Surface and Interfacial

Phenomena
 

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Objectives
By the end of this lecture, the student
will be able to:
1. Define surface and interfacial tension
2. Calculate surface and interfacial
tension and select the method for
measuring them
3. Define spreading coefficient and
predict factors affecting it 2
• Interface is the boundary between two or more
phases exist together
• Interface : boundary between any two phases.
• Surface : boundary between any two phases one
of them is gas
• The properties of the molecules forming the
interface are different from those in the bulk that
these molecules are forming an interfacial phase.

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 Classification of interfaces

Phase Interfacial tension Types and examples of interfaces

G-G - No interface

G-L LV Air – water; aerosols and foams

G-S SV Air – beaker and table top

L-L LL Water – oil; emulsion

L-S LS Water – insoluble solid; suspension

S-S SS Mixture of powders

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 Importance

Importances of interface
 Adsorption of drug
 Penetration of molecules through biological
membranes
 Emulsion formation & stability
 Suspension formation & stability
 Drug dissolution
 Film coating
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• Surface and Interfacial Tensions
• In the liquid state, the cohesive forces between
adjacent molecules are well developed.
• For the molecules in the bulk of a liquid
• They are surrounded in all directions by other
molecules for which they have an equal
attraction.

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• For the molecules at the surface (at the liquid/air
interface)
 Only attractive cohesive forces with other liquid
molecules (below and adjacent to them).
 They can develop adhesive forces of attraction
with the molecules of the other phase in the
interface
 So, the molecules at the surface of the liquid have
an inward force towards the bulk of the liquid (pull
the molecules and contract the surface) 7
• To keep the equilibrium, an equal force must be
applied to oppose the inward tension in the surface
• Thus SURFACE TENSION [γ ] is the force per unit
length that must be applied parallel to the surface
so as to counterbalance the net inward pull and
has the units of dyne/cm
• INTERFACIAL TENSION is the force per unit length
existing at the interface between two immiscible
liquid phases and has the units of dyne/cm
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• Interfacial tensions are less than surface tensions
because an adhesive forces, between the two
liquid phases forming the interface are greater
than when a liquid and a gas phase exist together.
• If two liquids are completely miscible, no
interfacial tension exists between them.
• Greater surface tension reflects higher
intermolecular force of attraction, thus, increase in
hydrogen bonds or molecular weight cause
increase in ST 9
Influence of temperature
• For most liquids ↑ temperature → ↓ surface
tension. This decrease is approximately linear.
• As the temperature approaches the critical
temperature for a liquid (i.e. the temperature when
the liquid structure is lost), the intermolecular
cohesion forces approach zero and the surface
tension becomes very small.

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Methods for measuring surface and interfacial
tension
1- Capillary rise method
2- Ring (Du Nouy) tensiometer
3- Drop weight method (Stalagmometer)

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 The choice of the method for measuring
surface and interfacial tension depend on:
• Whether surface or interfacial tension is to be
determined.
• The accuracy desired
• The size of sample

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 Capillary Rise Method

The Principle
• When a capillary tube is placed in a
liquid, it rises up the tube a certain
distance. By measuring this rise, it is
possible to determine the surface
tension of the liquid.
• It is not possible, to obtain interfacial
tensions using the capillary rise method
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• Cohesive force is the force existing between like
molecules in the surface of a liquid
• Adhesive force is the force existing between unlike
molecules, such as that between a liquid and the
wall of a glass capillary tube
• When the force of Adhesion is greater than the
cohesion, the liquid is said to wet the capillary
wall, spreading over it, and rising in the tube.

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• If a capillary tube of inside radius =r immersed in
a liquid that wet its surface, the liquid continues
to rise in the tube due to the surface tension, until
the upward movement is just balanced by the
downward force of gravity due to the weight of
the liquid

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• The upward force
resulting from the surface tension of the liquid at
any point on the circumference is given by:
a = 2 π r γ cos Ө Where
Ө = the contact angle between the surface of the
liquid and the capillary wall
2 π r = the inside circumference of the capillary.
For water and other commonly used liquids, the
angle Ө is insignificant, i.e. the liquid wets the
capillary wall so that Ө is zero and cos Ө = unity 16
 The downward force of gravity is given by
πr 2hpg
Where:
πr 2
= the cross-sectional area
h = the height of the liquid column to
p = the density of the liquid
g = the acceleration of gravity
At Maximum height, the opposing forces are in equilibrium
2 π r γ = π r 2h p g
γ = 1/2 r h p g
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 Ring (Du Nouy) Tensiometer

• For measuring surface and

interfacial tensions.
• the principle of the instrument
depends on the fact that: the force
necessary to detach a platinum-
iridium ring immersed at the
surface or interface is proportional
to the surface or interfacial
tension 18
• The force of detachment is recorded
in dynes on a calibrated dial
• The surface tension is given by:
γ = F / 2 π (R1 + R2)
Where:
F = the detachment force
R1 and R 2= the inner and outer radii
of the ring.

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 Drop Weight and drop volume method

If the volume or weight of a drop as it is detached

from a tip of known radius is determined, the surface
and interfacial tension can be calculated from
γ = Φ mg = Φ V pg
πr 2πr2
Where m = the mass of the drop
V = the volume of the drop
p = the density of the liquid
r = the radius of the tip
g = the acceleration due to gravity
Φ = a correction factor

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 Spreading Coefficient

When a liquid is placed on the surface of other

liquid, it will spread as a film if the adhesion force is
greater than the cohesive forces.

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The work of cohesion, the energy required to separate the
molecules of the spreading liquid so as it can flow over the
sub-layer=
Wc = 2 γ L
The work of adhesion, the energy required to break the
attraction between the unlike molecules
Wa = γ L + γ S - γ LS

γ L =the surface tension of the spreading liquid

γ S =the surface tension of the sub­layer liquid

γ =the interfacial tension between the two liquids. 22

Spreading occurs if the work of adhesion is
greater than the work of cohesion,
Wa > Wc or Wa - Wc > 0
Spreading Coefficient: is The
difference between the work of
adhesion and the work of cohesion
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 S = Wa - Wc = (γ L + γ S - γ LS ) - 2 γ L
S = γ S - γ L - γ LS

S = γ S – (γ L + γ LS )
Spreading occurs (S is positive) when the
surface tension of the sub-layer liquid is greater
than the sum of the surface tension of the
spreading liquid and the interfacial tension
between the sub-layer and the spreading liquid.
If (γ L + γ LS ) is larger than YS , (S is negative)
the substance forms globules or a floating lens
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and fails to spread over the surface.
 Factor affecting Spreading Coefficient
Molecular Structural:
• The greater the polarity of the molecule the more positive
[S] as ethyl alcohol and propionic acid
• Non polar substances as Liquid petrolatum have negative [S] fail
to spread on water
• For organic acids, as Oleic acid, the longer the carbon chain decrease
in polar character decrease [S]
• Some oils can spread over water because they contain polar
groups as COOH and OH

Cohesive forces:
Benzene spreads on water not because it is polar but
because the cohesive forces between its molecules are much
weaker than the adhesion for water. 25
 Application of Spreading coefficient in pharmacy

 The requirement of film coats to be spreaded over

the tablet surfaces
 The requirement of lotions with mineral oils to
spread on the skin by the addition of surfactants
 Stabilization of emulsion: A blend of surfactants
are mixed with an oil and its spreading on the
water surface layer is evaluated. So a suitable
blend of surfactants is selected for the preparation
of a stable emulsion 26