Surface tension

The existence of strong inter-molecular forces of attraction in liquids gives rise to an

important property: surface tension.
Consider a molecule somewhere in the body of the liquid. This is attracted equally in all
directions by other molecules which surround it, therefore cancel the effect of one
another.Consider, next, a molecule near the surface. The downward attractive forces are
greater than the upward forces because there are more molecules of the liquid below than in
the air above the surface.
These unbalanced attractive forces acting downward tend to draw the surface molecules into
the body of the liquid and, therefore, tend to reduce the surface to a minimum.
Since the attractive forces are more predominant in the bul of the liquid than at the surface,
the molecules in the bulk of the liquid are associated with lower energy than at the surface.
!n other words, the molecules at the surface possess greater energy than those in the bul. !t is
the extra energy of the surface molecules which gives rise to their tendency to move into the
bul of the liquid, i.e., the molecules tend to move from a state of higher energy to a state of
lower energy. "s a consequence of this transfer, the number of molecules at the surface is less
than that in the bul.
The distance between any two molecules at the surface, therefore, becomes greater than in the
bul.Consequently, the surface molecules tend to move closer to one another in order to
acquire a normal distance between them as before.
Surface tension, therefore, tends to contract the surface.
!t is for this reason that drops of a liquid or bubbles of a gas are spherical in shape.
A sphere has a minimum surface for a given volume of a liquid or gas.
"s a result of the tendency to contract, surface of a liquid behaves as if it were in a state of
tension.
Surface tension may be defined as the force in dynes acting at right angles to the surface of a
liquid along one centimeter length of the surface.
It is generally represented by the symbol and expressed in dynes cm
-
.
Surface tension of water #$.%, &thyl alcohol $$.#, "cetone $'.# at $()C.
*+eason- Stronger inter-molecular forces in water than those in organic liquids,
Surface energy
The effect of surface tension is to reduce the area of the surface to a minimum. !f we wish to
increase the area of the surface of a liquid, we have to wor against the force of surface
tension.
!he work that is required to be done in order to extend the area of the surface of a liquid by
sq.cm.is called surface energy of of the liquid. !t is expressed in ergs-cm
$
. !t may also be put
as *dynes . cm, cm
-$
, i.e., dynes cm
-
/, which is also the unit of surface tension.Thus0 surface
tension is equal to surface energy numerically as well as dimensionally.
Some effects of surface tension
/
1. The effect of surface tension is to reduce the area of the surface to a minimum.
1ence drops of a liquid or bubbles of a gas are spherical in shape as stated before. A
sphere has a minimum surface for a given volume.
2. The rise of a liquid in a capillary tube*e.g., rise of oil in the wic of a lamp, rise of
under-ground water on to the surface of earth,
Capillary rise method
" method of measuring surface tension
Consider a capillary tube lowered in a liquid that wets its surface *e.g., water,.The liquid will
rise almost instantaneously up to a certain height depending upon its surface tension and
density. The column of the liquid in the capillary is, evidently, being supported by some force
acting along the surface of the water. This is force of surface tension.
Suppose a liquid of density d, rises in a capillary tube of radius r, through a height h.
2et be the force of surface tension in dynes per cm. Then, the total force due to surface
tension, raising the liquid column upward 3 x inside circumference of the capillary, i.e., 3
"# r dynes.
4orce of gravity pulling the liquid downward 3 weight of the liquid column.
5eight of the liquid in the column 3 v dg dynes where v is the volume of the liquid in the
tube.
6ut v $ # r
"
h.
1ence, for equilibrium,
"# r $ # r
"
h dg
$ r h dg% " dynes per cm.
!t is assumed in the above derivation that the contact angle 7 between the glass and the liquid
is 8ero, that is, wetting is perfect. !f this is not so, it can be shown that
$ r h dg% "cos 7
This gives us, incidentally, a method of measuring surface tension, nown as the capillary
rise method. 4or this purpose, it is required to measure the height *h, through which the liquid
rises and the radius*r, of the capillary tube, both in cm.The height is measured by a
cathetometer and the radius of the capillary tube by a traveling microscope. The contact angle
in most such cases is 8ero.
The Drop Weight Method
!n physical chemistry, surface tension is usually measured by the drop weight method as this
is more convenient. This method is based on the principle that the weight *w, of a drop of
liquid, falling from a given capillary tube held vertically is approximately proportional to the
surface tension of the liquid. Thus, if surface tensions of any two liquids are
/
and
"
, then,

/
%
"
3 w
/
-w
$
5here w/ and w$ are mean weights of their drops falling from the same capillary tube. The
instrument used is nown as stalagmometer.
!t is more convenient to count the number of drops formed by a given volume of a liquid than
to find the weight of a drop.
$
Suppose, equal volumes *9, of two liquids, when allowed to fall through the same
stalagmometer, form n
/
and n
$
drops. Then, mean weights of such drops w/ and w$ are given
as:
w
/
39 d
/
-n
/
w
$
39 d
$
-n
$
5here d
/
and d
$
are densities of the two liquids.
1ence

/ %

"
3 w
/
-w
$
3 9 d
/
-n
/
/ 9 d
$
-n
$
3 n
$
d
/
-n
/
d
$
!f surface tension of one of the liquids is nown, that of the other can be easily calculated.
The densities of the liquids may be determined by the usual specific gravity bottle or
pynometer method.
Procedure
The stalagmometer is first thoroughly cleaned with chromic acid mixture and dried. !t is then
filled with water up to the mar : by sucing at the other end of the tube. The water is then
allowed to come out in the form of drops which are counted. The number of drops per minute
should not exceed $( as otherwise they will not be properly formed. The rate can be
controlled with the help of a pinch coc attached to a rubber tube at the upper end of the
stalagmometer.
The stalagmometer is again thoroughly washed and dried and now filled with the liquid under
examination upon the same mar :. The number of drops is counted as before. 2et the
number of drops of water and the liquid under examination be n/ and n$ and let d/ and d$ be
their respective densities.
Then, surface tension of the liquid, n
$
d
/

"
-n
/
d
$
, where
"
is the surface tension of water at the
same temperature.
Interfacial Tension
Suppose, two immiscible liquids are present one above the other in a vessel. Then, the force
acting per unit length along the interface is called interfacial tension. This is less than the
surface tension of the liquid with a higher value. The reason is that the unbalanced forces
acting along the surface of each liquid are partly compensated by force of mutual attraction
between the molecules of the two liquids.
!t may be emphasi8ed that surface tension and interfacial tension involve the same type of
force. 5hen one speas of surface tension of a liquid, it is understood that the force is acting
along the surface of separation between the liquid and its vapour.5hen one speas of
interfacial tension, it is understood that the force is acting along the surface of separation of
two immiscible liquids in contact with each other.
ffect of temperature on surface tension
"ccording to the inetic theory, molecular inetic energy is proportional to absolute
temperature. The rise in temperature of a liquid, therefore, is accompanied by increase in
energy of its molecules. The intermolecular forces of attraction, therefore, decrease with rise
in temperature. 1ence surface tension of a liquid decreases with rise in temperature.
'
"t critical temperature, since the surface of separation between a liquid and its vapour
disappears, the surface tension falls to 8ero.
&otvos found that surface tension varies linearly with temperature.
1e suggested that the following expression for the variation of surface tension with
temperature:
*:-d,
$-'
3 a ; k t
5here : is the molecular weight the density and the surface tension of the liquid at the
temperature t0 a and k are constants.
&%d ' evidently' is molecular volume of the liquid. Assuming this volume to be spherical
(since area of a sphere is minimum)' we may take (&%d)
"%*
as proportional to the molecular
surface of the liquid. Since ' the surface tension' is also surface energy per square
centimetre' it is evident that the expression (&%d)
"%*
is proportional to molecular surface
energy.
"t the critical temperature *i.e., when t 3 t
c
, the surface tension is 8ero. Substituting these
values we may write
( 3 a- k t
c
a 3 k t
c
Therefore The &otvos equation, therefore, may be written as:
*:-d,
$-'
3 k *t
c
;t,
This equation has been found to be satisfactory in giving variation of surface tension with
temperature in the case of a number of liquids over a wide range of temperature.
Surface !cti"e !gents
" number of substances are nown which, when added to water, lower its surface tension.
These substances are called surface active agents. Thus liquids lie methanol, ethanol,
acetone and acetic acid when added to water lower its surface tension.
Salts of higher sulphonic acids and higher amines which behave in this manner. They are all
surface active materials. These substances act as detergents. To tae an example, we may
explain the action of soap as a detergent. :ost of the dirt or dust stics on to grease or oily
materials which somehow gather on cloth. "s grease is not readily wetted by water, it is
difficult to clean the garment by water alone. The addition of soap lowers the interfacial
tension between water and grease so as to facilitate the mixing of the two. The soap
molecules get oriented at the interface between water and oil *or grease, in such a way that
their polar end *-C<<=a, is dipping in water and the hydrocarbon chain*+-, in the oil.
This helps in bringing the two liquid phases in more intimate contact with each other. !n other
words' the presence of soap causes emulsification of grease in water. The mechanical action,
such as rubbing, etc., releases the dirt.
>
#iscosity
9iscosity implies resistance to flow. !t is well-nown that all liquids do not flow equally
readily. Those liquids which flow slowly*for example,glycerine,castor-oil,honey and coal-
tar, are said to have high viscosity while those which flow readily*for example,water,alcohol
and ether, are said to have low viscosity.
The significance of viscosity may be further elucidated by considering the flow of a liquid
through a narrow pipe. "ll parts of the liquid do not move with the same velocity. " thin
layer, immediately in contact with the walls of the tube, is almost stationary. &ach succeeding
thin layer of the liquid moves with gradually increasing velocity which becomes maximum as
the centre of the tube is approached.
!he resistance that one part of a liquid flowing with one velocity offers to another part of the
liquid flowing with a different velocity is known as viscosity.
Alternatively' viscosity may be looked upon as the force of friction between two layers of a
liquid moving past one another with different velocities.
Suppose a cylindrical liquid layer of area " sq.cm. moves over another similar layer at a
distance of S cm.with a velocity difference of u cm.per sec.Then, the tangential force of
friction *f,, required to maintain a constant difference of velocity, is given by
f 3 ? " u - S
5here ? is a constant at a given temperature, depending upon the nature of the liquid and is
nown as the coefficient of viscosity.
!f " is / sq.cm., u is / cm.per sec. and S is / cm., then f 3 ?.
!he coefficient of viscosity of a liquid may' therefore' be defined as the force in dynes per
square centimetre required to maintain a difference of velocity of cm.per sec. between two
parallel layers of the liquid held at a distance of cm. from one another.
The reciprocal of viscosity is called fluidity and denoted by @.
Thus @ 3 /- ?
Determination of #iscosity
There are a number of methods of different inds for measuring viscosity. The method
commonly employed is based on poiseuilleAs law which connects the rate of flow of a liquid
through a capillary tube with the coefficient of viscosity of the liquid and is expressed by the
equation:
? 3 # r
+
t p % , - l
5here 9 is the volume in c.c.of the liquid flowing in t seconds through a narrow tube of
radius r cm. and length l cm.under a hydrostatic *driving, pressure of p dynes per square
centimetre and ? is the coefficient of viscosity in poises*i.e., dynes per square centimeter,.
Since the hydrostatic pressure p of a liquid column is given by
. 3 hdg
B
5here h is the height of the column and d the density of the liquid, the poiseuilleAs equation
may be written as:
? 3 # r
+
t h d g % , - l
!t is not necessary to measure all quantities on the right hand side of the above equation. The
viscosity of water at different temperatures has been very accurately determined. The usual
procedure is to determine the viscosity of a liquid with reference to that of water.
This is termed as relati"e "iscosity. "ll that is done is to measure the times of flow for equal
volumes of water and the liquid under examination, through the same capillary. !f t
/
and t
$
are
the times of flow of the same volume of water and the liquid, respectively, and ?
/
and ?
$
are
the respective coefficients of viscosity, then
?
/
- ?
$
3 # r
+
t

h d

g , - l / , - l # r
+
t
"
h d
"
g
The value of h is the same in both cases since equal volumes of both liquids are taen and,
therefore, they stand at the same height.
Therefore,
?
/
- ?
$
3 d

t

% d
"
t
"
$s%ald&s #iscometer
<swaldAs viscometer is used for measuring viscosity by the above method. !t is first
thoroughly cleaned with chromic acid mixture and dried. " nown volume of water, usually
/( to $B ml.depending upon the capacity of the bulb ", is pipetted into the bulb 6* bulb 6 is
bigger than ",.!t is then suced into the bulb " with the help of a rubber tube attached at the
end C till it rises to the mar :. The time taen by this water to flow through the capillary
tube C& is noted by means of a stop watch. 2et it be t
/
.The viscometer is dried and the same
volume of the liquid under examination is taen into the bulb 6 *so that the pressure head
remains the same, and the process repeated as before. 2et the time of flow now be t
$
.Then,
evidently,
?
/
- ?
$ 33
d

t

% d
"
t
"
5here d

and d
"
are the densities of the two liquids which can be determined by specific
gravity bottle or by pynometer method. Dnowing the coefficient of viscosity of water * ?
/
,,
that of the other liquid * ?
$
, can easily be calculated.
'nit of "iscosity
"s we have equation, 0 $ f S%Au
Since f is measured in dynes, S in cm. " in cm.
$
and u in cm.-sec., 1ence the units of 0 are
dynes x cm. / cm.
$
x cm.-sec. 3 dynes cm
.-$
sec.Thus viscosity is measured in dynes sec. -cm
$
.
4or simplicity, the units of viscosity dynes sec.cm
-$
are called poises.
Still more convenient units of viscosity are centipoises and millipoises *one millipoise 3
(.((/ poise and one centipoise 3 (.(/ poise,.
Elycerine has high viscosity because of the formation of a networ of hydrogen bonds
between the molecules. The networ which extends throughout the liquid maes the flow
difficult.
F
ffect of temperature on "iscosity
5ith rise in temperature, inetic energies of molecules increase. The inter-molecular forces of
attraction.therefore.decrease.1ence,lie surface tension, viscosity of a liquid also decreases
with rise in temperature. The effect of temperature on viscosity is, however, much greater
than on surface tension. !n most cases, the viscosity of a liquid falls by about " percent per
degree centigrade rise of temperature.
The variation of viscosity with temperature is best expressed by the empirical equation:
0 $ A e
1 % 2!
5here " and & are constant for a given liquid,+ is the Gniversal gas constant and T is the
temperature on absolute scale.
#