SCHOOL OF PHARMACEUTICAL SCIENCES

UNIVERSITI SAINS MALAYSIA

FAR221/3 PHYSICAL PHARMACY I

SEMESTER 1: SESSION 2020/2021

PRACTICAL REPORT 1:
SURFACE PHENOMENA

GROUP NUMBER: GROUP B1-1

NAME MATRIC NO
KASHVIN A/L JEVA 146677
KHAYRIN AMALYN BINTI KHAMKI 149427
KHELVY KEBBY KILI 146550
KHOK YI YING (GROUP LEADER) 147108
KURNIATI BINTI SUR’AN 146440

LECTURER : PROF. DR. HABIBAH BINTI A. WAHAB

DATE OF SUBMISSION : 27th JANUARY 2021

PART (A) DETERMINATION OF CRITICAL MICELLE CONCENTRATION (CMC)
USING SURFACE TENSION

INTRODUCTION

The molecules of a fluid experience a specific force which is an attractive force that exerted
on it by all its neighboring molecules and the molecules are attracted equally in all directions in
the bulk phase of a liquid which causes a net force of zero on the molecule. However, at the surface
or near the surface, the molecules experience an attractive force or inward force which tends to
attract them to the interior of the liquid. It creates a force on the surface that tries to minimize its
area and leads to the little interaction with the molecules in air which leads to excess energy at the
liquid interface and a work such as surface free energy is done in order to prevent the shrinking of
the surface because of the inwardly attractive force.

Surface free energy can be described as the surface tension of a liquid or work per unit area
done by the inward force that creates the contracted surface. Surface tension is defined as the force
per unit length that must be applied parallel to the surface so as to counterbalance the net inward
pull.

The SI unit of surface tension is Nm-1

1 mNm-1 = 1 dyne cm-1

 Surface-active agents or known as surfactant are substance that used to lower the surface
tension between two phases and generally consists of two distinct regions in their molecules which
are the hydrophobic portion (hydrocarbon chain – non polar group) and the hydrophilic portion
(polar group). The amphiphilic nature of surfactant-active agents that causes them to be adsorbed
at interfaces. When the surfactant is dissolved in a water, a negative change of entropy occurs
because of the re-structure of the water molecules around the hydrophobic region. Thus, it will
increase the arrangement of water molecules. The non-polar groups of surfactants tend to keep a
distant themselves from the water molecules to overcome this situation and there are two ways to
be achieved to overcome the negative entropy such as at the present of surfactant the molecules
will aggregate at the surface with the non-polar part turning towards the air. Thus, it can reduce
the work or surface tension by reducing the work needed to expand the surface.

Moreover, depending on the type of surface active agent, these molecules tend to form
spherically shaped aggregates known as micelle at a specific concentration by touching the water
with their polar groups while their non-polar groups are placed together in the middle of micelle.
The further increase of concentration of surfactant will result in the more formation of micelles
and the surface tension will remain constant. The critical micelle concentration (CMC) is the first
micelle detectable and the value can be determined by measuring the surface tension.

REAGENTS
The surface active agents used are:

a. Sodium lauryl sulphate B.P (Sodium monododecyl sulphate C12H25 OSO3-Na+, molecular
weight 288, an anionic surfactant).

b. Cetrimide B.P (a mixture of tetradecyl, dodecyl and hexadecyl trimethyl ammonium bromide,

molecular weight 369, a cationic surfactant).

c. Cetomacrogol 1000 B.P (a polyoxyethylene-n-alkanol with mean formula of C16H35

(CH2CH20)23OH, molecular weight 1256, a non-ionic surfactant).

RESULTS

1. Sodium Lauryl Sulphate B.P

Surface tension (N/m)

Concentration
(M)
1st reading 2nd reading 3rd reading 4th reading mean
0.05 0.27 0.26 0.31 0.30 0.285
0.025 0.29 0.28 0.33 0.32 0.305
0.01 0.31 0.35 0.30 0.35 0.328
0.0075 0.50 0.56 0.49 0.57 0.530
0.0025 0.72 0.81 0.71 0.82 0.765
0.00075 0.92 1.05 1.03 0.90 0.975
0.0005 0.98 1.12 1.10 0.96 1.040
0 1.20 1.37 1.34 1.18 1.273

A graph of surface tension (N/m) vs concentration of sodium

lauryl sulphate (M)
1.4

1.2
Surface tension (N/m)

0.8

0.6
CMC
0.4 0.328

0.2

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Concentration (M)
The critical micelle concentration of sodium lauryl sulphate is 0.01 mol/L.
2. Cetrimide B.P

Surface tension (N/m)

Concentration
1st 2nd reading 3rd reading 4th reading mean
(M)
reading
0.05 0.54 0.61 0.51 0.53 0.548

0.025 0.55 0.63 0.52 0.54 0.560

0.01 0.69 0.57 0.72 0.70 0.670

0.0075 0.74 0.70 0.75 0.72 0.728

0.0025 0.82 0.79 0.80 0.84 0.813

0.00075 1.00 0.95 1.14 0.99 1.020

0.0005 1.20 1.12 1.28 1.10 1.175

0 1.20 1.37 1.34 1.18 1.273

A graph of surface tension (N/m)

vs concentration of cetrimide (M)
1.4

1.2
Surface tension (N/m)

0.8

0.56
0.6

0.4
CMC
CMC
0.2

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Concentration (M)

The critical micelle concentration of cetrimide is 0.025 mol/L.

3. Cetomacrogol 1000 B.P

Concentration
Surface tension (N/m)
(M)
1st reading 2nd reading 3rd reading 4th reading mean
0.0005 0.40 0.52 0.40 0.44 0.44

0.0001 0.52 0.68 0.51 0.57 0.57

0.000075 0.49 0.64 0.49 0.54 0.54

0.000025 0.74 0.96 0.73 0.81 0.81

0.00001 0.93 1.21 0.92 1.02 1.02

0.0000075 1.00 1.30 0.99 1.10 1.10

0.0000025 1.10 1.43 1.09 1.21 1.21

0 1.20 1.37 1.34 1.18 1.27

A graph of surface tension (N/m) vs concentration of

cetomacrogol 1000 (M)
1.4

1.2
Surface tension (N/m)

0.8

0.6 0.54

0.4

0.2
CMC
0
0 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006
Concentration (M)

The critical micelle concentration of cetomacrogol 1000 is 0.000075 mol/L.

DISCUSSION

Surfactants is an organic compound and an amphipathic molecule which means that it has
hydrophilic part and hydrophobic part in their structure. Surfactants is also known as surface-active
agents. Surfactants are classified based on their polar head which is the hydrophilic part because
mostly the hydrophobic part of all surfactants is similar to each other. If the hydrophilic part of a
surfactant has no charge, the surfactant is called a non-ionic surfactant. If the hydrophilic part has
positive and negative charge, then the surfactant is called cationic surfactant and anionic surfactant,
respectively. If both positive and negative charge are present in the hydrophilic part, the surfactant
is called zwitterionic surfactant. A zwitterionic surfactant is pH-sensitive because the surfactant
will behave like cationic surfactant or anionic surfactant based on the pH of its surrounding.

In this experiment, 3 types of surfactants are being used to determine their CMC values,
respectively. First, Sodium Lauryl Sulphate B.P is an anionic surfactant because it contains anionic
functional groups which is the lauryl sulphate ions, SO32-. Secondly, Cetrimide B.P is a cationic
surfactant because the presence of quaternary ammonium cation, N(CH3)3+ and thirdly,
Cetomacrogol 1000 BP is non-ionic surfactant as no charged ion is present in the hydrophilic
region. Theoretically, Cetomacrogol 1000 B.P can reduce the surface tension more easily as
compared to the other two surfactants because of its non-charged characteristic. As it can reduce
the surface tension much easily, it will have the least surface tension value thus having the lowest
CMC value among the three surfactants. For Sodium Lauryl Sulphate B.P, it has the highest CMC
value because of its anionic characteristic and just below Sodium Lauryl Sulphate is Cetrimide
B.P, which has a lower CMC value because of its cationic characteristic.

In aqueous solution, the repulsion between the surfactant’s hydrophobic part and polar
water molecules causing no bond can be formed between them. Thus, free energy is formed. When
surfactants are added into aqueous solution, the surfactant molecules will arrange themselves on
the surface of the aqueous solution so that the hydrophilic part is in the water and the hydrophobic
part at in the air. Due to that, there is a reduce in the free energy (by disrupting the cohesive energy
on the surface) which then making the surface tension of the solution is reduced. As the
concentration of surfactant increases, the surface tension decreases up until a certain point is
reached where the surface is loaded by surfactants. This point is known as Critical Micelle
Concentration (CMC). After reaching the CMC point, any newly added surfactant molecules will
form micelles. The formation of micelles is due to hydrophobic effect with water molecules – by
mean, all the hydrophobic parts are gathered inside the micelles. This phenomena of forming
micelles are a spontaneously reaction to balance entropy and enthalpy.

1. Surface tension for Sodium Lauryl Sulphate B.P in different concentration

Sodium Lauryl Sulphate B.P (an anionic surfactant) is used to determine the CMC. This
compound is very soluble in water at room temperature and is used pharmaceutically as a
preoperative skin cleaner as it has bacteriostatic action against gram-positive bacteria.

From the graph, it shows that at certain critical point, further addition of Sodium Lauryl
Sulphate B.P will not affect the surface tension. Thus, the theory is approved. The CMC can be
obtained from the graph of surface tension against concentrations. The CMC obtained from the
graph is 0.01 mol/L at surface tension of 0.328 N/m.

2. Surface tension for Cetrimide BP in different concentration

Cetrimide B.P (a cationic surfactant) is also used to determine the Critical Micelle
Concentration (CMC). As a cationic surfactant, Cetrimide B.P can reduce the surface tension of
water by adsorption at the liquid-gas interface. This compound is used as topical antiseptic because
the cetrimonium cation is effective against bacteria and fungi.

From the graph, it shows that at very low concentration of Cetrimide B.P, only a slight
change in the surface tension. But as the surface tension decrease along the increasing
concentration of Cetrimide B.P, at concentration of 0.025 M, no more changes in surface tension
even more Cetrimide B.P is added. As result, the CMC value of Cetrimide B.P obtained from the
graph is 0.025 mol/L at surface tension of 0.560 N/m.

Theoretically, the CMC value for Cetrimide B.P should be lower than the CMC value for
Sodium Lauryl Sulphate B.P because of Cetrimide B.P’s high hydrophobicity in nature. But based
on the graph and data given, the CMC value for Cetrimide B.P (0.025 M) is higher than the CMC
value for Sodium Lauryl Sulphate B.P (0.01 M). Thus, the theory is not approved.
3. Surface tension for Cetomacrogol 1000 BP in different concentration

Cetomacrogol 1000 BP (non-ionic surfactant) is also used to determine the CMC. This
compound is used as a solubilizer and emulsifying agent in foods, cosmetic, and pharmaceutical –
often as ointment base.

From the graph, it shows that at very low concentration, Cetomacrogol 1000 B.P is the
same as Cetrimide B.P where only a slight change in the surface tension. The concentration
increases more than the surface tension starts to decrease. At the concentration of 0.000075 mol/L,
CMC is already reached and supposedly no more changes in surface tension after that. However,
the data and the graph show that there is a sudden increase in surface tension even after the CMC
has been reached. This situation may be caused by errors during the experiment because the surface
tension should be maintained same as the CMC value. Thus, the theory is not approved in
Cetomacrogol 1000 B.P. The CMC obtained from the graph is 0.000075 mol/L at surface tension
of 0.540 N/m.

The CMC value for Cetomacrogol 1000 B.P is the lowest among the other two surfactants
because Cetomacrogol 1000 B.P itself is a non-ionic surfactant which is generally has lower CMC
value than that of ionic surfactants. Other than that, the long hydrocarbon chain also results in the
decrease in the CMC value.

PRECAUTIONS

1. Make sure the volume of surfactants is measured and diluted correctly to get the correct
concentration of surfactants. This can be done by making sure the eye is perpendicular to
the scale of pipette when pipetting the surfactant out to avoid parallax error.
2. Make sure the value of surface tension is read correctly to get the correct value of
surfactants’ surface tension. This can be done by making sure the eye is perpendicular to
the scale of Du Nouy Tensiometer to avoid parallax error.
3. Make sure all the beakers used are labelled accordingly so that no mistake and no confusion
during measuring the surface tension of every surfactant at different concentration.
4. Make sure the Du Nouy Tensiometer’s ring is touching the surface of the solution just right
and not too deep into the solution or not only barely touch the solution so that the correct
measurement of surface tension can be obtained.
 5. Make sure the Du Nouy Tensiometer’s needles is calibrated correctly so that both needles
are exactly on the zero point before moving the Du Nouy Tensiometer’s arm.
6. Make sure to move the Du Nouy Tensiometer’s arm slowly and gradually so that the exact
measurement of surface tension can be obtained correctly.

QUESTIONS

1. Why are there differences in the CMC value of the three surface active agents?

The CMC values of surfactants in aqueous solution are affected by several factors such as
influenced by the type of surfactants, intermolecular forces between molecules in the
surfactants, length of hydrophobic chain of the surfactants, and the electrolyte content added
to the surfactants. According to the table below, sodium lauryl sulphate is an anionic
surfactant meanwhile cetrimide and cetomacrogol are cationic and nonionic surfactant
respectively.

Sodium Lauryl Sulphate BP Cetrimide BP Cetomacrogol 1000 BP

Anionic Cationic Non-ionic

Sodium Lauryl Sulphate and cetrimide are both ionic surfactants. They will ionise in water
to form anions and cations surfactant respectively. In water, sodium lauryl sulphate will form
lauryl sulphate ions, SO32- while cetrimide will form quaternary ammonium ions N(CH3)3+.
Based on the diagram above, the stable SO32- which faces towards the water is more effective
in reducing the surface tension of the water compared to the ammonium ion with methyl.
However, Cetrimide B.P has longer hydrophobic carbon chain which can form bonds with
water more efficiently and stabilize it. Cetrimide may promote micelle formation at lower
concentration compared to Sodium Lauryl Sulphate BP. Thus, Cetrimide B.P is expected to
 have lower CMC value than Sodium Lauryl Sulphate B.P. However in this experiment,
Cetrimide has higher CMC value than Sodium Lauryl Sulphate may be due to inaccuracy in
the method of using the tensiometer and parallax error.

Next, non-ionic surfactants such as Cetomacrogol 1000 has much lower CMC values and
higher aggregation numbers than its ionic counterparts with similar hydrocarbon chain.
Cetomacrogol 1000 B.P has long hydrocarbon chains which can bind with water and air
molecules at the surface of solution when the surfactant molecules arrange themselves by
pointing the hydrophobic hydrocarbon chain above the surface of the solution and the
hydrophilic portion (-OH) towards the water molecules in aqueous solution. Therefore,
Cetomacrogol is the most effective surfactant and will have the lowest CMC value among the
three surfactants. There is no electric force present because Cetomacrogol is non-ionic. The
presence of electric force will disrupt the formation of micelles. Non-ionic structure of
Cetomacrogol causes the formation of micelles becomes easier as there are no ionic forces
needs to be overcome during micelle formation. Therefore, only a small amount of
Cetomacrogol B.P is needed to reduce the surface tension.

2. Explain if there are abnormalities, which may be observed in the plot of your surface
tension vs. concentration.

Theoretically, the graph surface tension of solution is against the concentration of the
surfactant obtained should be a smooth hyperbolic curve and remains constant after critical
micelle concentration (CMC) as shown in the diagram below.
 However, based on the experiment carried out, there are abnormalities or deviation
observed in the graph plot and this may due to some reasons. Firstly, the abnormalities of the
graphs may due to improper handling of the Du Nouy Tensiometer. When determining the
reading of the surface tension, parallax errors may occur when the eyes of the observer are
not parallel to the scale. Besides, a defective tensiometer may cause errors during the
measurement of surface tension.
Apart from that, the abnormalities may also occur due to inaccuracy in serial dilution.
Insufficient time are given for the dissolution of surfactant molecules with water molecules.
The solutions are not properly mixed between the surfactant and water molecules. Thus, the
varies in concentration of surfactants will affect the readings of surface tension. Thus,
sufficient time should be given to allow complete mixing of surfactant with water molecules.
Next, inaccurate results may due to presence of impurities from the contamination of
apparatus such as measuring cylinder, pipette and the contamination of solution in the bottle.
The presence of impurities may affect the saturation of surfactant at the surface of the water
and air interface, which could decrease the interaction between surfactant and water
molecules, thus will affect the effect of surfactant and increase in the surface tension.

CONCLUSION

Critical micelles concentration (CMC) of surfactant can be determined by measuring the

surface tension of the solution. From this experiment, the CMC value for Sodium Lauryl Sulphate
B.P is 0.01 mol/L while Cetrimide B.P is 0.025 mol/L and Cetomacrogol 1000 B.P is 0.000075
mol/L. Cetomacrogol is the most effective surfactant because it is a non-ionic surfactant. It has the
best ability to reduce the surface tension compared to Sodium Lauryl Sulphate B.P and Cetrimide
B.P. The CMC values can be influenced by the type of surfactants used, intermolecular forces
between molecules in the surfactants, length of hydrophobic chain of the surfactants, and the
electrolyte added to the surfactants.
PART (B) CONDUCTIVITY OF SURFACE ACTIVE AGENT SOLUTIONS

INTRODUCTION
Specific Resistance or Resistivity is a fundamental property of a material that quantifies
how strongly the flow of electric current is opposed by the material. The reciprocal for resistivity
is conductance and for Specific Resistance is Specific Conductance or conductivity. Electrolyte
solutions has close association with the number of existing ions and the rate of the movement of
the ions. Thus, the quantity of conductivity is usually used. Through the movement of ions electric
current moves in the solution and this obeys Ohm’s Law which is:

Current (in ampere) = different potential (volt)

Resistance(ohms)

A pure solution does not conduct electricity. Conductivity can be seen when there is a
soluble electrolyte in the solution. Most properties are similar to those of a simple electrolyte at
low concentration except for surface tension, which decreases rapidly with increasing surfactant
concentration. However, all the properties showed an abrupt change at a particular concentration,
which is consistent with the fact that at and above this concentration, surface active ions or
molecules in solution associate to form larger units known as micelles and the first formed
aggregates are generally approximately spherical. conductivity decreases as the concentration
increased and micelle is formed.
Conductivity

Concentration
CMC

The critical micelle concentration (CMC) is the concentration at which this association
phenomenon occurs. Each surfactant molecule has a characteristic CMC at given temperature and
concentration. The most common technique for measuring CMC is by determining the surface
tension which shows break at the CMC after which remains virtually constant with further increase
in concentration.

Other techniques can be used as well to determine the CMC. The movement of ions towards
the electrode is inhibited by the viscous drag in the solutes applied onto the charged particles. A
large micelle will have larger viscous drag thus exhibits a decrease in conductivity. However, the
effect of counter ions are not taken into account because:

1) The opposite charge interaction and inhibition leads to a barking effect on the ionic opposite
charge conditions around a micelle.

2) Few opposite ions attached to micelle and move together in the same direction opposite to its
usual movement due to big size and charged micelle. The effective charge of the micelle is reduced
due to these bound ions.

The conductivity is reduced by the effect of opposite ions and the reduction is greater than
the viscous drag effect. This leads to overall reduction of the conductivity during micelle
formation. Therefore, conductivity measurement of surface active agents’ solution may be used to
determine CMC. CMC can be measured by plotting the conductivity against the concentration of
surface active agent and determining the meeting point of the two lines formed by the curve of the
graph by extrapolating the two lines.
METHOD
1. 50 mL of Sodium Lauryl Sulphate B.P. and cetrimide B.P. are pipetted into a suitable beaker.

2. The conductivity of each solution are measured by using a conductometric titration apparatus.
The solutions are diluted by adding 10 mL of water from burette and stirred using a magnetic
stirrer. The conductivity of surfactant solution is measured and recorded.

3. The solutions are diluted repeatedly until the total amount of added water reach 200 mL.

4. The concentrations of surface-active agent in the solutions are calculated after each addition
of water.

5. The graph of conductivity against the concentration of surface-active agent are plotted. The
point of critical micelle concentration is recorded.

RESULTS
1. Sodium lauryl sulphate B.P.

Total amount of Total volume of Concentration of sodium Conductivity

water added/ mL final solution/ mL lauryl sulphate B.P (mol/L) (µS cm-1)
0 50 0.0200 185.27
10 60 0.0167 183.40
20 70 0.0143 181.55
30 80 0.0125 180.21
40 90 0.0111 180.10
50 100 0.0100 178.25
60 110 0.0091 177.48
70 120 0.0083 175.25
80 130 0.0077 164.32
90 140 0.0071 162.98
100 150 0.0067 150.87
110 160 0.0063 142.25
120 170 0.0059 138.69
130 180 0.0056 128.41
140 190 0.0053 123.29
150 200 0.0050 111.11
 Graph of Conductivity Against Concentration Sodium Lauryl
Sulphate B.P.
450

400
Conductivity (mcS/cm)

350
y = 19913x + 16.78
300

250
y = 780.17x + 170.24
200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Concentration of Sodium Lauryl Sulphate B.P. (M)

Calculation of interception point for CMC:

Line 1: y = 19913x + 16.78

Line 2: y = 780.17x + 170.24

19913x + 16.78 = 780.17x + 170.24

19132.83x = 153.46

x = 8.0208 × 10-3 mol/L

The two lines intercept when x = 8.0208 x 10-3. Therefore, the critical micelle concentration of
Sodium Lauryl Sulphate B.P. 8.0208 x 10-3 mol/L.
2. Cetrimide B.P.
Total amount of Total volume of final Concentration of Conductivity (µS
water added/ mL solution/ mL Cetrimide B.P (mol/L) cm-1)
0 50 0.00500 342.68
10 60 0.00417 341.98
20 70 0.00357 339.45
30 80 0.00313 298.21
40 90 0.00278 287.13
50 100 0.00250 278.26
60 110 0.00227 268.45
70 120 0.00208 251.23
80 130 0.00192 235.47
90 140 0.00179 225.36
100 150 0.00167 213.45
110 160 0.00156 210.58
120 170 0.00147 190.87
130 180 0.00139 170.79
140 190 0.00132 167.65
150 200 0.00125 149.73
 Graph of Conductivity Against Concentration Cetrimide B.P.
500

450

400
Conductivity (mcS/cm)

y = 2229.7x + 331.86
350

300

250

200 y = 79652x + 71.997

150

100

50

0
0 0.001 0.002 0.003 0.004 0.005 0.006
Concentration of Cetrimide B.P. (M)

Calculation of interception point for CMC:

Line 1: y = 79652x +71.997

Line 2: y = 2229.7x + 331.86

79652x + 71.997 = 2229.7x + 331.86

77422.3x = 259.863

x = 3.3564 × 10-3 mol/L

The two lines intercept when x = 3.3564 x 10-3. Therefore, the critical micelle concentration of
Cetrimide B.P. is 3.3564 x 10-3 mol/L.
RESULT ANALYSIS

1. Based on the formula of standard free energy for micellization,

ΔG= RT ln C0*,
where,
ΔG = Standard energy of micellization
R= Gas constant (8.314 mol K ) -1 -1

T= Absolute temperature (300 K)

C0*= Critical concentration expressed as mole fractions

CMC
C0 = CMC + Water Concentration

CMC
= 1000
CMC +
18

a) Sodium Lauryl Sulphate B.P.

CMC = 8.0208 × 10⁻³ M
Co * = CMC
CMC+Water Cocentration

= CMC
CMC+1000
18
= 8.0208 x 10-3
8.0208 x 10-3 + 1000
18
= 1.4435 x 10-4

ΔG = RT ln Co*
= 8.314 (273+25) ln (1.4435 x 10-4)
= -22.06 kJ/mol
b) Cetrimide B.P.

CMC = 8.0208 × 10⁻³ M

Co * = CMC
CMC+Water Cocentration

= CMC
CMC+1000
18
= 3.3564 x 10-3
3.3564 x 10-3 + 1000
18
= 6.0412 x 10-5

ΔG = RT ln Co*
= 8.314 (273+25) ln (6.0412 x 10-5)
= -24.23 kJ/mol

2. Calculation of enthalpy, ΔH for sodium monododecylsulphate at room temperature

(270C)

The relationship between enthalpy for the micellization, ΔH and (CMC) is:
∆𝐻 𝑑𝑙𝑛Co ∗
2
=
𝑅𝑇 𝑑𝑡

Temperature/ oC Absolute CMC/ mol L-1 Co* ln Co*

Temperature/ K

36 309 8.6 × 10-3 1.548 × 10-4 -8.773

42 315 8.9 × 10-3 1.602 × 10-4 -8.739

46 319 9.1 × 10-3 1.638 × 10-4 -8.717

 Graph of In C0* against Absolute Temperature
-8.71
-8.717
308 310 312 314 316 318 320
-8.72

-8.73
-8.739
-8.74
In C0*

y = 0.0056x - 10.505
-8.75

-8.76

-8.77 -8.773

-8.78
Absolute temperature

𝑑𝑙𝑛Co∗
Slope of the graph = 𝑑𝑡

−8.773−(−8.739)
= 309−315

= 5.67 × 10-3 K-1

At room temperature (27 ˚C),

𝑑𝑙𝑛Co∗
∆H = × RT2
𝑑𝑡

∆H = (5.67 × 10-3) (8.314) (3002)

∆H = 4240.39 J mol-1

∆H = 4.24 kJ mol-1

At room temperature, ΔH of sodium monododecyl sulfate is 4.24 kJ/mol.

3. Calculation of the entropy, ΔS of micellization for sodium monododecyl sulphate
ΔS= ΔH- ΔG
T

The relationship between Free Energy, Entalphy and Entrophy for a system is given by Gibbs-
Helmhotz equation.

According to the graph,

Equation y = 0.0056x - 10.505
InCo* = y
InCo* = 0.0056(300)-10.505
InCo* = -8.825

ΔG = RT ln Co*
= (8.314)(300)(-8.825)
ΔG = -22011.315 J/mol
= = -22.01 kJ mol-1

According to the equation,

ΔS= ΔH- ΔG
T
4.24−(−22.01)
ΔS = 300

ΔS = 0.0875 kJ mol-1 K-1

ΔS = 87.5 J mol-1 K-1
DISCUSSION

Theoretically, surfactant solution alters both physical properties of surface tension and
electrical conductivity. Surfactant is mainly adsorbed on the surface of solution and a thin
monolayer is formed, thus it is known as a surface active agent. In this experiment, the ionic surface
active agent is used because the presence of electrolytes are needed for the electrical conductivity
of solution. For example, sodium lauryl sulphate BP and cetrimide are used to determine the
critical micelle concentration (CMC) in which critical micelle concentration is referred as the
concentration at which the aggregate of surfactant molecules(micelle) is formed after each
subsequent addition of 10mL distilled water during the dilution process.

In the presence of surfactant, the surface tension is directly proportional to the

concentration of surfactant solutions. As the concentration of ionic surfactant increases, surface
tension decreases while the electrical conductivity increases due to the presence of free moving
ions. Distilled water has a very high surface tension due to the strong intermolecular hydrogen
bonding among the hydroxyl groups. Therefore, when the distilled water is gradually added onto
the surfactant, the increasing of water concentration allows the amphiphilic characteristics of
surfactant molecules which then lead to the self-assembly of aggregates and formation of micelles.
Micelles are spherical structures with the surfactant molecules as its monomers. This structure
consists of the hydrophilic and hydrophobic region in which the polar region faces outwards of the
micelles and the non-polar region forms the core. However, the surface tension will become
independent of the concentration when it reaches beyond the critical micelle concentration (CMC).
After the micelles are formed, any increase in the concentration of surfactant will only increase
the formation of micelles and the surface tension is not affected. Beyond the critical micelle
concentration, further addition of surfactant will cause a lower electrical conductivity.

According to the graph, critical micelle concentration (CMC) can be obtained by plotting
the interception between two regression lines. In this experiment, the critical micelle concentration
of Sodium Lauryl Sulphate B.P of 8.0208 x 10-3 mol/L is obtained. Based on the formula of
standard free energy for micellization,

ΔG= RT ln C0*
the Gibbs free energy of Sodium Lauryl Sulphate B.P is found to be -22.06 kJ/mol. The negative
values of Gibbs free energy for micellization (ΔG) indicates that the micellization of surfactants
occur spontaneously. In addition, enthalpy change (ΔH) obtained at room temperature is 4.24 kJ
mol-1 while the entropy (ΔS) of micellization of sodium lauryl sulphate B.P is 87.5 J mol-1 K-1. For
the surfactant of cetrimide, the critical micelle concentration of 3.3564 x 10-3 mol/L is obtained
while the Gibbs free energy of is found to be -24.23 kJ/mol. The negative value of Gibbs free
energy also indicates that the reaction is spontaneous.

Thermodynamically, at the CMC point, surface condition in this system is unstable, thus
further addition of surfactant will expand the contracted surface of solvent spontaneously. A
reduction in free energy occurs spontaneously as it is needed for the system to be more stable.
When the monolayer is formed, it displaced the water molecules that exist on the surface, hence
resulting in the breaking of strong cohesive forces between water molecules and left with the weak
adhesive forces of attraction between water molecules and the hydrophilic region of surfactant. As
the result, Gibbs free energy is reduced while the entropy of micellization is increased.

From this experiment, theoretically, the formation of micelles will increase the electrical
conductivity due to the smaller radius in size and tend to experience less drag effect as compared
to the individual surfactant molecules, hence resulting in a lower resistance in electrical
conduction. However, the rate of electrical conductivity is lowered as proven in the graph due to
the interaction of counterions or oppositely charged ions with the micelles and this has reduced
the electrical conductivity as it is a stronger force as compared to the drag effect. Thus, viscosity
increases and leads to a smaller increment of electrical conductivity once the micelles are formed.

PRECAUTIONS

1. Stir the solution to ensure the ions are evenly distributed in the solution.

2. After each measurement, the electrode used to measure the conductivity need to be rinsed with
distilled water to avoid inaccuracy of the reading.

3. Parallax error should be avoided when measuring the solution by placing the calibration of the
apparatus at eye level along with the meniscus of the solution.
4. The electrode should not touch the surface of the beaker to avoid inaccuracy of the reading when
measuring the conductivity.

5. Distilled water is added slowly to the Sodium Lauryl Sulphate solution and Cetrimide solution
respectively to prevent the formation of bubbles as it may affect the conductivity.

CONCLUSION

Critical micelles concentration (CMC) of surfactant can be determined by measuring the

electrical conductivity. From this experiment, the CMC value for Sodium Lauryl Sulphate B.P is
8.0208 x 10-3 mol/L while the CMC value for Cetrimide B.P is 3.3564 x 10-3 mol/L. The Gibbs
free energy for micellization at room temperature (300K) of Sodium Lauryl Sulphate B.P is -22.06
kJ/mol while the Gibbs free energy for micellization of Cetrimide B.P is -24.23 kJ/mol. Besides,
the entropy change, ΔS of Sodium Lauryl Sulphate B.P is 87.5 J mol-1 K-1.

REFERENCES

1. Critical micelle concentration (CMC) and surfactant concentration. (n.d.). Retrieved

January 23, 2021, from https://www.kruss-scientific.com/en/know-how/glossary/critical-
micelle-concentration-cmc-and-surfactant-concentration
2. Laurén, S. (n.d.). What is critical micelle concentration? Retrieved January 23, 2021, from
https://www.biolinscientific.com/blog/what-is-critical-micelle-concentration
3. Critical Micelle Concentration. (n.d.). Retrieved January 23, 2021, from
https://www.sciencedirect.com/topics/materials-science/critical-micelle-concentration
4. Surfactants & critical micelle concentration (CMC). (n.d.). Retrieved January 23, 2021,
from https://www.dataphysics-instruments.com/knowledge/understanding-
interfaces/surfactants-cmc/
5. FAR 221/3 Physical Pharmacy 1 Practical Manual, School of Pharmaceutical Sciences,
Universiti Sains Malaysia
6. Kruss.de, (2015). CMC. [online] Available at: http://www.kruss.de/services/education-
theory/glossary/cmc/ [Accessed 22 January 2021].