CY 20202 Physical Chemistry II

Module 3:
Physical Chemistry of Soft matter:
Colloids, Surfaces and Macromolecules

LECTURES 4-6

Department of Chemistry
Indian Institute of Technology Kharagpur
Spring 2023-2024

The hydrophobic interaction

Nonpolar molecules dissolve slightly in polar solvents
Strong interactions between solute and solvent are not possible

Each individual solute molecule is surrounded by a solvent cage

Thermodynamics of transfer of a nonpolar hydrocarbon solute from a

nonpolar solvent to water, a polar solvent. 1

Experiments show that the process is endergonic (ΔtransferG > 0)

but exothermic (ΔtransferH < 0)

Large decrease in the entropy of the system (ΔtransferS < 0)

⟹ positive Gibbs energy of transfer

The hydrophobic interaction

CH4(in CCl4) → CH4(aq)

At 298 K
ΔtransferG = +12 kJ mol-1 ; ΔtransferH = −10 kJ mol−1 ;ΔtransferS = −75 J K−1 mol−1

Substances characterized by a positive Gibbs energy of transfer from a

nonpolar to a polar solvent are called hydrophobic.

Quantification of hydrophobicity of a small molecular group R

hydrophobicity constant, π defined as 𝑆
𝜋 log
𝑆

where S is the ratio of the molar solubility of the compound R-A in octanol,
a nonpolar solvent, to that in water,
and S0 is the ratio of the molar solubility of the compound H-A in octanol to that in
water.

The hydrophobic interaction

Hydrophobicity constant 𝜋 log

Positive values of π indicate hydrophobicity and

negative values of π indicate hydrophilicity
2
π values of most groups do not depend on the nature of A (R-A)

Group additivity of π values exist

For example, π values for R = CH3 (0.5), CH2CH3 (1.0), (CH2)2CH3 (1.5),
(CH2)3CH3 (2.0) and (CH2)4CH3 (2.5)

Acyclic saturated hydrocarbons become more hydrophobic with increase in the

carbon chain length
3
4
5
 Colloidal stability requires a repulsion force

Lyophobic colloids may also be stabilized by lyophilic colloids

van der Waals radius = it represents the minimum contact distance between
two atoms. It can be approximately considered as the interatomic distance beyond
which the repulsive energy rapidly rises 𝒓𝑽𝒅𝑾 𝝈

The van der Waals radius also defines a van der Waals area (SVdW) and
volume (VVdW). They represent areas and volumes that cannot be
penetrated (excluded areas and volumes).
6
The van der Waals volume of a molecule is approximately given by the
sum of the van der Waals volumes of the atoms or groups of atoms
forming the molecule.
4
𝑆 𝜋 𝜎2 𝑉 𝜋 𝜎3
3

Two primary criteria which must be considered in the discussion of colloid

stability: (1) frequency of particle collisions (2) effectiveness of the collisions
At long range intermolecular distances we can approximately neglect
quantum effects and describe nuclei and electrons as point charges
following the laws of classical electrostatics (Coulombs law).

The interaction energy between a charge qi and a charge distribution qj

is simply given by the sum of the pair Coulomb contributions:

q
V q
R ij

1 q 𝑞
V ⋅
4𝜋𝜀 R 12

Interaction energy between two charges

𝑸𝟏 𝒁𝟏 𝒆 and 𝑸𝟐 𝒁𝟐 𝒆 separated by a distance 𝒓

𝑄 𝑄 𝑍 𝑍 𝑒
𝑉 𝑟 𝑉 𝑟
4𝜋𝜖 𝑟 4𝜋𝜖 𝑟 7
 Dipole moment
The dipole moment is a vector measuring the distance between
the center of the positive and negative charge distributions:
l
𝜇⃗ 𝑞𝑟⃗
 
- +
Unit positive and negative charges separated by a
1 Å distance:
μ

8
 Interaction Distance Energy Type
dependence (kJ mol-1)
Ion-ion R-1 250 ion
Ion-dipole R-2 15

Dipole-dipole R-3 2 Fixed dipoles

R-6 0.3 Rotating
dipoles
Dipole- R-6 0.3
induced
dipole
Dispersion R-6 2 All the
(London) molecules

Attractive interaction between two rotating molecules

𝑪𝟔
𝑽 = - 𝒍 ≪𝑹
𝑹𝟔

Repulsive interaction between two molecules

9

𝑹
Hard sphere 𝑽 𝑹 = ∞ 𝑹< 𝝈
repulsion
= 𝟎 𝑹> 𝝈

𝝈 𝝈
Attractive interaction between two rotating molecules

𝑪𝟔
𝑽 = - 𝒍 ≪𝑹
𝑹𝟔

Repulsive interaction between two molecules

𝑹

Hard sphere 𝑽 𝑹 = ∞ 𝑹< 𝝈

repulsion
= 𝟎 𝑹> 𝝈

𝝈 𝝈

Attractive interaction between two rotating molecules

𝑪𝟔
𝑽 = - 𝒍 ≪𝑹
𝑹𝟔

Repulsive interaction between two molecules

10

Hard sphere 𝑽 𝑹 = ∞ 𝑹< 𝝈

repulsion
= 𝟎 𝑹> 𝝈

Soft sphere 𝑪𝒏
repulsion 𝑽 𝑹 =
𝑹𝒏
van der Waals Attractive Forces
• Forces with the greatest effect are :

• London Dispersion Forces or Universal Attractive Forces.

• Keesom or Orientation Forces (Dipole-Dipole Interactions),

e.g. hydrogen bonding

• Debye Forces (Dipole Induced Dipole Interactions).

• Magnitude of the interactions affect properties such as

surface/interfacial tension

Lennard-Jones 6-12 potential

𝑟 𝑟
𝑉 𝑟 4𝜀
𝑟 𝑟

11
 V(r) Repulsive region V(rm)=-ε, Fattr=Frep

r=σ V(σ)=0, Vattr=Vrep

rm r

Attractive region

εm

Short range interactions are dominated by interelectronic repulsion, The

quantitative treatment of such interactions necessarily requires QM description
(Pauli effects).

These interactions substantiate the concept of sterical hindrance.

Strength of interparticle forces

Encounters between particles occur as a result of Brownian

motion and stability of a suspension is determined by the
interaction between particles during these encounters

Stability depends on the balance of There is no repulsion 12

attractive and repulsive interactions

Attraction from van der Waals forces

Repulsion is a consequence of interaction between
similar charged electric double layers and/or
particle -solvent affinity

Repulsion prevents particles to get close enough There is repulsion

 The stability of lyophobic colloids are influenced by:
• van der Waals attractive forces
• Leads to product instability

• Electrostatic and steric interactions

• Stabilises the dispersion
Electrosteric stabilization
combination of electrostatic and
steric repulsion, achieved by the
adsorption of charged polymers
(polyelectrolytes) onto the particle
surfaces.

Brownian motion & drag force

Sources of interfacial charge

• Immersion of some materials in an electrolyte solution.
Two mechanisms can operate.

(1) Direct Ionization of surface groups.

H H H
O O O
- 13
M
H M OH M + H2O
O O O O O O O O O

(2) Specific ion adsorption OH

M
O O O
+ + +
(3) Differential ion solubility
Some ionic crystals have a slight imbalance
in number of lattice cations or anions on
surface, eg. AgI, BaSO4, CaF2, NaCl, KCl

(4) Substitution of surface ions HO O O O OH

eg. lattice substitution in kaolin Si Al Si Si
HO O O O OH

Electrostatic interaction - Charged interfaces

++ Surfaces often charged (or made to be):

+ + - Structural origin
+
+
+ - Surface groups
+
+ - Selective adsorption 14

In polar solvents, most substances become charged:

● Preferential adsorption of ions.
● Dissociation of surface groups (ionization).
● Unequal ion dissolution.
● Ion replacement.
● Charged crystal surfaces. Manipulate and control
through surface chemistry
56
 Electrical Double Layer (EDL)

If we put a charged particle in a suspension with ions, then the primary charge will
attract counter ions (opposite charged ions) by electrostatic attraction.

The primary charge cannot attract an equal amount of counter charge because a
gradient of counterions is established that drives the counterions away from the
surface.

The formation of the electrical double layer (EDL) then occurs via attraction of
oppositely charged counterions by the primary surface charge and then a diffusion
of the counterions away from the surface. The counterions are mobile, the primary
charge is not.

60

Electrostatic repulsion between overlapping double layers

15
The loosely held countercharges
form “electric double layers.”

The electrostatic repulsion results

from the interpenetration of the
diffuse part of the double layer
around each charged particle.
 Electrostatic repulsion between overlapping double layers

VR

The loosely held countercharges form “electric double layers.” The electrostatic
repulsion results from the interpenetration of the diffuse part of the double layer
around each charged particle.

1936-1937 de Boer and Hamaker publish papers on theoretical aspects of

"dispersion forces acting between colloidal objects.“

1941 Derjaguin and Landau publish first big paper leading to DLVO theory

1948 Verwey and Overbeek publish second big paper contributing to DLVO theory

1956 Lifshitz publishes "The Theory of Molecular Attractive Forces between Solids“
16
1964 Derjaguin et. al. make experimental discovery of one of the first non-DLVO
forces

1978 First accurate macroscopic surface measurements in aqueous solution carried

out by Israelachvili and Adams (using surface forces apparatus)

1991 Atomic force microscopy adapted for measuring interactions of a colloidal

particle and a solid surface 65
 Electrical Double Layer (EDL)
+ x
- SOLVENT MOLECULES -
-
- + -
- +
- +
-
- + - -
-
Ψ0 COUNTER IONS
OHP
CO IONS

Helmholtz (1850s) proposed that surface charge is

balanced by a layer of oppositely charged ions
66

Gouy-Chapman Model (1910-1913)

- x
+
- + -
+
-
- -
- +
- +
+
-
- - 17
-
Ψ0-
Diffusion plane
• Assumed Poisson-Boltzmann distribution of ions from surface
• ions are point charges
• ions do not interact with each other
• Assumed that diffuse layer begins at some distance from the surface
67
Stern (1924) / Grahame (1947) Model
Gouy/Chapman diffuse double layer and layer of adsorbed charge.
Linear decay until the Stern plane.
x
- Diffusion layer
- -
Ψζ- +
+ +
-
- -
- -
+ + +
-
-
- - -
- +
- -
Ψ0-
Stern Plane Shear Plane Gouy Plane Bulk Solution
- 68

Stern (1924) / Grahame (1947) Model

In different approaches the linear decay is assumed to be until the shear
plane, since there is the barrier where the charges considered static.
x
- Diffusion layer
- -
- +
+
- + 18
Ψζ - + -
- -
+ +
-
+
- +
- - -
+
-
Ψ0- -
OHP Shear Plane Gouy Plane Bulk Solution
69
19
20
The attraction and repulsion between particles and surfaces have enormous significance in the
adsorption of surfactants at interfaces, adhesion, stability of colloids and micellization of
surfactants.

Some of the most important forces are van der Waals forces, electrostatic double layer forces,
solvation and steric forces.

21

Two primary criteria which must be considered in the discussion of colloid

stability: (1) frequency of particle collisions (2) effectiveness of the collisions
 Hamaker model - Calculate the attraction between particles from molecular attractions

Molecules in Molecules in depends on geometry

particle 1 particle 2

Attraction of bodies London (dispersion) attraction of molecules (molecules act ndependently)

The effect is additive. One molecule of the first colloid has a van der Waals attraction to each
molecule in the second colloid. This is repeated for each molecule in the first colloid, and the
total force is the sum of all of these.

An attractive energy curve is used to indicate the variation in van der Waals force with
distance between the particles.

Molecular origins of van der Waals attraction between particles

Attraction between atoms/ molecules in vacuum r

𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉 𝑟
𝑟
22
Dispersion attraction between atoms / molecules is additive so it effects in
case of macroscopic bodies too.
𝐴𝑎
depends on geometry
H 𝑉 𝐻
a 12𝐻

A Hamaker constant
An attractive energy curve is used to indicate the variation in
van der Waals force with distance between the particles.

VA ( H ) , J

VA ( H ) ≈−
Aa
12H

23
 Routes To Instability - Kinetic Mechanisms

Creaming Coalescence

Colloidal dispersion

Flocculation Sedimentation

Removal of Hydrophobic Colloids from the Aqueous Phase

1. Destabilization (or Coagulation) - reduce the forces acting to

keep the particles apart after they contact each other (i.e., lower
repulsion forces).

2. Flocculation – process of bringing destabilized colloidal particles

together to allow them to aggregate to a size where they will settle
by gravity.
24

After coagulation /flocculation, gravity sedimentation, and

sometimes filtration, are employed to remove the flocculated
colloids.
 Methods to Destabilize Colloids
( Coagulation Processes)
1. Double layer compression: This can
be accomplished by addition of an
indifferent electrolyte (charged ions
with no specific attraction for colloid
primary surface). Adding indifferent
electrolyte increases the ionic strength
of solution which has the effect of
compressing the EDL.

As the counterions are pushed closer to the surface the repulsion

forces becomes easier to negate by van der Waals forces.

2. Adsorption and Charge Neutralization: If charged (+) counterions have

a specific affinity for the surface of the colloid (not merely electrostatic
attraction) then adsorption of the counter-ion will reduce the primary
charge of the colloid. This will reduce the net potential, {r}, at any
particular r thus making the attraction forces more effective.

25
Charge on the added indifferent electrolyte is important
according to the Schulze-Hardy rule that states the effective
coagulation is logarithmically related to charge.
For example the concentration of Na+, Ca2+ and Al3+ required
for effective coagulation will vary in ratio of 1:10-2:10-3
 ZETA POTENTIAL

Point of Zero Charge (PZC) - pH at which surface potential = 0

Isoelectric Point (IEP) - pH at which zeta potential = 0
Question: What will happen to a mixed suspension of Alumina and Si3N4
particles in water at pH 4, 7 and 9?

26
 ZETA POTENTIAL
-- Effect of Ionic Strength --

50
40 Increasing
30
Ionic Strength
Zeta Potential (mV)

20
10
0
-1 0
-2 0
-3 0
-4 0 A lu m in a
-5 0
1 2 3 4 5 6 7 8 9 10 11
pH

Features

Immobile layer of ions that adhere tightly to the surface of the colloidal particle,
and which may include water molecules (if that is the support medium).

The radius of the sphere that captures this rigid layer is called the radius of
shear and is the major factor determining the mobility of the particles.
27
The electric potential at the radius of shear relative to its value in the distant,
bulk medium is called the electrokinetic potential, ζ (or the zeta potential).

Second, the charged unit attracts an oppositely charged atmosphere of mobile

ions. The inner shell of charge and the outer ionic atmosphere constitute the
electrical double layer.
 counter cations in
counter anions in area shield
area shield negative charge
positive charge

Coulomb potential experienced by an ion

The Coulomb potential at a distance r from an isolated ion of charge 𝑧 𝑒 in a

medium of permittivity ε is

𝑍 𝑧𝑒 the ionic atmosphere causes the potential to

𝜑 𝑍 decay with distance more sharply than this 28
𝑟 4𝜋𝜀
expression indicates

Coulomb potential modified by the shielded Coulomb potential

𝑍 ⁄
𝜑 𝑒 where 𝑟 is the Debye length
𝑟
The ionic atmosphere causes the potential to decay with distance more
rapidly than implied by the expression

Shielding – shielded Coulomb potential

𝑍i - r ⁄ r
Modified expression 𝜑i = 𝑒 D where 𝑟D is called the Debye length
𝑟
𝒓𝑫 large

Shielded potential similar to unshielded potential

𝒓𝑫 small

Shielded potential smaller than unshielded potential

62

R = separation of centres
s = separation of the surfaces of the two 29
particles (s = R − 2a for spherical particles
of radius a)

rD >> a - small particles with a thick double layer

/
rD << a - double layer is thin 𝑟 ⊖
 Potential energy arising from the repulsion of double layers on particles of
radius a has the form

When (rD >> a) - small particles with a thick double layer

ζ ⁄ /
𝑉𝑟𝑒𝑝𝑢𝑙𝑠𝑖𝑜𝑛 + 𝑒 𝑟 ⊖

A = constant
ζ = zeta potential
R = separation of centres
s = separation of the surfaces of the two particles (s = R − 2a for spherical particles of radius a)
rD = thickness of the double layer.

When (rD << a) – double layer is thin

1 ⁄
𝑉𝑟𝑒𝑝𝑢𝑙𝑠𝑖𝑜𝑛 𝐵 𝑎2 𝜁2 ln 1 𝑒
2

B = constant
ζ = zeta potential, 30
R = separation of centres
s = separation of the surfaces of the two particles (s = R − 2a for spherical particles of radius a)
rD = thickness of the double layer

/
𝑟 ⊖
 Potential energy arising from the attractive interaction has the form

𝐶
𝑉𝑎𝑡𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛 –
𝑠
C = constant
s = separation of the surfaces of the two particles (s = R − 2a for spherical particles of radius a)
R = separation of centres

rD >> a – double layer is thick ζ ⁄

𝑉𝑟𝑒𝑝𝑢𝑙𝑠𝑖𝑜𝑛 + 𝑒
1 ⁄
rD << a – double layer is thin 𝑉𝑟𝑒𝑝𝑢𝑙𝑠𝑖𝑜𝑛 𝐵 𝑎2 𝜁2 ln 1 𝑒
2

rD >> a - small particles with

a thick double layer

rD << a - double layer is thin

31

The variation of the potential energy of interaction with separation of the centres of the two
particles and with the ratio of the particle size a to the thickness of the electrical double
layer, rD.

The regions labelled coagulation and flocculation show the dips in the potential energy
curves where these processes occur.
Stability of lyophobic colloids

• DLVO theory (Derjaguin, Landau and Verwey, Overbeek):

stability of lyophobic colloids
–The double layer, zeta potential, the balance of repulsion &
attraction, the energy barrier

– Rates of flocculation

Lyophobic colloid includes charged particles of weak solvent affinity

Colloidal Stability and DLVO Theory

An energy barrier resulting from combination of the attractive and

repulsive forces prevents particles approaching each other closely.

32
+/- 30mV
considered
suitable
threshold value
for stability

So long as particle Kinetic Energy does not exceed this barrier

coagulation should not occur.
Total Interaction= sum of attractive and repulsive interactions

V= V
T

The height of the energy barrier

A R

+V
depends upon the zeta potential
and 1/κ (Debye length)

33
 Electrostatic Forces & van der Waals Forces
jointly influence Flocculation / Coagulation

Suspension of Al2O3 at
different solution pH

Critical for Water Treatment Processes

DLVO Theory
Hard Sphere
Repulsion (< 0.5 nm) No Salt added

J/
m Energy Barrier

34
x
(distance) Secondary Minimum
(Flocculation)

Primary Minimum
(Coagulation)
Effect of Salt 100 nm Alumina, ζ =-30 mV

Steric Stabilization
1. Good Solvent for Polymers
Rg 2. Long chains
3. Strongly grafted

35
V(h)

κ-1
h
Poor Solvent for Polymer:
segment length Unstable (Larger effective R)
l

Problem: Molecular weight

EO PEO needed to stabilize a colloid?
36