Intrefacial Phenomena

Interfacial phenomena
By:
Fanta G
06/01/2023 Fanta G.(B. Pharm,Msc) 1

Learning objectives
At the end this lecture you should able to:
 Describe the terms surface and interfacial and their
application
 Explain the different methods of surface and interface tension
measurements
 Classify the surface-active agents
 Differentiate the application of the surface-active agents
 Describe the mechanisms of adsorption on liquid and solid
interfaces and their application

Interfaces
 Substance can exist in any of 3 phases: gas, liquid or solid.

 When two or more materials are put together, interface
forms
 surface is an interface, which is defined as the boundary of
separation of two phases,

interfaces ….
 There are several types of interfaces at the boundaries
between any two states of matter

Surface tension
 Surface tension is an effect within the surface layer of
a liquid
 Caused by the attraction between the liquid's molecules by
various intermolecular forces

Surface tension of various liquids
Comment on these values!

 This force, the surface tension, has the units of dynes/cm and
of N/rn in the Si system,
 It is similar to the situation that exists when an object dangling
over the edge of a cliff on a length of rope is pulled upward by
a man holding the rope and walking away from

The wire frame experiment
 Three sided wire frame with a movable bar of length (L) is
used to demonstrate the principle of surface tension.
 A soap film is formed over the area
 The soap film has two liquid—gas interfaces, the total
length of contact is equal to twice the length of the bar

Liquid interfaces
 When we have two phases immiscible with each other, the

boundary between two phases is known as an interface.
 Interfacial tension is the force per unit length existing at the
interface between two immiscible liquid phases
 it depends on the difference between adhesive and cohesive
force.
 In general the interfacial tension is less than surface tension…
why???

Factors that affects interfacial tension
 the addition of solutes that migrate to the surface and modify
the molecular forces there.
 The surface tension decrease with increase temperature
Water has ST 76, 72,63 dyne/cm at 0˚,20 ˚, and 75 ˚ C.
Comment on the following data:

Mercury, surface tension = 476 dynes/cm
interfacial tension against water= 375 dynes/cm

Problems
Q1. If the length of the bar. L. is 5 cm and the mass required to
break a soap film is 0.50g. what is the surface tension of the soap
solution? Recall that the downward force is equal to the mass
multiplied by the acceleration due to gravity
Q2 In relation to the surface tension at the air–water interface,
indicate whether each of the following statements is true or
false:
A. Surface tension is due to spontaneous expansion of the surface.
B. Surface tension arises because of the downward pull of
molecules in the water.
C. Surface tension has units of N m–1.
D. Surface tension is lowered by surface-active agents.
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.
 each molecule near the surface of liquid possesses a certain
excess of potential energy
 The higher the surface of the liquid, the more molecules have
this excessive potential energy.
 Because this energy is proportional to the size of the free
surface, it is called a surface free energy

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.
 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.

Surface Free Energy…
 To evaluate the amount of work in increasing the surface area,
we can write previous eqn as y x 2L =f.
 When the bar is at a position AD in Figure Fig.4 and a mass is
added to extend the surface by a distance ds.
the work dW (force multiplied by distance) is

dW=fxds=yx2Lxds
 Since 2Lx ds is equal to the increase in surface
area, dA, produced by extending the soap film,
dW = ydA
For a finite change
06/01/2023
W=yΔA Fanta G.(B. Pharm,Msc) 15
Q3 If the length of the bar. L. is 5 cm and the
mass required to break a soap fIlm is 0.50g.
What is the work required to pull the wire down 2 cm?

Surface and interfacial tension measurements
1-Capillary rise method

Depending on capillary action which is
due to
 Rising of liquid stopped when
downward force (weight of liquid )
equal to upward force
 Suitable only for measuring the
surface tension
Surface and interfacial tension measurements…
The liquid rises in the tube

when adhesive forces are
greater than cohesive forces
between the liquid
molecules.
The height to which liquid will
reach is limited by surface tension

Where
γ Surface tension
r radius of capillary tube
h height of liquid
P density of liquid
g acceleration due to gravity
 Eg. A sample of chloroform rose to a height of 3.67 cm at 20 c in

a capillary tube having an inside radius of 0.01cm. What is the
surface tension of chloroform at this temprature? The density of
chloroform is 1.476g/cm3

Drop weight & drop count method
 known volume of a liquid is allowed to fall as drops from a

dropper or a graduated pipette under the effect of
gravity and the No. of drops is counted

The drop will fall when 2 forces are balanced:
- Force due to surface tension=
- Gravitational force = m g

Ring method
 widely used for measuring surface and interfacial tensions
 The principle of the instrument depends on the fact that the
force necessary to detach a latinum—iridium ring immersed
at the surface or interface is
proportional to the surface or
interfacial tension

Ring method…
 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 detachment force is related to the surface or interfacial
tension by the expression
where F is the pull on the ring, R is the mean radius of the

ring and  is a correction factor

By using Harkin’s and Jordan’s β values from tables
Two va1ue, R3/V and R/r are needed to enter the tables of
Harkins and Jordan’ to obtain the correction factor by
interpolation.
 By using the following formula:

• Use the above eqn. calculate the surface tension correction at 20°C, for a =
0.7250, b = 0.09075 m sec1 for all tensiometer rings, and c = 0.04534 —
1.6790 r/R. with R the radius of the ring in m, r the radius in m of the wire
from which the ring is constructed. M the mass in kg of the liquid lifted
above the liquid surface as the ring breaks away from the surface, g the
acceleration due to gravity in m/sec2, ρi the density of(the liquid in kg/m3.
and ρ2 the density of the air saturated with the liquid in kg/rn3; that is, the
upper phase of an interfacial system. With the following data, which must
be expressed in SI units for use in the equation to obtain the corrected
surface tension. The terms of equation in SI units are R = 0.012185 m, r =
0.0002008 m, M = 0.00121% kg, g = 9.80665 m/sec2, ρi = 998.207kg/rn3,
and = 1.2047 kg/rn3. Finally. c = 0.04534—1.6790 r/R = 0.017671
a. Calculate surface tension correction

b. Calculate surface tension
Spreading coefficient
• A liquid (e.g. oleic acid) is placed on the surface of water, will
spread and form a film if the force of adhesion between the
liquid molecules and the water molecules is greater than the
cohesive forces between the oleic acid molecules themselves.
 Consider a hypothetical cylinder (Cross sectional area: 1 cm2)
of
- Sublayer liquid: S
- Spreading liquid: L
Work of adhesion: energy required
• To break the attraction between unlike
molecules

• Work of cohesion: energy required
to separate the molecules of
the spreading liquid
Spreading coefficient; S
S, --if + ve spreading occurs

if – ve the liquid forms globules or floating lenses and fails
to spread over the surface (e.g. mineral oil on water).
• Example: If the surface tension of water (yS ) is 72..8 dyne/cm at
20°C, the surface tension of benzene(yL) is 28.9 and the
interfacial tension(yLS) is 35.0, what is the spreading coefficient
Relation between molecular structures and
spreading coefficients
 An oil spreads over water because it contains polar groups
such as COOH or OH
 When the carbon chain increases, the ratio of polar/ non
polar
 character decreases and the spreading coefficient on water
decreases.
 Many non polar substances such as liquid petrolatum fail to
spread on water.
 Benzene (non polar) but spreads on water, because the
cohesive forces between its molecules are weaker than
adhesion for water

Applications of spreading coefficient in pharmacy
The requirement of film coats to be spreaded

over the
tablet surfaces
The requirement of lotions with mineral oils to
spread on the skin by the addition of surfactants

Adsorption Processes
 Adsorption – the phenomenon of higher concentration of

molecular species on the surface of a solid/liquid than in the
bulk
 Adsorbent – an adsorptive material, such as activated
charcoal
 Adsorbate: the substances that get adsorbed on the solid
surface due to intermolecular attraction

Difference between Adsorption and Absorption

Adsorption
Chemical (chemisorption)
Physical (physisorption)
- van der Waals interactions - Chemical bonds between

(result in attractive forces adsorbate and adsorbent formed
between adsorbent and adsorbate
molecules) - Adsorbed molecules loose their
- Adsorbed molecules maintain identity
their identity
- Multilayers - Monolayers
- No activation energy
- Always reversible - Often activation energy required
- irreversible
Adsorption at liquid interface
 Certain molecules and ions, when dispersed in the liquid.
move of their own accord to the interface
 Their conc. at the interface exceeds their concentration in the bulk of
the Liquid.
 Added molecules are partitioned in favor of the interface, is

Positive adsorption… se surface tension
 Partitioned in favor of the bulk…negative adsorption
e.g., inorganic electrolytes

increase in surface free energy and surface tension
Adsorption at liquid interface
Surface-Active Agents
 Substance that when dissolved in water or an aqueous
solution reduces its surface tension
or the interfacial tension.

 Surfactants are usually organic
compounds that are amphipathic

 It is the amphiphilic nature of surface-active agents that
causes them to be absorbed at interfaces

Hydrophilic Lipophilic Balance
 A scale showing classification of surfactant function on the
basis of HLB values of surfactants.
The higher the HLB of a surfactant
the more hydrophilic it is.
Eg: Spans with low HLB are lipophilic.
Tweens with high HLB are hydrophilic

Determination of HLB
 Polyhydric Alcohol Fatty Acid Esters (Ex. Glyceryl
monostearate
HLB = 20 ( 1 – S / A )
S = Saponification number of the ester
A = Acid number of the fatty acid
 Surfactants with no Saponification no (Ex. Bees wax and lanolin
HLB =E + P / 5
E = The percent by weight of ethylene oxide
P=The percent by weight of polyhydric alcohol group in the molecules
 Surfactants with hydrophilic portion have only oxyethylene
groups
06/01/2023 HLB =E /5
Fanta G.(B. Pharm,Msc) 35
 The HPL value of polyoxyehtylene sorbitan
monolaurate (Tween 20), for which S = 45.5 and A =
276. is ???
 The choice of the mixture of emulsifiers and the total
amount of the emulsifier phase is left to the
formulator
Q. If 20 mL of an HLB of 9.0 are required, what will be the
ratio of two surfactants (with HLB values of 8 and 12) in the
blend?

• A mathematical formula for determining the minimum
amount of surfactant mixture was suggested by Bonadeo
RHLB of the emulsion is obtained by multiplying the rHLP value

of each oil-like component by their weight fraction
We can calculate the weight of each emulsifying components

Exercise
we want to produce oil in water (w/o) type of emulsion
Q1.
obtain water in oil emulsion is?
Q2 calculate the weight of each emulsifying components

Home work
a. What is the amount Q in grams of the mixture

of sorbital Tristearate (PLB=2.1) and dietylene
glycol monostearate (PLB=4.7) the O/W type of
emulsion? Density of oil phase 0.85g/cm3
b. calculate the weight of each emulsifying
components
The density of the surfactant mixture is 1.07
The required HLP value of paraffin and bees
was for O/W are 10 and 9, respectively.
Homework 2
• HLB of Tween 80 = 15
• HLB of Span 80 = 4.3
• We need 2 g of Tween 80 and Span 80 blend
having a HLB value of 10.6. How much Tween
80 and Span 80 are needed?


Classification
 According to the presence of ions in the surfactant molecule

Anionic surfactants
 Sodium dodecyl sulfate /Sodium Lauryl Sulfate : toothpaste and ointments

 Triethanolamine dodecyl sulfate is used in shampoos and other cosmetics
 Sodium dodecyl benzene sulfonate is a detergent.
 Sodium dialkvlsulfosuccinates are good wetting agents.

Cationic surfactants
 Are chiefly quaternary ammonium compounds.

 They have bacteriostatic activity.
 Some most popular antiseptics in this category are
benzalkonium chloride, cetylpyridinium chloride and
cetyltrimethylammonium bromide

Ampholytic surfactants

Nonionic surfactants
 Widely used in pharmaceutical formulations e.g. Tweens,
Spans.
 Surfactants based on sorbitan are of pharmaceutical importance.

 Esterification of the primary hydroxyl group with lauric,
palmitic, stearic or oleic acid forms sorbitan monolaurate,
monopalmitate, monostearate or monooleate
 These are water-insoluble surfactants called Span 20, 40, 60 or 80,
respectively.
 Addition of ethylene oxide molecules produces the water-
soluble surfactants called polysorbate or Tween 20, 40. 60 or
80.
 As a Surface active substance contains a hydrophilic and a
hydrophobic portions, it is adsorbed as a monolayer at the
interfaces
At water-air interface
• Surfaceactive molecules will be adsorbed at water-air
interfaces and oriented so that the hydrocarbon chains of are
pushed out of the water and rest on the surface, while the polar
groups are inside the water.
 Perhaps the polar groups pull the hydrocarbon chains partly
into the water
At oil-water interface
• Surface active molecules will be oriented so that the
hydrophobic portion is inside the oil phase and the
hydrophilic portion inside the water phase
At low surfactant concentrations:

 The hydrocarbon chains of surfactant molecules adsorbed in
the interface lie nearly flat on the water surface.

At higher concentrations:
 They stand upright because this permits more surfactant
molecules to pack into the interfacial monolayer.
 As the number of surfactant molecules adsorbed at the water
air interface increased, they tend to cover the water with a
layer of hydrocarbon chains.
 Thus, the water-air interface is gradually transformed into
an non polar-air interface.
 This results in a decrease in the surface tension of water.

 When the surfactant molecules adsorbed as a monolayer have
become so closely packed that additional molecules cannot be
accommodated with ease, the polar groups pull the
hydrocarbon chains partly into the water
 At certain concentration the interface phase become saturated
with monomers
 Excess surfactants add will begin to agglomerate
in the bulk forming aggregates called micelles

 The lowest concentration at which micelles first appear
is called the critical concentration for micelle formation [CMC ]

Wetting agent
 When the forces of adhesion are greater than the forces of
cohesion, the liquid tends to wet the surface and vice versa.
 Place a drop of a liquid on a smooth surface of a solid.
According to the wettability, the drop will make a certain
angle of contact with the solid.
 A contact angle is lower than 90°,the solid is called wettable
 A contact angle is wider than 90°, the solid is named non-
wettable.
 A contact angle equal to zero indicates complete wettability

Micellar solublization
Surfactant molecules accumulate in the interfaces between
water and water insoluble compound.
Their hydrocarbon chains penetrate the outermost layer of insoluble
compound which combine with the water insoluble molecules.
Micelles form around the molecules of the water insoluble compound
-bring them into solution in an aqueous medium.
This phenomenon is called micellar solubilization.
Drugs which are soluble in oils and lipids can be solubilized

Foaming and Anti Foaming agents
Foams are dispersion of a gas in a liquid (liquid foams as that

formed by soaps and detergents )
 the gas-in-liquid dispersion is being stabilized by a foaming
agent
 useful in toothpastes compositions

Detergents
 Detergents are surfactants used for removal of dirt.
 Detergency involves:
• Initial wetting of the dirt and the surface to be cleaned.
• Deflocculation and suspension, emulsification or solubilisation

of the dirt particles
• Finally washing away the dirt.

The Solid-Gas Interface
 physical adsorption: reversable
the removal of the adsorbate from the adsorbent being

known as desorprion.
 Chemical adsorption or Chemisorption: irreversible
 The degree of adsorption of a gas by a solid depends on:
 the chemical nature of the adsorbent, the adsorbate,

 the surface area of the adsorbent,
 the temperature and the partial pressure of the adsorbed
gas.
 Adsorption isotherm: The relationship at constant
temperature between the equilibrium adsorbed amount of
gas and the pressure of the gas.

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 on
the basis of one or more of the following equations.
Schematic of apparatus used to

measure the absorption ofFantagases
06/01/2023
on solids
G.(B. Pharm,Msc) 58
 The fraction of centers occupied by gas molecules at
pressure p is represented by Ө, and the fraction of sites
not occupied is I—Ө.
 The rate r1, of adsorption or condensation of gas
molecules on the surface is proportional to the
unoccupied spots, 1-Ө, and to the pressure, p. or
r =k1(l —Ө)p
 The rate, r2, of evaporation of molecules bound on the
surface is proportional to the fraction of surface
occupied Ө, or
r2= k2Ө and at equilibrium r1 = r2, or
k1 p(l —Ө)=k2Ө
By rearrangement
 We can replace k1/k2 by b and Ө by Y/Ym,
- y is the mass of gas adsorbed per gram of adsorbent at pressure p
and at constant temperature
-ym’ is the mass of gas that I g of the adsorbent can adsorb
.
 Inserting these terms into equation produces the formula
Lingmuir isotherm
• By inverting equation and multiplying through by p, we can write

this for plotting as
• A plot of p/y against p should yield a straight line, and ym and b

can be obtained from the slope and intercept.
• The above equ. works only type one isotherm
• Extensive experimentation, however, has shown that there
are four other types of isotherms.
• Type II isotherms are sigmoidal in shape and occur when
gases undergo physical adsorption onto nonporous solids to
form a monolayer followed by multilayer formation

 Type ii isotherms are best described by an expression derived by
Brunauer, Emmett, and Teller-’ and termed (for convenience the
BET equalion.
 p is the pressure of the adsorbate in mm Hg at w/c mass y, of vapor per

gram of adsorbent is adsorbed,
 p0,is the vapor pressure when the adsorbent is saturated with adsorbate
vapor,
 Ym is the quantity of vapor adsorbed per unit mass of adsorbent when the
surface is covered with a monomolecular layer,
 b is a constant proportional to the difference between the heat of
adsorption of the gas in the first layer and the latent heat of condensation of
successive layers
Solid liquid interface
 Drugs such as dyes, alkaloids, fatty acids, inorganic acids and
bases can be absorbed from solution onto solids such as
charcoal and alumina
 The adsorption of solute molecules from solution can be
treated in a manner analogous the adsorption of molecules
at the solid—gas interface.

• Isotherms that fit one or more of the equations
mentioned previously can be obtained by
substituting solute concentration for the vapor
pressure term used for solid—gas systems

Activated Charcoal
-residue from distractive
distillation organic materials
- Amorphous
- Hydrophobic
- 400-1200m2/g
- Organic trace removals
- air filters

Pharmaceutical applications of adsorption
• Adsorption of poisons/toxins
 activated charcoal, magnesium oxide and tannic acid
 Taste masking
 diazepam may be adsorbed onto solid substrate
 Adsorption in drug formulation
 adsorption of surfactants and polymers in the stabilisation of
suspensions,
 adsorption of surfactants onto poorly soluble solids to increase
their dissolution rate

Intrefacial Phenomena

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Intrefacial Phenomena

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Interfacial phenomena

06/01/2023 Fanta G.(B. Pharm,Msc) 1

06/01/2023 Fanta G.(B. Pharm,Msc) 2

 Substance can exist in any of 3 phases: gas, liquid or solid.

06/01/2023 Fanta G.(B. Pharm,Msc) 3

06/01/2023 Fanta G.(B. Pharm,Msc) 4

06/01/2023 Fanta G.(B. Pharm,Msc) 5

Comment on these values!

06/01/2023 Fanta G.(B. Pharm,Msc) 7

06/01/2023 Fanta G.(B. Pharm,Msc) 8

06/01/2023 Fanta G.(B. Pharm,Msc) 9

 When we have two phases immiscible with each other, the

06/01/2023 Fanta G.(B. Pharm,Msc) 10

Water has ST 76, 72,63 dyne/cm at 0˚,20 ˚, and 75 ˚ C.

Comment on the following data:

06/01/2023 Fanta G.(B. Pharm,Msc) 11

06/01/2023 Fanta G.(B. Pharm,Msc) 13

06/01/2023 Fanta G.(B. Pharm,Msc) 14

the work dW (force multiplied by distance) is

06/01/2023 Fanta G.(B. Pharm,Msc) 16

1-Capillary rise method

The liquid rises in the tube

06/01/2023 Fanta G.(B. Pharm,Msc) 18

 Eg. A sample of chloroform rose to a height of 3.67 cm at 20 c in

06/01/2023 Fanta G.(B. Pharm,Msc) 19

 known volume of a liquid is allowed to fall as drops from a

gravity and the No. of drops is counted

06/01/2023 Fanta G.(B. Pharm,Msc) 20

06/01/2023 Fanta G.(B. Pharm,Msc) 21

where F is the pull on the ring, R is the mean radius of the

06/01/2023 Fanta G.(B. Pharm,Msc) 22

06/01/2023 Fanta G.(B. Pharm,Msc) 23

a. Calculate surface tension correction

06/01/2023 Fanta G.(B. Pharm,Msc) 25

S, --if + ve spreading occurs

06/01/2023 Fanta G.(B. Pharm,Msc) 27

The requirement of film coats to be spreaded

06/01/2023 Fanta G.(B. Pharm,Msc) 28

 Adsorption – the phenomenon of higher concentration of

06/01/2023 Fanta G.(B. Pharm,Msc) 29

06/01/2023 Fanta G.(B. Pharm,Msc) 30

- van der Waals interactions - Chemical bonds between

 Added molecules are partitioned in favor of the interface, is

e.g., inorganic electrolytes

or the interfacial tension.

compounds that are amphipathic

06/01/2023 Fanta G.(B. Pharm,Msc) 33

 A scale showing classification of surfactant function on the

basis of HLB values of surfactants.

The higher the HLB of a surfactant

the more hydrophilic it is.

Eg: Spans with low HLB are lipophilic.

Tweens with high HLB are hydrophilic

06/01/2023 Fanta G.(B. Pharm,Msc) 34

06/01/2023 Fanta G.(B. Pharm,Msc) 36

RHLB of the emulsion is obtained by multiplying the rHLP value

06/01/2023 Fanta G.(B. Pharm,Msc) 37

Q2 calculate the weight of each emulsifying components

06/01/2023 Fanta G.(B. Pharm,Msc) 38

a. What is the amount Q in grams of the mixture

06/01/2023 Fanta G.(B. Pharm,Msc) 40

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