Interfacial Phenomena

Interfaces & Surfaces

• An interface is the boundary between two immiscible phases.

• A surface is the boundary between two immiscible phases, one of

them is gas.

• 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 interfaces exist, depending on whether the two

adjacent phases are in the solid, liquid or gaseous state.

• In general, the interfaces are divided into liquid interfaces and solid
interfaces.
 Interfaces & Surfaces

Phase Types and Examples of

Interfaces
Gas-Gas No interface possible

Gas-Liquid Liquid surface, body of water

exposed to the atmosphere
Gas-Solid Solid surface, table top

Liquid-Liquid Liquid-liquid interface, emulsion

Liquid-Solid Liquid-solid interface, suspension

Solid-Solid Solid-solid interface, powder

particles in contact
 Pharmaceutical Relevance
• Interfacial phenomena are present and contribute significantly in
different pharmaceutical systems.

• Interfacial phenomena affect drug adsorption of drugs onto

pharmaceutical adjuncts in solid dosage forms as well as onto
containers, penetration of drugs through biologic membranes,
emulsion formation and stability and the dispersion of solid particles
in liquid media to form suspensions.
 Surface and Interfacial Tensions

• In the liquid state, molecules in the bulk of the liquid are

surrounded in all directions by other liquid molecules and
the same forces are exerted on that molecule from all
directions.
• The net force exerted on such molecules is zero.

Liquid Molecules in the

bulk
 Surface and Interfacial Tensions
• In contrast, molecules at the interface are subjected to
differing forces because they are exposed to different
types of surrounding molecules.
• Theses molecules experience high attractive forces from
molecules of the same type and lower attractive forces
from molecules of the neighboring phase.
• This difference in the attraction between molecules is
what creates different and distinct phases and if the
molecules of one phase were attracting the molecules of
the other phase with stronger attractive forces than their
own, the two components would be miscible and mix
together.
 Surface and Interfacial Tensions
• So instead of a net force of zero in case of molecules in the bulk of the
phase, molecules at the interface are subjected to a force called the
surface tension or interfacial tension.

• This “tension” in the surface is the force per unit length that must be
applied parallel to the surface so as to counterbalance the net inward pull.

• As a force per unit length, the surface and interfacial tensions have the
unit of dyne/cm in the cgs system and of N/m in the SI system.

• Surface tension refers usually to the force per unit length existing at the
interface between a liquid and vapor phase (LV) or a solid and vapor
phase (SV).

• Interfacial tension refers usually to the force per unit length existing at the
interface between two immiscible liquids (LL), two solids (SS) and a liquid-
solid interface (LS).
Surface Tensions (substance-air at 20 o C)

Substance Surface Tension

(dyne/cm)
Water 72.8

Glycerin 63.4

Oleic Acid 32.5

Benzene 28.9

Chloroform 27.1

Carbon Tetrachloride 26.7

Castor Oil 39.0

Olive Oil 35.8

Cotton Seed Oil 35.4

Liquid Petrolatum 33.1

Interfacial Tensions (substance-water at 20 o C)

Substance Interfacial Tension

(dyne/cm) Against
water at 20oC
Mercury 375

n-Hexane 51.1

Benzene 35.0

Chloroform 32.8

Oleic acid 15.6

n-Octyl alcohol 8.52

Caprylic Acid 8.22

Olive Oil 22.9

Ethyl ether 10.7

 Adsorption Phenomena
• The surface of a material can hold molecules of other
substances that can come into contact with it.

• The phenomena is called adsorption and refers to the

process by which a molecule (adsorbate) binds to the
surface of a substrate (adsorbent).
 Adsorption Phenomena

• Adsorption at an interface can be classified as:

– Physical adsorption (physisorption)
– Chemical adsorption (chemisorption)

• Physical adsorption is associated with van der Waal’s forces and is

reversible with the removal of the adsorbate from the adsorbent
being called desorption.

• Chemisorption involves the formation of chemical bonds (ionic or

covalent) between the adsorbent and the adsorbate. Chemisorption
is an irreversible process.
 Adsorption Phenomena
• Why adsorption is important?
• Adsorption from solution at a solid interface is of special
importance in pharmacy:
– Drugs in solutions may adsorb onto containers thus reducing
the dose the patient receives.
– Preservative can also adsorb onto containers affecting the
susceptibility of the preparation to microbial contamination
– Bactericidal cationic surfactants have to be adsorbed onto
the surface of bacteria to exert its effect.
– Used in chromatography
– Water purification
– Gas mask
 Adsorption Phenomena
Factors affecting adsorption include:
1.Chemical structures of adsorbate and adsorbent.
2.Surface area of adsorbent
3.Concentration of adsorbate.
4.Solubility of the adsorbate: In general, the extent of adsorption of
a solute is inversely proportional to its solubility in the solvent from
which adsorption occurs
 In a nonpolar solvent, polar adsorbate will preferentially
adsorb onto polar adsorbent.
 In a polar solvent, nonpolar adsorbate will preferentially
adsorb onto nonpolar adsorbent.
5.The temperature: since adsorption is usually an exothermic
process, an increase in temperature normally leads to a decrease
in the amount adsorbed. Small variations in temperature tend not
to alter the adsorption process to a significant extent
 Adsorption of surfactants at Liquid Interfaces
• Certain molecules when dispersed in a liquid,
move on their own accord to the interface.
• The concentration of these compounds at the
interface exceeds their concentration in the bulk of
the liquid.
• Molecules that are adsorbed at the interface are
called surface active agents or surfactants.
• Sometimes they are described as amphiphiles;
which denotes that the molecule or ion has a
certain affinity for both polar and nonpolar
solvents.

In such a system, surface

tension and hence surface free
energy decreases because of
this selective distribution.
 Adsorption at Liquid Interfaces
• The amphiphilic nature of a surfactant is what makes it
able to concentrate at the interface..
• For example: amyl alcohol (C5H11OH) when added to
water concentrates on the interface.
– The polar alcohol group is able to associate and form
H-bonds with the water molecules so that the
adhesive forces it makes with water molecules is
close to the cohesive forces the water molecules
exert on each other.
– The alkyl chain can not form such bonds and the
adhesive force it can develop with water are small in
comparison with the cohesive forces between the
adjacent water molecules.
• As a result, in an oil-water interface the lipophilic chains
are directed up into the oil phase while the heads are
immersed in the aqueous phase.
 Surfactant Monolayers and Micelles
• When the surfactant concentration increases so that the water
surface is fully occupied, the added molecules will go into bulk
solution forming aggregates called micelles, where the surfactant
molecules orient themselves so that the hydrophilic groups are
located at the surface facing water while the hydrophobic parts
are located in the interior away from water forming a hydrophobic
core.
• This concentration is called the critical micelle concentration
(CMC).
 CMC
• At the CMC, the surface is saturated with the surfactant
molecules and any further increase in their concentration
will cause them to form micelles in the bulk to protect their
hydrophobic groups from the aqueous environment.
• Micelles can be defined as aggregates of surface active
agents, the size of micelles vary but it is more than 0.1 m.
• The number of molecules in micelles is approximately 50-
100.
• Micelles are always in an equilibrium with the monomers of
the surface active agent in solution.
 CMC
How to determine CMC for a surfactant?

Oil

Surface tension and hence

surface free energy decreases
until reaching a platue when full
coverage of the interface is
occurred and micelles start
Water
forming….
Surface Tension,  Dyne/cm

The surface excess

concentration of surfactant
molecules remains
approximately constant in the
presence of micelles and hence
the Ɣ–log concentration plot
becomes almost horizontal

CMC Surfactant Concentration (LogC)

 CMC
How to determine CMC for a surfactant?
Oil
In addition, CMC could be
determined by solubility
profiles of hydrophobic
drugs in aqueous media.

Water Solubility of drug is

increased by the addition
of surfactant and this
Drug Solubility

increase is significantly
apparent after CMC where
micelles are forming and
encapsulating hydrophobic
drug molecules into their
cores

Solubilization by
micellization

CMC Surfactant Concentration (LogC)

 Adsorption Phenomena
• The relation between the concentration of a material adsorbed on
an interface and the equilibrium concentration at constant
temperature yields an adsorption isotherm.
• The term isotherm refers to a plot at constant temperature.
• The number of moles, grams or milliliters of adsorbate that adsorb
on unit weight of adsorbent at standard temperature and pressure
is plotted on the vertical y axis while the equilibrium concentration of
adsorbate is plotted on the horizontal x axis.
Saturation
Amount of Adsorbate
o rbe d of
Co nc e ntratio n
adsweight
adsorbent
per unit

AdsorbateCo nc e ntratio n in
concentration in solution
s o lutio n
 Adsorption Models : Langmuir Isotherm

Two types of adsorption isotherms can describe the

adsorption of surfactant onto interfaces:
– Langmuir Isotherm

x G max KCeq
G= =
m 1+KCeq
 Langmuir Isotherm: Intro
• Langmuir developed a semi-empirical equation based on the theory that
the molecules of adsorbate are adsorbed on active sites of the adsorbent
to form a layer one molecule thick (monolayer).
• Langmuir model is used to describe the adsorption of various adsorbates
(such as gases, drugs or surfactants) to different adsorbents (gas-liquid,
liquid-liquid or solid-liquid..etc interfaces).
• The Langmuir isotherm is based on the following assumptions:
– Sites for adsorption are equivalent and limited (can be saturated!)
– There is no lateral interaction between adsorbate molecules
(independent adsorption)
– Monolayer adsorption
– Equilibrium model
Deviations from typical Langmuir plot can occur at high concentrations
and are then attributed to the formation of a multilayer.
 Langmuir Isotherm: The equation
• The final form of the Langmuir equation is:

x KCeq
G = =G max
m 1+KCeq
Where:
– x is the amount of the adsorbate adsorbed by unit
weight m of the adsorbent at equilibrium
– Ceq is the adsorbate concentration remaining in
solution at equilibrium (freely available!!)
– K is adsorption constant
– G max is the maximum amount of adsorbate
adsorbed by unit weight m of the adsorbent
(Adsorption capacity)
[ D ]bound K [ D ] free
r v
?Do you remember this? Are they similar [ P ]total 1  K [ D ] free
 Langmuir Isotherm: The curve
• Consider the adsorption of surfactant from solution on
the oil-water interface in a biphasic system
• A Langmuir isotherm shows that the amount of
surfactant adsorbed onto the interface increases with
surfactant concentration added to the system until it
reaches a maximum and remains constant after that.
x
G= =G max
m
x
KCeq
Saturation
x
  max m
1 KCeq Co nc e ntratio n
ads o rbe d
m

x
G = =G max KCeq
m
Co nc e ntratio n in Ceq
s o lutio n
 Langmuir Isotherm: Linear Form

m
x
x KCeq
G = =G max
m 1+KCeq s lo p e =
1
G K
1 m 1 1 m ax

= = +
G x G max KCeq G max
1
G m ax

1
C eq
 Langmuir Isotherm: Example

• The following experimental data represents the amount of acetic

acid adsorbed on charcoal at different concentration at 0oC.

– Do these data fit a Langmuir isotherm?

– What is the amount of acetic acid required to cover 1 gm of
charcoal?

Ceq(mM) x/m (mmol/g)

100 0.15
200 0.27
300 0.38
400 0.46
500 0.55
C eq (mM) x/m (mmol/g) 1/Ceq (mM)-1 m/x (g/mmol)
100.0000 0.1500 0.0100 6.6667 1 m 1 1
200.0000 0.2700 0.0050 3.7037   
300.0000 0.3800 0.0033 2.6316  x max KCeq max
400.0000 0.4600 0.0025 2.1739
500.0000 0.5500 0.0020 1.8182 1
 0.6405
max
max  1.56mmole / g
m 8.0000
y = 604.01x + 0.6405 1.56 mmole of AA
7.0000
x 6.0000
R² = 0.99974
required to cover 1 gm
5.0000
of adsorbent
4.0000

3.0000
1
2.0000 slope =
1.0000
G max K
0.0000 1
0.0000 0.0020 0.0040 0.0060 0.0080 0.0100 0.0120 604.01 =
1.56K
1
K =1.06 X10 - 3 (mM )- 1
Ceq
 Wetting,
Spreading
Coefficient,
contact angel
and surface
tensions
 Spreading Coefficient

• Lotions, creams, sunscreens as well as many other cosmetic

and pharmaceutical preparations have to be spread on the
skin to exert their effect.

• When a liquid spreads over a substrate, it covers all parts of

the surface that could be either a solid or an immiscible liquid.

• When applying a formula onto the skin, one in essence is

applying it to the sebaceous secretions covering the skin
(triglycerides, free fatty acids, wax esters, squalene and
cholesterol) and acting to protect the skin against moisture
loss or infections.
 :Spreading Coefficient
• When a drop of oil is added on the surface of
water, three things may happen:
– The drop may spread as a thin film on the
surface of water
– It may form a liquid lens if the oil can not
spread on the surface of water
– The drop may spread as a monolayer film
with some areas having oil lenses.

• The criterion that determines the more

favorable of the three possibilities is that of the
attainment of a minimum free energy state.
 Spreading Coefficient
• Spreading depends on the surface
tension of the liquids involved and the
interfacial tension between them.
• For a liquid to spread over a substrate,
the spreading coefficient, S, must be
positive:

S=s- l- sl

Where:

s is the surface tension of the substrate

l is the surface tension of the spreading
liquid
sl is the interfacial tension between the
liquid and substrate
 Spreading Coefficient

• If oleic acid (l =32.5) is placed on top of water (s =72.8)

and the interfacial tension between both of them was (sl
=15.6) then:

• The spreading coefficient is:

S=72.8 - 32.5 - 15.6 = 24.7

• Oleic acid will spread on the surface of water