CHEE2940: Particle Processing

Lecture 16: van der Waals forces

This Lecture Covers

History of van der Waals forces

Origin of van der Waals forces
van der Waals interactions between particles and
surfaces

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14.1 INTRODUCTION

HISTORY OF VAN DER WAALS FORCES

• State equation for ideal gases: Relates the
pressure, P, molar volume, V, of gases

PV = RT

T … absolute temperature
-1 -1
R … universal gas constant (8.314 J mol K )

Ideal gases have no interaction between molecules.

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 • State equation for real gases

( P + a / V ) (V − b ) = RT
2

Famous van der Waals equation (1873)

- Parameter, a, depends on the attractive forces

between molecules.
- Parameter, b, depends on repulsive forces.

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 Johannes van der Waals (1837-1923)
Obtained and published his famous equation in
his doctorate in 1873 (at age 36).
- van der Waals forces between molecules
- The specific volume of gas molecules.
Awarded Nobel Prize for Physics in 1910.
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14.2 ORIGIN OF VAN DER WAALS FORCES

WHAT ARE THE VAN DER WAALS FORCES?

• They are the physical forces of attraction and
repulsion existing between molecules & atoms.
• They are not the chemical (covalent) forces
that make up the molecule (chemical bonds).

For example: A water molecule is made up of

hydrogen and oxygen, which are bonded
together by the sharing of electrons. These
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 electrostatic forces that keep a molecule intact
are existent in covalent and ionic bonding but
they are NOT the van der Waals forces.

• They come from the polarisation of molecules

into dipoles and occurs due to the interactions
between:
- Two freely rotating dipoles (Keesom), or
- A freely rotating dipole and an induced
dipole (Debye), or
- Two induced dipoles (London).

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 (Israelachvili, 1997)

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 WHAT IS A (ELECTRIC) DIPOLE?

Is a pair of electric charges

(poles) of equal magnitude but
opposite polarity, separated by a
small distance.
Dipoles are characterised by their A half of electric field around
dipole moment, a vector quantity a dipole

with a magnitude equal to the product of the charge

and the distance from the positive to negative pole.
G G
u = q ⋅l
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 POLARISATION OF ATOMS AND MOLECULES:
TEMPORARY FLUCTUATING DIPOLES AND INTERMOLECULAR ATTRACTION

On average, the negative charge of

the electrons in an atom or molecule is
spread evenly.

For brief periods of time, the electrons

are concentrated on one side of the
atom or molecule more than the other.
This gives the atom or molecule a temporary
partial negative charge - a temporary dipole
moment.
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The dipole moment will induce a
temporary dipole in a neighbouring
atom/molecule by attracting its electron
charge cloud (by the van der Waals
attraction).

A fraction of a second
later the electron
distribution changes
causing and the
temporary dipole-dipole
attraction (van der Waals
attraction) to break.
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VAN DER WAALS FORCE BETWEEN MOLECULES

It’s due to the interaction between dipole

moments of three (Keeson, Debye and London)
polarisation effects.
It acts only over relatively short distances.
Its energy is proportional to the inverse of the
sixth power of the intermolecular distances, r
CvdW Corient + Cind + Cdisp
wvdW ( r ) = − 6 = − 6
r r
C … energy coefficients
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Note the following alternative names:

- The Keeson interaction = the orientation

interaction

- The Debye interaction = the induction interaction

- The London interaction = the dispersion

interaction

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 (Israelachvili, 1997)

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In general, the dispersion interaction is the most
significant component of the van der Waals
interaction (compare the energy coefficients)

The van der Waals interaction is

sometime called the dispersion interaction

The Lennard-Jones potential

(referred to as the L-J potential or 6-12 potential)

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Unbounded atoms and molecules are subject to
two distinct forces in the limit of large distance,
and short distance: an attractive van der Waals
force at long ranges and a repulsion force due to
overlapping electron orbitals at short ranges.

 σ 
12
σ  
6

V ( r ) = 4ε   −   
 r   r  

where ε is the well depth and σ is the hard

sphere diameter. These parameters can be fitted to reproduce
experimental data or deduced from results of accurate quantum chemistry calculations.

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Interaction energy of argon dimer. The long-
range part is due to London dispersion forces.
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14.3 VAN DER WAALS INTERACTIONS
BETWEEN PARTICLES AND SURFACES

VAN DER WAALS ENERGY AND FORCE BETWEEN

PARTICLES AND SURFACES CAN BE OBTAINED BY
SUMMING (INTEGRATING) THE VAN DER WAALS
ENERGY BETWEEN ATOMS/MOLECULES COMPRISING
THE MACROSCOPIC BODIES.

Results are shown in the following table.

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 1

2 3

van der Waals energy between atoms, molecules, particles and surfaces
(Israelachvili, 1997)
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 Hamaker constant

van der Waals energy between two particles

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1. Molecule-planar surface interaction

- We sum the interaction between the

molecule and the molecules contained in
a circular ring with the cross-sectional
area dxdz and radius x

z =∞ x =∞
w( D) = ∫ ∫ w ( r ) ⋅ 2πρ xdxdz
z = D x =0

molecule-molecule # of molecules in
interaction the ring
Density of solid
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molecules 19
 C
Interaction energy between molecules: w ( r ) = − 6
r
Pythagoras’ theorem: r = x + z 2 2 2

z =∞ x =∞
xdxdz
w ( D ) = −2πρ C ∫ ∫
(x )
3
z = D x =0
2
+z 2

πρ C
w( D) = − 3
6D

van der Waals energy between a molecule and a

planar surface
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2. Interaction between planar surfaces

- We sum the interaction, w(D), between a

molecule and a planar surface, giving

z =∞
πρ1C
W ( D) = ∫ − 3
⋅ ρ 2 dz
z=D
6z

molecule-planar # of molecules per unit area in

surface interaction the object 2 with the planar
surface
Energy per unit
area
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 πρ1ρ 2C
W ( D) = − 2
12 D

Hamaker constant: A = π C ρ1ρ 2 2

A
W ( D) = −
12π D 2

van der Waals energy (per unit area) between

two planar parallel surfaces separated by a
distance D
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3. Interaction between a sphere & a planar surfaces

- We sum the interaction, w(D), between a

molecule and a planar surface, giving

z =2 R
πρ1C
W ( D) = ∫ − ⋅ ρ 2π x dz
2

6( D + z )
3
z =0

molecule-planar # of molecules in the sphere

surface interaction
Molecule density
in the sphere
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 R
x

Pythagoras’ theorem: R = x + ( R − z ) 2 2 2

x = 2 Rz − z
2 2

z =2 R
2 Rz − z 2
W ( D ) = −π ρ1ρ 2C
2
∫ 6( D + z ) 3
dz
z =0

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  R D + R 1 D + 2R 
W ( D ) = −π ρ1ρ 2C 
2
− ln 
 3 D D + 2 R 6 D 

In terms of the Hamaker constant

 R D + R 1 D + 2R 
W ( D) = − A − ln 
 3 D D + 2 R 6 D 

For short separation distances: D → 0

AR
W ( D) = −
6D
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 SUMMARY OF VAN DER WAALS FORCES AND
ENERGIES BETWEEN PARTICLES AND SURFACES

Energy
A
Flat-flat surfaces W ( D) = − per unit area
12π D 2

AR
Sphere-flat surface W ( D ) = −
6D
A R1R2
Sphere-sphere W ( D) = −
6 D R1 + R2
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 d ( Energy )
Force = −
dD

Force
A
Flat-flat surfaces F ( D) = − per unit area
6π D 3

AR
Sphere-flat surface F ( D ) = − 2
6D
A R1R2
Sphere-sphere F ( D) = −
6 D R1 + R2
2

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THE HAMAKER CONSTANT

- Depends on the properties of the interacting

surfaces and the medium.

- Weakly depends on the system geometry and

separation distance: The retardation effect
• Can be examined using the Lifshitz
quantum approach.
• Is beyond the scope of the Hamaker
theory (and this course).
• Can be neglected at short distances.
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 - Is positive for (attractive) interactions between
solid particles, air bubbles, and oil drops.

- Is negative for (repulsive) interaction between

an air bubble and a solid particle (in flotation).

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 Typical Hamaker constants
Material 1 Medium Material 2 A (10-20J) Examples
Alumina Alumina 5.0
Silica Silica 0.7
Water Mineral suspensions
Zirconia Zirconia 8.0
Titania Titania 5.5
Metal Water Metal 30 to 40
Air Water Air 3.7 Foams
Alumina Alumina 15.0
Silica Silica 6.5
Air Dry mineral powders
Zirconia Zirconia 20.0
Titania Titania 15.0
Water Octane Water 0.4 Water in oil emulsions
Water Octane Air 0.5
Silica Water Air -0.9 Mineral flotation
Octane Water Air -0.2 Oil flotation
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