UNIT 4 SURFACE TENSION

Structure
4.1 Introduction
4.2 Surface Tensio?
Surface Free Energy
Interfac~alTension
Cap~llaryAct~on
4.3 Factors Affecting Surface Tension
Effect of Surfactants
Effect of Temperature
4.4 Measurement of Surface Tension
4.5 Experiment 1 : (i) Determination of Surface Tension of an Aqueous
Solution of a Detergent
(ii) The Study of Variat~onof Surface Tension with the
Concentration of a Detergent (Optional)
Pr~nc~ple
Requ~rements
Procedure
Observations
Calculat~ons
Result

4.1 INTRODUCTION
You already know that matter can exist in three possible states-solid, liquld o r gas.
In gases, the kinetic energy of the particles is sufficiently high to overcome the
intermolecular forces of attraction. As a result of this, the gaseous molecules arL
free to move randomly in straight lines. In solids, the forces of attraction exmed the
net kinetic energy of the molecules. The result is that the molecules become
strongly packed together, giving them a shape rather fixed and restricted.

The properties of liquids are in betwmn those of the gases and solids. In liquids,
relatively short range forces of attraction are a t work which hold their molecules at
moderate distances. Though, the speed o f the molecules in liquids is relatively
slower than molecules in gases, their motion is still rapid enoughuo prevent them
from being confined in definite positions. Hence, liquids have no specific shape and
their molecules easily slide pass each other permitting them to take any possible
shape allowed by the container.

Thus, not only the particular state of the substances but also their subsequent
physical properties can be regarded as a result of the net balance between the
kinetic energy of the molecules, which tend to keep them apart, and the
intermolecular forces of attraction which tend to keep the molecules together.
Here, in this unit you are going to study about the measurement of one such
important property of liquids, name$ the Surface Tension.
Froperlies of Liquids a n d Objectives
Thermochemistry
After going through this unit and performing Experiment 1, you should be able to:

define surface tension and surface free energy, and give their units,
8 express clearly the correlation between the molecular forces of attraction a n d t h e
phenomenon of surface tension in liquids,
8 explain interfacial tension and capillary action,
comment on various methods of measuring surface tension and the principle
involved therein,
discuss how the surface tension varies with temperature and provide possible
reasons for this variation, and
explain why the surface tension of an aqueous solution should decrease in the
presence of surface active agents.

4.2 SURFACE TENSION

Fig. 4.1 shows that a molecule in the interior of a liquid is completely surrounded
by the other molecules, and experiences the force of attraction equally in all
directions. On the other hand, a molecule at the surface experiences the attractive
forces onlyfrom downward direction,and this results in a net inward pull. Thus,
under the influence of the molecular forces of attraction from within, a liquid
Pig. 4.1 : Forces of altraclion a1
the surface and in the develops a tendency to contract its surface such that it acquires the smallest
interior or R liquid. possible area for a given volume. That is why drops of a liquid and bubbles of a gas
in a liquid tend to acquire a spherical shape. As a result of this contraction, a liquid
surface eventually comes i n d e r the state of stretch or tension, and the force
(stretching) acting equally at every point in all directions along the surface, is
T h e surface tension may also he known as the Surface Tension.
defined in c.g.s. system a s the force
in dynes acting a t right angle t o any
line of o n e centimetre length along
~ , surface tension denoted as y, may be defined in SI units as the
~ u a n t i t i t i v e l the
the Iiquid surface, ~n this case, ,he force in newtons (N) acting at right angle to any line of One metre length along the
force in dynes acts along a distances surface of the liquid. Since, the force in newtons acts along a distance of one metre,
Of One so Ihe surface
the unit of surface tension is expressed as N m-'.
tension is expressed in dynes cm-'.
In o t h e r words, w e can also say. Related to the surface tension is the property of surface free energy. Let us now
that dynes cm-.' x lo--' = N m-'
understand what d o we mean bythis term.

4.2.1 Surface Free Energy

T h e c.g.s. units of surface free
The surface free energy, as such, is a characteristic property of the surface and
energy a r e ergs ~ m - ~ .
arises due to surface tension. The surface tension acts inwards allowing a minimum
1.1 =1N1n surface area for a given volume of liquid. Therefore, extension of a surface against
I J = l ~ ~ m ~ m - ~~ the force of surface tension requires some work to be done which results in an
increase in the energy of the surface by the same amount. T h e work required to
= 1 N m-'
increase the surface area by o n e unit by moving the molecules from interior of the
liquid to surface, is called the surface free energy. T h e SI unils of surface free
energy are joule metre-2. The two quantities, the surface,free energy (J m-2) and
the surface tension (N m-l) and are mathematically equivalent. T h e surface tension
for some substances is given in 'Table 4.1.
 Table 4.1: Surface Tension of Some Substances Surface Tension

I
( Platinum
Copper
Surface tension is measured for
Aluminium liquids. You can see high
Lead temperatures being used for the
first four entries mentioned in
Table 4.1 which are required for
1 YI:rn: reaching their melting point.

Benzene
Chloroform
Ethanol

When a system contains more

than one phase, the region
4.2.2 Interfacial Tension where the phases meet, is called
the Interface or interfacial
The surface of a liquid is, infact, a surface of separation o r an interface between the region. The common example
liquid and its vapour phase, and the value of the surface tension is the force acting of the interface being the
per unit length along this liquidhapour interface. surface of separation between
two immiscible or partially
miscible liquids.
In general, the force acting per unit length along the surface of separation or
interface is known as the interfacial tension. This is also expressed in Newton
metre-' (N m-') units.

Having understood the term interfacial tension, let us turn to the phenomenon of
capillaly action. You must be familiar with the fact that water rises in a capillary
tube. Also you must have seen that mercury shows a depression of level in a
capillary tube. The rise or fall (depression) of liquid level in a capillary tube is
known as capillary action. Can you guess what is responsible for this phenomenon?
It is the surface tension which is responsible for rise (or fall) of a liquid in the
capillary. Let us now study it in more detail.

4.2.3 Capillary Action

Water in a capillary tube is pulled upwards due to the force of surface tension and
is pulled downwards due to the force of gravity. Water continues to rise in the
capillary till a balance between the two forces is reached. Such a rise is depicted in
Fig. 4.2 (a).

This can be more clearly understood if we take into account the forces operating at
the molecular level. Two types of forces operate when a glass capillary is dipped in
water viz. cohesive and adhesive forces. Cohesive forces are the intermolecular
forces among the molecules of water whereas adhesive forces operate between the
molecules of water and the molecules of the glass which constitutes the capillary
walls. The adhesive forces pull water upwards and lead to the wetting of glass
(capillary walls). On the other hand, cohesive forces act downwards. The height of
the resulting column of water in the capillary is determined by the balance of
adhesive and cohesive forces.
Properties of Liquids and
Thermochemistry

Ycos 0

Meniscus

F b 4.2: Caplllmr~rr U o n : (a) RI.c of mter ln a capillary.

(b) l k p ~ i o of
n mercury i m l ln a c a p l l l y .

You must have also noticed the shape of the meniscus when water rises in a glass
capillary. The shape is concave indicating that the adhesivei'fbks between water
and glass are stronger than the cohesive forces between water molecules. In some
cases, e.g., in case of mercury, the shape of the meniscus is convex and there is a
depression in the level of mercury inside the capillary, see Fig. 4.2 @). This is due
to stronger cohesive forces as compared to adhesive forces.

Let us now derive an expression which relates the above forces with the surface
tension.

A force vector (e.g. Y) can be resolved The force in the downward direction, Fd, - i.e. cohesive force is given by mass of the
into two rectangular components : liquid column (m) above the flat surface of liquid multiplied by the acceleration
Y a s 8 and Y sin B as shown below :
due to gravity (g). Again mass of the liquid is equal to the product of volume (V)
and density (d) of the liquid. Considering the particular bit of liquid portion as
cylindrical, the volume can be given by the formula d h .

tY'
0
YI x-
where r is the radius of the capillary and h is the height of the liquid column.

F@ A3 : ResohUon of a Vector Inlo

The upward force, F,, i.e. the adhesive force is equal to the vertical component (See
eomponenIs. Fig. 4.3) of the surface tension (= Y cos 8 ) multiplied by the circumference of the
capillary (b). Therefore F,,, can be represented as given below

where3 is the contact angle as shown .in Fig 4.2 At'equilibrium, Fd = F,,. Hence,
we can write from Eqs. 4.1 and 4.2 that

We can use Eq. 4.3 for the determination of surface tension (7).
 Surface Tension
Having understood the above discussion, answer the following S.QQ.

SAQ 1

i) Why d o the tiny drops of a liquid look spherical in shape?

ii) Surface tension of a liquid i s . . . . . . . . . . . . . . .in newton atright angles to a

line of o n e meter length along the ............. of the liquid.

iii) What is the surface free energy?

iv) ' T h e unit of interfacial tension is ...................... and that of

surface free energy is . . . . . . . . . . . . . . . . . . . . . .

4.3 FACTORS AFFECTING SURFACE TENSION

We will now focus o u r attention o n some of the factors affecting the surface
tension. We will first explain the effect of surfactants and then discuss the effect of
temperature.

4.3.1 Effect of Surfactants

Surfactants are surface active materials and they generally consist of molecules
containing polar and nonpolar parts. These parts have a strong tendency t o orient
themselves at the interfaces of two immiscible o r partially miscible liquids. T h e
tendency of the surfactant molecules to align a t a n interface favours its expansion.
The common examples of surfactants
This expansion must be balanced against the tendency of the interface t o contract
are soaps and detergents. Gaps are
under surface tension forces. Hence, the presence of a surfactant in aqueous salts of long-chain fatty acids. The
solutions lowers the surface tension. detergents are of two types - anionic
and cationic. The anionic detergents
are sodium salts of linear allcylbenzene
(LAB) sulphonic acids. Their general
where, x is the expanding pressure o r surface pressure due t o absorbed layer o f structure can be reoresented as.
surfactant and yo is the surface tension of the liquid in the absence of the
surfactant. kd
The cationic detergents are generally
the quaternary ammonium salts of the
4.3.2 Effect of Temperature following type

As the temperature increases, the kinetic energy of the molecules increases. This
causes a decrease in their intermolecular forces of attraction. This results ib a where R is allcyl chain having 12-18
carbon atoms.
decrease in the surface tension of the liquid. For thepajority of compounds the
temperature dependence of the surface tension can b e given as, By lowering the surface tension, the
surfactants help the grease or dirt
(non-polar in nature) to dissolve in
water. This solubilised grease is then
where, A and B are the constants and T is the temperature in degree celsius. T h e wasted away with water. This forms the
basis for the cfcaoslng action of soaps
values of A and B for various compounds are available due to the research work
and detergents.
done s o far. After studying this section, answer the following SAQ.
Properties of Liquids and 8AQ 2
Thermoshemistry

i) Addition o f a detergent to water will .........................its surface tension.

ii) At higher temperature, the surface tension of a liquid ........................ because
....................decreases.

4.4 MEASUREMENT OF SURFACE TENSION

There are various methods for determining the surface tension of a liquid. The
names of such methods are given below:

i) Capillary rise method

ii) Torsion balance method

iii) Maximum bubble pressure method

iv) Stalagmomeler method

Here, we will be discussing the stalagmometer method only because this method
you will be using in the determination of the surface tension in Experiment 1.

4.5 EXPERIMENT 1 : I) DETERMINATION OF '

SURFACE TENSION OF AN AQUEOUS SOLUTION
OF A DETERGENT
11) THE STUDY OF VARIATION OF SURFACE
TENSION WITH THE CONCENTRATION OF A
DETERGENT (OPTIONAL)
Here, in this experiment you are going to use a stalagmometer. This is shown in
Fig. 4.4 and is called Traube's Stalagmometer. It is a simple apparatus and is
frequently employed when the values of surface tension of two o r more different
liquids are to b e compared.

Fig. 4.4 : Traube's Slalagmomeler.

It consists of a bulbed capillary tube, the erid of which is flattened and grounded
carefully so that there is a large dropping surface. There a r e two marks, A and B,
on it which are arbitrarily etched; o n e of them is above the bulb and the other is
below the bulb. A liquid is sucked up to the level A and th6n allowed to flow at a
slower rate drop by drop until it reaches the level B. T h e speed of the drop'
formation can be adjusted by attaching a piece of rubber tube with a screw pinch
cock a t the upper end o f the tube. Before going to the actual details of the
 Surface Tension
procedure, you should understand the principle involved in this method, which is
explained below.

4.5.1 Principle
When a liquid is allowed to flow through a capillary tube, a drop begins to form at
its lower end, and increases in size to a certain extent, and then falls off. The size of
the drop will depend on the radius of the capillary and the surface tension of the
liquid. The total surface tension supporting the drop is 2nr. Y, where r is the outer Capillary
radius of the capillary tube, see Fig. 4.5. The drop will fall when its weight w, just
exceeds the force of surface tension acting along the circumference. Therefore,
Wall thickness
w=hrY ..... (4.6)
where w, is the weight of the drop and h r is the outer circumference of the -
Surface
capillary tube. tension
acting
From the above expression,.it is clear lhat the surface tension of a liquid can be along the
determined if the weight of a single drop w and the outer radius of the dropping circumference
tube, r are known.
Force (F,)
If, we have two liquids, such that
Fig. 4.5 : Formation o f a drop at the
WI = hrY1,
end o f the cnplilary.
and wa = 2nr Y2,

then, we can say that

If Y1 for one of the liquids is known, Y2 for other liquid can be determined without
needing a measurement of r, the outer radius of the dropping end of the capillary,
provided the weights of the individual drops of two liquids are known. This method
of determination is also known as Drop Weight Method. Alternatively, the surface
tension can also be determined using the Drop Number method as given below.

Drop Number Method

Instead of finding the weights of individual drops, it is easier to count the number
of drops formed by equal volumes of two liquids. With two different liquids, the
weights of equal volumes a r e proportional to their densities. If nl and n2 are the
number of drops formed by the same volume V of the two liquids, then; vl, the
volume of a single drop of first liquid (i.e., liquid one) = V/nl.

Thus, Weight o f an object is the force

experienced by it due to gravitation
weight of the single drop = wl = V/nl x dl x g for first when it is freely suspended (as in
spring balance). '1 herefore,
of the first liquid liquid, where dl is the density
of the first liquid. weight = mass X acceleration due
and to gravity
weight of the single drop = w2 = V/n2 x d2 x g for second
of the second liquid liquid, where d2 is the density
of the second liquid.
and w2 = m2 x g

Substituting the above values of wl and w2 in Eq. 4.7, we get ml x g

Thus, -W=
1
- m1
=-
W2 m2xg "'2
Properties-of Liquids and We get,
Themochemistry

where, Y1 and Y2 are the surface tensions of two individual liquids, and d l and d2
are their densities, respectively. Thus, for the determination of surface tension of
any liquid, the number of drops produced from equal volume of two liquids and
their densities must be known, in addition to the surface tension of the reference
liquid (e.g. water).
You can also check your understgnding about the Eq. 4.8 involved in the
determination of surface tension by answering the following SAQ.
SAQ 3

Calculate the ratio of number of drops of water to those of mercury if the values of
density for mercury and water are 13.6 kg dm-3 and 1.00 kg dm-3, respectively. Use .
the values of surface tension of the two liquids as given in Table 4.1.

Let us n@wfocus our attention o n the actual procedure and requirements for the
experiment.

4.5.2 Requirements
Traube's Stalagmometer 1
Weighing bottle/conical flask (50 ml)/ 1
Outer jacket of transition
temperature of C.S.T. apparatus
Rubber stopper 1
Rubber tube (small piece) 1
Pinch cock 1
Clamp stand 1
Specific gravity bottle 1
1
Thermometer (lloO)- -degree 1
10
Large beaker o r glass trough 1
In addition, you will be provided with different solutions (upto 3 or 4 in numbers) of
household detergents (with varying concentrations) and also a bottle of distilled water.
Chromic acid is prepared by
dissolving pbtassium dichromate
4.5.3 Procedure
(K2Crz0,) in conc. H2S0,. ,
Before starting the experiment, the stalagmometer should be cleaned by chromic
acid solution to remove oil, grease etc. sticking on the inner capillary surface and
then washed with distilled water and finally with acetone or alcohol, and dried by
passing air. Now take a weighing bottle, tightly fitted with a rubber stopper having
two holes. Insert the stalagmometer through one of the holes. Through the other
hole, pass a glass tube for air ventillation (see Fig. 4.6). Attach a small rubber
tubing with a screw pinch cock to the upper end of the stalagmometer. Take out
 Surface '1 cn\lon
the stalagmometer from the bottle, and fill it with distilled water by sucking it up to
the mark A. Close the pinch cock and insert the stalagmometer into the weighing
bottle. Now, clamp the stalagmometer in a thermostat and allow it t o acquire the
temperature of the bath. Now, open the pinch cock gently such that the liquid flows
out slowly. Adjust the air inflow so that the number of drops formed should not
exceed 15 drops per minute. Count the number of drops obtained when a fixed
volume of water flows between the marks A and B, i.e., count the number of drops
when the water level changes from A t o B.

Refill the ~ t a l a ~ m o m e t and

e r repeat the countirg of drops thrice, and record it in
the o b s e ~ a t i o ntable, shown as Table 4.2.

Screw pinch cock

Fig. 4.6 : Apparatus for the determination of surface tension.

Now remove the stalagmometer from the weighing bottle, wash it thoroughly and
dry it. Fill it with the given detergent solution and reset the stalagmometer in the
weighing bottle. Count the number of drops fallen for the same volume of the
detergent solution between the marks A and B. Repeat the counting process thrice
and record in the observation table.
While doing the experiment, the following precautions should be taken.

Precautions
The stalagmometer should be cleaned and dried before use.
While sucking the liquid into the stalagmometer, no air bubble should be formed.
Stalagmometer should be held in a vertical position throughout the drop counting
process.
Drop formation should be adjusted a t a slower rate and should not exceed fifteen
drops per minute.
You can record your observations in the space given below.

4.5.4 Observations
Temperature, t - ......................."C
Density of water at t°C = dw = ...................kg dm-3
Surface tension of water at t°C = YW - .................... N m-I
(use from Table 4.3)
 Properties of Liquids and Table 4.2
Thennochemistry

Number of drops formed from equal volume of liquids

(between marks A and B)

SI. Water Detergent Solutions

No. s1
I s2 s3 S4

i ..... ..... ..... ..... .....

ii ..... ..... ..... ..... .....
iii ..... ..... ..... ..... .....
Specific gravity is a term sometimes
used in place of density. Specific Gravity
is the ratio of density of a substance to
Average ..... ..... ..... ..... .....
that of water. Since it is a ratio of two n, "s1 "SI? "s3 "54
densities, it is expressed without units.

Specific Gravity =
densityof solution(in kgdm") mass of empty specific gravity bottle = w l = ....g
density ofwater(in kg dm3 3) +
mass of specific gravity bottle detergent solution = w2 = ....g
The density of water is 1 kg dm"; mass of Specific gravity bottle Water + = wg = ....g
therefore, specific gravity of a liquid or The calculations to be done are also explained below:
solution is its density expressed without
units.
From the following steps, you can verify
4.5.5 Calculations
the relationship between the density of a
Density of the detergent solution 1 =
solufion and density of water as given by
specific gravity measurement.
Mass of the detergent solution
Specific gravity of a solution = 4, = Mass of water x density of water
'Dasityof
- a solution -
-
Density of water
Mass of solution/Volume of solution
Mass ofwater/(same) Volume of water
= Mass of solution/Mass of water Relative surface tension of the detergent solution (sl) =
Since we use same specific gravity bottle
for measuring the masses of water and
solution, volume is same in both the
cases.
Hence Density of a solution = Absolute surface tension of the detergent solution (s,) =
Mass ofsolution
x Density of water
Mass of water
dSl nw
This relationship holds only if masses of Ys, = "/w X -= ..........N m-'
water and solution are measured using
dw x ns
same specific gravity bottle.
Likewise repeat the determination of density and calculations of surface tension for
other solutions and get Ys2, Ys, etc.
 Surface Tension
The surface tension of water Y,, at different temperatures is given in Table 4.3 for
your reference.
Table 4.3 : Surface Tension of water at different temperatures

~ern~eraturJ"~ Surface Tension ( 10% IN m-')

0 75.83
5 75.09
10 74.36
15 73.62
20 72.88
21 72.73
22 72.58
23 72.43
24 72.29
25 72.14
26 71.99
27 71.84
28 71.69
29 71.55
30 71.70
35 70.66
40 69.92
45 69.18
50 68.45
55 67.71
60 66.97
100 61.80

The result obtained can be reported as shown below:

4.5.6 Result
i) The absolute surface tension of the detergent solutions (sl, s2, s3, s4) at
temperature ....."C are as follows:

ii) Similarly, you can determine the surface tension values for iolSions of the
same detergent having different concentrations and plot a graph of surface
tension Vs concentration values (cl, c2, c3 etc.). Discuss this graph with your
counsellor and find the possible reasons for the variation of surface tension
with concentration of the detergent solution.

4.6 ANSWERS
Self Assessment Questions

1 i) Because of surface tension, a liquid develops a tendency to acquire

smallest possible area for a given volume. A sphere has the smallest
surface area for a given volume.

ii) force, surface

 iii) Work required to be done in order to expand the surface area by one
unit.

L. i) reduce

ii) decreases, intermolecular forces

3 Let subscript 2 represent water and subscript 1 represent mercury. Then Eq.
4.8 becomes,

(rounded to three significant figures)