Colloid and Interfacial Engineering

/Interfacial Science and Engineering

(CH-455, CH-639)
Instructor: Dr. Santanu Paria
Phone: 2262 (O), 3262 (R), 9437684864 (M)
E-mail: santanuparia@yahoo.com, sparia@nitrkl.ac.in

Lecture Notes available at:

Website: http://intranet.nitrkl.ac.in/course_info.asp?dept=4&dispstat=
http://geocities.com/santanuparia

Department of Chemical Engineering

N.I.T. Rourkela.
Syllabus
 Syllabus
• General Introduction
• Colloids • Instrumental
– Stabilization principles
– Destabilization – Surface/interfacial tensiometer
– Interactions – Zetameter
• Interface – Particle size analyzer
– Interfacial phenomena
– Surfactants
– Surface and Interfacial tension
– Micellization
– Adsorption
 Books/References
Books:
• Hiemenz, P. C. and Rajagopalan, R., Principles of Colloid and Surface Chemistry, 3rd Edition, Marcel
Dekker, N.Y., 1997.

• M. J. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience Publication, New York, 1978.

• Adamson, A. W. Gast, A. P. Physical Chemistry of Surfaces, Wiley-Interscience, New York, 1997.

• D. J. Shaw, Colloid & Surface Chemistry, Butterworth Heinemann, Oxford, 1991.

• Jacob Israelachvili, Intermolecular and Surface Forces, Academic Press, New York, 1992.

Journals:

• J. Colloid & Interface Sci., Elsevier.

• Colloids and Surface A, Elsevier.
• Advances in Colloid and Interface Sci., Elsevier.
• Langmuir, American Chemical Society.
• J. Phys. Chem. B., American Chemical Society.
 Institutions which are offering Interfacial
Science and Engineering
•Indian Institute of Science, Bangalore

•Indian Institutes of Technology, Kanpur

•Indian Institutes of Technology, Guwahati,

•Indian Institutes of Technology, Mumbai.

 Interdisciplinary Area
Chemistry
Physics

NanoTech.

Chemical Colloids and

Engg. Interfacial
Engineering Mat. Sci.

Bio Metallurgy,
Technol. Mining,
Civil
 Area of Applications

• Cleaning: Detergency
• Emulsion: Dispersion of oil and aqueous phase, cosmetics, medicine
• Dispersion: Paint, Ink
• Flotation: Concentration of ores
• Solubilization: Drugs solubilization, Drug delivery
• Environmental Science: Colloid-Enhanced transport, Removal of organic
contaminants
• Oil recovery: Enhanced oil recovery
• Chemical Reactions: Enhancement of reaction rate by increasing mass
transfer by contact angle and surface tension change.
Processes Involving Colloidal/Interfacial
Phenomena
Adhesion Lubrication
Detergency Wetting
Ore flotation Water repellency
Precipitation Water evaporation control
Road surfacing Sugar refining
Electrophoratic deposition Soil conditioning
Emulsion polymerization Enhanced oil recovery
Heterogeneous catalysis Corrosion inhibition
 Basic Introduction to the Area
• Different states of matter: (i) gas, (ii) liquid, and (iii) solid.

• What is Colloid and Interface Science ?

Colloid and interface science deals with multi-phase systems in which one or more
phases are dispersed in a continuous phase of different composition or state. Some
typical systems:
– Aerosols of liquid droplets or solid particles
– Foams
– Emulsions
– Sols or suspensions
– Solid foams, emulsions or suspensions

• What is colloid? A “colloidal system” can be defined as one of these states finely
dispersed in another.

• Origin of the term: “Kolla” was a Greek word for glue. In 1861, Thomas Graham found
that certain solutions would pass through a membrane and others would not. He found a
stable, intermediate state of matter, and applied the term “colloidal” (meaning “glue-
like”; from kolla = glue) to this intermediate state.
 Basic Introduction to the Area
•A colloid consists of two separate phases: A dispersed phase and a
continuous phase.
Dispersed phase

Continuous phase

•Colloids based on sizes: Size of the dispersed phase particles

usually have dimensions between 1 nm (0.001micron) to 1000 nm
(1 micron).
0 1 nm 1000 nm
1 nm 100 nm
Nanoparticle Colloidal particle
 Length Scales with Examples
Atom

Colloidal range

Nano range
 Surface Energy
Why colloidal particles plays an important role?
• High surface-to-volume ratio and high surface energy of the.

Surface Energy: The work required to increase the surface area of a substance by
unit area.
•The hydrophobicity generally decreases as surface energy increases. Hydrophilic
surfaces such as glass therefore have high surface energies, whereas hydrophobic
surfaces such as PTFE or polystyrene have low surface energies.
•Molecules at the surface will try to reduce this free energy by interacting with
molecules in an adjacent phase.
Substrate material Surface energy mJ/m2
Mica 4500
Gold 1000
Mercury 485
Water 72.8
Octadecane 28
PTFE 19
Colloid Classification and Examples
Examples of Colloidal Systems

Aerosols Food stuffs

Agrochemicals Ink
Cosmetics Paint
Dyestuffs Pharmaceuticals
Emulsions Plastics
Foams Rubber
Ice cream Soil
 When does interface become important?
Consider N mono-dispersed spheres of radius r. The surface-to-volume ratio is
S 4π r2N 3 S
= = (1); i.e. r ↓ ⇒ ↑
V (4π / 3)r N r
3
V
Suppose we have a cube of material, and we want to estimate the ratio, Ns/Nv, where
Ns is the number of molecules at the surface/area and Nv is the number of
molecules/volume in the bulk volume.
To simplify the estimation, let’s further suppose that each molecule is a tiny cube of
side h.
Using this approximation, we have,
S = Nsh2 (2); V = Nvh3 (3)
Ns
Ns S r ↓⇒ ↑
Now = h ; S/V ∝ 1/r. Therefore, Ns/Nv ∝ h/r, i. e. Nv
Nv V
Thus, for macroscopic dimensions (large r compared to h), contribution from surface
molecules is not important. As the dimension decreases, however, surface contribution
becomes more critical.
 Example
• Suppose the molecular dimension, h, is 2 Å (0.2 nm). Using Ns/Nv = h/r, we have

r Ns/Nv
100 Å 0.12

1 µm 0.0012
1 cm 1.2 × 10−7
 Importance of Size in Colloidal Range
Suspension
Fundamental forces operate on fine particles are:
• A gravitational force, tending to settle or raise particles depending on their
density relative to the solvent
•A viscous drag force, which arises as a resistance to motion, since the fluid has to
be forced apart as the particles moved through it.
The viscous drag force is given by: Fdrag = 6πrVη = 4πr3(ρp - ρw)/3 = F gravity, the
gravitational force, V is settling velocity.
η = viscosity of water, if we assume density difference is 1 g cm-3

µm)
r (µ 0.01 0.1 1 10 100
V (cm s-1) 2 × 10-8 2 × 10-6 2 × 10-4 2 × 10-2 2
 Stabilization and Destabilization of
Colloidal Dispersion

• Stabilization of a colloidal dispersion:

Stabilization serves to prevent colloids from aggregating
by eletrostatic or steric repulsion

• Destabilization of a colloidal dispersion:

Unstable colloidal dispersions form flocs as the particles
aggregate due to interparticle attractions (Van der Waals
Interaction).
 Interfaces
Interface: The term interface indicates a boundary between any two
immissible phases.

Surface: The term surface denotes an interface when one phase is a gas,
usually air.

Types of Interfaces:
 Interfacial Free Energy
Interfacial Free Energy: The minimum amount of work required to create unit area
of the interface or to expand it by unit area.

•The interfacial free energy per unit area is what we measure when we determine
the interfacial tension between the two phases.

•The minimum work required for expanding the interface, Wmin = EIF × ∆A
= γ × ∆A

Surface active agents adsorb at the interfaces and significantly change the amount
of work required to expand those interfaces. Surfactants usually act to reduce the
interfacial free energy rather than to increase it.

•Surface tension of liquids corresponds to surface energy of solids.

A+∆A
 Surface-Active Agents or Surfactants
•Surfactants: Surfactant represents a heterogeneous and long-chain molecule
containing both hydrophilic (“water-loving”) and hydrophobic (“water-
fearing”) moieties.
Hydrophilic (Head)
+ Hydrophobic (Tail)

•Types of surfactants

(i) Cationic – Head group is positively charged

(ii) Anionic – Head group is negatively charged
(iii) Nonionic – Head group is neutral
(iv) Dimeric – Gemini
(V) Zwitterionic – Both the charges
 Types of Surfactants
Types Example
Anionic

Sodium dodecylsulfate (SDS)

Nonionic

Triton X-100

Cationic
Cetyltrimethylammoniumbromide (CTAB)

Gemini

Zwitterionic
N-dodecyl-N,N-dimecylammonio- butane-sulfonic acid (DDABS)
 Surfactants in Aqueous Medium
• Soluble in aqueous medium
• Adsorption
• Adsorption of surfactants is a process where surfactant molecules are accumulated at
the interface from the bulk solution.
• Adsorption of surfactants results in reduction in surface tension. Surface concentration
increases until CMC is reached

3-50 nm
Air
Hydrophilic
S u rface ten sio n, γ [m N /m ]

Region
C > CMC
Water

cmc

Surfactant Monomer Micelle

Log CB Hydrophobic
Region, core
• CMC (critical micelle concentration): Critical concentration of the surfactants where micellization
occurs
 Determination of CMC Values

Amount of Organics Solubilized

CMC
Surface tension

Conductivity
CMC
CMC
Monomer and Micelle Conc.

Conc. of surfactant sol. Conc. of surfactant sol. Conc. of Surfactant Sol.

CMC

Monomer
C > CMC

Micelle
Naphthalene
Conc. of surfactant sol.

•Surface tension Surfactant Monomer Micelle Solubilization

•Conductivity
•Solubilization
 Surfactants in Aqueous
Medium a0

lc
v

•Micellar shape: Spherical, Cylindrical, Rod like, etc.

•Micellar aggregation number: Number of surfactant
molecules present in a micelle.

The curvature of a micelle can be expressed as

dimensionless parameter known as “Critical Packing
parameter” p = v/(a0lc)
Molar volume: v; v = (27.4 + 26.9 n) m (Å3); n = no. of
carbon atoms, m = no. of hydrocarbon chains.
Tail length: lc; Hear group area: a0
lc = 1.5 + 1.265 n (Å)
•Spherical micelle p<< 1/3
•Ellipsoidal & cylindrical 1/3 < p < ½
•Bilayer p > 1/2
Example: Show that the packing parameter of a surfactant has to be less than 1/3 for it to
form spherical micelle
For a spherical micelle radius RS and aggregation number na
πRS3]/v = 4π
So, na = [(4/3)π πRS3/a0; or v/a0 = RS/3
P = v/(a0lc) = (RS/lc)(1/3)
Since Rs has to be less than or equal to lc; P has to be less than or equal to 1/3 for the
micelle to be spherical.
 Micellar Kinetics
• Micelles are NOT static structures.
• Micelles are unstable structures with two characteristic relaxation times – fast
relaxation time (τ1) and slow relaxation time (τ2)
Fast relaxation: This process can be considered to be the collision between surfactant
monomers and micelles.
τ2 is attributed to the micelle formation and dissolution process (i.e., the lifetime of the
micelle).
• Nonionic surfactants and mixed surfactant systems, τ2 can be as long as minutes

τ1
+
Fast relaxation time, microseconds

+ +
τ2

Slow relaxation time, milliseconds to minutes

Different Interfacial Property Changes at
CMC

CMC
Detergency
Solution Parameter

Surface tension
Interfacial tension

Conductivity
Solubilization

Concentration of Surfactant
 The Cause of Surface Tension
Definition: Surface or interfacial tension can be defined as the force
needed to oppose the natural pull of the molecules in the surface or
interface to increase in area of surface or interface.

We must work against this net force, i. e. energy is

required. to move a molecule from the bulk to the
interface.
Net force is not zero
Net force is zero
The interface, or surface in this case, therefore possesses an “excess” free energy,
and we define this surface free energy per unit area as surface tension.
Surface free energy
= Surface tension
Area

The dimension for energy per unit area (e.g. J/m2) is equivalent to force per unit
length, i.e. surface tension. A commonly used unit for surface tension is mN/m or
dyne/cm (1 N = 105 dyne).
Polar solvent: High surface tension
 Practical Examples

Water droplet Soap bubble Water strider

•Water adhering to the tap gaining mass until it is stretched to a point where the surface tension
can no longer bind it to the tap.
W (4/3 πr3ρ.g) = 2π πrγγ or r ∝√γ

•Bubbles cannot be formed from pure water because water has very high surface tension.

•If the gravitational force is less than the surface tension then the object will float on the surface of
the water.
 Practical Examples
The body uses surfactants to reduce surface tension at the air-liquid interface in the
lungs. The human body does not start to produce lung surfactants until late in fetal
development. Therefore, premature babies are often unable to breathe properly, a
condition called Respiratory Distress Syndrome (RDS). Administration of artificial
surfactants virtually eliminates this health problem.

γ < 1-5 mN/m

Wall of alveolus
Alveoli

Biophysical Journal 94:855-868 (2008)

 2γ
LaPlace’s Law ∆P = Pi − P0 =
r
P0 Pi r
If γ = 50 dyne/cm and r1 – 0.05 cm and r2 = 0.025 cm
γ
Then if for inhalation P = 2 γ/r1 for exhalation P > 2 γ/r2 ;
Thus, as alveolar radii decrease, the (2 γ/r2) or alveolar wall tension gets
larger than the pressure and then alveoli would collapse. How do alveoli
adjust to prevent this?
Surface tension: Due to its polar nature, water molecules adhere together,
giving rise to surface tension at air - water interfaces
Driving and Opposing Forces of Micelle
Formation
•Forces driving micelle formation:
a) Hydrophobic force
b) Entropy gain (∆∆G = ∆H - T ∆S)

•Forces opposing micelle formation:

a) Concentration gradient
b) Thermal (Brownian) motion
c) Charge repulsion between ionic polar heads
 Parameters Affecting CMC of Surfactants
Effect of Hydrophobic part (Tail):

• Longer the tail length of the surfactant, lower the solubility, lower the CMC value of the surfactant,
and higher the aggregation number.

• Lower the CMC values, lower the surface tension and greater the surface activity.
Example: CH3(CH2)15N(CH3)3 CMC ~ 1 mM; CH3(CH2)13N(CH3)3 CMC ~ 3 mM; CH3(CH2)11N(CH3)3 CMC ~ 10 mM; CH3(CH2)9N(CH3)3 CMC ~ 40 mM.

• Similar chain length nonionic surfactants are having lower CMC than the ionics.

Effect of hydrophilic part (head):

• Longer the hydrophilic chain length of the nonionic surfactants higher the CMC.
Effect of Electrolytes: Ionic Micelle in water
Addition of electrolytes reduce the CMC of the ionic surfactants and negligible effect on nonionic
surfactant. Valance of counter ion is very much effective in reducing CMC.
Effect of Temperature:
• The effect of temperature on the CMC of surfactants in aqueous medium is complex. CMC decreases
with increase in temperature first and then after a minimum increases with increase in temperature.
Temperature increase causes decreased hydration of the hydrophilic group, which favors
micellization. However, temperature increase also causes disruption of the structured water
surrounding the hydrophobic group, an effect that disfavors micellization. The relative magnitude of
these two opposing effects, therefore, determines whether the CMC increases or decreases over a
particular temperature range.

Note: cmc’s of nonionic surfactants are much lower than those of ionic surfactants.
Ionic Micelle in water
 HLB Value
HLB value: Hydrophilic Lipophilic Balance

• Changing the tail length of surfactant molecule HLB value will change.

• HLB value is a kind of index numbered from 0 to 20.

HLB value
Lipophilic 0 10 20
Hydrophilic
(Oil soluble) (Water
soluble)

A commonly used general formula for non ionic or ionic surfactant is

HLB = 7 + Σ(Hydrophilic group numbers) - Σ (hydrophobic group numbers)

Surfactants Application Based on HLB
Values

HLB Values Applications

3-6 W/O Emulsion
7-9 Wetting agents
8-12 O/W Emulsion
12-15 Detergents
15-20 Solubilizer or hydrotrope
Practical Applications of Surfactants
•Detergency
•Mineral/Particulate flotation
•Surfactant-enhanced carbon regeneration
•Stability of particulate suspension
•Filtration of ultra fine particles
•Deinking from paper and plastic film
•Herbicide dispersions
•Fabric softeners, Antistatics, Textile auxiliaries
•Hair conditioners
•Germicides
Reverse Micelle

Oil
 Microemulsion
• Microemulsion: Microemulsion is a thermodynamically stable phase consisting
of water, hydrocarbon, surfactant, and co-surfactant
• Reverse (W/O) microemulsion: When the continuous phase is oil, the
microemulsion is called reverse microemulsion

R=
[water ]
[surfactant ]

+ Water + Oil +

Surfactant Co-surfactant

Reverse Microemulsion (W/O)

 Work of Adhesion and Cohesion
Consider a cylindrical column composed of two types of material, A and B. If we pull this
column apart and separate it into column A and column B, then the change in free energy
can be expressed as
γA + γ B − γ AB = WAB
γA, γ B = Surface free energy per unit area for material A and B, respectively.
γ AB = Interfacial free energy per unit area between material A and B.
WAB = Work of adhesion (per unit area), which is the work required to separate
the two blocks of material.

γA + γ B is the total surface free energy in the

final state (state 2), and γ AB accounts for the
interfacial energy between the two materials in
the initial state (state 1).
If materials A and B are the same, then γAA = γ
BB = 0, and W AA = 2 γA and W BB = 2 γB

WAA (or WBB) is the work of cohesion. The State 1 State 2

work of cohesion is simply the work required
to create two surfaces of the same material. γ AB = Interfacial tension or Interfacial free energy
1
γ AB = (WAA + WAB ) − W AB
2
 Surface Wetting vs. Adhesive and
Cohesive Forces

Adhesive forces > cohesive forces: At the liquid-solid surface interface, if the
molecules of the liquid have a stronger attraction to the molecules of the solid
surface than to each other wetting of the surface occurs.

Cohesive forces > adhesive forces: If the liquid molecules are more strongly
attracted to each other than the molecules of the solid surface the liquid beads-up
and does not wet the surface.
 Forces of Nature
There are four known types of forces that interact with matter to define our universe.
They are the [(i) strong, (ii) weak], [(iii) electromagnetic, and (iv) gravitational forces].
First group: Act between neutrons, protons, electrons, and other elementary particles. Very short
range of action, 10-5 nm, and belong to the domain of nuclear and high energy physics.
Second group: Act between atoms, molecules (as well as between elementary particles). The forces are
effective from subatomic to practically infinite distance.
Example: Electromagnetic forces - the source of all intermolecular interactions – determine the
properties of solid, liquid, gas, behavior of particles in solution, chemical reactions etc.
 Intermolecular Forces
Short range forces: Force field around the atoms or molecules, rarely extending one
< 1 nm). Molecular forces.
or two atomic distances (<

Long range forces: Forces acting in colloidal range (~ 100 nm). Electrical double
layer, van der Waals forces, steric interactions etc.

If interaction potential w(r) between two molecules or particles, the interaction

potential is related to the force between that is F = - dw(r)/dr.
d /d . Since the derivative of
w(r) with respect to distance r gives the force, the work that can be done by the
force, w(r) is often referred as free energy or available energy.
 Intermolecular Forces Q1 r Q2

Coulomb forces for charge-charge interactions:

Coulomb force between two charged atoms or ions is the strongest of the physical forces , even
stronger than most chemical binding forces.
The free energy for coulomb interaction between two charges Q1 and Q2 if given by
1 Q1Q2 z1 z 2 e 2
w(r ) = =
4πε 0ε r 4πε 0εr
ε0 (8.854 × 10-12 C2J-1m-1), ε are the relative permittivity, dielectric constant of vacuum and the
medium respectively. Dielectric constant equal to the ratio between its permittivity in the medium
and the permittivity in vacuum.
r is the distance between two charges, e = 1.602 × 10-19 C, z is the ionic valency. The coulombic
force is given by dw(r ) Q1Q2 z1 z 2e 2
F= = =
dr 4πε 0εr 2 4πε 0εr 2
For like charges both F and w are positive and the force is repulsive, for unlike charges both
are negative and the force is attractive.
πε0εr2) Vm-1
The electric field E at a distance r away from a charge Q1 is defined by E = Q1/(4πε
This field, when acting on a second charge Q2 at r, gives rise to a force F = Q2E
Example: For two isolated ions (e.g. Na+ and Cl-) in contact r is the sum of the two ionic radii
(0.276 nm), and the binding energy is w(r) = - (1.602 × 10-19)2/4π
π(8.854 × 10-12) (0.276 × 10-9) =
- 8.4 × 10-9 J

Born energy
Origin: When a single ion is in a vacuum or medium, even though it may not interaction with other ions, it
still has an electrostatic free energy – equal to the electrostatic work done in forming the ion – associated
with it. In vacuum this is called self-energy, when in medium, it is Born or solvation energy of an ion.
This is the solvation energy of an ion. Consider a charged atom or sphere of radius a by
gradually increasing the charge from zero to till its full charge Q. At any stage of this process
let the ionic charge be q, and let this be incremented by dq. The work done to bring
additional charge from infinity to r = a is therefore (putting Q1 = q, Q2
= dq, r = a) dw =
q dq
4π ε0 ε a
So, the born energy or total free energy of charging the ion,
Q
q dq Q2 (z e)2
µ = ∫ dw= ∫
i
= =
0
4π ε 0 ε a 8π ε 0 ε a 8π ε0 ε a
The free energy change on transfering an ion from a medium of low dielectric constant ε1 to
high dielectric constant ε2 is negative, i. e. thermodynamically favorable

z2 e2  1 1 
∆µ = −
i
 − 
8π ε0 a ε1 ε2 
Electrical work or potential energy, electric
potential, electric field strength

Electrical force (F): q1 q 2

F=
4π ε0 ε r 2

Electrical work (We) or potential energy (V):

r
q1 q 2
We or V = − ∫ F dr = = F ×r
∞
4π ε 0 ε r
Electrical potential: q2
φ = ; W e orV = q 1φ
4π ε0 ε r

Electric field strength:

q2
E = ; F = q1 E
4π ε0 ε r 2
 Polarizability of Atoms and Molecules
Induced dipole in presence of field E is
µind = ∝E
In presence of electric field E the
electron orbit is shifted by a distance l
from the nucleus, then induced dipole
moment, µind = ∝0E = l.e
Now the external force Fext on the External field E, µind = ∝0E
No external field, µind = 0
electron due to the field E is: Fext = e. E

This is like Coulomb force e2/4πε0R2 resolved along the direction of the field. The
internal (restoring force is therefore
e2 e2 e
Fint = Sinθ ≈ ≈ µind
4πε 0 R 2
4πε 0 R 3
4πε 0 R 3
At equilibrium, Fext = Fint, which leads to
µind = 4πε0R3E = ∝0E
So, ∝0 = πε0R3
 van der Waals forces
•Ideal gas law (Boyle): PV = nRT • • • •
Attractive force between the gases are negligible
Equation proposed by J. D. van der Waals • • • •
 a
 P+ 2 (V −b) = RT • •
 V 

Account for the finite size of the molecules • •

Account for the finite attractive intermolecular forces
• The attractive forces between the atoms, molecules, and particles are
collectively called “van der Waals forces”.
• Forces that act between electrically neutral molecules.
• Origin: dipole or induced dipole
• Example of van der Waals force: condensation of vapor form liquid
Play important role in phenomena like: adhesion, physical adsorption, gas
properties, flocculation etc.
 van der Waals forces…
Almost all interfacial phenomena are influenced to various extents by forces
that have their origin in atomic and molecular level interactions due to
induced and permanent polarities created in molecules by electric fields of
neighboring molecules or due to the instantaneous dipoles caused by
positions of the electrons around the nuclei.

x
Dipole moment: µ = q×
×x, unit Debye (D) = 3.336 10-30 C m. -q +q

Induced dipole: µi = α×E;

α× α = polarizability, E = Electric field
 Van der Waals forces…
The forces consist of three major categories known as
(i) Keesom interactions: Permanent dipole / permanent dipole
interactionss
(ii) Debye interactions: Permanent dipole / induced dipole
interactions
(iii) London interactions: Induced dipole/ induced dipole
interactions

The three are known collectively as the van der Waals interactions
•London force is always present (like gravitational force), because it does not require the
existence of permanent polarity or charge induced polarity in the molecules.
•They are relatively long ranged compared to other atomic or molecular level forces
(range is 0.2 nm to over 10 nm).
Combined effect of van der Waals attraction and inter particle repulsion at the molecular
level may be represented by: Φ = ζx-12 - βx-6
Types of interactions
Types of interactions
Types of interactions

London or
 Molecular interactions and power law
Description Φ Notations Attributed Value of n
Φ ∝ x-n
Ion-Ion z1 z 2e 2 Coulomb 1
4 πε 0 x
Ion-permanent Angle between line of Coulomb 2
dipole ( ze)1 µ2 cosθ centers and axis of dipole
4πε0x2
Permanent ( const.)µ1µ2 Const. depend on Coulomb 3
(dipole-dipole) √2,
orientation of dipole (√
4πε0 x3 2, -2)
Parmanent ∝0 = polarizability (-Ve) Debye 6
α0,2µ12 +α0,1µ22
dipole – −
induced dipole (4πε0 )2 x6
Permanent 2 µ12 µ2 2 Free rotation of dipole Kessom 6
(dipole-dipole) − (always negative)
3 ( 4πε0 ) kBTx
2 6

Induced 3h ν1ν2 α0,1α0,2 ν = characteristic London 6

(dipole-dipole)− vibrational freequency of
2 ν1 +ν2 (4πε0)2 x6 electron (always neg.)
ξ
Repulsion + 12
x 12
 Debye interaction
The fixed dipole µ1 oriented at an angle θ to the line joining it to a polarizable
molecule.

The field is a vector quantity:

µ1/4πε
1. Parallel to the line of the centers: E11 = -(2µ πε0)x-3cosθθ (1)
2. Perpendicular to the line of centers: E1 = -(µ µ1/4πε
πε0)x-3sinθθ (2) E11
The total field :
µ1/4πε
E = -(µ πε0)x-3(sin2θ + 4cos2θ)1/2 = -(µ
µ1/4πε
πε0)x-3(1 + 3cos2θ)1/2
x
Dipole moment of second molecule: µ2 = α2 E E1
Potential energy due to this field: -µµ2E = -αα2 E2 θ
The energy necessary to induced the dipole =(1/2) α2 E2 µ1
Total potential energy of the second dipole is
φ2 =- α2 E2 + (1/2) α2 E2 = -(1/2) α2 E2 = -(1/2) α2 ×(µ
µ1/4πε
πε0)2x-6(1 + 3cos2θ)
Averaging over all orientations, angle averaged energy = -[α α2 µ12/(4πε
πε0)2]x-6 ;
Angle average of cos2 θ = 1/3
Second dipole interact in similar fashion on the first dipole, So,
Total potential energy of attraction: φD = -[(α α2 µ12 + α1 µ22)/(4πε
πε0)2]x-6
 Dipole –Dipole interaction (Keesom)
For two point dipoles of moments µ1 and µ2, the interaction energy when they are fixed and the
dipoles are mutually aligned is given by:
µ1µ2 x
φ ( x,θ1,θ2 ,ϕ ) = − [2 cosθ1 cosθ2 − sinθ1 sinθ2 cosϕ ]
4πε0ε x3
Case-II
Case-I: When two dipoles are lying in line (Max. attraction) Case-I
φ 2 µ1µ 2
( x , 0 , 0 ,ϕ ) = −
4 πε 0 ε x 3
Case-II: When two dipoles are aligned parallel to each other the energy is
φ µ1µ 2
( x , 90 , 90 ,180 ) = −
4 πε 0 ε x 3
The energy is half of the previous value at the same inter dipole separation.
There are many degrees of freedom. A Boltzmann averaging of the interaction energy over all
orientations leads to the angle-average interaction free energy of: (Here ∝ replace by ∝orient = µ2/3KT
from Debye equation) 2µ12 µ2 2 µ1µ 2
φK = − for k BT 〉
3(4πε 0 ) 2 k BTx 6 4πε 0 x3

The Boltzmann-averaged interaction between two permanent dipoles is usually referred to as the
Keesom interaction. It depends upon temperature.

Dipole-dipole interactions are generally weak

 Induced (dipole-dipole) or London (Dispersion) interaction

This weakest among all inter molecular forces. It is possible for two adjacent neutral
molecules to affect each other. The forces between instantaneous dipoles are called
London dispersion forces.

London dispersion forces increase as molecular weight increases.

London dispersion forces exist between all molecules.

London dispersion forces depend on the shape of the molecule.

The greater the surface area available for contact, the greater the dispersion forces.
The dispersion energy between two identical atoms or molecules is:
− C disp 3 α 02 h ν 3 α 02 I
φ= =− =−
x6 4 ( 4πε 0 ) 2 x 6 4 ( 4πε 0 ) 2 x 6

where h is the Planck constant and ν is the orbiting frequency of the electron, hν = 2.2 ×
10-18 J. This is energy needed to ionize the atom or first ionization potential I.
For two dissimilar atoms
3 α 01α 02 hν 1ν 2 3 α 01α 02 I1 I 2
φL = − = −
2 (4πε 0 ) 2 x 6 (ν 1 +ν 2 ) 2 ( 4πε 0 ) 2 x 6 ( I1 + I 2 )
 London (Dispersion) interaction

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
 Total van der Waals force
Debye Keesom London

1  µ1α 0 , 2 + µ 2α 0 ,1 2 µ1 µ 2 3 α 0 ,1α 0 , 2 I1 I 2 
2 2
φA = − 6  + + 
x  ( 4πε 0 ) 2
3( 4πε 0 ) k BT 2 ( 4πε 0 ) ( I1 + I 2 ) 
2 2

For a pair of identical molecules net van der Waals attraction

1  2 µ1
4
3  −6
φA = − 2 
2α µ 2
+ + h ν α 2
1 0 ,1  x = − β11 x −6
( 4πε 0 ) 
0 ,1 1
3k BT 4 

β11 indicate pair of identical molecules.

Percentage of Debye, Keesom, and London contributions to the van der Waals attraction
between various molecules
 Ion-Dipole interaction
Interaction between a charged atom and a polar molecule. Ex. Na+ and H2O
Coulomb energies of Q with –q at B and Q with +q at C;
Total interaction energy will be the sum of the Coulomb energies:
1
 1
2
 1  2
2
C, +q
Qq  1 1  AB =  x − l cos θ  +  l sin θ  
φ( x ) = − −
4πε 0ε  AB AC 
  2  2  
1
x l θ
 1
2
 1  2
2
AC =  x + l cos θ  +  l sin θ   A, Q
 2  2   H2O
Na+
At separation x exceeding the dipole’s length l these B, -q
distance can be written approximately, AB =x-(1/2)lcosθ θ,
AC = x+(1/2)lcosθθ , and the interaction energy in this
limits becomes
   
Qq  1 1  Qq  l cos θ 
φ( x ) = φ( x,θ ) = −  −  =−  
4πε 0ε  x − 1 l cos θ x + 1 l cos θ  4πε 0ε 1
 x 2 − l 2 cos 2 θ 
 2 2   4 
Qµ cos θ ( ze) µ cos θ
=− = −
4πε 0εx 2 4πε 0εx 2
 Hamaker Constant
Van der Waals force: Molecular level in the form of pair potential φ = -β
β12/x6
For “two-body” one may integrate the energies of all the atoms in one body with all the atoms in
other and thus obtain the “two-body” potential for an atom near a surface.
Hamaker constant:
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 from London dispersion interaction energy
A y y  x 2 + xy + x 
φ=−  2 + 2 + 2 ln 2 
12  x + xy + x x + xy + x + y  x + xy + x + y 
Where x = H/(a1 + a2) and y = a1/a2
For equal spheres, with a1 = a2 = a (x = H/2a

A 1 1  x( x + 2) 
φ =−  + + 2 ln  
2 
12  x( x + 2) ( x + 1) 2  ( x + 1) 
If a small inter particle separation is assumed such as H << a (i.e. x << 1) This equation simplifies to
 Hamaker Constant
A 1 Aa
φ=− =−
12 2 x 12 H
Aa
van der Waals force = −
12 H 2

a = particle radii, H = separation distance (For liquids, 0.16 nm; For solids, 0.3 nm), A =
Hamaker Constant (Material property)
Hamaker constant may be defined as
A = π2Cρ ρ1ρ2 ~ 10-19 J (in vacuum)
Where ρ1 and ρ2 are the number of atoms per unit volume in the two bodies. C is the
coefficient in the molecular / atom atom pair potential, London parameter.
If a body composed of atoms for which C = 10-77 Jm6 and a number density ρ = 3 × 1028
m-3 (corresponding to atoms of radius ~ 0.2 nm), Hamaker constant is
A = π2 10-77 (3 × 1028)2 ≈ 10-19 J.
The interaction energy calculated using above equation will be over estimated for large
distances (H > ~ 10 nm)
 Estimation of A (Vacuum or non-vacuum media),
combining relations

A132 ≈ ± A131A 232 A132: Interaction of 1 and 2 across medium 3

A12 ≈ A11 A 22 A12: media 1 & 2 interacting across

vacuum
A131 ≈ A 313 ≈ A11 + A 33 − 2A13 ≈ ( A11 − A 33 )
2

A132 ≈ ( A11 − A 33 )( A 22 − A 33 )
 van der Waals Interaction Potential for
various configurations
Expression for
Configuration Schematic van der Waals force
potentials

Molecule - Molecule
C
WM − M = − 6
r
πC
Cρρ
Molecule - Plate WM − P = −
6H 3

AR
Sphere - Plate WS− P = −
6H
Sphere - Sphere AR
WS−S =−
12 H
van der Waals Interaction Potential for
various configurations
 Intermolecular Forces:
Contrast with gravitational forces
17th Century: Newton postulated the law of gravitation
Gm1m2 Gm1m2
Potential: w( r ) =− Force: F( r ) = −
r r2

G = Gravitational Constant, mi (i = 1, 2) Mass of bodies

r = distance of separation between centers of bodies
19th Century: Scientists postulated that one simple force law
would eventually account for all intermolecular attractions
The interaction potential w(r) and force F(r) were of the form

Cm1m 2 dw ( r ) nCm 1m 2
w( r ) = − or F( r ) = =−
r n dr r n +1
 Intermolecular Forces:
Contrast with gravitational forces
nCm 1m 2
F( r ) = − When n = 1, we have gravitational forces
r n +1
Argument: If Intermolecular Forces are not to extend over
long ranges, then n ≥ 3. How?
For simplicity, let us express the general term for interaction
potential between two molecules as:
Cm1m 2
w( r ) = −
rn
Consider a region of space where number density of these
molecules are ρ (The region can be solid/liquid/gas)
The number of molecules in a region of space between r and
(r+dr) will be ρ4πr2dr (4πr2dr is the volume of a spherical shell
of radius r and r+dr)
 Intermolecular Forces:
Contrast with gravitational forces
The total interaction energy of one molecule with all the other molecules in the
system will be given by:
C
w=−
rn L
L
σ= Molecular diameter
Energy = ∫
σ
w ( r ) ρ 4 π r 2 dr = − 4 π C ρ ∫
σ
r 2 − n dr
L = size of the system, i.e
n−3
− 4π C ρ  σ   dimension of solid,
= 1 −   
( n − 3 )σ n − 3   L   gas container.
4π C ρ
= −
( n − 3 )σ n − 3

σ<< L and σ/ L <1; Large distance contributions to the interaction will disappear
only for the value n greater than 3.
For n less than 3 second term will be greater, and the contribution from the more
distant molecule will be dominant over the nearby molecule. In such cases size of the
system must be taken into account.
Interaction between two semi-infinite
blocks
 Practical example
Unique ability of gecko’s to climb walls and hang from ceilings

How??

Vacuum principle??
 van der Waals force
Article in Nature: Adhesive force of a single gecko foot-hair. Kellar Autumn, Yiching
A. Liang, S. Tonia Hsieh, Wolfgang Zesch Wai Pang Chan, Thomas W. Kenny, Ronald
Fearing, Robert J. Full, Nature, 405, 681-685, 2000.
Setae:
Setae
•Gecko’s foot has ~500,000 hair or
µm and ~ 5
•Setae of each 30-130µ
µm dia.
•5000 setae/mm-2
Spatulae:
•Branches of 100-1000 hair Seta Spatulae
•Length 0.2-0.5 µm
•Spatula shaped ending
•10-20 µN force/seta
Gecko can produce 10 -100 N/100 mm2 pad area or 0.1 Nmm-2
Each seta produce 0.1/5000 = 20 µN force

Spatula radius = 2 µm, adhesion distance D ~ 0.3 nm

Spatulae force (S-P) = -AR/6D2 , A = Hamakar constant = 10-19 J
Spatulae force = 0.4 µN
Setal force = 0.4 × (100-1000) = 40-400 µN
 Force of single seta

(a) After an initial push towards the surface the parallel adhesive force to the surface
increased until the setal began to slide off the edge of the sensor
(b) Setal force parallel to the surface increased with the perpendicular preloading force
Maximum parallel force was observed if the seta was allowed to slide ~ 5 µm.
 Force of single seta

Consider spatula is a curved segment of sphere (R=2 µm) and is separated by a

small distance. Flat surface were van der Waals forces become significant
atomic gap distance (D = 0.3 nm)
Spatulae force (S-P) = -AR/6D2 , A = Hamakar constant = 10-19 J
Spatulae force = 0.4 µN
Setal force = 0.4 × (100-1000) = 40-400 µN
 Applications
September 2005 / Volume 2 / Issue 9 / ISSN 1744-1560 / CTHEC2 / www.rsc.org/chemicaltechnology

1. B. Yurdumakan, N. R. Raravikar, P. M. Ajayan, A. Dhinojwala, Synthetic gecko foot-

hairs from multiwalled carbon nanotubes. Chem Comm, 3799-3801, 2005.
2. H. Lee, B. P. Lee, P. B. Messersmith, A reversible wet/dry adhesive inspired by mussels
and geckos. Nature 488, 338-342, 2007.
3. L. Ge, S. Sethi, L. Gi, P. M. Ajayan, A. Dhinojwala, Carbon nanotube-based synthetic
gecko tapes. PNAS 104, 10792-10795, 2007.
 Dry adhesive tape
Normal viscoelastic tape:
•Rarely hang heavy objects on wall
•Stickiness is time- and rate dependent
•Do not work under vacuum (Space applications, for climbing of robots)

Carbonnanotube based “Gecko tape”

•Comparable shear stress on hydrophilic &
hydrophobic surface
•Shear force supported by the gecko tape is
very stable & time independent
• Visco elastic tape is stronger than gecko
when measured for a short period of time
 µm and 0.16 m cm2
Force for peeling the tape of 500µ

Angle (o) Force (N.m)

45 16
30 20
10 96

θ > 10 decreased breaking of CNT

Detachment energy depend on surface energy of the surface

Detachment energy = G = F(1-cosθ θ)/width
At 45 O, G = 5 J/m2 for mica and 2.2 J/m2 for teflon
Colloid stability, van der Waals attraction,
potential energy curves
(a) (b) (c)
+ RS + +
Repulsion & attraction comparable

Interaction Energy
Interaction Energy

Interaction Energy
Repulsion Repulsion < Attraction

0 0 0
r = 2Rs

Attraction Unstable Metastable

- r - r - r
+ (d) Potential energy minimum
Interaction Energy

Repulsion > Attraction

Separated particles are lower in energy than the aggregate

Stable
- r
 Potential energy curve

The energy barrier has to overcome access

to that primary minimum. +
Repulsion & attraction comparable

Maximum

Interaction Energy
The system is possessing a degree of kinetic
stability even though it is thermodynamically
unstable. 0

Coagulation is predicted here, but it is expected

to occur slowly. Secondary minimum
Metastable
- r
Primary minimum
 What is kinetically and thermodynamically stable?
The mixture is said to be kinetically stable: this means that it reacts extremely slowly, or
not at all. The time it takes for a reaction to occur is a measure of kinetic stability. The
slower a reaction, the greater the kinetic stability. The energy barrier is very high.

Though a mixture of H2(g) and O2(g) is kinetically stable, it is certainly not

thermodynamically stable (energetically stable). A substance (or mixture) that would be
mostly converted into something else at equilibrium is said to be thermodynamically
unstable.

So, chemical stability, or ‘resistance to change’, has two meanings. It must be considered
in terms of both kinetic stability and thermodynamic stability.

On the other hand, the decomposition of pure hydrogen peroxide may occur explosively.
H2O2(l) → H2O(l) + ½O2(g)
H2O2(l) is both thermodynamically unstable and kinetically unstable.

The lyophilic colloids-macromolecules and association colloids-are known to be

thermodynamically stable.
Dispersions of socalled lyophobic colloids (emulsions and finely divided solids) were
considered to be thermodynamically unstable (kinetically stable).
Brownian motion
A

C1 C2

x x
B