Molecular properties

Surface and interfacial tension

Surface tension is a property of the surface of
a liquid that allows it to resist an external force
In dealing with multiphase systems, it necessary
to consider the effect of the forces at the interface
when to immiscible fluid are in contact.
When these two fluids are liquid and gas, the
term surface tension is used to describe the
forces acting on interface.
When the interface is between two liquid, the
acting force are called interfacial tension.
Surface/Interfacial Tension
Surface tension: the
contracting force per unit
length around the perimeter of
a surface if the surface
separates gas from liquid or
solid phases.
Interfacial tension refers to
the same contracting force if
the surface separates two
nongaseous phases, e.g. oil
droplet in water.

Unit: dynes/cm or mN/m
(1 dyne/cm = 1 mN/m)
Shape of water droplet is
determined by surface tension
of water on a surface
Surface tension of water
enables water strider to
stay
afloat
Surface/Interfacial Tension
More definitions:
Surface tension is the reversible work required to
create a new area of a liquid.

Unit: energy per unit surface area; i.e. erg/cm2, or
mJ/m2
Significance:
Transport of molecules from bulk to surface region,
across phase boundaries, especially in micro-scale
phenomena
In nature and biological systems
Surface tensions of common
liquids
SUBSTANCE
SURFACE
TENSION
water H(OH) 72.7 dyne/cm
diethyl ether (CH
3
-
CH
2
)
2
O
17.0
benzene C
6
H
6
40.0
glycerin C
3
H
2
(OH)
3
63
mercury (15C) 487
n-octane 21.8
sodium chloride
solution (6M in water)
82.5
sucrose solution
(85% in water)
76.4
sodium oleate (soap)
solution in water
25
The table shows the surface
tensions of several liquids at
room temperature.

Note especially that hydrocarbons
and non-polar liquids such as ether
have rather low values

One of the main functions of soaps
and other surfactants is to reduce the
surface tension of water

Mercury has the highest surface
tension of any liquid at room
temperature. It is because mercury
does not flow in the ordinary way, but
breaks into small droplets that roll
independently.
Water retention and
transport in plants
Water strider walking on water surface
Foam/Emulsions
Phenomenon of Surface Tension

There is a nett force of attraction between the
molecules of water (or any other liquid)
holding the molecules together.
For a molecule in the middle of the liquid,
these forces, acting equally in all directions,
more or less balancing out.
For a molecule in the surface layer of the
liquid, the forces do not balance out, and all
the molecules in the surface layer are pulled
towards each other and towards the bulk of
the liquid.
This brings these molecules closer to their
neighbors until increasing forces of repulsion
create a new balance, and gives rise to the
phenomenon of surface tension.

When an object falls onto the
surface, it has to push the water
molecules apart.
If the effect of the weight of the
object is insufficient to match the
attractive forces between
molecules in the surface layer, the
object will not enter the surface.
Careful observation of the floating
needle will show that the water
surface is bent down under the
weight of the needle, the surface
tension causing it to behave as if
the needle was supported by a
flexible skin
Measurement of surface tension
Methods for measuring surface and interfacial tension three
will be discussed:
Capillary rise method
Ring (Du Nouy) tensiometer
Drop weight method (Stalagmometer)
The choice of the method for measuring surface and
interfacial tension depend on:
Whether surface or interfacial tension is to be
determined.
The accuracy desired
The size of sample.




Capillary rise method
The difference in pressure across a curved
meniscus results in the phenomenon of capillarity
A liquid which meets the surface of a fine pore or
tube will rise in it if the end of the tube dips into a
pool of the liquid.
The smaller the diameter of the tube, the higher will
be the capillary rise.
Capillary rise results from a combination of two
effects:
the tendency of the liquid to wet the surface of the tube
(measured by the value of the contact angle)
the action of the liquid's surface tension to minimize its
surface area.
h = elevation of the liquid (m)
= surface tension (N/m)
= contact angle (radians)
= density of liquid (kg/m
3
)
g = acceleration of gravity(m/s
2
)
r = radius of tube (m)
Ring (Du Nouy) tensiometer
This method utilizes the interaction
of a platinum ring with the surface
being tested.
The ring is submerged below the
interface and subsequently raised
upwards.
As the ring moves upwards it raises
a meniscus of the liquid. Eventually
this meniscus tears from the ring and
returns to its original position.
Prior to this event, the volume, and
thus the force exerted, of the
meniscus passes through a
maximum value and begins to
diminish prior to the actually tearing
event.
13
1 - The ring is above the surface
and the force is zeroed.
2 - The ring hits the surface and
there is a slight positive force due to
the adhesive force between ring
and surface.
3 - The ring must be pushed
through the surface (due to the
surface tension) which causes a
small negative force.
4 - The ring breaks through the
surface and a small positive force is
measured due to the supporting
wires of the ring.
5 - When lifted through the surface
the measured force starts to
increase.
6 - The force keeps increasing until
7 - The maximum force is reached
8 - After the maximum there is a
small decrease of in the force until
the lamella breaks.
The process is shown in the diagram below:
Drop weight method (Stalagmometer)
A stalagmometer is used for measuring or
comparing surface tensions of liquids.
This method is based on the direct
proportionality between the surface
tension and the weight of liquid drops from
a vertical capillary tube.
The stalagmometer is a pipette-like glass
tube with a smooth capillary end C and
two calibrated portions of the stem G with
an intervening bulb B
In the experiments, the drops of the
specific fluid are flowing slowly from the
tube in a vertical direction.

The drops hanging on the bottom of the tube start to
fall when the volume of the drop reaches the
maximum value which is dependent on the
characteristic of the solution.
In this moment, the weight of the drops is in
an equilibrium state with the surface tension.

Based on the Tates law:




The drop is falling when the weight (mg) is equal to
the circumference (2r) multiplied by the surface
tension (). The surface tension can be calculated
when we know the radius of the tube (r) and the mass
of the fluid droplet (m).

Surfactants
The surface tension of water can be
reduced to about one-third of its normal
value by adding some soap or synthetic
detergent.
These substances known as surfactants
-generally hydrocarbon molecules having
an ionic group on one end.
The ionic group, being highly polar, is
strongly attracted to water molecules
(hydrophilic). The hydrocarbon
(hydrophobic) portion is just the opposite
Inserting surfactant into water would break up the
local hydrogen-bonding forces and is therefore
energetically unfavorable.
The surfactant molecules migrate to the surface
with their hydrophobic ends sticking out,
effectively creating a new surface.
Because hydrocarbons interact only through very
weak dispersion forces, this new surface has a
greatly reduced surface tension.