Intermolecular and Surface Forces by Jacob N. Israelachvili by Jacob N. Israelachvili - Read Online

Book Preview

Intermolecular and Surface Forces - Jacob N. Israelachvili

You've reached the end of this preview. Sign up to read more!
Page 1 of 1

Table of Contents

Cover image

Fundamental Constants

Intermolecular and Surface Forces

Copyright

Preface to the Third Edition

Preface to Second Edition

Preface to the First Edition

Units, Symbols, Useful Quantities and Relations

Definitions and Glossary

1. Historical Perspective

1.1. The Four Forces of Nature

1.2. Greek and Medieval Notions of Intermolecular Forces

1.3. The Seventeenth Century: First Scientific Period

1.4. The Eighteenth Century: Confusion, Contradictions, and Controversy

1.5. The Nineteenth Century: Continuum versus Molecular Theories

1.6. Intermolecular Force-Laws and Interaction Potentials: Long- and Short-Range Forces

1.7. First Successful Phenomenological Theories

1.8. First Estimates of Molecular Sizes

1.9. The Twentieth Century: Understanding Simple Systems

1.10. Recent Trends

2. Thermodynamic and Statistical Aspects of Intermolecular Forces

2.1. The Interaction of Molecules in Free Space and in a Medium

2.2. Self-Energy and Pair Potential

2.3. The Boltzmann Distribution and the Chemical Potential

2.4. The Distribution of Molecules and Particles in Systems at Equilibrium

2.5. The Van der Waals Equation of State (EOS)

2.6. The Criterion of the Thermal Energy kT for Gauging the Strength of an Interaction

2.7. Classification of Forces and Pair Potentials

2.8. Theoretical Analyses of Multimolecular Systems: Continuum and Molecular Approaches

2.9. Molecular Approaches via Computer Simulations: Monte Carlo (MC) and Molecular Dynamics (MD)

2.10. Newton’s Laws Applied to Two-Body Collisions

2.11. Kinetic and Statistical Aspects of Multiple Collisions: the Boltzmann Distribution

Chapter 3. Strong Intermolecular Forces

3.1. Covalent or Chemical Bonding Forces

3.2. Physical and Chemical Bonds

3.3. Coulomb Forces or Charge-Charge Interactions, Gauss’s Law

3.4. Ionic Crystals

3.5. Reference States

3.6. Range of Electrostatic Forces

3.7. The Born Energy of an Ion

3.8. Solubility of Ions in Different Solvents

3.9. Specific Ion-Solvent Effects: Continuum Approach

3.10. Molecular Approach: Computer Simulations and Integral Equations of Many-Body Systems

4. Interactions Involving Polar Molecules

4.1. What Are Polar Molecules?

4.2. Dipole Self-Energy

4.3. Ion-Dipole Interactions

4.4. Ions in Polar Solvents

4.5. Strong Ion-Dipole Interactions in Water: Hydrated Ions

4.6. Solvation Forces, Structural Forces, and Hydration Forces

4.7. Dipole-Dipole Interactions

4.9. Hydrogen Bonds

4.10. Rotating Dipoles and Angle-Averaged Potentials

4.11. Entropic Effects

5. Interactions Involving the Polarization of Molecules

5.1. The Polarizability of Atoms and Molecules

5.2. The Polarizability of Polar Molecules

5.3. Other Polarization Mechanisms and the Effects of Polarization on Electrostatic Interactions

5.4. Interactions between Ions and Uncharged Molecules

5.5. Ion-Solvent Molecule Interactions and the Born Energy

5.6. Dipole-Induced Dipole Interactions

5.7. Unification of Polarization Interactions

5.8. Solvent Effects and Excess Polarizabilities

6. Van der Waals Forces

6.1. Origin of the Van der Waals-dispersion Force between Neutral Molecules: the London Equation

6.2. Strength of Dispersion Forces: Van der Waals Solids and Liquids

6.3. Van der Waals Equation of State

6.4. Gas-Liquid and Liquid-Solid Phase Transitions in 3D and 2D

6.5. Van der Waals Forces between Polar Molecules

6.6. General Theory of Van der Waals Forces between Molecules

6.7. Van der Waals Forces in a Medium

6.8. Dispersion Self-Energy of a Molecule in a Medium

6.9. Further Aspects of Van der Waals Forces: Anisotropy (Orientation), Nonadditivity (Many-Body), and Retardation Effects

7. Repulsive Steric Forces, Total Intermolecular Pair Potentials, and Liquid Structure

7.1. Sizes of Atoms, Molecules, and Ions

7.2. Repulsive Potentials

7.3. Total Intermolecular Pair Potentials: Their Form, Magnitude, and Range

7.4. Role of Repulsive Forces in Noncovalently Bonded Solids

7.5. Packing of Molecules and Particles in Solids

7.6. Role of Repulsive Forces in Liquids: Liquid Structure

7.7. The Effect of Liquid Structure on Molecular Forces

8. Special Interactions

8.1. The Unique Properties of Water

8.2. The Hydrogen Bond

8.3. Models of Water and Associated Liquids

8.4. Relative Strengths of Different Types of Interactions

8.5. The Hydrophobic Effect

8.6. The Hydrophobic Interaction

8.7. Hydrophilic Interactions

9. Nonequilibrium and Time-Dependent Interactions

9.1. Time- and Rate-Dependent Interactions and Processes

9.2. Rate- and Time-Dependent Detachment (Debonding) Forces

9.3. Energy Transfer (Dissipation) during Molecular Collisions: the Deborah Number

9.4. Energy Transfer during Cyclic Bonding-Unbonding Processes

9.5. Relationships between Time, Temperature, and Velocity (Rate) in Complex Processes

10. Unifying Concepts in Intermolecular and Interparticle Forces

10.1. The Association of Like Molecules or Particles in a Medium

10.2. Two Like Surfaces Coming Together in a Medium: Surface and Interfacial Energy

10.3. The Association of Unlike Molecules, Particles, or Surfaces in a Third Medium

10.4. Particle-Surface and Particle-Interface Interactions

10.5. Engulfing and Ejection

10.6. Adsorbed Surface Films: Wetting and Nonwetting

11. Contrasts between Intermolecular, Interparticle, and Intersurface Forces

11.1. Short-Range and Long-Range Effects of a Force: Qualitative Differences in the Interactions of Particles and Small Molecules

11.2. Interaction Potentials between Macroscopic Bodies

11.3. Effective Interaction Area of Two Spheres: the Langbein Approximation

11.4. Interactions of Particles Compared to Those between Atoms or Small Molecules

11.5. Interaction Energies and Interaction Forces: the Derjaguin Approximation

11.6. Body Forces and Surface Forces

Chapter 12. Force-Measuring Techniques

12.1. Direct and Indirect Measurements of Intermolecular, Interparticle, and Surface Forces

12.2. Different Direct Force-Measuring Techniques

12.3. Mechanics of Direct Force Measurements and Problems of Interpretation

12.4. Measuring Force-Distance Functions, F(D)

12.5. Instabilities

12.6. Measuring Adhesion Forces and Energies

12.7. Measuring Forces between Macroscopic Surfaces: the SFA, OP/OS and Related Techniques

12.8. Measuring Forces between Microscopic (Colloidal) and Nanoscopic Particles: AFM and TIRM Techniques

12.9. Measuring Single-Molecule and Single-Bond Interactions: OT and MC Techniques

Chapter 13. Van der Waals Forces between Particles and Surfaces

13.1. Van der Waals Force-Laws for Bodies of Different Geometries: the Hamaker Constant

13.2. Strength of Van der Waals Forces between Bodies in a Vacuum or Air

13.3. The Lifshitz Theory of Van der Waals Forces

13.4. Particle-Surface Interactions

13.5. Nonretarded Hamaker Constants Calculated on the Basis of the Lifshitz Theory

13.6. Van der Waals Forces between Conducting Media

13.7. Theoretical and Experimental Hamaker Constants for Interactions in a Vacuum or Air

13.8. Applications of the Lifshitz Theory to Interactions in a Medium

13.9. Repulsive Van der Waals Forces: Disjoining Pressure and Wetting Films

13.10. Van der Waals Forces at Large Separations: Retardation Effects

13.11. Electrostatic Screening Effects in Electrolyte Solutions

13.12. Combining Relations

13.13. Surface and Adhesion Energies

13.14. Surface Energies of Metals

13.15. Forces between Surfaces with Adsorbed Layers

13.16. Experiments on Van der Waals Forces

14. Electrostatic Forces between Surfaces in Liquids

14.1. The Charging of Surfaces in Liquids: the Electric Double-Layer

14.2. Charged Surfaces in Water: No Added Electrolyte—Counterions Only

14.3. The Poisson-Boltzmann (PB) Equation

14.4. Surface Charge, Electric Field, and Counterion Concentration at a Surface: Contact Values

14.5. Counterion Concentration Profile Away from a Surface

14.6. Origin of the Ionic Distribution, Electric Field, Surface Potential, and Pressure

14.7. The Pressure between Two Charged Surfaces in Water: the Contact Value Theorem

14.8. Limit of Large Separations: Thick Wetting Films

14.9. Limit of Small Separations: Osmotic Limit and Charge Regulation

14.10. Charged Surfaces in Electrolyte Solutions

14.11. The Grahame Equation

14.12. Surface Charge and Potential of Isolated Surfaces

14.13. Effect of Divalent Ions

14.14. The Debye Length

14.15. Variation of Potential ψx and Ionic Concentrations ρx Away from a Surface

14.16. Electrostatic Double-Layer Interaction Forces and Energies between Various Particle Surfaces

14.17. Exact Solutions for Constant Charge and Constant Potential Interactions: Charge Regulation

14.18. Asymmetric Surfaces

14.19. Ion-Condensation and Ion-Correlation Forces

14.20. More Complex Systems: Finite Reservoir Systems and Finite Ion-Size Effects

14.21. Van der Waals and Double-Layer Forces Acting Together: the DLVO Theory

14.22. Experimental Measurements of Double-Layer and DLVO Forces

14.23. Electrokinetic Forces

14.24. Discrete Surface Charges and Dipoles

15. Solvation, Structural, and Hydration Forces

15.1. Non-DLVO Forces

15.2. Molecular Ordering at Surfaces, Interfaces, and in Thin Films

15.3. Ordering of Spherical Molecules between Two Smooth (Unstructured) Surfaces

15.4. Ordering of Nonspherical Molecules between Structured Surfaces

15.5. Origin of Main Type of Solvation Force: the Oscillatory Force

15.6. Jamming

15.7. Experimental Measurements and Properties of Oscillatory Forces

15.8. Solvation Forces in Aqueous Systems: Monotonically Repulsive Hydration Forces

15.9. Solvation Forces in Aqueous Systems: Attractive Hydrophobic Forces

16. Steric (Polymer-Mediated) and Thermal Fluctuation Forces

16.1. Diffuse Interfaces in Liquids

16.2. The States of Polymers in Solution and at Surfaces

16.3. Repulsive Steric or Overlap Forces between Polymer-Covered Surfaces

16.4. Interparticle Forces in Pure Polymer Liquids (Polymer Melts)

16.5. Attractive Intersegment and Bridging Forces

16.6. Attractive Depletion Forces

16.7. Polyelectrolytes

16.8. Nonequilibrium Aspects of Polymer Interactions

16.9. Thermal Fluctuations of and Forces between Fluid-Like Interfaces

16.10. Short-Range Protrusion Forces

16.11. Long-Range Undulation Forces

17. Adhesion and Wetting Phenomena

17.1. Surface and Interfacial Energies

17.2. Adhesion Energies versus Adhesion Forces

17.3. Highly Curved Surfaces and Interfaces: Clusters, Cavities, and Nanoparticles

17.4. Contact Angles and Wetting Films

17.5. Wetting of Rough, Textured, and Chemically Heterogeneous Surfaces

17.6. Contact Angle Hysteresis

17.7. Adhesion of Solid Particles: the JKR and Hertz Theories

17.8. Adhesion Hysteresis

17.9. Adhesion of Rough and Textured Surfaces

17.10. Plastic Deformations

17.11. Capillary Forces

18. Friction and Lubrication Forces

18.1. Origin of Friction and Lubrication Forces

18.2. Relationship between Adhesion and Friction Forces

18.3. Amontons’ Laws of (Dry) Friction

18.4. Smooth and Stick-Slip Sliding

18.5. Lubricated Sliding

18.6. Transitions between Liquid- and Solid-Like Films

18.7. The Real Area of Contact of Rough Surfaces

18.8. Rolling Friction

18.9. Theoretical Modeling of Friction Mechanisms

19. Thermodynamic Principles of Self-Assembly

19.1. Introduction: Soft Structures

19.2. Fundamental Thermodynamic Equations of Self-Assembly

19.3. Conditions Necessary for the Formation of Aggregates

19.4. Effect of Dimensionality and Geometry: Rods, Discs, and Spheres

19.5. The Critical Micelle Concentration (CMC)

19.6. Infinite Aggregates (Phase Separation) versus Finite Sized Aggregates (Micellization)

19.7. Hydrophobic Energy of Transfer

19.8. Nucleation and Growth of Aggregates

19.9. 2D Structures on Surfaces: Soluble and Insoluble Monolayers

19.10. Line Tension and 2D Micelles (Domains)

19.11. Soluble Monolayers and the Gibbs Adsorption Isotherm

19.12. Size Distributions of Self-Assembled Structures

19.13. Large and More Complex Amphiphilic Structures

19.14. Effects of Interactions between Aggregates: Mesophases and Multilayers

20. Soft and Biological Structures

20.1. Introduction: Equilibrium Considerations of Fluid Amphiphilic Structures

20.2. Optimal Headgroup Area

20.3. Geometric Packing Considerations

20.4. Spherical Micelles

20.5. Nonspherical and Cylindrical Micelles

20.6. Bilayers

20.7. Vesicles

20.8. Curvature/Bending Energies and Elasticities of Monolayers and Bilayers

20.9. Other Amphiphilic Structures and the Transitions between Them

20.10. Self-Assembly on Surfaces and Interfaces: 2D Micelles, Domains, and Rafts

20.11. Biological Membranes

20.12. Membrane Lipids

20.13. Membrane Proteins and Membrane Structure

21. Interactions of Biological Membranes and Structures

21.1. Van der Waals Forces

21.2. Electrostatic (Double-Layer) and DLVO Forces

21.3. Repulsive Entropic (Thermal Fluctuation, Steric-Hydration) Forces: Protrusion, Headgroup Overlap, and Undulation Forces

21.4. Attractive Depletion Forces

21.5. Attractive Hydrophobic Forces

21.6. Biospecificity: Complementary, Site-Specific and Ligand-Receptor (LR) Interactions

21.7. Bridging (Tethering) Forces

21.8. Interdependence of Intermembrane and Intramembrane Forces

21.9. Biomembrane Adhesion, Bioadhesion

21.10. Membrane Fusion

22. Dynamic Biointeractions

22.1. Subtleties of Biological Forces and Interactions

22.2. Interactions that Evolve in Space and Time: Some General Considerations

22.3. Biological Rupture and Capture: the Bell and Jarzynski Equations

22.4. Multiple Bonds in Series and in Parallel

22.5. Detachment versus Capture Processes: Biological Importance of Rare Events

22.6. Dynamic Interactions between Biological Membranes and Biosurfaces

22.7. Self-Assembly versus Directed Assembly: Dynamic Phases and Tunable Materials

22.8. Motor Proteins, Transport Proteins, and Protein Engines

References

Index

Fundamental Constants

Intermolecular and Surface Forces

Third Edition

Jacob N. Israelachvili

University of California Santa Barbara, California, USA

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

Academic Press is an imprint of Elsevier

Copyright

Academic Press is an imprint of Elsevier

225 Wyman Street, Waltham, MA 02451, USA

525 B Street, Suite 1900, San Diego, CA 92101-4495, USA

The Boulevard, Langford Lane, Kidlington, Oxford, OX51GB, UK

Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands

Third edition 2011

Copyright © 2011, Elsevier Inc. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher

Permissions may be sought directly from Elsevier's Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: permissions@elsevier.com. Alternatively you can submit your request online by visiting the Elsevier web site at http://www.elsevier.com/locate/permissions and selecting: Obtaining permission to use Elsevier material

Notice

No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made

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 978-0-12-391927-4 (alk. paper)

1. Intermolecular forces. 2. Surface chemistry. I. Title.

QD461.I87 2011

541'.226–dc22

2010031067

ISBN: 978-0-12-391927-4

For information on all Academic Press publications visit our website at elsevierdirect.com

Printed and bound in USA

10 11 12 10 9 8 7 6 5 4 3 2 1

Preface to the Third Edition

Intermolecular forces embrace all forms of matter, and yet one finds very few university courses devoted to all aspects of this important subject. I wrote this book with the aim of presenting a comprehensive and unified introduction to intermolecular and surface forces, describing their role in determining the properties of simple systems such as gases, liquids, and solids, but especially of more complex, and more interesting, systems. These are neither simple liquids nor solids, but rather a myriad of dissolved solute molecules, small molecular aggregates, or macroscopic particles interacting in liquid or vapor. It is the forces in such systems that ultimately determine the behavior and properties of everyday things: soils, milk and cheese, paints and ink, adhesives and lubricants, many technological processes, detergents, micelles, biological molecules and membranes, and we ourselves—for each of us is one big biocolloidal system composed of about 75% water, as are most living organisms.

This subject therefore touches on a very broad area of phenomena in physics, chemistry, chemical engineering, and biology, in which there have been tremendous advances in the past 15 years. These advances can be viewed in isolation within each discipline or within a broader multidisciplinary framework. The latter approach is adopted in this book, where I have tried to present a general view of intermolecular and surface forces with examples of the various and often seemingly disparate phenomena in which they play a role.

Because of the wide range of topics covered and the different disciplines to which the book is addressed, I have presumed only a basic knowledge of the molecular sciences: physics (elementary concepts of energy and force, electrostatics), chemistry (basic thermodynamics and quantum mechanics), and mathematics (algebra and elementary calculus). The mathematical and theoretical developments, in particular, have been kept at a simple, unsophisticated level throughout. Vectors are omitted altogether. Most equations are derived from first principles followed by examples of how they apply to specific situations. More complicated equations are stated but are again carefully explained and demonstrated.

In a book such as this, of modest size yet covering such a wide spectrum, it has not been possible to treat each topic exhaustively or rigorously, and specialists may find their particular subject discussed somewhat superficially.

The text is divided into three parts, the first dealing with the interactions between atoms and molecules, the second with the interactions between hard particles and surfaces, and the third with soft molecular aggregates in solution such as micelles (aggregates of surfactant molecules) and biological membranes (aggregates of lipids and proteins). While the fundamental forces are, of course, the same in each of these categories, they manifest themselves in sufficiently different ways that, I believe, they are best treated in three parts.

The primary aim of the book is to provide a thorough grounding in the theories and concepts of intermolecular forces so that the reader will be able to appreciate which forces are important in whatever system he or she is dealing with and to apply these theories correctly to specific problems (research or otherwise). The book is intended for final-year undergraduate students, graduate students, and nonspecialist research workers.

I am deeply grateful to the following people who have read the text and made valuable comments for improving its presentation: Derek Chan, David Gruen, Bertil Halle, Roger Horn Stjepan Marcelja, John Mitchell, Håkan Wennerström, and Lee White. My thanks also extend to Diana Wallace for typing the manuscript and to Tim Sawkins for his careful drawing of most of the figures. But above all, I am indebted to my wife, Karina, without whose constant support this book would not have been written.

Canberra, Australia

October 24, 1984

Preface to Second Edition

Since 1985, when the first edition of this book appeared, there has been much experimental and theoretical progress in this multidisciplinary subject. The nature of some old forces have been clarified while new forces have been discovered. The subject has matured into a rigorous discipline and a unifying area of chemistry, physics, and biology, and many university courses now routinely contain material on molecular and surface interactions. On the more practical side, many industrial and chemical engineering processes are now beginning to be understood and controlled at the fundamental level. It is with these developments in mind, together with the feedback I received from numerous colleagues, that the second edition was prepared.

The second edition is basically an updated version of the first, but it contains more than 100 problems. Most appear at the end of each chapter, but some appear as worked examples in the text. These problems should enhance the suitability of the book as an advanced undergraduate or graduate textbook. The problems have been devised to stimulate the mind; many are based on genuine research problems, others are tricky, some are extensions of the text into more advanced areas, and a few are open-ended to invite further reading, discussion, and even speculation.

The text itself has been expanded to include recent developments in the areas of surface-force measurements, solvation and structural forces, hydration and hydrophobic forces, ion-correlation forces, thermal fluctuation forces, and particle and surface interactions in polymer melts and polymer solutions.

I am grateful to many colleagues who commented on the first edition, and I have used their suggestions in writing the second. In particular, my thanks go to Hans Lyklema, Håkan Wennerström and Jacob Klein, to Helen Vydra and Josefin Israelachvili for typing the manuscript, to Dottie McLaren for drawing many of the figures, to my wife Karina who supported me throughout, and finally to my students who have sat through my lectures and by their questions have unwittingly contributed the most.

Santa Barbara, California

October 24, 1989

Preface to the First Edition

Intermolecular forces embrace all forms of matter, and yet one finds very few university courses devoted to all aspects of this important subject. I wrote this book with the aim of presenting a comprehensive and unified introduction to intermolecular and surface forces, describing their role in determining the properties of simple systems such as gases, liquids, and solids, but especially of more complex, and more interesting, systems. These are neither simple liquids nor solids, but rather a myriad of dissolved solute molecules, small molecular aggregates, or macroscopic particles interacting in liquid or vapor. It is the forces in such systems that ultimately determine the behavior and properties of everyday things: soils, milk and cheese, paints and ink, adhesives and lubricants, many technological processes, detergents, micelles, biological molecules and membranes, and we ourselves—for each of us is one big biocolloidal system composed of about 75% water, as are most living organisms.

This subject therefore touches on a very broad area of phenomena in physics, chemistry, chemical engineering, and biology, in which there have been tremendous advances in the past 15 years. These advances can be viewed in isolation within each discipline or within a broader multidisciplinary framework. The latter approach is adopted in this book, where I have tried to present a general view of intermolecular and surface forces with examples of the various and often seemingly disparate phenomena in which they play a role.

Because of the wide range of topics covered and the different disciplines to which the book is addressed, I have presumed only a basic knowledge of the molecular sciences: physics (elementary concepts of energy and force, electrostatics), chemistry (basic thermodynamics and quantum mechanics), and mathematics (algebra and elementary calculus). The mathematical and theoretical developments, in particular, have been kept at a simple, unsophisticated level throughout. Vectors are omitted altogether. Most equations are derived from first principles followed by examples of how they apply to specific situations. More complicated equations are stated but are again carefully explained and demonstrated.

In a book such as this, of modest size yet covering such a wide spectrum, it has not been possible to treat each topic exhaustively or rigorously, and specialists may find their particular subject discussed somewhat superficially.

The text is divided into three parts, the first dealing with the interactions between atoms and molecules, the second with the interactions between hard particles and surfaces, and the third with soft molecular aggregates in solution such as micelles (aggregates of surfactant molecules) and biological membranes (aggregates of lipids and proteins). While the fundamental forces are, of course, the same in each of these categories, they manifest themselves in sufficiently different ways that, I believe, they are best treated in three parts.

The primary aim of the book is to provide a thorough grounding in the theories and concepts of intermolecular forces so that the reader will be able to appreciate which forces are important in whatever system he or she is dealing with and to apply these theories correctly to specific problems (research or otherwise). The book is intended for final-year undergraduate students, graduate students, and nonspecialist research workers.

I am deeply grateful to the following people who have read the text and made valuable comments for improving its presentation: Derek Chan, David Gruen, Bertil Halle, Roger Horn Stjepan Marcelja, John Mitchell, Håkan Wennerström, and Lee White. My thanks also extend to Diana Wallace for typing the manuscript and to Tim Sawkins for his careful drawing of most of the figures. But above all, I am indebted to my wife, Karina, without whose constant support this book would not have been written.

Canberra, Australia

October 24, 1984

Units, Symbols, Useful Quantities and Relations

Much of the published literature and equations on intermolecular and surface forces are based on the CGS system of units. In this book the Système International (SI) is used. In this system the basic units are the kilogram (kg) for mass, the meter (m) for length, the second (s) for time, the kelvin (K) for temperature, the ampére (A) for electrical quantities, and the mole (mol) for quantity of mass. Some old units such as gramme (1 gm = 1 g = 10 −3 kg) , centimeter (1 cm = 10 −2 m), ångstrom (1 Å = 10 −10 m) and degree centigrade (°C) are still commonly used, although they are not part of the SI system. The SI system has many advantages over the CGS, not least when it comes to forces. For example, force is expressed in newtons (N) without reference to the acceleration due to the earth's gravitation, which is implicit in some formulae based on the CGS system. Note that units, prefixes, words, and abbreviations are usually unitalicized—that is, in text format (e.g., J, K, m, N, volts V), whereas variables are italicized (e.g., stiffness K, mass m, number N, maximum number Nmax, velocity or volume V).

Definitions of Terms and Symbols Used in the Text

Abbreviations

Conversion from CGS to SI

1 Å (ångstrom) = 10 −10 m = 10 −8 cm = 10 −4 μm = 0.1 nm

1 liter = 10 −3 m ³ = 1 dm ³

Density, ρ(kg m −3) = 10 ³ρ(g/cm ³)

Molecular weight, M (kg mol −1) = 10 −3M (gm/mole)

1 erg = 10 −7 J

1 cal = 4.184 J

1 kcal mole −1 = 4.184 kJ mol −1

1 kT = 4.114 × 10 −14 erg = 4.114 × 10 −21 J at 298 K (~25°C)

= 4.045 × 10 −14 erg = 4.045 × 10 −21 J at 293 K (~20°C)

= 4.281 × 10 −14 erg = 4.281 × 10 −21 J at 310 K (body temperature, ~37°C)

1 kT per molecule = 0.592 kcal mole −1 = 2.478 kJ mol −1 at 298 K

1 eV = 1.602 × 10 −12 erg = 1.602 × 10 −19 J

1 eV per molecule = 23.06 kcal mol −1= 96.48 kJ mol −1

1 cm −1 (wave number unit of energy) = 1.986 × 10 −23 J

1 dyne = 1 g cm s −2 = 10 −3 kg 10 −2 m s −2 = 10 −5 N

1 dyne cm −1 = 1 erg cm −2 = 1 mN m −1 = 1 mJ m −2 (unit of surface tension or energy)

1 dyne cm −2 = 10 −1 Pa or N m −2 (unit of pressure).

1 atm = 1.013 × 10 ⁶ dyne cm −2 = 1.013 bar = 1.013 × 10 ⁵ Pa (N m −2)

1 Torr = 1 mm Hg = 1.316 × 10 −3 atm = 133.3 Pa (N m −2)

0°C = 273.15 K (triple point of water)

1 esu = 3.336 × 10 −10 C

1 poise (P) = 1 dyne s cm −2 = 0.1 N s m −2 = 0.1 Pa s (unit of viscosity)

1 Stokes (St) = cm ² s −1 = 10 −4 m ² s −1 (unit of kinematic viscosity: viscosity/density)

Debye (D) = 10 −18 esu = 3.336 × 10 −30 C m (unit of electric dipole moment)

Conversion from SI to CGS

1 nm = 10 −9 m = 10 Å = 10 −7 cm

1 J = 10 ⁷ erg = 0.239 cal = 6.242 × 10 ¹⁸ eV = 5.034 × 10 ²² cm −1 = 7.243 × 10 ²² K

1 kJ mol −1 = 0.239 kcal mole −1 = 0.404 kT per molecule at 298 K

mass or weight of 0.102 kg (102 gm) in a gravitational field of g = 9.81 m s −2

1 Pa = 1 N m −2 = 10 dyne cm −2 = 9.872 × 10 −6atm = 7.50× 10 −3 torr = 1.45 × 10 −4 psi (lb/in ²)

1 bar = 10 ⁵ N m −2 = 10 −5 Pa = 0.9868 atm = 750.06 mm Hg

Useful Quantities and Relations, Other Conversions

Mass of any atom or molecule = M/N 0 (also MW/N 0) g

Mean volume occupied per molecule = M/(N 0 × mass density) m ³

Converting mass density ρm (kg m −3) to number density ρn (molecules m −3): ρn = ρmN 0/ M

Molar concentration: 1 M = 1 mol dm −3 (mole/litre) = 6.022 × 10 ²⁶ molecules per m ³

Number density (solution concentration): ρ = M × 6.022 × 10 ²⁶ molecules per m ³

Standard volume of ideal gas = 22.414 × 10 −3 m ³ mol −1 (22.414 liters/mole)

4 πɛ0 = 1.113×10 −10 C ² J −1 m −1

kT/ e = RT/F = −25.69 mV at 298 K (~25°C) = −26.72 mV at 310 K (~37°C, body temperature)

1 C m −2 = 1 unit charge per 0.16 nm ² (16 Å ²)

κnm for 1:1 electrolyte at 298 K (25°C)

Mass of the earth = 5.976 × 10 ²⁴ kg

Density of earth (mean) = 5.518 × 10 ³ kg m −3

Values of gravitational acceleration, g: Standard gravity (9.80665 m s −2), Equator (9.780 m s −2), North and south poles (9.832 m s −2), New York (9.801 m s −2), London (9.812 m s −2).

Some Geometric Relations for Truncated Sphere and Cap of Height d (Shaded)

Height of cap: d = R(1−cos θ), sin θ = r/ R

≈ 2 Rd for R » d

volume of cap

= 2 πR²(1 − cos θ)

= 2 πR²(1 + cos θ)

Area of flat circular base of cap: πr

Definitions and Glossary

These days, online information is so good and readily accessible that it is no longer necessary to define or introduce basic terms or concepts in a text book. The reader should refer to such sources whenever new or unfamiliar terms are used, such as simple harmonic motion, resonance frequency, the Grotthuss Mechanism, the Vroman effect, and von Schröder's Paradox. It is for this reason that this glossary is so short.

Amphiphile

Molecules such as surfactants and lipids where one part is hydrophilic (the headgroup) and the other is hydrophobic, usually a long hydrocarbon chain.

Classical

An adjective that describes nonquantum mechanical systems whose molecules obey Boltzmann statistics.

Colloid

A colloid is a dispersion of particles in solution. The size of colloidal particles is in the microscopic regime, ranging from 0.005 to 100 μm. Only one dimension of a particle needs to be in this range to qualify it as a colloidal particle—for example, a 5 nm thick lipid bilayer of macroscopic area. Particles in the size range from 1 to 100 nm are now referred to as nanoparticles, this being the range of sizes where atomic properties make the transition to microscopic or macroscopic properties.

Critical micelle concentration (CMC), critical aggregate concentration (CAC)

The concentration at which further addition of solute molecules to a solvent makes them go into finite sized micelles (aggregates) while the monomer concentration remains unchanged at the CMC (CAC).

Directed assembly

See Self-assembly.

Energy dissipated

The energy that one system (molecule, particle or lattice) transfers to another system during an interaction. This can be in the form of translational kinetic energy or heat (e.g., internal vibrational and rotational energy).

Engineering conditions

Range of time, length, mass, temperature, and so on, encountered in everyday phenomena (see Table 9.1).

Equilibrium

Mechanical equilibrium is one where a small deviation from the equilibrium state brings the system back to that state; thermodynamic equilibrium is the lowest free-energy state—the state of true equilibrium. A system in mechanical equilibrium is not necessarily in the true equilibrium state, from which it may be separated by an energy barrier. A state can also be in thermal equilibrium (the temperature is uniform throughout), but not in mechanical or thermodynamic equilibrium. See Section 22.2 for more on nonequilibrium systems.

Extensive

Thermodynamic term for property that depends on the number of molecules N or moles n or the total volume V of the system—for example, the mass or total energy of the system. Cf. Intensive, Specific.

Intensive

Thermodynamic term for property that does not depend on the size or number of molecules in a thermodynamic system, for example, pressure, temperature, viscosity, surface tension. Cf. Extensive, Specific.

Self-assembly

The natural (spontaneous, thermodynamically driven) organization of atoms and molecules into multimolecular structures. Directed or engineered assembly refers to external energy-requiring processes that lead to nonequilibrium, but often long-lived, structures, or to a stable steady-state organization but only so long as there is a constant rate of energy input.

Specific

(i) Thermodynamic term for intensive property produced by dividing one extensive property by another—for example, specific molecular volume (volume occupied per molecule) v = V/ N, specific molar volume v = V/ n. Cf. Intensive, Extensive. (ii) Biological term for interaction or bond between two specialized groups that uniquely recognize each other. Specific bonds do not have to be strong. Also complementary, lock-and-key, ligand-receptor (L-R or LR) bonding.

1. Historical Perspective

1.1. The Four Forces of Nature

It is now well-established that there are four distinct forces in nature. Two of these are the strong and weak interactions that act between neutrons, protons, electrons, and other elementary particles. These two forces have a very short range of action, less than 10 −5 nm, and belong to the domain of nuclear and high-energy physics. The other two forces are the electromagnetic and gravitational interactions that act between atoms and molecules (as well as between elementary particles). These forces are effective over a much larger range of distances, from subatomic to practically infinite distances, and are consequently the forces that govern the behavior of everyday things (Figure 1.1). For example, electromagnetic forces—the source of all intermolecular interactions—determine the properties of solids, liquids, and gases, the behavior of particles in solution, chemical reactions, and the organization of biological structures. Gravitational forces account for tidal motion and many cosmological phenomena, and when acting together with intermolecular forces, they determine such phenomena as the height that a liquid will rise in small capillaries and the maximum size that animals and trees can attain (Thompson, 1968).

This book is mainly concerned with intermolecular forces. Let us enter the subject by briefly reviewing its historical developments from the ancient Greeks to the present day.

1.2. Greek and Medieval Notions of Intermolecular Forces

The Greeks were the first to consider forces in a nonreligious way. They found that they needed only two fundamental forces to account for all natural phenomena: Love and Hate. The first brought things together, while the second caused them to part. The idea was first proposed by Empedocles around 450 B.C., was much improved by Aristotle, and formed the basis of chemical theory for 2000 years.

The ancients appear to have been particularly inspired by certain mysterious forces, or influences, that sometimes appeared between various forms of matter (forces that we would now call magnetic or electrostatic). They were intrigued by the action-at-a-distance property displayed by these forces, as well as by gravitational forces, and they were moved to reflect upon their virtues. What they lacked in concrete experimental facts they more than made up for by the abundant resources of their imagination (Verschuur, 1993). Thus, magnetic forces could cure diseases, though they could also cause melancholy and thievery. Magnets could be used to find gold, and they were effective as love potions and for testing the chastity of women. Unfortunately, some magnetic substances lost their powers if rubbed with garlic (but they usually recovered when treated with goat’s blood). Electric phenomena were endowed with attributes no less spectacular, manifesting themselves as visible sparks in addition to a miscellany of attractive or repulsive influences that appeared when different bodies were rubbed together. All these wondrous practices, and much else, were enjoyed by our forebears until well into the seventeenth century and may be said to constitute the birth of our subject at the same time as alchemy, astrology, and the search for perpetual motion machines, which paved the way for chemistry and physics.

Still, notwithstanding the unscientific or prescientific nature of these practices, some important conceptual breakthroughs were made that deserve to be recognized. Ask any schoolboy or schoolgirl what the three most memorable scientific discoveries of antiquity are, and they will very likely mention Archimedes, Galileo, and Newton (see Figure 1.1). In each case, what happened (or is alleged to have happened) is well known, but what is less well known are the conceptual breakthroughs whose implications are with us today. Put into modern jargon, when Archimedes (287–212 B.C.) discovered Archimedes’ Principle, he had discovered that the force of gravity on a body can change—even its sign from attraction to repulsion—when it is placed in a medium that it displaces. Later we shall see that such displacement effects occur with many other types of interactions, such as van der Waals forces, with important consequences that in some cases have only recently been appreciated.

1.3. The Seventeenth Century: First Scientific Period

The notion of doing experiments to find out how nature works was an unknown concept until Galileo (1564–1642) demonstrated its power in his classic experiments on gravity, the motion of bodies, optics, astronomy, and proving the existence of a vacuum. In this he introduced the modern scientific method (Table 1.1).

But Galileo also introduced a new way of thinking that was not purely metaphysical. As an example, his experiment of throwing two different balls from the Tower of Pisa was conducted only after he had worked out the answer by applying a new form of reasoning—what we would today call scaling arguments—to Aristotelean Physics (see Problem 1.1), and his testing of his hypothesis by direct experiment was at the time also highly novel. ¹ This is also true of Newton’s discovery of the Law of Gravitation when an apple fell on his head. We must pause to think about how many previous heads, when struck by a falling apple, were prompted to generalize the phenomenon to other systems such as the orbit of the moon around the earth when acted on by the same force—a thought process that requires a leap of the imagination by a factor of 10 ⁶ in time, 10 ⁸ in distance, and 10 ²⁴ in mass.

¹Galileo’s English contemporary Francis Bacon (1561–1626) may be credited with the introduction of inductive reasoning and the first to practice experimental research. Unfortunately, his first experiment was also his last: While testing the effects of cold on preserving meat by stuffing a disemboweled chicken with snow, he caught a chill and died.

But trouble was just round the corner. In 1662 Robert Boyle (1627–1691) published his famous gas law, PV = constant. Twenty-five years later, Isaac Newton (1642–1727) published his famous law of gravity. Boyle’s Law suggested that molecules repel each other (the pressure P in PV = constant is repulsive), while gravity suggested that they attract. Newton also concluded that the molecules of a gas must ultimately attract each other, since they condense into liquids or solids. These apparent contradictions sowed the first of many seeds that were to lead to heated controversies in the two centuries to come.

Worked Example 1.1

Question: If the experimental observation that PV , where ρ is the density? Do not use any concepts that came after the eighteenth century.

Answer: In the eighteenth century, matter and space were believed to be made up of corpuscles that were stationary. There was no kinetic theory of gases, no collisions between molecules, and no thermodynamics. The concept of potential energy was still unknown, and everything was described in terms of mechanical forces that were mediated by some intervening medium or fluid known as the aether or caloric.

Let the repulsive force between two molecules be given by + C/ rn. Consider a cube of gas with sides of length L and volume V = L³. Let there be N molecules within this volume, each occupying a volume v = r³, where r is the distance between any two molecules. We therefore have N = V/ v = L³/ r³, so that for constant N, r L. Now, each side of area L² will have L²/ rand, therefore, a pressure of P . Thus, if experimentally P ∝ 1/ V, we may write P ∝ 1/ V ∝ 1/ L³ ∝ 1/ r³ (since r L), and we finally obtain n = 3 – 2 = 1, implying that the repulsive intermolecular force-law is F = + C/ r. More generally, for P ∝ (1/ V) m ρ m, we obtain n = 3 m – 2.

1.4. The Eighteenth Century: Confusion, Contradictions, and Controversy

The above conclusion, and much else—including his gravitational force-law and the development of the calculus—was published by Newton in his famous Principia (1687, 1713, 1726). ² But in spite of the tremendous advances made by Newton, the period between his Principia and the beginning of the nineteenth century was marked by confusion, contradictions, and controversy (Rowlinson, 2002). Here are some of the most notable ones:

²The three dates refer to the three editions of this—probably the most influential scientific text of all time. It includes his Opticks, published in 1704. The calculus, discovered jointly with Leibniz in the 1680s, allowed for the mathematical analysis and development of scientific theories.

• The derivation of an inverse distance law to account for the behavior of gases was known (even by Newton) to be unphysical when integrated over many molecules and/or large distances (see Section 1.6).

• Newton’s law of gravity required an instantaneous force to act across a vast vacuum. The idea of action at a distance with no intervening substance or mechanism for its transmission led to accusations that this was tantamount to invoking some supernatural or occult force that the new field of natural philosophy was supposed to avoid.

• When considering the forces between particles over distances from the very large to the very small, an unsettling picture emerged where these forces start off being attractive (the gravitational force), then repulsive (in gases, as concluded in Worked Example 1.1), then attractive again (to account for solids and liquids), and finally repulsive (to account for the fact that matter does not disappear into itself). The notion of a generic oscillatory force between all particles was proposed by Boskovich (1711–1787), and heat was believed to be a substance (caloric) that increased the repulsive part of this interaction.

• The observations that the capillary rise of liquids did not depend on the capillary wall thickness, however thin, ³ implied that interparticle forces must be of very short range. However, the equally undeniable fact that the liquid rises to a substantial height, even in tubes having macroscopic inner radii, suggested that these forces must be of long range, since they are able to reach the liquid molecules in the center of the tube.

³These experiments and many others were performed by Francis Hauksbee (1666–1713), who was Newton’s demonstrator at the Royal Society.

But the eighteenth century also saw major advances in pure and applied mathematics by Euler, LaGrange, Laplace, and others (see Table 1.1) that proved to be invaluable for analyzing and interpreting experimental data.

1.5. The Nineteenth Century: Continuum versus Molecular Theories

The first half of the nineteenth century saw a continuation of the controversy about whether matter was a continuum or made up of molecules (atoms, particles, or corpuscles), with the balance slowly tilting toward the continuum picture. Newton had believed that matter, including light, was made of particles, but Young’s work on optical interference fringes showed that light behaved like waves. There were also theoretical successes in explaining many physical phenomena in terms of continuum field theories without the need to invoke molecules. And so the belief in molecules declined. According to Maxwell (1831–1879), the main reason that, by the mid-nineteenth century, no one believed in molecules any longer was not because anyone had shown that they did not exist but because all those who believe in molecules are now dead.

Much of the progress during the nineteenth century came from work on liquid surfaces, especially the capillary rise of liquids in glass tubes. In 1808 Clairaut suggested that capillarity could be explained if the attraction between the liquid and glass molecules was different from the attraction of the liquid molecules for themselves. It was also noticed that the height of rise of a liquid column does not depend on the capillary wall thickness, which led to the conclusion that these forces must be of very short range or, in the language of the time, extended over insensible distances.

⁴Although, as was noted in Section 1.4, the same phenomenon also seemed to suggest that these forces act over large distances.

The latter half of the nineteenth century saw the return of molecules, thanks to the successes of the new kinetic theory and the van der Waals equation of state, both of which required attracting molecules to explain them. Clausius (1822–1888), Maxwell (1831–1879), van der Waals (1837–1923), and Boltzmann (1844–1906) were the main players⁵ in unifying continuum theories such as thermodynamics and mean-field theories with molecular theories through the new field of statistical mechanics (see Table 1.1). But the origin of the forces themselves remained a mystery until the advent of quantum theory in the 1920s.

⁵Or natural philosophers, as they were still called. Articles by Maxwell, Rayleigh, and others in the ninth edition of the encyclopedia Britannica of 1878 are still a good read. This edition was the last attempt to include the whole of science, as it was then known, in one encyclopedia.

1.6. Intermolecular Force-Laws and Interaction Potentials: Long- and Short-Range Forces

An important theoretical advance of the nineteenth century, thanks to the mathematical developments of the previous century, was the use of energy to analyze interactions and the properties of many-body systems; this allowed progress to be made in various areas, including thermodynamics. William Rankine (1820–1872) is generally considered to have pioneered the science of energetics whereby the vector forces and motions of Archimedes, Galileo, and Newton were replaced by scalar energy functions. ⁶ As we shall see, in many cases the two approaches are equivalent, but where time- and rate-dependent interactions are involved, they are not. In other words, the force is not always simply the derivative of the energy-distance function (see Problems 1.4, 1.5, and 9.1, 9.4). New terms were coming into usage in addition to simple energy and force: internal energy, available energy, energy or force per unit length, per unit area, per unit volume (energy density), internal pressure, applied pressure, and more, and it remains an intellectual challenge to this day to be able to clearly distinguish among the many different types of energies and forces (Figure 1.2).

⁶Many others contributed to the development of the concept of energy in different fields (see Chapter 2).

During the nineteenth century, it was believed that one simple universal force law or potential energy function, similar to Newton’s law for the gravitational force, would eventually be found to account for all intermolecular attractions. To this end, a number of interaction potentials were proposed that invariably contained the masses of the molecules, attesting to the belief at the time that these forces are related to gravitational forces. Thus, typical attempts to model interaction potentialsw( r) for two molecules were of the form w( r) = − Cm1m2/ r n, which is related to the force law F( r) between the molecules by

⁷Also pair potential, in units of energy (Joules, J).

(1.1)

where m1, m2 are the molecular masses, r their separation, C a constant, and n some integer believed to be 4 or 5, ⁸ which may be compared with n = 1 for the gravitational interaction:

⁸See footnote 3 in Chapter 6 to find out why Eq. (1.1) was almost successful. For an account of the lively theoretical activities of this time, see the introductory History of Intermolecular Forces in Margenau and Kestner (1971).

(1.2)

It is instructive to see how the power-law index n was so chosen. It arose partly from a frantic attempt to fit experimental data to equations containing n as an adjustable parameter but also from an appreciation of the fact, first noted by Newton, that if intermolecular forces are not to extend over large distances, the value of n must be greater than 3. Why this is so can be simply established as follows: Suppose the attractive potential between two molecules or particles to be of the general form w( r) = – C/ r n, where n is an integer. Now consider a region of space where the number density of these molecules is ρ. This region can be a solid, a liquid, a gas, or even a region in outer space extending over astronomical distances. Let us add all the interaction energies of one particular molecule with all the other molecules in the system. The number of molecules in a region of space between r and ( r+ d r) away will be ρ4 πr²d r (since 4 πr²d r is the volume of a spherical shell of radius r and thickness d r—in other words, of area 4 πr² and thickness d r). The total interaction energy of one molecule with all the other molecules in the system will therefore be given by

(1.3)

(1.4)

where σ is the diameter of the molecules and L is the size of the system—for example, the dimensions of a solid or the size of the box containing a gas. We can see that since σ must be smaller than L (i.e., σ/ L < 1), large distance contributions to the interaction will disappear only for values of n greater than 3—that is, for n = 4, 5, 6, . . . . But for n equal to or smaller than 3, ⁹ the second term in Eq. (1.3) will be greater than 1, and the contribution from more distant molecules will dominate over that of nearby molecules. In such cases the size of the system must be taken into account, as occurs for gravitational forces where n =