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.
