AL-Mustaqbal university college

Pharmacy department

Physical pharmacy II
lec5
Ghada Ali PhD candidate
[email protected]

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 Interfacial phenomena

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Objectives
1- Differentiate among different types of interfaces and describe
relevant examples in the pharmaceutical sciences.
2- Understand the terms surface tension and interfacial tension and
their application in pharmaceutical sciences.
3- Appreciate the different methods of surface and interface tension
measurements.
4- Calculate surface and interface tensions, surface free energy, its
changes, work of cohesion and adhesion, and spreading coefficient for
different types of interfaces.
5- Understand the mechanisms of adsorption on liquid and solid
interfaces.
6- Classify surface-active agents and appreciate their applications in
pharmacy.

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When phases exist together, the boundary between two of them is
termed an interface.
•The properties of the molecules forming the interface are often
sufficiently different from those in the bulk of each phase that they
are referred to as forming an interfacial phase.
• Several types of interface can exist, depending on whether the two
adjacent phases are in the solid, liquid, or gaseous state .For
convenience, these various combinations are divided into two
groups, namely, liquid interfaces and solid interfaces

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‫‪5‬‬ ‫‪ 22‬أيار‪21 ،‬‬
Surface and Interfacial Tension
 Surface: The term surface is commonly used when referring to either
a gas-solid or a gas-liquid interface.
“Every surface is an interface.”
 Cause of surface tension:
Surface tension is caused by the attraction between the liquid's
molecules by various intermolecular forces.
 In the bulk of the liquid: each molecule is pulled equally in all
directions by neighboring liquid molecules net force of zero .
 At the surface of the liquid, molecules are pulled inwards by other
molecules deeper inside the liquid and are not attracted as intensely
by the molecules in the neighboring medium. i.e.:
-- They develop attractive cohesive forces with other liquid molecules
situated below & adjacent to them.
-- They create adhesive forces of attraction With the other phase
involved at the interface.
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Representation of the unequal attractive forces acting on molecules
at the surface of a liquid as compared with molecular forces in the
bulk of the liquid

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Surface tension- a force pulling the molecules of the interface together
resulting in a contracted surface.
- Force per unit length applied parallel to the surface . Unit in dynes/cm
or N/m

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Interfacial tension
•Is the force per unit length existing at the interface between two
immiscible liquid phases and like surface tension, has the units of
dyne/cm

Surface Free Energy

To move a molecule from the inner layers to the surface , work must be
done against the force of surface tension .In other words , each
molecule near the surface of liquid possesses a certain excess of
potential energy as compared to the molecules in the bulk of the liquid .
The higher the surface of the liquid, the more molecules have this
excessive potential energy.

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Therefore , if the surface of the liquid increases , e.g. when water is
broken into a fine spray), the energy of the liquid also increases.
Because this energy is proportional to the size of the free surface, it is
called a surface free energy.
•Each molecule of the liquid has a tendency to move inside the liquid
from the surface ; therefore the liquid takes form with minimal free
surface and with minimal surface energy . for example , liquid droplets
tend to assume a spherical shape because a sphere has the smallest
surface area per unit volume.
Surface Free energy
W=γΔA
where W is work done or surface free energy increase express in
ergs(dyne cm); gamma(γ) is surface tension in dynes/cm and Δ A is
increase in area in 𝑐𝑚2 .

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Example
What in the work required to increase area of a liquid droplet by 10
𝑐𝑚2 if the surface tension is 49 dynes/cm?
W=γΔA
Because the area is increased by 10 𝑐𝑚2 , the work done is given
by the equation
W = 49 dynes/cm×10 𝑐𝑚2 = 490 ergs
Repeat the calculations using SI units. We have

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Spreading Coefficient
When oleic acid is placed on the surface of a water , a film will be
formed if the force of adhesion between oleic acid molecules and water
molecules is greater than the cohesive forces between the oleic acid
molecules themselves.
Work of adhesion (Wa), which is the energy required to break the
attraction between the unlike molecules(water to oil)

figure 1
Representation of the work
of adhesion involved in
separating a substrate and an
overlaying liquid.

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 Work = Surface tension x Unit area change
Accordingly, it is seen in figure 1 that the work done is equal to the
newly created surface tensions ,yL and YS ,minus the interfacial tension
,YLS that has been destroyed in the process.
Wa= YL+YS-YLS

Work of cohesion ( Wc ), required to separate the molecules of the

spreading liquid so that it can flow over the sublayer.

figure 2

Representation of the work of

cohesion involved in separating
like molecules in a liquid

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Obviously , no interfacial tension between the like molecules of the
liquid , and when the hypothetical 1 𝑐𝑚2 cylinder in figure 2 is divided ,
two new surfaces are created each with surface tension of YL,
therefore the work of cohesion is
Wc =2YL

Spreading of oil to water occurs if the work of adhesion (a measure of

the force of attraction between the oil and the water) is greater than
the work of cohesion.
•The term (Wa-Wc) is known as the Spreading coefficient(S)

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If it is Positive (+) the oil will spread over a water surface.
Wa-Wc
S=(YL+YS-YLS) -2YL
rearrangement :
S= Ys-YL-YLS
Or S= Ys – (YL+YLS)

Spreading occurs (S is positive) when the surface tension of the

sublayer liquid is greater than the sum of the surface tension of the
spreading liquid and interfacial tension between the sublayer and
the spreading liquid .
•If (YL+YLS)is greater than YS i:e negative(-) , the substance forms
globules or a floating lens fails to spread over the surface . An
example is mineral oil on water.

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Example
Spreading Benzene over Water
If the surface tension of water γS is 72.8 dynes/cm at 20◦C, the
surface tension of benzene, γL, is 28.9 dynes/cm, and the interfacial
tension between benzene and water, γLS, is 35.0 dynes/cm, what
is the initial spreading coefficient? We have
S= Ys – (YL+YLS)
S = 72.8−(28.9+35.0) = 8.9 dynes/cm (or 8.9 ergs/cm2)

Therefore, although benzene spreads initially on water, at equilibrium

there is formed a saturated monolayer with the excess benzene
(saturated with water) forming a lens

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Effects of Molecular Structure on Spreading Coefficient(S)
• Polar groups such as COOH or OH such as propionic acid and ethanol
have high values of S.
•Increase in carbon chains of acids will lead to decrease of polar-
nonpolar character ratio thus decrease in S on water. Ex are nonpolar
liquid petrolatum fail to spread on water.
•Benzene spreads in water because of its weak cohesive forces.
• For lotions with mineral oil base to spread freely and evenly on the
skin , its polarity and spreading coefficient should be increase by the
addition of surfactants.

petrolatum

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‫‪18‬‬ ‫‪ 22‬أيار‪21 ،‬‬
 Adsorption at Liquid Interfaces
Certain molecules and ions ,when dispersed in the liquid ,move of their
own to the interface.
•the surface tension of the system automatically reduced (why?)
•Such a phenomena when the added molecules are partitioned in
favor of interface is called adsorption.
•The molecules and ions that are adsorbed at the interface are termed
surface active agents or surfactant or (amphiphile)
Surface active agents
A surfactant molecule is described schematically as a cylinder
representing the hydrocarbon (hydrophobic) portion with a sphere
representing the polar(hydrophilic) group attached at one end.

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Surface Active Agents
•It is the amphiphilic nature of surface active agents that causes them
to be absorbed at interfaces,
• Thus, in an aqueous dispersion of amphiphile the polar group is able
to associate with the water molecules .The nonpolar portion is
rejected,
•As a result, the amphiphile is adsorbed at the interface

Adsorption of fatty acid molecules Adsorption of fatty acid

At water–oil interface molecules at a water–air
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interface
 For the amphiphile to be concentrated at the interface, it must be
balanced with the proper amount of water and oil soluble groups
•If the molecule is too hydrophilic, it remains within the body of the
aqueous phase and exerts no effect at the interface
•if it is too lipophilic it dissolves completely in the oil phase and little
appears at the interface
.

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Surfactants are classified as:
• Anionics:
Sodium Dodecylsulphate (SDS):
CH3(CH2)11 SO4− Na+
• Cationic:
Dodecylamine hydrochloride:
CH3(CH2)11 NH3+ Cl−
• Non ionics
Polyethylene Oxides (PEO):
e.g. CH3 (CH2 )11(OCH2CH2 )n OH
(Spans) sorbitan esters)
(Tweens )polyoxyethylene sorbitan esters)
• Ampholytics
Dodecyl betaine
C12H25 N++ (CH3)2(CH2COO− )

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Hydrophilic Lipophilic Balance (HLB)
It is an arbitrary scale from 0 to 20 serve as a measure of the
Hydrophilic/Lipophilic balance of a surfactant
• Products with low HLB are more oil soluble
• High HLB represents good water solubility
• The oil phase of the oil water(o/w) emulsion requires a specific HLB
called the required hydrophilic lipophilic balance (RHLB)
• A different RHLB is required to form a water in oil emulsion(w/o) from
the same oil phase

scale showing surfactant function

on the basis of hydrophilic–
lipophilic balance (HLB) values.
Key: O/W=oil in water.
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Micelle formation
The surface tension of a surfactant solution decreases progressively
with increase of concentration as more surfactant molecules enter
the surface or interfacial layer However, at a certain concentration
this layer becomes saturated and an alternative means of shielding
the hydrophobic group of the surfactant from the aqueous
environment occurs through the formation of aggregates (usually
spherical) of colloidal dimensions, called micelles
The concentration at which micelles first form in solution is termed
the critical micelle concentration or CMC.

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Some probable shapes of
micelles: (a) spherical
micelle in aqueous media,
(b) reversed
micelle in nonaqueous
media, and (c) laminar
micelle, formed at higher
amphiphile concentration,
in aqueous media.

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 Surface tension decrease with
increasing conc. Of surfactant
Until CMC is reached then
become constant

• The CMC decreases with an increase

in the length of the hydrophobic chain
• The addition of electrolytes to ionic surfactants
decreases the CMC and increases the micellar size
•The effect is simply explained in terms of a
reduction in the magnitude of the forces of
repulsion between the charged head groups in
the micelle, allowing the micelles to grow and
also reducing the work required for their Formation

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Micellar Solubilization
Surfactant molecules accumulate in the interfaces between
water and water insoluble compound Their hydrocarbon
chains penetrate the outermost layer of insoluble compound
which combine with the water insoluble molecules .Micelles
form around the molecules of the water insoluble compound
inside the micelles’ cores and bring them into solution in an
aqueous medium This phenomenon is called micellar solubilization.
The inverted micelles formed by oil soluble surfactant which
dissolves in a hydrocarbon solvent can solubilize water soluble
compound which is located in the center of the micelle, out of
contact with the solvent

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Adsorption at solid interfaces
Adsorption of materials at solid interfaces can take place from
either an adjacent liquid or gas phase.
•The study of adsorption at gases arises in applications as removal
of objection able odors from rooms or food.
•The principle of solid liquid adsorption are used in decolorizing
solutions ,adsorption chromatography ,detergency and wetting

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 Wetting
• Adsorption at solid surfaces is involved in the phenomena of wetting
and detergency
• When a liquid comes into contact with the solid the forces of attraction
between the liquid and the solid phases begin to play a significant role
• In case of water and glass attractive forces between the solid and
liquid molecules are greater than the forces between molecules of
liquid themselves And so the liquid is able to wet the surface of the glass
• The most important action of wetting agent is to lower the contact
angle between the surface of and the wetting liquid
•The contact angle is the angle between a liquid droplet and the surface
over which it spreads.
•The contact angle may be 0°,signifying complete wetting ,or may be
180° at which wetting is in significant.
•Or any value between these limits.

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A contact angle is lower than 90 the solid is called wettable
•A contact angle is wider than 90 the solid is named non wettable
•A contact angle equal to zero indicates complete wettability

wettable non wettable

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Wetting agent A wetting agent is a surfactant that ,when dissolved in
water, lowers the advancing contact angle, aids in displacing an air
phase at the surface, and replaces it with a liquid phase. Examples
of the application of wetting to pharmacy and medicine include
the displacement of air from the surface of sulfur, charcoal, and
other powders for the purpose of dispersing these drugs in liquid
vehicles; the displacement of air from the matrix of cotton pads
and bandages so that medicinal solutions can be absorbed for
application to various body areas; the displacement of dirt and
debris by the use of detergents in the washing of wounds; and
the application of medicinal lotions and sprays to the surface of
the skin and mucous membranes.

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 Detergents

Are surfactants that are used for the removal of dirt . Detergency is a
complex process involving the removal of foreign matter form
surfaces.
The process includes :
 Initial wetting of dirt and of the surface to be cleaned .
 Deflocculation and suspension Emulsification or solubilization of the
dirt particles .
 And sometimes foaming for washing away the particles.

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‫‪33‬‬ ‫‪ 22‬أيار‪21 ،‬‬
Calculate the amount of surfactants that need to be combined to
prepare 20ml of surfactant with an HLB of 9.0,Arlacel 60,HLB4.7&
Tween60,HLB,14.9

Tween 14.9 4.3

9.0
Arlacel 4.7 5.9
20ml 10.2

20𝑚𝑙
x4.3 = 8.4 ml
10.2

20𝑚𝑙
x 5.9=11.6ml
10.2

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