INTERMOLECULAR AND SURFACE

FORCES

SECOND EDITION

JACOB N. ISRAELACHVILI

Department of Chemical & Nuclear Engineering

and Materials Department
University of California, Santa Barbara
California, USA

ACADEMIC PRESS
Harcourt Brace Jovanovich, Publishers
London San Diego New York Boston
Sydney Tokyo Toronto


Contents

PART ONE
The Forces Between Atoms and Molecules:
Principles and Concepts
Chapter 1 Historical Perspective 3
1.1 The four forces of nature 3
1.2 Greek and medieval notions of intermolecular forces 3
1.3 Early scientific period: contrasts with gravitational forces 5
1.4 First successful phenomenological theories 8
1.5 Modern view of the origin of intermolecular forces 11
1.6 Recent trends 11
Problems and discussion topics

Chapter 2 Some Thermodynamic Aspects of Intermolecular 16

Forces

2.1 Interaction energies of molecules in free space and in a 16

medium
2.2 The Boltzmann distribution 20
2.3 The distribution of molecules and particles in systems at 21
equilibrium
2.4 The van der Waals equation of state 23
2.5 The criterion of the thermal energy kT for gauging the 24
strength of an interaction
2.6 Classification of forces 27
Problems and discussion topics

Chapter 3 Strong Intermolecular Forces: Covalent and Coulomb 31

Interactions

3.1 Covalent or chemical bonding forces 31

3.2 Physical and chemical bonds 32

v

vi CONTENTS

3.3 Coulomb forces or charge-charge interactions 32

3.4 lonic crystals 35
3.5 Reference states 36
3.6 Range of Coulomb forces 36
3.7 The Born energy of an ion 37
3.8 Solubility of Ions in different solvents 38
3.9 Specific ion-solvent effects 42
3.10 Continuum approach 43
3.11 Molecular approach: computer simulations 44
Problems and discussion topics

Chapter 4 Interactions Involving Polar Molecules 48

4.1 What are polar molecules? 48

4.2 Dipole seif-energy 50
4.3 Ion-dipole interactions 50
4.4 Ions in polar solvents 54
4.5 Strong ion-dipole interactions: hydrated Ions 55
4.6 Solvation forces, structural forces, hydration forces 56
4.7 Dipole-dipole interactions 57
4.8 Rotating dipoles and angle-averaged potentials 60
4.9 Entropic effects 63
Problems and discussion topics

Chapter 5 Interactions Involving the Polarization of Molecules 67

5.1 The polarizability of atoms and molecules 67

5.2 The polarizability of polar molecules 70
5.3 Interactions between Ions and uncharged molecules 71
5.4 Ion-solvent molecule interactions and the Born energy 73
5.5 Dipole-induced dipole interactions 74
5.6 Unification of polarization interactions 75
5.7 Solvent effects and 'excess polarizabilities' 76
Problems and discussion topics

Chapter 6 van der Waals Forces 83

6.1 Origin of the van der Waals dispersion force between 83

neutral molecules: the London equation
6.2 Strength of dispersion forces: van der Waals solids and 85
Iiquids
6.3 van der Waals equation of state 90
6.4 Gas-liquid and liquid-solid phase transitions 91
6.5 van der Waals forces between polar molecules 93
6.6 General theory of van der Waals forces between molecules 96


CONTENTS vii

6.7 van der Waals forces in a medium 99

6.8 Dispersion self-energy of a molecule in a medium 103
6.9 Further aspects of van der Waals forces: anisotropy, non- 105
additivity and retardation effects
Problems and discussion topics

Chapter 7 Repulsive Forces, Total Intermolecular Pair Potentials 109
and Liquid Structure

7.1 Sizes of atoms, molecules and ions 109

7.2 Repulsive potentials 112
7.3 Total intermolecular pair potentials 113
7.4 Role of repulsive forces in non-covalently bonded solids 115
7.5 Role of repulsive forces in liquids: liquid structure 117
7.6 Effect of liquid structure an molecular forces 119
Problems and discussion topics

Chapter 8 Special lnteractions: Hydrogen-Bonding, 122

Hydrophobic and Hydrophilic Interactions

8.1 The unique properties of water 122

8.2 The hydrogen bond 123
8.3 Models of water and associated liquids 125
8.4 Relative strengths of different types of interactions 127
8.5 The hydrophobic effect 128
8.6 The hydrophobic interaction 131
8.7 Hydrophilicity 133
Problems and discussion topics

PART TWO
The Forces Between Particles and Surfaces

Chapter 9 Some Unifying Concepts in Intermolecular and 139

Interparticle Forces
9.1 Factors favouring the association of like molecules or 139
particles in a medium
9.2 Two like surfaces coming together in a medium: surface 144
and interfacial energy
9.3 Factors favouring the association of unlike molecules, 145
particles or surfaces in a third medium
9.4 Particlesurface interactions 147


VIII CONTENTS

9.5 Adsorbed surface films: wetting and non-wetting 149

Problems and discussion topics

Chapter 10 Contrasts Between Intermolecular, Interparticle and 152

Intersurface Forces

10.1 Short-range and long-range effects of a force 152

10.2 Interaction potentials between macroscopic bodies 155
10.3 Effective interaction area of two spheres: the Langbein 159
approximation
10.4 Interactions of large bodies compared to those between 159
molecules
10.5 Interaction energies and interaction forces: the Derjaguin 161
approximation
10.6 Experimental measurements of intermolecular and surface 165
forces
10.7 Direct measurements of surface and intermolecular forces 168
Problems and discussion topics

Chapter 11 van der Waals Forces Between Surfaces 176

11.1 The force laws for bodies of different geometries: the 176
Hamaker constant
11.2 Strength of van der Waals forces between bodies in 178
vacuum or air
11.3 The Lifshitz theory of van der Waals forces 179
11.4 Hamaker constants calculated on the basis of the Lifshitz 183
theory
11.5 Applications of the Lifshitz theory to interactions in a 188
medium
11.6 Repulsive van der Waals forces: disjoining pressure and 192
wetting films
11.7 Retardation effects 196
11.8 Screened van der Waals forces in electrolyte solutions 199
11.9 Combining relations 200
11.10 Surface and adhesion energies 201
11.11 Surface energies of metals 204
11.12 Forces between surfaces with adsorbed layers 206
11.13 Experiments on van der Waals forces 207
Problems and discussion topics

Chapter 12 Electrostatic Forces Between Surfaces in Liquids 213

12.1 The charging of surfaces in liquids: the electric 'double 213

layer'
 CONTENTS ix

12.2 Charged surfaces in water (no added electrolyte) 215

12.3 The PoissonBoltzmann (PB) equation 215
12.4 Surface charge, electric field and counterion concentration 217
at a surface
12.5 Counterion concentration profile away from a surface 219
12.6 Origin of the ionic distribution, electric field, surface potential 221
and pressure
12.7 The pressure between two charged surfaces in water: the 223
contact value theorem
12.8 Limitations of the PoissonBoltzmann equation 227
12.9 Thick wetting films 229
12.10 Limit of small separations: charge regulation 230
12.11 Charged surfaces in electrolyte solutions 231
12.12 The Grahame equation 233
12.13 Surface charge and potential in the presence of monovalent 234
ions
12.14 Effect of divalent ions 237
12.15 The Debye length 238
12.16 Variation of potential and ionic concentrations away from 239
a charged surface
12.17 The electrostatic double-layer interaction between charged 241
surfaces in electrolyte
12.18 van der Waals and double-layer forces acting together: 246
the DLVO theory
12.19 Experimental measurements of double-layer and DLVO 250
forces
12.20 Effects of discrete surface charges and dipoles 254
Problems and discussion topics

Chapter 13 Solvation, Structural and Hydration Forces 260

13.1 Non-DLVO forces 260

13.2 Molecular ordering at surfaces and interfaces and in thin 261
films
13.3 Origin of main type of solvation force: the oscillatory force 265
13.4 Measurements and properties of solvation forces: oscillatory 269
forces in non-aqueous liquids
13.5 Solvation forces in aqueous systems: repulsive 'hydration' 275
forces
13.6 Solvation forces in aqueous systems: attractive 'hydro- 282
phobic' forces
Problems and discussion topics

Chapter 14 Steric and Fluctutation Forces 288

14.1 Diffuse interfaces 288

14.2 Polymers at surfaces 289
X CONTENTS

14.3 Repulsive 'steric' or 'overlap' forces between polymer- 293

covered surfaces
14.4 Forces in pure polymer liquids (polymer melts) 298
14.5 Attractive 'intersegment,"bridging' and 'depletion' forces 299
14.6 Non-equilibrium aspects of polymer interactions 303
14.7 Thermal fluctuation forces between fluid-like surfaces 304
14.8 Protrusion forces 304
14.9 Undulation and peristaltic forces 307
Problems and discussion topics

Chapter 15 Adhesion 312

15.1 Surface and interfacial energies 312

15.2 Surface energies of small clusters and highly curved surfaces 317
15.3 Contact angles and wetting films 319
15.4 Hysteresis in contact angle and adhesion measurements 322
15.5 Adhesion force between solid particles: the JKR and Hertz 326
theories
15.6 Effect of capillary condensation an adhesion 330
Problems and discussion topics

PART THREE
Fluid-Like Structures and Self-Assembling Systems:
Micelles, Bilayers and Biological Membranes
Chapter 16 Thermodynamic Principles of Self-Assembly 341
16.1 Introduction 341
16.2 Fundamental thermodynamic equations of self-assembly 345
16.3 Conditions necessary for the formation of aggregates 348
16.4 Variation of pg, with N for simple structures of different 349
geometries: rods, discs and spheres
16.5 The critical micelle concentration (CMC) 351
16.6 Infinite aggregates (phase separation) versus finite-sized 352
aggregates (micellization)
16.7 Size distributions of self-assembled structures 354
16.8 More complex amphiphilic structures 360
16.9 Effects of interactions between aggregates: mesophases and 362
multilayers
16.10 Conclusion 364
Problems and discussion topics
 CONTENTS xi

Chapter 17 Aggregation of Amphiphilic Molecules into Micelles, 366

Bilayers, Vesicles and Biological Membranes

17.1 lntroduction: equilibrium considerations of amphiphilic 366

structures
17.2 Optimal headgroup area 367
17.3 Ceometric packing considerations 370
17.4 Spherical micelles 371
17.5 Non-spherical and cylindrical micelles 374
17.6 Bilayers 375
17.7 Vesicles 378
17.8 Factors affecting changes from one structure to another 380
17.9 Curvature elasticity of bilayers and membranes 382
17.10 Biological membranes 385
17.11 Membrane lipids 387
17.12 Membrane proteins and membrane structure 389
Problems and discussion topics

Chapter 18 The Interactions between Lipid Bilayers and Biological 395

Membranes

18.1 lntroduction 395

18.2 Attractive van der Waals forces 395
18.3 Electrostatic (double-layer) forces 396
18.4 Hydration forces 399
18.5 Limitations of the hydration mode) 402
18.6 Steric forces 405
18.7 Hydrophobic forces 408
18.8 Specific interactions 410
18.9 Interdependence of intermembrane and intramembrane 412
forces
18.10 Adhesion 414
18.11 Fusion 416
Problems and discussion topics

References 422
Index 437