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Chapter - 2
Abstract
Critical Micelle Concentration (CMC) is the key point for surface chemistry as
well as chemist and systematic data collection and day-to-day development in
this regard is very essential. Hence, we have analyzed the CMC of surfactant,
mixed surfactant and polymer at room temperature (280C), with the change in
surfactant, mixed surfactant and polymer concentration CMC values were
observed by two methods, surface tension and conductometric method. The
result of CMC values of surfactant, mixed surfactant and polymer show
different characteristics and out comes. The CMC values follows below order:
Polymer >SurfactantPolymer > Mixed Surfactant > Surfactant
Introduction
The role of micellar catalysis in recent years has been no need to say its
importance in different area such as pharmaceuticals, oil recovery industry,
environmental as well as Nano technological system (Proceedings ICCE
Indore 2005). The role of micellar catalysis may not be understood without its
critical micelle concentration. This is the concentration where surfactant will
work as micelle. Therefore, it is very interested as well as important to know
this factor very correctly and accurately. Our group had done some work in
this area. Nevertheless, systematic and new out comes develop this work.
The present work is an investigation of critical micelle concentration of
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The surface active amphiphilic anions are absorbed on the water surface
where they create a characteristic monolayer. The lipophilic dodecyl alkyls CH3(CH2)11 are oriented outside from the water surface, while the hydrophilic OSO3 - headgroups are directed into the aqueous environment. When the
concentration of sodium dodecyl sulfate reaches its corresponding CMC
value, the dodecyl sulfate anions starts to aggregate into the negatively
charged globular micelles. The lipophilic core of the micelles is built up from
the non-polar hydrocarbon alkyl chains while anionic groups localized on the
micelle surface with orientation to the polar aqueous environment. Negatively
charged micelles bind by electrostatic forces certain fraction of the Na+
counterions or other cations which may be present in the solution. Cationic
surfactant - carbethopendecinium bromide (Septonex) - is a well known
quaternary
ammonium
salt
with
strong
antimicrobial
activity.
Its
which
virtually
all
additional
surfactants
enters
the
micellar
state.(Desando 1986) .
The variation of the CMC with chemical and physical parameters provides a
good insights into the nature of the surfactant self-association. There are quite
abrupt changes in the concentration dependence of a larger number of
physico chemical properties at a particular concentration , this led to CMC
concept(Lindman 1980, Moroi 1988) shown diagrammatically in the Figure
2.1. Below the CMC negligible aggregation of the surfactants takes place
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differences in the sensitivity and reliability. The physical methods for CMC
determination includes conductivity, solubility, viscosity, light scattering,
measuring the surface tension by Wiebelmy slide method or by the method of
maximum bubble pressure , measurement of ion activity and by dye
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formed and destroyed, i.e, at low salt concentrations, ionic micelles change
their aggregation number in a regular fashion, while for high salt
concentration, micelles can also coalesce and break into pieces (Lebney
1981) . The micelles must therefore be considered as an extremely complex
dynamic entity which is capable of rapid break down and formation.
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(1)
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Effect of Additives
Examination of the literature shows that additives have a marked effect on the
CMCs of both ionic and nonionic surfactants, the more ionized groups present
in the surfactant, the higher the CMC, due to the increase in electrical work to
form the micelles.
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A detailed study of the effect of the nature of the polar head group of the ionic
surfactants on the micellar properties has been reported by Anacker and
Coworkers. The effect of different ionic groups on CMC is small, provided
complex dissociation occurs, as the extent of work necessary to overcome
electrical repulsion between ions of same charge is similar. Since the effect of
electrical repulsion is absent in non-ionic surface active agents, aggregation is
facilitated and the CMC are much lower than those ionic surface active
agents.
As far as the effect of number of hydrophilic groups are concerned, increase
in the number of any hydrophilic group increases the solubility of surface
active agents, leading to increase in CMC(36). The position of ionic groups
also affect the micellar properties. A marked increase in the CMC of Sodium
Alkyl Sulphate was observed with change in position of sulphate from terminal
position to a medial position along the chain (Evans). A similar increase in
CMC was observed for the polyoxy ethylated either type of non-ionic
surfactant with increase in the chain length of polyoxy ethylene chain and
decrease in micelle size.
For a compound to be qualified as a surfactant, it should also exhibit surface
activity. It means that when the compound is added to a liquid at low
concentration, it should be able to absorb on the surface or interface of the
system and reduce the surface or interfacial excess free energy. The surface
is a boundary between air and liquid and the interface is a boundary between
two immiscible phases (liquidliquid, liquidsolid and solidsolid).
Surface activity is achieved when the number of carbon atoms in the
hydrophobic tail is higher than 8. Surfactant activities are at a maximum if the
carbon atoms are between 10 and 18 at which level a surfactant has good but
limited solubility in water. If the carbon number is less than 8 or more than 18,
surfactant properties become minimal. Below 8, a surfactant is very soluble
and above 18, it is insoluble. Thus, the solubility and practical surfactant
properties are somewhat related.
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Surface Tension
72-73
78
28-30 (at or above
CMC)
Ethanol
22
Chloroform
27
Bromoform
45
Hexane
18
Octane
22
Dodecane
25
Hexadecane
27
Diethyl ether
17
Mercury
480
monomers are the cause of the surface activity. Micelles have no surface
activity and any increase in the surfactant concentration does not affect the
number of monomers in the solution but affects the structure of micelles. The
typical CMC values at room temperature are 103 to 102M for anionic
surfactants, 103 to 101M for amphoteric and cationic surfactants and 105 to
104Mfor non-ionic surfactants. The CMC of several surfactants in aqueous
media can be found in (Rosen 2004, Mukherjee 1971). Surfactant structure,
temperature, the presence of electrolyte, existence of organic compounds and
the presence of a second liquid has an effect on the CMC. The following
factors contribute CMC decrease (Porter 1994, Rosen 2004, Evans 1956,
Schick 1962, Ray 1971, Schick 1957, 1965, Herzfeld 1950, Hunter 1987):
(a) An increase in the number of carbon atoms in the hydrophobic tails
(b) The existence of polyoxypropylene group
(c) Fluorocarbon structure
(d) An increased degree of binding of the counterions
(e) The addition of electrolyte to ionic surfactants
(f) The existence of polar organic compounds (such as alcohols and
amides)
(g) The addition of xylose and fructose
The following factors contribute to CMC increase (Porter 1994, Rosen 2004,
Evans 1956, Schick 1962, Ray 1971, Schick 1957, 1965, Herzfeld 1950,
Hunter 1987):
(a) Branch hydrophobic structure
(b) Double bonds between carbon atoms
(c) Polar groups (O or OH) in hydrophobic tail
(d) Strongly ionised polar groups (sulphates and quaternaries)
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small and their radius is approximately equal to the maximum stretched out,
length of the surfactant molecule.
Cylindrical micelles are formed where the surfactant packing parameter is
between 1/3 and 1/2 (single chain surfactants with small head group areas
such as non-ionic surfactants and ionic surfactants in high salt concentration).
Any change in solution properties which causes a reduction in the effective
size of hydrophilic head groups will change the aggregate size and shape
from spherical to cylindrical form. For example, the addition of electrolyte
reduces the effective hydrophilic area of ionic surfactants because the
increased counterions reduce the repulsion between ionic polar head groups.
Addition of co-surfactant with a smaller head group size also contributes to
mixed micelle formation of cylindrical shape. Increasing the temperature,
reduces the ethoxylated non-ionic head groups. Furthermore, changing the
pH changes the degree of protonation of amphoteric surfactants and affects
the head size. Vesicles, liposomes and flexible bilayers are formed where the
surfactant packing parameter is between 1/2 and 1 (double chain surfactants
with large head group areas such as phospholipids, surfactants with bulky or
branched tail groups and the mixture of anionic and cationic surfactants with
single chain at nearly equimolar concentration). These types of surfactants
cannot pack themselves into a close micelle and form bilayers (lamellar
structure). As the packing parameter approaches unity, the lamella becomes
flat and planar (double chain anionic surfactants in high salt concentration).
Only the flexible lamellar bilayer bends around and joins in a sphere (vesicle).
This structure keeps aqueous solution both inside and outside of the sphere.
Liposomes are concentric spheres of vesicles (layers of an onion
arrangement) they are more than a micrometer in size and formed by gentle
shaking of surfactant in water. The internal bilayer structures of the liposomes
are optically active. Hence, they can easily be identified with a polarising light
microscope. Vesicles are formed from liposomes by ultrasonication,
ultrafiltration or microfluidisation. They are nanometre in size and can only be
detected by electron microscopy. Vesicles are used as drug delivery agents,
model components for cell membranes and cationic softeners in detergency.
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Functionalized monomers
Functionalized monomers are sometimes regarded as polymerizable
surfactants. Vinyl or allyl monomers are reacted with ethylene oxide (EO),
propylene oxide (PO) or butylenes oxide (BO) in a sequential or random
78 | P a g e
addition mode. The terminal hydroxyl group can be optionally reacted with
methyl or benzyl chloride to produce Williamson ethers (if the hydroxyl group
has to be deactivated) or are further sulfated to deliver electrosteric
stabilization. Functionalized monomers can be copolymerized with other
ethylenically unsaturated monomers for permanent polymer modification. The
drawback of allylic, acrylic and vinylic polymerizable groups is their tendency
to homopolymerize. Allylic derivatives, furthermore, are susceptible to
degradative chain transfer.
Derivatives from pure ethylene oxide are water soluble and result in silicon
polyols with water solubility or dispersibility. Propylene oxide and even more
butylene oxide allow for more compatibility with organic media, e.g. butylene
oxide gives compatibility with organic oils. Depending upon the demanded
balance of hydrophilicity/hydrophobicity, different proportions and order of
addition of the alkoxide can be used. Incertain instances blocking of the
terminal hydroxyl group may be required, e.g. by reaction with methyl or, less
commonly, benzyl chloride.
Propylene oxide undergoes rearrangement in the presence of base and forms
allyl alcohol, thus forming in situ initiators during the alkoxylation process.
Unless properly accounted for, this decreases the molecular weight of the
polyether produced. The hydrosylilation of the allyloxy polyether intermediate
by a siloxane hydride is catalyzed by e.g. chloroplatinic acid and is
exemplified in eqn. 1.
(Me3SiO)2MeSiH + H2C=CHCH2O(EO)xH (Me3SiO)2MeSi(CH2)3O(EO)xH
Where, EO stands for ethylene oxide.
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and
Kosmella
(1993)
have
observed
that
in
the
emulsion
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Nature
Feature
Comments
Copolymerizable
emulsifiers for the
emulsion
polymerization of
vinyl
acetate,
acrylates,
styrene/acrylates
Addition
during
emulsion
polymerization
improve
latex
stability
and
reduce grit levels
Reduce
water
uptake of polymer
films
Copolymerizable
emulsifier for the
emulsion
polymerization of
vinyl
axetate,
acrylates,
styrene/acrylates
Improve
grit
levels
Reduce
water uptake of
polymer films
82 | P a g e
Copolymerizable
emulsifiers for the
emulsion
polymerization of
vinyl
acetate,
acrylates,
styrene/acrylates
Anionic monomer
with
surface
activity can be
used
without
additional
emulsifier
improve
latex
stability
and
reduce grit levels
reduce
water
uptake of polymer
films
Methacrylic acid
esters of alky Nonionic
polyethylene
glycol ethers Allyl
polyethylene
glycol ethers
Hydrophilic
Alkyl
can
be
monomers
for methyl or lauryl
emulsion, inverse
emulsion
and
solution
polymerization
Used to produce
surface
active,
water-soluble
silicone
ethers
(antifoams)
Used
in
the
copoly merization
with acrylates to
produce
water
soluble polymers
83 | P a g e
84 | P a g e
of
polymerizable
surfactants
in
emulsion
polymerization
This will cause poor stability during polymerization and broadening of the
particle size distribution.
Most of the reactive surfactants used for emulsion polymerization have the
reactive group at the end of the hydrophobic moiety of the molecule, on the
assumption that the polymerization process takes place in the latex particle.
Work of Ferguson et al. shows, indeed, a lower stability of lattices produced
with Surfmers with an acrylate group attached to the end of the hydrophilic
chain than those produced with the equivalent terminated with an thyl ester
group.
86 | P a g e
Figure 2.12. The specific conductivity (a) and molar conductivity (b) as a
function of concentration.
surfactant solutions. Because of the surface activity of there substances,
measurements of the surface tension of surfactant solutions represent the
principal method of CMCs determination. 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
87 | P a g e
= 0 - c
Determination of CMC
The surface tension measurements were made by a Surface Tensiometer
(CBVP-A3, Face) and a Dynamic Contact Angle Analyzer (DCA322,Cahn). A
sandblasted platinum plate of dimensions 1.95 1.00 x 0.02 cm was used.
Solutions were contained by a double-walled Pyrex vessel thermostatted at
25.00.2C or at 80.0 0.5C. To prevent the contam ination of solution from
dust in air during the operation, the vessel had a cover with a hole only
allowing a thin wire hanging the platinum plate to go through, and the whole
vessel was placed inside a closed sample chamber of the surface
Tensiometer or the dynamic contact-angle analyzer. Solutions were allowed
to equilibrate until the surface tension stabilized.
tension was measured as a function of time. It was found that the surface
tension decreases as time evolves. It is believed that this dynamic behavior of
surface tension is simply due to the rearrangement of surfactant molecular
configuration at the interface. For certain systems, this phenomenon is very
pronounced and it even took more than 20 h to reach equilibrium. The
equilibrium surface tension was then determined whenever the tension
revelled off to ensure the system reached fully equilibrium.
The surfactant CTAB, CPC, CPB, SLS, TX-100, Brij 35, PEG 300 extra
pure, AR grade was obtained with a high grade of purity (99%) which were
used through out the experiment. All Solutions were prepared with weighing
accuracy
0.001gm
Denver
make
balance
at
room
temperature.
1000mL volumetric
flasks, surfactants were weighed on mass basis and emptied into the
volumetric flask and then double distilled water was used to complete the
solution to the final weight (1kg). After preparation of the stock solution, it was
diluted to obtain desired concentration. CTAB, CPC, CPB, SLS, TX-100, Brij
35, PEG 300 Solutions were prepared at concentrations ranged from 1 x 103
M to 2.5 x 10-3. Mixed surfactant solutions were prepared by mixing the listed
solutions of the same weightas per the listed experimental use . Mixed
surfactant solutions were allowed to equilibrate for at least 5hrs before any
measurements were made.
CMC measurement
The CMC values obtained through conventional plot of the surface tension
versus the surfactant concentration. The CMC concentration corresponds to
the point where the surfactant first shows the lowest surface tension. The
surface tension remains relatively constant after this point.
tension method. Using these CMC data, is helpful to find shape, structure of
micelle, surface activity, solubilization, absorption, wetting phase behavior etc.
In the Table 2.2 and Table 2.3, the CMC values for different surfactant,
polymer, and polymer-Surfactant, mixed surfactant has been successfully
determined by surface tension method and the values are increasing with
increasing molar concentration. We can easily find out the drastic change in
surface tension in all cases. The points have been shown in following figures.
Table 2.3: Determination of CMC (Surfactant and Polymer PEG-300) by
Surface tension
MOLAR
Surface Tension
CONC
SLS
CPC
CTAB
CPB
TX-100
BRIJ35
PEG300
0.21
47.5
41.2
49.6
32.2
31.9
45.6
74.5
0.32
49.2
42.3
50.3
33.0
32.5
48.3
75.9
0.44
50.2
45.6
52.3
34.2
33.6
49.6
77.4
0.58
51.2
48.2
55.3
35.2
34.2
51.2
78.9
0.68
55.6
49.2
56.8
35.6
34.5
55.6
80.5
0.72
56.5
51.6
59.0
36.6
34.8
56.3
83.8
0.8
57.5
58.6
65.2
41.0
35.1
58.9
87.5
1.5
55.9
60.3
66.3
41.9
35.4
59.3
93.7
2.5
53.7
65.2
67.5
42.9
36.1
61.2
98.3
92 | P a g e
The measurement of
TX100
PEGBRIJ35 300
MOLAR
CONC x 103
1.00
SLS
0.44
1.00
CPC
0.90
0.73 1.00
CTAB
0.84
0.80 0.99
1.00
CPB
0.87
0.73 0.99
0.99
1.00
TX-100
0.81
0.83 0.94
0.94
0.91 1.00
BRIJ35
0.81
0.88 0.96
0.97
0.94 0.97
1.00
PEG-300
0.95
0.65 0.98
0.96
0.97 0.90
0.92
1.00
93 | P a g e
of
critical
micellar
concentration
through
conductivity
SLS+PEG
CPB+PEG
CPC+PEG
CTAB+PEG
BRIJ35+PEG
TX-100+
PEG
PEG
Conc.x103
Molar
Conc.x10-3
1.00
SLS+PEG
0.02
1.00
CPB+PEG
0.98
0.18
1.00
CPC+PEG
0.99
0.14
1.00
1.00
CTAB+PEG
0.99
0.11
0.99
1.00
1.00
BRIJ-35+PEG
0.01
1.00
0.16
0.13
0.09
1.00
TX-100+PEG
0.99
0.14
1.00
1.00
0.99
0.12
1.00
PEG
-0.04
0.98
0.11
0.08
0.03
0.99
0.07
94 | P a g e
1.00
103
S.L.S
C.T.A.B.
C.P.C.
C.P.B.
Brij-35
TX-100
S.L.S.+Brij-35
S.L.S.+TX-100
0.0
2.59
2.59
2.59
2.59
2.59
2.59
2.59
2.59
0.21
3.48
3.29
4.60
2.74
4.36
3.38
4.32
3.75
0.32
3.76
3.34
5.61
3.46
5.00
4.10
4.74
4.13
0.44
7.64
4.75
7.71
6.16
6.55
6.90
4.53
7.20
0.58
8.41
5.79
8.55
6.70
7.25
7.70
9.13
8.14
0.68
8.66
7.10
9.67
7.46
10.17
8.55
10.20
8.75
0.72
8.79
7.20
10.40
9.07
10.52
8.36
9.40
8.61
0.89
8.82
7.70
11.20
7.97
10.63
9.33
10.52
9.07
1.5
14.02
11.40
12.80
11.88
15.93
15.18
15.13
13.23
2.5
NA
16.36
16.00
16.89
19.99
NA
NA
18.97
1.5
14.02
11.40
12.80
11.88
15.93
15.18
15.13
13.23
2.5
NA
16.36
16.00
16.89
19.99
NA
NA
18.97
NA not analyzed
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Molar conc. x
3M
10-
PEG300+
S.L.S
PEG300+CPC
PEG300+CTAB
PEG300+CPB
PEG300+
TX100
S.L.S.+Brij35
PEG+CPC
0.89
0.98
1.00
PEG+CTAB
0.86
0.97
0.99
1.00
PEG+CPB
0.79
0.93
0.95
0.94
1.00
PEG+TX-100
0.92
0.98
0.97
0.93
0.94
1.00
S.L.S.+Brij-35
0.85
0.97
0.96
0.91
0.94
0.97
1.00
PEG-300
0.95
0.96
0.98
0.97
0.91
0.96
0.91
96 | P a g e
PEG300
1.00
97 | P a g e
Surfactant
/Mixed
surfactant
Surface Conductivity
tension
SLS
0.44
0.44
SLS+PEG
0.72
0.51
CTAB
0.99
0.99
CPB+PEG
0.59
1.10
CPC
0.44
0.44
CPC+PEG
0.44
1.00
CPB
0.99
0.99
CTAB+PEG
0.44
1.00
SLS+Brij-35
0.58
0.58
Brij35+PEG
0.68
1.00
SLS+TX-100
0.44
0.44
TX100+PEG
0.32
0.99
Brij-35
0.99
1.50
PEG-300
0.78
0.81
TX-100
0.44
0.44
Since the Critical micellar concentration values for polymer & mixed polymer
are all most different in both the methods of determination. In surface tension,
CMC values are almost half than the CMC values determined through
conductivity in maximum cases. The degree of correlation for CMC values
determined through surface tension and conductivity, was almost 50%( corr.
value = 0.49). Here we find that in simple polymer CMC values is higher than
or almost equal to the values of mixed in both case ,surface tension and
conductivity. This variation in values are also due to hydrophobicity Hence the
finally CMC values are increases as follows:
Surfactant < Mixed surfactant < Polymer < Surfactant Polymer
98 | P a g e
Conclusion
The value of CMC decreases with increase in the hydrophobic chain length of
the molecule. Hydrophobic interaction opposed by electrostatic repulsion
among the ionic head groups derives the process of micellization .A list of CMC
data of some surfactant, mixed surfactant, polymer, surfactant polymer
determined by surface tension and conduct metric method shown in table 9.9.
The values of CMC for surfactant & mixed surfactant are allmost same with
surface tension & conduct metric. It proves the authenticity of result. However,
the CMC values of surfactant are low as compared to mixed surfactant due to
long hydrophobic group (Menger 1993)
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