Subject Chemistry

Paper No and Title 10: Physical Chemistry –III (Classical Thermodynamics,

Non-Equilibrium Thermodynamics, Surface Chemistry,
Fast Kinetics
Module No and Title 24: Adsorption from solution: surface tension and
applications
Module Tag CHE_P10_M24

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 TABLE OF CONTENTS
1. Learning outcomes
2. Adsorption from solution
3. Surface tension and surface energy
4. Measurement of surface tension
5. Applications of surface tension
5.1 Capillary action
5.2 Formation of bubbles
6. Summary

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 1. Learning outcomes

After studying this module, you shall be able to:

 Know what is surface tension and surface energy

 Know how do we measure surface tension
 Study what are the applications of surface tension

2. Adsorption from solution

In the earlier modules, we have seen the adsorption of gases on the surface of a solid
adsorbent in detail. Now we shall discuss the second category of adsorption process,
which is clearly understood. This is the adsorption of the dissolved substances from the
solution.
Before we discuss this, we shall understand the phenomenon of surface tension and
surface energy, as they are related to adsorption.

3. Surface tension and surface energy

If we consider a close-packed arrangement of spherical molecules in a solid, we know

that each molecule in the bulk is bounded by twelve other molecules. Therefore, the bond
strength is ε/12, where, ε is the binding energy (cohesive energy) per molecule equal to
E/NA (where E is the cohesive energy per mole). However, if we consider a molecule on
the surface layer, then each such molecule is bounded by only nine neighbours.
Therefore, the total binding energy of the surface molecule is 9ε/12 = 3/4ε. Thus we see
that the surface molecule is bounded with only 75% of the binding energy as compared to

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 a molecule in the bulk. In other words, we can say that the surface molecule has higher
energy relative to a molecule in the bulk.
The same picture is true in the case of liquids. The molecules in bulk of the liquid are
surrounded by other molecules from all its sides (such that net force of attraction is zero).
However, the molecule at the surface is surrounded by more number of molecules inside
the liquid as compared to that in the vapor phase (Fig. 1a). It is well known that the

attractive forces tend to decrease the energy of the system and, in the present case, the
attractive forces are more predominant in the bulk of the liquid than at the surface. Thus,
we see that surface molecules are associated with higher energy as compared to those in
the bulk of the liquid. It is because of this extra energy of the surface molecules that they
experience a net inward pull and move into the bulk of the liquid, that is, from a state of
high energy to a state of low energy. Consequently, number of molecules at the surface
become less as compared to that in the bulk. As a result of this, the distance between any
two surface molecules becomes greater than that in the bulk. In order to acquire a normal
distance between them as before, the surface molecules tend to move closer to one
another, i.e., the surface of the liquid tends to contract as if it were under some sought of
tension. This force that tends to contract the surface area of a liquid is called as ‘surface
tension’.
Mathematically, it is defined as the force acting per unit length at right angles to any line
drawn on the surface of the liquid. It is represented by ‘ϒ’.

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 (a) (b)
Fig. 1: (a) Surface tension (b) A stretched liquid film on a frame
If we wish to increase the area of the surface, then we need to bring some molecules from
the bulk of the liquid to its surface. This process requires energy and therefore some work
will be done in bringing the molecules from the bulk to the surface, against the inward
attractive pull. The amount of work done in increasing the surface area by unity is termed
as ‘surface energy’. This surface energy acts as a measure of the inward pull, as larger
the attractive forces, more will be the amount of work done.
Mathematically, this can be explained as follows. Let us consider a liquid film stretched
on a movable frame of length ‘l’ (Fig. 1b) and we wish to increase the surface area of the
film by an amount ‘dA’. The work done in the process will be ‘f dx’, where f is the force
required to move the wire by a distance x. During the process, the Gibbs energy of the
film increases by ‘ϒ dA’, where ϒ is the surface Gibbs energy per unit area.
Equating the two, we get,
f dx = ϒ dA (1)
But dA = 2 (l dx) (2)
(The factor two appears as the film has two sides)
Substituting equation (2) in equation (1), we get,
f dx = ϒ (2l) dx
or, f = ϒ (2l) (3)

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 The total length of the film in contact with the wire is ‘2l’. Thus, the force acting per unit
length, i.e., surface tension, ϒ = f/(2l). This force of surface tension opposes the increase
in the surface area.

The SI unit of surface tension ,ϒ, is N/m, which is equal to Gibbs energy per unit area, in
J/m2. Thus, surface tension is numerically equal to surface energy.
𝐹𝑜𝑟𝑐𝑒 𝑁 𝑑𝑦𝑛𝑒𝑠
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑡𝑒𝑛𝑠𝑖𝑜𝑛 = = (𝑆𝐼 𝑢𝑛𝑖𝑡𝑠) 𝑜𝑟 (𝐶𝐺𝑆 𝑢𝑛𝑖𝑡𝑠)
𝐿𝑒𝑛𝑔𝑡ℎ 𝑚 𝑐𝑚

𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑓𝑜𝑟𝑐𝑒 ✕ distance

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 = =
𝑎𝑟𝑒𝑎 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 2
𝑁 𝑑𝑦𝑛𝑒𝑠
= (𝑆𝐼 𝑢𝑛𝑖𝑡𝑠) 𝑜𝑟 (𝐶𝐺𝑆 𝑢𝑛𝑖𝑡𝑠)
𝑚 𝑐𝑚
Both have the same dimensions (MT-2)

4. Measurement of surface tension

If we can measure the force required to stretch the liquid film on a movable frame, we
can measure the surface tension. There are a number of devices made for the purpose for
measuring surface tension.
A device called, duNouy tensiometer or the ring-pull device, is one such convenient and
simplest device used (Fig. 2). The device is calibrated by the addition of small masses to
the end of the beam and setting up of the torsional scale to keep the beam in level. For
measuring the surface tension, the ring is placed on the beam and the level of the liquid,
whose surface tension is to be measured, is raised until the ring is completely immersed
in it and the beam is leveled. Now the height of the platform on which liquid is kept is
lowered and the ring is pulled out slowly by turning the torsion wire. Through the
experiment, the beam level is maintained. When the ring just pulls free from the liquid,
the torsion scale is read.
CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 The reading can be converted in to an equivalent force, F, with the help of calibration.
This force can be obtained by multiplying the length of the wire that is in contact with the
ring, and the surface tension γ. The former is two times the circumference as the liquid is
in contact with both the inside and outside of the ring. An empirical correction factor ‘f’
is also introduced into the expression. This accounts for the shape of the liquid being
pulled up and the fact that the diameter of the wire itself, 2r, is not zero. Thus, we have
the expression as:
𝐹 = 4𝜋𝑅𝛾𝑓
(4)
The values of ‘f’ as a function of R and r can be obtained from the literature. Making use
of the equation (4), we can find the surface tension of the liquid.
Another method similar to the ring-pull method is the Wilhelmy slide method. An
extremely thin plate such as a microscope cover galss or a mica sheet is hung from one
arm of the balance and is allowed to dip in the solution (Fig. 3). The downward force
acting on the slide due to surface tension is ‘γ × p’, where ‘p’ is the perimeter of the
slide. If ‘F’ and ‘Fa’ are the forces acting downward when the slide is touching the
surface and when it is suspended freely in air respectively, then,
𝐹 = 𝐹𝑎 + 𝛾𝑝
(5)

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 Fig. 2: duNouy ring-pull apparatus for measuring surface tension of a liquid

This equation (5) is based on the assumption that the depth of the immersion is
negligible. It can be used to measure equilibrium surface or interfacial tension at an air–
liquid or liquid–liquid interface.

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 Fig. 3: Wilhelmy slide apparatus

Another device commonly used in laboratories to measure surface tension of liquids is

the stalagmometer (Fig. 4). It consists of a small glass bulb. This is attached to a fine
capillary with a sharp edge, from which the liquid falls drop by drop. The method is
based on the assumption that the force of surface tension acts around the circumference
of the capillary and holds the two parts of the liquid column together. This force acts in
the upward direction and is balanced by the force due to the weight of the liquid, acting in
the downward direction. As the size of the liquid drop increases, its weight increases.
When the latter become infinitesimally greater than the upward force of surface tension,
the drop breaks off from the apparatus and falls down. Care must be taken that the drop
size and drop rate should be small so that the drop falls off under its own weight only.
If ‘r’ is the radius of the capillary tube, and ‘m’ is the mass of the liquid drop, then:
Upward force = Downward force

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 (2 𝜫 𝒓)𝜸 = 𝒎𝒈 (6)
where, g = acceleration due to gravity

Fig. 4: Stalagmometer
To avoid the measurement of ‘r’, one makes use of the relative method, i.e., the
experiment is repeated with a liquid (say, water), whose surface tension is known at that
temperature.

Thus, we have:
𝑚1 𝑔 = 2𝜋𝑟𝛾1 𝑎𝑛𝑑 𝑚𝑤 𝑔 = 2𝜋𝑟𝛾𝑤

𝑜𝑟 𝛾 𝑚1 𝛾𝑤
1 = 𝑚𝑤
(7)

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 In the ‘drop weight method’, mass of ‘n’ drops of the liquid (or water) are calculated
and from this, the mass of a single drop of liquid (or water) can be calculated.
In the ‘drop number method’, the number of drops in a definite amount of liquid
volume, say V, is counted. The mass of a single drop of a liquid is then counted from the
density measurements as follows:
𝑉𝜌1
𝑚1 = 𝑣1 𝜌1 = (8)
𝑛1

where, 𝑚1 and 𝑣1 are the mass and volume of single drop of liquid, respectively, n1 is
the number of drops and V is the total volume of the liquid.
If we take the reference liquid as water, then we have:
𝛾1 𝑚1 𝜌1 𝑛𝑤
= =
𝛾𝑤 𝑚𝑤 𝜌𝑤 𝑛1
(9)

5. Applications of surface tension

Surface tension is an important phenomenon that has many applications. Some of them
are discussed as follows:

5.1 Shape of liquid drops

We have studied that surface tension reduces the surface area of a liquid. Since for a
given volume, sphere has the least surface area, the drops of a liquid are spherical in
nature, in the absence of gravity.
5.2 Capillary action
Have we ever wondered how does underground water rise on to the surface of earth or
inside the plants or how oil rises in a wick! These all familiar examples are of capillary
action.

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 When a capillary tube is partially immersed in a liquid, there occurs either a rise or a fall
of liquid level inside the tube. In other words, the liquid is present at different levels
inside and outside the capillary tube; the nature of liquid-vapor interface being different-
flat outside and curved inside the tube. This phenomenon of rise and fall of liquid in a
capillary tube is called ‘capillary action’. It occurs due to surface tension of the liquid.
The two cases are discussed in detail as follows:
If the adhesive forces (attractive forces between unlike molecules, i.e., liquid molecules
and solid surface of capillary tube) are greater than the cohesive forces (attractive forces
between like molecules, i.e., between liquid molecules), then the liquid has a tendency to
spread on the solid surface of the capillary tube. These types of liquids are called wetting
liquids. They rise in the capillary tube with their meniscus facing concave upwards. The
angle of contact is less than 90o. The latter is defined as the angle measured within the
liquid between the wall of the capillary tube and the tangent drawn at the liquid surface of
the tube (Fig. 5).

Fig. 5: Measurement of contact angle

On the other hand, if the cohesive forces are greater than the adhesive forces, then the
liquid has a tendency to detach from the solid surface of the capillary tube. These types of
liquids are called as non-wetting liquids. Their level falls inside the capillary tube with
their meniscus facing convex upwards. The angle of contact for these liquids is greater
than 90o.

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 Mathematical expression:
Now know that surface tension is responsible for capillary action. We shall a derive a
mathematical relation between the liquid level in the capillary tube, surface tension and
the density of the liquid.
Let us suppose we have a wetting liquid of density ‘ρ’ that rises to a height ‘h’ in a
capillary tube of radius ‘r’. The force of surface tension will act around the circumference
of the capillary tube in the upward direction, and will be responsible for the rise of the
liquid level in the capillary tube (Fig. 6).

Fig. 6: Rise of a wetting liquid inside a capillary tube

From Fig. 6, we see that the force acting in the upward direction is (𝛾 cos 𝜃) 2𝜋𝑟
This is balanced by the force due to the weight of the liquid acting in the downward
direction, equal to 𝑚𝑔 = 𝜋𝑟 2 ℎ

At equilibrium, (𝛾 cos 𝜃) 2𝜋𝑟 = 𝜋𝑟 2 ℎ (10)

1 ℎ𝜌 𝑔 𝑟
Or, 𝛾= (11)
2 cos 𝜃
CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 The height ‘h’ can be measured using cathetometer and radius of the capillary tube ‘r’.
using a travelling microscope. Thus, making use of equation (11), we can also evaluate
the surface tension ’𝛾’ of the liquid.

The value of 𝜃 for most of the wetting liquids is very small, i.e., close to zero, so that

cos 𝜃 = 1 and,
1 ℎ𝜌 𝑔 𝑟
𝛾= 2
(12)

For non-wetting liquids, the value of ‘h’ will come out to be negative. For example, in the
case of mercury, the value of θ= 180o and cos 180 = −1 making ‘h’ negative. This is the
reason, when a mercury drop falls on a clean levelled surface, it becomes a truncated
sphere.

Pressure difference across curved surface: Young-Laplace equation

Thomas Young (1773-1829) and by Pierre Simon de Laplace (1749-1827) proved that
there exists a pressure difference between two sides of a curved surface. They formulated
an equation, known as Young-Laplace equation, given by:
2𝛾
𝑃𝛼 − 𝑃𝛽 = (13)
𝑟

where, 𝑃𝛼 and 𝑃𝛽 are the respective internal and external pressures, and r is the radius of
the spherical surface.
The equation is based on the fact that some work is always required for an infinitesimal
increase in the surface area of an interface, at constant temperature and constant volume
of the system. It can be derived as follows:
Let us consider a single spherical drop of a liquid (𝛼 phase) in equilibrium with its vapor
(𝛽 phase). At a constant temperature T, let 𝑃𝛼 be the internal pressure of the drop and
CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 𝑃𝛽 be the external pressure of the vapor. Let this liquid drop be cut into two halves by an
imaginary plane, to get two hemispheres (Fig. 7). The force of surface tension tends to
reduce the surface area (and hence volume) of the drop, and acts along the circumference
of the hemisphere. The former will then be equal to 2πrγ, where γ if the surface tension of
the liquid. The force of surface tension is opposed by the pressure difference across the
liquid-vapor interface, which tries to increase the surface area (and hence volume) of the
drop. The force acting due to pressure difference is equal to pressure difference
multiplied by the projected area of the hemisphere, that is, (𝑃𝛼 − 𝑃𝛽 ) × 𝜋𝑟 2
At equilibrium, the two opposing forces will balance each other, and
(𝑃𝛼 − 𝑃𝛽 ) × 𝜋𝑟 2 = 2 𝜋𝑟 × 𝛾 (14)

Equation (14) on solving gives the Young-Laplace equation (15).

2𝛾
𝑃𝛼 − 𝑃𝛽 = (15)
𝑟

Fig. 7: A liquid drop cut into two hemispheres by an imaginary plane.

𝑃𝛼 and 𝑃𝛽 are the internal pressure of the drop and external pressure of the vapor,
respectively.

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 There is another method to derive the Young-Laplace equation.
Let us consider a syringe fitted with a piston and a sharp needle, in thermal equilibrium
with the surroundings at any temperature T. It is filled with an incompressible liquid of
surface tension 𝛾. In order to form a liquid drop, some pressure
𝑃𝛼 , 𝑔𝑟𝑒𝑎𝑡𝑒𝑟 𝑡ℎ𝑎𝑛 external pressure 𝑃𝛽, has to be applied on the piston of the syringe.
The net work done in the process will be equal to:
𝑑𝑊 = (𝑃𝛼 − 𝑃𝛽 ) 𝑑𝑉 (16)
where, dV is the change in volume
This net work done increases the surface area of the liquid drop.
Therefore, we can also write: 𝑑𝑊 = 𝛾𝑑𝑆 (17)
Where, dS is the increase in the surface area
Equating equation (16) and equation (17), we get:
(𝑃𝛼 − 𝑃𝛽 ) 𝑑𝑉 = 𝛾𝑑𝑆 (18)

If the radius of the liquid drop increases by a small amount dr, then
4𝜋(𝑟 + 𝑑𝑟)3 4𝜋𝑟 3
𝑑𝑉 = − = 4𝜋𝑟 2 𝑑𝑟
3 3
𝑑𝑆 = 4𝜋(𝑟 + 𝑑𝑟)2 − 4𝜋𝑟 2 = 8𝜋𝑟𝑑𝑟 (19)

Substituting the values of dV and dS in equation (18), we get:

(𝑃𝛼 − 𝑃𝛽 ) 4𝜋𝑟 2 𝑑𝑟 = 𝛾 8𝜋𝑟𝑑𝑟
On solving, we get: (20)
2𝛾
𝑃𝛼 − 𝑃𝛽 =
𝑟
From the Young-Laplace equation derived above, we see that the pressure inside a
spherical drop is always greater than the pressure outside, by an amount proportional to
the surface tension and inversely proportional to the drop radius. When the surface

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 becomes flat, the radius of curvature becomes infinite, and the pressure difference
reduces to zero. The equation breaks down before the radius tends to zero, thus avoiding
pressure difference tending to infinity.
If the interface is not spherical but has 𝑟1 and 𝑟2 as the maximum and minimum radii of
curvature at any point, then:
1 1
𝑃𝛼 − 𝑃𝛽 = 𝛾( + )
𝑟1 𝑟2

(21)
The Young-Laplace equation derived above has been experimentally validated by the
phenomenon of capillary action. We know that the liquid is present at different levels
inside and outside the capillary tube. Since the liquid-vapor interface is curved inside but
flat outside, a relation between the rise in liquid level inside the capillary tube (h), radius
of capillary tube (r), surface tension of the liquid (𝛾), and relative densities of liquid and
vapor phases (𝜌𝛼 , 𝜌𝛽 ) is as follows:
2𝛾 cos 𝜃
(𝜌𝛼 − 𝜌𝛽 ) 𝑔ℎ =
𝑟
(22)
Here 𝜃 is the contact angle. This equation bears the same results as equation above.

5.3 Formation of bubbles

The formation of bubbles is basically due to surface tension. From the Young-Laplace
equation derived above, we have seen that the pressure acting on the concave side of the
drop is greater relative to the one acting on the convex side. This gives rise to the
formation of stable bubbles.
With increase in the pressure, the chemical potential of the liquid also increases by an
amount 𝑑𝜇 𝑙 = 𝑉𝑚𝑙 𝑑𝑃𝑙 , where 𝑉𝑚𝑙 is the molar volume of the liquid.

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 Since the liquid is in equilibrium with the vapor, the chemical potential of the vapor also
increases by the same amount, i.e.,
𝑑𝜇 𝑙 = 𝑑𝜇 𝑔 (23)
But 𝑑𝜇 = −𝑆𝑚 𝑑𝑇 + 𝑉𝑚 𝑑𝑃
At constant temperature T, 𝑑𝜇 = 𝑉𝑚 𝑑𝑃 (24)
Using (23) in equation (24), we get,
𝑔
𝑉𝑚 𝑑𝑃 = 𝑉𝑚𝑙 𝑑𝑃𝑙 (25)
where, P is the vapor pressure of the vapor.

If the vapor is assumed to be ideal, and integrating equation (25), we get,

𝑃 𝑃2
𝑅𝑇
∫ 𝑑𝑃 = ∫ 𝑉𝑚𝑙 𝑑𝑃𝑙
𝑃1 𝑃 𝑃1

If 𝑉𝑚𝑙 is assumed to be constant, then the above equation can be written as

𝑃
𝑅𝑇 ln 𝑃 = 𝑉𝑚𝑙 (𝑃2 − 𝑃1 ) (26)
1

Using Young-Laplace equation (16) in equation (26), we get,

𝑃 2𝛾
𝑅𝑇 ln 𝑃 = 𝑉𝑚𝑙 ( 𝑟 ) (27)
1

If the interface between the liquid and vapor is planar, i.e., 𝑟 → ∞, then 𝑃 = 𝑃1 =
𝑃𝑜 (saturation pressure)
Thus, we can write equation (27) as:
𝑃 𝑙
𝑉𝑚 2𝛾 𝑀 2𝛾
ln = ( 𝑟 ) = 𝜌𝑅𝑇 ( 𝑟 ) (28)
𝑃𝑜 𝑅𝑇

where, M and 𝜌 are the molar mass and density of the liquid, respectively.
Equation (28) is known as the Kelvin equation for liquid droplets.
The Kelvin equation can easily explain the processes like vapor condensing in small
capillaries at pressure much below the saturation pressure (if the liquid wets the capillary,
r is negative, and meniscus is concave upwards). It also explains the phenomenon of
CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical
Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications
 supersaturation (extensively useful in preparation of compounds and cloud seeding) and
mechanism of emulsion breakdown (Ostwald ripening).

4. Summary

 The force that tends to contract the surface area of a liquid is called as ‘surface
tension’. It is numerically and dimensionally equal to surface energy
 Surface tension can be measured by different devices such as duNouy
tensiometer, Wilhelmy slide apparatus or a stalagmometer
 Surface tension explains the spherical nature of liquid drops, capillary action and
the formation of stable bubbles

CHEMISTRY Paper No. 10: Physical Chemistry –III (Classical

Thermodynamics, Non-Equilibrium Thermodynamics,
Surface Chemistry, Fast Kinetics
Module No. 24: Adsorption from solution: surface tension
and applications