SURFACE

TENSION

SURFA
CE
TENSI
ON

Surface Tension is defined as the tension of

the surface film of a liquid caused by the
attraction of the particles in the surface layer
by the bulk of the liquid, which tends to
minimize
area.
It is due tosurface
the phenomena
of surface tension that
the drops of water tend to assume a spherical
shape to attain minimum surface area.

 The effect of surface tension on the interface area between two liquids may be equivalently
defined either through force or through energy.
1. In terms of force: surface tension of a liquid is one-half the force per unit length required to
keep still a movable side of a frame over which the liquid is stretched (say, into a thin film).
To visualize this, imagine a rectangular frame which is composed of
three unmovable sides that form a "U" shape, and the fourth,
movable side that can slide, along the two parallel unmovable sides,
either towards or away from the unmovable "bottom" side of the
"U." Now imagine that a liquid is stretched into a thin film on this
frame, much like soap water gets stretched over a bubble-blowing
ring after the ring is dunked into soapy water. Then it is observed
that the movable side will be pulled by the film towards the
"bottom" of the "U"; the force F required to stop the movable side
from sliding turns out to be proportional to the length L of the
movable side. Thus the ratio F/L depends only on the intrinsic
properties of the liquid (composition, temperature, etc.), but not on
its geometry; for example, if the frame has a more complicated
shape, the ratio F/L, with L the length of the movable side and F the
force required to stop it from sliding, is found to be the same for all
shapes. We therefore define the surface tension as

=F/2L
The reason for the 1/2 is that the film has two sides, each of which
contributes equally to the force; so the force contributed by each

2. In terms of energy: surface tension of a liquid is the ratio of 1) the

change in the energy of the liquid, and 2) the change in the surface area
of the liquid (that led to the change in energy).
This can be easily related to the previous definition in terms of force:
If F is the force required to stop the side from starting to slide, then this is also the force
that would keep the side in the state of sliding at a constant speed (by Newton's Second
Law).
But if the side is moving, then the surface area of the stretched liquid is increasing
while the applied force is doing work on the liquid. This means that increasing the
surface area increases the energy of the film.
The work done by the force F in moving the side by distance x is
W=F * x
At the same time the total area of the film increases by A =2 L x (the factor of 2 is
here because the liquid has two sides, two surfaces). Thus, multiplying both the
numerator and the denominator of = (1/2)F/L by
x, we get

= F/2L= F x/2L x=
W/A

SURFACE TENSION
1. For the phenomena of surface tension to come into picture, a surface of
separation between two fluids (interface) has to be defined. Without any
interface, for a single expense of fluid, the concept of surface tension
does not exist.
2. Usually, when two fluids are separated by an interface (i.e. two gases or
two liquids) the phenomena is called INTERFACIAL TENSION. The term
surface tension is used when the interface is defined by a liquid and a
gas.
3. Surface tension is not the property of the liquid itself but it is the binary
property of the liquid and the gas forming the interface.
4. The work done in bringing a molecule from the interior of a liquid onto
the surface depends not only on the cohesive forces among the
molecules of the liquid but also on the adhesive forces between the
liquid and gas molecules.

CONCEPT OF SURFACE
ENERGY

Consider a liquid air interface. A

molecule inside the liquid is attracted
by other surrounding molecules
through intermolecular cohesive forces.
From kinetic theory of matter the
average attractive force over a time in
a molecule is same in all the directions.
These attractive forces are
considerable up to distance 2 to 3
times the intermolecular separation.
Therefore we can assume a sphere of
influence of attractive forces over the
molecule.
A mechanical work against a net inward
cohesive force is done when a molecule
is brought from the interior of the liquid
to the interface. This physically means
that if we want to create a liquid
surface, or if we want to increase the
area of an already existing interface,

TENSION
1. TEMPERATURE
Surface tension is dependent on
temperature. For that reason,
when a value is given for the
surface tension of an interface,
temperature must be explicitly
stated. The general trend is that
surface tension decreases with
the increase of temperature,
reaching a value of 0 at the
critical temperature.There are
only empirical equations to
relate surface tension and
temperature

Etvs rule
The Etvs rule, named after the Hungarian physicist Lornd (Roland) Etvs (18481919)
enables the prediction of the surface tension of an arbitrary liquid pure substance at all
temperatures. The density, molar mass and the critical temperature of the liquid have to be
known. At the critical point the surface tension is zero.
The assumptions of the Etvs rule are:
1. The surface tension is a linear function of the temperature.
This assumption is approximately fulfilled for most known liquids. When plotting the surface
tension versus the temperature a fairly straight line can be seen which has a surface
tension of zero at the critical temperature.
The Etvs rule also gives a relation of the surface tension behaviour of different liquids in
respect to each other:
2. The temperature dependence of the surface tension can be plotted for all liquids in a
way that the data collapses to a single master curve. To do so either the molar mass, the
density, or the molar volume of the corresponding liquid has to be known.

If V is the molar volume and Tc the critical temperature of a liquid the surface tension is given by
where k is a constant valid for all liquids. The Etvs constant has a value of 2.1107 J/(Kmol2/3).
More precise values can be gained when considering that the line normally passes the temperature axis
6 K before the critical point:
The molar volume V is given by the molar mass M and the density
The term

is also referred to as the "molar surface tension" mol :

As John Lennard-Jones and Corner showed in 1940 by means of the statistical mechanics the constant k
is nearly equal to the Boltzmann constant.
For water, the following equation is valid between 0 and 100 C.

Guggenheim-Katayama

is a constant for each liquid and n is an empirical factor, whose value is 11/9 for organic
liquids. This equation was also proposed by van der Waals, who further proposed that this
constant could be given by the expression,

Where
is a universal constant for all liquids, and
is the critical pressure of the liquid
(although later experiments found
to vary to some degree from one liquid to another)
Both Guggenheim-Katayama and Etvs take into account the fact that surface tension
reaches 0 at the critical temperature, whereas Ramay and Shields fails to match reality at
this endpoint.

2. SOLUTE CONCENTRATION
Solutes can have different effects on surface tension depending on their structure:
Little or no effect, for example sugar
Increase surface tension, inorganic salts
Decrease surface tension progressively, alcohols
Decrease surface tension and, once a minimum is reached, no more effect: surfactants
What complicates the effect is that a solute can exist in a different concentration at the
surface of a solvent than in its bulk. This difference varies from one solute/solvent combination
to another.
Gibbs isotherm states that

is known as surface concentration, it represents excess of solute per unit area of the
surface over what would be present if the bulk concentration prevailed all the way to the
surface. It has units of mol/m2
C is the concentration of the substance in the bulk solution.
R is the gas constant and T the temperature
Certain assumptions are taken in its deduction, therefore Gibbs isotherm can only be
applied to ideal (very dilute) solutions with two components.

3. INTERMOLECULAR FORCES
If force of attraction between molecules is high then surface tension will
also be high.

4.HYDROGEN BONDING
Liquids that have H-bond such as water, have high values of
surface tension.

Unit of surface tension

N/m (in S.I system)
Dyne/cm (in C.G.S system)
Joule/m2 (in S.I system)
Erg/cm2 (in C.G.S system)

CAPILLARITY
ability of aliquidto flow in narrow spaces without the assistance of,
and in opposition to, external forces likegravity.

Phenomena and physics of capillary

action
A common apparatus used to
demonstrate the first phenomenon
is thecapillary tube. When the
lower end of a vertical glass tube is
placed in a liquid, such as water, a
concavemeniscusforms.Adhesion
occurs between the fluid and the
solid inner wall pulling the liquid
column up until there is a sufficient
mass of liquid forgravitational
forcesto overcome these
intermolecular forces.

The contact length (around the

edge) between the top of the liquid
column and the tube is proportional
to the diameter of the tube, while the
weight of the liquid column is
proportional to the square of the
tube's diameter. So, a narrow tube
will draw a liquid column higher than
a wider tube will.

Height of a meniscus

The heighthof a
liquid column is
given by:

Variation of Height
Water
height in a
capillary
plotted
against
capillary
diameter

Capillarity is the effect of Surface Tension

It can be seen everywhere around us.

Examples

In plants and trees

The capillary action is
enhanced in trees by branching,
evaporation at the leaves
creating depressurization, and
probably byosmotic
pressureadded at the roots and
possibly at other locations inside
the plant, especially when
gathering humidity withair
roots.

Examples

Capillary action is essential

for the drainage of constantly
producedtearfluid from the
eye.
Capillary action is observed
inthin layer chromatography,
in which a solvent moves
vertically up a plate via
capillary action. In this case
the pores are gaps between
very small particles.

Examples

Capillary action
drawsinkto the tips
offountain pennibsfrom
a reservoir or cartridge
inside the pen.

MATHEMATICS
BACKGROUND OF
SURFACE TENSION

A SPHERICAL BALL RESTING ON THE

SURFACE OF WATER

Governing Equations

The motion of a fluid of uniform density and viscosity is governed

by the Navier-Stokes equations, which represent a continuum
statement of Newtons laws.
(u/t + u u)= p + F + 2u
1
u=0
2
This represents a system of 4 equations in 4 unknowns (the fluid
pressure p and the three components of the velocity field u). Here F
represents any body force acting on the fluid.
Surface tension acts only at the free surface; consequently, it does not
appear in the NavierStokes equations, but rather enters through the
boundary conditions.

Surface Tension and Bubbles

Thesurface tensionof water provides the necessary wall tension

for the formation of bubbles with water. The tendency to
minimize that wall tension pulls the bubbles into spherical
shapes.
Thepressuredifference between the inside and outside of a
bubble depends upon the surface tension and the radius of the
bubble. The relationship can be obtained by visualizing the
bubble as two hemispheres and noting that the internal pressure
which tends to push the hemispheres apart is counteracted by
the surface tension acting around the cirumference of the circle.

Bubble Pressure

For a bubble with two surfaces providing tension

tension, the pressure relationship is:

The net upward force on the top hemisphere of the

bubble is just the pressure difference times the
area of the equatorial circle:

Thesurface tensionforce downward around circle is

twice the surface tension times the circumference,
since two surfaces contribute to the force.

This gives

Capillary Action

Capillary actionoccurs when the adhesionto the walls is

stronger than thecohesiveforces between the liquid molecules.
The height to which capillary action will take water in a uniform
circular tube is limited bysurface tension. Acting around the
circumference, the upward force is

SOME IMPORTANT DIMENSIONLESS

NUMBERS

Re = Ua/ = INERTIA/VISCOSITY = Reynolds number

Fr = U2/ga = INERTIA/GRAVITY = Froude number

Bo = ga^2/ = GRAVITY/CURVATURE = Bond number

We =U^2a/ = INERTIA/CURVATURE = Weber number

Ca =U/ = VISCOUS/CURVATURE = Capillary number

Circular Sheet of Fluid

when a vertical fluid jet strikes a small horizontal circular

impactor then it will create a cicular sheet of fluid,if the flow
rate is sufficiently high that gravity does not influence the sheet
shape.
The sheet radius is prescribed by a balance of radial forces;
specifically, the inertial force must balance the curvature force:
u^2h = 2
3
Continuity requires that the sheet thickness h depend on the
speed u, jet flux Q and radius r as
h =Q/2ru
4

Experiments (specifically, tracking of

particles suspended within the sheet)
indicate that the sheet speed u is
independent of radius; consequently,
the sheet thickness decreases as 1/r.
Solving equation 3 and 4 yields the
sheet radius, or so-called Taylor radius:
r =Qu/4

CONTACT ANGLE AND WETTING

PROPERTIES

The topic of wetting has received tremendous interest from both

fundamental and
applied points of view. It plays an important role in many industrial
processes, such
as oil recovery, lubrication, liquid coating, printing, and spray quenching .
recent years, there has been an increasing interest in the study of
superhydrophobic
surfaces, due to their potential applications in, for example, self-cleaning,
Wettability studies usually involve the measurement of contact angles as
nanofluidics,
the primary data, which indicates the degree of wetting when a solid and
and electro wetting .
liquid interact. Small contact angles (<90) correspond to high
wettability,
while large contact angles (>90) correspond to low
wettability.

SURFACE TENSION AND CONTACT ANGLEYOUNGS EQUATION

Consider a liquid drop resting on a flat, horizontal solid surface (Fig. 1.1). The contact angle
is defined as the angle formed by the intersection of the liquid-solid interface and the liquid
vapor interface (geometrically acquired by applying a tangent line from the contact point
along the liquid-vapor interface in the droplet profile). The interface where solid, liquid, and
vapor co-exist is referred to as the three phase contact line. Figure 1.1 shows that a small
contact angle is observed when the liquid spreads on the surface, while a large contact
angle is observed when the liquid beads on the surface. More specifically, a contact angle
less than 90 indicates that wetting of the surface is favorable, and the fluid will spread
over a large area on the surface; while contact angles greater than 90 generally means
that wetting of the surface is unfavorable so the fluid will minimize its contact with the
surface and form a compact liquid droplet. For example, complete wetting occurs when the

contact angle is 0 , as the droplet turns into a flat puddle.

For superhydrophobic
surfaces, water contact
angles are usually greater
than 150, showing almost
no contact between the
liquid drop and the surface,
which can rationalize the
lotus effect [13].
Furthermore, contact
Surface tension is caused by the
angles are not limited to
unbalanced forces of liquid molecules
at the surface
the liquid vapor interface
on a solid; they are also
As
first described
by Thomas Young in 1805, the contact angle of a liquid drop on
applicable
to the liquidan
ideal
solid surface
is defined by the mechanical equilibrium of the drop under
liquid
interface
on a solid.
the action of three interfacial tensions :

lv cos Y = sv sl
where lv , sv, and sl represent the liquid-vapor, solid-vapor, and solid-liquid
interfacial tensions, respectively, and Y is the contact angle is usually referred to
as Youngs equation, and Y is Youngs contact angle.

METHODS OF
MEASUREMENT
(SURFACE TENSION)

CAPILLARY RISE METHOD

This is the oldest method used for surface tension
determination .
A consequence of the surface tension appearance at the
liquid/gas interface is moving up of the liquid into a thin
tube, that is capillary, which is usually made of glass.
This phenomenon was applied for determination of the
liquid surface tension.

For this purpose, a thin circular capillary

is dipped into the tested liquid.
Along the perimeter of the meniscus
there acts a force due to the surface
tension presence.
f1= 2r cos
where ,r = the capillary radius
= the liquid surface tension
= the wetting contact angle

-(1)

The force f1 in Eq.(1) is equilibrated by the gravity force f2

f2 = r2hdg

-(2)

In equilibrium (the liquid does not moves in the capillary)

i.e. f1 = f2

DROP VOLUME METHOD

(STALAGMOMETRIC METHOD)

The stalagmometric method is one of the most common

methods used for the surface tension determination.
For this purpose the several drops of the liquid leaked out of
the glass capillary of the stalagmometer are weighed.
If the weight of each drop of the liquid is known, we can also
count the number of drops which leaked out to determine the
surface tension.

The pendant drop at the tip starts to

detach when its weight (volume)
reaches the magnitude balancing
the surface tension of the liquid.
This method was first time described
by Tate in 1864 who formed an
equation, which is now called the
Tates law.
Where: W is the drop weight, r is the
capillary radius, and is the surface
tension of the liquid.

The drop starts to fall down when its weight is equal to the
circumference multiplied by the surface tension.
In the case of a liquid which wets the stalagmometer's tip the r
value is that of the outer radius of the capillary and if the liquid
does not wet the r value is that of the inner radius of the
capillary .

Up to 40% of the drop volume may be left on the

stalagmometer tip. Therefore a correction f has to be
introduced to the original Tate's equation.
Harkins and Brown found that the factor f is a function of the
stalagmometer tip radius, volume of the drop v, and a
constant, which is characteristic of a given stalagmometer.

MAXIMUM BUBBLE PRESSURE

METHOD
This method is also called the bubble pressure method.
In this method air gas bubble is blown at constant rate
through a capillary which is submerged in the tested liquid.
The pressure inside the gas bubble is increasing. Its shape
from the very beginning is spherical but its radius is
decreasing. This causes the pressure increase inside it and the
pressure is maximal when the bubble has a hemispherical
size. At this moment the bubble radius equals to the radius of
the capillary, inner if the liquid wets the tip of the capillary
and outer if it does not wet it.

The maximum pressure

difference Pmax is described by
the Laplace equation.

If the capillary tip is dipped into

the liquid to a depth h from the
liquid surface, then the correction
reducing Pmax should be
introduced. The correction is due
to the additional hydrostatic
pressure caused by the liquid
layer of thickness h, the pressure
that the detaching bubble has to
overcome,

For very accurate determination of the surface tension, other

corrections are needed. They can be found in special tables.
The accuracy of this method is about several tenth of percent
and it is applied both for surface and interface tensions
measurement.

Tensiometer
A Tensiometer as it applies to physics is an instrument used to
measure the surface tension of liquids or surfaces
Tensiometers are used in research and development
laboratories to determine the surface tension of liquids like
coatings, lacquers or adhesives.
A further application field of tensiometers is the monitoring of
industrial production processes like parts cleaning or
electroplating.

Use of tensiometer for soil

testing
Equipment that measures the tension that water is holed in
soil. The tension readings are in the range from 0 to 0.80
atmospheres (80 centibars). In tensions above, air penetrates
into the pores of the ceramic cup. The result is, discontinuation
between the water in the columns of the ceramic cup to the
water in the soil columns.
The tension measured by tensiometer occurs due to capillary
tension (matrix potential) of the soil.
The measurements are not influenced by the osmotic pressure,
therefore in saline soils pre calibration is necessary.

Curves In
The
Tension
Level That
Tensiomet
er Is
Functional

TYPES OF
TENSIOMETER
Goniometer/Tensiometer:
Surface scientists sometimes use a Goniometer/Tensiometer to measure
the surface tension and interfacial tension of a liquid using the pendant or
sessile drop methods. A drop is produced and captured using a CCD
camera.
The drop profile is subsequently extracted, and sophisticate software
routines then fit the theoretical Young-Laplace equation to the
experimental drop profile.
The surface tension can then be calculated from the fitted parameters.
Unlike other methods, this technique requires only a small amount of liquid
making it suitable for measuring interfacial tensions of expensive liquids.

Measuring contact angle Goniometer

method
The droplet is deposited by a syringe pointed
vertically down onto the sample surface, and a
high resolution camera captures the image,
which can then be analyzed either by eye (with a
protractor) or using image analysis software
The size of the droplet can be increased
gradually so that it grows proportionally, and the
contact angle remains congruent. By taking
pictures incrementally as the droplet grows, the
user can acquire a set of data to get a good
average
If necessary, the receding contact angle can also
be measured by depositing a droplet via syringe
and recording images of the droplet being

Energy

Determining Surface

The Zisman Theory:

The Zisman theory simply defines the surface energy as being equal to the surface
energy of the highest surface energy liquid that wets the solid completely
That is to say, the droplet will disperse as much as possible, i.e. completely wetting the
surface, for this liquid and any liquids with lower surface energies, but not for liquids
with higher surface energies.
Since this probe liquid could hypothetically be any liquid, including an imaginary liquid,
the best way to determine the surface energy by the Zisman method is to acquire data
points of contact angles for several probe liquids on the solid surface in question, and
then plot the cosine of that angle against the known surface energy of the probe liquid
By constructing the Zisman plot, one can extrapolate the highest liquid surface
energy, real or hypothetical, that would result in complete wetting of the sample with a
contact angle of zero degrees

Du Noy Ring Tensiometer

This type of Tensiometer uses a platinum ring which is
submersed in a liquid. As the ring is pulled out of the
liquid, the tension required is precisely measured in
order to determine the surface tension of the liquid.
This method requires that the platinum ring be nearly
perfect; even
small blemish or scratch can greatly
alter the accuracy of the results.
A correction for buoyancy must be made. This method
is
considered inaccurate compared to the plate
method but is still widely used for interfacial tension
measurement between two liquids.

Wilhelmy Plate tensiometer

The Wilhelmy Plate tensiometer
requires a plate to make contact
with the liquid surface
It is widely considered the
simplest and most accurate
method for surface tension
measurement

Bubble pressure
Tensiometer
Due to internal attractive forces of a liquid,
air bubbles within the liquids are
compressed. The resulting pressure (bubble
pressure) rises at a decreasing bubble radius
The bubble pressure method makes use of
this bubble pressure which is higher than in
the surrounding environment (water). A gas
stream is pumped into a capillary that is
immersed in a fluid
The resulting bubble at the end of the
capillary tip continually becomes bigger in
surface; thereby, the bubble radius is
decreasing

The resulting bubble at the end of the capillary tip continually

becomes bigger in surface; thereby, the bubble radius is
decreasing
The pressure rises to a maximum level. At this point the bubble has
achieved its smallest radius (the capillary radius) and begins to
form a hemisphere. Beyond this point the bubble quickly increases
in size and soon bursts, tearing away from the capillary, thereby
allowing a new bubble to develop at the capillary tip. It is during
this process that a characteristic pressure pattern develops (see
picture), which is evaluated for determining the surface tension
Because of the easy handling and the low cleaning effort of the
capillary, bubble pressure Tensiometers are a common alternative
for monitoring the detergent concentration in cleaning or
electroplating processes

Du Noy-Padday method
This method uses a rod which is lowered into a
test liquid. The rod is then pulled out of the
liquid and the force required to pull the rod is
precisely measured
This is a rather novel method which is accurate
and repeatable. The Du Noy-Padday Rod Pull
Tensiometer will take measurements quickly
and unlike the ring and plate methods, will
work with liquids with a wide range of
viscosities