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Interfacial Phenomena
When phases exist together, the
Interfacial Phenomena
SURFACE TENSION
INTERFACIAL TENSION
Interfacial Phenomena
Several types of interface can exist,
depending on whether the two
adjacent phases are in the solid,
liquid or gaseous state.
For convenience, we shall divide these
various combinations into two
groups, namely liquid interfaces and
solid interfaces.
Interfacial Phenomena
Importance I Pharmacy
a.Adsorption of drugs onto adjuncts in
dosage forms.
b.Penetration of molecules through
biological membranes.
c. Emulsion formation and stability.
d.Dispersion of insoluble particles in
liquid media to for suspensions.
Interfacial Phenomena
Classification of
Interfaces
Phase
Interfacial Types & Examples of Interface
Tension
Gas - gas
Gas - liquid
Gas - solid
Liquid - liquid
Liquid - solid
Solid - solid
No interface possible
LV
ySV
yLL
yLS
ySS
Liquid Interfaces
Surface and Interfacial Tension
Surface
The term surface is customarily used
when referring to either a gas-solid or
a gas-liquid interface.
Every surface is an interface.
Liquid Interfaces
Surface
tension-
a force
pulling the
molecules of the
interface together
resulting in a
contracted
surface.
- Force per unit area
applied parallel to
the surface.Unit in
dynes/cm or N/m
Liquid Interfaces
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..
Liquid Interfaces
Surface Free
energy increase
in energy of the
liquid and the
surface of the
liquid increase.
-work must be done
to increase liquid
surface.
surface tension
or surface free
energy per unit
surface.
Liquid Interface
Surface Free energy
W = A
where W is work done or surface free energy increase
expess in ergs(dynecm); is surface tension in dynes/cm
and A is increase in are in cm sq.
Liquid Interfaces
Measuring Surface and Interfacial
Tension
1. Du Nouy Ring Method
2.
Liquid Interfaces
When oleic acid is
placed on the
surface of a water ,
a film will be formed
if the force of
adhesion b/n oleic
accid molecules and
water molecules is
greater than the
cohesive forces b/n
the oleic acid
molecules
themselves.
Liquid Interfaces
Work of adhesion(Wa), which is the energy
Liquid Interfaces
Surface and Interfacial Tension
When a drop of oil is added on the
Liquid Interfaces
Organic liquids on water are unstable
Effects og Molecular Structure on Spread
Coefficient(S)
a. Polar groups such as COOH or OH
such as propionic acid and ethanol have
high values of S.
b. Increase in carbon chains of acids will
lead to decrease of polar-nonpolar char
ratio thus decrease in S on water. Ex are
nonpolar liq petrolatum fail to spread on
water.
Benzene spreads in water because of its
Liquid Interfaces
For lotions with
Liquid Interfaces
Initial Spreading Coefficients, S, at 20 C
Substance
Ethyl alcohol
Propionic acid
Ethyl ether
Acetic acid
Acetone
Undecyclenic acid
Oleic acid
Chloroform
Benzene
Hexane
Octane
Ethylene dibromide
Liquid petrolatum
S (dynes/cm)
50.4
45.8
45.5
45.2
42.4
32 (250)
24.6
13
8.9
3.4
0.22
-3.19
-13.4
Interfacial Phenomena
Interfacial Phenomena
Application of Surface
Active Agents
In addition to the use of surfactants
Interfacial Phenomena
Application of Surface
Active Agents
Foams and Antifoaming agents
Interfacial Phenomena
Application of Surface
Active Agents
Agents such as alcohol, ether, castor
Interfacial Phenomena
Interfacial Phenomena
Electric Properties of
Interfaces
The Electric Double Layer
Interfacial Phenomena
Electric Properties of
Interfaces
Nernst and Zeta Potentials
Interfacial Phenomena
Electric Properties of
Interfaces
The potential located at the sheer
Interfacial Phenomena
Electric Properties of
Interfaces
Zeta potential has practical
Adsorption at Liquid
Interfaces
Occurs at the surface or interfaces of liquids
Surface Active Agents/ Surfactants/
Amphifiles
Substances with part of their molecule lipophilic
and part hydrophilic move on their own to the
surfaces or interfaces of the liquid, where they
lower the surface or interfacial tension
The dual character of their molecule[hydrophilic &
lipophilic]
Often represented in a graphic form as a circle
with a tail
Circle- Hydrophilic part or the polar part
Tail- lipophilic or the non-polar part
Micelles
Are formed when the active
HLB
Value
Use
0-3
Antifoaming agents
4-6
7-9
Wetting agents
8-18
13-15
Detergents
10-18
Solubilizing agents
Example
The concentration of a surfactant in
water is 0.01 mole/L, and d/dC is 5.87
dyne liter mole-1 cm-1. What is the surface
concentration of the surfactant at 20C?
Solution:
= (0.01 mole/L)
Tilted-drop Measurement
The tilted-drop measurement (Fig. 2e) is another angle measurement. In
this technique, a droplet is added to the surface and the advancing and
retreating contact angle are measured as the surface is tilted up until the
droplet reaches a point where it almost moves. This technique is useful to
measure both the receding and advancing contact angles at the same time.
In general, contact angle measurements serve as a good initial technique to
characterize a surface. However, contact angle measurements need to be
analyzed with care as a number of factors including operator error, surface
roughness, surface heterogeneity, contaminated fluids, and sample
geometry can influence the overall result.
Figure 3. A generalized
Interfacial Tension
surface tension
Decreases with increasing
concentration of the surface active
agent until the CMC is reached, then
becomes constant
Osmotic Pressure
Increases as the surface active agent
increases
But at CMC it reaches a plateau
MicelLes
Are aggregates of surface active
agents
Size varies, but is more than 0.1m
# of molecules is approximately 50100
Are always in equilibrium with
monomers of surface active agents in
soln
interfacial tension
Can be synthetic or natural
Anionic, cationic,nonionic and
zwitterionic
cosmetic industries
Have an unpleasant taste
Have skin irritation potential
Not compatible with cationic surface
active agents
Compatible with nonionics and
zwitterionic surface active agents
Sulfates-most popular
Toothpaste,shampoos and other cosmetic products as well as
in fabric detergents
Acyl isethionate
Used in soaps and shampoos for their mildness and foaming
properties
Salt- germicide
emulsifiers
-are also very effective
germicides
agents
Can be anionic, cationic or zwitterionic
depending on the pH of the medium they
are in
Main use is as cosurfactants to boost the
foaming properties of other surfactants
N-alkylbetaines-lead to minimal skin irritation
-hard waters does not affect their foaming
properties
Walking on water
Small insects such as the water strider can walk
on water because their weight is not enough to
penetrate the surface.
Floating a needle
If carefully placed on the surface, a small needle
can be made to float on the surface of water
even though it is several times as dense as
water. If the surface is agitated to break up the
surface tension, then needle will quickly sink.
Don't touch the tent!
Common tent materials are somewhat rainproof
in that the surface tension of water will bridge
the pores in the finely woven material. But if you
touch the tent material with your finger, you
break the surface tension and the rain will drip
through.