GOABAONE KGOPA

17001016
CHEM 408
EXPERIMENT 1
DETERMINATION OF CMC VALUE OF SODIUM DODECYL SULPHATE AND INVESTIGATING
THE EFFECTS OF ELECTROLYTES ON CMC VALUE USING CONDUCTOMETRY METHOD
1.ABSTRACT
Electrical conductivity is a measurement of a material's or solution's ability to conduct an
electric current. The number and mobility of ions and charged particles present in a solution
determines its electrical conductivity. The electrical conductivity of ionic surfactants
increases as the surfactant concentration rises.The formation of micelles affects 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.From this experiment, it was found that conductometric
determination of the CMC below the CMC, the addition of surfactant to an aqueous solution
causes an increase in the number of charge carriers and consequently, an increase in the
conductivity. Above the CMC, further addition of surfactant increases the micelle
concentration while the monomer concentration remains approximately constant (at the
CMC level). Since a micelle is much larger than a SDS monomer it diffuses more slowly
through solution and so is a less efficient charge carrier. A plot of conductivity against
surfactant concentration is, thus expected to show a break at the CMC. The results were
found to be PART A 0.009 mol/dm3, 0.003 mol/dm3, 0.01 mol/dm3, 0.006 mol/dm3 and part
B 0.009mol/dm3, 0.0048 mol/dm3, 0.004 mol/dm3, 0.0095 mol/dm3

2.AIM
To use conductivity measurements to determine the CMC values of SDS and evaluate the
effects of other electrolytes on the CMC value of SDS.
3.INTRODUCTION
Surfactants (tensides) are organic compounds that, at low concentrations, significantly
reduce the surface tension of water and are, at least partially, water soluble. Surfactants are
known as surface active substances because they are adsorbed primarily on the solution's
surface, forming a thin monolayer. When dissolving them, after they reach a certain value of
concentration, molecules or ions of surfactants begin to associate and to organize
themselves into more complex units, called micelles. The characteristic concentration value,
where the association process begins, is called the critical micelle concentration and it is
labeled with symbol c or abbreviation CMC (Mukerjee, P., and K. J. Mysels,). The CMC is one
of the most useful physicochemical characteristics of many biologically active substances
and drugs. From the chemical point of view, surfactants are mostly low-molecular
compounds, so when dissolved, they form a true solutions in concentration ranges below
the CMC (Algarova et al. 2001). Micelles are aggregates of a larger number of simple
molecules or ions of surfactants (e.g. several dozens), so the resulting size of such structures
is in the colloidal range.
The determination of CMC is generally based on the localization of the position of a breaking
point in the concentration dependencies of selected physical or chemical properties of
surfactant solutions. Because of the surface activity of this substances, measurements of the
3 surface tension of surfactant solutions represent the principal method of CMCs
determination (Algarova et al. 2001).. However, it is rather tedious and time-consuming
procedure. In the case of ionic surfactants, the utilization of electrochemical measurements
is much more convenient, especially the measurements of the electrical conductivity of their
solutions with varying concentration. The conductometric method is based on the finding of
a breaking point on the curves, which describe the concentration dependence of
conductivity. It is well-known, that the conductivity of any solution is directly proportional to
the concentration of its ions (Jungquera and Aicart 2002) . The point, where the micelle
formation starts, is indicated on the concentration dependence of specific conductivity (κ) as
a breaking point. It is easy to find the breaking point, because it marks a significant change
the slope of the linear dependence: κ =f(c)
In this experiment we are going to use conductivity measurements to determine the CMC
value of a common surfactant, sodium dodecyl sulfate. Conductometry is the most often
used electrochemical technique for CMC determination due to its experimental simplicity
and inexpensive instrumentation. In dilute solutions, ionic surfactants behave like strong
electrolytes and have strong conductivity. Conductivity measurements show characteristic
discontinuities of conductivity versus surfactant concentration plots. The principle of
conductometry is that after reaching the CMC value of the surfactant, micelle formation
leads to solution composition changing as well as the conductivity of the solution. The
simplest approach is to plot the conductivity (k) against surfactant concentration to obtain
two almost straight lines which intersect at the CMC.
4.PROCEDURE
A) Determination of CMC of pure SDS
An initial solution of the sodium dodecyl sulfate surfactant of concentration 0.016 mol dm-3
in 25 ml volumetric flask was prepared. 0.1153488 g of the calculated amount of the SDS
was weighed using analytical balance and was dissolved to make a solution. The solution
was poured into a clean dry beaker and the conductivity of the solution was measured and
the temperature of the solution was noted. Using Table 1, the next solution was prepared in
a 25 ml volumetric flask by using the previous solution, and the conductivity was also
measured. The above step was repeated until all the conductivity of all the concentrations in
Table 1 have been measured.
CALCULATIONS
The following calculation were carried out to determine the mass to be used in the next
step:
Where, n is the number of moles
V is the volume
= 0.016 mol dm -3 x 0.025 dm -3
= 0.0004 mol
Therefore, where m is mass and M is the molar mass.
= 0.004 mol x 288.372 g/mol
= 0.1153488 g

The formula below was used to identify the volume to be measured;

C1V1=C2V2
V 1 = C 2 V 2 /C 1
= (0.015 mol dm -3 x 0.025 dm -3 )/ 0.016 mol dm -3
= 0.02343 dm -3
0.023 dm -3 (23.43 ml) of solution with concentration C 1 = 0.016 mol dm -3 was used to
prepared
25 ml solution with concentration C 2 = 0.015 mol dm -3 . Therefore, 23.43 ml of solution
with concentration 0.016 mol dm -3 should be taken away at first and then the same
volume (25 ml) of redistilled water should be added to get 25 ml of solution with
concentration 0.015 mol dm -3 solution in the conductivity vessel.

B) Determination of CMC of SDS in the presence of other electrolytes.

3 5.0 10 M −  solution of NaCl was prepared.

Then an initial solution of the sodium dodecyl sulfate surfactant of concentration 0.016 mol
dm-3 in a 25 ml volumetric flask by dissolving the appropriate mass of the solid in 3 5.0 10
M −  solution of NaCl was prepared . Then the steps in part A) from the step where the
solution was poured into a clean beaker and conductivity of the solution was measured until
all the conductivity of all the concentrations in Table 1 have been measured was followed
but unlike in A) where distilled water was used for dilution this time NaCl was used instead.

5.RESULTS
PART A
Table 1: Conductivity values of sodium dodecyl sulphate (SDS) in pure water at 25 °C as a
function of SDS concentration

volume Molar
Concentration to be Conductivity, Temperature conductivity √c (mol/dm³)
(mol dm-3 ) diluted k (µS/cm) (ᴼC) Conductivity, (S m2
(ml) k (S/m) mol−1)
0.016 25 420 27.2 0.0420 0.002625 0.12649
0.015 23.44 369 27.3 0.0369 0.00246 0.12247
 0.00242857
0.014 21.86 340 27.4
0.0340 1 0.11832
0.012 18.75 303 27.6
0.0303 0.002525 0.10954
0.011 17.19 273 27.6 0.0273 0.00248571 0.10488
0.01 15.63 247 27.9 0.0247 0.00247 0.1
0.009 14.06 220 27.1 0.0220 0.00244444 0.09487
0.008 12.5 212 26.8 0.0212 0.00265 0.08944
0.007 10.94 201   26.7 0.0210 0.003 0.08366
0.00291666
0.006 9.38  175  27.3
0.0175 7 0.07071
0.005 7.81  155  26.8 0.0155 0.0031 0,07071
0.004 6.25     0 0

Table 2; Conductivity values of sodium dodecyl sulphate (SDS) in 0.015 M NaCl solution at 25
°C as a function of SDS concentration

Molar
volume
conductivit
Concentratio to be Conductivity Temperatur
y (S m2 √c (mol/dm³)
n (mol dm-3 ) diluted , k (µS/cm) e (ᴼC)
Conductivity, mol−1)(1 x
(ml)
k (S/m) 10-3)
0.016 25 733 27.2 0.0733 0.004581 0.12649
0.015 23.43 685 27.3 0.0685 0.004567 0.12247
0.014 23.33 638 27.4 0.0638 0.004557 0.11832
0.012 21.42 590 27.6 0.0590 0.004917 0.10954
0.011 22.91 568 27.6 0.0568 0.005164 0.10488
0.01 22.72 542 27.9 0.0542 0.00542 0.1
0.009 22.50 507 27.1 0.0507 0.005633 0.09487
0.008 22.22 479 26.8 0.0479 0.005988 0.08944

0.007 21.875  453 27.2 0.08366002

0.0453 0.006471
21.428
0.006  423 27.3 0.077459666
5 0.0423 0.00705

0.005 20.83  396 27.4 0.070710678

0.0396 0.00792

0.004 20  391 27.6 0.063245553

0.0391 0.009775
 Graph Cmc(M)
conductivity against concentration of 0,009
sodium dodecyl sulphate (SDS) in pure
water
molar conductivity (Sm²/mol) against 0,003
square root of conductivity( mol/dm^3) of
SDS in pure water

Conductivity values of sodium dodecyl 0,01

sulphate (SDS) in 0.015 M NaCl solution
molar Conductivity values of sodium 0,006
dodecyl sulphate (SDS) in 0.015 M NaCl
solution

Conductivity, k (µS/cm) against

concentration(mol /dm^3)
450
400
350
conductivity(µS/cm)

300
250
200
150
100
50
0
0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
concentration(mol /dm^3)

Figure 1; showing conductivity against concentration of sodium dodecyl sulphate (SDS) in

pure water at 25 °C as a function of SDS concentration
 molar Conductivity (Sm^2/mol )against
concentration(mol /dm^3)

0.0035
molar conductivity (Sm^2/mol)

0.003
0.0025
0.002
0.0015
0.001
0.0005
0
4 6 8 10 12 14 16 18
concentration(mol/m^3)

Figure 2 ; showing molar conductivity (Sm²/mol) against square root of conductivity(

mol/dm^3) of SDS in pure water

conductivity(k, µScm-1) vs SDS Concentration

(mol dm-3)
800
700
Conductivity, k, µScm-1

600
500
400
300
200
100
0
0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
SDS Concentration (mol dm-3

Figure 3 showing Conductivity values of sodium dodecyl sulphate (SDS) in 0.015 M NaCl
solution at 25 °C as a function of SDS concentration.
 Molar conductivity (S m2 mol−1 vs √c (mol/dm³)
0.14
Molar conductivity (S m2 mol−1

0.12

0.1

0.08

0.06

0.04

0.02

0
0.004 0.005 0.006 0.007 0.008 0.009 0.01 0.011
√c (mol/dm³)

Figure 4 showing molar conductivity vs √c sodium dodecyl sulphate (SDS) in 0.015 M NaCl
solution at 25 °C as a function of SDS concentration.

PART B
Table 1: Conductivity values of sodium dodecyl sulphate (SDS) in pure water at 25 °C as a
function of SDS concentration

Conc(mol/ conductivity conductivity conc √c molar

dm³) (µS/cm) (S/m) (mol/m³) (mol/dm³) conductivity(Sm²/mol
)
0.004 283 0.0283 4 0.063246 0.007075
0.005 351 0.0351 5 0.070711 0.00702
0.006 399 0.0399 6 0.07746 0.00665
0.007 450 0.045 7 0.083666 0.006429
0.008 522 0.0522 8 0.089443 0.006525
0.009 581 0.0581 9 0.094868 0.006456
0.015 724 0.0724 15 0.122474 0.004827
0.02 848 0.0848 20 0.141421 0.00424
0.023 880 0.088 23 0.151658 0.003826
0.025 957 0.0957 25 0.158114 0.003828
0.028 1003 0.1003 28 0.167332 0.003582
0.035 1174 0.1174 35 0.187083 0.003354

Table2. Conductivity values of sodium dodecyl sulphate (SDS) in 0.015 M NaCl solution at 25
°C as a function of SDS concentration
 Conc(mol/ conductivity conductivity conc √c molar conductivity
dm³) (µS/cm) (S/m) (mol/m³) (mol/dm³) (Sm²/mol)
0.0007 182 0.0182 0.7 0.026458 0.026
0.0013 186 0.0186 1.3 0.036056 0.014308
0.002 190 0.019 2 0.044721 0.0095
0.0025 193 0.0193 2.5 0.05 0.00772
0.0035 199 0.0199 3.5 0.059161 0.005686
0.004 202 0.0202 4 0.063246 0.00505
0.005 205 0.0205 5 0.070711 0.0041
0.006 208 0.0208 6 0.07746 0.003467
0.0065 209 0.0209 6.5 0.080623 0.003215
0.007 210 0.021 7 0.083666 0.003
0.0075 212 0.0212 7.5 0.086603 0.002827
0.008 213 0.0213 8 0.089443 0.002663
0.0085 214 0.0214 8.5 0.092195 0.002518
0.009 215 0.0215 9 0.094868 0.002389

Graph Cmc(M)

conductivity against concentration of 0.009

sodium dodecyl sulphate (SDS) in pure
water

molar conductivity (Sm²/mol) against 0.0048

square root of conductivity( mol/dm^3) of
SDS in pure water

Conductivity values of sodium dodecyl 0.004

sulphate (SDS) in 0.015 M NaCl solution

molar Conductivity values of sodium 0.0095

dodecyl sulphate (SDS) in 0.015 M NaCl
solution

SAMPLE CALCULATION FOR √c

c =0.016mol dm-3
√ c = 0.126491106 mol dm-3
=0.126 mol dm-3

SAMPLE CALCULATION FOR  AND c

733 µS cm-1 /1000=0.733S/m
0.016 mol/dm3 *1000=16 mol/m3

SAMPLE CALCULATION FOR 

=  / c
0.016 mol/dm3 =16 mol/m3
=0.733S/m / 16 mol/m3
=0.04581 S m2 mol-1

conductivity(k, µScm-1) vs SDS Concentration

(mol dm-3)
1400
1200
Conductivity, k, µScm-1

1000
800
600
400
200
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04
SDS Concentration (mol dm-3)

Figure 5 showing k vs concentration of values of sodium dodecyl sulphate (SDS) in pure

water at 25 °C as a function of SDS concentration.

Molar conductivity (S m2 mol−1 vs √c (mol/dm³)

0.2
0.18
Molar conductivity (S m2 mol−1

0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
0.003 0.0035 0.004 0.0045 0.005 0.0055 0.006 0.0065 0.007 0.0075
√c (mol/dm³)

Figure 6 ; showing molar conductivity (Sm²/mol) against square root of conductivity(

mol/dm^3) of SDS in pure water.
 conductivity(k, µScm-1) vs SDS Concentration
(mol dm-3)
220

210
Conductivity(k, µScm-1)

200

190

180

170

160
0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.01
SDS Concentration (mol dm-3)

Figure 7 showing k vs concentration of sodium dodecyl sulphate (SDS) in 0.015 M NaCl

solution at 25 °C as a function of SDS concentration.

Figure 8 showing molar conductivity vs √c sodium dodecyl sulphate (SDS) in 0.015 M NaCl
solution at 25 °C as a function of SDS concentration
6.DISCUSSION
The essential micelle concentration (CMC) of sodium dodecyl sulfate was calculated using
the conductivity method in this experiment. The amphiphilic surfactant sodium dodecyl
sulfate (SDS), NaOSO-3C12H25, has both hydrophobic and hydrophilic properties. In the
aqueous solution, SDS was ionized, resulting in Na + and - OSO-3C12H25 ions. SDS self-
dissociation into micelles is highly cooperative and occurs at a specific concentration known
as the essential micelle concentration. The amphiphile dissolves as monomers below CMC.
The monomers concentration remains constant as the concentration exceeds CMC, while
the micelle concentration increases (Varun B et.al 2012). The conductivity method of the
SDS solution can be used to calculate the CMC. Na + and - OSO-3C12H25 ions are known as
charge carriers which will increase the conductivity of the solution when ionization takes
place.
A small amount of SDS is applied to the distilled water at the start of the experiment. Since
the concentration of SDS in a dilute solution is less than its CMC, it acts like a regular
electrolyte and ionizes to give out Na +, which is soluble in the aqueous phase, while - OSO-
3C12H25 ions solubilize its hydrophilic head in the water and hydrophobic tail extending out
the water surface. Due to the low SDS concentration, the ions exist as a solvated monomer
rather than a micelle( Deep S and Ahluwalia J C 2001 ). As the amount of SDS solution was
added to the solution, the number of monomers increased. At the same time, the rise in
conductivity caused by the addition of SDS ions brought more charges within the solution.
Once the amount of SDS solution added into the aqueous solution is equals to the CMC, the
first micelle start to form spontaneously in the solution (Deep S and Ahluwalia J C 2001).
Just above CMC, the monomers self-assemble to form aggregates in the solution,
transforming the homogeneous solution into a colloidal system. The micellar solution is
known as a colloidal dispersion (association colloid) of organized surfactant molecules. The
micelle formed in the solution would have spherical structure in which the hydrophilic head
groups were exposed to the solution while the hydrophobic tails were faced toward the
interior of the micelle structure (Mukerjee, P., and K. J. Mysels 2009). The exterior of the
micelle is built up from the ionic –OSO3 groups which form the Stern layer which associated
by water molecules. The further layer that surrounding the Stern layer is composed of the
positive counter ions and oriented water molecule called Gouy-Chapman layer. Both Stern
layer and Gouy-Chapman layer are known as electric double layer. This double layer will
maintain the stability of the colloidal system (Varun B et.al 2012). The higher concentration
of SDS caused nucleation for the micelle to form increased and hence more micelle was
formed in the solution. Above the CMC, the concentration of micelle definitely increases.
However, the concentration of monomers almost remained unchanged in the solution.
Monomers tend to form the micelle at the same time the added SDS solution ionized in the
solution to replace the monomers that used to build micelle. But, the charge carriers could
be increased slowly because the rate of micellization is slower than the rate of monomers
were used in the building of micelle and hence the conductivity of the solution increased at
a slower rate in an ideal condition. This can be noticed in the Figures which shows the
increasing rate of conductivity had became slower obviously. This is because the formation
of micelle required the ionic monomers and some of the ions had been attracted towards
the micelle surrounding to form the electric double layer. As a result, some monomers are
no longer free in the solution but for those ions are not strongly attracted still can carry
charge in the solution. Hence, the conductivity of the solution increased slower. However, at
the final part in graph shows a sudden increase in the conductivity of the may be due to the
formation of bubbles inside the solution. Above the CMC, when bubbles start forming,
micelles will be broken down to form monomers to expand the bubbles. As more SDS
monomers being formed back, the conductivity shoot up because SDS monomers is a more
effective charge carrier than micelles. Precautions which were taken to ensure that errors
were avoided include; ensuring that the poles' surfaces are totally immersed in the sample
solution at all times. Since the effect of dilution is not linear, conductivity samples and
regular solutions should never be diluted. Although the configuration of the electrode is
important, the location of the sensor in the sample beaker may have a significant impact on
measuring results due to boundary effects beyond the electrode surfaces. The sensor should
be placed in the center of the beaker containing the solution.
7.CONCLUSION
It is then concluded that the solution of surfactant, e.g. sodium dodecyl sulfate, behaves as
the strong univalent type of electrolyte in the concentration range below the CMC and the
linear function of dependence of the molar conductivity on the second root of
concentration has a small negative slope and therefore the dependence of the molar
conductivity (Λ) on the second root of concentration (c) can be used for more precise
determination of CMC of ionic surfactants. The results were found to be PART A 0.009
mol/dm3, 0.003 mol/dm3, 0.01 mol/dm3, 0.006 mol/dm3 and part B 0.009mol/dm3, 0.0048
mol/dm3, 0.004 mol/dm3, 0.0095 mol/dm3

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