Determination of the surface pressure by bubble-pressure method

The surface tension of liquids

The molecules of liquids attract each other by cohesive forces resulting into small
distances between the molecules (on the order of 0.1 nm). Hence the compressibility of
liquids is lower then that of gas, while the density is much higher. On the other hand,
these cohesive forces are not strong enough to result into the fixed position of molecules
that can be seen in solid matter. Liquids do not keep a fixed shape, but adapt the shape of
a container. Attractive cohesive forces are short range forces which are based on the
electronic interactions. They affect only molecules in their close vicinity (zone of
molecular interaction). In the bulk of the liquid, each molecule is attracted equally in all
directions by the neighboring molecules, thus resulting in a total force of zero (Fig. 1).
However, the molecules at the surface do not have other like molecules on all sides of
them and they are pulled inwards the liquid core by non-zero total force (Fig. 1).
Consequently, they cohere more strongly to those directly associated with them on the
surface and form a surface "film". Nevertheless, these surface molecules are in the
energetically unfavorable state, which makes liquid to minimize the surface area. The
geometrical requirement of smallest surface area at the fixed volume is satisfied by the
sphere. It is the reason why the free drops of water form spherical droplets.





Figure 1:
Cohesive forces in a case of the
molecule at the liquid surface and
in the bulk.

Surface area increase, S, is balanced out by the increase of energy, E, where
S E = [1]
The coefficient defines the surface tension in the units of J/m
2
=N/m. Each liquid is
characterized by its own surface tension, which decreases with an increasing temperature
(see Table 2).
The molecules of the liquid interact with the walls of the container through
adhesive forces. The surface bends up (concave meniscus) when the adhesive
intermolecular forces are stronger than the cohesive forces inside the liquid (e.g. water in
a glass container shown on Figure 2), while it bends down (convex meniscus) when the
adhesive forces are weaker (e.g. mercury in a glass container).


Figure 2:
The glass capillary of a radius r
immersed in water.





Capillary action is the result of interplay between the surface tension and adhesive
forces. Water inside the capillary arises above the water level in the container (capillary
elevation). Capillary pressure, p
k
, that draws water into capillary is determined by the
radius of capillary, r, and the surface tension of water, , as follows from

r
p
k
2
= [2]
Capillary pressure and capillary elevation is higher for narrower capillary.
In a contrary to water, capillary action in a case of mercury has an opposite
direction. The mercury level inside the capillary is lower than that in the container
(capillary depression).

r
h
The method of surface pressure determination by pushing the bubbles
through the capillary

The capillary of radius r is immersed in the liquid of density and surface tension
, such that the bottom of capillary is at the depth of h bellow the water level (Figure 2).
We would need to apply pressure equivalent to the capillary pressure, p
k
, to bring the
liquid level in the capillary to the same level as that in the container. The additional
pressure p
h

g h p
h
= [3]
where g is a gravitational acceleration, would than cause water to be pushed out of the
capillary completely. p
h
is the hydrostatic pressure at a depth h, and it is a result of the
weight of the liquid above this point (see Figure 2). The pressure equal or greater than

h k
p p p + = [4]
would push the air all the way through the capillary and will create a bubble at its end.
The combination of equations [2] and [3] with the equation [4] yields
g h
r
p + =
2
[5]
It is the equation that establishes the method of surface tension determination via pushing
the bubbles through the capillary. Figure 3 describes the standard apparatus employed in
such a measurement. The investigated liquid is contained in a beaker, with the capillary
immersed in it. Water contained in a funnel A will create the desired pressure upon the
opening of the knob C
1
. This pressure is measured by the manometer M, which consists
of a U-shape glass tube filled with water. The water levels in the both arms of manometer
are equivalent at the beginning of the experiment. However, pressure p will create a
difference in water levels, h
V
, after opening the knob C
1
. This pressure is determined by
g h p
V V
= [6]
where
V
is a density of water.
The combination of the equation [6] and [5] determines the surface tension as
( ) g h h
r
V V
=
2
[7]
where the water density is
V
=1 g/cm
3
=1000 kg/m
3
, and the density of the investigated
liquid is marked on a beaker of stock solution. The capillary radius r can be determined
from the control measurement in which we measure the known surface tension of water.
It is shown in Table 2 as a function of temperature. The radius r is than expressed from
equation [7] using the known parameters (,
V
and ) and measured water levels h and
h
V
.


Figure 3.:
The apparatus for the
determination of surface tension
via pushing the bubbles through
the capillary.




Equiment:
Apparatus displayed in Figure 3, capillary, 2 beakers, liquids with unknown surface
tension, ethanol for cleaning the capillary

Experimentl procedure:
1. Flush the capillary K with distilled water and ethanol, and dry it using the water
aspirator. Mount the capillary on the apparatus arm.
2. Fill the smaller beaker with the liquid of unknown surface tension and immerse the
capillary into it.
3. Fill the funnel A with water, while the knobs C
1
and C
2
stay closed.
4. Slowly open the knob C
1
, thus create an additional pressure in the apparatus. Watch
the bubbles that are being pushed through the capillary. The pressure p decreases as
the water level in funnel A decreases, which results into the slow reduction in a rate of
h
h
v
A
K
M
C
1
C
2
bubbling. Close the knob C
1
right at the moment when the bubble formation stops.
Read out the water levels h and h
V
.
5. Open the knob C
2
to release water form apparatus into the larger beaker.
6. Repeat the measurement (sections 3 and 4) 10 times and write the measured values
into a table. Calculate the average values of h and h
V
.
7. Wash the beaker and capillary.
8. Repeat the measurement using a different liquid.
9. Measure the room temperature t. Determine water surface tension at this temperature
using the Table 2. Calculate the surface tension of the investigated liquids using the
equation [7].

Tab. 1. The difference of water levels h
V
in manometer and the depth of capillary
immersion h.
water liquid n.1 liquid n.2 liquid n.3
measurement
h
V
[m] h[m]

h
V
[m] h[m] h
V
[m] h[m] h
V
[m] h[m]
1
2
3
4
5
6
7
8
9
10

Tab. 2: Water surface tension as function of the temperature.

t[C] [N/m]
15 0,07349
16 0,07334
17 0,07319
18 0,07305
19 0,07290
20 0,07275
21 0,07259
22 0,07244
23 0,07228
24 0,07213
25 0,07197


References:

1. Kopeck, F.: Physics for Students of Pharmacy I. Bratislava, UK 1999. 184 s. (in
Slovak)
2. Edition of Department of Physical Chemistry: Laboratory Practice in Physics for
Students of Pharmacy. Faculty of Pharmacy, Comenius University, Bratislava, UK
1991.
3. Oremusov J., Vojtekov M.: Surface pressure of liquids. Manual for laboratory
practice. (in Slovak)




The manual written by RNDr.J.Gallov, CSc.
English version prepared by N. Kuerka, PhD.