CONDUCTIMETRIC

DETERMINATION OF CRITICAL
MICELLE CONCENTRATION
(CMC)

Date Performed:
October 3, 2014

Date Submitted:
October 22, 2014

Group Code: ChE412LTUE03

Group Members:

Conag, Angelique

Delos Angeles, Tiara Noelle

Introduction:

Surfactants are organic substances, which significantly decrease the surface tension of
water, at least partially soluble. The molecular structure of surfactants is amphiphilic, it consists
of both hydrophilic and hydrophobic parts. Surfactants are absorbed mainly on the surface of
the solution thus they are called surface active substances. When dissolved in a solvent, after
they reach a certain concentration, the molecules of surfactants begin to associate and form
micelles. The concentration at which the formation of micelles begins is the critical micelle
concentration. Micelles are aggregates of larger number of simple molecules or ions of
surfactants. The resulting size is in the colloidal range. The molecular structure of surfactants is
amphiphilic, it consists of both nonpolar and polar parts (Figure 1).

Figure 1. An illustration of the micelle of sodium dodecyl sulfate (SDS)

The hydrophobic part of the micelle consists of hydrocarbon groups. Meanwhile, the
hydrophilic part may consist of non-ionic polar groups or ionic groups. Based on the charge and
the nature of the ion which creates surface activity, the ionic surfactants are divided into: (1)
anionic surfactants, (2) cationic surfactants, and (3) ampholytic surfactants. SDS is an anionic
surfactant. When the concentration of SDS reaches its CMC, the SDS anions start to aggregate
into the negatively charged globular micelles. The hydrocarbon tail is faced inside the micelle
while the polar tail is orientated to the polar environment. The CMC indicates the usually
narrow range of concentrations separating the limits, when the surfactant is in the monomeric
state and when all additional surfactants enter the micellar state (Desando, 1986). The micelle
formation is always affected by the effect of the length of the hydrocarbon chain and the
nature of the solution added. The CMC decreases greatly when the hydrophobic part of the
surfactant is increased; the decrease is faster for the nonionic than for ionic surfactants
(Lindman, 1984).

Methodology:

1. Two 100-mL aqueous stock solutions of 0.05 M sodium dodecyl sulfate were prepared.
A 100-mL aqueous solution of 0.02 M of NaCl and 0.01 N KCl solution were also
prepared.
2. The conductivity meter was calibrated with the prepared KCl solution. The cell constant
was recorded from the calibration.
3. 70 mL of distilled water was measured and pipetted into a clean 200-mL beaker. The
container was placed on top of a magnetic stirrer and was placed in a small stirring bar.
The stirrer and the conductivity meter were turned on simultaneously and the value of
the conductivity was recorded.
4. With a pipet, 0.3 mL of the prepared SDS solution was added to the distilled water. The
conductivity was read after a minute upon the addition of the SDS. 0.3 mL aliquots of
the SDS were continued to be added and still reading the conductivity after a minute
upon the addition of the SDS. The conductivity values were recorded.
5. After 15 aliquots were added, 0.5 mL aliquots of the SDS solution were continued to be
added to the solution and the conductivity was read and recorded after a minute of
addition of the SDS.
6. After using water as solvent for the first run of the conductivity reading, 70 mL of the
aqueous solution of the 0.02 M NaCl was measured and its conductivity was measured
just like how the conductivity of water was measured above. The conductivity was read
and recorded.
7. 0.2 mL aliquots of the SDS solution were added to the NaCl solution and 45 more aliquot
additions were added. For every addition of an aliquot, the conductivity was read and
recorded after a minute of adding the SDS solution.
Illustration and Description of Experimental Setup

A F

E I J
D
B C

Figure 1. The Conductimetric Determination of the Critical Micelle Concentration Experimental Setup

Parts:

A – Display: where the conductivity reading is displayed

B – Function Knob: knob to set which mode the conductivity meter will display
C – Set K Knob: knob used to adjust the value of K or the cell constant
D – Tuner
E – Range knob: adjusts the range at which the conductivity will read the conductivity
measurements
F – Conductivity Meter: measures the conductivity of the solutions introduced to the meter
G – Electrode: provides the current to the solution under observation
H – Solution: the solution which is under observation
I – Magnetic stirrer: stirs the solution with a use of a magnet
J – Stirrer Knob: adjusts the speed of the stirring to be done on the solution

Sample Calculations:

 Calculating the mass (g) of SDS needed to prepare 100 mL of 0.05 M SDS solution:

1𝐿 0.05 𝑚𝑜𝑙 𝑆𝐷𝑆 288.305 𝑔 𝑆𝐷𝑆 1

𝑚𝑆𝐷𝑆 = (100 𝑚𝐿) ( )( )( )( ) = 1.70 𝑔 𝑆𝐷𝑆
1000 𝑚𝐿 𝐿 𝑚𝑜𝑙 𝑆𝐷𝑆 0.85
  Calculating the mass (g) of NaCl needed to prepare 100 mL of 0.02 M NaCl solution:

1𝐿 0.02 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 58.45 𝑔 𝑁𝑎𝐶𝑙 1

𝑚𝑁𝑎𝐶𝑙 = (100 𝑚𝐿) ( )( )( )( ) = 0.1170 𝑔 𝑁𝑎𝐶𝑙
1000 𝑚𝐿 𝐿 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 0.999

 Calculating the concentration (C) of the solution

1
𝑚𝑜𝑙 𝑀𝑆𝐷𝑆 𝑉𝑆𝐷𝑆,𝑎𝑑𝑑𝑒𝑑
𝐶 ( )= 1000
𝐿 1
(𝑉𝑆𝐷𝑆,𝑎𝑑𝑑𝑒𝑑 + 70) 1000

Where:
𝐶= concentration of the solution, mol/L
𝑀𝑆𝐷𝑆 = concentration of stock SDS, mol/L (0.05 mol/L)
𝑉𝑆𝐷𝑆,𝑎𝑑𝑑𝑒𝑑 = volume of stock SDS added, mL

When 0.3 mL SDS was added with water as solvent:

1𝐿
(0.05 𝑚𝑜𝑙/𝐿)(0.3 𝑚𝐿)( )
1000 𝑚𝐿
𝐶 = 1𝐿
(0.3 𝑚𝐿 +70 𝑚𝐿)( )
1000 𝑚𝐿

𝐶 = 2 𝑥 10−4 𝑚𝑜𝑙/𝐿

 Calculating the conductivity of the solution

𝐾 = 𝐺𝐶𝐾

Where:
𝐾 = conductivity of the solution, S/cm
𝐺 = conductance of the solution, S
𝐶𝐾 = cell constant, 1/cm (0.80/cm)

When 0.3 mL SDS was added with water as solvent:

0.80
𝐾 = 6 𝑥 10−5 𝑆 ( )
𝑐𝑚

𝐾 = 5 𝑥 10−5 𝑆/𝑐𝑚
Results and Analysis
g SDS used 1.7003 g
Table 1. Constants
M SDS used 0.05 mol/L
g NaCl used 0.1183 g
Cell constant reading 0.80/cm
Table 2. Conductance of the SDS solution at different concentrations using water as solvent

Volu N Concen 8.00 22 3.20E-04 0.0051 2.56E-04

me tration 8.50 23 3.30E-04 0.0054 2.64E-04
of of Conducti 9.00 24 3.50E-04 0.0057 2.80E-04
Aliqu solutio vity of 9.50 25 3.60E-04 0.0060 2.88E-04
ot Conductance n solution, 10.00 26 3.70E-04 0.0063 2.96E-04
(mL) of solution (S) (mol/L) K (S/cm) 10.50 27 3.80E-04 0.0065 3.04E-04
0 0 6.00E-05 0.0000 4.80E-05 11.00 28 4.00E-04 0.0068 3.20E-04
0.30 1 6.00E-05 0.0002 4.80E-05 11.50 29 4.10E-04 0.0071 3.28E-04
0.60 2 7.00E-05 0.0004 5.60E-05 12.00 30 4.30E-04 0.0073 3.44E-04
0.90 3 7.00E-05 0.0006 5.60E-05 12.50 31 4.40E-04 0.0076 3.52E-04
1.20 4 8.00E-05 0.0008 6.40E-05 13.00 32 4.50E-04 0.0078 3.60E-04
1.50 5 9.00E-05 0.0010 7.20E-05 13.50 33 4.60E-04 0.0081 3.68E-04
1.80 6 1.10E-04 0.0013 8.80E-05 14.00 34 4.70E-04 0.0083 3.76E-04
2.10 7 1.20E-04 0.0015 9.60E-05 14.50 35 4.80E-04 0.0086 3.84E-04
2.40 8 1.30E-04 0.0017 1.04E-04 15.00 36 4.90E-04 0.0088 3.92E-04
2.70 9 1.40E-04 0.0019 1.12E-04 15.50 37 5.00E-04 0.0091 4.00E-04
3.00 10 1.50E-04 0.0021 1.20E-04 16.00 38 5.10E-04 0.0093 4.08E-04
3.30 11 1.60E-04 0.0023 1.28E-04 16.50 39 5.20E-04 0.0095 4.16E-04
3.60 12 1.70E-04 0.0024 1.36E-04 17.00 40 5.30E-04 0.0098 4.24E-04
3.90 13 1.80E-04 0.0026 1.44E-04 17.50 41 5.40E-04 0.0100 4.32E-04
4.20 14 1.90E-04 0.0028 1.52E-04 18.00 42 5.50E-04 0.0102 4.40E-04
4.50 15 2.00E-04 0.0030 1.60E-04 18.50 43 5.60E-04 0.0105 4.48E-04
5.00 16 2.20E-04 0.0033 1.76E-04 19.00 44 5.60E-04 0.0107 4.48E-04
5.50 17 2.40E-04 0.0036 1.92E-04 19.50 45 5.70E-04 0.0109 4.56E-04
6.00 18 2.50E-04 0.0039 2.00E-04 20.00 46 5.80E-04 0.0111 4.64E-04
6.50 19 2.70E-04 0.0042 2.16E-04 20.50 47 5.80E-04 0.0113 4.64E-04
7.00 20 2.80E-04 0.0045 2.24E-04 21.00 48 5.90E-04 0.0115 4.72E-04
7.50 21 3.00E-04 0.0048 2.40E-04 21.50 49 6.00E-04 0.0117 4.80E-04
22.00 50 6.10E-04 0.0120 4.88E-04

Concentration of Water-SDS solution vs

Conductivity
Figure 2.
A graph of Concentration of the 0.0006
y = 0.0323x + 0.0001
Conductivity, K (S/cm)

SDS solution versus conductivity using 0.0005 R² = 0.9938

water as solvent
0.0004
0.0003
y = 0.0423x + 3E-05
0.0002R² = 0.9974
0.0001
0.0000
0.0000 0.0050 0.0100 0.0150
Concentration, C (mol/L)
Table 3. Conductivity of SDS solution at different concentrations using NaCl solution as solvent

Volu N
5.4 27 2.46E-03 0.0036 1.97E-03
me of Conducta Concentr Conducti
5.6 28 2.47E-03 0.0037 1.98E-03
Aliqu nce of ation of vity of
5.8 29 2.48E-03 0.0038 1.98E-03
ot solution solution solution,
6.0 30 2.49E-03 0.0039 1.99E-03
(mL) (S) (mol/L) K (S/cm)
6.2 31 2.50E-03 0.0041 2.00E-03
0 0 2.24E-03 0.0000 1.79E-03
6.4 32 2.51E-03 0.0042 2.01E-03
0.2 1 2.27E-03 0.0001 1.82E-03
6.6 33 2.52E-03 0.0043 2.02E-03
0.4 2 2.28E-03 0.0003 1.82E-03
6.8 34 2.53E-03 0.0044 2.02E-03
0.6 3 2.28E-03 0.0004 1.82E-03
7.0 35 2.53E-03 0.0045 2.02E-03
0.8 4 2.29E-03 0.0006 1.83E-03
7.2 36 2.54E-03 0.0047 2.03E-03
1.0 5 2.29E-03 0.0007 1.83E-03
7.4 37 2.55E-03 0.0048 2.04E-03
1.2 6 2.29E-03 0.0008 1.83E-03
7.6 38 2.56E-03 0.0049 2.05E-03
1.4 7 2.29E-03 0.0010 1.83E-03
7.8 39 2.57E-03 0.0050 2.06E-03
1.6 8 2.29E-03 0.0011 1.83E-03
8.0 40 2.58E-03 0.0051 2.06E-03
1.8 9 2.29E-03 0.0013 1.83E-03
8.2 41 2.59E-03 0.0052 2.07E-03
2.0 10 2.30E-03 0.0014 1.84E-03
8.4 42 2.60E-03 0.0054 2.08E-03
2.2 11 2.31E-03 0.0015 1.85E-03
8.6 43 2.60E-03 0.0055 2.08E-03
2.4 12 2.32E-03 0.0017 1.86E-03
8.8 44 2.61E-03 0.0056 2.09E-03
2.6 13 2.33E-03 0.0018 1.86E-03
9.0 45 2.62E-03 0.0057 2.10E-03
2.8 14 2.34E-03 0.0019 1.87E-03
9.2 46 2.63E-03 0.0058 2.10E-03
3.0 15 2.35E-03 0.0021 1.88E-03
9.4 47 2.64E-03 0.0059 2.11E-03
3.2 16 2.36E-03 0.0022 1.89E-03
9.6 48 2.65E-03 0.0060 2.12E-03
3.4 17 2.37E-03 0.0023 1.90E-03
9.8 49 2.66E-03 0.0061 2.13E-03
3.6 18 2.37E-03 0.0024 1.90E-03
10.0 50 2.67E-03 0.0063 2.14E-03
3.8 19 2.38E-03 0.0026 1.90E-03
4.0 20 2.39E-03 0.0027 1.91E-03
4.2 21 2.40E-03 0.0028 1.92E-03
4.4 22 2.42E-03 0.0030 1.94E-03
4.6 23 2.43E-03 0.0031 1.94E-03
4.8 24 2.44E-03 0.0032 1.95E-03
5.0 25 2.45E-03 0.0033 1.96E-03
5.2 26 2.46E-03 0.0035 1.97E-03

Concentration of NaCl-SDS solution vs

Conductivity
Figure 3. A graph of Concentration
0.003
of the SDS solution versus
Conductivity, K (S/cm)

Conductivity using NaCl solution 0.002 y = 0.0597x + 0.0018

as solvent 0.002 y = 0.0391x + 0.0018 R² = 0.9978
R² = 0.9387
0.002
0.002
0.002
0.0000 0.0020 0.0040 0.0060 0.0080
Concentration (mol/L)
 Table 4. Critical Micelle Concentration of SDS

Solvent Critical Micelle

Concentration of
SDS
Water 7.1 x 10-3 mol/L
NaCl 2.2 x 10-3 mol/L.
solution

The critical micelle concentration (CMC) of SDS was obtained by using the method of
conductivity. SDS is a known amphiphilic surfactant that both has hydrophilic and hydrophobic ends.
Below CMC, SDS dissolves as monomers. Because of the presence of ions, there will be an increase in
the conductivity of the solution.
The conductivity of the SDS was is greater when the solvent used the NaCl solution compared to
when the solvent was water. This is because of the presence of more ions that carry the charge. The
CMC of SDS is attained faster in NaCl solution compared to the CMC of SDS in water. The presence of
addition electrolytes in the NaCl solution triggered the formation of the micelle; hence micelles form
faster when they are in the NaCl solution.
During CMC, the hydrophobic ends of the surfactants meet together to form micelles. Beyond
CMC, the formation of micelles becomes spontaneous. There is no abrupt change in properties at the
CMC, instead there is a transition point where the physical properties of the solution will vary.

Conclusions

The critical micelle concentration of the sodium dodecyl sulfate in water is 7.1 x 10-3 mol/L while
its CMC in NaCl solution is 2.2 x 10-3 mol/L.

The conductivity of sodium dodecyl sulfate is greater when it is in an environment where there
are ions rather than in an environment where water serves as the solvent.

The presence of an electrolyte decreases the critical micelle concentration, thus CMC is reached
faster.

Answers to Questions
1. Determine the SDS concentration at each of the following conductivity readings.

Concentrations of the SDS at the conductivity readings are presented at tables 2 and 3.
2. Plot κ/C vs C1/2

Λm vs C^(1/2) (water as solvent)

0.2500

0.2000
Λm, (S/cm-mol)

0.1500

0.1000

0.0500

0.0000
0.0000 0.0200 0.0400 0.0600 0.0800 0.1000 0.1200
C^(1/2), (mol/L)^(1/2)

Λm vs C^(1/2) (NaCl solution as

solvent)
14.0000
12.0000
Λm (S/cm-mol)

10.0000
8.0000
6.0000
4.0000
2.0000
0.0000
0.0000 0.0200 0.0400 0.0600 0.0800 0.1000
C^(1/2), (mol/L)^(1/2)

3. Estimate the CMC from the intersection or inflection of the plot

From the graphs above, the CMC for SDS-Water solution is 1.156 x 10-3mol/L while that of the
SDS-NaCl solution is 5.18 x 10-3mol/L.

4. What can you say about the CMC of SDS in pure water and NaCl solution?

The CMC of SDS in pure water is achieved slower rather than in the NaCl Solution.
Bibliography
Atkins, P., & de Paula, J. (2010). Atkins' Physical Chemistry (9th ed.). Oxford: Oxford University Press.

(n.d.). Critical Micelle Concentration of Surfactant, Mixed Surfactant and Polymer by Different Methods
at Room Temperature and Its Importance.

Lindmann, B. (1984). In "Surfactants". Academic Press, London Chap. 4