Physical Chemistry of Polyelectrolyte Solutions, Volume 158

Examines the intersection of polyelectrolyte solutions and chemical physics

The Advances in Chemical Physics series is dedicated to reviewing new and emerging topics as well as the latest developments in traditional areas of study in the field of chemical physics. Each volume features detailed comprehensive analyses coupled with individual points of view that integrate the many disciplines of science that are needed for a full understanding of chemical physics.

Volume 158 explores the latest research findings, applications, and new research paths in the field of polyelectrolyte solutions. It introduces topics from thermodynamic properties to the ionic binding of polyelectrolytes, and intersects key elements with applications of chemical physics.

With contributions from an international team of leading experts, Volume 158 offers six comprehensive reviews including:

Introduction to the strengths and chemistry of polyelectrolyte solutions Thermodynamic Properties of Polyelectrolyte Solutions                      Ionization Equilibrium and Potentiometric Titration of Weak Polyelectrolytes  Molecular Conformation of Linear Polyelectrolytes                          Radius of Gyration and Intrinsic Viscosity of Linear Polyelectrolytes          Transport Phenomena of Linear

Reviews published in Advances in Chemical Physics are typically longer than those published in journals, providing the space needed for readers to fully grasp the topic: the fundamentals as well as the latest discoveries, applications, and emerging avenues of research. Extensive cross–referencing enables readers to explore the primary research studies underlying each topic.

 

Preface  iii

Introductory Remarks 1

0.1 Strong Electrolytes 2

0.2 Polymer Science 4

0.3 Polyelectrolyte Solutions 12

0.4 (Supplement) Preparation of Linear Polymers with Narrow Molecular Weight Distribution (NMWD) 15

1 Thermodynamic Properties of Polyelectrolyte Solutions 23

1.1 Introduction: Non–ionic Polymer Solution 23

1.2 Electrostatic Free Energy of Polyelectrolyte Solutions 33

1.3 Donnan Membrane Equilibrium (Concentrated Solution) 43

1.4 Dilute Solution Properties of Polyelectrolyte 48

1.5 (Appendix) Anomalous Osmosis of Water into Animal Cells 57

2 Ionization Equilibrium and Potentiometric Titration of Weak Polyelectrolytes 67

2.1 Introduction 67

2.2 Theory of Ionization Equilibrium 68

2.3 Free Energy of Ionization in Solutions with Added–salt 75

2.3.1 Potentiometric Titration of Spherical Macro–ions (Proteins) 75

2.3.2 Potentiometric Titration of Rod–like and Randomly Coiled Polyelectrolytes 83

2.3.3 Potentiometric Titration of polyelectrolytes in Salt–free Systems 92

2.4 Application of Potentiometric Titration to the Study of Conformational

Transition of Macromolecules 94

2.4.1 Helix–Coil Transition of Macromolecules 94

2.4.2 Dissociation and Association of Proteins 106

3 Molecular Conformation of Linear Polyelectrolytes 115

3.1 Introduction 115

3.2 Unperturbed Dimension 117

3.3 Particle Scattering Factor 122

3.4 Stiffness of the Polyion Backbone 132

3.4.1 Particle Scattering Factor of Stiff Polymers 134

3.4.2 Study on Local Conformation of Polymer Chains 136

4 Radius of Gyration and Intrinsic Viscosity of Linear Polyelectrolytes 153

4.1 Introduction 153

4.2 Expansion Factor of Non–ionic Polymer Coils due to the Excluded Volume Effect 159

4.3 Expansion Factor of Polyelectrolyte Molecules in the Presence of Added–salt 164

4.4 Worm–like Chain Model for Intrinsic Viscosity 181

4.5 In Pure aqueous Solution 185

5 Transport Phenomena of Linear Polyelectrolytes 191

5.1 Introduction 191

5.2 Porous Sphere Model 193

5.3 Sedimentation and Diffusion 198

5.4 Electrophoresis 211

5.5 Diffusion in Pure Aqueous Solution 220

5.6 (Appendix) Anomalous Osmosis through Charged Membranes 227

6 Ion–Binding 237

6.1 Introduction 237

6.2 Complex Formation 240

6.3 Ion–Pair in Simple Electrolyte Solutions 244

6.4 Ion–Binding of Polyelectrolytes 247

6.4.1 Na+ –Binding in Strong Polyelectrolyte Solutions 248

6.4.2 H+ in Aqueous Solution of Strong Polyacid 261

6.4.3 Nature of Ion–Binding 263

MITSURU NAGASAWA, PhD, is Professor Emeritus of Nagoya University, Japan. He has served as Honorary President of the Toyota Technological Institute since 2010. His accolades include the Japan Academy Award (1977).

STUART A. RICE, PhD,received his master s degree and doctorate from Harvard University and was a junior fellow at Harvard for two years before joining the faculty of The University of Chicago in 1957, where he is currently the Frank P. Hixon Distinguished Service Professor Emeritus.

AARON R. DINNER, PhD,received his bachelor s degree and doctorate from Harvard University, after which he conducted postdoctoral research at the University of Oxford and the University of California, Berkeley. He joined the faculty at The University of Chicago in 2003.