11
Introduction	p. 11
Geometric structure of macromolecules	p. 12
Bond probability distributions	p. 13
Rotational isomeric state approximation	p. 14
Mean-squared end-to-end distance	p. 17
Statistics of the random coil	p. 20
Chain flexibility and the persistence length	p. 23
Measuring polymer structure	p. 25
Introduction	p. 25
Polymer composition and sequence distribution	p. 25
NMR spectroscopy of polymers	p. 26
Measuring local conformations of polymers	p. 27
Vibrational spectroscopy	p. 30
Conformational statistics of n-hexane	p. 31
Global measures of the chain structure	p. 31
Light scattering from dilute polymer solutions	p. 32
The macromolecular basis of rubber elasticity	p. 35
Introduction	p. 35
The thermodynamics of ideal-rubber elasticity	p. 36
The statistical theory of rubber elasticity	p. 38
Thermoelastic inversion point	p. 40
The force of extension of real rubber	p. 40
Structure and properties of polymers in dilute solution	p. 43
Introduction	p. 43
The structure of macromolecules in dilute solution	p. 44
Flory theory of chain expansion	p. 47
Thermodynamics of two component solutions	p. 48
Osmotic pressure	p. 49
Flory theory of the second virial coefficient	p. 51
Light scattering from two-component solutions	p. 53
Flory theory of light scattering in dilute solution	p. 54
Diffusion of particles in solution	p. 57
Kirkwood theory of macromolecular friction	p. 59
Concentration fluctuations and mutual diffusion	p. 62
The viscosity of dilute polymer solutions	p. 65
The effect of molecular-weight polydispersity	p. 68
Structure and properties of polymers in semidilute solution	p. 75
Introduction	p. 75
The remarkable behavior of semidilute solutions	p. 76
Microscopic theory of semidilute solutions	p. 78
Viscosity in semidilute solutions	p. 81
Structure near overlap	p. 82
Structure and properties of polymers in concentrated solution	p. 83
Introduction	p. 83
Flory-Huggins theory of concentrated solutions	p. 84
The thermodynamics of swollen rubber: gels	p. 89
Light scattering from concentrated solutions	p. 90
Real solutions and the Flory-Orwoll theory	p. 90
Diffusion in concentrated solutions	p. 94
Viscoelasticity in concentrated polymer solutions	p. 95
Structure and properties of polymers in the pure amorphous liquid state	p. 99
Introduction	p. 99
Free volume and viscosity	p. 100
Viscosity of low-molecular-weight chain liquids	p. 100
Phenomenology of the glass transition	p. 101
Temperature and pressure dependence of relaxation near the glass transition	p. 105
Structure and properties of rodlike polymers in solution	p. 111
Introduction	p. 111
Characterization of rodlike polymers in solution	p. 111
Second osmotic virial coefficient	p. 114
Thermodynamics of rodlike polymer solutions	p. 114
Structure and properties of polyelectrolyte chains in solution	p. 119
Introduction	p. 119
Structure of linear polyelectrolyte chains in dilute solution	p. 119
Thermodynamics of polyelectrolyte solutions	p. 124
Viscosity of polyelectrolyte solutions	p. 126
References	p. 129
Index	p. 131
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Physical Chemistry of Macromolecules

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