CHEM-E2150

Interfacial Phenomena in
Biobased Systems

Surface interactions part 1:

Van der Waals Forces
Monika Österberg
Spring 2018
Content
Colloidal stability
van der Waals Forces

Surface Forces and their Effect on Colloidal

Stability
•Why is colloidal stability important?
•Why are surface forces important?

•Why are van der Waals forces important

About colloidal stability

Flocculation: reversible association

Coagulation: irreversible association
Difference between lyophilic and lyophobic colloids
Lyophilic colloids are thermodynamically stable colloids
The Stability of Colloids

Flocculation/coagulation:

Factors affecting flocculation:

Frequency of collision is aff. by: Energy of collision is affected by:
- Concentration
- Mixing - The interactions between particles
- Particle shape - The distance dependence
- Diffusion rate of the interactions
- Sedimentation, convection

4
Attractive and Repulsive Interactions
The total interaction is the sum of several components, some attractive,
some repulsive
Interaction energy
 The sum may be
Repulsion
a curve with maxima and minima

We learn about surface forces Sum

to be able to predict this
behavior. D

Should the interaction be

repulsive or attractive for Attraction
colloidal stability?
D
Stable colloid means that the
particles stays apart – net
repulsive interaction needed
Structure and Strength of Flocs

Fast coagulation, Slow coagulation,

strong adhesion weak adhesion

Porous, fragile floc Weaker but tighter

Fast percolation floc, which
percolate poorly
Surface Forces

DLVO theory on colloidal stability

DLVO = Derjaguin – Landau –Verwey – Overbeck

The interactions between two surfaces is the sum of the van

der Waals forces and the electrostatic double layer forces
• Today. van der Waals Forces
• Next lecture: Electrostatic Double Layer Forces and non DLVO
interactions
Why are the Forces between Molecules
Important?

Forces between molecules → forces between surfaces. These

surface forces again affect the properties of colloidal
dispersions and other technical systems.

8
What are the forces between
molecules?
Interactions between particles, surface tension, cohesion, adhesion
and adsorption are dependent on molecular interactions.
The interactions are electromagnetic and can be classified:
1. Interactions between permanent dipoles or ions
– Ion – ion
• Ion – dipole
• Dipole – dipole
2. Interactions between permanent and induced dipoles or ions
• Ion – induced dipole
• Dipole – induced dipole
3. Interactions between two induced dipoles
4. Overlap of electron clouds
5. Hydrogen bonding
– bridge between one hydrogen atom bonded to a electronegative atom
(F, O, N, Cl) and another electronegative atom
6. Lewis acid/base interactions
– Donation of electron from one functional group to another
9
Intermolecular forces

Interactions between ions

+ -
(Coulomb forces)

-
+
Van der Waals forces: forces induced +
-
by dipole moments
H
O
Acid/base interactions, H

Hydrogen bonds
O
H H 10
Interactions between ions: Coulomb
forces
Coulombs law: The force between two charges in vacuum is:
q1q2 q q
Fc  o = vacuum permittivity = 8,854·10 N m
-12 -1 -2
1 2
4 o d 2 d

The magnitude and sign of each ionic charge (q1 and q2) is given in terms of the
elementary charge (eo = 1,602·10-19 C ) multiplied by the valency (z1, z2 )
 q1 = z1eo, q2 = z2eo

Coulombs law: The force between two ions in a solvent is:

q1q 2 z1z2eo2
Fc    = relative permittivity (or dielectric constant) of solvent
4 o d 2
4 o d 2

The interaction energy of the ions at distance d is:

d
z1z2eo2
Uc    Fc ds  
 4 o d
11
 Why does salt dissolve in water?
The Coulomb forces keep the ion crystal together. Compare the
coloumb force with the kinetic energy
Consider two monovalent ions, at a distance d = 0,5 nm from each other.
1 3 3
The kinetic energy of the ion (T = 25oC) = mv 2  kT  1,38 1023 J/K  298 K = 6,17 1021 J
2 2 2
In vacuum ( = 1):

Uc  
z1 z2e02

 2
1,602 1019 C 2
4 0 d 4 1 8,854 1012 C 2 N -1m -2  0,5 109 m 2
 4,62 1019 J >> kT
Note: add a
minus sign
In water  = 78,5: UC= - 5,9·10-21J ≈ kT

In water the interaction energy between ions is about the same as the thermal energy.

The forces keeping the ions together in water are so small that the salt dissolves
when the mixing entropy increases. 12
Note

Positive force = ions repel each other.

The electrostatic forces decrease slowly with increasing
distance.
The Coloumb forces decrease when (εr ) increase.

Question: Why does salt dissolve better in water than in oil?

Note: εr ~ 2 for many nonpolar solvents so

the Coloumb force is much stronger in oil
than i water

13
Permanent dipole moment – polar
molecules
The dipole moment of a polar molecule consisting of
charges +q and -q at a distance r is:
_ _
d  qr
The dipole moment is a vector with the direction from the negative to the positive charge.

Neutral molecules often have a dipole moment due to the q1

+
different electronegativity of the atoms. r1
r2
– + q2
A molecules permanent dipole moment is the
vector sum of the dipole moments of the bonds r3
+ q
3
_ _
 d   qi ri
i
H
The electric field around a dipole interacts
with other molecules.
O

14

H
Interaction between an ion and a permanent
dipole
Consider an ion and a adjacent water molecule.
The water molecule has a permanent dipole moment (6,17·10-30 C m)
d +
+
q r
-
Assuming that the water molecule is bound with a permanent angle q.
The interaction energy between the ion and the water molecule at a
distance d
(if d >> r cos qis: ze  cosq
Uiondipole   o
4 od 2


If the water molecule is in contact with a sodium ion d=0,23 nm.

Inserting the dipole moment of water and d = 0,23 nm we get:
( = 1)

Uion-dipole = - 1,7·10-19J ≈ -40 kT (T = 25oC ).

The first hydration layer is rigidly bonded (the hydration effect). 15
Note

The interaction depends on the angle between the ion and the
dipole.
• The maximum attraction between a cation and a dipole is reached
when q = 0, cos q = 1 ;
The maximum repulsion is reached when q = 180º, cos q = 0.
The interaction decreases faster as a function of the distance
than the interaction between two ions.

16
 Polarizability
The molecules in bulk phase are usually organized so that + - + -
the electric fields of their dipole moments cancel each other - + - +
+ - ++ + -
- + - -+

In an external electric field a substance is polarized. The field attempts to flip the
dipole moments of the molecules in the direction of the field.

The substance acquires a dipole moment µs that is proportional to the field E:

 s  s E
s = orientational polarizability
The orientational polarizability is larger the larger the dipole moment of the
molecule is, and decreases with temperature. The total polarizability of a polar
molecule is:
s
2
s 
3kT
17
 Induced dipole moment
In addition to the orientational polarization molecules can have
induced dipole moments close to permanent dipoles or ions.
Example:
Interaction between water and ion at larger distances
If another water molecule is between the ion and the water molecule we can
assume that  ≈ 78 and Uion-dipole decrease to ≈ 0,5 kT
ze o
  E 
4 o d 2
The field around the ion induce a dipole moment (µ) on
the molecule at distance d: d +
 + -
l

When l << d and the molecule rotate freely.

18
 The interaction energy between the ion and this induced
dipole is.
 ( zeo )2 Ci id
Uionind.dipole    4
2( 4 o ) d
2 4
d

Uion-ind. dipole ja Uion-dipole are of about the same magnitude at

this distance.

Only the first molecular layer around an ion is oriented.

19
 Lifshitz-van der Waals interactions
Lifshitz-van der Waals interactions are the interactions between permanent
and induced dipole moments of molecules.
1) Udipole-dipole (Keesom interactions)
The interaction between two freely rotating molecules
with permanent dipole moments µ1 and µ2 is:
12 22 Cd d
Udipoledipole   
3( 4 o )2 kTd 6 d6
Udipole-dipole is always attractive

2) Udipole-ind.dipole (Debye interaction)

The permanent dipoles of molecules induce dipole moments in other molecules.
The interaction between two freely rotating molecules is:

121  22 2 Cd id

Udipoleind.dipole   
3( 4 o )2 kTd 6 d6
The molecules have permanent dipole moments µ1 and µ2 and their polarizabilities are
α1 and α2. The interaction is always attractive but weaker than the Keesom interactions.
20
 Dispersion interactions (London)
Dispersion interactions are always present (even in non-polar molecules)

Although the time average dipole moment for a non-polar atom is zero, there
exists at any instant a finite dipole moment at a given instantaneous position
of the electrons about the nuclear protons. This instantaneous dipole induces
a dipole moment in any nearby atom.

The dispersion interaction or London interaction is:

3h1 2 I1I2 Cid id

Uind.dipoleind.dipole     6
2( 4 o ) d I1  I2
2 6
d
1, 2 = polarizability
I1, I2 = ionization energy
d = distance between molecules
h = Planck constant, 6,63·10-34 Js

21
 Summary of LW-interactions
The interaction between neutral molecules (i.e. the Lifschitz-van der Waals
interactions) can be estimated from the following equation:
Cd id Cd d Cid id CLW
ULW  Udipoleind.dipole  Udipoledipole  Uind.dipoleind.dipole      
d6 d6 d6 d6
The interactions are considerably weaker than ion-ion interactions and ion-
dipole interactions.
The interaction between single neutral molecules are smaller than the thermal
energy already at distances larger than a few molecule diameters.
The interaction energy between particles (consisting of many molecules) can
be of a significant magnitude at larger distances.
The interactions are very important in surface and colloid chemistry because
they explain the long-ranged attractions sometimes observed between particles.
They also explain the adhesion between particles and surfaces.

22
Questions

What is the distance dependence of van der Waals interactions

between molecules?
What forces are present between non-polar molecules?
What molecular properties are important for these forces?

23
 Van der Waals Forces between Molecules
Origin: Attraction between permanent or induced dipoles
Molecular properties: dipole moment, polarisability

+ - + -
- + - + + - + -
+ - ++ +-
- + - - -+

Permanent dipoles Induced dipoles

Distance dependence:
 6
Interaction energy W  6 Force F  7
D D
The molecular properties are included in β, D = distance

Note: Energy denoted here with W,

earlier with U, many possible symbols
in literature
Important conclusion:
These forces are always present

Other names:
London force, dispersion force, Keesom
force...
 Van der Waals Forces
between Molecules
Name Between Molecular properties
Keesom force Freely rotating permanent Dipole moment
dipoles
Debye force Induced dipole/ permanent Dipole moment,
dipole polarisibility
London or Dispersion force Induced dipoles polarisability

All these forces have the same dependency on distance:

 6
Interaction energy W  6 Force F  7
D D
D = distance between The molecular properties are included in β
molecules Which force is always present?
Van der Waals Forces between Surfaces –
the Hamaker Method
Assumption
• ”The force between two macroscopic bodies is the sum of the
forces between the individual atoms”
Restrictions
• The principle of pairwise additivity ignores the influence of the
neighboring atoms
• Retardation effects are neglected
• Temperature effects are neglected
• The properties of the medium are neglected
The Hamaker constant (AH)

 N A  ρ = density
AH     NA = Avogadro constant
 M  M = molecular weight

Using the Hamaker constant the vdW interactions can be written:

AH Between two flat surfaces

W 
12D 2 D = distance between particles

AHR Between a sphere with radius R and a flat

W  surface
6D
The vdW interaction energy depends on the chemistry (the
Hamaker constant) and the geometry of the system
Force (F(D)) = d W(D)/dD
Between a sphere with radius R and a flat
AHR surface
W 
6D
The force R D

AH R
F ( D )  dW ( D )dD 
12 D 2
Laitoksen nimi
1.2.2018
29
The Lifshitz Theory for
van der Waals Interactions
The theory:
In the Lifshitz theory the atomic structures are ignored and the forces
between large bodies, now treated as continuous media, are derived in
terms of such bulk properties such as their dielectric constants and
refractive indices.

Advantages with the Lifshitz theory:

• The medium is taken into account
• The temperature effects are included
• The retardation effects are included (not in the formulas shown here, though)
• Easy to calculate the Hamaker constant

Drawbacks
• Difficult to derive the Lifshitz theory
The Lifshitz theory

surface or medium surface or

particle particle
The materia 1 is
interacting with
1 2 3 materia 3 across
materia 2

ε1, n1 ε2 , n 2 ε3, n3
 The Hamaker constant according to Lifshitz theory

3kT   1   2   3   2 
AH     
4   1   2   3   2 
3h n 2

 n22 n32  n22 
 n 
1

8 2 n 2
1  n22  n 2
3  n22 2
1  n   n
2
2
2
3  n22
k= Boltzmann constant
T = temperature
h= Planck constant
ν = UV absorption frequency
ε = static dielectric constants for the three media
n = refractive indices for the three media
Conclusions about the
van der Waals Force

Always attractive in vacuum

Always attractive between similar surfaces
Can be repulsive between different surfaces
Question: Why do these conclusions hold?
 Values of Hamaker Constants
Hamaker constants/10-20J
Material (M) M|air|M M|water|air M|water|M

Pentane 3,75 0,153 0,363

Hexane 4,07 - 0,0037 0,360
Dodecan 5,04 - 0,344 0,502
Quartz, crystal 8,83 - 1,83 1,70
Calcite 7,20 - 2,26 2,23
Polystyren 6,58 - 1,06 0,950
Polytetrafluor- 3,80 0,128 0,333
ethylene
Water 3,70
Cellulose 8.4
0,84 0.8
0,086
(i) The attraction between two particles in water is smaller than in air
(ii) The attraction between air bubbles and other particles is weak in aqueous solutions
and the interaction might even be repulsive (negative Hamaker constant)
You should know:

That the van der Waals forces are always present

The most important contributions to the van der Waals
force
Understand (not know by heart) the Lifshitz equation
for the Hamaker constant
When are the vdW forces attractive?
When are the vdW forces repulsive?
What is the effect of the media?

Why are van der Waals forces important?

Note: Many symbols for

energy: U, W , E,
Example: Alumina particles across decalin

Ceramic components are often formed from a concentrated suspension of

ceramic particles. The suspension is flocculated into a mould, the solvent
is driven off and the material is sintered.

For maximum strength and hardness, the particle concentration in the

mould should be as high as and homogeneous as possible. If not,
material tensions able to induce fraction, are formed.

How to make a homogeneous particle suspension?

Example: Alumina particles across
decalin cont.
1. What forces are important?
ε(decalin) = 2.1, ε(aluminium oxide) = 11.6,
n(decalin)=1.475 and n(aluminiumoxide)=1.752
What does these data tell about
a) the van der Waals force?
b) the electrostatic forces?
Calculate the vdW interaction

Strong vdW attraction, rigid open structure, poor

packing. How should the interaction energy be
changed to achieve close packing?

We need to decrease
the vdW attraction
Adsorption of an Amphiphile to the Surface
Attraction Repulsion

Distance between two particles

(nm)
 Test
The ceramic suspension is allowed to settle, whereafter the particle
concentration in the sedimentation tube is measured as a function of
the distance from the bottom.
Conclusion:
It is possible to influence the vdW force by
covering the particles with a layer with
dielectrical properties similar to those of
the medium. In this way the properties,
such as the homogeneity of the ceramic
suspension, can be improved which leads
to increased strength of the moulded
ceramic item.

Questions:
What would be the effect of adding
surfactant if the adsorbed layer had the
same dielectrical properties as the particles?
Which force causes the sedimentation?
How can the speed of the sedimentation be
increased?
Useful reading
Simplified:
Between molecules:
http://www.chemguide.co.uk/atoms/bonding/vdw.html

Everything (and more than) you need to know:

Israelachvili Intermolecular and Surface Forces
Intermolecular and Surface Forces - (Third Edition) –
ScienceDirect Chapter 6: van der Waals forces

If you are interested:

Review on surface forces in lignocellulosics (no theory):
Österberg, M.* and Valle-Delgado, JJ. (2016) “Surface forces in
lignocellulosic systems” Current Opinion in Colloid and Interface
Science 27, 33-42 DOI: 10.1016/j.cocis.2016.09.005 2/1/2018
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