Physical (II)

Surface
Tension
Dr Rana Obeidat

TENDENCY OF LIQUIDS TO REDUCE THEIR

EXPOSED SURFACE TO THE SMALLEST
POSSIBLE AREA. A DROP OF WATER, FOR
EXAMPLE, TENDS TO ASSUME THE SHAPE
OF A SPHERE.

The molecules within the liquid

are attracted equally from all
sides, but those near the surface
experience unequal attractions
and thus are drawn toward the
center of the liquid mass by this
net force. The surface then
appears to act like an extremely
thin membrane, and the small
volume of water that makes up a
drop assumes the shape of a
sphere, held constant when an
equilibrium between the internal
pressure and that due to surface
tension is reached.

Definition of Surface
Tension

The surface tension: is the

magnitude F of the force
exerted parallel to the
surface of a liquid divided
by the length L of the line
over which the force acts:

force

length

Unit of Surface Tension:

N/m

Surface Versus Interfacial

Tension
Interfacial

tension is the force

per unit length existing at the
interface between two
immiscible liquid phases.

Three sided wire frame.

Movable bar.
Soap film.
=f/2L
L: length of the movable bar.
F: force required to the break the film.

Surface Free Energy

Work done (energy) in

increasing the surface
area.
Note : f=*2L
dW=f*ds= *2L*ds
dW= *dA

Pressure Differences Across

Curved Interfaces

Wexternal= 4 (r-dr)2
Winternal=p*4 r 2*(-dr)
p= 2/r

Measurement Surface
Tension & Interfacial
Tension

Capillary Rise Method.

DuNoy Ring Method.

Drop weight Method.

Bubble pressure.

Pendent drop.

Sessile drop.

Whilmey plate.

Choice of the method

depends on:
1.

Aim of the experiment is surface or

interfacial tension.

2.

Accuracy and Convenience.

3.

Size of the sample available.

4.

Effect of time on surface tension is to be

studied or not.

There is no one best method for all systems.

Capillary Action

Force Upward = Force Downward

Surface Tension Force = Weight Force

(Surface Tension * Circumference) =

(Volume * Density *Gravity
Acceleration)
2r = h r2g

Surface Tension==(1/2) rhg

Sources Of Errors
Considering

contact angle ()
equal to zero, and cos () = 1

Ignorance

to the weight over h.

DuNoy Ring Method.

For Both Surface and Interfacial tension .

Force
needed
to
detach a platinumiridium ring immersed
at
the
surface
or
interface is proportional
to
the
surface
or
interfacial tension.

Force recorded on
Dyne on a calibrated
dial.

Correction Factor Must Be

Used
If

correction factor () not used, error

may reach 25%. correction factor ()
depends on:
Radius of the wire r that form the ring,
Radius R of the tensiometer.
Volume of liquid raised out of the
surface (V).
Refer to Harkins and Jordan values of
.

Number of Drops Method:

It is a qualitative method
to determine surface
tension. It is based on the
principle of As surface
tension is reduced, the
drop volume will
decrease, and the
number of drops for
certain volume will
increase. You need only
a dropper for such a
method. It cannot be
applied for interfacial
tension measurements.

Wilhelmy Plate
Method

Factors Affecting Surface and

Interfacial Tension Values:
1. Adsorption at liquid interface:

A) Positive adsorption: molecules are partitioned in

favors of the interface. Examples are surfactants (SAA,
amphiphile). These tend to decrease surface and
interfacial tension.
B) Negative adsorption: molecules are partitioned
in favor of the bulk. Example on these inorganic
electrolytes. They tend to increase surface tension.

2. Temperature:
3. Presence of impurities:
Impurities affect surface tension, so cleanliness is a very
important factor in determining surface tension.

Adsorption at Liquid Interface

Electrolytes

Surface tension results from cohesive forces. Solute

can alter these.

Surface tension increases when solute molecules attract

solvent molecules more strongly than solvent molecules
attract each other.

Adsorption at Liquid
Interface Surfactants
Substances

which have a
tendency to concentrate at the
surface or interface are called
surface active agents. They can
have a number of effects on the
nature of the surface.
They decrease surface tension.

Adsorption At Liquid
Interfaces Surfactants
Surface Active Agents or Surfactants.
Strongly adsorb at air-water interface
Polar and non-polar parts.
Three types - cationic, anionic, nonionic
Form micelles, hydrophobic tails in centre of
micelle and hydrophilic heads on outside.
Concentration at which micellisation begins to
occur is called the critical micellar
concentration (cmc).

Determination of
(CMC)

The critical micelle formation concentration (CMC) can

be determined by carrying out surface tension
measurements on a series of different surfactant
concentrations. Surfactants exhibit a specific surface
tension curve as a function of the concentration. Initially
the surfactant molecules increasingly enrich themselves
at the water surface. During this phase the surface
tension decreases linearly with the logarithm of the
surfactant concentration. When the CMC is reached, i.e.
when the surface is saturated with surfactant molecules,
a further increase in surfactant concentration no longer
has any appreciable influence on the surface tension.

Effect Of Temperature On
Surface Tension
Increase in temperature will increase kinetic energy of
molecules, which will decrease surface tension linearly. So,
temperature should be controlled in all experiments

Spreading Coefficient

OLEIC ACID ON WATER SURFACE

DUPLEX FILM (100A OR MORE)

Work Of Cohesion

Lets imagine that we

have a tube of water
or some other pure
liquid whose crosssectional area is one
cm2. We apply a force
to the liquid such that
it separates. The work
we have done is
called the Work of
Cohesion. It is defined
as the surface tension
times the amount of
new area created.

Wc=2L

Work Of Adhesion

Let's now imagine that

our tube of liquid is
made up of two liquids
which do not dissolve in
each other (Oil &
water). If we again
apply a force along the
tube to cause the
liquids to separate, we
have done three things
and the work we have
done is called the work
of adhesion ( Wa).

Wa=L + s - Ls

Spreading Coefficient
S

S=

Wc

+ - - 2L

= Wa
L

Ls

+
Spreading Occur If S positive.
S= s

(L

Ls )

It is initial spreading, which may change

after equilibrium (Reversal Spreading)

Water has a surface tension of 72.8 dynes/cm;

benzene has a surface tension of 28.9 dynes/cm
and the interfacial tension between water and
benzene is 35.0 dynes/cm.
Will benzene spread on water??
After some time, the benzene will begin to
saturate the water and the surface tension of
water saturated with benzene will change to 62.2
dynes/cm.

Initial Spreading Coefficient of

Organic Liquid on Water at 20C

Adsorption At Liquid Interfaces

(Surfactants)

HLB - Hydrophilic Lipophilic Balance

It is useful to correlate the characteristics of

surfactants with the properties that are needed to
make various heterogeneous systems. A
common system which is used to do this is the HLB
system. The HLB value for a given surfactant is the
relative degree to which the surfactant is water
soluble or oil soluble. The lower the HLB, value the
more lipophilic. The higher the HLB value, the
more hydrophilic. I will not go over how these
numbers are derived. You can look it up if you
like. The range is usually between 1 and 20.

HLB Values and the use for those

surfactants

Required HLB
RHLB

HLB Values
Low

HLB values: Span, Sorbitan

Esters (1.8-8.6).
High HLB: Tweens,
Polyoxyethylene derivatives of
spans (9.6-16.7).

Emulsions (O/W or W/O)

Ingredient

Amount
(g)

RHLB
(O/W)

Emulsions require
specific HLB value.

Beeswax

15

Check Table 14-6.

Lanolin

10

12

Study Example 148.

Paraffin wax

20

10

Cetyl Alcohol

15

Emulsifier

Preservative

0.2

Color

As required

Water,
purified, qs

100

 Step

(1)

Total Weight of Oil Phase:

15+10+20+5=50 g.

Step

(2)

Partial Effect Of Each Component On Total RHLB:

Weight fraction of ingredient (component weight/total
weight) * (RHLB)ingredient
Beeswax: (15/50)*9=2.7
Lanolin: (10/50)*12=2.4
Paraffin Wax: (20/50)*10=4
Cetyl alcohol (5/50)*15=1.5

Step (3):
Calculate total RHLB (Summation of partial effect):
2.7+2.4+4+1.5=10.6

Step (4):
Select two emulsifying agents: one above RHLB and
one below.
Tween 80: 15
Span 80: 4.3

Step

(5):

Apply The low:

% Tween 80=(RHLB-HLBlow)/(HLBhigh-HLBlow)

% Tween 80 =(10.6-4.3)/(15-4.3) = 0.59

Step

(4):

Calculate Exact weight:

If total Emulsifier was 2 gm
Tween 80: 2*0.59 = 1.18 g.
Span 80: 2-1.18=0.82g.

Minimum Amount Of Surfactant

Mixture

6( s / )
4Q
Qs

10 0.5 RHLB 1000

Qs: amount surfactants in gram.
s: density of surfactant mixture.
: density of internal phase (dispersed).
Q: % dispersant continuous phase.

Types Of Monolayer at
Liquid Surface

Soluble Monolayer

Eg. Amyl alcohol.

Insoluble Monolayers.

Eg. Cetyl Alcohol

Depends on solubility of adsorbate in the liquid

subphase.
It is used to find surface area per molecule.

Adsorption At Solid Interfaces

Adsorption from gas or from

liquid.

Gas/adsorption:

Removable of odours.
Gas masks.
Measurement of particle dimensions.

Solid/Liquid:

Decolorizing solution.
Adsorption chromatography.
Detergency.
Wetting.

Why Adsorption
Occur?
This

is the method for

solid to decrease
surface free energy.

Solid-Gas Interface
Degree

Of adsorption depends on:

Physicochemical properties of adsorbent
and adsorbate.
Surface area of adsorbent.
Temperature.
Partial Pressure of Gas.
Purity of adsorbent.
Type of adsorption:
Chemical (irreversible).
Physical (Reversible, desorption).

Adsorption Isotherm
How these studies
done??

Special apparatus.

Type 1 Isotherm

Freundlich Isotherm

Y: mass of gas x adsorbed per unit mass m of adsorbent.

K, n : constants

Langmuir

Previous models only for

type 1 Isotherm
What applies for gas
applies for liquid but
instead of P (pressure) we
put C (concentration)

Type II Isotherm

Sigmoidal Shape.

Gases adsorbed onto nonporous

solid to form monolyer followed by
multilayer formation.

First inflection: formation of

monolayer.

Best described by Brunauer,

Emmett, and Teller (BET)

For simplest case: one monolayer

formed type II reduce to langmuir.

b>2

b: constant proportional
to the difference between
heat of adsorption of gas
in the first layer and
latent heat of
condensation of
successive layers.

Solid-Solid interface
ADSORPTION OF A FINE COHESIVE POWDER
AT THE SURFACE OF A COARSE FREE
FLOWING ORDERED MIXTURES.
SUCH AS DRY BLEND OF SUCROSE AND
ANTIBIOTICS.

Wetting
SAA

is used
as wetting
agent.
Detergency
involve
wetting step
of dirts.

Uses Of SAA
Emulsifying

agent.

Affect

drug activity:
penetration
Detergents.
hexylresorcinol into
Wetting Agents.
pinwarm
ascaris.
Solubilizing agents.
Foaming agent.
Antibacterial.
Affect drug activity. Antifoaming agent.