Interfacial Phenomena

Ana Marie L. Rubenicia,RPh

Interfacial Phenomena
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 from those in the bulk
of each phase that they are
referred to as forming an
interfacial phase .

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

Liquid surface, body of water

exposed to atmosphere

ySV
yLL
yLS
ySS

Solid surface, table top

Liquid-liquid interface,
emulsion
Liquid-solid interface,
suspension
Solid-solid interface, powder
particles in contact.

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.

What in the work required to increase area of a

liquid droplet by 10 cm sq if the surface tension is
49 dynes/cm?
W = 49 dynes/cm x 10 cm sq = 490 ergs

Liquid Interfaces
Measuring Surface and Interfacial
Tension
1. Du Nouy Ring Method

This method also is called the detachable ring method

and is used to measure both the l surface tension
and interfacial tension. It employs a tensiometer
that consists of a hanging platinum-indium ring of
defined geometry connected with a microbalance.
to the surface tension y of the liquid.

2.

Capillary Rise Method

If a capillary tube is placed in a liquid that wets
the surface of the capillary, the liquid will rise
inside the capillary tube and its surface will be
concave.

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

required to break the attraction between the

unlike molecules.(water to oil)
Work of cohesion(Wc), required to separate
the molecules of the spreading liquid so that it
can flow over the sublayer.(oil to oil and water
to water)
Spreading of oil to water occurs if the work of
adhesion is greater than the work of cohesion.

Spreading coefficient(S) difference

between Wa and Wc.
Positive S if oil spreads over a water surface.

Liquid Interfaces
Surface and Interfacial Tension
When a drop of oil is added on the

surface of water, three things may

happen:

1. The drop may spread as a thin film

on the surface of water.(positve S)
2. It may form a liquid lens if the oil
cannot spread on the surface of
water.(negative S)
3. The drop may spread as a
monolayer film with areas that are

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

mineral oil base

to spread freely
and evenly on the
skin , its polarity
and spreading
coefficient
should be
increase by the
addition of
surfactants.

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

as emulsifying agents, detergents,

wetting agents and solubilizing
agents, they find application as
antibacterial and other protective
agents and as aids to the absorption
of drugs in the body.
A surfactant may affect the activity of

a drug or may itself exert drug action.

Interfacial Phenomena
Application of Surface
Active Agents
Foams and Antifoaming agents

Any solutions containing surface-active

materials produce stable foams when mixed
intimately with air. A foam is relatively stable
structure consisting of air pockets enclosed
within thin films of liquid, gas-in-liquid
dispersion stabilized by a foaming agent. The
foam dissipates as the liquid drains away from
the area surrounding the air globules, and the
film finally collapses.

Interfacial Phenomena
Application of Surface
Active Agents
Agents such as alcohol, ether, castor

oil, and some surfactants may be

used to break the foam and are know
as antifoaming agents.
Foams are sometimes useful in
Pharmacy but are usually nuisance
and are prevented or destroyed when
possible. The undesirable foaming of
solubilized liquid preparations poses
a problem in formulation.

Interfacial Phenomena

Interfacial Phenomena
Electric Properties of
Interfaces
The Electric Double Layer

Consider a solid surface in contact with a

polar solution containing ions, for

example, an aqueous solution of
electrolyte.

Interfacial Phenomena
Electric Properties of
Interfaces
Nernst and Zeta Potentials

- The potential at the solid surface

aa, due to the potential determining
ion, is the electrothermodynamic
(Nernst) potential, E, and is defined
as the difference between the actual
surface and the electroneutral region
of the solution.

Interfacial Phenomena
Electric Properties of
Interfaces
The potential located at the sheer

plane bb is known as the

electrokinetic, or zeta potential. The
zeta potential is defined as the
difference in potential between the
surface of the tightly bound layer
(shear plane) and the electroneutral
region of the solution.

Interfacial Phenomena
Electric Properties of
Interfaces
Zeta potential has practical

application in the stability of systems

containing dispersed particles, since
this potential, rather than the Nernst
potential governs degree of repulsion
between adjacent, similarly charged,
dispersed particles.

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

molecules saturate the surface of the

water
Often spherical; but may also come in
different forms
Cationic-cations
Anionic-anion
Amphoteric-amphoteric ions
Nonionic-nonions

Hydrophile- Lipophile Balance

[HLB]
The number that describes and makes

possible to organize info about the

hydrophilic-lipophilic nature of the surface
active molecule
An arbitrary scale which was developed by
GRIFFIN in 1949
Davis and Rideal23 formula:
HLB= [Hydrophilic group #] [lipophilic group #]+7

HLB
Value

Use

0-3

Antifoaming agents

4-6

W/O emulsifying agents

7-9

Wetting agents

8-18

O/W emulsifying agents

13-15

Detergents

10-18

Solubilizing agents

Trial and error

The combination of the surface active agents has a new HLB

value equal to the algebraic mean of both HLB values:

HLBmixture= HLB1 +(1-)HLB2

Where is the fraction of surfactant 1 and the fraction of surfactant 2 is (1-)

Monolayers at the Surfaces

Substances that reduces the

surface tension of a liquid

Gibbs Adsorption Equation:

Where: =Surface concentration in moles per unit area of surface

C=concentration of the substance
= surface tension
R= gas constant
T= temperature
/ C= change in the surface tension

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)

Critical Micelle Concentration

[CMC]
Shows that the surface tension decreases with

increasing concentrations of the surface active agent

then after a certain concentration of the surface active
agent, the surface tension stops decreasing and
reaches a plateau.
The surface is saturated with surface active molecules

and any inc in their conc will cause them to form

micelles in the bulk to protect their hydrophobic groups
from the aqueous envt.
In aqueous media, decreases as the # of carbons in the

hydrophobic grp of the surface active agent increases

Decreases with electrolytes in soln

Critical Micelle Concentration

[CMC]
Molecules can form aggregates in which the hydrophobic

portions are oriented within the cluster and the

hydrophilic portions are exposed to the solvent. Such
aggregates can show a variety of conformations. The
shapes of the aggregates depends largely of the
properties of the amphiphilic molecules.
The proportion of molecules present at the surface or as
aggregates in the bulk of the liquid depends on the
concentration of the amphiphile. At low concentrations
amphiphiles will favor arrangement on the surface. As
the surface becomes crowded with amphiphiles more
molecules will arrange into aggregates. At some
concentration the surface becomes completely loaded
with amphiphile and any further additions leads to
arrangement into aggregates. This concentration is
called the Critical Micelle Concentration(CMC). A graph of
surface tension vs log of concentration may be used to
determine the CMC point.

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 1 Figures 1A and 1B demonstrate a

difference in wettability. Figure 1A shows

how a water droplet might appear on a
hydrophobic surface such as wax. Figure 1B
shows how a water droplet might appear on
a hydrophilic surface such as a contact lens

Figure 2. Five ways that the contact angle (q) can be

measured. (A.) Sessile or Static drop. (B.) Wilhelmy
plate method. (C.) Captive air bubble method. (D.)
Capillary rise method. (E.) Tilting substrate method.
Figure adapted from Ratner, et. al.

Figure 3. A generalized

contact angle plot showing the

advancing (qAdv) and receding (qRec) contact angles.

The concentration of the

surface active agent
affects:
a. Interfacial tension
b. Osmotic pressure
c. Detergency[ability to remove soil]
d. Light scattering
e. Solubility

Interfacial Tension

Follows a path parallel to that of the

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

Detergency, Solubility, Light

Scattering Ability
Increases sharply when the

concentration of the surface

active agent increases beyond
the CMC concentration.

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

Surface Active Agents

Hydrophilic and lipophilic
Reside at interfaces and lower the

interfacial tension
Can be synthetic or natural
Anionic, cationic,nonionic and
zwitterionic

Anionic Surface Active

Agents
Has a negative charge
Widely used in the pharmaceutical and

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

Types of Anionic Surface

Active Agents

SOAPS-fatty acid chain ranges between 12-18

Sulfates-most popular
Toothpaste,shampoos and other cosmetic products as well as
in fabric detergents

Sulfonates-sulfur atom connected to the carbon atom

Molecule is less liable to hydrolysis than are sulfates

N-Acyl taurines- good skin compatibility

Exhibit a good stability over wide ranges of pH
Compatible with hard water since their Mg and ca salts are
soluble

Monoalkyl phosphate-low skin irritation potential

Used in face and body liquid cleansers

Acyl isethionate
Used in soaps and shampoos for their mildness and foaming
properties

N-Acyl sarcocinate-produce a rich foam and have excellent skin

compatibilities

Cationic Surface Active

Agents
Has a positive charge
Can be used as bactericidal agents
Absorb onto negatively charged surfaces
Are used as hair conditioners and fabric
softeners
Are electrolytes and are incompatible with
anionic surface active agents
Compatible with nonionics and zwitterionics
Quaternary ammonium cmpds are among the
most extensively used cationic surface active
agents

Types of Cationic Surface

Active Agents
Alkylbenzyldimethyl Ammonium

Salt- germicide

Alkyl trimethyl Ammonium Salt-

emulsifiers
-are also very effective
germicides

Nonionic Surface Active

Agents
Not electrolytes
Has no charge
Are not affected as much by the

presence of salts or charges in pH

Hydrophilic group may contain
hydroxyl groups, polyoxyethylene
groups, or saccharides

Types of Nonionic Surface

Active Agents

Polyoxyethylene Alkyl Ether- are widely used in the

pharmaceutical and cosmetic industries

The longer the polyoxyethylene chain, the more hydrophilic

the molecule and the higher the HLB value
Fatty acid Alkanolamides- are used extensively in shampoos as
foam stabilizers and viscosity enhancers
Sorbitan Fatty Acid Esters- are oil-soluble and form w/o emulsions

Are widely used in the combination with poloxyethylene

sorbital fatty acid esters
Polyoxyethylene Sorbitan fatty Acid Esters [TWEEN]-hydrophilic
and form o/w emulsions

Used extensively in the pharmaceutical, cosmetic, and food

industries
Alkyl Polyglucoside-used in dishwashing detergents and
shampoos

Zwitterion Surface Active

Agents
Compatible with all types of surface active

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

Insoluble Monolayers at Liquid

Surfaces
Molecules which are not soluble in

the bulk of liquids

A.k.a. Langmuir films

If the number of molecules on the

surface of the water is low, the
molecules will be far away from each
other, trying to cover the whole
surface

Langmuir Film Balance

An instrument that can control the area of water

surface available for the floating fatty acid

molecules
movable barrier that moves tangiential to the
water surface
Data are presented as plots of the surface
pressure as a function of the area A per molecule
Surface pressure-the horizontal force between the
pure substrate, 0, and the surface tension of the
substate with the film on it.

Langmuir Film Balance

A Langmuir film balance facilitates the

controlled preparation of model

membranes at the air/water interface

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.

Soaps and detergents

help the cleaning of clothes by lowering the surface tension of
the water so that it more readily soaks into pores and soiled
areas.
Clinical test for jaundice
Normal urine has a surface tension of about 66 dynes/cm but if
bile is present (a test for jaundice), it drops to about 55. In the
Hay test, powdered sulfur is sprinkled on the urine surface. It will
float on normal urine, but sink if the S.T. is lowered by the bile.
Washing with cold water
The major reason for using hot water for washing is that its
surface tension is lower and it is a better wetting agent. But if the
detergent lowers the surface tension, the heating may be
unneccessary.
Surface tension disinfectants
Disinfectants are usually solutions of low surface tension. This
allow them to spread out on the cell walls of bacteria and disrupt
them. One such disinfectant, S.T.37, has a name which points to
its low surface tension compared to the 72 dynes/cm for water.