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Surface Tension

Compiled By: Bertha Yonata


From several sources
Objectives
Students are able to explain
The surface tension phenomena
The methods to measure surface tension
Factors affecting surface tension
Video 1 (why the water still in the
turning glass?)

Discussion
Explain why does water still in the turning
glass
Definition
The surface tension of a liquid results
from an imbalance of intermolecular
attractive forces, the cohesive forces
between molecules:
A molecule in the bulk liquid
experiences cohesive forces with other
molecules in all directions.
A molecule at the surface of a liquid
experiences only net inward cohesive
forces.
Surface tension is measured as the energy required to
increase the surface area of a liquid by a unit of area.
Video 2 (cohesion, adhesion, surface
tension)

A microscopic view of water illustrates the difference between
molecules at the surface of a liquid and water molecules within a
liquid.
The molecules at the surface of this
sample of liquid water are not
surrounded by other water
molecules. The molecules inside the
sample are surrounded by other
molecules. The average lifetime of a
molecule at the surface of a liquid is
10
-6
s

The unbalanced attraction of molecules at
the surface of a liquid tends to pull the
molecules back into the bulk liquid leaving
the minimum number of molecules on the
surface. It required energy to increase the
surface area of a liquid because a larger
surface area contains more molecules in
the unbalanced situation
As many molecules as
possible will leave the
liquid surface will
therefore tend to
contract spontaneously.
For this reason, droplets
of liquid and bubbles of
gas tend to attain a
sperical shape

Video 3 (36 drops of water on penny)

Discussion
What is the difference between surface and
interface?
Surface vs Interface
There is no fundamental distinction between
the terms surface and interface
Surface: the boundary between two phases
one of which is gaseous phase
Interface: the boundary between two non-
gaseous phases
Surface tension and interfacial tension against water for
liquid at 20C
Liquid
0

i
Water 72.8 -
Benzene 28.9 35.0
Acetic acid 27.6 -
Acetone 23.7 -
CCl
4
26.8 45.1
Ethanol 22.3 -
n-octanol 27.5 8.5
n-octane 21.8 50.8
Mercury 485 375
Additivity of Intermolecular Forces at Interface
The short-range intermolecular forces which are
responsible for surface/interfacial tension include Van
der Waals forces and hydrogen bonding (in water) and
metal bonding (in mercury)
The relatively high values of the surface tensions of
water and mercury reflect the contributions of hydrogen
bonding and metal bonding respectively
The surface tension of water



For mercury:

h
W
d
W W
+ =
m
Hg
d
Hg Hg
+ =
Oil-Water Dispersion
The interfacial tension for oil-water dispersion
is given by:


2 / 1
) . ( 2 ) (
d
O
d
W
h
W
d
W
d
O OW
+ + =
Curved Interfaces
(The Kelvin Equation)
As a consequence of surface tension,
there is a balancing pressure difference
across any curved surface
The pressure being greater on the
concave side
Young-Laplace equation



For spherical surface:

|
|
.
|

\
|
+ = A
2 1
1 1
r r
p
r
p
2
= A
Contd
If the radius of droplet increase from r to r +
dr, the surface area increase from 4r
2
to
4(r+dr)
2
and the surface free energy will be
8...r.dr
Assuming ideal gaseous behaviour:

dr r
p
p
T R dn
r
. . . . 8 ln . . .
0
t =
Since

so


A liquid which wets the wall of capillary will have a
concave liquid-vapour interface and lower vapour
pressure in the capillary than in the bulk phase. So
Kelvin equation will be written:
M
dr r dn

t . . . . 4
2
=
r
V
r
M
p
p
RT
m r

2 2
ln
0
= =
Kelvin equation
r
V
p
p
RT
m r
u cos 2
ln
0
=
Measurement of Surface and Interfacial
Tensions
1. Capillary Rise Method
This method is only used when the contact
angle is zero, owing to the uncertainty in
measuring contact angles correctly (
=
liquid

vapour
)



For zero contact angle:
u

cos 2
g rhA
=
2
g rh

A
=
Capillary Action
The tendency of liquids
to rise up in narrow
tubes - capillary action.
Due to the
phenomenon of surface
tension.
The Complication of Contact Angles
The balance of forces
that results in a contact
angle, u
c
.
The contact angle gives
information on the
wettability of a
surface.
Capillary Rise
The pressure exerted by
a column of liquid is
balanced by the
hydrostatic pressure.
This gives us one of the
best ways to measure
the surface tension of
pure liquids and
solutions.
r 2
gh
gh r 2

=
=
2. Wilhelmy Plate Methods
A thin mica plate or microscope slide is suspended from
the arm of a balance and dips into the liquid.
Detachment the container holding the liquid is
gradually lowered and the pull on the balance at the
point of detachment is noted



Staticfor measuring changes in surface tension. The
change in the force required to maintain the palte at
constant immersion as the surface tension alters is
measured
) ( 2
. det
y x W W + =
X =length of the plate
Y= breadth of the plate
W=weigh (at zero contact angle)
The Wilhelmy Plate Method
a) detachment
b) static

3. Ring Method
The force required to detach a ring from a
surface or interface is measured either by
suspending the ring from the arm of a balance
or by using torsion-wire arrangement (du
Noy tensiometer)

R
F
t
|

4
=
F= the pull of the ring
R=the mean radius of the ring
=correction factor
The Du Noy Ring Method
Measure the force required to pull the ring from
the surface of the liquid or an interface by
suspending the ring from one arm of a sensitive
balance
Water
F
R
The Correction Factor
The correction factor takes into account of the
small droplets that are pulled up by the ring
when it detaches from the surface

4. Drop Weight/Drop Volume Method
A stream of liquid (e.g., H
2
O) falls
slowly from the tip of a glass tube as
drops
Drop Weight Method
The drop weight is found by
Counting the number of drops for a specified
liquid volume passing through the tip;
Weighing a counted number of drops
Vg= mg = 2t rg|
A correction factor - F
| r/v
1/3
5. Sessile Drop Method
The surface tension of a liquid may be
obtained from the shape and size of a
sessile drop resting on a horizontal
surface
u
e
Surface
Sessile Drop
h
Sessile Drop Method (Contd)
Three techniques for obtaining the surface
tension from the image of the sessile drop
Measure the height of the top of a large sessile
drop above its maximum diameter.
Estimate the shape factor of the drop from the
coordinates of the drop profile.
Fit the drop profile to ones that are generated
theoretically.
Drop Profiles
The sessile drop method may also be used to
obtain the value of the equilibrium contact
angle.
Contact angle, u
e
< 90
u
e

The Maximum Bubble Pressure
Method
The maximum pressure required to force a
bubble through a tube is related to the
surface tension of the liquid.

gas stream
b
l
The Bubble Pressure Technique
The maximum bubble pressure is related to the
surface tension of the liquid as follows
P = g l A + 2 / b
A = the density difference between the liquid and
the vapour
b = radius of curvature at the apex of the bubble
l = hydrostatic height to the bottom of the bubble
g = 9.807 m / s
2

The Differential Maximum Bubble
Pressure Method
Two probes of different diameters.
A differential pressure is generated, AP.
b
2

gas stream
b
1

z
2

z
1

t
The Differential Bubble Pressure
Equations
The maximum bubble pressure is related to the
surface tension of the liquid as follows
AP = g z
1
A
1
+ 2 / b
1
- g z
2
A
2
+ 2 / b
2
A
1
= the density difference between the liquid
and the vapour of the first bubble
A
2
= the density difference between the liquid
and the vapour of the second bubble
z
1
= the distance from the tip to the bottom, of
the first bubble
z
2
= the distance from the tip to the bottom, of
the second bubble
Methods of Measuring Surface Tension
Method Pure Liquids Solutions
Wilhelmy
Plate
quick and
easy to
operate
Good, suitable
when ageing
occurs
Du Nuy Ring Satisfactory n/a
Sessile Drop Very Good Good when
surface
ageing occurs
Drop Weight Suitable Poor when
surface
ageing occurs
Capillary
Height
Very Good n/a if
u = 0
Bubble
pressure
Very Good Good when
ageing occurs
Molecular Contributions to an Oil-
water Interfacial Tension






= Oil = water
Oil Phase
Water Phase

oil

water
(
oil
x
d
water
)
1/2
(
oil
x
d
water
)
1/2
Surface Tension Examples
Walking on water: Small insects
such as the water strider can walk
on water because their weight is
not enough to penetrate the
surface.
Floating a needle: If carefully
placed on the surface, a small
needle can be made to float on the
surface of water even though it is
several times as dense as water. If
the surface is agitated to break up
the surface tension, then needle
will quickly sink
Contd
Don't touch the tent!: Common tent materials are
somewhat rainproof in that the surface tension of
water will bridge the pores in the finely woven
material. But if you touch the tent material with your
finger, you break the surface tension and the rain will
drip through.
Washing with cold water: The major reason for using
hot water for washing is that its surface tension is
lower and it is a better wetting agent. But if the
detergent lowers the surface tension, the heating
may be unneccessary


A spreading drop u
e
< 90
u
e

Solid Surfaces/Different Contact
Angles
Examine the following two surfaces.

A drop with a contact angle << 90
u
e

The Derivation of Youngs Equation

la

sa

ls
u
e
change in the liquid-solid
interfacial area = dA
dA
u
e
change in the solid-air
interfacial area = - dA
change in the liquid-air
interfacial area = dA Cos u
e
Youngs Equation
For a liquid (as a drop or at at the surface of
a capillary) making a contact angle u
c
with
the solid surface
c la sl sa
Cos u + =
= Cos
la
sl sa
c


u
Adhesional Wetting
The ability of the liquid to wet the solid will
be dependent on its ability to stick to the
solid




liquid droplets
Solid Surface

la
droplets adhering
to solid surface

sl
from the Young Equation
W
G
A
A
A
sa la sl
=

= +
A

u
sa sl la
Cos = +
e
W Cos
A la e
= + u ( ) 1
Note: the solid is completely
wetted if u
e
= 0; it is partially
wetted for finite values of u
e
.
Immersional Wetting
Immerse a solid substance in a pure
liquid or solution
area of the solid-air interface decreases
interfacial contact between solid and
liquid is increased
solid particle
Water

sa
immersed
solid particle

sl
Work required to immerse the solid in the
liquid
Examine the difference ion the solid-air
surface tension and the solid-liquid interfacial
tension



sl sa
I
I
A
G
W =
A
=
Applying youngs equation



e la
I
I
Cos
A
G
W u =
A
=
If
sa
>
sl
, spontaneous wetting while
if
sa
<
sl
, work must be done to wet
the surface
Objectives:
students are able to
Describe the action of surfactant
Explain the effect of detergent in dirt removing
Explain the effect of temperature in surface
tension and interfacial tension

Video 4 (the affect of detergent/soap
adding to surface tension)

How surfactant work

53
What are surfactants?
Emulsifier, Dispersant, Wetting agent
Common examples:
cleaning dirty clothes and kitchenware,
writing on paper with a pen,
greasing of cooking surfaces
Use of surfactants in industry:
emulsion polymerisation, paper coating
food, pharmaceuticals, cosmetics
The Function of Detergency
The function of detergency or cleaning is a
complex combination of all functions. The
surface to be cleaned and the soil to be
removed must initially be wet and the soils
suspended, solubilised, dissolved or separated
in some way so that the soil will not just re-
deposit on the surface in question

Explain these pictures