CHM 203

INTRODUCTION TO COLLOID SCIENCE

• Colloid science deals with the study of colloidal
systems.
• Colloidal systems are systems comprising a
collection of small particles or liquid droplets
having a dimension of order of 10 µm or less which
are dispersed in a second phase.
• Either or both phases may be in gas, liquid or solid.

• Many industrial products like paint, mayonnaise and

milk, are colloidal systems.
 INTERFACIAL AREA
Colloidal particles or liquid droplets are
characterized by large interfacial areas and these
areas are associated with a substantial amount of
interfacial energy. Thus, the particles tend to
aggregate in order to reduce their interfacial energy.

V – volume of the dispersion (m3)

R – colloid particle radius (m)
 𝟑𝑽 𝟑 × 𝟏 × 𝟏𝟎−𝟔
𝑨= =
𝑹 𝟐𝟎 ×𝟏𝟎−𝟗

𝑨 = 𝟏𝟓𝟎 𝒎𝟐
CLASSIFICATION OF COLLOIDAL SYSTEMS

Colloidal systems can be classified into

three:
1. Colloidal dispersions
2. True solutions
3. Association colloids
COLLOIDAL DISPERSIONS
Colloidal dispersion is a heterogeneous system which is
made up of dispersed phase and dispersion medium.
In colloidal dispersion one substance is dispersed as
very fine particles in another substance
called dispersion medium.
TRUE SOLUTIONS
• True Solution is a homogeneous mixture of two or
more substances in which the substance (solute)
dissolved in a solvent. The particle size is less than
10-9 m or 1 nm.
• Particles of true solution cannot be filtered through
filter paper and are not visible to naked eye. True
solutions of macromolecular material (natural or
synthetic) are thermodynamically stable and
reversible. That is they can easily be reconstituted
after separation of solute from solvent.
ASSOCIATION COLLOIDS
• Association colloids are microheterogeneous
systems for which the dispersed phase (micelles) is
formed by the agglomeration of molecules or ions
of the substance dissolved in the dispersion
medium. An example of this system is a micelle.
• A micelles are an aggregate of surfactant
molecules dispersed in a liquid medium.
• It an aggregate of amphiphilic molecules that
associate in a dynamic and thermodynamically
driven process.
• In a micelle, the hydrocarbon chains are orientated
towards the interior of the micelle, leaving the
hydrophilic groups in contact with the aqueous
medium.
• The concentration above which micelle formation
becomes appreciable is termed the critical micelle
concentration (c.m.c).

The structure of a micelle

 AGGREGATION NUMBER
• The number of surfactants in a micelle is called the
“aggregation number” (Nagg) and is about 50–100
for spherical micelles but can be higher for other
structures, depending also on the surfactant type.
• The aggregation number can be estimated from the
ratio of the volume of the micelle to the volume of
a surfactant molecule or, equivalently, as the
surface area of a micelle divided by the surface
area of the surfactant head
CMC and aggregation numbers for some families of ionic surfactants.
 THERMODYNAMICS OF MICELLIZATION
The energy (Gibbs, enthalpy) and entropy changes
during the micellization process can be predicted if
the CMC and its dependency on temperature are
known.

where Rig = 8.314 J mol–1 K–1 AND T IS TEMPERATURE.

SURFACE ACTIVE AGENTS
• Surface-active agents are organic molecules that
when dissolved in a solvent at low concentration
have the ability to adsorb (or locate) at interfaces,
thereby altering significantly the physical
properties of those interfaces.
• The term ‘interface’ is commonly employed here
to describe the boundary in liquid/liquid,
solid/liquid and gas/liquid systems.
• The adsorption behaviour can be attributed to the
solvent nature and chemical structure of
surfactants (i.e. having both polar and non-polar
groups in a single molecule).
 The structure of a surfactant.

Surfactants can be classified as anionic, cationic,

non-ionic or ampholytic according to the charge
carried by the surface-active part of the molecule.
Some common examples are given in Table below.
Surface-active agents
 CRITICAL PACKING PARAMETER PARAMETER
A very important characteristic of surfactant molecules, which
quantifies their hydrophilic and hydrophobic character, is the so-called
CPP (critical packing parameter). CPP is a geometric parameter of the
surfactant defined as:

where Vsurf denotes the tail chain volume, lc is the critical tail chain
length and αo is the head-group area. The CPP depends significantly on
salt, pH, temperature, double bonds and double chains. Approximate
expressions for Vsurf and lc of surfactants as a function of the carbon
number chain are presented below.

where n is the number of carbon atoms in the hydrocarbon

(hydrophobic) chain and m is the number of hydrocarbon (hydrophobic)
chains.
 Hydrophilic–Lipophilic Balance (HLB)
• The hydrophilic–lipophilic balance (HLB) is a very useful
parameter which, in conjunction with several other semi-
empirical tools (like the Bancroft rule), can be used in the
design of emulsion-based products.
• The HLB is just an empirical parameter. Values below 8
indicate hydrophobic surfactants (emulsifiers), while
values above 8 (or 10) indicate hydrophilic surfactants.
• The most well-known method for estimating the HLB is the
group contribution method of Davies and Rideal:

where ni is the number of groups of a particular type in the

molecule being considered. The group values for HLBi given
 SURFACE AND INTERFACIAL TENSIONS
• Surface tension γo (or surface energy) is defined
as the work, W required in order to isothermally
increase the area of a surface, A usually in air by
unit amount (dW/dA).
• The surface tension (γo) of a liquid is often
defined as the force acting at right angles to any
line of unit length on the liquid surface.
• On a molecular level, the surface tension
describes the unequal distribution of forces at a
(liquid–air) interface compared to the forces in the
bulk of the liquid.
Concept of surface tension and its origin due to the
inequality of surface forces compared to the forces in the
bulk liquid. Shaw (1992).
 ADSORPTION
• Adsorption is adhesion of atoms, ions or molecules
from a gas, liquid or dissolved solid to a surface.
• Molecules and atoms can attach to surfaces in two
ways (physisorption and chemisoption).
• In physisorption (an abbreviation of ‘physical
adsorption’), there is a van der Waals interaction
(for example, a dispersion or a dipolar interaction)
between the adsorbate and the substrate.
• In chemisorption (an abbreviation of ‘chemical
adsorption’), the molecules (or atoms) stick to the
surface by forming a chemical (usually covalent)
bond.
 Surface coverage
The extent of surface coverage is normally
expressed as the fractional coverage, θ:

The fractional coverage is often expressed in

terms of the volume of adsorbate adsorbed by θ =
V/V∞, where V∞ is the volume of adsorbate
corresponding to complete monolayer coverage.
The rate of adsorption, dθ/dt, is the rate of change
of surface coverage, and can be determined by
observing the change of fractional coverage with
time.
 Adsorption isotherms
The variation of θ with pressure at a chosen temperature is
called the adsorption isotherm. The free gas and the
adsorbed gas are in dynamic equilibrium, and the fractional
coverage of the surface depends on the pressure of the
overlying gas.
(a) Langmuir isotherm
This simplest physically plausible isotherm is based on three
assumptions:
1 Adsorption cannot proceed beyond monolayer coverage.
2 All sites are equivalent and the surface is uniform (that is,
the surface is perfectly flat on a microscopic scale).
3 The ability of a molecule to adsorb at a given site is
independent of the occupation of neighbouring sites (that is,
there are no interactions between adsorbed molecules).
 KINETICS OF ADSORPTION
Let us consider a system in a dynamic equilibrium

with rate constants ka for adsorption and kd for

desorption. The rate of change of surface coverage
due to adsorption is proportional to the partial
pressure p of A and the number of vacant sites
N(1 − θ), where N is the total number of sites. Thus,
the rate of adsorption is
The rate of change of θ due to desorption is
proportional to the number of adsorbed species, Nθ:

At equilibrium there is no net change (that is, the

sum of these two rates is zero), and solving for θ
gives the Langmuir isotherm equation:
 (b) Freundlich isotherm
This isotherm attempts to incorporate the role of
substrate–substrate interactions on the surface.
According to the Freundlich isotherm
𝟏
𝜽 = 𝑪𝟏 𝑷 𝑪𝟐
log θ = log c1 + 1/c2log ρ

When 1/c2 = 0, θ is constant

When 1/c2 = 1, θ is proportional to ρ i.e adsorption is
directly proportional to pressure.
 BREAKDOWN PROSESSES
• After formation, the properties of dispersed
systems tend to change with time through some
breakdown processes which eventually affect the
stability.
• The breakdown processes are controlled by some
factors, such as the amount of emulsifier, the
difference in density between the droplets and
the continuous phase, difference in solubility
between the two phases and the strength of van
der Waals attractive versus the repulsive forces.
 Ostwald ripening sedimentation

coalescence flocculation

creaming phase inversion

• Creaming is a breakdown process associated with o/w emulsions. It
is the movement of oil drops under gravity or in a centrifuge to form
a concentrated layer at the top of the emulsion but without a
change in the drop size distribution.
• In w/o emulsions, the similar phenomenon is called sedimentation.
An emulsion will sediment if the droplets are denser than the
continuous phase making them settle down.
• Coalescence is the fusion of two or more droplets which results in
an increase in the mean drop size over a period.
• Ostwald ripening is caused by the molecular diffusion between
drops in emulsions which causes an increase in the size of large
drops at the expense of smaller ones because of the difference in
chemical potential of the material within the droplets.
• Flocculation is the coming together (aggregation) of droplets
without a change in the drop size. It occurs as a result of attractive
forces (van der Waals) which exist between the droplets.