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

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

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ISBN: 9780471242475 | 0471242470
Cover: Hardcover
Copyright: 2/17/1999

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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.

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

(44)

1.1 Amphiphilic Self-Assembly Processes Are Spontaneous, Are Characterized by Start-Stop Features, and Produce Aggregates with Well-Defined Properties

(5)

1.2 Amphiphilic Molecules Are Liquidlike in Self-Assembled Aggregates

(3)

1.3 Surfactant Numbers Provide Useful Guides for Predicting Aggregate Structures

(5)

1.4 Understanding the Origin of Entropy and Enthalpy of Mixing Provides Useful Molecular Insight into Many Colloidal Phenomena

(7)

1.4.1 The Ideal Mixing Model Provides a Basis for Understanding the Formation of a Miscible Phase

(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

(2)

1.5 The Chemical Potential is a Central Thermodynamic Concept in the Description of Multicomponent Systems

(8)

1.5.1 Having an Expression for the Free Energy We Can Determine the Chemical Potential by Differentiation

(1)

1.5.2 Mixtures and Solutions Differ Through the Choice of Standard States

(1)

1.5.3 The Chemical Potential of the Solvent is Often Expressed in Terms of the Osmotic Pressure

(1)

1.5.4 The Chemical Potential Enters into Many Thermodynamic Equalities

(1)

1.5.5 Chemical Potentials Can Be Generalized to Include the Effect of External Fields

(2)

1.6 Understanding Brownian Motion Provides an Important Enabling Concept in Analyzing Colloidal Systems

(4)

1.6.1 The Diffusional Motion of Individual Molecules Can be Analyzed in Terms of a Random Walk

(3)

1.6.2 Diffusional Motion Leads to a Net Transport of Molecules in a Concentration Gradient

(1)

1.7 Solvophobicity Drives Amphiphilic Aggregation

(8)

2 / Surface Chemistry and Monolayers

(54)

2.1 We Can Comprehend Surface Tension in Terms of Surface Free Energy

(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

(2)

2.1.2 Two Complementary Concepts Define Surface Tension: Line of Force and Energy Required to Create New Surface Area

(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

(4)

2.1.4 The Young-Laplace Equation Relates Pressure Differences Across a Surface to Its Curvature

(2)

2.2 Several Techniques Measure Surface Tension

(5)

2.2.1 Surface Tension Governs the Rise of a Liquid in a Capillary Tube

(2)

2.2.2 The Wilhelmy Plate Method Measures the Change in Weight of a Plate Brought into Contact with a Liquid

(2)

2.2.3 The Shapes of Sessile and Pendant Drops Can Be Used to Determine Surface or Interfacial Tension

(1)

2.2.4 Contact Angles Yield Information on Solid Surfaces

(1)

2.3 Capillary Condensation, Ostwald Ripening, and Nucleation Are Practical Manifestations of Surface Phenomena

(9)

2.3.1 Surface Energy Effects Can Cause a Liquid to Condense on a Surface Prior to Saturation in the Bulk Phase

(2)

2.3.2 Surface Free Energies Govern the Growth of Colloidal Particles

(1)

2.3.3 Surface Free Energies Oppose the Nucleation of a New Phase

(2)

2.3.4 Combining the Kelvin Equation with a Kinetic Association Model Provides an Expression for the Rate of Homogeneous Nucleation

(4)

2.4 Thermodynamic Equations That Include Surface Contributions Provide a Fundamental Basis for Characterizing Behavior of Colloidal Particles

(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

(1)

2.4.2 The Gibbs Adsorption Equation Relates Surface Excess to Surface Tension and the Chemical Potential of the Solute

(3)

2.4.3 The Langmuir Equation Describes Adsorption at Solid Interfaces Where We Cannot Measure Surface Tension Directly

(1)

2.5 Monolayers Are Two-Dimensional Self-Organizing Systems

(3)

2.5.1 Monolayers Formed by Soluble Amphiphiles Can Be Characterized by Surface Tension Measurements Using the Gibbs Adsorption Isotherm

(1)

2.5.2 Monolayers Formed by Insoluble Amphiphiles Behave as Separate Phases and Are More Readily Characterized Using the Langmuir Balance

(2)

2.6 Pi(s) Versus a(0) Surface Isotherms for Monolayers Containing Insoluble Amphiphiles Parallel P Versus V Isotherms for Bulk Systems

(4)

2.6.1 The Insoluble Monolayer Displays Several Aggregation States

(2)

2.6.2 Fluorescence Microscopy Can Visualize the Aggregation State of Monolayers Directly

(2)

2.6.3 The Langmuir-Blodgett Technique Provides a Way to Deposit Monolayers or Multilayers onto Solid Surfaces

(1)

2.7 Scanning Tunneling and Atomic Force Microscopies Permit Imaging of Molecular Structures at Solid Interfaces

(14)

3 / Electrostatic Interactions in Colloidal Systems

(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

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

Summary

Author Biography

Table of Contents

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

Summary

Author Biography

Table of Contents

Supplemental Materials

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