Interfacial Phenomena

3.
Interfacial Phenomena
By SHIMELIS K., (B.Pharm, M.Sc.)

Chapter objectives
 After completion the chapter student will be able to
 Differentiate among different types of interfaces and
describe relevant example in the pharmaceutical sciences

 Understand the terms surface tension and interfacial
tension and their application in pharmaceutical sciences

 Appreciate the different methods of surface and
interfacial tension measurements

 Calculate surface and interface tensions, surface free
energy, work of cohesion and adhesion and spreading

2 Shimels K. Lecturer, CHMS, HU 11/19/2023
coefficient for different types of interfaces
 Understand the mechanisms of adsorption on liquid
and solid interfaces

 Clarify surface-active agents and appreciate their
application in pharmacy
 differentiate between different types of monolayers
and recognize basic methods for their characterization

 Recognize the electric properties of interfaces and
effects of electrolyte
Outline
Surface tension and interfacial tension
Surface free energy
Spreading coefficient
Measuring surface and interfacial tension
Surface active agents
Classification of surfactants

Floating without floating

Water striders are light (like ants) thus don’t
“break” surface
Ooh! Look at
me! I have
hydrophobic
feet and I
weigh less
So I can walk

anywhere

Even a piece of steel can do this trick
if it is small (steel  ~ 8x water)

What’s the reason behind? Surface tension…
 Surface chemistry deals with the behavior of matter where such
behavior is determined largely by forces acting on the surfaces
Interfaces and Surfaces
 Interface is the boundary between
two or more phases exist together
 The properties of the molecules
forming the interface are different
from those in the bulk
 Several types of interface can exist
depending on whether the two

adjacent phases are in solid, liquid or
8 Shimels K. Lecturer, CHMS, HU gaseous state. 11/19/2023
Surface and Interfacial Tensions
In the liquid state, the
cohesive forces between
adjacent molecules are
well developed
For the molecules in the

bulk of a liquid
 Surrounded in all directions

by other molecules for which
they have an equal attraction
Surface tension…
 For the molecules at the surface (at
the liquid/air interface)
 Only attractive cohesive forces with

other liquid molecules which are
situated below and adjacent to them
 The net effect: the molecules at the

surface of the liquid experience an
inward force towards the bulk of the
liquid and pull the molecules and
contract the surface with a force F

Surface tension…
 Thus SURFACE TENSION [γ ] (dyne/cm or N/m) is the force per unit length
that must be applied parallel to the surface so as to counterbalance the net
inward pull
 INTERFACIAL TENSION is the force per unit length existing at the interface
between two immiscible liquid phases
 Ordinarily, the interfacial tensions are less than surface tensions
 If two liquids are completely miscible; no interfacial tension exists between

them

Classification of interfaces

Surface tension and interfacial tension (against water)

Surface tension…
 Greater surface tension reflects higher intermolecular force of
attraction, thus, increase in hydrogen bonds cause increase in

ST

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
 If the surface of the liquid increases, the energy of the liquid also
increases
 The work “w” required to increase the surface area of a liquid by

1 cm2
W α ΔA W is surface free energy increase
W=γΔA erg/cm2 x cm2 = erg
γ = W/Δ A erg/cm2 W=γ∆A
 Surface tension: surface free energy change per unit area
increase
Surface Free Energy…
 The greater the area of interfacial contact between the
phases, the greater the free energy
 For equilibrium, the surface
free energy of a system must

be at a minimum
 Thus Liquid droplets tend to
assume a spherical shape

since a sphere has the
smallest surface area per unit
volume.
Spreading Coefficient “S”
 When a liquid is placed on the surface of other liquid, it will
spread as a film if the adhesion force is greater than the

cohesive forces

Spreading Coefficient…
The work of adhesion
 The energy required to break the attraction between the
unlike molecules
 γLS is destroyed after separation and γL and γS are created
Wa = γ L + γ S - γ LS
The work of cohesion
 The energy required to separate the molecules of the
spreading liquid so it can flow over the sub-layer
Wc = 2 γ L
 Spreading occurs if Wa > Wc, i.e., Wa-Wc is positive value
 S is the d/ce b/n Wa and Wc
S = Wa - Wc = (γ L + γ S - γ LS ) - 2 γ L
S = γ S - γ L - γ LS
S = γ S – (γ L + γ LS )
 If (γ L + γ LS ) is larger than YS , (S is negative) the substance
forms globules or a floating lens and fails to spread over the
surface.
Liquid Substrate
Example
Spreading benzene over water
o If the surface tension of water is 72.8 dynes/cm at 20
o
C, the surface tension of bezene is 28.9 dynes/cm
and the interfacial tension between benzene and water
is 35.0 dynes/cm, what is the initial spreading
coefficient? Following equilibrium is 62.2 dynes/cm
and is 28.8 dynes/cm. what is the final spreading
coefficient?

Factor affecting Spreading Coefficient
Molecular structural
 The greater the polarity of the molecule the more +ve S
Example : ethyl alcohol
 Non polar substances (-ve S) fail to spread on water
Cohesive forces
 Benzene spreads on water, not because it is polar but because
the cohesive forces between its molecules are much weaker

than the adhesion for water

The applications of spreading coefficients in pharmacy
should be fairly evident.

For a lotion with a mineral oil base to spread freely
and evenly on the skin, its polarity and hence its

spreading coefficient should be increased by the
addition of a surfactant.

Measurement of Surface Tension and Interfacial
Tension
 Methods for measuring surface and interfacial tension
 Capillary rise method
 Ring (Du Nouy) tensiometer
 Drop weight method (Stalagmometer)

 The choice of the method for measuring surface and
interfacial tension depends on:

 Whether surface or interfacial tension is to be
determined
 The accuracy desired
 The size of sample
 Whether the effect of time on surface tension to be

studied

Capillary rise method
 If a capillary tube of inside radius, r immersed in a liquid
that wet its surface
 When adhesive force > cohesive force: the liquid wet the
capillary wall, spreading over it and rising up in the tube
 The liquid continues to rise in the tube due to the surface

tension until the upper movement is just balanced by the
downward force of gravity due to the weight of the liquid.
At equilibrium
 Upward force (surface tension) = Downward force
(mass of liquid)

Capillary rise method…
 It is not possible, to
obtain interfacial
tensions using the
capillary rise method

Capillary rise method…
Example
o 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 is 1.476 g/cm3
o A given liquids rise 3.19 cm in a capilary tube the

redius of which is 0.038 cm and density of the given
liquid is 0.778 g/cm3. Calculate the surface tension of
the liquid.

Ring Method (The DuNouy Tensiometer): ST & IT
 The principle: the F necessary to detach a platinum-iridium

ring immersed at the surface or interface is proportional to the
ST or IT
 The F of detachment is recorded in dynes on a calibrated dial
 The surface tension is given by:
γ = F / 2 π (R1 + R2)
 R1 and R 2= the inner and outer radii of the ring.

Ring Method…
The ST is the maximum

force needed to detach the
ring from the aqueous liquid
surface
Drop Weight and drop volume method (ST)
 If a liquid fall slowly from tube, forms a drop at the end of the tube
which increases in size and finally detaches from the end when the
weight of the drop equals the surface tension
 If the volume or weight of a drop as it is detached from a tip of known

radius is determined, the surface tension can be calculated from
γ = Φ mg = Φ V pg
πr 2πr2
m = the mass of the drop V = the volume of the drop

p = the density of the liquid r = the radius of the tip
g = the acceleration due to gravity Φ = a correction factor
Factors affecting surface tension
 The surface tension decrease with increase temperature
 Water has ST 76, 72,63 dyne/cm at 0˚,20 ˚, and 75 ˚ C
 The surface energy may altered by the addition of solutes

that migrate to the surface and modify the molecular forces
there.
surface active agents

Do U know that

Importance in pharmacy
 Adsorption of drugs on solid adjuncts of d/t formulation
 Penetration of drug through biological membranes
 Heterogeneous formulation stability: suspension and
emulsions
 Interfacial phenomena affect drug delivery systems.

Adsorption at liquid interfaces
Surface Active Agents/Surfactants
 Molecules that are adsorbed at interfaces
 They have a certain affinity for both polar and nonpolar
solvents
If high number of polar groups: hydrophilic SAA

If high number of nonpolar groups: lipophilic SAA
Well balanced molecule between these two extremes

What does surfactant do ?
Water & Oil

Interfacial
are mortal
tension
enemies
between
two liquids
Surfactants act
as clamp
binding Water
& Oil together

Why does surfactant work ?
Water : Hydrophobic Hydrophilic

Oil : Lipophilic Lipophobic

How does surfactant work?

How does surfactant work…

Micelle formation
Extremely Dil. Soln Soln at Soln

Dil. Soln CMC above
40 Shimels K. Lecturer, CHMS, HU CMC11/19/2023
micelle…

Micelle
 When surface tension is
plotted against the logarithm

of surfactant concentration, log
C
 Surface excess or surface
concentration is the amount of

the amphiphile per unit area of
surface in excess of that in the
bulk of the liquid
Structures of Micelles

Classification of Surfactants
Structural classification

Anionic surfactants
 The surface-active (head) portion of the molecule has a negative charge, such
as a sulfonate, sulfate, or carboxylate group
 They are the metal salts of long chain fatty acids as lauric acid
 Sodium stearate, sodium oleate, sodium dodecylsulphate [C12H25OSO3- Na+],
sodium dodecanoate [C11H23COO- Na+]
Sulfosuccinate
Monoester
FAS
Alkyl benzene Sulphonates

Uses of Anionic Surfactants
 Anionic surfactants are cheap and the most widely used
types
 Cleansing Formulation
Shampoo
Hand wash
Bath gels
Tooth Paste
Soaps & Detergents

Cationic surfactants
 The surface-active portion (head) bears a positive charge
localized at the nitrogen atom
 Hexadecyl trimethyl ammonium bromide [C16H33N+(CH3)3Br-]
 dodecyl trimethyl ammonium chloride [C12H25N+(CH3)3Cl−]

Cationic surfactants…
 Cationic surfactants are expensive
 but their germicidal action makes them useful for many industrial
applications
Amphoteric Surfactants
Cocobetaine (CB)
CH3
N+ CH2COO-
CH3
Cocoamidopropylbetaine ( CAPB)
CH3
CONH (CH2)3 N+ CH2COO-
CH3
Non-ionic surfactants
 These surfactants do not contain charged groups
 Widely used in pharmaceutical formulations
 They are polyethylene oxide products
H—[OCH2CH2]n—

Sorbitan esters (Span)
 Esterification of the primary hydroxyl group of sorbitan
with lauric, palmitic, stearic or oleic acid forms sorbitan

monolaurate, monopalmitate, monostearate or
monooleate

Polysorbates (Tween)
 Polyethylene glycol derivatives of the sorbitan esters give
us polysorbates

Water Solubility of Nonionics
Reason

Applications nonionic surfactants
Cleansing agent in detergents

Emulsifying agents
Solublizing agent
Wetting agents in textile processing, agrochemical
formulations, pharmaceutical formulation.

Hydrophilic/ lipophilic balance
 The HLB of a surfactant is expressed using an arbitrary scale which for non-
ionic surfactants ranges from 0 to 20.
 Products with low HLB are more oil soluble. High HLB represents good
water solubility

HLB Value
HLB Value 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Water in oil
Oil in water Emulsifiers
emulsifier
Use
Wetting Agents Detergents
Solubilizer

Determination of HLB
 HLB of polyhydric alcohol fatty acid esters such as
GMS(glyceryl mono stearate)
HLB = 20 (1 - S/A)
Where S V = Sap value of ester of polyhydric alcohol

AV = Acid value of fatty acid used

For those materials with which it is not possible to
obtain good saponification number, e.g., beeswax
and lanolin derivatives:
HLB = (E+P)/5
E and P are percent by weight of oxyethylene chains and

poyhydric alcohols groups in the molecules.
Surfactants with only oxyethylene groups
HLB =E / 5

Example
Calculation of HLB value of PEG-7-glyceryl-cocoate
AV of cocofatty acid = 265 mg KOH/g

SV of PEG-7-glyceryl-cocoate = 95
HLB = 20 ( 1 - 95/265 ) = 12.8

Example
Determine the HLB value of polyoxyethylene sorbitan
monolaurate for which SV = 45.5 and AV = 276. What

is the use this surfactant?

Example (Surfactants with only
oxyethylene groups)
% Ethylene oxide in the molecule divide by 5

Example 2
o Determine the HLB value and function of surfactant
with molecular formula of C12-alcohol + 8 EO.

Hydrophile-lipophile balance…
o We can calculate HLB values directly from the chemical
formula using empirically determined group numbers

o The formula is then:

Hydrophile-lipophile balance…
 Tab: Group numbers of some commonly occurring groups

Functional Classification
 Wetting agents
 Solubilizing agents
 Emulsifying agents
 Foaming and antifoaming agents
 Detergents

Wetting agent
 when dissolved in water, lower the contact angle and aids in displacing the
air phase at the surface and replacing it with a liquid phase
 Paraffin or new cotton cloth barely wetted by water But

 When surfactant is added to water their surface easily becomes wet

Wetting agent
 The drop is in equilibrium by balancing three forces

Young’s Equation
 The contact angle may have any value between the limits:0-
180o
 At equilibrium, the surface and interfacial tensions can be
resolved:
γSV = γSL + γLV cos θ

Wetting…
complete no
incomplete wetting
wetting wetting
Ө = 0° Ө 90° <Ө 90° = Ө 90° > Ө 180° =
γ s – γsL> 0 γ s – γsL ≈ 0 γ s– γsL< 0

Wetting…
 When the forces of adhesion are greater than the forces of
cohesion, the liquid tends to wet the surface and vice versa
 The surface of liquid water (meniscus) has a concave shape

because water wets the surface and creeps up the side
 The surface of Mercury has a convex shape it does not wet

glass

Solubilizing and emulsifying agents, micelle
Micelles form around the molecules of the waterinsoluble
compound inside the micelles’ cores and bring them into
solution in an aqueous medium.

Foams and Antifoaming Agents
 Any solutions containing surface active materials produce stable foams

when mixed intimately with air.
 Foam: air pockets enclosed within thin films of liquid or the gas-in-liquid
dispersion being stabilized by a foaming agents.
 Antifoaming agents: agents such as alcohol, ether and some surfactants

used to break the foam. (HLB: 1-3)
 The undesired foaming of solubilized liquid preparations poses a problem

in formulation

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 solubilization of
the dirt particles
Finally washing away the dirt

Required Effects when Cleaning

How Surfactants Work

We now have COMPLETE POWER
OVER WATER STRIDERS!!!
simply add soap and they’re SCREWED!

Interfacial Phenomena

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Interfacial Phenomena

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3.

By SHIMELIS K., (B.Pharm, M.Sc.)

 Differentiate among different types of interfaces and

describe relevant example in the pharmaceutical sciences

tension and their application in pharmaceutical sciences

interfacial tension measurements

energy, work of cohesion and adhesion and spreading

and solid interfaces

and recognize basic methods for their characterization

4 Shimels K. Lecturer, CHMS, HU 11/19/2023

5 Shimels K. Lecturer, CHMS, HU 11/19/2023

So I can walk

6 Shimels K. Lecturer, CHMS, HU 11/19/2023

7 Shimels K. Lecturer, CHMS, HU 11/19/2023

depending on whether the two

For the molecules in the

 Surrounded in all directions

 Only attractive cohesive forces with

 The net effect: the molecules at the

10 Shimels K. Lecturer, CHMS, HU 11/19/2023

 Ordinarily, the interfacial tensions are less than surface tensions

 If two liquids are completely miscible; no interfacial tension exists between

11 Shimels K. Lecturer, CHMS, HU 11/19/2023

12 Shimels K. Lecturer, CHMS, HU 11/19/2023

13 Shimels K. Lecturer, CHMS, HU 11/19/2023

 Greater surface tension reflects higher intermolecular force of

attraction, thus, increase in hydrogen bonds cause increase in

14 Shimels K. Lecturer, CHMS, HU 11/19/2023

 The work “w” required to increase the surface area of a liquid by

 For equilibrium, the surface

free energy of a system must

assume a spherical shape

spread as a film if the adhesion force is greater than the

17 Shimels K. Lecturer, CHMS, HU 11/19/2023

21 Shimels K. Lecturer, CHMS, HU 11/19/2023

the cohesive forces between its molecules are much weaker

22 Shimels K. Lecturer, CHMS, HU 11/19/2023

should be fairly evident.

and evenly on the skin, its polarity and hence its

23 Shimels K. Lecturer, CHMS, HU 11/19/2023

 Methods for measuring surface and interfacial tension

 Capillary rise method

 Ring (Du Nouy) tensiometer

 Drop weight method (Stalagmometer)

24 Shimels K. Lecturer, CHMS, HU 11/19/2023

interfacial tension depends on:

 The size of sample

 Whether the effect of time on surface tension to be

25 Shimels K. Lecturer, CHMS, HU 11/19/2023

 The liquid continues to rise in the tube due to the surface

26 Shimels K. Lecturer, CHMS, HU 11/19/2023

27 Shimels K. Lecturer, CHMS, HU 11/19/2023

o A given liquids rise 3.19 cm in a capilary tube the

28 Shimels K. Lecturer, CHMS, HU 11/19/2023

 The principle: the F necessary to detach a platinum-iridium

 R1 and R 2= the inner and outer radii of the ring.

29 Shimels K. Lecturer, CHMS, HU 11/19/2023

The ST is the maximum

 If the volume or weight of a drop as it is detached from a tip of known

m = the mass of the drop V = the volume of the drop

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

 The surface energy may altered by the addition of solutes

surface active agents