Interfacial Phenomena

Interfacial phenomena
 Interface is the boundary between two phases.
 Surface is an interface between liquid and gas or
solid and gas.
 Interfacial phenomena are significant factors that
affect:
 emulsion formation and its stability,
 dispersion of insoluble particles in liquids to form
suspensions,
 adsorption of drugs onto solid adjuncts in dosage forms,
 penetration of molecules through biological membranes.
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 Surface/interfacial tension
 In the bulk portion of each phase, molecules are
attracted to each other equally in all directions, such
that no resultant forces are acting on any one
molecule.
 At the boundary between phases, however,
molecules, are acted upon unequally because they
are in contact with other molecules exhibiting
different forces of attraction.
 Thus, molecules situated at the interface experience
interaction forces dissimilar to those experienced in
the bulk phase. 3
Surface/interfacial tension (cont’d)

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 Surface/interfacial tension (cont’d)

 In liquid systems such unbalanced forces can be

satisfied by spontaneous movement of molecules
from the interface to the bulk phase.

 This leaves fewer molecules per unit area at the

interface (greater intermolecular distance) and
reduces the actual contact area between dissimilar
molecules.

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 Surface/interfacial tension (cont’d)
 Any attempt to reverse this process by increasing the
area of contact between phases – i.e., bringing more
molecules into the interface – causes the interface
to resist expansion and behave as though it is under
tension everywhere in a tangential direction.
 The force of this tension per unit length of interface
generally is called the interfacial tension/surface
tension.
 Surface tension is expressed in units of dynes per
centimeter (dyne/cm). In the SI system, interfacial tension
is expressed in mN/M
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 Surface free energy
 To move a molecule from the inner layers to the
surface, work needs to be done against the force of
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 energy.

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 Surface free energy (cont’d)

 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 free
surface, it is called surface free energy.
 Each molecule of the liquid, has a tendency to move
inside the liquid from the surface; to take form with
minimal free surface and with minimal surface
energy.

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 Surface free energy (cont’d)

 For example, liquid droplets tend to assume a

spherical shape because a sphere has the smallest
surface area per unit volume.
 The relationship between interfacial tension and
surface energy can be expressed by the following
equation.

Where, ∆G is change in surface energy, ∆A is change in surface

area and ϒ is surface tension.

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 Spreading
 If a small quantity of an immiscible liquid is placed on a
clean surface of a second liquid, it may spread to cover
the surface with a film or remain as a drop or lens.
• Which of the two applies depends on the achievement of
a state of minimum free energy.
• The spreading coefficient S is the difference between the
work of adhesion WA,B between the phases and the work
of cohesion WA,A of the phase under consideration.

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 Spreading (cont’d)

 The ability of one liquid to spread over another can also be

assessed in terms of the spreading coefficient (S):
difference between the surface tensions and the interfacial tension

positive value of S is required for spreading to

occur,
zero it will sit there,
negative it will contract.
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 Adsorption at liquid interfaces
 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 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.

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Adsorption at liquid interfaces (cont’d)
 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 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.

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 Surface active agents (surfactants)
 Molecules and ions that are adsorbed at interfaces
are termed surface-active agents (surfactants).
 An alternative term is amphiphile, which suggests
that the molecule or ion has a certain affinity for
both polar and non polar solvents.
 Depending on the number and nature of the polar
and non polar groups present, the amphiphile may
be predominantly hydrophilic (water-loving),
lipophilic (oil-loving), or reasonably well balanced
between these two extremes.
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 Surface active agents (cont’d)

 For example, straight-chain alcohols, amines, and

organic acids are amphiphiles that change from
being predominantly hydrophilic to lipophilic as the
number of carbon atoms in the alkyl chain increased.
 If a molecule is too hydrophilic, it remains within the
body of 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.

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 The HLB System
 Griffin devised an arbitrary scale of values to serve as
a measure of the hydrophilic-lipophilic balance
(HLB) of surface active agents.
 The HLB scale is a numerical scale extending from 1
to approximately 50.
 The more hydrophilic surfactants have high HLB
numbers (in excess of 10).
 Whereas, surfactants with HLB numbers from 1 to 10
are considered to be lipophilic.

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The HLB System (cont’d)

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 The HLB system and application (cont’d)
 The HLB of polyhydric alcohol fatty acid esters such as glyceryl
monostearate may be obtained from equation

S is saponification value of the ester and

A is acid value of the fatty acid
• S is the weight in mg of KOH required to saponify 1 g of fat
or oil
• A is the weight in mg of KOH required to react with 1 g of
fatty acid.
• Note this formula can also be used to determine HLB of
polysorbates and sorbitan esters 18
 The HLB system and application (cont’d)
 For polysorbates (Tweens®) and sorbitan esters (Spans®)

 E is the percentage by weight of oxyethylene chains

 P is the percentage by weight of polyhydric alcohol
group (sorbitol or glycerol)

 Polysorbates (Tweens)

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 The HLB system and application (cont’d)

Calculation of HLB of a polysorbate

o For example, Polysorbate 20 has a molecular weight
of approximately 1300 and contains 20 oxyethylene
groups and two sorbitan rings.

HLB = (68 + 14)/ 5 = 16.4

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 The HLB system and application (cont’d)

 Alternatively, HLB value can be calculated by

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 Adsorption at solid interfaces
 The study of adsorption of gases on solids has
applications as the removal of objectionable odors
from rooms and foods, the operation of gas masks,
and the measurement of the dimension of particles
in a powder.

 The principles of solid-liquid adsorption are used in

decolorizing solutions, adsorption chromatography,
and wetting.

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 Adsorption at solid-gas interfaces
 The degree of adsorption of a gas by a solid depends
on:
 chemical nature of the adsorbent (the material used
to adsorb the gas) and the adsorbate (the substance
being adsorbed),
 surface area of the adsorbent,
 temperature, and
 partial pressure of the adsorbed gas.
 The types of adsorption are generally recognized as
physical or van der Waals adsorption and chemical
adsorption or chemisorption.
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 Adsorption at solid-gas interfaces
(cont’d)
 Physical adsorption, associated with van der Waal
forces, is reversible,
 The removal of the adsorbate from the adsorbent is
known as desorption.
 For example, physically adsorbed gas can be
desorbed from a solid by increasing temperature and
reducing the pressure.
 Chemisorption, in which the adsorbate is attached to
the adsorbent by primary chemical bonds, is
irreversible unless the bonds are broken.
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 Adsorption at solid-gas interfaces
(cont’d)
 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.
 The term isotherm refers to a plot at constant
temperature.
 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
mmHg on the horizontal axis is shown on the next
slide 25
Type I isotherm

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 Adsorption at solid-gas interfaces
(cont’d)
 Freundlich suggested a relationship, the Freundlich
isotherm,

where y is the mass of gas, x, adsorbed per unit

mass, m, of adsorbent, and K and n are constants
reflecting adsorption affinity and capacity.
 The equation is handled more conveniently when
written in logarithmic form

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 Adsorption at solid-gas interfaces
(cont’d)
 Langmuir developed an equation based on the
theory that molecules or atoms of gas are adsorbed
on active sites of a solid to form a layer one molecule
thick (monolayer).
 The fraction of centers occupied by gas molecules at
pressure P is represented by θ, and fraction of sites
not occupied is 1- θ.
 The rate, r1 , of adsorption or condensation of gas
molecules on the surface is proportional to the
unoccupied spots, 1- θ, and to the pressure, P, or
r1 = K1(1- θ)p …………………….1 28
 Adsorption at solid-gas interfaces
(cont’d)
 The rate, r2 ,of evaporation(desorption) of molecules
bound on the surface is proportional to the fraction
of surface occupied, θ, or r2 = k2θ ………………………2
 At equilibrium, r1 = r2 or
K1(1- θ)p = k2θ ………………………3
 By rearrangement, we obtain

……………4

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 Adsorption at solid-gas interfaces
(cont’d)
 We can replace K1/k2 by b, and θ by y/ym ,
 where y is the mass of gas adsorbed per gram of
adsorbent at pressure p and at constant temperature
and ym is the mass of gas that 1 g of the adsorbent
can adsorb (total) when the monolayer is complete.
 Inserting these terms into equation (4 ) produces
the formula

………….5 ( Langmuir isotherm)

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 Measurement of surface/interfacial
tension
• There are several methods for determination of
surface/interfacial tension.
• The choice of a particular method often depends on
several factors such as
– surface or interfacial tension to be determined,
– the accuracy and convenience desired,
– the size of sample available, and
– whether the effect of time on surface tension is to
be studied.
• There is no one best method for all systems.
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 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.

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Capillary Rise Method……..(cont’d)

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 Capillary Rise Method……..(cont’d)

 To examine more closely the factors giving rise to the

phenomenon of capillarity, consider the case of a
liquid that rises to a height, h, above the bulk liquid
in a capillary having a radius, r ,

 If the contact angle of water on glass is 0, a force, F,

will act upward and vertically along the circle of
liquid – glass contact

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Capillary Rise Method……..(cont’d)

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 Capillary Rise Method……..(cont’d)
 Based upon the definition of surface tension, this
upward force will be equal to the surface tension, ϒ,
multiplied by the circumference of the circle, 2πr,
 Thus, F= ϒ2πr………………………(1)
 This upward force must support the column of water,
and, the force W opposing the movement upward
will be
w = mg = πr2ρgh……………….(2)
because the mass, m, of the column is equal to the
density, ρ, multiplied by the volume of the column,
πr2h. 36
 Capillary Rise Method……..(cont’d)

 Equating the two forces at equilibrium, gives,

πr2ρgh = ϒ2πr
so that

 If the contact angle of liquid is not zero(0) (see next

slide), the same relationship may be developed,
except the vertical component of F which opposes
the weight of the column is Fcosθ, and, therefore,

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Capillary Rise Method……..(cont’d)

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 Capillary Rise Method……..(cont’d)
 Example, a sample of chloroform rose to a height of
3.67 cm at 20 oC in a capillary tube having an inside
radius of 0.01 cm. What is the surface tension of
chloroform at this temperature? The density of
chloroform is 1.476 g/cm3

ϒ= ½ x 0.01 cm x 3.67 cm x 1.476 g/cm3 x 981 cm/s2

ϒ = 26.6 g/s2 = 26.6 dyne/cm

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