Interfacial Science and

Engineeering
Colloids…
Major topics to be covered …

Introduction to Colloids, Surfaces and Interfaces,

Interaction forces and potentials
Electrostatic forces and electric double layer, DLVO
theory, Hamaker constant, Boltzmann distribution,
Debye theory, Zeta potential
Theory of capillarity – Young Laplace equation
Surface tension, wetting, Young’s equation
Gibbs adsorption equation, Adsorption isotherms,
surfactant adsorption
 Surfactants, self assembly thermodynamics,
bilayers, vesicles and Micelles
• Stability of colloids – emulsions, microemulsions, foams,
aerosols, HLB number, polymers at interface clusters,
Nanomaterials, Light scattering by small particles, Self-
organization
• Application involving various colloidal systems

Ref : 1) Drew Myers, Surfaces, Interfaces, and Colloids:

Principles and Applications. 2nd Ed., Wiley-VCH, 1999

2) D. J. Shaw, Colloid & Surface Chemistry, 4th Edition,

Butterworth-Hienemann, 2003
Some More Reference Texts

1. Principles Of Colloid And Surface Chemistry. 3rd Ed. (P. C.

Hiemenz and R. Rjagopalan) Marcel Dekker, New York, 1997.

2. Physical Chemistry of Surfaces, Arthur W. Adamson, 5th

edition, Wiley, 1990.

3. Foundations of Colloid Science, Robert J. Hunter, Clarendon,

Oxford, Volumes 1 & 2, 1989.

4. Intermolecular and Surface Forces, Jacob N. Israelachvili,

Academic Press, 1992 or later editions.
Colloids…
Colloid/interfacial phenomena in industries
Colloids…
Colloid (kŏl'oid) [Gr.,=glue like], a mixture in which one
substance is divided into minute particles (called
colloidal particles) and dispersed throughout a second
substance. The mixture is also called a colloidal system,
colloidal solution, or colloidal dispersion. Familiar
colloids include fog, smoke, homogenized milk, and
ruby-colored glass.
Colloids…
Classification of dispersed systems

• Particle diameter
• < 10-9 m 10-9 - 10-6 m > 10-6 m
homogenous Colloid Non homogenous
mixture mixtures

• Particles are not resolved by ordinary microscope although

they may be detected under ultramicroscope
• Visible in the electron microscope
• Pass through filter paper but don’t pass through
semipermeable membrane
• Diffuse very slowly
Colloids…
Colloids…
Colloids…
Hydrocolloids
• A hydrocolloid is defined as a colloid system wherein the colloid
particles are dispersed in Water. A hydrocolloid has colloid particles
spread throughout water and depending on the quantity of water
available can take on different states, e.g., gel or sol (liquid).

• Hydrocolloids can be either irreversible (single-state) or reversible.

For example, agar, a reversible hydrocolloid of seaweed extract, can
exist in a gel and sol state, and alternate between states with the
addition or elimination of heat.

• Many hydrocolloids are derived from natural sources. For example,

carrageenan is extracted from seaweed, gelatin has bovine (cow)
and fish origins, and pectin is extracted from citrus peel and apple
pomace.
Colloids…
Colloids…

2) Lyophobic sols (colloids): These sols are "solvent hating," are

thermodynamically unstable, the particles tend to aggregate, and
they are irreversible systems.
• Unstable in the presence of even small conc. of electrolytes
leading to aggregation, depends on the type and valency of
counter ion of electrolyte
• Concentration of the electrolyte
• Little interaction between particles and the dispersion medium.
• Viscosity of the dispersion medium is not affected by the
presence of lyophobic colloidal particles
Examples: water-insoluble drugs, kaolin, and oils form lyophobic
dispersions
Colloids…
Colloids…
Colloids…
Colloids…

Classification Based on the State of the Dispersed Phase and

Dispersion Medium

Dispersion Medium Dispersed phase Type of colloid Example

Gas Liquid Aerosol Fog, clouds
Gas Solid Aerosol Smoke
Liquid Gas Foam Whipped cream,
soda water
Liquid Liquid Emulsion Milk, hair cream
Liquid Solid Sol Paints, cell fluids
Solid Gas Foam Pumice, plastic foams
Solid Liquid Gel Jelly, cheese
Solid Solid Solid Sol Ruby glass
Colloids…
Classification of Colloids Based on Type of Particles of the Dispersed
Phase
a) Multimolecular colloids  usually have lyophobic character.
Ex: gold and sulphur sols

b) Macromolecular colloids  resemble true solutions

Ex: proteins, cellulose, starch and polymers such as polyethylene, nylon and
polystyrene

c) Associated colloids  type of micelle it forms depends on the nature of

solvent (hydrophilic or hydrophobic)
Kraft Temperature (Tk )
Critical micelle concentration (CMC)
Ex: soaps and synthetic detergents

Surfactant Micelle
Colloids…
Structural characteristics of colloids

A. Experimental methods

The experimental procedures for determining particle size and shape

can roughly be categorized, as follows:
1. Observation of the movement of particles in response to an
applied force,
2. Direct observation of particle images SEM and TEM
3. Observation of the response of particles to electromagnetic
radiation.
4. Measurements which relate to the total surface area of the
particles (gas adsorption and adsorption from solution)
B. Particle shape

Particle asymmetry is a factor in determining the overall properties

(especially mechanical) of colloidal systems.

• Colloidal particles can be classified according to shape

as corpuscular, laminar or linear.

• The exact shape may be complex but, to a first approximation, the

particles can often be treated theoretically in terms of models, which
have relatively simple shapes (Figure 1.1).
 Some model representations for non-spherical particles
1. The Spherical Model
The easiest model to treat theoretically is the sphere (many
colloidal systems contain spherical or nearly spherical particles).
• Emulsions, latexes, liquid aerosols, etc., contain spherical
particles.
• Certain protein molecules are approximately spherical.
• The crystallite particles in dispersions such as gold
and silver iodide sols are sufficiently symmetrical to behave like
spheres.
2. Corpuscular Shape
• Corpuscular particles which deviate from spherical shape can often
be treated theoretically as ellipsoids of revolution. Many proteins
approximate this shape.
• An ellipsoid of revolution is characterized by its axial ratio, which is
the ratio of the single half-axis a to the radius of revolution b. i.e ratio
a/b
– The axial ratio a/b > 1 for a prolate, and a/b < 1 for an oblate
(discus-shaped) ellipsoid.
Iron(III) oxide and clay suspensions are examples of
systems containing plate-like particles.
 3. Thread-like Shape

• High-polymeric material usually exists in the form of long

thread-like straight or branched-chain molecules

• As a result of inter-chain attraction or cross-linking

(arising from covalent bonding, hydrogen bonding or van
der Waals forces) and entanglement of the polymer
chains, these materials often exhibit considerable
mechanical strength and durability

• This is not possible when the particles are corpuscular or

laminar..
Remarks

• In nature, thread-like polymeric material fulfills an

essential structural role.

– Plant life is built mainly from cellulose fibers.

– Animal life is built from linear protein material such as
collagen in skin, sinew, and bone, and keratin in nails and hair.

• Finally, When particles aggregate together, many

different shapes can be formed. These do not necessarily
correspond to the shape of the primary particles.
Flexibility

Thread-like polymer molecules show considerable flexibility due to

rotation about carbon-carbon and other bonds.
• A better theoretical treatment is to consider the polymer
molecules as random coils (even though this model is not completely
accurate).
• The relative magnitudes of polymer-polymer and polymer-solvent
forces must also be taken into account.
– If the segments of the polymer chain tend to stick to one
another, then a tighter than random coil, and possibly
precipitation, will result;
– whereas a looser coil results when the polymer segments
tend to avoid one another because of strong solvation
and/or electrical repulsion,
Solvation
• Colloidal particles are usually solvated, often to the extent of
about one molecular layer, and this tightly bound solvent must be
treated as a part of the particle

• Sometimes much greater amounts of solvent can be immobilized

by mechanical entrapment within particle aggregates

• In solutions of long thread-like molecules the polymer chains may

cross-link, and/or become mechanically entangled so that a
continuous three-dimensional network is formed

• If all of the solvent becomes mechanically trapped and

immobilized within this network, the system as a whole takes on a
solid appearance and is called a “gel”
Polydispersed nature

• Colloidal systems are generally of a poly-dispersed nature - i.e.

the molecules or particles in a particular sample vary in size,
Why? Answer: By virtue of their stepwise build-up

• Colloidal particle and polymer molecular sizes tend to have skew

distributions, as illustrated in Figure 1,2, for which [like Poisson
distribution].
• Very often, a detailed determination of relative molecular mass
or particle size distribution is impracticable.
• The significance of the word average: depends on the property
which being measured. Therefore two values may be obtained:
– Number Average, and
– Mass Average.
Preparation of colloids:

The formation of colloidal material involves either degradation

of bulk matter or aggregation of small molecules or ions

lyophilic sols  easy to prepare

lyophobic sols  unstable and irreversible, difficult to prepare

a) Condensation or aggregation method

b) Dispersion method
 Condensation or Aggregation method
Chemical methods:

• By Reduction: Metal sols are generally prepared by this method

HCHO
Ex: HAuCl4¯ (aq) Au (sol)

H2, 50-60 0C
AgO (aq) Ag (sol)

• Sulphur sols are easily obtained by mixing equal volumes of aqueous

solutions (10-3 to 5 x 10-3 mol dm-3) of Na2S2O3 and HCl

• By hydrolysis: To obtain sols of oxides or hydroxides of weakly

electropositive metals

Ex: FeCl3 + 3H2O Fe(OH) 3 (sol) + 3HCl

Nucleation and growth

• The formation of a new phase during precipitation

involves two distinct stages - nucleation (the formation of
centers of crystallisation) and crystal growth - and
(leaving aside the question of stability)

• A high degree of dispersion is obtained when the rate of

nucleation is high and the rate of crystal growth is slow

• The rate of particle growth depends mainly on the

following factors:
1. The amount of material available
2. The viscosity of the medium, which controls the rate
of diffusion of material to the particle surface
 3. The ease with which the material is correctly
orientated and incorporated into the crystal lattice of the
particle

4. Adsorption of impurities on the particle surface, which

act as growth inhibitors

5. Particle-particle aggregation

• At very low concentrations, c. 10-4 to 10-3 mol dm-3 the

supersaturation is sufficient for extensive nucleation to
occur, but crystal growth is limited by the availability of
material, with the result that a sol is formed.
• At moderate concentrations, c. 10-2 mol dm-3, the extent of
nucleation is not much greater, so that more material is
available for crystal growth and a coarse filterable
precipitate is formed.

• At very high concentrations, c. 2 to 3 mol dm-3, the high

viscosity of the medium slows down the rate of crystal
growth sufficiently to allow time for much more extensive
nucleation and the formation of very many small particles to
gels
Organo-platinum Gel

SEM image
 Monodispersed sols
• Aggregation methods usually lead to the formation of poly-dispersed
sols, mainly because the formation of new nuclei and the growth of
established nuclei occur simultaneously, and so the particles finally
formed are grown from nuclei formed at different times

• However, there are obvious advantages attached to the use of

monodispersed systems. The preparation of such systems requires
conditions in which nucleation is restricted to a relatively short period
at the start of the sol formation
• This is achieved by a) supersaturated solution with very small
particles or
b)under conditions which lead to a short burst of homogeneous
nucleation
• For example, HAuCl4 is neutralized with
potassium carbonate and a part of the solute
is reduced with a small amount of white
phosphorus to give a highly dispersed gold sol
with an average particle radius of c. 1 nm. The
remainder of the HAuCl4 is then reduced
relatively slowly with formaldehyde in the
presence of these small gold particles.
aq. colloidal gold
 • The monodispersed sol which has been prepared under
condition which lead to a short burst of homogeneous
nucleation is sulphur sols, formed by mixing very dilute aqueous
solutions of HCl and Na2S2O3

• Once supersaturation is achieved, the nuclei then grow uniformly

by a diffusion-limited process and a sol of monodispersed particles
is formed
USES

1. Monodispersed polystyrene sols are used as calibration

standards for electron microscopes, light scattering
photometers, Coulter counters, particle sieves, etc.

2. Monodispersed silica is used for antireflection lens coatings.

3. Monodispersity (even at a modest level) can usefully be

exploited in photographic film, magnetic devices,
pharmaceutical preparations and catalysis.
 Macromolecular colloids
Macromolecular chemistry covers range of polymeric material,
such as proteins, cellulose, sodium carboxymethyl cellulose, rayon
and vulcanized rubber and the purely synthetic polymers, such as
polythene and many polymerizations

-*- A polymerisation method which is of particular interest to the

colloid scientist is that of emulsion polymerisation -*-

Emulsion polymerisation and polymer latexes

-- In bulk polymerisation, even at moderate degrees of polymerisation
the resulting high viscosity of the reaction mixture makes stirring and
efficient heat transfer very difficult.

The solution for this problem is Emulsion Polymerisation.

• Monodispersed sols containing spherical polymer
particles (e.g. polystyrene latexes) can be prepared by
emulsion polymerisation

• These are particularly useful as model systems for

studying various aspects of colloidal behavior
Macromolecular colloids - examples
 Dialysis and gel filtration (colloids purification)

The use of membranes for separating particles of

colloidal dimensions is termed dialysis.

Membranes with various, approximately known,

pore sizes can be obtained commercially (usually
in the form of 'sausage skins' or 'thimbles') the
permeability of a membrane is also affected by
factors such as electrical charge repulsion and
adsorption

Dialysis is particularly useful for removing small dissolved molecules

from colloidal solutions or dispersions - e.g. extraneous electrolyte
such as KNO3 from Agl sol
• Ultra filtration: colloidal sols are filtered through ultra-filtrers.
pore size of filter paper is decreased such that it will restrict the
passage of colloidal particles.

• Ultra-centrifugation: Centrifugation is carried out at very high

speeds such that the colloidal particles settle down at the bottom
of the tube and the impurities remain in the solution .

• Electrophoresis techniques also are widely used for colloidal

purifications based electrokinetic phenomena
 Electrodialysis

sed for purification of blood in case of kidney failure.

Major topics to be covered …

Introduction to Colloids, Surfaces and Interfaces,

Interaction forces and potentials
Electrostatic forces and electric double layer, DLVO
theory, Hamaker constant, Boltzmann distribution,
Debye theory, Zeta potential
Theory of capillarity – Young Laplace equation
Surface tension, wetting, Young’s equation
Gibbs adsorption equation, Adsorption isotherms,
surfactant adsorption
 Surfactants, self assembly thermodynamics,
bilayers, vesicles and Micelles
 Surface and interfaces
In general, one usually finds that the term ‘‘surface’’ is
applied to the region between a condensed phase (liquid or
solid) and a gas phase or vacuum

 While ‘‘interface’’ is normally applied to systems involving

two condensed phases
Target-oriented Applications Of Interfacial Engineering
Microelectronic devices
• Silicon semiconductors have grown tremendously in terms of
memory and logic. Every four years produce an order of
magnitude improvement in the performance, keeping the
cost almost constant, and sometimes lower.

• As the physical limits of the conventional silicon chips are

being approached, researchers are seeking the next small
thing in electronics through chemistry. By making devices from
small groups of molecules, researchers may be able to pack
computer chips with billions of transistors, more than 10 times
as many as the current technology can achieve.
 Hydrogen storage
• Safe storage of hydrogen for fueling motor vehicles and
driving portable electronics can be made employing the metal-
organic frameworks (MOFs).

• Lightweight and compact materials are being developed that

can rapidly adsorb and desorb large amounts of hydrogen
under ambient temperature and pressure conditions.
The MOF, Zn4O(BDC)3 where BDC is 1,4-benzene-dicarboxylate
It has a sturdy cubic open-framework structure with a very
large surface area (2500–3000 m2/g), and good thermal
stability 600–700 K

Coatings
Coating on solid surfaces has a wide variety of applications such
as paints, adhesives, coated papers, automobiles, industrial
equipment, domestic appliances, photographic films, and
aluminum disks coated with iron oxide which make computer
hard disks.
 Variety of coating methods are available and any chosen
method depends on the rheology of the coating liquid, type of
solid surface, desired coating thickness and uniformity.
Enhanced petroleum recovery

The water flood residual oil is left in the form of oil ganglia trapped in the
larger pores (in water-wet reservoirs) where the viscous forces of the driving
water flood could not completely overcome the capillary forces holding the oil
in a place.
Tertiary oil recovery involves reducing the capillary forces restraining the oil
and/or altering the viscosities in order to modify the viscous forces to drive the
oil out of the pores.
SURFACE FREE ENERGY

 When the two new interfaces are separated by what can

be termed practical infinity, the free energy of the system
becomes constant. The ‘‘additional’’ energy is termed the
‘‘surface free energy’’ or more accurately the ‘‘excess’’
surface free energy.

 When the term ‘‘specific’’ excess surface free energy is

used it refers to energy per unit area, usually in mJ/m2.
 The surface tension may be defined as a force acting
parallel to the surface and perpendicular to a line of unit
length anywhere in the surface.

 The definition for a curved surface is somewhat more

complex, but the difference becomes significant only for a
surface of very small radius of curvature.
 The specific thermodynamic definition of surface
tension for a pure liquid is given by

where AH is the Helmholtz free energy of the system, W is the amount of

reversible work necessary to overcome the attractive forces between the
units at the new surface

A is the area of new surface formed; The proportionality constant σ, termed

the ‘‘surface tension,’’ is numerically equal to the specific excess surface free
energy for pure liquids at equilibrium

Also for two pure, mutually immiscible liquids having

a common flat interface we can define the terms
‘‘interfacial tension’’ and ‘‘excess interfacial free
energy.’’
 Surface Tension
 The storage of energy at the
surface of liquids. Surface
tension has units of erg cm-2 or
dyne cm-1. It arises because
atoms on the surface are missing
bonds. Energy is released when
bonds are formed, so the most
stable low energy configuration
has the fewest missing bonds.
Surface tension therefore tries to
minimize the surface area,
resulting in liquids forming
spherical droplets and allowing
insects to walk on the surface
without sinking.
Surface Tension in Actions
Surface tension value of some of the liquids in (mN/m)
 The SI (International System of Units) units of surface tension
are mN/m, which can be interpreted as a two-dimensional
analog of pressure (mN/m2)

The surface tension of liquid can be experimentally measured by

several methods.

The Parachor method, drop-weight method, du Noüy ring method,

Wilhelmy plate method and the maximum bubble pressure method
du Noüy ring method
This is one of the most widely-used methods for measuring
the surface tension and does not need to be calibrated using
solutions of known surface tension

The measurement is performed by an instrument known as

Tensiometer. This instrument has an accurate microbalance
and a precise mechanism to vertically move the sample liquid
in a glass beaker.

The modern tensiometer has a computer-controlled

arrangement that can move the table holding the liquid very
slowly (~100 micrometer/s)
The micro-balance continuously records the force applied on the
ring when it pulls through the air-liquid interface. The surface
tension is the maximum force needed to detach the ring from the
liquid surface. The detachment force is equal to the surface
tension multiplied by the periphery of the surface detached.
Therefore, for a ring,

where Rr is the radius of the ring. The force measured by the

balance includes the weight of the ring
Du Noüy ring method

Principle:
The force is measured on a ring shortly before a liquid film tears
using a torsion meter. The surface tension is calculated from the
diameter of the ring and the tear-off force.
 One condensed phase (solid or liquid), we talk of surface tension
whereas if two condensed phase are in contact we talk about interfacial
tension.

 Both the terms represent energy per unit surface area or force per unit
length. In the process of adhesion, that is, formation of an interface
between two different condensed phases

 Phases 1 and 2 are being brought under contact in a vacuum or an inert

gas, thus forming an interface
 Cohesion & Adhesion
The work of cohesion, Wc, is defined as the reversible work
required to separate two surfaces of unit area of a single material
with surface tension s

Wc is a reversible thermodynamic function and represents a

minimum amount of work for carrying out the process
work of adhesion, Wa(12), defined as the reversible work
required to separate unit area of interface between two different
materials (1 and 2) to leave two ‘‘bare’’ surfaces of unit area

Loss of excess surface energy by changing the phases

(a) solid-vacuum interface

(b) solid-liquid or gas

interface
A ‘‘typical’’ solid interfacial region will be characterized by an
irregular physical profile (a) and a parallel variable concentration
profile (b)
 Structure of Silicon Surface
Measured using STM

Scanning tunnelling microscope

image of a Si surface, ~0.3° off
(100) orientation showing the type
A steps (Si dimers parallel to
steps) and type B steps (Si
dimers perpendicular to steps).
Uppermost part of the surface is
at lower right, with downward tilt
to upper left. Scale is ~110 nm
square (Prof. Max Lagally).

http://www.chm.ulaval.ca/chm10139/
 Interfacial tension

The molecules at the surface of both of these liquids experience

unbalanced forces of attraction.

These unbalanced forces at the surface of separation between the

two immiscible liquids (i.e., at the interface) give rise to interfacial
tension.

It can be defined in the same way as the surface tension.

Antonoff’s rule
Fowkes correlation on interfacial tension
 Measurement of interfacial tension
The drop-weight method and the du Noüy ring method are
extensively used for measuring the interfacial tension. In the du
Noüy ring method, the ring pierces the liquid–liquid interface.

 In the drop-weight method, the drop of one liquid is formed

inside the other liquid.

 A very useful technique for measuring the interfacial tension is

the spinning-drop method. It is especially suitable for measuring
ultra-low interfacial tensions in presence of surfactant mixtures,
which are used in microemulsions.

 Interfacial tension can also be measured from the analysis of

drop shape.
 Spinning-drop method

 In this method, a small drop is placed in a denser liquid

enclosed in a glass tube which is subjected to rotation at a
high angular velocity (say, 1000 rad/s) about its horizontal
axis

 The method is based upon the principle of gyrostatic

equilibrium, which is the state of uniform rotation in which
every bit of the fluid inside the tube is at rest with respect to
the wall of tube.

 Gyrostatic equilibrium is achieved at high angular velocities

when the gravitational force perpendicular to the axis of
rotation is negligible as compared with the centrifugal force
 When the tube rotates with high velocity, the drop migrates
to the axis of rotation and assumes a cylindrical shape with
hemispherical ends. For each angular velocity, the drop comes
to an equilibrium shape which is characteristic of that
velocity.

The drop cannot elongate indefinitely. When the interfacial

tension everywhere balances the centrifugal force that produces
the pressure difference across the interface, the elongation
ceases.
Spinning drop method facilitates the measurement of interfacial
tension compared to other widely used methods. Because in this
method, measuring the contact angle is not required between a
solid surface and the liquid.

Another advantage of the method is that, it is not necessary to

estimate the curvature at the interface, which usually brings
difficulties with taking the first and second derivatives describing
the shape of the fluid drop.
Interaction forces and potentials

Attractive Forces
&
van der Waals Forces

Israelachvili: Intermolecular and Surface Forces

 Areas where Intermolecular Forces are
important
• Colloidal Stability
• - Paints, CMP
•
• Rheological behavior
• - Paints, paper processing
•
• Solid / Solid Separations
• - Minerals
• Examples:
Colloidal Stability in Dispersions/Emulsions:
- Attractive forces promote instability of dispersions
- Repulsive forces are needed to stabilize dispersions
 Areas where Intermolecular Forces are
important
• The Gecko’s ability to walk on walls is NOT
due to the traditionally (mis)understood
vacuum theory:

- It is due to van der Waals attractive forces

between spatulae (1 billion) on the Gecko’s leg and
the wall

Many observed phenomena in nature have their basis in

intermolecular forces!
Short-range forces have long-range (macroscopic) effects.
Identifying & quantifying intermolecular forces is key to the
successful design of stable/unstable systems as required
Characteristic Strengths of Covalent Bonds

Electrostatic or Coulombic forces

 Intermolecular Forces

6
Interaction Force/Radius (mN/m) van der Waals
5 Electrostatic
Steric
4 Depletion
Hydrophobic
3 Solvation
2
1
0
-1
-2
0 10 20 30 40 50
Separation Distance (nm)
Inducing polarization in non-polar molecules
 The Polarization of Polar Molecules
If a molecule has a freely rotating permanent dipole, which has
a time-averaged dipole moment of zero, in the presence of an
external field E, there may develop an induced orientational
dipole.
Its energy in the field will be given by

The total polarizability of the molecule, a, will be the sum of

the electronic and orientational polarizabilities
 Ion–Dipole Interactions

At distances greater than the dipole

length the interaction energy can be
estimated by

That point aside for the moment, when the dipole is pointing away from the
charge ( angle = 0, ) the interaction will be at its most negative value
(attractive). For angle = 180, the value will be its most positive (repulsive).
consequence of the ion–dipole interaction is that it is often
strong enough to bind polar solvent molecules to the ion and
establish a local aligned or ‘‘frozen’’ structure composed of the
ion and several associated polar molecules within the matrix of
the solution

which corresponds to a value of 123 kJ/mol, compared to the

experimental value of 142 kJ/mol.
Characteristic Molecular and Bond Dipole Moments (in
Debye Units)
 Ion Solvation
Ion-dipole interactions such as Li-ion and water, surrounding shell
of water molecules constitute the waters of solvation or hydration
of the ion. The number of water molecules associated with an ion
(its hydration number) is characteristic of that ion but normally
ranges between 4 and 6. Waters of hydration are not completely
and irreversibly bound to a given ion, of course.

They are slowly (on a molecular timescale), but continually

exchanged for other bulk water molecules.

For small monovalent and polyvalent ions, the effect will produce
a ‘‘shell’’of oriented water molecules bound to the ion, with the
orientation angle favoring 0 for cations and 180 for anions.
Solvation leads to structuring effect, which decays in an
approximately exponential way but may extend several molecular
diameters into the bulk liquid.
 This region of enhanced structuring in the solvent is referred
to as the ‘‘solvation zone around the ion.’’ This solvation or
structuring effect can have a number of important
consequences for the interactions between ions, molecules,
colloidal particles, and interfaces.

In particular, there are found to be differences in density,

dielectric constant, conductivity, and other parameters due
to solvation effects.
Dielectric constant of the solvation zone may differ significantly
from the bulk value because the molecules there cannot respond
to an imposed electric field in the same way as in the bulk liquid.

Effective dielectric constant in the solvation zone is less than the

bulk, as is most often the case, then the interaction will be
stronger
 Interactions Between Ions and Nonpolar Molecules
When a nonpolar molecule is near an ion generating an electric
field E, where

ion will induce a dipole moment in the molecule of

attractive force between ion and induced dipole

overall interaction free energy

 van der Waals Forces
The three components that constitute van der Waals Forces

Interaction Origin of Equation

Component Interactions
Keesom Dipole-dipole w(r )  
u12 u 22 1
3( 4o  r ) 2 k BT r 6
Debye Dipole – induced u 1 2  1o  u 2 2  2 o 1
w(r )  
dipole (4 o r ) 2 r6
London Induced Dipole – w ( r )   3  o1 o 2 I1I 2 1
(Dispersion) Induced Dipole 2 ( 4  o ) 2
( I1  I 2 ) r 6

The London component is the most dominant.

n = 6 indicates van der Waals forces are short range
 Keesom (dipole - dipole) component
u12 u 22 1
w(r )  
3( 4o  r ) 2 k BT r 6

ui (i = 1, 2): dipole moment, o : Permittivity of free space

r : Relative Permittivity, kB: Boltzmann’s constant,
r: distance between dipoles, T: Temperature

- Dipole-dipole interactions are

generally weak
- These weak dipole-dipole interactions becomes
significant when 2 interacting dipoles approach each
other closely. e.g. O–-H+, N–-H+, F–-H+
(These strong dipole-dipole interactions are the well known
Hydrogen Bond)
 Debye (dipole – induced dipole)
component
O: polarizability,
u o 1
2
w(r )   r: Relative Permittivity
( 4o  r ) 2 r 6
r: distance between
dipole and induced dipole
- Interaction of a polarizable molecule with a dipole

- Polarizablility: Electron cloud of molecule

responds to an electric field by a localized shift

- Debye interactions are independent of temperature

 London (Dispersion) component
3  o1 o 2 I1I 2 1 Ii (i = 1,2): Ionization
w(r )  
2 ( 4o ) 2 ( I1  I 2 ) r 6 Potential
The most important component of van der Waals interaction

Keesom and Debye interactions require the presence of at

least 1 permanent dipole, but London interactions do not

Hence, London interaction exist between all molecules

The London interaction component was always known,

but evolved only after the development of quantum
mechanics
Dispersion forces are important in a wide variety of phenomena,
including the condensation of nonpolar molecules to the liquid
and solid states; the boiling points, surface tensions

other physical properties of condensed states; adsorption,

adhesion, and lubrication processes; the bulk physical strength of
primarily covalent materials

The aggregation and flocculation of molecular and particulate

systems; and the structures and interactions of synthetic
polymers, proteins, and other complex biological systems
• Provides molecular level reasoning that at room temperature
for small molecules (Ar, He, CH4) gases

• Bigger molecules (hexane, decane) are liquids and even

bigger molecules (C35H71) are solids.
Total potential energy of
interaction between two units will
be the sum of the attractive and
repulsive interactions and is
illustrated by curve (c)

The above equation is commonly referred to as the Lennard-

Jones 6–12 potential
 Interactions between Surfaces and
Particles
- Microscopic Approach -
1937: Hamaker calculated the total interaction between two
spherical particles by adding contributions for each atom in the
solid F = van der Waals Force
R = particle radii
AR H = separation distance
F( H )   2 (For liquids, 0.16 nm: For solids, 0.3 nm)
12H A = Hamaker Constant (Material property)

Note that the Hamaker constant may be defined as

A   C 1 2
2

Where 1 and 2 are the number of atoms per unit volume in

the two bodies. ( = number density)
 van der Waals Interaction Potential for
various configurations
Expression for
Configuration Schematic van der Waals force
potentials
Molecule - Molecule C
WM  M   6
r
C
Molecule - Plate WM  P  
6H 3

AR
Sphere - Plate WS P 
6H

Sphere - Sphere AR
WSS 
12H
Example:
Considering only van der Waals
attraction, what is the force and energy
of adhesion between two particles of
radius 1 m with A = 10-19 J ?
(H = H0  3Å)
 Example:
Considering only van der Waals attraction, what
is the force and energy of adhesion between
two particles or radius 1 m with A = 10-19 J ?
(H = H0  3Å)

Force of
adhesion
AR  10 19 J  10 6 m 
F( H )   
  10 2

2 
8
 9.25  10 N
 12  (3  10 ) m 
2
12H
Energy of
adhesion
AR AR  10 19 J  10 6 m 
W( H )    F( H )dH    dH    
 10

  28  10 18
J  6800kT
12H 2
12H  12  (3  10 )m 
However, the potentials for the following cases
have n = 1
AR
Sphere – Plate WS P 
6H
AR
Sphere – Sphere WSS 
12H

Why does this happen?

 Consider: Sphere – Plate Interaction
Integrate interaction of every element on the sphere with the
plate

C z
WSP   2Rzdz
0
6( H  z ) 3

 2 2 CR AR R
WSP   H
6H 6H
dz
The bulk material contributing to the interaction terms
causes n to collapse to 1, due to integration of large
number of individual sphere elements with the plate

Reinforces the fact that van der Waals forces are more
ignificant for small molecules at small distances
 The case of the Gecko Walk!
A C
WP - P  WM- M = - 6
12H 2 r

Spatulae
Check the Seta 1 billion of them, all
Gecko feet’s Satae
in the van der
microstructure Waals domain

Feet microstructure enables the Gecko

reach van der Waals domains of attraction,
hence they scale walls with ease!
This is also why...
A
WP - P  C
12H 2 WM - M = - 6
r

Spatulae
Satae Seta
 Estimation of A
(Vacuum or non-vacuum media)

Combination Rules: Allows quick approximation

A132  A131 A 232 A132: Interaction of 1 and 2 across medium

3
A12  A11A 22 A12: What does this stand for
physically?
A131  A 313  A11  A 33  2 A13   A11  A 33 
2

A132   A11  A 33  A 22  A 33 
Limitations:
• “A” may be a function of many other intermolecular forces
• Approach ignores many molecule interactions
Israelachvili: Intermolecular and Surface Forces, p. 200
 Values of Hamaker Constants for
different material
Hamaker Constants (10-20 J)
Material Vacuum Medium n-Dodecane
Water
6H-SiC 25 13 1
tetra-ZrO2 20 8.8 6.8
b-Si3N4 18 7.0 5.0
a-Al2O3 15 5.2 3.6
Y2O3 13 4.0 2.6
MgO 12 3.2 1.9
MgAl2O4 13 3.5 2.1
6.5 0.83 0.15
SiO2

Bergström, L (1997), Adv. Colloid and Interface Sci., 70, 125

 Values of “A” in different media for
selected material
Medium C  A
(10-79 J m6) (1028 m-3) (10-19 J)
Hydrocarbon 50 3.3 0.5
CCl4 1500 0.6 0.5
H2O 140 3.3 1.5
Israelachvili: Intermolecular and Surface Forces, p. 178

• Note the similarity in the magnitude A

• Typical values in vacuum (air) only vary from (0.4 to 4) x 10 -19
J
• 1  10-19 J is a good approximation for most dielectric
materials
van der Waals Force as a function of
A

Sphere/Shpere
van der Waals Force as a function
of R

Sphere/Shpere
 Repulsive van der Waals
Medium: Cyclohexane
F
Silica
Alumina
Silica or Alumina
particle
TeflonAF

Hamaker Constant: System1

Cyclohexane: 5.2×10-20 J Alumina | Cyclohexane |
Silica: 6.5×10-20 J Teflon A132=-0.55×10-20 J
Alumina: 15.6×10-20 J → System 2
Teflon: 3.8×10-20 J Silica | Cyclohexane | Teflon
A132=-0.089×10-20 J
Lee et al. Colloids and Surfaces A, Volume 204, Issues 1-3, 23 May 2002, Pages
 DERJAGUIN APPROXIMATION
Relates interaction energy of flat surfaces and
interaction forces of curved surfaces

Allows interactions to be calculated between different

shapes

Important condition:
Range of distance where surface forces are
significant << radius of curvature
Approach:

For concentric rings of radius x and thickness dx,

calculate the specific force between a projection of that
ring on the sphere as if it were two plates of area 2pxdx
separated by H´
Integrate from x = 0 to x =
R

H´ H0
dx x
For the Sphere/Plate interaction

F(H)sph-plt = 2R W(H)plt

W(H) is the energy/area between two flat plates.

Other geometries such as spheres and cylinders may

also be calculated

W(H)plt-plt =

Sphere/Plate F(H)sph-plt/2R
Sphere/Sphere F(H)sph-sph/R
Crossed Cylinders F(H)cyl-cyl/2R
 Theoretical Determination of Surface
Tension (van der Waals Approach)
A11
W11  2
 2
12 H 0
A11

24 H 02
H0 between liquid atoms at an interface  0.165 nm
Example for silica:
A = 10-19 J and H0 = 0.3 nm:
gtheoretical = A/(24pH02) = 15 mJ/m2
but gexperimental = 30-73 mJ/m2

(H-bonding causes the difference)