The Colloidal Domain Where Physics, Chemistry, Biology, and Technology Meet

by Evans, D. Fennell; Wennerströ; m, Hå; kan

• ISBN13: 9780471242475
• ISBN10: 0471242470
• Edition: 2nd
• Format: Hardcover
• Copyright: 1999-02-17
• Publisher: Wiley-VCH

Summary

This new edition provides students and professionals with a comprehensive and up-to-date treatment of colloid science theory, methods, and applications. Emphasizing the molecular interactions that determine the properties of colloidal systems, the authors provide an authoritative account of critical developments in colloid science that have occurred over the past several decades. Combining all of the best features of a professional reference and a student text, the Second Edition features: * Concept maps preceding each chapter that put subject matter into perspective. * Numerous worked examples - many new to this edition - illustrating key concepts. * More than 250 high-quality illustrations that help clarify processes described. * A new chapter that integrates the development of colloid science and technology in the twentieth century with challenges facing the field today. The Colloidal Domain, Second Edition is an indispensable professional resource for chemists and chemical engineers working in an array of industries, including petrochemicals, food, agricultural, ceramic, coatings, forestry, and paper products. It is also a superb educational tool for advanced undergraduate and graduate-level students of physical chemistry and chemical engineering.

Author Biography

D. FENNELL EVANS, PhD, is Professor of Chemical Engineering and Materials Science and Director of the Center for Interfacial Engineering at the University of Minnesota. HÅKAN WENNERSTRÖM, PhD, is Professor of Chemistry at the Chemical Center of the University of Lund, Sweden.

Table of Contents

Preface to the First Edition	xxi	(2)
Preface to the Second Edition	xxiii	(2)
Acknowledgments	xxv	(2)
Symbols	xxvii	(4)
References	xxxi	(1)
Author Biographies	xxxii	(1)
Introduction Why Colloidal Systems Are Important	xxxiii
The Colloidal Domain Encompasses Many Biological and Technological Systems	xxxiii	(3)
Understanding of Colloidal Phenomena Is Advancing Rapidly	xxxvi	(1)
Association Colloids Display Key Concepts That Guided the Structures of This book	xxxvii
1 / Solutes and Solvents, Self-Assembly of Amphiphiles	1	(44)
1.1 Amphiphilic Self-Assembly Processes Are Spontaneous, Are Characterized by Start-Stop Features, and Produce Aggregates with Well-Defined Properties	5	(5)
1.2 Amphiphilic Molecules Are Liquidlike in Self-Assembled Aggregates	10	(3)
1.3 Surfactant Numbers Provide Useful Guides for Predicting Aggregate Structures	13	(5)
1.4 Understanding the Origin of Entropy and Enthalpy of Mixing Provides Useful Molecular Insight into Many Colloidal Phenomena	18	(7)
1.4.1 The Ideal Mixing Model Provides a Basis for Understanding the Formation of a Miscible Phase	20	(3)
1.4.2 The Regular Solution Model Provides a Simple Description of Nonideal Mixing whic Ultimately Leads to the Formation of a Liquid Two-Phase System	23	(2)
1.5 The Chemical Potential is a Central Thermodynamic Concept in the Description of Multicomponent Systems	25	(8)
1.5.1 Having an Expression for the Free Energy We Can Determine the Chemical Potential by Differentiation	27	(1)
1.5.2 Mixtures and Solutions Differ Through the Choice of Standard States	28	(1)
1.5.3 The Chemical Potential of the Solvent is Often Expressed in Terms of the Osmotic Pressure	29	(1)
1.5.4 The Chemical Potential Enters into Many Thermodynamic Equalities	30	(1)
1.5.5 Chemical Potentials Can Be Generalized to Include the Effect of External Fields	31	(2)
1.6 Understanding Brownian Motion Provides an Important Enabling Concept in Analyzing Colloidal Systems	33	(4)
1.6.1 The Diffusional Motion of Individual Molecules Can be Analyzed in Terms of a Random Walk	33	(3)
1.6.2 Diffusional Motion Leads to a Net Transport of Molecules in a Concentration Gradient	36	(1)
1.7 Solvophobicity Drives Amphiphilic Aggregation	37	(8)
2 / Surface Chemistry and Monolayers	45	(54)
2.1 We Can Comprehend Surface Tension in Terms of Surface Free Energy	49	(10)
2.1.1 Molecular Origins of Surface Tension Can Be Understood in Terms of the Difference in Interaction Between Molecules in the Bulk and at the Interface	49	(2)
2.1.2 Two Complementary Concepts Define Surface Tension: Line of Force and Energy Required to Create New Surface Area	51	(2)
2.1.3 The Work of Adhesion and Cohesion Is Related to Surface Tension and Can Determine the Spontaneous Spreading of One Liquid on Another	53	(4)
2.1.4 The Young-Laplace Equation Relates Pressure Differences Across a Surface to Its Curvature	57	(2)
2.2 Several Techniques Measure Surface Tension	59	(5)
2.2.1 Surface Tension Governs the Rise of a Liquid in a Capillary Tube	59	(2)
2.2.2 The Wilhelmy Plate Method Measures the Change in Weight of a Plate Brought into Contact with a Liquid	61	(2)
2.2.3 The Shapes of Sessile and Pendant Drops Can Be Used to Determine Surface or Interfacial Tension	63	(1)
2.2.4 Contact Angles Yield Information on Solid Surfaces	64	(1)
2.3 Capillary Condensation, Ostwald Ripening, and Nucleation Are Practical Manifestations of Surface Phenomena	64	(9)
2.3.1 Surface Energy Effects Can Cause a Liquid to Condense on a Surface Prior to Saturation in the Bulk Phase	64	(2)
2.3.2 Surface Free Energies Govern the Growth of Colloidal Particles	66	(1)
2.3.3 Surface Free Energies Oppose the Nucleation of a New Phase	67	(2)
2.3.4 Combining the Kelvin Equation with a Kinetic Association Model Provides an Expression for the Rate of Homogeneous Nucleation	69	(4)
2.4 Thermodynamic Equations That Include Surface Contributions Provide a Fundamental Basis for Characterizing Behavior of Colloidal Particles	73	(5)
2.4.1 The Gibbs Model Provides a Powerful Basis for Analyzing Surface Phenomena by Dividing a System into Two Bulk Phases and an Infinitesimally Thin Dividing Surface	73	(1)
2.4.2 The Gibbs Adsorption Equation Relates Surface Excess to Surface Tension and the Chemical Potential of the Solute	74	(3)
2.4.3 The Langmuir Equation Describes Adsorption at Solid Interfaces Where We Cannot Measure Surface Tension Directly	77	(1)
2.5 Monolayers Are Two-Dimensional Self-Organizing Systems	78	(3)
2.5.1 Monolayers Formed by Soluble Amphiphiles Can Be Characterized by Surface Tension Measurements Using the Gibbs Adsorption Isotherm	78	(1)
2.5.2 Monolayers Formed by Insoluble Amphiphiles Behave as Separate Phases and Are More Readily Characterized Using the Langmuir Balance	79	(2)
2.6 Pi(s) Versus a(0) Surface Isotherms for Monolayers Containing Insoluble Amphiphiles Parallel P Versus V Isotherms for Bulk Systems	81	(4)
2.6.1 The Insoluble Monolayer Displays Several Aggregation States	81	(2)
2.6.2 Fluorescence Microscopy Can Visualize the Aggregation State of Monolayers Directly	83	(2)
2.6.3 The Langmuir-Blodgett Technique Provides a Way to Deposit Monolayers or Multilayers onto Solid Surfaces	85	(1)
2.7 Scanning Tunneling and Atomic Force Microscopies Permit Imaging of Molecular Structures at Solid Interfaces	85	(14)
3 / Electrostatic Interactions in Colloidal Systems	99	(54)
3.1 Intermolecular Interactions Often Can Be Expressed Conveniently as the Sum of Five Terms	104	(1)
3.2 Multipole Expansion of the Charge Distribution Provides a Convenient Way to Express Electrostatic Interactions Between Molecules	105	(9)
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	114	(1)
3.4 Induced Dipoles Contribute to Electrostatic Interactions	115	(3)
3.5 Separating Ion-Ion Interactions from Contributions of Dipoles and Higher Multipoles in the Poisson Equation Simplifies Dealing with Condensed Phases	118	(7)
3.6 The Poisson Equation Containing Solvent-Averaged Properties Describes the Free Energy of Ion Solvation	125	(2)
3.7 Self Assembly, Ion Adsorption, and Surface Titration Play an Important Role in Determining Properties of Charged Interfaces	127	(4)
3.8 The Poisson-Boltzmann Equation Can be Used to Calculate the Ion Distribution in Solution	131	(12)
3.8.1 The Gouy-Chapman Theory Relates Surface Charge Density to Surface Potential and Ion Distribution Outside a Planar Surface	131	(5)
3.8.2 Linearizing the Poisson-Boltzmann Equation Leads to Exponentially Decaying Potentials and the Debye-Huckel Theory	136	(2)
3.8.3 The Gouy-Chapman Theory Provides Insight into Ion Distribution near Charged Surfaces	138	(5)
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	143	(10)
3.9.1 There Are Several Equivalent Expressions for the Electrostatic Free Energy	143	(2)
3.9.2 In the Debye-Huckel Theory the Electrostatic Contribution to the Chemical Potential of an Ion is Obtained by a Charging Process	145	(1)
3.9.3 The Electrostatic Free Energy of a Planar Charged Surface Can Be Calculated in Closed Form	146	(7)
4 / Structure and Properties of Micelles	153	(64)
4.1 Micelle Formation is a Cooperative Association Process	157	(8)
4.1.1 Several Models Usefully Describe Micellar Aggregation	157	(6)
4.1.2 Thermodynamics of Micelle Formation Provide Useful Relationships Between Free Energies and Surfactant Chemical Potentials and Explicit Relations for Enthalpy and Entropy	163	(2)
4.2 We Can Measure Critical Micelle Concentrations, Aggregation Numbers, and Characteristic Lifetimes by a Number of Methods	165	(18)
4.2.1 We Can Determine CMCs by Surface Tension, Conductance, and Surfactant Ion Electrode Measurements	165	(5)
4.2.2 Micellar Aggregation Numbers Can Be Measured Most Simply by Light Scattering or with Fluorescent Probes	170	(7)
4.2.3 Kinetic Experiments Provide Valuable Insight into the Time Scales of Dynamic Processes in Micellar Solutions	177	(3)
4.2.4 Dynamics of Solutes Dissolved in Micelles Provide a Measure of the Time Scales for Solubilization Processes	180	(1)
4.2.5 Diffusion Plays an Important Role in Virtually All Micellar Processes	181	(2)
4.3 The Properties of Many Micellar Solutions Can Be Analyzed Quantitatively	183	(15)
4.3.1 The Poisson-Boltzmann Equation Describes Head Group Interactions in Ionic Micelles	185	(3)
4.3.2 Variations in the CMC Caused by Electrostatic Effects Are Well Predicted by the Poisson-Boltzmann Equation	188	(3)
4.3.3 The Contribution of the Solvophobic Free Energy DeltaG(HP) Decreases when Micelles Form in Nonaqueous Solvents	191	(1)
4.3.4 Enthalpy and Entropy of Micellization Change Much More Rapidly with Temperature than the Free Energy	191	(2)
4.3.5 Unchanged Surfactants Have Much Lower CMCs than Ionic Ones	193	(4)
4.3.6 Micelles Can Grow in Size to Short Rods, Long Polymer-Like Threads, and Even Branched Infinite Aggregates	197	(1)
4.4 Micellar Solutions Play a Key Role in Many Industrial and Biological Processes	198	(19)
4.4.1 Commercial Detergents Contain a Mixture of Surfactants	198	(4)
4.4.2 Digestion of Fats Requires Solubilization by Bile Salt Micelles	202	(2)
4.4.3 Solubilization in Micellar Solutions Involves a Complex Combination of Solution Flow and Surface Chemical Kinetics	204	(6)
4.4.4 Micellar Catalysis Exploits the Large Surface Areas Associated with Micelles and Also Illustrates the Graham Equation	210	(7)
5 / Forces In Colloidal Systems	217	(78)
5.1 Electrostatic Double-Layer Forces Are Long-Ranged	225	(14)
5.1.1 A Repulsive Electrostatic Force Exists Between a Charged and a Neutral Surface	225	(4)
5.1.2 We Can Solve the Poisson-Boltzmann Equation when Only Counterions Are Present Outside the Charged Surface	229	(2)
5.1.3 Ion Concentration at the Midplane Determines the Force Between Two Identically Charged Surfaces	231	(2)
5.1.4 The Bulk Solution Often Provides a Suitable Reference for the Potential	233	(3)
5.1.5 Two Surfaces with Equal Signs but Different Magnitudes of Charge Always Repel Each Other	236	(2)
5.1.6 As Surfaces Bearing Opposite Signs Move Closer Together, Long-Range Electrostatic Attraction Changes to Repulsion	238	(1)
5.2 Van der Waals Forces Comprise Quantum Mechanical Dispersion, Electrostatic Keesom, and Debye Forces	239	(15)
5.2.1 An Attractive Dispersion Force of Quantum Mechanical Origin Operates Between Any Two Molecules	239	(1)
5.2.2 We Can Calculate the Dispersion Interaction Between Two Colloidal Particles by Summing Over the Molecules on a Pairwise Basis	240	(5)
5.2.3 The Presence of a Medium Between Two Interacting Particles Modifies the Magnitude of the Hamaker Constant	245	(3)
5.2.4 The Derjaguin Approximation Relates the Force Between Curved Surfaces to the Interaction Energy Between Flat Surfaces	248	(2)
5.2.5 The Lifshitz Theory Provides a Unified Description of van der Waals Forces Between Colloidal Particles	250	(4)
5.3 Electrostatic Interactions Generate Attractions by Correlations	254	(5)
5.3.1 Ion Correlations Can Turn the Double-Layer Interaction Atractive	254	(2)
5.3.2 Surface Dipoles Correlate to Yield an Attraction	256	(2)
5.3.3 Domain Correlations Can Generate Long-Range Forces	258	(1)
5.4 Density Variations Can Generate Attractive and Oscillatory Forces	259	(16)
5.4.1 Packing Forces Produce Oscillatory Force Curves with a Period Determined by Solvent Size	261	(3)
5.4.2 Capillary Phase Separation Yields an Attractive Force	264	(5)
5.4.3 A Non-Adsorbing Solute Creates an Attractive Depletion Force	269	(2)
5.4.4 Adsorption Introduces on Average an Increased Repulsion	271	(4)
5.5 Entropy Effects Are Important for Understanding the Forces Between Liquidlike Surfaces	275	(4)
5.5.1 Reducing Polymer Configurational Freedom Generates a Repulsive Force	276	(1)
5.5.2 Short Range Forces That Encompass a Variety of Interactions Play Key Roles in Stabilizing Colloidal Systems	276	(2)
5.5.3 Undulation Forces Can Play an Important Role in the Interaction of Fluid Bilayers	278	(1)
5.6 The Thermodynamic Interpretation of the Hydrophobic Interaction Is Problematic Due to Entropy-Enthalpy Compensation	279	(10)
5.6.1 Understanding the Mysteries of Water	279	(7)
5.6.2 Strong Attraction Exists Between Hydrophobic Surfaces Although Experiments Have Failed to Establish the Distance-Dependence of this Force	286	(3)
5.7 Hydrodynamic Interactions Can Modulate Interaction Forces	289	(6)
6 / Bilayer Systems	295	(56)
6.1 Bilayers Show a Rich Variation with Respect to Local Chemical Structure and Global Folding	300	(10)
6.1.1 Many Amphiphiles Form a Bilayer Structure	300	(1)
6.1.2 Membrane Lipids Exhibit Chemical Variations on a Common Theme	301	(2)
6.1.3 Comparing the Properties of Spherical Micelles and Bilayers Provides Useful Insight into the Many Distinctive Molecular Properties of Bilayers	303	(3)
6.1.4 Pure Amphiphiles Form a Range of Bulk Bilayer Phases	306	(2)
6.1.5 Vesicles Can be Formed by Several Methods	308	(2)
6.2 Complete Characterization of Bilayers Requires a Variety of Techniques	310	(17)
6.2.1 X-Ray Diffraction Uniquely Identifies a Liquid Crystalline Structure and Its Dimensions	310	(3)
6.2.2 Microscopy Yields Images of Aggregate Structures	313	(2)
6.2.3 Nuclear Magnetic Resonance Provides a Picture of Bilayer Structure on the Molecular Level	315	(3)
6.2.4 Calorimetry Monitors Phase Transitions and Measures Transition Enthalpies	318	(2)
6.2.5 We Can Accurately Measure Interbilayer Forces	320	(5)
6.2.6 Measurements of Interbilayer Forces Play a Key Role in Testing Theories of Surface Interactions	325	(2)
6.3 The Lipid Bilayer Membranes has Three Basic Functions	327	(13)
6.3.1 Diffusional Processes Are Always Operating in the Living System	328	(7)
6.3.2 The Lipid Membrane Is a Solvent for Membrane Proteins	335	(2)
6.3.3 Cell Membranes Fold into a Range of Global Structures	337	(3)
6.4 Transmembrane Transport of Small Solutes Is a Central Physiological Process	340	(11)
6.4.1 Solutes Can Be Transported across the Membrane by Carriers, in Channels, by Pumps, or by Endocytosis/Exocytosis	340	(3)
6.4.2 The Chemiosmotic Mechanism Involves Transformations Between Chemical, Electrical, and Entropic Forms of Free Energy Through Transmembrane Transport Processes	343	(3)
6.4.3 Propagation of a Nerve Signal Involves a Series of Transmembrane Transport Processes	346	(5)
7 / Polymers in Colloidal Systems	351	(50)
7.1 Polymers in Solution	355	(17)
7.1.1 Chain Configurational Entropy and Monomer-Monomer Interactions Determine the Configuration of a Single Polymer Chain	358	(2)
7.1.2 Persistence Length Describes the Stiffness of a Polymer Chain	360	(2)
7.1.3 When Polymers Dissolve into a Solvent Many More Coil Configurations Become Accessible	362	(1)
7.1.4 Charged Polymer Chains Display a More Extended Conformation	363	(2)
7.1.5 Protein Folding Is the Result of a Delicate Balance Between Hydrophobic and Hydrophilic Interactions and Configurational Entropy	365	(1)
7.1.6 Scattering Techniques Provide Information about Molecular Weight and Chain Conformation	366	(4)
7.1.7 Polymer Self-Diffusion and Solution Viscosity Reflect the Dynamic and Structural Properties of a Polymer Coil	370	(2)
7.2 Thermodynamic and Transport Properties of Polymer Solution Change Dramatically with Concentration	372	(10)
7.2.1 Different Concentration Regimes Must Be Distinguished to Describe a Polymer Solution	372	(3)
7.2.2 The Semidilute Regime is Well Described by the Flory-Huggins Theory	375	(1)
7.2.3 In a Semidilute or Concentrated Solution, Polymer Diffusion Can Occur Through Reptation	376	(3)
7.2.4 Polymer Solutions Show a Wide Range of Rheological Properties	379	(3)
7.3 Polymers May Associate to Form a Variety of Structures	382	(8)
7.3.1 Block Copolymers Show the Same Self-Assembly Properties as Surfactants	382	(1)
7.3.2 Polymers with Amphiphilic Monomer Units Often Form Ordered Helix Structures	383	(3)
7.3.3 Polymers Form Gels Through Chemical Crosslinking and by Self-Association	386	(1)
7.3.4 Polymers Facilitate the Self-Assembly of Amphiphiles	387	(3)
7.4 Polymers at Surfaces Play an Important Role in Colloidal Systems	390	(11)
7.4.1 Polymers Can Be Attached to a Surface by Spontaneous Adsorption or by Grafting	390	(3)
7.4.2 Kinetics Often Determines the Outcome of a Polymer Adsorption Process	393	(1)
7.4.3 Forces Between Surfaces Change Drastically when Polymers Adsorb	393	(1)
7.4.4 Polyelectrolytes Can Be Used Both To Flocculate and to Stabilize Colloidal Dispersions	394	(7)
8 / Colloidal Stability	401	(42)
8.1 Colloidal Stability Involves Both Kinetic and Thermodynamic Considerations	406	(3)
8.1.1 The Interaction Potential Between Particles Determines Kinetic Behavior	406	(2)
8.1.2 Particles Deformed upon Aggregration Change the Effective Interaction Potential	408	(1)
8.2 The DLVO Theory Provides Our Basic Framework for Thinking About Colloidal Interactions	409	(8)
8.2.1 Competition Between Attractive van der Waals and Repulsive Double-Layer Forces Determines the Stability or Instability of Many Colloidal Systems	409	(3)
8.2.2 The Critical Coagulation Concentration Is Sensitive to Counterion Valency	412	(3)
8.2.3 A Colloidal Suspension Can Be Stabilized by Adsorbing Surfactants or Polymers	415	(2)
8.3 Kinetics of Aggregation Allow Us To Predict How Fast Colloidal Systems Will Coagulate	417	(11)
8.3.1 We Can Determine the Binary Rate Constant for Rapid Aggregation from the Diffusional Motion	417	(3)
8.3.2 We Can Calculate Complete Aggregation Kinetics if We Assume That Rate Constants Are Practically Independent of Particle Size	420	(4)
8.3.3 Kinetics of Slow Flocculation Depends Critically on Barrier Height	424	(2)
8.3.4 Aggregates of Colloidal Partices Can Show Fractal Properties	426	(2)
8.4 Electrokinetic Phenomena Are Used to Determine Zeta Potentials of Charged Surfaces and Particles	428	(15)
8.4.1 We Can Relate the Electrophoretic Velocity of a Colloidal Particle to the Electrical Potential at the Slip Plane	429	(5)
8.4.2 We Can Determine the Zeta Potential for a Surface by Measuring the Streaming Potential	434	(2)
8.4.3 Electro-osmosis Provides Another Way to Measure the Zeta-Potential	436	(7)
9 / Colloidal Sols	443	(46)
9.1 Colloidal Sols Formed by Dispersion or Condensation Processes Usually Are Heterogeneous	448	(4)
9.1.1 Controlling Nucleation and Growth Steps Can Produce Monodisperse Sols	449	(3)
9.2 The Concentration of Silver and Iodide Ions Determines the Surface Potential of Silver Iodide Sols	452	(5)
9.2.1 Potential-Determining Ions Play an Important Role in Controlling Stability	455	(2)
9.3 Clays Are Colloidal Sols Whose Surface Charge Density Reflects the Chemistry of Their Crystal Structure	457	(8)
9.3.1 Directly Measurable Interaction Forces Between Two Mica Surfaces Provide Insight into the Complexities of Colloidal Systems	460	(3)
9.3.2 Coagulated Structures Complicate the Colloidal Stability of Clay Sols	463	(2)
9.4 Monodisperse Latex Spheres Can Model Various States of Matter as Well as the Phase Transformations Between Them	465	(8)
9.4.1 Long-Range Electrostatic Repulsions Dominate the Solution Behavior of Ionic Latex Spheres	466	(4)
9.4.2 Sterically Stabilized Latex Spheres Show Only Short-Range Interactions and Form Structured Solutions Only at Higher Concentrations	470	(3)
9.5 Homocoagulation and Heterocoagulation Occur Simultaneously in Many Colloidal Systems	473	(6)
9.6 Aerosols Involve Particles in the Gas Phase	479	(10)
9.6.1 Some Aerosols Occur Naturally, But Many Other Are Produced in Technical Processes	479	(1)
9.6.2 Aerosol Properties Differ Quantitatively from Those of Other Colloidal Dispersions in Three Respects	480	(1)
9.6.3 Aerosol Particles Interact by van der Waals Forces as Well as Electrostatically and Hydrodynamically	481	(2)
9.6.4 Aerosol Particles Possess Three Motion Regimes	483	(6)
10 / Phase Equilibra, Phase Diagrams, and Their Application	489	(50)
10.1 Phase Diagrams Depicting Colloidal Systems Are Generally Richer Than Those for Molecular Systems	493	(12)
10.1.1 Several Uncommon Aggregation States Appear in Colloidal Systems	493	(5)
10.1.2 The Gibbs Phase Rule Guides the Thermodynamic Description of Phase Equilibria	498	(1)
10.1.3 In a Multicomponent System with Two Phases in Equilibrium, the Chemical Potential of Each Component Is the Same in Both Phases	499	(2)
10.1.4 Phase Diagrams Conveniently Represent Phase Equilibria	501	(2)
10.1.5 Determining Phase Equilibria Is a Demanding Task	503	(2)
10.2 Examples Illustrate the Importance of Phase Equilibria for Colloidal Systems	505	(9)
10.2.1 Purely Repulsive Interactions Can Promote the Formation of Ordered Phases	507	(1)
10.2.2 Ionic Surfactants Self-Assemble into a Multiplicity of Isotropic and Liquid Crystalline Phases	507	(2)
10.2.3 Temperature Changes Dramatically Affect Phase Equilibria for Nonionic Surfactants	509	(1)
10.2.4 Block Copolymers Exhibit as Rich a Phase Behavior as Surfactants	510	(2)
10.2.5 Monomolecular Films Show a Rich Phase Behavior	512	(2)
10.3 We Obtain an Understanding of the Factors That Determine Phase Equilibria by Calculating Phase Diagrams	514	(17)
10.3.1 The Regular Solution Model Illustrates Liquid-Liquid Phase Separation	514	(3)
10.3.2 Liquid State Miscibility and Solid State Demixing Lead to a Characteristic Phase Diagram	517	(3)
10.3.3 Two Lipids that Exhibit Different Melting Points but Ideal Mixing in Both the Gel and Liquid Crystalline Phases Produce a Simple Phase Diagram	520	(2)
10.3.4 The Presence of an Impurity Broadens a Phase Transtion by Introducting a Two-Phase Area	522	(2)
10.3.5 The Short Range Stabilizing Force Influences the Equilibrium Between Liquid Crystalline and Gel Phases in Lecithin-Water Systems	524	(2)
10.3.6 The Isotropic to Nematic Transition can be Caused by an Orientation Dependent Excluded Volume	526	(5)
10.4 Continuous Phase Transitions Can Be Described by Critical Exponents	531	(8)
10.4.1 Phase Changes Can Be Continuous	531	(1)
10.4.2 Continuous Transitions Are Characterized by the Values of Critical Exponents	532	(2)
10.4.3 We Can Use the Regular Solution Theory to Illustrate the Ising Model and to Calculate Mean Field Critical Exponents	534	(1)
10.4.4 Nonionic Surfactants Show a Critical Demixing When the Temperature Increases	535	(1)
10.4.5 The Term Continuous Phase Transition Sometimes Characterizes Less Well-Defined Phase Changes	536	(3)
11 / Micro- and Macroemulsions	539	(62)
11.1 Surfactant Form a Semiflexible Elastic Film at Interfaces	544	(6)
11.1.1 We Can Characterize the Elastic Properties of a Film Through Five Phenomenological Constants	544	(4)
11.1.2 With Some Effort We Can Measure Elastic Constants	548	(2)
11.2 Microemulsions Are Thermodynamically Stable Isotropic Solutions That Display a Range of Self-Assembly Structures	550	(18)
11.2.1 Microemulsions Can Contain Spherical Drops or Bicontinuous Structures	550	(3)
11.2.2 Temperature Controls the Structure and Stability of Nonionic Surfactant Microemulsions	553	(6)
11.2.3 We Often Need Electrolytes to Obtain Microemulsions for Ionic Surfactants	559	(2)
11.2.4 DDAB Double-Chain Surfactants Show Bicontinuous Inverted Structures	561	(7)
11.3 Macroemulsions Consist of Drops of One Liquid in Another	568	(22)
11.3.1 Forming Macroemulsions Usually Requires Mechanical or Chemical Energy	568	(3)
11.3.2 Turbulent Flow during the Mixing Process Governs Droplet Size	571	(2)
11.3.3 A Chemical Nonequilibrium State Can Induce Emulsification	573	(2)
11.3.4 A Number of Different Mechanisms Affect the Evolution of an Emulsion	575	(2)
11.3.5 To Stabilize an Emulsion, the Dispersed Phase in Different Drops Should Be Prevented from Reaching Molecular Contact	577	(3)
11.3.6 Emulsion Structure and Stability Depend on the Properties of the Surfactant Film	580	(8)
11.3.7 We Can Catalyze Coalescence by Changing the Spontaneous Curvature and by Inducing Depletion Attraction	588	(2)
11.4 Foams Consist of Gas Bubbles Dispersed in a Liquid or Solid Medium	590	(11)
11.4.1 A Surface Film Develops on Bubbles as They Rise	591	(2)
11.4.2 Concentrated Foams Consist of Polyhedral Gas Compartments Packed in an Intriguing Way	593	(1)
11.4.3 Foams Disintegrate by Ostwald Ripening and Film Rupture	594	(1)
11.4.4 Macroscopic Liquid Films Stabilized by Surfactants Can Be Used to Study Surface Forces and Film Stability	595	(6)
12 / Epilogue	601	(12)
12.1 Colloid Science has Changed from a Reductionistic to a Holistic Perspective During this Century	602	(2)
12.2 Quantum Mechanics, Statistical Mechanics, and Thermodynamics Provide the Conceptual Basis for Describing the Equilibrium Properties of the Colloidal Domain	604	(2)
12.3 Intramolecular, Intermolecular, and Surface Forces Determine the Equilibrium Properties and Structure of Colloidal Systems	606	(2)
12.4 Crucial Interplay Between the Organizing Energy and the Randomizing Entropy Governs the Colloidal World	608	(3)
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	611	(2)
Index	613