Pharmaceutics B

(1103213)

Interfacial Phenomenon

Dr. Zahid Hussain (PhD)

Office : M23-143
Email : zhussain@sharjah.ac.ae
Phone : +971504081850
 Learning objectives

At the end of this lecture, student are expected to understand:

 Interfaces and types
 Interfacial Phenomenon
 Surface Tension
 Interfacial Tension
 Application in Pharmacy
 Surface Free Energy and factor affecting
 Interface

 When two or more than two phases exist together, the

boundary between these phases is termed as interface.

 The properties of the molecules forming the interface are

sufficiently different from those in the bulk of each phase that
they are referred to as forming an Interfacial phase .
Interface
 Types of Interface

• Several types of interfaces can exist in a system depending on

the types of phases involved such as solid, liquid or gas.

• These interfaces can mainly be divided into two groups:

1. Liquid interfaces
2. Solid interfaces
 Types of Interface

Liquid interfaces
1. Liquid / gas interface

2. Liquid / liquid interface

Solid interfaces
3. Solid/ gas interface

4. Solid / liquid interface

5. Solid / solid interface

 Types of Interfaces

Types Examples of interfaces

Gas - gas No interface possible
Gas - liquid Liquid surface exposed to the atmosphere
Gas - solid Solid surface, e.g., table top exposed to the atmosphere
Liquid - liquid Liquid-liquid interface, emulsion
Liquid - solid Liquid-solid interface, suspension
Solid - solid Solid-solid interface, powder particles in contact
 Liquid Interfaces

1. Surface interface
2. I n t e r f a c i a l i n t e r f a c e

for which the

1- Surface interface
driving force is
the conc. gradient
 In liquid interfaces, the surface interface refers to a gas-liquid
between the blood
and extravascular
interface.
tissues
 In solid interface, the surface interface refers to a gas-solid
interface.
 Liquid Interfaces

2- Interfacial interface
 In liquid interfaces, the interfacial interface refers to a liquid-liquid
interface. For example, in emulsion.
for which the
 In solid interfaces,
driving forcethe
isinterfacial interface a solid-liquid
the conc. gradient
interface.
between Forthe
example,
blood in suspension.
and extravascular
tissues
 Question

• What type of interface exists in the following figure?

for which the

driving force is
the conc. gradient
between the blood
and extravascular
A. Surface interface
tissues
B. Interfacial interface
 Question
• Which of the following pictures shows interfacial interface?

for which the

driving force is
2
1 conc. gradient 3 4
the
between the blood
A. 1 only
and extravascular
B. 2 and 3 tissues
C. 3 only
D. 2 and 3
E. 3 and 4
 Question
• How many surface/interfacial interfaces are present inside
this system?

A. 1
B. 2
C. 3
D. 4
E. 5
Properties of molecules forming the interface are
sufficiently different
Why Molecules at the surface/interfacial interfaces
behaves differently from those in the bulk?

Air

Liquid drop
Why Molecules at the surface/interface behaves
differently from those in the bulk?
• Consider a pure liquid in a beaker or a drop of water.
• Molecules at the surface develop attractive cohesive
forces (stronger) only with other liquid molecules that are
below or adjacent to them. Air
• They may develop adhesive forces (weaker) with the
molecules of the other phase (air) that constitutes the
surface.
• There is an uneven distribution of forces.
• Similar uneven distribution of forces also happened on the
boundary of two immiscible liquids in a beaker.
• This gives rise to surface or interfacial tension, which is Liquid drop
given the symbol, “gamma” ()
• In contrast, the molecules in the bulk of the liquid are
surrounded in all directions by other molecules for which
they have equal attraction.
 Surface Tension

The net effect is:

• Due to uneven distribution of forces,
molecules at the surface of the liquid
experience an inward/pulling force
toward the bulk.
• Such a force pulls the molecules of the
surface toward the bulk, causing
contraction of the surface and is called
as surface tension.
 Interfacial Tension
 Similar to the surface tension, the
force pulling the molecules
forming the interface towards
their respective bulk, results in a
contracted interface which is
known as interfacial tension.
 Similar to surface tension, its It may cause separation of two phases,
as cohesive forces are stronger than
units dynes/cm or N/m adhesive forces
 Interfacial Tension

 Interfacial tension is the

force per unit length
existing at the interfacial
interface between the two
immiscible liquids.
 Interfacial Tension

NOTE
 Interfacial tension DOES NOT
exist in TRUE SOLUTION.
 It only exists in DISPERSE
SYSTEMS in which both
phases are not completely
soluble or miscible.
Surface Tension Vs. Interfacial Tension ()
• Interfacial tension is usually less than the surface tension
because the adhesive forces (or interaction) between two
immiscible liquid phases forming an interface are greater than
that happened between the liquid and gas phases.
 Surface/interfacial Tension
Surface Tension / Interfacial Tension

Surface

Bulk Interface

Air/Liquid Liquid/Liquid
Interfacial Tension

Mix
+
 Importance of interfacial phenomenon in Pharmacy

 Dispersion and stability of insoluble drug particles in a liquid

medium to form a suspension and/or aerosol (is an example
of ??? interface).
 Dispersion and stability of oil droplets in water to form
emulsions (is an example of ??? interface).
 Adsorption of drugs onto solid additives in dosage forms (is an
example of ??? interface).
Surface Free Energy and Factor
affecting
 Surface Free Energy
• Each molecule near the surface/interface of liquids possesses a
certain excess of potential energy (due to position) as compared to
the molecules in the bulk of the liquid because of the tension at the
surface/interface.
• The higher the surface area of the contact between the two
immiscible liquids phases, higher will be the potential energy.
• Therefore, when the surface area of the liquids increases (e.g.
when oil is broken into a fine droplets), the free energy of the
system also increases.
• Because the free energy is proportional to the surface area, hence,
it is called the surface free energy.
 Question

1 2

Which one of these two emulsions has higher surface free energy?
A. 1
B. 2
C. Both have the same surface free energy
 Question

1 2
Which one of these two emulsions has higher interfacial tension?
A. 1
B. 2
C. 1 and 2 has the same interfacial tension
 Question

1 2

Which one of these two emulsions is pharmaceutically acceptable?

A. 1
B. 2
C. Both are pharmaceutically acceptable
 Question

1 2

How you keep emulsion 2 stable?

A. Reduce the surface free energy
B. Reduce the interfacial tension
C. Both A and B
 Surface Free Energy
What could happen if you don’t reduce the surface free energy
or interfacial tension in the emulsion?
 Surface Free Energy

• To minimize the surface free

energy, most of the liquids tends to
adopt a shape with the smallest
surface area.

• For this reason liquid droplets tend

to form a spherical shape because
a sphere has the smallest surface
area per unit volume.
 Surface Free Energy & Surface Tension

∆G (W) =  ∆A
∆G: Change in surface free energy
 : Interfacial tension between the liquid and gas/solid/liquid
∆A: Increase in surface area of contact between the two phases

• Higher the surface free energy, the less stable is the system.
• To reach a stable state, the system tend to reduce ∆G and
maximum stability occurs at ∆G = zero

 Surface area of contact between the two

phases (agglomeration   )
To decrease ∆G
 Interfacial tension between the two
immiscible phases by the addition of SAA 
 Surface Free Energy & Surface Tension

Surface Free energy

∆G (W) = γ ∆ A
Where “W" is work done or change in surface free energy express in
ergs(dyne/cm); "γ" is the surface tension in dynes/cm and "∆A" is
an increase in surface area in cm sq.

Calculate the surface free energy, when the surface area of a liquid
droplet increases by 10 cm sq. and the surface tension is 49
dynes/cm?

∆G (W) = 49 dynes/cm x 10 cm sq = 490 ergs (dynes/cm)

Factors affecting Surface Free Energy
 1- Effect of Temperature
• An increase in temperature increases the thermal energy of the molecules,
and hence, molecules experience less tension because they stay less time
at the surface, and thus the surface and/or interfacial tension will be
reduced.
• At the boiling point of a liquid, the surface tension will become zero.

• For example:
• The surface tension of water is 72.8 dynes/cm at 20C and 63.5 dynes/cm
at 75C.
 2- Effect of additives

• Surface (interfacial) tension results from a difference between

molecular interactions in the bulk (cohesive forces) and those
at the surface/interface (adhesive forces). This leads to an
imbalance of forces at the interface.

• Additives which affect these molecular interactions,

particularly at the interface (surface/interfacial), will affect this

imbalance and thus the surface or interfacial tensions ().

 Effect of additives on 

Additives are classified into 3 categories

• Type I – Alcohols

• Type II – Electrolytes

• Type III – Surfactants

 Type 1 : Alcohol addition

• Alcohols (particularly, low molecular weight, e.g. C2–C7) contain

hydrophilic head and hydrophobic hydrocarbon (HC) chain.
• These molecules tend to develop interaction between two
immiscible liquids at the interfacial interface, and hence, lower
the interfacial tension.
• The size of HC chain (and hence its solubility in water) governs migration to the interface
and hence determines the extent of the effect.

• Which of these two alcohols would lower the surface tension of

water more? Explain
A. Hexanol
B. Methanol
 Type 2 : Electrolytes addition

• Type II behaviour results in a slight increase in .

• Exhibited by highly hydrated electrolytes and some sugars

(containing –OH groups).
 Question

Complete the following sentence

Addition of electrolytes to a disperse system may ………. the

surface tension.

A. Increase
B. Decrease
C. No change
 Question
• Addition of electrolytes to an aqueous dispersion will increase
the surface tension because:

A. Electrolytes prefer to stay in the bulk

B. They will displace bulk molecules to the surface
C. They will increase the surface free energy
D. They increase the net imbalance of forces at the surface
E. All of the above
 Type 3 : Surfactant addition

• SAA or Surfactants are known as Type III additives.

• They greatly decrease surface/interfacial tension.

• When surfactants are added to water, they reduces the

cohesive forces (hydrogen bonding network) in water and
decreases its .

• Surfactants form micelles.

 Surfactant addition improves spreading

 To spread freely and evenly

on the skin, the polarity and
spreading coefficient of
mineral oil based lotions can
be improved by the addition

of surfactants.
 Reference/Recommended Books

1. Howard C. Ansel & Shelly J. Stockton. Pharmaceutical calculations, 15th

edition, Lippincott Williams and Wilkins, Baltimore, MD (2017).
2. Ansel’s Pharmaceutical Dosage Forms and Drug Delivery Systems. Ed. L.
V. Allen & H. C. Ansel, 10th Edition, 2011, Pub. Lippincott Williams and
Wilkins, Baltimore. ISBN: 9781451188769.