CHM170L Physical Chemistry 1 Laboratory

1st Quarter SY 2015-2016

Experiment No. 3: Surface Tension of Liquids

Soriano, Allan N.1,
Authors:
Bagumba, Ivan
Bilog, Jhaselyn Klevy
Bucud, Katrina
Cruz, Patricia Anne
Domingo, Angelo2
CHM170L / A11
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; 2Student (s), Subject/Section, School of Chemical Engineering,
Chemistry and Biotechnology, Mapua Institute of Technology
1

ABSTRACT
Surface tension is defined as the force (acting perpendicular to the surface) per unit length. The force generated acts mostly
upon surface molecules since the forces balance within bulk molecules of a liquid, resulting to zero net force. In order to
change the shape of a liquid, the required surface free energy must be applied on the substance as dictated by surface tension
for pure solvents and by surface concentration for solutions of liquid-liquid mixture and/or partly miscible interface. The
experiment utilizes the Tensiometer -ring method or the Du Nuoy method in determining the surface tension of 0.1 M to 0.8 M nbutanol solutions. Distilled water was used for calibration procedures. The Du Nuoy method uses a platinum-iridium alloy ring
in order to measure the maximum force generated upon submersion on the surface of the liquid samples. The obtained
surface tension of water was relatively high, The plot of concentration versus surface tension for n-butanol showed a
decreasing trend; increasing the concentration of n-butanol decreases the solution surface tension due to non-uniformity of
solute upon the surface of the solution. Using the Gibbs isotherm as well as the slope of the plot generated, the surface
concentration of the n-butanol set was found to be 2.497 x 10 -12 moles/cm2 at 28O C. A strong correlation coefficient of 0.9697
was noted for the data points collected. The objectives of the experiment were met with a few recommendations.
Keywords: surface tension, du nouy ring, surface concentration, gibbs isotherm

INTRODUCTION

Two forces are dominant upon liquid systems.

Cohesive forces are responsible for holding atoms
and/or molecules together; intermolecular in a sense.
Adhesive forces are accountable for the adherence of
the mixtures within containers or for the tension
between two systems (liquid to any other phase) at the
surface.
Surface tension is the amount of surface
energy per unit area required to alter the shape of a
substance. Surface free energy refers to the amount of
work needed to increase the area occupied by the
molecules of a substance. Upon physical aspects,
surface tension is the liquid property which causes the
substance to behave as if a thin sheet of film is
covering its surface. This behaviour is caused by the

Experiment 03 Group No. 3 Date July 27, 2015

tendency of the liquid molecules to assume the lowest

possible free energy to attain equilibrium. Liquid
molecules tend to contract to an ideal shape at a given
temperature and pressure.
Among liquids, two types of molecules are
considered: molecules within the bulk of the liquid and
molecules at the surface. The difference is the
direction as well as magnitude of the force attraction;
the molecules within the liquid bulk is surrounded by
other molecules on all sides, allowing for attraction in
all directions. Hence, zero net force is applied for bulk
molecules. However, molecules on the liquid surface
are attracted by a force directed inward to the
molecule. In order to change the shape of a liquid,
work must be applied on both the bulk molecules and

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the surface molecules so as to extend the surface area

occupied by the substance.
Among solutions, the surface tension
corresponding to the force attraction on the interface of
two different substances is known as interfacial
tension. The factors that affect surface tension
(interfacial) are concentration and type of the solute
dissolved as well as the presence of any surfactants.
Gibbs isotherm represents the relationship between
the factors of surface tension and surface
concentration.
The experiment utilizes static method of
determination of the surface tension of the interface
between two liquids in an aqueous solution (n-butanolwater mixture), specifically, the tensiometer-ring
method. The objectives were to measure the surface
tension of pure liquids and of an aqueous solution,
obtain the effect of bulk solute concentration for
aqueous solution surface tension and to evaluate the
variables affecting Gibbs isotherm using graphical
method.

trials were performed. The Du Nuoy ring method

utilizes a platinum-iridium alloy ring which hangs
parallel to the surface of the liquid. Upon operation, the
ring is sunk into a designated level into the liquid. In a
vertical direction, the ring is gradually drawn apart.
Throughout this process, the surface tension of the
liquid generates a force upon the ring. The surface
tension is measured using the changes with the force
generated, wherein the maximum force value and the
properties of the platinum ring were related by a
correction factor.
The Gibbs adsorption isotherm was also
utilized in the experiment:

where: u = surface concentration (moles/cm2)

= surface tension (dynes/cm)
C = bulk concentration (moles/cm3)
T= temperature, K

METHODOLOGY

The experimental procedures made use of the

Du Nuoy method which utilizes the following
apparatus: 8 - 50 mL volumetric flask, 2 - 250 mL
beaker, 3 - 5mL pipet, 2 - suction bulb and Du Nuoy
Tensiometer.
The Du Nuoy instrument calibration was
performed by measuring the surface tension of distilled
water for three trials. A correction factor ( ) was
obtained and was utilized for the succeeding
measurements of n-butanol.
*
8 different concentrations of n-butanol were
prepared as test samples. For each concentration, five

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RESULTS and DISCUSSIONS

In determining the surface tension of various
n-butanol solutions, the tensiometer was first
calibrated. Upon calibration of the instrument, the
surface tension of distilled water was taken at 28 O C.
Data obtained (see Table 1) during calibration were
treated and used as the correction factor for the nbutanol solutions. The correction factor takes into
account the shape of the liquid which is held up by the
platinum-iridium ring. The ring is slightly bent and
circular in shape, allowing for a few liquid molecules to
flow downward. As a consequence, the surface
tension is not perfectly even on the surface. The use of
the correction factor accounts for the irregularities with
the ring method.

Surface Tension
(dynes/cm)

Concentration (mol / L)

Corrected Surface
Tension (dynes/cm)

0.10

73.57

0.20

64.33

0.30

56.73

0.40

52.96

0.50

49.59

0.60

45.41

0.70

43.06

0.80

40.73

72.6

Trial 1
Trial 2

72.5

Trial 3

65.1

Avg. Surface Tension

70.07

Literature value

71.501

Correction factor

It is found, however, that the surface tension

of n-butanol solutions are different from the surface
tension of water. The expected literature value for the
surface tension of pure n-butanol is only 24.2
dynes/cm. Thus, the surface tension for the dilute nbutanol solutions is expected to range from 35 to 50
dynes/cm. The high discrepancy of the data obtained
(Table 2) from the expected values can be accounted
for the calibration procedure performed as well as the
sensitivity of the tensiometer.
Table 2. Surface Tension of n-butanol solution at varying
concentrations

Table 1. Surface Tension of Water

Measurement

other pure solvents. An example 4 of the tendency of

water molecules to contract to the smallest possible
area is the formation of water droplets and the
appearance of meniscus when water is held in
containers.

1.0204

It is observable (Table 1) that water has a

relatively high surface tension. Again, surface tension
is defined as the force acting over the surface of a
solution per unit length of the surface perpendicular to
the force. Lower area occupied by the molecules mean
higher surface tension. Hence, surface tension is a
result of the intermolecular forces that cause the
molecules to occupy the smallest possible area in
order to achieve equilibrium 3. The intermolecular
forces acting among water molecules are strong due
to hydrogen bonding, thus, the molecules occupy a
small area resulting to higher surface tension than

Experiment 03 Group No. 3 Date July 27, 2015

A plot of the corrected surface tension of nbutanol as a function of the natural logarithm of the
various concentrations (Figure 1) show a decreasing
trend. The dependence of surface tension on
concentration can be explained using the Gibbs

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adsorption isotherm5 (see Methodology) which

provides for the relationship between surface tension,
solution concentration and temperature. Based on the
Gibbs isotherm, the slope of the plot of concentration
versus surface tension of the n-butanol solutions is
equal to the negative reciprocal of the product of the
surface concentration, temperature and the ideal gas
constant.
Figure 1. Concentration versus corrected surface tension of nbutanol solutions

Using the Gibbs isotherm the slope of the plot,

the surface concentration7 for the set of n-butanol
solutions at 28OC was found to be 2.497 x 10 -12
moles/cm2. This surface concentration yield is
conducive with the theories since a decrease in
surface tension must result to a positive surface
concentration based on the Gibbs isotherm. Surface
concentration may also be used to
determine the amount of surface
area occupied of each molecule
using Avogadro's number8. The
abovementioned
data
gives
insight on the amount of surface
energy required for n-butanol and
may be combined with results
from pressure tensiometers (and
other types) for adsorption
coefficient determination.

CONCLUSIONS
RECOMMENDATIONS

Interfacial tension is applicable when two

phases are present6. In this case, a two-liquid interface
was applied in the experiment. Due to the adhesive
forces caused by interfacial tension, an interface, or an
interaction at the surface, occurs between the water
and butanol molecules. Increasing the concentration of
n-butanol adds more butanol molecules to the solution,
thereby increasing the non-uniformity of solute
concentration near the surface. This increase along
the surface can be classified as positive surface
concentration; when free energy is increased by this
surface concentration along with the decreasing
surface tension, equilibrium is reached.

Experiment 03 Group No. 3 Date July 27, 2015

AND

The surface tension of

substances shows how much
surface free energy is needed to
bring the bulk molecules to the
surface in order to break or change the area of the
substance's surface. Smaller area translates to higher
surface tension and is usually dictated by the
intermolecular forces; water has a high surface tension
due to hydrogen bonding. The surface tension of nbutanol decreases as the concentration increases due
to interfacial tension which then results to an increase
in free energy. Liquids, whether present as pure
solvents or solutions, will always assume the smallest
possible area in order to reach state equilibrium. The
Gibbs isotherm relates temperature, surface
concentration and surface tension wherein a positive
surface concentration leads to reduced surface tension
while a negative surface concentration gives an
increase on surface tension.

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Despite the errors noted in the experiment, a

correlation of 0.9697 for the plot of concentration
versus surface tension of n-butanol serves as a strong
indication of the relationship between the data points.
The objectives of the experiment were met although a
few recommendations were noted. Due to the
sensitivity of the platinum-iridum alloy ring used, the
method itself is not perfectly reliable for determination
of the surface tension at the equilibrium state. Further
use of the Du Nouy method requires careful handling
of the instrument.

REFERENCES
1. Physical Chemistry, 3rd ed. Mortimer, R. (Data
interpolated from source)
2. Surface Tension. Patel, I. (pdf version)
3. Physical Chemistry of Surfaces, 6th ed. Adamson,
A., and Gast, A. John Wiley, New York. 1997
4. Fluids: Surface Tension. Ducree, J. (pdf version)
5. Physical Chemistry I Laboratory Manual, Part 1.
Caparanga, A., Baluyut, J., Soriano, A. Manila.
2006
6. Interfacial Tension.
Non-Newtonian Fluid
Dynamics Research Group. MIT (retrieved from
database, 7/24/15)
7. IUPAC: Compendium of Chemical Terminology,
2nd ed. ("The Gold Book"). Compiled by
McNaught, A. and Wilkinson, A. Blackwell
Scientific Publications, Oxford. 1997
8. Surface excess concentration. Kruss Surface
Science Group. Hamburg, Germany. 2015
(retrieved from database, 7/24/15)

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