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CHE 412L
Physical Chemistry Laboratory 2
by
Flores, Dharyl C.
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1. Introduction
Surfactant is an abbreviation for surface-active agent, which includes molecules that are
active at surfaces. These molecules have a tendency to reside rather at the surface than in
bulk solutions due to their amphiphilic nature. Amphiphilic molecules consist of at least two
parts: one of which being hydrophobic and the other hydrophilic. A typical surfactant molecule
consists of a long hydrocarbon tail that dissolves in hydrocarbon and other nonpolar solvents
water; hydrophilic) as shown in Figure 1. Surfactants have two main features making them
essential; one of them is the tendency to adsorb at interfaces and lower the surface tension
Surfactants have the general formula RX, in which R is a hydrocarbon chain and X is a
polar group. The hydrocarbon chains in the molecule are ordinarily C8 or greater, may be
saturated or unsaturated, may be linear or branched, and may contain an aromatic ring.
However, the polar group in the amphipathic molecule may be nonionic or ionic. Sodium
used in the experiment for the determination of its critical micelle concentration (CMC) in a
different solution pure water and 0.02 M aqueous NaCl solution. The amphiphilic ion is
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above a sharp surfactant concentration (Khan, 2007). Such changes in various physical
as critical micelle concentration (CMC), because these surfactant molecular aggregates are
called micelles.
congregate through hydrophobic interactions while their hydrophilic head groups provide
protection. Micelle formation among surfactant molecules takes place when their hydrophobic
ends collect themselves away from the water molecules while the hydrophilic ends surround
them and are the ones oriented toward the water molecules. The centers of these micelles
are somewhat hollow so that they can still accommodate a few more molecules and thus,
water with surfactant micelles can now easily dissolve the otherwise insoluble hydrocarbons
Micelles form only above the critical micelle concentration (CMC) and above the Kraft
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the solution, particularly the molar conductivity. There is no abrupt change in properties at the
the CMC where physical properties vary smoothly but nonlinearly with the concentration
Figure 3. The typical variation of some physical properties of an aqueous solution of sodium dodecyl
sulfate (SDS) close to the CMC (Atkins and de Paula, 2010)
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3. Methodology
3.1. Methodological Framework
Preparation of sodium
dodecyl sulfate (SDS) and
aqueous sodium chloride
solutions.
Calibration of conductivity
meter with 0.01 N KCl
solution as standard
solution.
Determination of Critical
Micelle Concentration
(CMC) of SDS solution.
Determination of Critical
Micelle Concentration
(CMC) of SDS solution.
3.2. Materials
Materials used were Ssodium dodecyl sulfate (NaOSO3C12H25) solution, potassium chloride
(KCl) and sodium chloride (NaCl) aqueous solutions.
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3.3. Equipment
The equipment used for this experiments were the Orion Star A215 pH/Conductivity
Meter which is used to measure the conductivity of the samples. Also, analytical balance,
weighing boats, pipette and pipettor, stirring rod, magnetic stirrer, beakers and wash bottle were
used.
3.4. Procedures
Preparation of Solutions
For the preparation of 0.5M sodium dodecyl sulfate (NaOSO3C12H25), 1.5178 g of sodium
dodecyl sulphate was weighed, dissolved, and diluted to 100-mL in a 250-mL beaker. Another
For the preparation of 0.2 M aqueous NaCl solution, 1.6770 g of solid NaCl was weighed,
For the preparation of standard (0.01 N) KCl solution, 10-mL of standard solution was pipetted
Initially, the conductivity meter was turned on and measurement mode was set to conductivity.
The conductivity cell and the electrodes were then connected to the meter also. In the measurement
mode, f1 (cal) was pressed. In order to highlight the conductivity-channel, the set-up or
log/print was pressed then the f2 (select). After, the electrodes and conductivity cell were rinsed
with distilled water using the wash bottle and dry it with a lint-free tissue before immersing it into
the prepared standard (0.1 N KCl). Next, f3 (start) was pressed to begin the calibration. Until the
conductivity value on the meter remained constant, f2 (accept) was pressed to display the cell
constant.
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In a clean 200-mL beaker, 70-mL of distilled water was measured and pipetted. The beaker
was placed in top of a magnetic stirrer and inside it a small stirring bar. The conductivity cell and
other electrodes were then set up and the settings were set. The value of the measured conductivity
was than measured. Using a pipet, 0.3-mL of the prepared solution of SDS was added. The
conductivity was then recorded again. 0.3-mL aliquots of the SDS solution were continuously
added every minute and the readings of conductivity were recorded every addition. After 15
aliquots of 0.3-mL SDS solution were added, instead of 0.3-mL, 0.5-mL of SDS solutions were
The same procedure was employed as the conductivity measurement for CMC of SDS in Pure
water to SDS in 0.02M NaCl solution, except that 45 more additions of 0.2-mL aliquots of SDS
solution were added.
concentrations
The conductivity meter (Polyscience Model 4010) was used to measure the conductivity
of an aqueous sodium dodecyl sulfate solution at different concentrations. Before determining the
conductivity of the surfactant solution, there is a need for calibration of the conductivity meter
apparatus by immersing the conductivity cell into 0.01 N KCl solution. The data gathered in the
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Temperature Displayed () 30
Temperature Reading () 30
RPM of Magnetic Stirrer () 400
different concentrations, 70-mL of distilled water is put inside a 100ml beaker. Then this was
placed on top of a magnetic stirrer which operates in the settings shown in Table 1. The
conductivity of water is then read and tabulated. Using a 1-mL pipette, 0.3-mL aliquots of 0.05 M
SDS solution was added into the beaker every 1-minute interval for the first 15
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minutes. After the 15 additions 0.5-mL are added into the solution for every 1-minute interval.
This is done while reading and recording the conductivity of the solution with each aliquot addition.
600.00
500.00
Conductivity (S/cm)
400.00
300.00
200.00
100.00
0.00
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014
Concentration (mol/L)
From Figure 4 above, it can be observed that the conductivity of the solution increases as
the concentration of SDS in the solution increases. Though the magnitude of the increase of
conductivity with concentration varies at a point. It can be seen that there is a greater increase in
the conductivity of the solution with every increase in concentration before the intersection of the
two trend lines, than after the intersection. This is evidenced by the greater value of the slope of
the first trend line 61891 than in the second trend line 34355 .
carriers (ions) present in it. Before CMC point, the addition of the surfactant SDS into the solution
will tend to increase the number of cations and anions in the solution since SDS, when added to
+
the solution, will dissociate into () and 12 25 3() ions and therefore, it is expected that
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the solutions conductivity increases as more SDS is added. After the CMC point, upon addition
+
of SDS into the solution, the SDS will not anymore ionize into () and 12 25 3() ions but
instead cause micelle nucleation which would increase the micelle concentration upon further
SDS addition but would leave the monomer (ions) concentration unchanged. And since micelles
+
are bulkier than that of () and 12 25 3() ions they move slower and thus are less
effective charge carrier causing smaller increase in conductivity of the solution with increase in
SDS concentration than what was observed before reaching the CMC.
surfactant molecules in the bulk solutions to form aggregates with different geometries like disks,
spheres, cylinders, etc. The simplest aggregates are generally spherical in shape and are called
micelles. However, this phenomenon occurs only when the surfactant concentration exceeds a
threshold known as the critical micelle concentration (CMC). In a micelle, the hydrophobic part of
the surfactant molecule is directed toward the interior of the cluster and the polar headgroup
toward the aqueous solution as shown in Figure 1a. When a surfactant adsorbs from aqueous
solution at a hydrophobic surface, it orients its hydrophobic group toward the surface and exposes
its polar group to water as shown in Figure 1b. The driving force for self-assembly is said to be
the hydrophobic effect. As micelles form as shown in Figure 1c, sharp changes occur in many
physical properties such as the surface tension, viscosity, conductivity, and sometimes turbidity
of the solution.
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some property as a function of concentration and extrapolating the results at low and high
concentrations to an intersection point (Lindman & Wennerstrom, 1980). That is, at the said point
260000
210000
k/C (S-L/cm-mol)
160000
110000
60000
10000
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.11 0.12
-40000
C1/2 (mol/L)1/2
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conductivity. The determination of the critical micelle concentration (CMC) was done through
1. Conductivity of solution per molarity of solution (/C) vs. the square root of the SDS
concentration (C1/2)
260000
210000
k/C (S-L/cm-mol)
160000
110000
60000
10000
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.11 0.12
-40000
C1/2 (mol/L)1/2
Figure 6. CMC Determination from the Plot of /C vs C1/2 of SDS in Pure Water at T= 30.7
, 400 RPM
In this plot, two tangent lines were drawn and since the point of intersection is away from
the graph and the corresponding c1/2 value cannot be directly determined, the angle bisector of
the angle formed by the two lines was drawn and its point of intersection with the graph was
determined to find the c1/2 value. The critical micelle concentration was determined by squaring
this value. From this plot, the square root of the critical micelle concentration of the aqueous SDS
solution obtained is 3.40 102
. Squaring this value, the critical micelle concentration from
this plot is 1.1560 103
. The ratio between conductivity and concentration, k/C, is known as
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molar conductivity, . As observed in Figure 6, there is a drastic change in the molar conductivity
of the solution from the starting square root of concentration until it reaches the critical micelle
concentration.
Small amounts of SDS was added into the distilled water. At the beginning of the
experiment, a dilute solution of SDS was formed where its concentration is below its critical micelle
concentration. Below the critical micelle concentration, SDS behaves as a normal electrolyte
+
wherein when dissolved in water, it ionizes to produce () and 12 25 3() . The addition
low concentrations, below the CMC, only monomers exist in the solution.
As the amount of the SDS solution was added to the water, the number of monomers
increased. The SDS solution was continuously added then it reached to a point that the amount
of this surfactant added was equal to the critical micelle concentration. At this point, micellization
occurred. In addition, it is at this point that micelles start forming, being in equilibrium with the
monomers. The increase in the concentration of SDS in water above CMC, caused nucleation for
the micelle to form. Thus, there is an increase of in the concentration of micelles in the solution.
However, the concentration of monomers remained unchanged in the solution. Since a micelle is
much larger than a monomer, it diffuses more slowly through solution and so is a less efficient
According to Kohlrauschs law that at low concentrations the molar conductivities of strong
electrolytes (substances that are fully dissociated into ions in solution) vary linearly with the
= 1/2
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where = , is the conductivity, c is the concentration of the added electrolyte and is the
molar conductivity of solution. This variation is called Kohlrauschs law. The constant is the
limiting molar conductivity, the molar conductivity in the limit of zero concentration (when the ions
are effectively infinitely far apart and do not interact with one another). The constant K is found to
depend more on the stoichiometry of the electrolyte than on its specific identity. The 1/2
dependence arises from interactions between ions: when charge is conducted ionically, ions of
one charge are moving past the ions of interest and retard its progress (Atkins and de Paula,
2010).
Objective 3: To determine the effect of the presence of an electrolyte on the critical micelle
The critical micelle concentration (CMC) is at the point at which surfactant molecules
aggregate together in the liquid to form groups known as micelles. The CMC of a surfactant
indicates the point at which surface active properties are at the optimum and performance is
inorganic builders and alkali consequently decreases the CMC of a surfactant. This reduction
affects the adsorption, wetting and emulsifying properties of surfactants (Savale, 2016).
In the experiment, the effect of sodium chloride aqueous solution on micellar systems of
an anionic surfactant such as sodium dodecyl sulfate was studied. It has been observed that the
critical micelle concentration (CMC) decreases with the presence of an electrolyte than pure water
alone. The effect of additives on CMC of an aqueous solution of a surfactant depends on the
nature of interaction between additive and micellized surfactant molecules. Molecular interaction
between interacting molecules may involve some or all of the following interactions: dipoledipole,
iondipole, ionion, van der Waals/dispersion forces, and hydrogen bonding. Energetically
favorable interactions between additive and micellized surfactant molecules will increase the
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175000
140000
/C (S-L/cm-mol)
105000
70000
35000
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
C1/2 (mol/L)1/2
Figure 7. CMC Determination from the Plot of /C vs / of SDS in 0.02 M Aqueous NaCl
Solution at 30.3 , 400 rpm
dodecyl sulfate at 30.3 and 400 rpm is 8.4100 104 /. The technique employed was
done similarly to the previous method described in Objective 2. The trend is almost the same with
that of the determination of CMC in pure water except that in this curve, it is almost approaching
linearity at a constant molar conductivity value. Moreover, a lesser addition of SDS solution to the
electrolyte solution of NaCl was needed for the change in conductivity to approach a constant
value.
Table 2. Critical Micelle Concentration of SDS in Pure Water and in 0.03 M Aqueous NaCl
Solution
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From the table above, comparing the obtained CMC values, the CMC of SDS in NaCl
solution is lower than the CMC of SDS in pure water. Thus, the presence of an electrolyte in a
solution lowers the CMC of the surfactant. The addition of salt in surfactant solution is a way of
reducing the CMC of a surfactant because the repulsive forces between the head groups of ionic
surfactants are fighting against it aggregation which implies that the repulsive forces of head
groups of SDS decreases due to the electrostatic shielding effect resulting in formation of micelle
at a lower CMC.
Ions of salts normally assist micelle formation, and help to formally bind the counter ions,
increase the micelle aggregation number description of the number of molecules present in a
micelle once the critical micelle concentration (CMC) has been reached, affect the electrokinetic
potential (zeta potential), and as well inuence the energetics of the process (Naskar, et al., 2013).
However, large errors that may have resulted in the determination of critical micelle concentration
of SDS in different solutions may be due to the degradation of instrument and temperature
fluctuations. The cell constant of conductivity meter was determined to be only 0.431 1 when
In general, repulsive forces between the head groups of ionic surfactants are fighting
against the aggregation. This is due mainly to the decrease in the thickness of the ionic
atmosphere surrounding the ionic head groups in the presence of the electrolyte and the
consequent decreased electrical repulsion between them in the micelle. A decrease in the
electrical repulsion would then mean a faster aggregation of monomers into micelles due to lesser
resistance, thus a lower critical micelle concentration is obtained (Rosen & Kunjappu 2012).
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The depression of the CMC Below CMC, no micelles are formed and the conductivity is
due to the separate contributions of the dissociated ionic surfactants and of the free counterions.
Also, an ionic surfactant is completely dissociated and there is a linear relationship between the
molar conductivity, of the surfactant solution and its concentration as the surfactant monomers
behave as normal electrolytes and thus obeying Kohlrauschs Law of Independent Ion Migration,
= []( + ) Equation 1
where is the conductivity, [] is the amphiphile (surfactant) concentration below CMC, and
and are the molar ionic conductivities of the counterion and of the amphiphile,
respectively.
Kohlrauschs Law of Independent Ion Migration states that every ion contributes a definite
amount to the equivalent conductance of an electrolyte in the limit of infinite dilution, regardless
behave like weak electrolyte. The addition of surfactant molecules increases the concentration of
micelles, while the equilibrium monomer concentration remains constant. In this region, the
conductivity again increases linearly with surfactant concentration, but due to the reduced ionic
mobility of micelles compared to that of the monomers the slope of this linear trend is smaller
than that below the CMC. The conductivity above the CMC is the sum of four different
contributions: the ionic conductivity of the counterion and of the amphiphile at the CMC, the
micelle conductivity and the conductivity of the unbonded counterions from the micelles. The
= ( + ) + [] + ([] ) Equation 2
where is the dissociation degree and [] is the molar concentration of the micelles. If is the
average aggregation number, then [] = ([] )/ , and assuming that the micelle
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Equation 2
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conductivity is the sum of the conductivity of all the charged monomers in the micelle, that is,
= ( + )(1)+ ( + )[]
Then the slope of the trendline of the conductivity above the CMC provides once +
has been obtained for concentrations below the CMC the micelle ionization degree (Garti, &
Amar-Yuli, 2012)
A plot of molar conductivity of the surfactant versus the surfactant concentration gives a
Post-Lab Questions
1. Assume that the cavity of SDS micelle has a diameter of 3nm and that it contains dissolved
benzene molecules. What is the concentration of benzene in that micelle?
= /
= 3 , = 1.5 = 1.5 109
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4 4
= 3 = (1.5109 )3
3 3
= 1.4136 1026 3 = 1.4136 1023
1
3 = 4.9834 1024
6.02 1023
4.9834 1024
= = 0.35
1.4136 1023
5. Conclusions
The CMC of sodium dodecyl sulfate can be investigated via conductimetric techniques. In
this experiment, the critical micelle concentration (CMC) of sodium dodecyl sulfate was
low and high concentrations to an intersection point. That is, at the said point shows a significant
concentration of aqueous sodium dodecyl sulfate solution in pure water at T = 30.0 C and 400
RPM, is 1.1560 mmol/L. The 85.73 % error compared to the literature value which is 8.0 mmol/L
is due to the errors in the experiment such as the fluctuating temperature during the experiment
The critical micelle concentration of aqueous SDS solution in a 0.02 M NaCl solution is
0.8410 mmol/L. This shows that the addition of a dilute electrolyte solution decreases the critical
micelle concentration.
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References
Demissie, H., & Duraisamy, R. (n.d.). Effects of Electrolytes on the Surface and Micellar
Characteristics of Sodium Dodecyl Sulphate Surfactant Solution.
doi:http://www.jsirjournal.com/Vol5_Issue6_03.pdf
Naskar, B., Dey, A., & Moulik, S. P. (2013). Counter-ion Effect on Micellization of Ionic
Surfactants: A Comprehensive Understanding with Two Representatives, Sodium Dodecyl
Sulfate (SDS) and Dodecyltrimethylammonium Bromide (DTAB). Journal of Surfactants and
Detergents, 16(5), 785-794. doi:10.1007/s11743-013-1449-1
Garti, N., & Amar-Yuli, I. (2012). Nanotechnologies for Solubilization and Delivery in Foods
and Cosmetics Pharmaceuticals. Lancaster, PA: DEStech Publications.
Parker, S. P. (2003). The McGraw-Hill Dictionary of Scientific and Technical Terms. New
York: McGraw-Hill Professional.
doi:https://books.google.com.ph/books?id=xOPzO5HVFfEC&pg=PA1158&dq
Khan, M. N. (2007). Micellar Catalysis. Boca Raton, Fl: CRC/Taylor & Francis.
Bucak, S., & Rende, D. (2014). Colloid and Surface Chemistry a Laboratory Guide for
Exploration of the Nano World. Boca Raton, Fla.: CRC Press.
Atkins, P., de Paula, J. (2010). Atkins Physical Chemistry. 9th ed. Oxford: Oxford University
Press.
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ANNEX
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CMC Determination from the Plot of Conductivity vs Concentration of SDS in Pure Water at
T=30.7 , 400 RPM
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Conductivity of solution per molarity of solution (/C) vs. the square root of the SDS
concentration (C1/2)
CMC Determination from the Plot of /C vs C1/2 of SDS in Pure Water at T= 30.7 , 400
RPM
( ) 0.05 (0)
=
= = 0.00
70
( ) + ( ) (0 ) (70) + 0.05 (0.30 )
,1 = =
+ 70 + 0.30
= 0.0002134
1 (1 ) + ( ) (0.0002134 ) (70.30 ) + 0.05 (0.30 )
2 = =
1 + 70.30 + 0.30
= 0.0004249
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From Figure 3, inflection point is at = 4.8997 103 .
Since , = 4.8997 103
.
1
1/2
From Figure 6, 2 = 3.40 102 (
)
= 1.1560 103
Since , = 1 1.1560 103
Determination of CMC of aqueous SDS solution when added with 0.02M NaCl
Total Conductivit ( ) k/C
Volume
Time Temperatur
Added
Volume of y Mol SDS [mol/L]1/2 [S-
(min) e () Solution k (moles) [mol/L] L/cm-
(mL)
(mL) [S/cm]
mol]
0 29.9 0.0 70.0 2314 0.000000
194047.0
1 30.0 0.2 70.2 2316 0.000010 0.000142 0.01194
8
137585.3
2 30.1 0.4 70.4 2319 0.000020 0.000284 0.01685
1
112594.4
3 30.1 0.6 70.6 2321 0.000030 0.000425 0.02061
2
4 30.2 0.8 70.8 2322 0.000040 0.000565 0.02377 97689.72
5 30.2 1.0 71.0 2325 0.000050 0.000704 0.02654 87612.71
6 30.3 1.2 71.2 2326 0.000060 0.000843 0.02903 80126.11
7 30.3 1.4 71.4 2327 0.000070 0.000980 0.03131 74318.42
8 30.4 1.6 71.6 2328 0.000080 0.001117 0.03343 69645.73
9 30.4 1.8 71.8 2328 0.000090 0.001253 0.03540 65754.27
10 30.4 2.0 72.0 2329 0.000100 0.001389 0.03727 62493.63
11 30.4 2.2 72.2 2329 0.000110 0.001524 0.03903 59668.04
12 30.4 2.4 72.4 2330 0.000120 0.001657 0.04071 57231.43
13 30.4 2.6 72.6 2330 0.000130 0.001791 0.04232 55062.07
14 30.5 2.8 72.8 2330 0.000140 0.001923 0.04385 53132.17
15 30.5 3.0 73.0 2331 0.000150 0.002055 0.04533 51423.08
16 30.5 3.2 73.2 2330 0.000160 0.002186 0.04675 49836.95
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CMC Determination from the Plot of /C vs / of SDS in 0.02 M Aqueous NaCl Solution
at 30.3 , 400 rpm
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