EXPERIMENT NO: 11

PROPERTIES OF DETERGENTS: SURFACE TENSION MEASUREMENT

OF CRITICAL MICELLE CONCENTRATION

Objectives:
To introduce you to the fundamental properties of surfactants
To illustrate the properties of surfactants by measuring surface tension
To gain familiarity with the critical micelle concentration
To gain familiarity with the surface tensions of natural waters

Introduction
Soaps, detergents, and surfactants
Ordinary soap is a mixture of the sodium salts of monoprotic carboxylic acids containing 10-18
carbon atoms. Shorter chain salts are unable to emulsify oil in water, hereas longer chain salts are
too insoluble to function as effective detergents.
Soap is one type of surfactant. A surfactant affects the properties of a solvent to a much greater
extent than expected on the basis of its very small concentration. This marked effect is due to
(I) Adsorption of the surfactant at the solution interfaces
(2) Micelle formation in the bulk of the solution.
A surfactant increases the wetting ability of water, allowing it to loosen, solubilize, and/or emulsify
soils, and hold the loosened dirt in suspension, preventing it from settling back in to the cleaned
items. A surfactant usually displays its greatest surface activity when it is present close to its limit
of solubility, which is between 0.1 and 10mM for efficient surfactants.
A detergent is a cleansing agent and soap is one type of detergent. Detergents lower the surface
tension of a solvent to about one-third of its original value.

Theory
Surfactants form aggregates of molecules or ions called micelle when the concentration of the
solute exceeds a limiting value called the critical micelle concentration (CMC). The CMC is the
concentration at which micelles begin to form and its value varies with the solute-solvent system.
A micelle is a submicroscopic fundamental component of a surfactant. Since a surfactant has two
different groups, hydrophobic and hydrophilic, the hydrophobic groups tend to associate with each
other when they are in the body of the solution. The hydrophilic groups, on the other hand,
associate with the aqueous environment. Both properties can be realized by forming a micelle, as
shown in Figure 1.
The spontaneous dissolving of a normally insoluble substance by a relatively dilute solution of a
surfactant is called micellar solubilization. Solubilization and detergency begin at the CMC and
increase with increasing surfactant concentration.

The CMCs of nonionic surfactants are generally much lower than those of ionic surfactants of
comparable hydrocarbon chain length. For a series of surfactants, where the hydrophilic group
remains the same, CMC values decrease with increasing chain length of the hydrophobic group
for both ionic and nonionic surfactants. The CMCs of anionic surfactants increase with increasing
temperature, whereas the CMCs of nonionic surfactants decrease with increasing temperature.

The most frequently determined properties of a surfactant are its surface tension and its CMC. If
the properties of a surfactant solution are plotted as a function of the concentration of the
surfactant, the properties will usually vary linearly with increasing concentration up to the CMC,
at which point there will be a break in the curve. The CMCs of surfactants have been determined
by the:

1. Break in the surface tension versus log (concentration) curve

2. Break in the turbidity versus concentration curve
3. Iodine-solubilization method
4. Conductance versus concentration curve (for ionic surfactants)
5. Viscosity versus concentration curve

Surface Tension and Its Measurement

One of the most characteristic features of a liquid is its surface tension. It is due to unbalanced
intermolecular forces at the surface of the liquid. Most substances, when dissolved in water, reduce
the surface tension of water. Since most substances have a surface tension less than water, when
they are uniformly distributed at the water surface, they result in a smaller surface tension.
Detergents decrease the surface tension by a much greater amount than expected on the basis of
the small amounts present. A few substances, mainly ionic salts, increase the surface tension of
water, but only to a small extent.

The surface tension, may be defined as the amount of work necessary to extend the surface of a
liquid by unit amount,
γ = work/ΔA

Where A is area. The units of surface tension are erg/cm2, or dyn/cm (joules per square meter,
J/m2, or N/m in the S.I. system). The surface tension of water is 72.75 dyn/cm at 20 °C and that of
diethyl ether is 17.01 dyn/cm at 20 °C. The large surface tension of water is due to the very strong
hydrogen-bonding forces present, whereas the forces in ether are chiefly dispersion.

Several methods are available for measuring the surface tension. In the capillary-rise method, the
height of which a liquid rises in a glass capillary tube is measured. In the weight-drop method, the
weight of a drop that falls from a tube of known radius is determined. The ring method is based
on measuring the force necessary to pull a metal ring from the surface of a liquid. In this
experiment we shall use the capillary-rise method.
The Capillary-Rise Method
A liquid tends to assume a shape of minimum area. If a vertical capillary tube is dipped into a
liquid that "wets" the tube, a film of the liquid will run up the capillary wall. Then, to reduce the
surface area, the liquid rises in the tube until the force of gravity on the liquid column balances the
tension at the circumference. The simplest equation for calculating surface tension by capillary
rise is,
γ = rhρg / 2
where r is the capillary radius, h is the rise in the capillary , p is the density of the liquid, and g is
the acceleration due to gravity. More accurate equations can be used that take contact angle into
account, but the above equation is satisfactory for this experiment. The capillary rise method is
probably the most accurate way to measure surface tension.

Safety Precautions
I. Safety glasses must be worn at all times in the chemistry laboratory.
2. Wear neoprene gloves when handling concentrated nitric acid. Use nitric acid only in a fume
hood. This acid is highly oxidizing. Also avoid contact of nitric acid with organic matter since it
may be explosive.

Procedure
A: Calibration of the Capillary
Capillary tubes are cleaned, if necessary, by soaking in concentrated nitric acid. They should be
stored in pure water. Carry out the measurements as follows, referring to Figure 2.

1. Place enough sample in the large outer tube so that when the capillary-rise scale is placed inside,
the outer liquid level lies between 0 and 1 cm. The capillary can also be adjusted to some extent.
To avoid frothing, which will make it difficult to read the level of the outer liquid meniscus,
gently pour the liquid down the inside wall of the outer tube.

2. Rinse the capillary with sample by forcing solution into the capillary using a bulb on the side
arm.
3. Adjust the height of the liquid above its equilibrium value using the bulb and measure the final
height. Repeat both steps.
A good light and a magnifier may be needed to see the liquid level within the capillary.
(In each measurement, determine the distance between the lower meniscus in the outer tube and
the upper meniscus in the capillary.)
4. Average the values of two readings to obtain a value of h. A difference of more than 0.2 mm in
the readings indicates a dirty capillary.
Although the capillary usually comes with a known diameter (about 0.5mm, for precision work
the radius should be accurately determined, using water to calibrate. The values for the surface
tension & density of water are given in Table 1. From the measured height and the temperature of
the water, Equation 2 is used to calculate the value of r. Two measurements of h should be made
and two values of r calculated and the average value of r used in subsequent calculations.

When other liquids are to be examined in a tube that has been used, rinse the capillary with the
new fluid outside the apparatus and then reassemble the apparatus. Alternatively, rinse the
capillary with a solvent and then dry the capillary with a stream of gas.

Table 20-1 The Surface Tension and Density of Water at Various Temperatures

Temperature (C) Density (g/mL) Surface Tension (dyn/cm)

72.75
20 0.99823
71.97
25 0.99707
71.18
30 0.99567

Source: R.C. Weast, Editor-in-Chief, CRC Handbook of Chemistry and Physics,59th ed; CRC
Press, Inc.,Boca Raton, FL, 1978.

Determining the CMC of an Ionic Surfactant

1. Prepare a stock solution of the detergent in Dl water. Its concentration depends on the CMC of
the surfactant under study. For a detergent like sodium lauryl sulfate (SLS), with a CMC in the
vicinity of 0.01 (a 10 g/ 100 ml)stock solution is convenient). This is near the solubility limit,
and sudsing begins to become a problem such high concentrations.

2. Use pipettes and volumetric flasks to prepare 100 mL of each of 10 solutions with varying
concentrations of surfactant by appropriate dilutions of the stock solution. About five solutions
should have a concentration less than the CMC, and the other five should have concentrations
greater than the CMC.

3. Measure the capillary rise of each solution using the procedure in Part A.

Measuring the Surface Tension of Environmental Samples

1. Measure the capillary rise of four environmental sample-a stream, a pond, a well, and seawater
(if possible). These samples must be filtered to avoid clogging the capillary.
2. If time permits, the density of each sample is determined. For dilute solutions of surfactant, the
density will be about the same as that for pure water.
Data Analysis
1. Use a table to report your calibration data, the capillary rise, temperature, density and the radius
of the capillary. Compare your calculated capillary radius with a given value, if available, or
with previously measured values.
2. Calculate the surface tension for each solution studied. If the densities of the solutions were
experimentally measured, list their values in a table.
3. Prepare a plot of surface tension (ordinate) versus log (surfactant concentration). Draw the best
possible straight lines through the points on each side of the CMC and find their intersection,
which corresponds to the CMC. Report this value. Also try a plot of surface tension versus the
concentration and discuss the result.
4. Compare your experimental CMC with values expected for ionic surfactants. Discuss the
difference and experimental errors.
5. Calculate and discuss the surface tension results for the environmental samples. From the
values obtained, what can you conclude about the nature of the dissolved solids in the sample.

Notes
1. Frothing can be very troublesome in this experiment. When making the solutions they should
not be overly shaken and should be given some time to settle.
2. A thermometer magnifier or a cathetometer telescope can facilitate the measurements. A
magnifier “borrowed” from melting-point apparatus aids significantly in the measurements of
the liquid level in the capillary.

Discussion
1. Describe the cleaning process of detergents against dirt on clothes.

2. What is CMC? And why is it important in detergent’s action?