CHEM-C2230 Pintakemia Lab work 1: Determination of the c.m.c.

of a surfactant

Lab work 1: Determination of the critical micelle concentration of a surfactant

 Objective

The main objective of this lab work is to determine the critical micelle concentration of an
anionic surfactant, sodium dodecyl sulfate (SDS), with two different techniques: a) surface tension
measurements using the Du Nouy ring method; and b) conductivity measurements. The effect of
salt on the critical micelle concentration will be also analyzed in the latter case.

 Introduction

Surfactants are water-soluble amphiphilic

molecules that consist of a non-polar hydrophobic
part (usually a hydrocarbon or fluorocarbon chain)
and a polar hydrophilic part (head group). The
hydrophilic head group can be nonionic, anionic,
cationic, or zwitterionic. The balance between
hydrophobic and hydrophilic parts gives special
properties to surfactants, e.g. high affinity to
adsorb at interfaces and association in solution to
form micelles.

The concentration at which surfactants start to form micelles is called critical micelle
concentration (c.m.c.). Each surfactant has a characteristic c.m.c. at a given temperature and salt
concentration. The c.m.c. of a surfactant can be obtained by different techniques, which in general
are based on the measurement of a magnitude that shows an abrupt change at c.m.c. The surface
tension at the air/water interface and the electrical conductivity of a solution are examples of such
magnitudes.

The surface tension at the air/water interface decreases

when the surfactant concentration in the aqueous solution
increases. This effect is due to the adsorption of
surfactant molecules at the interface. The drop of surface
tension stops when the surfactant starts to form micelles
in solution (c.m.c.). The surface tension remains virtually
constant at surfactant concentrations above the c.m.c.
Therefore, the c.m.c. can be determined from surface
tension measurements at different surfactant
concentrations. The inflection point in graphs of surface
tension versus logarithm of surfactant concentration
gives the c.m.c. There are different methods to measure
the surface tension of an air/liquid interface. In this lab
work the surface tension will be measured using the Du
Nouy ring method (see Appendix).

The electrical conductivity is a magnitude that describes the ability of a material or solution to
conduct an electric current. The electrical conductivity of a solution depends on the number and
mobility of ions and charged particles present in the solution. In the case of ionic surfactants, the

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CHEM-C2230 Pintakemia Lab work 1: Determination of the c.m.c. of a surfactant

electrical conductivity increases as the surfactant

concentration increases. The formation of micelles affect
the conductivity of the solution. The c.m.c. can be
obtained from the inflection point (intersection of linear
fits) in the curve conductivity versus surfactant
concentration.

Surfactant concentration (mM)

Sodium dodecyl sulfate (SDS), also called sodium lauryl sulfate, is an anionic surfactant
commonly used in many cleaning and hygiene products. Its c.m.c. will be determined in this lab
work with two different techniques:

a) Surface tension measurements using the Du Nouy ring method.

b) Conductivity measurements.

Lab work 1.a) Determination of c.m.c. of SDS by surface tension measurements.

The surface tension of
different SDS solutions is
measured with a KSV
Sigma70 tensiometer or a
Krüss tensiometer using the
Du Nouy ring method. Please
carry out the lab work
according to the following
KSV Sigma70 tensiometer
instructions:

- Clean properly the vessel and the Du Nouy ring with aqua
regia (HNO3 : HCl, 1:3) and deionized water. Burn the ring in
the flame of a Bunsen burner to remove any impurity.

- Add 30 ml of deionized water to the vessel and place it on the

stage of the tensiometer. Hang the clean ring on the balance
hook over the vessel.

- If you are using the KSV Sigma70 tensiometer, open the

software sgserver and click on the Surface Tension
Measurement icon. Click File  New Experiment. Choose a
name for the experiment. Probe: standard ring. Vessel: small. Krüss tensiometer
Heavy phase: water (volume = 30 ml). Light phase: air. Press
the Start button and check the parameters in the next window: Speed up = 5 mm/min; Speed
down = 20 mm/min; Dwell down = 5%; Minimum number of points = 10; Minimum
measurement time = 0 s; Wait before start = 0 s; AutoZero: enabled. Press the Start button to
measure the surface tension of deionized water.

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CHEM-C2230 Pintakemia Lab work 1: Determination of the c.m.c. of a surfactant

- If you are using the Krüss tensiometer, set the instrument at 0 mN/m when the ring is hung in
the air. Lift the vessel stage with the screw and immerse the ring in the water. Turn the scale
knob and write down the value of surface tension just before the ring is pulled out the water.

- Prepare 10 ml of two solutions of SDS at 120 mM and 320 mM (MWSDS = 288.37 g/mol).
Repeat the process of surface tension measurement after adding different volumes of the SDS
solutions to the water in the vessel according to the following table:

Volume of SDS solution Total volume SDS concentration Surface tension

added to the vessel in the vessel (ml) in the vessel (mM) (mN/m)
0 30 0
100 μl of 120 mM SDS
Plus 50 μl of 120 mM SDS
Plus 100 μl of 120 mM SDS
Plus 150 μl of 120 mM SDS
Plus 120 μl of 120 mM SDS
Plus 150 μl of 120 mM SDS
Plus 130 μl of 120 mM SDS
Plus 220 μl of 120 mM SDS
Plus 280 μl of 120 mM SDS
Plus 340 μl of 120 mM SDS
Plus 510 μl of 120 mM SDS
Plus 550 μl of 120 mM SDS
Plus 1 ml of 120 mM SDS
Plus 740 μl of 320 mM SDS
Plus 1.3 ml of 320 mM SDS
Plus 2.5 ml of 320 mM SDS

- Clean everything after finishing the experiment.

Lab work 1.b) Determination of c.m.c. of SDS by conductivity measurements.

A conductimeter is used to measure the conductivity of a SDS solution. The concentration of
SDS in the solution is increased by continuous addition of other concentrated SDS solution with a
dispenser. The measurements are accomplished in the absence and presence of 10 mM NaCl. Please
carry out the lab work according to the following instructions:

1) - Prepare 50 ml of a solution 320 mM SDS (MWSDS = 288.37 g/mol).

- Introduce the conductivity electrode in 400 ml deionized water and write the conductivity
value. Gently stir the solution with a magnetic stirrer for the whole experiment.

- Add 0.5 ml of 320 mM SDS solution with the dispenser and write the new value of
conductivity (wait until the value is stable). Avoid the presence of air bubbles in the
dispenser tube.

- Repeat the process until the total volume of 320 mM SDS solution added is 25 ml.

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CHEM-C2230 Pintakemia Lab work 1: Determination of the c.m.c. of a surfactant

2) - Clean the dispenser with deionized water.

- Prepare 50 ml of a solution 160 mM SDS, 10 mM NaCl (MWNaCl = 58.44 g/mol).

- Introduce the conductivity electrode in 400 ml of 10 mM NaCl solution and write the
conductivity value. Gently stir the solution with a magnetic stirrer for the whole
experiment.

- Add 0.5 ml of 160 mM SDS, 10 mM NaCl solution with the dispenser and write the new
value of conductivity (wait until the value is stable). Avoid the presence of air bubbles in
the dispenser tube.

- Repeat the process until the total volume of 160 mM SDS, 10 mM NaCl solution added is
25 ml.

- Clean everything after finishing the experiment.

 Homework

- Fill in the table for lab work 1.a) and plot the experimental data of surface tension versus
logarithm of surfactant concentration. Determine the c.m.c. of SDS from the graph.

- Plot the experimental data of conductivity versus surfactant concentration for the cases of
no NaCl and 10 mM NaCl added to the system. Determine the c.m.c. of SDS from the
graphs (intersection of linear fits).

- Compare the c.m.c. values obtained from surface tension measurements and conductivity
measurements (no NaCl added) with the value found in the literature. Discuss the results.

- Discuss the effect of NaCl on the c.m.c. of SDS.

 Additional information

- This lab work is carried out in groups of 4 people: 2 people for lab work 1.a) and 2 people
for lab work 1.b). They should share the results of the experiments, analyze the data
together, and submit the answers to the homework in a common report within one week.

- Up to 3 points can be obtained for this lab work: up to 1 point for the work in the lab, and
up to 2 points for the report with the answers to the homework.

- Safety in the lab is a very important issue. You must always wear lab coat, gloves and
goggles when you work in the lab.