Name: Wandya Daniel

St #: 218057822
Applied and colloid Experiment 4:
DETERMINATION OF DEGREE OF MICELLE IONISATION
Date of experiment: 02 March 2020
Lab Partners: Senzuni p
Hoases T
Frans H
Abstract

The critical micelle concentration, cmc, and the degree of micelle ionization, β, of
cetyltrimethylammonium bromide (C16TAB) in water, is 0.003 M, solution was determined from the
electrical conductivity data in the temperature of 298 K. It has been found that cmc is decreasing
with increasing surfactant chain length and decreasing concentration of diluted
cetyltrimethylammonium bromide (C16TAB) , whereas the temperature dependence of cmc shows
the typical U-shaped form with a minimum around (306 ± 3) K. Further, β is decreasing with
lengthening the alkyl chain of surfactant and increasing with increasing temperature, but no distinct
influence of added salt has been found actually. It can be concluded that the effect of electrolyte on
micelle ionization is quite complex (Morris, 2018).

Introduction

Despite much progress that has been made at investigations of micellar systems there are still some
ambiguities in micellization properties, especially for surfactants in salt solutions. For ionic
surfactants it has been confirmed that critical micelle concentration, cmc, is decreasing with
increasing concentration of added salt due to the screened repulsion between charged head groups
of surfactant monomers because of the condensed counter ions, what leads to easier formation of
the micelles.1,2 Thus, the degree of micelle ionization, β, could be believed to decrease with
electrolyte addition on account of the excess counter ions in solution also. The effect of electrolytes
on micellar behavior of sodium dodecyl sulfate (SDS) has been investigated thoroughly by Dutkiewicz
and Jakubowska by electrical conductivity technique. The cmc values were found to decrease with
increasing electrolyte concentration. As could be expected, they strongly depend on the nature of
cation as well. Further, the reported results for β reveal not only the dependence of degree of
micelle ionization on the kind of electrolyte added, but show that there is no exact decrease in β
with increasing electrolyte concentration. Moreover, β values actually increase or decrease or
remain constant with increasing electrolyte concentration in solution indicating the very complex
effect of added electrolyte on the degree of SDS micelle ionization. Jakubowska has been studying
SDS and hexadecyltrimethylammonium bromide (CTAB) micellization by conductivity measurements
together with electrospray ionization mass spectrometry (ESI-MS) also (Davis, 2011).

Procedure
The procedure was properly followed as indicated in the manual but minor changes were
made with a specific purpose of time saving. Changes that were made are: The class was
split into four groups and each group were given to work on certain volume range.
Experimental data/Data analysis

Diluted Vol/mL Conductivity (𝒌) Temp ℃ Conc (M)

5 50.1 22.3 3.0× 10
6 54.7 22.4 3.6 × 10
7 57.4 22.9 4.2× 10
8 60.9 23.0 4.8× 10
10 62.9 22.8 6. 0 × 10
12 76.2 23.3 7.2× 10
13 78.9 22.9 7.8× 10
15 86.6 23.1 9.0× 10
20 107.5 23.3 1.2× 10
22 112.4 23.5 1.32× 10
25 114.7 23.1 1.5× 10
30 119.4 22.4 1.8× 10
35 128.2 22.7 2.1× 10
40 130.9 22.9 2.4× 10
45 133.1 22.4 2.7× 10
50 137.2 22.4 3.0× 10

1. The graph shows relationship between the conductivity and concentration before and after
the cmc.

Relationship between
conductivity(k) and concentration
(M) of a surfactant
200
y = 34085x +50.645
150
Conductivity (K)

R² = 0.8977

100

50

0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035
CONCETRATION (M)
1.1. The graph below shows a relationship between conductivity and concentration before the cmc

Relationship between conductivity

(k) and concentration (M) of a
surfactant
100
y = 59750x + 31.905
80 R² = 0.9762
Conductivity (K)

60

40

20

0
0 0.0002 0.0004 0.0006 0.0008 0.001
Concentratio (M)

1.2. The graph shows a relationship between conductivity and concentration after the cmc

Relationship between conductivity

(k) and concentration (M) of a
surfactant
160
140 y = 16117x + 90.691
120 R² = 0.9668
Conductivity (K)

100
80
60
40
20
0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035
Concentration (M)

∴ Based on the first graph above, 𝐶𝑀𝐶 is approximately: 0.0012 M

Calculations

Finding the final concentration at each initial volume from 5 cm3 to 50 cm3

Concentration at 5bmL:

C1V1 =C2V2

C2 = C1V1 / V2
 × ×
=

= 3.00 × 10 𝑀

Degree of ionization of the micelles:

=𝐴 𝑤ℎ𝑒𝑟𝑒 𝐶 < 𝑐𝑚𝑐 𝑦 = 59750𝑥 + 31.905 (Before the cmc) (Equation 5)

= 𝛼𝐴 𝑤ℎ𝑒𝑟𝑒 𝐶 > 𝑐𝑚𝑐 𝑦 = 16117𝑥 + 90.691 (After the cmc) (Equation 6)

Since the ratio of slopes of the two above equation can give the (𝛼) degree of ionization of micelles,

𝐴 = 𝛼𝐴
𝐴
𝛼=
𝐴
59750
𝛼=
16117
𝛼 = 3.71
2. Gibbs free energy: ∆𝐺° = (2 − 𝛼)𝑅𝑇 𝐼𝑛𝑐𝑚𝑐
8.314𝐽𝑚𝑜𝑙
= × 298𝐾 × 𝐼𝑛(0.0012)[2 − 3.71𝑀]
𝐾
= −16662.75𝐽(2 − 3.71 𝐽)

= −33325.49𝐽 + 61773.24𝐽
= 28447.75 𝐽
= 28.45𝑘𝐽

Questions

1. Chemical ionization uses ion-molecule reactions to produce ions from the analyte. The
chemical ionization process begins when a reagent gas such as methane, isobutane, or
ammonia is ionized by electron impact. A high reagent gas pressure (or long reaction time)
results in ion-molecule reactions between the reagent gas ions and reagent gas neutrals.
Some of the products of these ion-molecule reactions can react with the analyte molecules
to produce analyte ions (Morris, 2018).
•
Example (R = reagent, S = sample, e = electron, = radical electron, H = hydrogen): R + e 
• • •
R+ + 2e R+ + RH  RH+ + R RH+ + S SH+ + R (of course, other reactions can occur)

2. The decrease of the slope of a conductometric curve is dependent on larger aggregates (less
mobile ions) formation, while the increase of the slope is an index of an increase of "free"
 ions in solution. It seems that some kind of aggregates are formed that somehow are "fully
loaded" of monomers and the surfactant being added is not binding or assembling but now
it's free in solution.

3. Conductivity measurements cannot be used because adsorption behavior at the water-air

interface and volumetric properties of aqueous solutions of Triton X-100 and dodecyl
betaine were investigated by surface tension, viscosity, and density measurements of
solutions. The obtained values of the surface tension as a function of dodecyl betaine
concentration were compared with those calculated from the Fainerman and Miller
equation. On this basis it was stated that the Fainerman and Miller equation is useful for
prediction of surface tension only in the concentration range of Triton X-100 corresponding
to its unsaturated monolayer in the absence dodecyl betaine (Kelley, 2012).

4. It is found that ∆𝐺° decreases monotonically as the temperature increases over the
whole temperature range. Theoretically, both ∆𝐻º𝑚 and ∆𝑆º𝑚 appear to be decrease
monotonically with an increase in temperature. The compensation temperature was found
to be 42 º𝐶 by linear regression over the whole temperature range and for all two surfactant
systems together (Morris, 2018).

Conclusion
This experiment was successfully achieved because the micellization behavior of
cetyltrimethylammonium bromide (C16TAB) in water, at different concentration was investigated by
electrical conductivity measurements at the temperature of 298 K. From the experimental data the
critical micelle concentration, cmc, and the degree of micelle ionization, β, were determined for all
the investigated systems. From the first graph, the cmc is approximately 0.0012 M. The degree of
ionization was determined as the ratio of the slope before the cmc and the slope after the cmc,
which is 𝛼 = 3.71. Gibbs free energy was also deduced from its equation ∆𝐺° =
(2 − 𝛼)𝑅𝑇 𝐼𝑛𝑐𝑚𝑐 and given a value of 28.45𝑘𝐽. Evidently, cmc is decreasing with increasing alkyl
chain length of cetyltrimethylammonium bromide (C16TAB) and increasing concentration of added
salt for the studied surfactant.

References
Morris.T. (2018). Classic chemistry demonstrations.London.Royal Society of chemistry

Davis, W. M. (2011). Physical chemistry : A modern introduction, second edition.

Kelley, A. M., & Kelley, A. M. (2012). Electrochemistry 8th edition. Retrieved from
https://ebookcentral.proquest.com

Lin, S. H., Villaeys, A. A., & Fujimura, Y. (2004). Advances in electrochemistry processes.
Retrieved from https://ebookcentral.proquest.com