Surface and Interfacial Phenomenon

• When two phases are in contact with each other, the boundary present
between them is referred as interface.
• If one of the two phases is gas or vapour, the term surface is generally used
instead of interface.
• The physical properties of molecules present at the interface are usually
different than molecules present in bulk.
• Several types of interface can exist, depending on whether the two adjacent
phases are in the solid, liquid, or gaseous state.
• 1. Liquid interface: It is the association of a liquid phase with a gaseous or
another liquid phase will be discussed.
• 2. Solid interfaces: It is the association of solid with gaseous or liquid phase.
• Although solid–solid interfaces have practical significance in pharmacy (e.g.,
the adhesion between granules, the preparation of layered tablets, and the
flow of particles), little information is available to quantify these interactions.
 Liquid interface
• Surface and interfacial tension:
• In the liquid state, the cohesive forces between adjacent molecules are well
developed. Molecules in the bulk liquid are surrounded in all directions by
other molecules for which they have an equal attraction, as shown in Fig. 1.
• On the other hand, molecules at the surface (i.e., at the liquid–air interface)
can only develop attractive cohesive forces with other liquid molecules that
are situated below and adjacent to them.
• They can develop adhesive forces of attraction with the molecules constituting
the other phase involved in the interface. In the case of the liquid–gas
interface, this adhesive force of attraction is small.
• The net effect is that the molecules at the surface of the liquid experience an
inward force toward the bulk, as shown in Fig. 1.
• Such a force pulls the molecules of the interface together and, as a result,
contracts the surface, resulting in a surface tension.
 Liquid interface
• Definition:
• 1. Surface tension:
• The force per unit length that must be applied
parallel to the surface so as to counterbalance
the net inward pull.
• 2. Interfacial tension
• The force per unit length existing at the
interface between two immiscible liquid
phases
• Units for Surface and Interfacial tension
• cgs: dynes/cm system
• N/m: SI system
 Surface free energy
• To move a molecule from the inner layers to the surface,
work needs to 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. 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
• To increase the surface of the liquid without any additional changes in the
liquid state, in particular without changes in liquid temperature, work must be
done against the surface tension.
• To evaluate the amount of work in increasing the surface area, we can write
equation as γ × 2L = f.
• When the bar is at a position AD in Figure and a mass is added to extend the
surface by a distance ds, the work dW (force multiplied by distance) is and,
because 2L × ds is equal to the increase in surface area, dA, produced by
extending the soap film,
• For a finite change,

• where W is the work done, or surface free energy increase, expressed in

ergs, γ is the surface tension in dynes/cm, and ΔA is the increase in area in
cm2
Measurement of surface & interfacial tension
• 1. Capillary rise method:
• When a capillary tube is placed in a liquid
contained in a beaker, the liquid generally rises
up the tube a certain distance.
• Because the force of adhesion between the liquid
molecules and the capillary wall is greater than
the cohesion between the liquid molecules, the
liquid is said to wet the capillary wall, spreading
over it and rising in the tube (spreading is
discussed in some detail later).
• By measuring this rise in a capillary, it is possible
to determine the surface tension of the liquid.
• It is not possible, however, to obtain interfacial
tensions using the capillary rise method.
 Measurement of surface & interfacial tension
• Consider a capillary tube with an inside radius r immersed in a liquid that wets its
surface, as seen in Figure.
• Because of the surface tension, the liquid continues to rise in the tube, but because of
the weight of the liquid, the upward movement is just balanced by the downward force
of gravity.
• The upward vertical component of the force resulting from the surface tension of the
liquid at any point on the circumference is given by

• The total upward force around the inside circumference of the tube is

• where θ is the contact angle between the surface of the liquid and the capillary wall and
2πr is the inside circumference of the capillary.
• For water and other commonly used liquids, the angle θ is insignificant, that is, the
liquid wets the capillary wall so that cos θ is taken as unity for practical purposes
 Measurement of surface & interfacial tension
• The counteracting force of gravity (mass × acceleration) is given by the product of the
cross-sectional area, πr2, the height, h, of the liquid column to the lowest point of the
meniscus, the difference in the density of the liquid, ρ, and its vapor, ρ0, and the
acceleration of gravity: πr2 h(ρ - ρ0)g + w.
• The last term, w, is added to account for the weight of liquid above h in the meniscus.
• When the liquid has risen to its maximum height, which can be read from the
calibrations on the capillary tube, the opposing forces are in equilibrium, and
accordingly the surface tension can be calculated.
• The density of the vapor, the contact angle, and w can usually be disregarded; hence,
 Measurement of surface & interfacial tension
• 2. The DuNoüy Ring Method
• The DuNoüy tensiometer is widely used for
measuring surface and interfacial tensions.
• The principle of the instrument depends on the fact
that the force necessary to detach a platinum–
iridium ring immersed at the surface or interface is
proportional to the surface or interfacial tension.
• The force required to detach the ring in this manner
is provided by a torsion wire and is recorded in
dynes on a calibrated dial.
• The surface tension is given by the formula
[compare with equation]
 Measurement of surface & interfacial tension

• In effect, the instrument measures the weight of liquid pulled out of the plane
of the interface immediately before the ring becomes detached.
• A correction factor is necessary in equation because the simple theory does
not take into account certain variables such as the radius of the ring, the
radius of the wire used to form the ring, and the volume of liquid raised out of
the surface.
• Errors as large as 25% may occur if the correction factor is not calculated and
applied.
• The method of calculating the correction factor has been described; with care,
a precision of about 0.25% can be obtained.
Measurement of surface & interfacial tension
 Measurement of surface & interfacial tension
i. Drop weight method:
• The drop pipette or stalagmometer consists of a glass tube with a bulb blown
approximately in the middle of the tube.
• There are two marking A & B on the tube, one above the bulb & the other
below it.
• There is a capillary bore at the tip of the stalagmometer.
• The stalagmometer is mounted vertically & the test liquid is filled upto mark A.
• The liquid is then allowed to drop slowly from the tip of the pipette.
• 20 to 30 drops are collected from the pipette into a clean tarred vessel & the
weight of one drop of the liquid s determined (w).
• The surface tension of the liquid is then given by;
Measurement of surface & interfacial tension
Measurement of surface & interfacial tension
Measurement of surface & interfacial tension
 Measurement of surface & interfacial tension
4. Wilhelmy Plate method:
• The apparatus consists of a thin mica, glass or platinum plate suspended
vertically from a beam attached to a torsion balance.
• It provides a direct measurement of force exerted on the plate at the interface
between two immiscible liquids or surface of a liquid.
• The force exerted is equal to the surface tension multiplied by the perimeter of
the plate.
• Method: The liquid whose surface tension is to be determined is taken in a
container & the plate is immersed into it.
• The container is then gradually lowered till the plate detaches from the surface
of the liquid.
• The reading on the balance is noted just prior to the detachment.
• If the liquid completely wets the plate, the detachment force is equal to surface
tension multiplied by the perimeter of the surface detached.
Measurement of surface & interfacial tension
Spreading coefficient
Spreading coefficient
Spreading coefficient
Spreading coefficient
 Adsorption at liquid interface
• Certain molecules and ions, when dispersed in the liquid, move of their own accord
to the interface.
• Their concentration at the interface then exceeds their concentration in the bulk of
the liquid.
• Obviously, the surface free energy and the surface tension of the system are
automatically reduced. Such a phenomenon, where the added molecules are
partitioned in favor of the interface, is termed adsorption, or, more correctly, positive
adsorption.
• Other materials (e.g., inorganic electrolytes) are partitioned in favor of the bulk,
leading to negative adsorption and a corresponding increase in surface free energy
and surface tension.
• Adsorption, as will be seen later, can also occur at solid interfaces. Adsorption
should not be confused with absorption.
• The former is solely a surface effect, whereas in absorption, the liquid or gas being
absorbed penetrates into the capillary spaces of the absorbing medium.
• The taking up of water by a sponge is absorption; the concentrating of alkaloid
molecules on the surface of clay is adsorption.
 Surface-Active Agents
• It is the amphiphilic nature of surface-active agents that causes them
to be absorbed at interfaces, whether these are liquid–gas or liquid–
liquid interfaces.
• Thus, in an aqueous dispersion of amyl alcohol, the polar alcoholic
group is able to associate with the water molecules. The nonpolar
portion is rejected, however, because the adhesive forces it can
develop with water are small in comparison to the cohesive forces
between adjacent water molecules.
• As a result, the amphiphile is adsorbed at the interface. The situation
for a fatty acid at the air–water and oil–water interface is shown
in Figure. At the air–water interface, the lipophilic chains are directed
upward into the air; at the oil–water interface, they are associated
with the oil phase.
• 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. Likewise, if it is
too lipophilic, it dissolves completely in the oil phase and little
appears at the interface.
HLB scale
HLB scale
HLB scale
 Classification of Surfactant
• A molecule that contains both polar portion and a non
polar portion is called Amphiphilic substances.
• Surfactant are amphiphilic in nature.
• Surfactant shows positive adsorption i.e. they partition in
favor of surface over bulk.
• So that surface tension of liquid/liquids is/are decreases.
• Therefore they are also called as Surface Active Agents.
• A surfactant increases the solubility of insoluble
substances by decreasing interfacial tension or increasing
contact with liquid.
 Classification of Surfactant
• Surfactants can classify in numerous ways.
• Most common classification based on charge present on
surfactant molecules after ionization is adopted here.
1. Anionic
2. Cationic
3. Non-ionic
4. Amphoteric
 Classification of Surfactant
1. Anionic:
• Depending on pH or when dissociate in water it ionized as
anions i.e. Negative charge.
• Examples:
➢ Sodium stearte, sodium lauryl sulfate
✓ (~ 60% of industrial surfactants)
• Disadvantages
i. Incompatible with cationic substance.
ii. Stability depends on pH
iii. Incompatible with many excipients.
iv. Comparatively toxic in nature.
 Classification of Surfactant
2. Cationic:
• Depending on pH or when dissociate in water it ionized as
cations i.e. Positive charge.
• Examples:
• Cetyltrimethylammonium bromide (Cetrimide),
Benzalkonium chloride (BAC), Benzethonium chloride (BZT)
• Disadvantages
i. Incompatible with anionic substance.
ii. Stability depends on pH
iii. Incompatible with many excipients.
iv. Comparatively toxic in nature.
 Classification of Surfactant
3. Non-ionic:
• When dissociate in water, do not have any charge.
• Examples:
• Tween, Span, Brij
• Advantages
i. Compatible with most of substance & excipients.
ii. Stability is independent on pH.
iii. Comparatively less toxic than anionic & cationic surfactants.
iv. Formulate comparatively more stable emulsion
 Classification of Surfactant
4. Amphoteric:
• Amphoteric surfactants are characterized by the fact that
these surfactants can carry a positive charge on a cationic site
and a negative charge on an anionic site.
• The use of amphoteric terminology is still restrictive:
• The charge of the molecule must change with pH, showing a
zwitterionic form at an intermediate pH
• Example
• Lecithin
 Micellar Solubilization
• Surfactants can lower surface tension & improve the
dissolution of lipophilic drugs in the aqueous medium.
• When the concentration of surfactants exceeds their critical
micelle concentration (CMC, which is in a range of 0.05-
0.10% for most surfactants), micelle formation occurs,
entrapping the drugs within the micelles.
• This process is known as micellisation and generally results in
enhanced solubility of poorly soluble drugs.
• Micellar solubilization is a powerful alternative for
dissolving hydrophobic drugs in aqueous environments.
 Micellar Solubilization
• Surfactants are known to play a vital role in many processes
of interest in both fundamental and applied science.
• One important property of surfactants is the formation of
colloidal-sized clusters in solutions, known as micelles, which
have particular significance in pharmacy because of their
ability to increase the solubility of sparingly soluble
substances in water.
• Micelles are known to have an anisotropic water distribution
within their structure Micellar systems can solubilize poorly
soluble drugs and thus increase their bioavailability
 Micellar Solubilization
• Hydrophilic drugs can be adsorbed on the surface of the
micelle.
• Drugs with intermediate Solubility should be located in
intermediate positions within the micelle such as between
the hydrophilic head group of micelles in the Palisade Layer
between the hydrophilic group and the first few carbon
atoms of the hydrophobic group , that is the outer core.
• Completely insoluble hydrophobic drugs may be located in
the Inner Core of the micelle.
Fig: Mechanism of micellar solubilization
 Sites for solubilization:
A:
Site A: A nonpolar molecule
solubilized in the nonpolar region of the
micelle.
Example: Benzene, Toluene
Site B: A more polar molecule found
partly embedded in the central region
and partially extending into the palisade
region.
Example: Salicylic acid
Site C: A polar molecule found lying
well out in the palisade layer attracted
by dipolar forces to the polyoxyethylene
chains.
Example: Parahydroxybenzoic acid

Fig: A spherical micelle of nonionic surfactant molecules

 Detergency
• Detergency is a complex process involving the removal of
foreign matter from surfaces.
• The process includes the following main steps (Fig.:
a) The hydrocarbon tails of the detergent anions dissolve in the
grease;
b) the grease spot gradually breaks up and becomes
pincushioned by the detergent anions; and
c) small bits of grease are held in colloidal suspension by the
detergent.
• The anionic heads keep the grease from coalescing because
the particles carry the same electric charge.
 Detergency

Mechanism of detergent action. (a) The hydrocarbon tails of the detergent anions
dissolve in the grease; (b) the grease spot gradually breaks up and becomes
pincushioned by the detergent anions, and (c) small bits of grease are held in colloidal
suspension by the detergent.
 Adsorption at Solid interface
• Adsorption of material at solid interface may occur from adjacent liquid or gas.
• Adsorption of materials from a gas or a liquid onto a solid surface is similar to
that discussed for liquid surfaces.
• The Solid-Gas Interface:
• Adsorbent : the material used to adsorb the gas.
• Adsorbate : the substance being adsorbed.
• Adsorption: Adhesion of a particles to a surface. The particles may be gas,
liquid, or dissolve solids.
• The degree of adsorption of a gas by a solid depends on the
• 1. Chemical nature of the adsorbent and adsorbate.
• 2. Surface area of the adsorbent,
• 3. The temperature, and Adsorbent

• 4. The partial pressure of the adsorbed gas Adsorbate

 Adsorption at Solid interface
• Types of adsorption:
• 1. Physical or van der Waals adsorption: It is associated with Van der Waals
forces, is reversible, the removal of the adsorbate from the adsorbent being
known as desorption.
• A physically adsorbed gas can be desorbed from a solid by increasing the
temperature and reducing the pressure.
• 2. Chemical adsorption or chemisorption:. Chemisorption, in which the
adsorbate is attached to the adsorbent by primary chemical bonds, is
irreversible unless the bonds are broken.
• The relationship between the amount of gas physically adsorbed on a solid
and the equilibrium pressure or concentration at constant temperature yields
an adsorption isotherm when plotted as shown in Figure 1.
• The term isotherm refers to a plot at constant temperature.
 Adsorption at Solid interface

Fig. 1: Adsorption isotherms for a gas on a solid.

(a) Amount, x, of gas adsorbed per unit mass, m, of
adsorbent plotted against the equilibrium pressure.
(b) Log of the amount of gas adsorbed per unit mass of Fig. 2: Schematic of apparatus used to
adsorbent plotted against the log of the pressure. measure the absorption of gases on solids
 Adsorption at Solid interface
• The number of moles, grams, or milliliters, x, of gas adsorbed on, m, grams of
adsorbent at standard temperature and pressure is plotted on the vertical axis
against the equilibrium pressure of the gas in mm Hg on the horizontal axis,
as seen in Figure 1a.
• One method of obtaining adsorption data is by the use of an apparatus shown
in Figure 2.
• Which consists essentially of a balance contained within a vacuum system.
• The solid, previously degassed, is placed on the pan, and known amounts of
gas are allowed to enter.
• The increase in weight at the corresponding equilibrium gas pressures is
recorded. This can be achieved by noting the extension of a calibrated quartz
spring used to suspend the pan containing the sample.
• The data are then used to construct an isotherm by using Freundlich,
Langmuir, or Brunauer, Emmett, and Teller (BET) equation.
 Types of adsorption isotherm
• Type-I isotherm:
• It is often shown by adsorbents which are
predominantly microporous nature and majority of this
micropores are filled at relatively low pressure.
• The isotherm shows a rapid rise in the adsorption with
increasing pressure followed by leveling off (fig 3).
• Leveling off if mainly due to adsorption being
restricted to monolayer.
• It is shown by chemisorption type in which all
chemical groups available for chemisoprtion get
saturated very rapidly.
• It is explained by Freundlich and Langmuir adsorption
isotherms. Fig. 3: Type-I

• Example- Adsorption of nitrogen or hydrogen on

charcoal.
 Types of adsorption isotherm
• Type-II isotherm:
• It is sigmoidal in shape (fig.4)
• Often shown by physical adsorption of
gases onto non-porous solids.
• The first inflection point is due to the
formation of a monolayer.
• As the pressure is increased further,
multilayer formation occurs.
• This type of isotherm is described by BET
equation. Fig. 4: Type-II
• Example- Adsorption of nitrogen on silica
gel.
 Types of adsorption isotherm
• Type-III isotherm:
• This is convex to the relative pressure axis (fig.5).
• It is characteristic of weak adsorbate-adsorbent
interactions.
• Most commonly associated with both non-porous and
microporous adsorbents.
• Weak interactions between adsorbate and the
adsorbent lead to low adsorption at low relative
pressure.
• However once a molecule has been adsorbed at a
primary site, the adsorbate-adsorbent interaction,
which is much stronger, becomes the driving force of Fig. 5: Type-III
adsorption process, resulting in acceleration of uptake
at higher pressure.
• Example- Adsorption of bromine on silica gel.
 Types of adsorption isotherm
• Type-IV isotherm:
• It is seen during adsorption of gases on porous solids.
• The first inflection, when extrapolated to zero
pressure, represents the amount of gas required to
form monolayer on the surface of solid (fig.6).
• Multilayer formation and capillary condensation within
pores of the solid are thought to be responsible for
further adsorption.
• It reaches to limiting value before the saturation
vapour pressure is reached.
• Example- Adsorption of benzene on silica gel.

Fig. 6: Type-IV
 Types of adsorption isotherm
• Type-V isotherm:
• Like type-II isotherm, this type of isotherm shows a
curve that is convex to the relative pressure axis
(fig.7).
• It is characteristic of weak adsorbate-adsorbent
interactions.
• Like type-IV, capillary condensation is responsible for
further adsorption.
• It is arrive at to limiting value before the saturation
vapour pressure is reached.
• Example- Adsorption of water on charcoal.
Fig. 7: Type-V
Adsorption isotherm equation
Y

X
Adsorption isotherm equation
Adsorption isotherm equation
Adsorption isotherm equation