Intermolecular and Surface Forces 3rd Edition

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 Intermolecular
and Surface Forces
Third Edition
Jacob N. Israelachvili
UNIVERSITY OF CALIFORNIA
SANTA BARBARA , C ALIFORNIA, USA

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

PARIS • SAN DIEGOSAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

Academic Press is an imprint of Elsevier

Academic Press is an imprint of Elsevier
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Third edition 2011

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Library of Congress Cataloging-in-Publication Data
Israelachvili, Jacob N.
Intermolecular and surface forces / Jacob N. Israelachvili. – 3rd ed.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-12-375182-9 (alk. paper)
1. Intermolecular forces. 2. Surface chemistry. I. Title.
QD461.I87 2011
541’.226–dc22
2010031067

ISBN: 978-0-12-375182-9

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visit our website at elsevierdirect.com

Printed and bound in USA

10 11 12 10 9 8 7 6 5 4 3 2 1
 Contents
Preface to the Third Edition xvii
Preface to the Second Edition xix
Preface to the First Edition xxi

PART ONE THE FORCES BETWEEN ATOMS AND

MOLECULES 1
1. Historical Perspective 3
1.1. The Four Forces of Nature 3
1.2. Greek and Medieval Notions of Intermolecular Forces 3
1.3. The Seventeenth Century: First Scientific Period 5
1.4. The Eighteenth Century: Confusion, Contradictions,
and Controversy 7
1.5. The Nineteenth Century: Continuum versus
Molecular Theories 8
1.6. Intermolecular Force-Laws and Interaction
Potentials: Long- and Short-Range Forces 9
1.7. First Successful Phenomenological Theories 12
1.8. First Estimates of Molecular Sizes 15
1.9. The Twentieth Century: Understanding Simple Systems 16
1.10. Recent Trends 17
Problems and Discussion Topics 18
2. Thermodynamic and Statistical Aspects
of Intermolecular Forces 23
2.1. The Interaction of Molecules in Free Space and in a Medium 23
2.2. Self-Energy and Pair Potential 25
2.3. The Boltzmann Distribution and the Chemical Potential 26

v
vi Contents

2.4. The Distribution of Molecules and Particles in

Systems at Equilibrium 27
2.5. The Van der Waals Equation of State (EOS) 30
2.6. The Criterion of the Thermal Energy kT for Gauging
the Strength of an Interaction 31
2.7. Classification of Forces and Pair Potentials 34
2.8. Theoretical Analyses of Multimolecular Systems: Continuum
and Molecular Approaches 35
2.9. Molecular Approaches via Computer Simulations:
Monte Carlo (MC) and Molecular Dynamics (MD) 37
2.10. Newton’s Laws Applied to Two-Body Collisions 39
2.11. Kinetic and Statistical Aspects of Multiple Collisions:
the Boltzmann Distribution 43
Problems and Discussion Topics 49
3. Strong Intermolecular Forces: Covalent
and Coulomb Interactions 53
3.1. Covalent or Chemical Bonding Forces 53
3.2. Physical and Chemical Bonds 54
3.3. Coulomb Forces or Charge-Charge Interactions,
Gauss’s Law 55
3.4. Ionic Crystals 58
3.5. Reference States 59
3.6. Range of Electrostatic Forces 60
3.7. The Born Energy of an Ion 61
3.8. Solubility of Ions in Different Solvents 62
3.9. Specific Ion-Solvent Effects: Continuum Approach 66
3.10. Molecular Approach: Computer Simulations
and Integral Equations of Many-Body Systems 67
Problems and Discussion Topics 68
4. Interactions Involving Polar Molecules 71
4.1. What Are Polar Molecules? 71
 Contents vii

4.2. Dipole Self-Energy 73

4.3. Ion-Dipole Interactions 73
4.4. Ions in Polar Solvents 78
4.5. Strong Ion-Dipole Interactions in Water: Hydrated Ions 78
4.6. Solvation Forces, Structural Forces, and Hydration Forces 80
4.7. Dipole-Dipole Interactions 81
4.8. Magnetic Dipoles 83
4.9. Hydrogen Bonds 83
4.10. Rotating Dipoles and Angle-Averaged Potentials 84
4.11. Entropic Effects 86
Problems and Discussion Topics 88
5. Interactions Involving the Polarization of Molecules 91
5.1. The Polarizability of Atoms and Molecules 91
5.2. The Polarizability of Polar Molecules 93
5.3. Other Polarization Mechanisms and the Effects
of Polarization on Electrostatic Interactions 94
5.4. Interactions between Ions and Uncharged Molecules 96
5.5. Ion-Solvent Molecule Interactions and the Born Energy 98
5.6. Dipole-Induced Dipole Interactions 99
5.7. Unification of Polarization Interactions 99
5.8. Solvent Effects and “Excess Polarizabilities” 100
Problems and Discussion Topics 105
6. Van der Waals Forces 107
6.1. Origin of the Van der Waals-dispersion Force between
Neutral Molecules: the London Equation 107
6.2. Strength of Dispersion Forces: Van der Waals
Solids and Liquids 109
6.3. Van der Waals Equation of State 113
6.4. Gas-Liquid and Liquid-Solid Phase Transitions in 3D and 2D 115
6.5. Van der Waals Forces between Polar Molecules 117
viii Contents

6.6. General Theory of Van der Waals Forces between Molecules 119
6.7. Van der Waals Forces in a Medium 122
6.8. Dispersion Self-Energy of a Molecule in a Medium 126
6.9. Further Aspects of Van der Waals Forces:
Anisotropy (Orientation), Nonadditivity (Many-Body),
and Retardation Effects 127
Problems and Discussion Topics 130
7. Repulsive Steric Forces, Total Intermolecular
Pair Potentials, and Liquid Structure 133
7.1. Sizes of Atoms, Molecules, and Ions 133
7.2. Repulsive Potentials 136
7.3. Total Intermolecular Pair Potentials: Their Form,
Magnitude, and Range 136
7.4. Role of Repulsive Forces in Noncovalently Bonded Solids 140
7.5. Packing of Molecules and Particles in Solids 142
7.6. Role of Repulsive Forces in Liquids: Liquid Structure 145
7.7. The Effect of Liquid Structure on Molecular Forces 147
Problems and Discussion Topics 148
8. Special Interactions: Hydrogen-Bonding
and Hydrophobic and Hydrophilic Interactions 151
8.1. The Unique Properties of Water 151
8.2. The Hydrogen Bond 152
8.3. Models of Water and Associated Liquids 156
8.4. Relative Strengths of Different Types of Interactions 157
8.5. The Hydrophobic Effect 158
8.6. The Hydrophobic Interaction 161
8.7. Hydrophilic Interactions 163
Problems and Discussion Topics 166
9. Nonequilibrium and Time-Dependent Interactions 169
9.1. Time- and Rate-Dependent Interactions and Processes 169
 Contents ix

9.2. Rate- and Time-Depended Detachment

(Debonding) Forces 171
9.3. Energy Transfer (Dissipation) during Molecular
Collisions: the Deborah Number 175
9.4. Energy Transfer during Cyclic Bonding-Unbonding Processes 178
9.5. Relationships between Time, Temperature,
and Velocity (Rate) in Complex Processes 182
Problems and Discussion Topics 185

PART TWO THE FORCES BETWEEN PARTICLES

AND SURFACES 189
10. Unifying Concepts in Intermolecular and
Interparticle Forces 191
10.1. The Association of Like Molecules or Particles in
a Medium 191
10.2. Two Like Surfaces Coming Together in a Medium:
Surface and Interfacial Energy 196
10.3. The Association of Unlike Molecules, Particles, or Surfaces in
a Third Medium 197
10.4. Particle-Surface and Particle-Interface Interactions 198
10.5. Engulfing and Ejection 200
10.6. Adsorbed Surface Films: Wetting and Nonwetting 201
Problems and Discussion Topics 203
11. Contrasts between Intermolecular, Interparticle,
and Intersurface Forces 205
11.1. Short-Range and Long-Range Effects of a Force:
Qualitative Differences in the Interactions of Particles
and Small Molecules 205
11.2. Interaction Potentials between Macroscopic Bodies 208
11.3. Effective Interaction Area of Two Spheres:
the Langbein Approximation 211
11.4. Interactions of Particles Compared to Those between
Atoms or Small Molecules 212
x Contents

11.5. Interaction Energies and Interaction Forces:

the Derjaguin Approximation 215
11.6. “Body Forces” and “Surface Forces” 220
Problems and Discussion Topics 220
12. Force-Measuring Techniques 223
12.1. Direct and Indirect Measurements of Intermolecular,
Interparticle, and Surface Forces 223
12.2. Different Direct Force-Measuring Techniques 227
12.3. Mechanics of Direct Force Measurements and
Problems of Interpretation 231
12.4. Measuring Force-Distance Functions, F(D) 234
12.5. Instabilities 235
12.6. Measuring Adhesion Forces and Energies 237
12.7. Measuring Forces between Macroscopic Surfaces:
the SFA, OP/OS and Related Techniques 239
12.8. Measuring Forces between Microscopic (Colloidal)
and Nanoscopic Particles: AFM and TIRM Techniques 245
12.9. Measuring Single-Molecule and Single-Bond Interactions:
OT and MC Techniques 248
Problems and Discussion Topics 250
13. Van der Waals Forces between Particles and Surfaces 253
13.1. Van der Waals Force-Laws for Bodies of Different
Geometries: the Hamaker Constant 253
13.2. Strength of Van der Waals Forces between Bodies in a
Vacuum or Air 255
13.3. The Lifshitz Theory of Van der Waals Forces 256
13.4. Particle-Surface Interactions 259
13.5. Nonretarded Hamaker Constants Calculated on the
Basis of the Lifshitz Theory 260
13.6. Van der Waals Forces between Conducting Media 261
13.7. Theoretical and Experimental Hamaker Constants
for Interactions in a Vacuum or Air 263
 Contents xi

13.8. Applications of the Lifshitz Theory to Interactions

in a Medium 264
13.9. Repulsive Van der Waals Forces: Disjoining Pressure
and Wetting Films 267
13.10. Van der Waals Forces at Large Separations:
Retardation Effects 270
13.11. Electrostatic Screening Effects in Electrolyte Solutions 274
13.12. Combining Relations 274
13.13. Surface and Adhesion Energies 275
13.14. Surface Energies of Metals 280
13.15. Forces between Surfaces with Adsorbed Layers 281
13.16. Experiments on Van der Waals Forces 282
Problems and Discussion Topics 284
14. Electrostatic Forces between Surfaces in Liquids 291
14.1. The Charging of Surfaces in Liquids: the Electric
“Double-Layer” 291
14.2. Charged Surfaces in Water: No Added
Electrolyte—“Counterions Only” 293
14.3. The Poisson-Boltzmann (PB) Equation 293
14.4. Surface Charge, Electric Field, and Counterion
Concentration at a Surface: “Contact” Values 294
14.5. Counterion Concentration Profile Away from a Surface 296
14.6. Origin of the Ionic Distribution, Electric Field, Surface
Potential, and Pressure 298
14.7. The Pressure between Two Charged Surfaces in Water:
the Contact Value Theorem 300
14.8. Limit of Large Separations: Thick Wetting Films 303
14.9. Limit of Small Separations: Osmotic Limit
and Charge Regulation 305
14.10. Charged Surfaces in Electrolyte Solutions 306
14.11. The Grahame Equation 308
14.12. Surface Charge and Potential of Isolated Surfaces 309
xii Contents

14.13. Effect of Divalent Ions 311

14.14. The Debye Length 312
14.15. Variation of Potential jx and Ionic Concentrations rx
Away from a Surface 313
14.16. Electrostatic Double-Layer Interaction Forces and
Energies between Various Particle Surfaces 314
14.17. Exact Solutions for Constant Charge and Constant
Potential Interactions: Charge Regulation 318
14.18. Asymmetric Surfaces 321
14.19. Ion-Condensation and Ion-Correlation Forces 322
14.20. More Complex Systems: Finite Reservoir Systems and
Finite Ion-Size Effects 325
14.21. Van der Waals and Double-Layer Forces Acting
Together: the DLVO Theory 326
14.22. Experimental Measurements of Double-Layer
and DLVO Forces 331
14.23. Electrokinetic Forces 334
14.24. Discrete Surface Charges and Dipoles 335
Problems and Discussion Topics 338
15. Solvation, Structural, and Hydration Forces 341
15.1. Non-DLVO Forces 341
15.2. Molecular Ordering at Surfaces, Interfaces, and in Thin Films 342
15.3. Ordering of Spherical Molecules between Two Smooth
(Unstructured) Surfaces 345
15.4. Ordering of Nonspherical Molecules between
Structured Surfaces 347
15.5. Origin of Main Type of Solvation Force: the Oscillatory Force 349
15.6. Jamming 354
15.7. Experimental Measurements and Properties
of Oscillatory Forces 355
15.8. Solvation Forces in Aqueous Systems:
Monotonically Repulsive “Hydration” Forces 361
 Contents xiii

15.9. Solvation Forces in Aqueous Systems:

Attractive “Hydrophobic” Forces 370
Problems and Discussion Topics 378
16. Steric (Polymer-Mediated) and Thermal Fluctuation Forces 381
16.1. Diffuse Interfaces in Liquids 381
16.2. The States of Polymers in Solution and at Surfaces 381
16.3. Repulsive “Steric” or “Overlap” Forces between
Polymer-Covered Surfaces 387
16.4. Interparticle Forces in Pure Polymer Liquids
(Polymer Melts) 393
16.5. Attractive “Intersegment” and “Bridging” Forces 394
16.6. Attractive “Depletion” Forces 398
16.7. Polyelectrolytes 402
16.8. Nonequilibrium Aspects of Polymer Interactions 404
16.9. Thermal Fluctuations of and Forces between
Fluid-Like Interfaces 405
16.10. Short-Range Protrusion Forces 406
16.11. Long-Range Undulation Forces 408
Problems and Discussion Topics 411
17. Adhesion and Wetting Phenomena 415
17.1. Surface and Interfacial Energies 415
17.2. Adhesion Energies versus Adhesion Forces 419
17.3. Highly Curved Surfaces and Interfaces: Clusters,
Cavities, and Nanoparticles 422
17.4. Contact Angles and Wetting Films 429
17.5. Wetting of Rough, Textured, and Chemically
Heterogeneous Surfaces 434
17.6. Contact Angle Hysteresis 439
17.7. Adhesion of Solid Particles: the JKR and Hertz Theories 442
17.8. Adhesion Hysteresis 448
17.9. Adhesion of Rough and Textured Surfaces 452
xiv Contents

17.10. Plastic Deformations 453

17.11. Capillary Forces 456
Problems and Discussion Topics 461
18. Friction and Lubrication Forces 469
18.1. Origin of Friction and Lubrication Forces 469
18.2. Relationship between Adhesion and Friction Forces 476
18.3. Amontons’ Laws of (Dry) Friction 481
18.4. Smooth and Stick-Slip Sliding 482
18.5. Lubricated Sliding 485
18.6. Transitions between Liquid- and Solid-Like Films 490
18.7. The “Real” Area of Contact of Rough Surfaces 493
18.8. Rolling Friction 494
18.9. Theoretical Modeling of Friction Mechanisms 495
Problems and Discussion Topics 497

PART THREE SELF-ASSEMBLING STRUCTURES

AND BIOLOGICAL SYSTEMS 501
19. Thermodynamic Principles of Self-Assembly 503
19.1. Introduction: Soft Structures 503
19.2. Fundamental Thermodynamic Equations of Self-Assembly 504
19.3. Conditions Necessary for the Formation of Aggregates 509
19.4. Effect of Dimensionality and Geometry: Rods,
Discs, and Spheres 510
19.5. The Critical Micelle Concentration (CMC) 512
19.6. Infinite Aggregates (Phase Separation) versus Finite
Sized Aggregates (Micellization) 513
19.7. Hydrophobic Energy of Transfer 514
19.8. Nucleation and Growth of Aggregates 515
19.9. 2D Structures on Surfaces: Soluble and
Insoluble Monolayers 520
 Contents xv

19.10. Line Tension and 2D Micelles (Domains) 521

19.11. Soluble Monolayers and the Gibbs Adsorption Isotherm 524
19.12. Size Distributions of Self-Assembled Structures 524
19.13. Large and More Complex Amphiphilic Structures 527
19.14. Effects of Interactions between Aggregates:
Mesophases and Multilayers 528
Problems and Discussion Topics 530
20. Soft and Biological Structures 535
20.1. Introduction: Equilibrium Considerations
of Fluid Amphiphilic Structures 535
20.2. Optimal Headgroup Area 536
20.3. Geometric Packing Considerations 538
20.4. Spherical Micelles 540
20.5. Nonspherical and Cylindrical Micelles 543
20.6. Bilayers 544
20.7. Vesicles 548
20.8. Curvature/Bending Energies and Elasticities
of Monolayers and Bilayers 550
20.9. Other Amphiphilic Structures and the Transitions
between Them 558
20.10. Self-Assembly on Surfaces and Interfaces: 2D Micelles,
Domains, and Rafts 562
20.11. Biological Membranes 564
20.12. Membrane Lipids 564
20.13. Membrane Proteins and Membrane Structure 567
Problems and Discussion Topics 569
21. Interactions of Biological Membranes and Structures 577
21.1. Van der Waals Forces 577
21.2. Electrostatic (Double-Layer) and DLVO Forces 579
xvi Contents

21.3. Repulsive Entropic (Thermal Fluctuation,

Steric-Hydration) Forces: Protrusion, Headgroup
Overlap, and Undulation Forces 585
21.4. Attractive Depletion Forces 593
21.5. Attractive Hydrophobic Forces 595
21.6. Biospecificity: Complementary, Site-Specific
and Ligand-Receptor (LR) Interactions 599
21.7. Bridging (Tethering) Forces 603
21.8. Interdependence of Intermembrane
and Intramembrane Forces 605
21.9. Biomembrane Adhesion, Bioadhesion 607
21.10. Membrane Fusion 611
Problems and Discussion Topics 613
22. Dynamic Biointeractions 617
22.1. Subtleties of Biological Forces and Interactions 617
22.2. Interactions that Evolve in Space and Time:
Some General Considerations 617
22.3. Biological Rupture and Capture: The Bell
and Jarzynski Equations 619
22.4. Multiple Bonds in Series and in Parallel 622
22.5. Detachment versus Capture Processes: Biological
Importance of “Rare Events” 626
22.6. Dynamic Interactions between Biological Membranes
and Biosurfaces 626
22.7. Self-Assembly versus Directed Assembly: Dynamic Phases
and Tunable Materials 628
22.8. Motor Proteins, Transport Proteins, and Protein Engines 630
Problems and Discussion Topics 631

References 635

Index 661
 Preface to the Third Edition

Updating the first and second editions of Intermolecular and Surface Forces was not easy. The
field has exploded in many directions, both at the fundamental and applied levels, and into
new areas. New terms have appeared such as complex fluids, soft matter, nanoscience,
nanotechnology, nano-structured materials, biomimickry, and bio-inspired systems. Biolog-
ical systems are being increasingly understood and copied at all length scales, accompanied by
an increasing appreciation of dynamic (nonequilibrium, time- and rate-dependent) interac-
tions. Ever more sophisticated experimental techniques and powerful computers now allow
for highly complex systems to be studied and analyzed. Computers can now accurately mimic
complex systems and even derive new equations without actually understanding what is going
on (in the traditional sense).
The third edition contains updated material and also expands into new fields where
molecular forces play a role, such as friction, lubrication, and dynamic (non-equilibrium)
interactions. The aim has remained to provide basic physical insights and simple theoretical
methods for calculating or estimating the magnitudes of various interactions—linking the
fundamental science with practical and engineering applications. The focus is on fundamental
aspects that may be applied to different phenomena rather than particular systems or the hot
topics of the day.y
There are now many more worked examples scattered throughout each chapter and more
end-of-chapter problems. The Worked Examples are intended to illustrate different ways of
solving problems, both numerical and conceptual, that do not simply involve plugging
numbers into an equation. The problems and discussion topics at the end of each chapter are
similar, but they are often more subtle, and in some cases open-ended—in other words, ripe
for discussion. Difficult problems are starred ()), and many problems have the answers
provided but not how to solve them.
In preparing the third edition I have been helped by many. I am particularly grateful to
Erika Eiser, Suzanne Giasson, Yu Tian, Eric Kaler, Joe Zasadzinski, Dan Schwartz, William
Ducker, Marjorie Longo, Hongbo Zeng, Carlos Drummond, Stefan Karpitschka, Tonya Kuhl,
Uzi Landman, Mark Robbins, Patricia McGuiggan, Kai Kristiansen, Roger Horn, Hugo Chris-
tianson, Yuval Golan, Xavier Banquy, Travers Anderson, Wren Greene, Malte Hammer, Jing Yu,
Nataly Belman, Hernan Makse, Swapan Ghosh, Ayao Kitahara, Brian Vincent, Phil Pincus, and
Dov Levine. Special thanks to Marina Ruths for her thorough reading and critical comments,
Nancy Emerson for helping to organize the manuscript and references, Dottie McLaren for the
illustrations, and Trudi Carey for her loving support.
Santa Barbara, California
December, 29 2009

y
As another example of change, today’s “hot” topic should really be described as “cool.”

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