The Colloidal Domain
Description
An authoritative account of theory, methods and applications of colloid science, extensively updated with new developments and results.
The Colloidal Domain delivers a comprehensive and up-to date treatment of colloid science theory, methods and applications emphasizing the molecular interactions that determine properties on the colloidal length-scale. The book gives an authoritative account of the science describing the colloidal domain.
Concept maps preceding each chapter put subject matter into perspective. Numerous worked examples illustrate key concepts, and more than 250 illustrations help to clarify processes described. Exercises are provided at the end of each chapter.
In this new edition all chapters have been revised with inclusion of novel developments and original results. Special emphasis on
- Chemical potential as a central concept in the description of colloidal systems
- Experimental methods for studying surfaces and interfaces
- The molecular aspect of electrostatic interactions
- A comprehensive overview of scattering methods
- A classification of interparticle forces based on molecular mechanisms
- Function of bilayer systems in a biological context
- Association behaviour of biopolymers
- Amyloid formation as a colloidal instability
- Synthesis of colloidal particles
- Liquid-liquid phase separation as a general phenomenon
- Emphasizing role of monolayer spontaneous curvature in emulsions and foams
The Colloidal Domain is an indispensable resource for students, scientists and professionals in molecular bioscience, chemistry and chemical engineering. Applications span a wide range from cellular phenomena, formulation problems, pharmaceutical science, food technology, coating processes, cosmetics development, ceramics and paper products.
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Håkan Wennerström is an Emeritus Professor of Physical Chemistry at the Department of Chemistry, Lund University, Sweden. He is the author of more than 250 publications mainly in colloid science in the areas of surfactant and lipid phase behavior, surface forces, electrostatic interactions, and nuclear magnetic resonance spectroscopy. He was a member of the Nobel Committee for Chemistry for 14 years and its Chairman for three years.
Content
Preface to the First Edition xv
Preface to the Second Edition xvii
Preface to the Third Edition xix
Physical Constants xxi
Symbols xxiii
About the Author xxvii
Introduction/Why Colloidal Systems Are Important xxix
The Colloidal Domain Encompasses Many Biological and Technological Systems xxix
Understanding of Colloidal Phenomena Is Advancing Rapidly xxxi
Association Colloids Display Key Concepts That Guided the Structure of This Book xxxii
1 Solutes and Solvents, Self-assembly of Amphiphiles 1
1.1 Understanding the Origin of Entropy and Enthalpy of Mixing Provides Useful Molecular Insight into Many Colloidal Phenomena 3
1.2 The Chemical Potential Is a Central Thermodynamic Concept in the Description of Multicomponent Systems 10
1.3 Amphiphilic Self-assembly Processes Are Spontaneous, Are Characterized by Start-Stop Features, and Produce Aggregates with Well-defined Properties 17
1.4 Amphiphilic Molecules Are Liquid-like in Self-assembled Aggregates 22
1.5 Surfactant Numbers Provide Useful Guides for Predicting Aggregate Structures 25
1.6 Solvophobicity Drives Amphiphilic Aggregation 28
1.7 Brownian Motion Gives Rise to Molecular Diffusion 31
2 Surface Chemistry and Monolayers 41
2.1 We Can Comprehend Surface Tension in Terms of Surface Free Energy 44
2.2 Several Techniques Measure Surface Tension 52
2.3 Capillary Condensation, Ostwald Ripening, Nucleation, and Particle Adsorption on Interfaces Are Practical Manifestations of Surface Phenomena 54
2.4 Thermodynamics Can Be Extended to Include Surface Contributions 62
2.5 Monolayers of Insoluble Amphiphiles Form Independent Two-dimensional Systems 68
2.6 A Range of Experimental Methods Can Be Used to Study Surfaces and Interfaces 70
2.7 Evaporation at a Surface Leads to Intriguing Nonequilibrium Phenomena 75
3 Electrostatic Interactions in Colloidal Systems 85
3.1 Intermolecular Interactions Can Be Expressed as the Sum of Five Terms 88
3.2 Multipole Expansion of the Charge Distribution Provides a Convenient Way to Express Electrostatic Interactions Between Molecules 89
3.3 When Electrostatic Interactions Are Smaller than the Thermal Energy, We Can Use Angle-averaged Potentials to Evaluate Them and Obtain the Free Energy 95
3.4 Induced Dipoles Contribute to Electrostatic Interactions 98
3.5 Separating Ion-Ion Interactions from Contributions of Dipoles and Higher Multipoles in the Poisson Equation Simplifies Dealing with Condensed Phases 100
3.6 The Poisson Equation Containing Solvent-averaged Properties Describes the Free Energy of Ion Solvation 106
3.7 Self-assembly, Ion Adsorption, and Surface Titration Play an Important Role in Determining Properties of Charged Interfaces 107
3.8 The Poisson-Boltzmann Equation Can Be Used to Calculate the Ion Distribution in Solution 110
3.9 The Electrostatic Free Energy Is Composed of One Contribution from the Direct Charge-Charge Interaction and One Due to the Entropy of the Nonuniform Distribution of Ions in Solution 120
4 Structure and Properties of Micelles 129
4.1 Micelle Formation Is a Cooperative Association Process 132
4.2 We Can Measure Critical Micelle Concentrations, Aggregation Number, Micelle Structure, and Characteristic Lifetimes by a Number of Methods 142
4.3 Scattering Provides Very Useful Techniques for Studying Micellar Structure and Colloid Systems in General 150
4.4 Micelles Is Formed by Surfactants with a Variety of Head Groups and Can Adopt Several Shapes 160
4.5 Micelles Are Used to Solubilize Apolar Substances 167
5 Forces in Colloidal Systems 175
5.1 Electrostatic Double-layer Forces Are Long-ranged 180
5.2 van der Waals Forces Are Dominated by Quantum Mechanical Dispersion Forces 193
5.3 Electrostatic Interactions Generate Attractions by Correlations 205
5.4 Measuring Surface Forces 211
5.5 Density Variations Can Generate Attractive and Oscillatory Forces 217
5.6 Entropy Effects Influence the Forces Between Liquid-like Surfaces 226
5.7 The Strength of the Hydrophobic Interaction Shows an Unexpected Temperature Dependence 229
5.8 Hydrodynamic Interactions Influence the Dynamic Properties of Colloidal Systems 235
6 Bilayer Systems 241
6.1 Bilayers Show a Rich Variation with Respect to Local Chemical Structure and Global Folding 244
6.2 Bilayers Can Adopt Many Different Global Structures 254
6.3 Transport Across Bilayers Can Be Accomplished in Several Different Ways 262
6.4 The Lipid Bilayer Supports a Range of Central Metabolic Processes in the Living Cell 270
7 Polymers in Colloidal Systems 281
7.1 Single Polymer Chains Feature a Variety of Conformations in Solution 285
7.2 Thermodynamic and Transport Properties of Polymer Solutions Change Dramatically When Coils Overlap at Higher Concentrations 296
7.3 Polymers May Associate to Form a Variety of Structures 304
7.4 Polymers at Surfaces Play an Important Role in Colloidal Systems 309
8 Colloidal Stability 319
8.1 Colloidal Stability Involves Both Thermodynamic and Kinetic Factors 322
8.2 The DLVO Theory Provides a Basic Framework for Thinking About Kinetic Colloidal Stability 325
8.3 Kinetics of Aggregation Allow Us to Predict How Fast Colloidal Systems Will Coagulate 333
8.4 Electrokinetic Phenomena Are Used to Determine Zeta Potentials of Charged Surfaces and Particles 344
9 Colloidal Sols 355
9.1 Colloidal Sols Can Be Formed by Dispersion, Precipitation, or Chemical Synthesis 358
9.2 Colloidal Particles Acquire Surface Charges by Specific Ion Adsorption 362
9.3 Clays Are Colloidal Sols Whose Surface Charge Density Reflects the Chemistry of Their Crystal Structure 366
9.4 Polymer and Lipid-based Particles Can Be Made To Serve a Number of Purposes 369
9.5 Aerosols Involve Particles in the Gas Phase 373
10 Phase Equilibria, Phases, and Their Applications 383
10.1 Phase Diagrams Depicting Colloidal Systems Are Generally Richer Than Those for Molecular Systems 386
10.2 Examples Illustrate the Importance of Phase Equilibria for Colloidal Systems 397
10.3 We Obtain an Understanding of the Factors That Determine Phase Equilibria by Calculating Phase Diagrams 405
10.4 Continuous Phase Transitions Can Be Described by Critical Exponents 420
11 Microemulsions, Emulsions, and Foams 427
11.1 Amphiphiles Form a Semiflexible Elastic Film at Interfaces 430
11.2 Microemulsions Are Thermodynamically Stable Isotropic Solutions That Display a Range of Self-assembly Structures 433
11.3 Macroemulsions Consist of Drops of One Liquid in Another 444
11.4 Foams Consist of Gas Bubbles Dispersed in a Liquid or Solid Medium 459
12 Epilogue 469
12.1 Colloid Science Has Changed from a Reductionistic to a Holistic Perspective During the Twentieth Century 469
12.2 Quantum Mechanics, Statistical Mechanics, and Thermodynamics Provide the Conceptual Basis for Describing the Equilibrium Properties of the Colloidal Domain 471
12.3 Intramolecular, Intermolecular, and Surface Forces Determine the Equilibrium Properties and Structure of Colloidal Systems 473
12.4 Crucial Interplay Between the Organizing Energy and the Randomizing Entropy Governs the Colloidal World 474
12.5 The Dynamic Properties of a Colloidal System Arise from a Combination of the Thermal Brownian Motion of the Individual Particles and the Collective Motion of the Media 476
Index 479
Symbols
Symbol Name Unit Defining Equation A Helmholtz free energy J E Energy J G Gibbs free energy J H Enthalpy J S Entropy J/K U Internal energy J U┼ Effective internal energy J 3.5.18 Number of components 10.1.3 Degrees of freedom 10.1.3 Number of phases 10.1.3 Area m2 Surfactant head group area m2 1.5.1 Second virial coefficient m3 1.2.14 c Concentration (molar) M (mol/dm3) c* Concentration (per molecule) Capacitance F 3.5.5 C* Polymer overlap concentration M 7.2.2 Heat capacity J/K CCC Critical coagulation concentration M 8.2.11 CMC Critical micelle concentration M 4.1.11 Diffusion coefficient m2s-1 1.7.5 Electrical field Vm-1 Electromotive force V 4.2.1 Force N Static shear modulus Nm-2 7.2.16 G´ Storage shear modulus Nm-2 7.2.22 G" Loss modulus Nm-2 7.2.22 Radial distribution function 4.3.9 Free energy density of system Jm-3 5.5.8 Mean curvature m-1 1.5.8 Hamaker constant J 5.2.5 Spontaneous curvature m-1 6.2.1 Separation distance m 5.1.1 Current A Intensity of incident radiation Jm-2 4.3.5 Intensity of scattering Jm-2 4.3.5 Molecular flux m-2s-1 1.7.6 Area expansion elastic modulus 11.1.1 Equilibrium constant Optical constant m-2 4.3.11 Bulk conductivity ohm-1m-1 , Diffusion-controlled rate constant M-1s-1 1.7.11 Association rate constant M-1s-1 4.2.6 Dissociation rate constant s-1 4.2.6 Binary reaction rate constant M-1s-1; m-3s-1 8.3.2 Root mean square random walk length m2 7.1.11 Persistence length m 7.1.15 Random walk step length m 7.1.11 Surfactant hydrocarbon chain length m 1.3.3 Molecular weight Number-averaged molecular weight 7.1.6 Weight-averaged molecular weight 7.1.5 m Dipole moment D (Cm) 3.2.7 Micelle aggregation number Number-averaged degree of polymerization 7.1.3 Weight-averaged degree of polymerization 7.1.4 Surfactant number 1.5.1 Refractive index Number of moles Membrane permeability ms-1 6.3.1 Scattering form factor 4.3.6 p Pressure Nm-2, P Scattering vector m-1 4.3.2 Charge C Quenchers/Micelle 4.2.2 Electrical resistance ohm (V/A) Radius m Radius of gyration m , Radii of curvature m 1.5.8 Polymer end-to-end distance m 7.1.8 Rayleigh ratio m-1 4.3.14 Distance m Spreading coefficient 2.1.14 NMR order parameter 6.2.1 Surfactant aggregate Scattering structural factor 4.3.7 Total surfactant Dimensionless charge parameter 3.9.14 Temperature K Electrophoretic mobility m2V-1s-1 8.4.2 Molar volume m3 Interaction potential J Surfactant hydrocarbon chain volume m3 1.5.2 Molecular volume of compound m3 Interaction parameter J/mol 1.1.16 Colloidal stability ratio 8.3.18 Microscopic interaction energy J 1.1.12 Work J Mole fraction of component Configuration integral Valency of ion Number of nearest neighbors in bulk 1.1.12 Number of nearest neighbors at surface 2.1.2 Electrostatic potential V 3.2.1 Surface potential V 3.8.14 Fractional surface coverage 2.4.19 Osmotic pressure Nm-2 1.2.12 Surface pressure N/m 2.5.3 Surface excess of molecule...
