Anda di halaman 1dari 51

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Chapter - 2

Critical Micelle Concentration of Surfactant, Mixed Surfactant


and Polymer By Different Methods at Room Temperature And
Its Importance

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
55 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

different surfactant, polymer, and mixed micelle at room temperature (280C)


with reaction condition. Groundwater aquifers, facilitate/enhance residual oil
recovery and in soil-cleanup operations is well established, and both anionic
and nonionic surfactants have been used to remediate land polluted with oils
and hydrocarbons as well as many other organic contaminants. A
fundamental property of surfactants is their ability to form micelles (colloidal
sized clusters) in solution. This property is due to the presence of both
hydrophobic and hydrophilic groups in each surfactant molecule. It is the
formation of micelles in solution which gives surfactants their excellent
detergency and solubilization properties. Hence, the most important
parameter in terms of the ability of a surfactant to mobilize or solubilize
hydrophobic contaminants in contaminated soil is the surfactant CMC. The
CMC of a surfactant solution can be determined by any physical property (e.g.
surface tension used in this work) that shows a distinct transition around the
CMC. Based on this particle nucleation mechanism, the well-known SmithEwart theory predicts that the number of particles nucleated is proportional to
the surfactant concentration to the 0.6 power (Romsted 1977). This is
reasonable because for a given surfactant the number of micelles formed
generally increases with an increase in the surfactant concentration.
Surfactants are organic substances, which significantly decrease the surface
tension of water at relatively low concentrations, atleast partially water
soluble. Because surfactants are absorbed mainly on the surface of the
solution, creating a thin monolayer, they are called surface active substances.
When dissolved 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, also called micelles. The characteristic
concentration value, where the association process begins, is called the
critical micelle concentration and is labeled with symbol cc or abbreviation
CMC. 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,
form the true solutions in concentration ranges below the CMC. Micelles are
56 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

aggregates of 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. For this reason the micelle solutions of surfactants are regarded as
association colloids. The molecular structure of surfactants is amphiphilic
(biphilic), it consists of both nonpolar (hydrophobic, lipophilic) and polar
(hydrophilic) parts (Figure 2.1).

Figure 2.1. Amphiphilic structure of surfactants An illustration of a


spherical micelle (of dodecyl sulfate) emphasizing the liquid-like
character with a disordered hydrocarbon core and a rough surface.
(Redrawn from Jonsson, B., Lindman, B., Holmberg, K. and Kronberg,
B., Surfactants and Polymers in Aqueous Solution), 1998 John Wiley &
Sons Ltd., Chichester, Reprinted in April 2001, p. 36, Reproduced with
Permission)
The lipophilic part of the structure usually consists of hydrocarbon groups, in a
simple case, it is one long alkyl chain, typically with more than ten carbon
57 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

atoms. The hydrophilic part of the structure may be represented by non-ionic


polar groups or ionic groups and in this sense
we distinguish between non-ionic surfactants and ionic surfactants. The ionic
groups are much more hydrophilic than the non-ionic polar groups. The nonionic surfactants are dissolved as electroneutral molecules, e.g. higher fatty
alcohols or cholesterol which have polar hydroxyl groups. Ionic surfactants
dissociate in aqueous solutions into pairs of 2 cations and anions, but usually
only one kind of these ions are surface active, and ions with the opposite
charge are called counterions. Based on the charge and the nature of the ion
which generates surface activity, we can divide the ionic surfactants into
following classes:
1.

anion-active (anionic) surfactants - e.g. sodium or potassium salts of


higher fatty acids (soaps), salts like sodium dodecyl sulfate, sodium
tetradecyl sulfate etc.

2. cation-active (cationic) surfactants - e.g. quaternary ammonium salts


hexadecylpyridinium bromide, carb ethopendecinium bromide (Septonex)
etc.
3. ampholytic surfactants e.g. long-alkyl amino acids, with pH dependent
charges.
Surfactants form a numerous group of various natural and synthetic
compounds, In common practice, their mixtures are used as soaps,
saponates and detergents. Non-ionic neutral and some anionic surfactants
are used in pharmacy as useful excipients - additives, emulgators,
solubilizers, constituents of creams and ointments. Among the cationic
surfactants we can find a large number of especially antimicrobial substances.
Ionic surfactants are generally well soluble in water and at concentrations
below the corresponding CMC. They behave like fully dissociated strong
electrolytes. Anionic surfactant - sodium dodecyl sulfate - is dissociated into
the surface active CH3(CH2)11OSO3 - anin and the sodium cation Na+
(counterion) in the aqueous solution.
58 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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

carbethopendecinium cations form positively charged micelles in aqueous


solution at concentrations above its CMC value. The carbethopendecinium
cation has more complex structure, the nonpolar group is represented by an
alkyl chain and its positive ionic charge is on the quaternary nitrogen atom.

Critical Micellar Concentration (CMC)


The CMC of surfactants in recent literature, has been defined as the
concentration of the surfactant solution at which the molecules selfaggregate
to form spherically shaped micelles.(SHAH 1983) The Critical Micelle
Concentration indicates the usually narrow range of concentrations separating
the limits,at below which most of the surfactant is in the monomeric state and
above

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
59 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

which in turn occurs as extensive aggregates above the CMC (Lindman


1984). For surfactants containing long chain alkyl groups the value of CMC is
usually between 10-4 and 10-2 M. The Sharpness of the break in the physical
properties depends on the nature of the micelle and on the method of the
CMC determination. Among 70 known methods (Mukherjee 1971), there are
however are a great

Figure 2.2. Schematic representation of the concentration dependence


of some physical properties of solutions of a micelle-forming surfactant.
(Redrawn from Jnsson, B., Lindman, B., Holmberg, K. and Kronberg,
B., Surfactants and Polymers in Aqueous Solution), 1998 John Wiley &
Sons Ltd., Chichester, Reprinted in April 2001, p. 36, Reproduced with
Permission)

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

60 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

incorporation method, Gel filtration spectrophtometrically and counterion


magnetic resonance (Elworthy 1968, Cermakova 1986, Beg 1984).
Examination of the literature shows that the concentration of the monomers
present in the solutions increases after the CMC and there is a possibility of a
second marked aggregation, known as second CMC (Robertz and Jones
1973). These, undoubtly, reflect change in size, shape, polydispersity and
degree of concentration binding to binding to the micelle and also change rate
of hydration (Kubota 1973). A second CMC exists where the aggregates gain
positional order due to increased electrical repulsions among the micelles
(Kale 1980). According to Porte et al (1984), the second CMC arises from a
sphere to rod transition of the micelle geometry. Studies on micellization in
potassium n-Octanoate in deuterium oxide, over wide concentration and
temperature intervals , reveals that a second critical micelle concentration
exists around 1.0 M potassium at Ca-30-40 oC (Desando 1986).
It is noteworthy that micelles when formed are not independent (Lawrence
1958). The half life is about ten million seconds for pure ionic surfactants
(Elworthy 1968). The half life for the micelle of SDS and dodecyl pyridium
bromide is about 10-2 seconds (Jaycock 1964). Different NMR(Florence 1971)
and ultrasonic measurements (Craber 1970) reveal that the rate constant for
the dissociation of the monomer from a micelle is in the region 10-2-10-9
seconds-1.
Micelles donot have an indefinite lifetime but are constantly formed and
destroyed in the solution by kinetic processes (Kielmann 1976). The life time
of micelles depend in a very complicated way on the hydrocarbon chain
lengths, the dissociation degree, the aggregation numbers and additives
(Hoffmann 1985).

There are two mechanisms, by which micelles can be

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.
61 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

The micelle formation is invariably affected by the effect of hydrophobic


length and the nature of the additive added. The CMC decreases strongly as
the hydrophobic part of the surfactant is increased; the decrease is more rapid
for nonionic than for ionic surfactants (Lindman 1984). As a general rule for
ionic surfactants, the CMC is halved when the length of the straight
hydrocarbon chain is increased by one methylene group (Attwood 1970). An
even more pronounced decrease in CMC with increase of hydrocarbon length
has been noted with non-ionic surfactants, the addition of one more
methylene group causes the CMC to decrease to one third of its original
value.
The CMCs of the various homologs of surfactants with a linear alkyl chain
follow the equation:
Log CMC = A Bn

(1)

Where, n is the alkyl chain and A and B are constants


Figure 2.2 shows a linear relationship between log CMC and the no. of carbon
chain length. For Chain length above 16 carbon, this pronounced effect
gradually loss its significance and no further appreciable effect of CMC are
observed because of the coiling of the long chains is observed (Mukerjee
1967). In case of branched hydrocarbon chains, the effect on the CMC (with
increase in the number of carbon atom) is not higher than in the straight
chain.

62 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Figure 2.3. Variation of critical micelle concentration with hydrocarbon


chain length for (A) sodium alkyl sulphate and alkyl trimethyl ammonium
bromide (B) Hexaoxy ethylene monoalkyl ethers. (After Attwood and
Florence 1983).

Where A and B are constants for a homologous series. Branching of a


hydrocarbon chain causes an increase in CMC (Janjjap 1988). Since the
decrease in free energy arising from the aggregation of branch chain
molecules, is less than that obtained with linear molecules with the same
number of carbon atoms.
For a given alkyl chain, CMCs increase in the order nonionic (Polyoxyethylene
glycol monoethers)< Zwitterionic< ionic (Cationic or anionic) (Winterborn
1972).

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.
63 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.
64 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Determining Critical Micelle Concentration (Surface Tension


Method )
The molecules of a liquid attract each other due to dispersion, dipole-dipole
and dipole-induced-dipole forces, as well as hydrogen bonding. In the bulk
liquid, a molecule senses the same attractive and repellent forces in all
directions, while for a molecule at the surface, those forces are lacking in one
direction. This asymmetry of forces is the origin of the surface energy or
equivalent the surface tension. For the reasons mentioned above, a
compound will possess higher surface tension, the more polar it is. Likewise,
two liquids are immiscible if the surface tension between them is large, but for
entropic reasons they are miscible if that tension is low enough. Then
practically, what a surfactant does, to lower the surface tension. This leads to
increased solubility of non-polar molecules in aqueous solutions (e.g.
solubilization of micelles). Surfactants can also improve the stability of
dispersions, emulsions and foams. There is, of course, a practical limit to how
low the surface tension can be. With special formulations, so-called ultra low
interfacial tension, values in the range of 10-3 mN/m or lower can be reached.
Such microemulsion systems are of interest for the purpose of enhanced oil
recovery (EOR). A summary of the surface tension values of some liquids is
found in Table 2.1.

65 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Table 2.1 Surface tension values (in mN/m) of some liquids at 25 C


Solvent
water
10% aq. NaOH
Aqueous surfactant
solution

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

The properties of surfactant at low concentration in water are similar to those


of simple electrolytes except that the surface tension decreases sharply with
increase in concentration. At a certain concentration, surfactant monomers
assemble to form a closed aggregate (micelle) in which the hydrophobic tails
are shielded from water while the hydrophilic heads face water. The critical
aggregation concentration is called the critical micelle concentration (CMC)
when micelles form in an aqueous medium. The CMC is a property of the
surfactant. It indicates the point at which monolayer absorption completes and
the surface active properties are at an optimum. Above the CMC, the
concentrations of monomers are nearly constant. Hence, there are no
significant changes in the surfactant properties of the solution, since the
66 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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)
67 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

(e) Hydrophilic groups placed in the surfactant molecule centre


(f) Increase in the number of hydrophilic head
(g) Trifluoromethyl groups
(h) An increase in the effective size of hydrophilic head
(i) An increase in the pH of weak acids (such as soap)
(j) A decrease in pH from isoelectric region and increase in pH from
isoelectric region foramphoteric surfactants (low CMC at the isoelectric
region and high CMC outside the isoelectric region)
(k) addition of urea, formamide, and guanidinium salts, dioxane,
ethylene glycol and water soluble esters
The CMC decreases with temperature to a minimum and then increases with
further increase in temperature. The minimum appears to be around 25C for
ionic surfactants and 50C for non-ionic surfactants (Flow chart 1961, Crook
1967).
Several empirical correlations are available for the estimation of CMC values.
For straight and saturated single tail ionic surfactants, the CMC can be
calculated from (Klevens 1953)
Log CMC = A Bn
Where, n is the number of carbon atoms in the hydrophobic tail, and A and B
are temperature dependent constants for a given type of surfactant. The value
of B is around 0.3 is equivalent to log102 ) for the ionic surfactants because
the CMC of the ionic surfactants is halved for each carbon atom added to the
hydrophobic tail. B value is about 0.5(= 0.5 log 10) for the non-ionic and
amphoteric surfactants because the CMC will decrease by a factor of 10 for
each of the two methylene groups added to the hydrophobic tail. The values
of A and B for some surfactants can be found (Kreshech 1975).

68 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

The effect of electrolyte concentration on the CMC of ionic surfactant is given


by (Corrin et al 1947).
logCMC = a b log C
where a and b are constants for a given ionic hydrophilic head at a certain
temperature and C is the total counter ion concentration in equivalent per litre.
The effect of electrolyte concentration on the CMC of non-ionic and
amphoteric surfactants is given by Ray (1971) and Shinoda (1961).
logCMC = x yCe Where Ce < 1
where x and y are constants for a given surfactant, electrolyte and
temperature, and Ce is theconcentration of electrolyte in moles per litre.
Further discussion of the theoretical CMC equations can be found in [Rossen
2004, Hobbs 1951, Molyneux 1965).
In non-polar solvents, hydrophilic head groups interact due to dipoledipole
attractions and produce aggregates called reverse micelles.With this
structure, head groups of surfactant molecules orientate towards the
interiorandthehydrophobic tails orientate towards the nonpolar solvents. In the
absence of additives such as water, the aggregation numbers of reverse
micelles are small (mostly less than 10). On the other hand, in polar solvents
such as glycol, glycerol and formamide, surfactant aggregates are thought to
be similar to the aggregates in water since these polar solvents havemultiple
hydrogen bonding capacity. In general, the CMC of ionic and non-ionic
surfactants is higher in nonaqueous solvent than in water (Kaler 1994). The
CMC is a useful tool for the selection of surfactants for specific applications or
properties. For example, surfactants with a low CMC are less of an irritant
than those with high CMC. The CMC can be determined by measuring the
changes in physical properties such as electrical conductivity, turbidity,
surface tension, interfacial tension, solubilisation and auto diffusion. Detail
evaluation of different methods for the determination of CMC can be found in
(Mukherjee et al 1971). Amongst these methods, the surface tension method
is most commonly used in practice and ISO Standard 4311 describes this
69 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

method which is applicable to all types of surfactants in both commercial and


pure forms. It requires the strict control of test temperature for precise and
reproducible values. According to the procedure, 16 surface tension values
are measured over the range of surfactant concentrations; among these, six
values should be in the region close to CMC. Each value is repeated three
times and measurements are made within 3 h of solution preparation. The
average of each set of three values is plotted as surface tension versus the
log of the surfactant concentration. For a pure surfactant, the break point at
the CMC is sharp and well defined. The concentration at the minimum surface
tension gives the CMC value. Most formulators use more than one surfactant
to improve the properties of products. In addition, commercial surfactants are
mixtures because they are made from mixed chain length feedstock and are
mixtures of isomers and by-products depending on their synthesis. Purifying
the surfactant to a great extent is not economically feasible. Furthermore, a
mixture of surfactants was found to perform better than single surfactants in
many applications such as emulsion formation, detergents and enhanced oil
recovery. The CMC of the mixture is either the intermediate value between
theCMCvalues of each surfactant, less than any of the surfactant CMC
(positive synergism) or larger than any of the surfactant CMC (negative
synergism). The CMC of the mixture, if the mixture contains two surfactants
and mixed micelles, is an ideal mixture (activity coefficients of free surfactant
monomers for each surfactant type in the mixture are equal to unity.
CMCM = x1 CMC1 + (1 x1) CMC2
where x1 is the mole fraction of surfactant 1 in solution on a surfactant base,
and CMC1 and CMC2 are the critical micelle concentrations of pure
surfactants 1 and 2, respectively. Details and the equations for the non ideal
surfactant mixtures can be found in (Scamehorn 1986).

70 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Micellar Aggregate Structures and Shapes


A theory for the aggregate structure was developed, based on the area
occupied by the hydrophilic and hydrophobic groups of surfactant (Tanford
1980, Israelachvili 1992). For a stable formation of a surfactant aggregate
structure in an aqueous system, the internal part of the aggregate should
contain the hydrophobic part of the surfactant molecule while the surface of
the aggregate should be made up of the hydrophilic heads. The polar head
groups in water, if ionic, will repel each other because of same charge
repulsion. The larger the charge, the greater the repulsion and the lower the
tendency to form aggregates. The hydrophilic heads have also strong affinity
for water and they space out to allow water to solvate the head groups. On
the other hand, hydrophobic tails attract one another due to hydrophobic
effect. When the surfactant concentration is high enough, the surfactant
molecules pack together due to the interaction of the two opposing forces
between the surfactant molecules. The shape and the size of the aggregate
can be determined by using the surfactant packing parameter which is the
ratio of the hydrophobic group area to the hydrophilic head area. The and lc
are the volume and length of the hydrophobic tail in the surfactant aggregate:
= 27.4 + 26.9n
lc 1.5 + 1.265n
where n is the total or one less than the total number of carbon atoms of the
hydrophobic tail in the surfactant aggregate, is in cubic Angstrom (A3) and
lc is in A . For saturated straight chain, lc is 80% of the fully extended chain
(Tanford 1940). The structures of surfactant aggregates as a function of
surfactant packing parameter and shape are shown in Figure 2.3 (Israelachvili
1992).
Spherical micelles are formed, where the value of surfactant packing
parameter is less than 1/3 (single chain surfactants with large head group
areas such as anionic surfactants). The spherical aggregates are extremely
71 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.
72 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Inverted or reverse micelles are formed where the surfactant packing


parameter is greater than 1 (surfactants with small head groups or large tail
groups such as double tailed anionic surfactants). These structures are
formed in non-polar solvents. In these structures, head groups are clustered
together and tails are extended towards the solvent. They have the capacity
to take water into their cores and hence, form water-in-oil microemulsions.
Hydrophilic materials can also be solubilised into the reverse micellar core
(engine oil additives, hydraulic oils and cutting oils). Inverse micelles are often
used for the separation of biological molecules such as proteins. The
surfactant phase diagrams for several surfactants have been developed in
order to understand the phase tructureof surfactants in solution at high
concentration. With these

73 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Figure2.4. Schematic structures of surfactant self-assemblies as a


function of surfactant packing parameters and shape.

74 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

CMC and Micellar Growth


When added to an aqueous solution, surfactant molecules minimize their
energy by creating a monolayer on the air-water surface. This is a slow
process with large molecules, for example, polymers (equilibrium times can
vary from seconds to days), but considerably faster for surfactants (ms-s). In
order to minimize their free energy, the hydrophobic parts of the surfactants
are directed towards the less polar air, while the hydrophilic groups are
directed towards the polar water molecules. Upon increased surfactant
concentration, the surface becomes increasingly saturated by surfactant
molecules, which decreases the surface tension of the solution. In other
words, the surface tension will decrease upon the addition of surfactants. The
kinetic process can be followed by so called dynamic surface tension studies.
The low-concentration kinetics can be described by the Ward-Tordai equation,
which assumes diffusion from the bulk and absorption at the interface, here
NMR diffusion experiments can be useful for determining the diffusion
coefficient, using the Stokes-Einstein Equation of the surfactant. The
equilibrium situation is more commonly studied, and results in, among other
things, the acquisition of the CMC value (see below), which is an important
characteristic of the surfactants. The surface tension is commonly studied by
means of a Wilhelmy plate tensiometry apparatus. The minimum surface
tension reachable is determined by how effective the packing of the
surfactants is at the surface and on the interactions between the surfactants
at the interface) different hydrophobic and hydrophilic groups thus create
different minimum surface tensions. With concentrations above the saturation
point, called the critical micellization concentration, the CMC, the freely
dissociated surfactant molecules in the water bulk phase start to form closed
micellar structures, that can be spherical, oblate, prolate, tablet shaped or rodlike, with a hydrophilic surface and a hydrophobic interior (Figure 2.1). Such
micelles usually have hydrodynamic radii, RH, ranging from 20 to 400 . High
accuracy measurements of the force between two solid interfaces coated with
surfactants can be made by means of a MASIF apparatus (Measurement and
Analysis of Surface Interaction Forces) or other surface force instruments.
75 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

The CMC of polyoxyethylene-based surfactants decreases with increasing


temperature. Sugar-based surfactants, as well as SDS, seem to exhibit
minimum CMC values at given temperatures. The favorable decrease in
energy gained from micelle formation further increases the solubility of the
surfactant molecules themselves, as it also does with any non-polar organic
compound trapped in the micellar interior. At the CMC, usually in the order of
M-mM, almost all further surfactant molecules are incorporated into the
micellar structures and hence the absorption to surfaces is also saturated. No
noticeable decrease in surface tension is gained by increased surfactant
concentrations above the CMC. Thus, the CMC can easily be determined, by
application of the Gibbs isotherm, from a plot of the logarithmic surfactant
concentration (often in mM) vs. the surface tension (, often in mN/m) of the
solution. From such a plot it is also possible to calculate the absorbed amount
of surfactant at the interface, with the absorbed amount being proportional to
the slope of the surface tension isotherm (up to the CMC). For practical
formulations, the CMC itself can be lowered by the addition of a molecule that
is more hydrophobic than the surfactant itself, since the formation of micelles
is then stimulated. Small rather hydrophobic compounds such as short chain
alcohols also interact with surfactants. They affect the packing of the
surfactant at the interface (e.g. affecting the foam stability). So-called
hydrotropes are often small molecules with bulk hydrophobic groups and/or
charged polar groups. They interfere with the packing of the surfactant and
affects a range of properties, e.g. for ethylene oxide-based surfactants, they
increase the cloud point (the temperature at which the surfactant solution
turns turbid due to a liquid-liquid phase separation). The actual radii of the
micelles formed are determined by surfactant concentration and surfactant
geometry. The size and shape can be effectively measured, for example, by
using a SANS apparatus (Small Angle Neutron Scattering). With further
increased concentration the micelles increase in size, forming rod- or spongelike structures instead, and begin to pack into lamellar, hexagonal or cubic
structures Figure 2.5.

76 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

This phenomenon, which is also temperature-sensitive is often described for


surfactant-water mixtures by means of binary or ternary phase diagrams.
Furthermore, increased temperature induces a decrease in the hydration
number of the head group of the ethylene oxide-based surfactants, rendering
it more hydrophobic. Sugar-based surfactants are less affected by
temperature variations. Thus, with increased hydrophobicity, the ethylene
oxide-based surfactant will, when mixed with oil, gradually go from promoting
oil droplets in water to forming water droplets in oil. This change in structure
can be described as a result of changes in the spontaneous curvature, H, a
parameter that describes surfactant packing at different

Figure 2.5. Surfactant self-assembly leads to a range of different


structures, a few of which are shown here. (Redrawn from Jnsson, B.,
Lindman, B., Holmberg, K. and Kronberg, B., Surfactants and Polymers
in Aqueous Solution), 1998 John Wiley & Sons Ltd., Chichester,
Reprinted in April 2001, p. 34,
temperatures in a given system, with positive values giving oil-in-water
emulsions and negative values giving reversed micelles (water-in-oil
emulsions). The temperature at which the H-parameter is 0, meaning exact
balancing of hydrophobicity and hydrophilicity, is referred to as the phase
77 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

inversion temperature (PIT) of the surfactant in that particular system.


Mixtures of surfactants working synergistically are often characterized in
ternary phase diagrams, showing the various phases of different molar ratios,
molar fractions, weight fractions or weight percentages of the three
components involved. A number of phenomena, including wetting, dispersion,
emulsification and foaming, can be explained by the formation of micelles and
the minimizing of free energy of the systems. Several physical properties of a
solution are concentration-dependent on the presence of a micelle-forming
surfactant. Reactive surfactants can covalently bind to the dispersed phase
and as such have a distinct advantage over conventional surfactants that are
only physically adsorbed and can be displaced from the interface by shear or
phase changes with the subsequent loss of emulsion stability. Depending
upon the chemical structure and effects, there are different types of reactive
surfactants:
1. Functionalized monomers
2. Surface active initiators (Inisurfs)
3. Surface active transfer agents (Transurfs)
4. Polymerizable surfactants (Surfmers)
Inisurfs, Transurfs and Surfmers may be used to reduce/avoid the use of
conventional surfactants in emulsion polymerization. However, when Inisurfs
and Transurfs are used, the stability of the system cannot be adjusted without
affecting either the polymerization rate (Inisurfs) or the molecular weight
distribution (Transurfs). Furthermore, the efficiency rate of Inisurfs is low due
to the cage effect.

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.

Figure 2.6 Functionalized monomer.


79 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.

Surface active initiators


Surface active initiators or Inisurfs have the advantage of reducing the
number of ingredients in an emulsion polymerization recipe to water,
monomer and initiator, at least in the initial stages of the process. However,
the surface active properties of the Inisurfs may be reduced on formation of
the radicals and additional surfactant must be added to stabilize the latex if
high solid levels are wanted.
Inisurf molecules contain three moieties:
The radical generating moiety, which can be azo or peroxy
A hydrophobic moiety which is usually a hydrocarbon (alkyl or alkyl
phenyl), some times extended by the inclusion of propylene oxide

80 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

A hydrophilic moiety which can be anionic, cationic or nonionic


The molecules can be symmetrical, i.e. the structural moieties are the same
on both sides of the radical-generating group and two surface active radicals
are produced on decomposition. If the structure is asymmetrical only one
surface active radical is produced on decomposition. The key feature of
Inisurfs is their surfactant behavior. They form micelles and are absorbed at
interfaces, and as such they are characterized by a critical micelle
concentration (CMC) and an area/molecule in the adsorbed state. This
influences both the decomposition behavior and the radical efficiency, which
are much lower than those for conventional, low molecular weight initiators.
Tauer

and

Kosmella

(1993)

have

observed

that

in

the

emulsion

polymerization of styrene, using an Inisurf concentration above the CMC,


resulted in an increase in the rate constant of the production of free radicals.
This was attributed to micellar catalysis effects as described, for example, by
Rieger (1986). Conversely, if the Inisurf concentration was below the CMC the
rate constant of the production of free radicals decreased with an increase in
the Inisurf concentration, which was attributed to enhanced radical
recombination. Also note that a similar effect of the dependence of initiator
efficiency on concentration was reported by Van Hook and Tobolsky for
azobisisobutyronitrile (AIBN) (Van Hook 1958).

81 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Table 2.2. Examples of functionalized monomers


Chemical
Composition

Nature

Feature

Comments

Allyl Polyalkylene Nonionic


glycol ethers

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

Level of use 12%


active
materials based
on monomers

Vinyl polyalkylene Nonionic


glycol ethers

Copolymerizable
emulsifier for the
emulsion
polymerization of
vinyl
axetate,
acrylates,
styrene/acrylates
Improve
grit
levels
Reduce
water uptake of
polymer films

Level of use 12%


active
materials based
on monomers

82 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Allyl polyakkylene Anionic


glycol
ether
sulfate
ammonium salt

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

Allyl polyethylene Nonionic


glycol ether

Used to produce
surface
active,
water-soluble
silicone
ethers
(antifoams)

Allyl polyethylene Nonionic


glycol ether

Used
in
the
copoly merization
with acrylates to
produce
water
soluble polymers

Level of use 13%


active
materials based
on monomers

83 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Surface Active Transfer Agents (Transurfs)


Polymerizable surfactants are capable of working as transfer agents include
thiosulfonates, thioalkoxylates and methyl methacrylate dimer/trimer
surfactants. Thioalkoxylates with 1790 ethylene oxide units were produced
from ethoxylated 11 bromo-undecanol by replacing the bromine with a thiol
group via the thiazonium salt route (Vidal 1995). In the presence of watersoluble azo initiator the thio ended Transurfs (used at a concentration above
the CMC) gave monodispersed latex particles in emulsion polymerization of
styrene. However, the incorporation of the Transurf remained low, irrespective
of the process used for the polymerization (batch, semibatch, seeded). The
stability of the lattices when the surfactant and the transfer function were
incorporated in the same molecule was better than when they were
decoupled.

84 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Polymerizable surfactants (Surfmers)


Polymerizable surfactants may be considered as surface-active monomers
and essentially
consist of :
1 A hydrophilic moiety
2 A hydrophobic moiety
3 A polymerizable group
In common with conventional surfactants, Inisurfs and Transurfs, Surfmers
form micelles
in aqueous solutions above the CMC. The organized monomer aggregates of
colloidal dimension are microscopically heterogeneous and may affect
polymerization kinetics and polymer structure and properties.
HS C11 H22 O ( CH2 CH2 O ) - H
n = 17 to 90
Advantages

of

polymerizable

surfactants

in

emulsion

polymerization

processes include latex stabilization and resistance to electrolyte addition and


to freeze-thaw cycles. In film forming polymers, the most interesting property
is, however, the superior water resistance achievable compared to
conventional surfactants. This manifests in an increase in the hydrophobicity
of the films because the covalent bonding of the Surfmer to the particles
reduces migration to the surface.
One important requirement in replacing a conventional, nonreactive surfactant
with a reactive one is that neither the molecular weight nor the particle size
distribution of the latex may significantly change. Also, the Surfmer reactivity
is important: if the Surfmer is too reactive compared to the other monomers in
the recipe, it will become partially buried inside the growing polymer particles.
85 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.

Figure 2.9 Ionic surfmer

Figure 2.10. Transurf Structure.

86 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Figure 2.11. Ionic Surfmer


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

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

breaking point on the curves, which describes the concentration dependence


of conductivity. It is well-known, that the conductivity of any solution is directly
proportional to the concentration of its ions. The point, where the micelle
formation starts, is indicated on the concentration dependence of specific
conductivity (), as a breaking point. It is easy to find the breaking point,
because it marks a significant change of the linear slope of the dependence
=f(c).The requested value of CMC is the intercept of two linear functions with
mutually different slopes Figure 2.12(a).
The dependence of the molar conductivity, () on the second root of
concentration (c) can be used for more precise determination of CMC of ionic
surfactants, Figure 2.12(b). The solution of surfactant, e.g. sodium dodecyl
sulfate, behaves as a 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 has a slightly negative slope. This
concentration dependence of the molar conductivity is thus described by the
Onsager equation (8):

= 0 - c

where 0 is the corresponding molar conductivity at the infinitive dilution and


c is the concentration of the studied surfactant. Values of the molar
conductivity are calculated from the experimental values of specific
conductivity () and the concentration of solution. The basic unit of this
quantity is S m2 mol-1 (Eq. 9)
= k/c
Units and their transformation;
S m-1 is the main SI unit for specific conductivity. Because conductometers
often display the value in other subunits the following transformation
relationship could be useful:
1 S cm-1 = 10-4 S m-1
88 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.

Therefore, the surface

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.

Material and Method


The stock solution of the surfactant sodium dodecyl sulfate with concentration
c = 0.012 mol.dm-3 (or Septonex c = 0.0012) in 250 ml volumetric flask: - The
calculated amount of the studied substance should be weighed using
analytical balance directly in the analytical flask. - Dissolve the substance by
adding a small amount of redistilled water, and when it is fully dissolved add
the remaining volume of redistilled water, as it is given with the marker on the
analytical flask.
slow mixing motions was used to avoid the formation of foam. The stirrer was
inserted and the solution was poured in the conductivity vessel which was
previously stirred , cleaned and dried. As the temperature reached 25C, the
first conductivity of the various solutions were determined.
89 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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.

(Conductometer systronic make digital, glass surface tension was used).


Triton X-100 (TX100) extra pure, was purchased from Scharlau Chemie,
Spain. Sodium Dodecyl Sulphate (SDS) was obtained from Merck with a high
grade of purity (99%). All chemicals were used as received without further
purification. Selected physicochemical properties of the compounds are
presented in Table2.1.
The surfactant solutions were prepared in a standard

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.

Surface Tension Measurement


The surface tension technique was applied to determine the CMC in various
surfactant systems, applied in the work. The surface tension measurements
were carried out with Krss tensiometer (Krss GmbH, Hamburg, using a
platinum-iridium ring at constant temperature (251C). The Tensiometer was
calibrated using method described in ASTM Designation: D1331-89. Surface
tension measurements were undertaken according to the method described in
ASTM Designation: D1331-89. Krss tensiometer operates on the Du Nouy
principle, in which a platinum-iridium ring is suspended from a torsion
balance, and the force (in mN/m) necessary to pull the ring free from the
surface film is measured. Surface tension value was taken when stable
90 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

reading was obtained for a given surfactant concentration, as indicated by at


least three consecutive measurements having nearly the same value. The
average of a series of consistent readings for each sample was then
corrected to account for the tensiometer configuration, yielding a corrected
surface tension value . A correction factor, F is multiplied by the average dial
reading in order to obtain the corrected value for surface tension (ST).
Zuidema and Waters, proposed the following empirical correlation to calculate
the correction factor:

Where F= the correction factor;


R =the radius of the ring, cm;
r =the radius of the wire of the ring, cm;
ST =the apparent value or dial reading, dyne/cm (mN/m);
=the density difference between the lower and upper
phases, g/cc;
g= acceleration due to gravity, 980 cm/sec2 . The
Equation is applicable only when 0.045 gR3/(ST)
7.5

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.

Result and Discussion


Critical micelle concentration (CMC) is the concentration above which
monomer surfactant molecule abruptly aggregate to form micelle(Romsted
1977, Bunton 1979). It is mostly determined by conduct metric & surface
91 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

The measurement of

critical micellar concentration of pure surfactants

through surface tension at varying molar concentration from 0.21 x 10-3 M to


2.5 x 10-3 M indicate a marked correlation of surfactants mainly CPC, CTAB
and CPB with increase in concentration however less than PEG.
Figure 2. 4 Correlation Coefficient of surfactant (Pure/mixed) with PEG300.
MOLAR
CONC
x 10-3 SLS CPC CTAB CPB

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

In a similar experiment of determining critical micellar concentration of


surfactants mixed with PEG showed enhanced values compared to pure or
mixed surfactant as depicted in Table 2.3 and correlation coefficient in Table
2.4
Determination of Critical micellar concentration through conductivity
Determination

of

critical

micellar

concentration

through

conductivity

measurements of pure surfactants (Table 2.5 ) and Surfactant-PEG-300


mixture (Table ) too reveal higher values for the mixture than in the individual
surfactants shown in graph () and ().
Table 2.5 visualizes critical micellar concentration through surfactant-PEG
mixture which finds strong support for PEG combination with PEG-CPC,CTAB
,TX-100,SLS shown in Table-3.
Molar

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Table 2.6: Determination of CMC (Surfactant) by conductivity


Molar Conc.
CONDUCTIVITY

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

95 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Figure 2.7 Correlation coefficient of CMC determined by conductivity for


Surfactant/Polymer combination

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Correlation coefficient of CMC values of surfactant mixed with PEG-300


through conductometric method

too reveal the enhanced CMC for the

polymer polyethylene glycol-300 mixed with Brij-35, CPB, TX-100 ( corr.


coeff.= 0.98-1.00) as compared to those of pure surfactant(Table 2.5 & 2.7)
and their relative correlation coefficient values(Figure 1.6).
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 is
determined by surface tension and conduct metric method shown in table 2.4.
The values of CMC for surfactant & mixed surfactant are allmost same with
surface tension & conductmetric. It proves the authenticity of result. However,
the CMC values of surfactant are low as compared to mixed surfactant due to
long hydrophobic group.

97 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Table 2.8 Observed CMC Values of surfactant, mixed surfactant, polymer


&surfactant polymer By Surface tension and conductivity

Surfactant
/Mixed
surfactant

Surface Conductivity Polymer /


Tension
Surfactant
mixed

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

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

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)

Figure 2.12. Graphical representation for observed CMC Values of


surfactant, mixed surfactant, polymer &surfactantpolymer By Surface
tension and conductivity
Hence the final trend of Critical micellar concentration CMC for the present
work is
Surfactant < Mixed surfactant < Polymer < Surfactant Polymer

99 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

References
C.A.Bunton , Catal.Rev. Sci. Eng,(1979) 1,20.
Evans, H.C. (1956) Alkyl sulphates. Part 1. Critical Micelle Concentrations of the
sodium salts. J. Chem. Soc., 78, 57986.
Florence, A.T. and Parfitt, R.T. J.Phys. Chem. 75, 3554 (1971).
ISO Standard 4311. Determination of the critical micelle concentration method by
measuring surface tension with a plate, stirrup or ring.
Jaycock, M.J. and Ottewill, R.H. Proc. 4th. Intern. Congr. Surface Active
substances, Brussels, (1964), Gardon and Breach, N.Y. (1967).
Kielmann, Ulbritcht, W. Zana, R., Lang, J. and Tondre, C.J. Phys. Chem. 80, 905
(1976).
Kubota, Y. Kodama, M. and Miura, M. Bull. Chem. Soc. Jpn. 46, 100 (1973);
Kodama, M., Boku, R. Ishida, T. and Miura, M. ibid. 50 751 (1979).
Lindmann, B. In Surfactants, (Ed. T. F. Tadros). Academic Press, London Chap. 4
(1984).
Lindmann, B., Wennerstrom, H. And Elicke, H.F. Micelles Springer-Verlag,
Heidelberg (1980).
Mukherjee, P. Adv. Colloid Interface. Sci. 1, 241 (1967).
Porte, G., Poggi, Y. Appell, J. and Moret, G. J. Phys. Chem. 88, 5713 (1984).
S.K.Sar, P.K.Pandey, S.Nair, R.Sharma, A.K.Bhui, N.Mishra. International J.Chem.
Env., (2005) page no20.
Schick, M.J. and Fowkes, F.M. (1957) Foam stabilizing additives for synthetic
detergents. Interaction of additives and detergents in mixed micelles. J. Phys.
Chem., 61, 106268.

100 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

T.J .Broxton, J.R.Chirsitie and R.P.t.Chung, J .Org Chem., (1988),53 ,3081.


68. Hobbs, M.E. (1951) The effect of salts on the critical concentration, size, and
stability of soap micelles. J. Phys. Colloid Chem., 55(5), 67583.
Anacker E.W. and Geer R.D. (1971). J. Colloid Interface Sci. 35: 441.
Anacker E.W., Geary E.H., Jacobs P.T. and Petrariu L (1977). J. Colloid Interface
Sci.60: 514.
Attwood, D. and Florence, A.T. (1983). Surfactant systems. their chemistry ,
Pharmacy and Biology. 1st ed. Chapman and Hall, New York.
Attwood, D. Elworthy, P.H. and Kayne, S.B. (1970). J. Phys. Chem., 74, 3529.
Beg, A.E., Meakin, B.J. and Davis, D.J.G. Pharmazie 35, 3 (1980); ibid. 37, 12 (1982);
Sci. Pharm, 52, 229 (1984).
Cahn, A. (1979) J. Am. Oil Chemists Soc., 56, 809A.
Cermakova, L., Rosendorfola, J. and Malat, M. Collect. Czech. Chem. Common, 45,
210 (1980); Pand, L. and Behera, G.B. J.Phya. Chem. 96, 57870 (1986).
Craber, E., and Zana, R.Colloid-Z, 238, 479 (1970).
Desando, M.A. and Reeves, L.W. Can. J. Chem. 64. 1817 1823 (1986).
Elworthy P.H., Florence, A.T. and Macfarlane, C.B. Solunilization of surface active
agents and its application in chemistry and the biological science, Chapman
and Hall. London (1968).
Evans, H.C. (1956) Alkyl sulphates. Part 1. Critical micelle concentrations of the
sodium salts. J.Chem. Soc., 78, 57986.
F, I. and Henscheld, L.G. J. Chem. Educ. 60 865, (1983).
F.M.Menger and C.A Littau , J. Am.Chem. Soc. ,(1993),115,10083-10090.

101 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Ferguson, P., Sherrington, D.C. and Gough, A. (1993) Preparation, characterization


and use in emulsion polymerization of acrylated alkyl ethoxylate surface-active
monomers. Polymer, 34, 328192.
Flochart, B.D. (1961) The effect of temperature on the critical micelle concentration of
some
Florence, A.T. and Parfitt, R.T. J. Phys. Chem. 75, 3554 (1971).
formation by nonionic detergents. J. Am. Chem. Soc., 69(3), 68388.
Herzfeld, S.H., Corrin, M.L. and Harkins, W.D. (1950) The effect of alcohols and of
alcohols and salts on the critical micelle concentration of dodecylammonium
chloride. J. Phys. Chem., 54,27183.
Hoffmann, H.; Lobl, M., Rhag, M. and Wunderlich, I. Tenside Surfactant Detergents,
22 , 290 (1985).
Hunter, A.J. (1987) Foundations of Colloid Science, Vols I and II. Clarendon, Oxford.
Israelachvili, J. (1992) Intermolecular and Surface Forces, 2nd edn. Academic,
Orlandao, FL.
Janjjap, H., Nusselder, Degroot, Jan, T., Michel, T. and Engberts Jan, B.F.N. (1988).
J. Org. Chem., 53 (11), 243-6.
Jaycock, M.J. and Ottewill, R.H. Proc. 4th. Intern. Congr. Surface Active Substances,
Brussels, 1964. Gardon and Breach. N.Y. (1967).
K.K.Ghosh and S.K.Sar, Reaction kinetics and Catalysis Letter, Hungary (2004)
Vol.81, No.1, 161-168.
Kale, K. M.; Cussler, E.L. and Evans, D.F. J. Phys. Chem. 84, 593 (1980).
Kaler, E.W. (1994) Basic surfactant concepts. K.R. Lange (ed.), Detergents and
Cleaners A Handbook for Formulators. Hanser, New York, pp. 128.

102 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Kallol K. Ghosh and Santosh K. Sar ,J.Indian Chem. Soc.,(1998),75,39-41.


Klevens, H.B. (1953) Structure and aggregation in dilute solutions of surface active
agents. J. Am. Oil Chem. Soc., 30, 7480.
Kreshech, G.C. (1975) Surfactants in Water A Comprehensive Treatise. Plenum,
New York.
Kubota, Y., Kodama, M. and Miura, M. Bull. Chem. Soc. Jpn. 46, 100 (1973);
Kodama, M., Boku, R. Ishida, T. and Miura, M. ibid. 50 751 (1979)
L.S. Romsted in Micellization Solubilsation and Microemulsions K.L.Mittal Plenum
Press , New York , (1977) ,Vol. II ,509.
Lawrence, A.S.C. Discuss Faraday Scic. 25, 51 (1958).
Lebner, E., Teubner, M.; and Kahlweit, M.J. Phys. Chem. 85, 3167 (1981).
Lo, F.Y. , Escott, B.M. Fendler, E.J., Adams, E.T. , Larson, R.D. and Smith, P.W. J.
Phys. Chem. 79, 2609. (1975); Mysels, K.J. and Mukherjee, P. Pur. Appl.
Chem. 51, 1083 (1979); Rukenstein, E. and Nagarjan, R.J. Pys. Chem.. 85,
3010 (1981).
Molyneux, P., Rhodes, C.T. and Swarbrick,

J. (1965) Thermodynamics of

Micellization of N-alkyl betaines. Trans. Faraday Soc., 61, 104352.


Moroi, Y. and Muturra, R. Bull. Chem, Jpn. 61, 333 (1988).
Mukerjee, P. and Mysels, K.J. Critical Micelle Concentration of Aqueous Surfactant
Systems, Data Sevr. Natl. Bur. Stand. U.S 36, US Government Printing. Office,
Washington, D.C. (1971).
Mukerjee, P. and Mysels, K.J. (1971) Critical Micelle Concentrations of Aqueous
Surfactant Systems. nonionic detergents. J. Am. Chem. Soc., 93(25), 678793.
paraffin-chain salts. J. Colloid Sci., 16, 48492.
Porte, G., Poggi, Y. Appell, J. and Moret, G. J. Phys. Chem, 88, 5703 (1984).

103 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Porter, M.R. (1994) Handbook of Surfactants, 2nd edn. Chapman & Hall, London.
Proceeding International Conference of Chemistry and Environment , Indore (2001).
Ray, A. and Nemethy, G. (1971) Effects of ionic protein denaturants on micelle
formation by Rieger, M.M. (1986) Skin irritation: Physical and Chemical
Considerations. Cosmet. Toiletries, 101,856, 88, 902.
Roberts, R.T. and Jones, G.P. Mol. Cryst. Liq. Cryst. Liq. 17, 281 (1972); Lindman, B.
and Brun, B.J. Colloid Interface Sci. 42, 388 (1973); BouaaH, K. and Ache. H.J.
ibid. 85, 2444 (1981); Klason, T. NMR Studies of Solubilization, hydrocarbon
chain motion and the state of water in amphiphile-water systems. The Royal
Institute of Technology Stockholm. (1983).
Rosen, M.J. (2004) Surfactant and Interfacial Phenomena, 3rd edn.Wiley, New York.
S. K.Hait and S.P.Moulik ,Current Science , 2002,Vol82,1101-1111.
S.K.Sar ,R.mandavi ,P.K.Pandey and

K.K.Ghosh , J.Dis .Sci.Tech. USA,(2006)

(26)04
Scamehorn, J.F. (1986) Phenomena in Mixed Surfactant Systems, ACS Symp. Series
311. ACS, Washington, DC.
Schick, M. J. (1962) surface film of nonionic detergents. I. Surface tension study. J.
Colloid Sci., 17, 80113.
Schick, M.J. and Gilbert, A.H. (1965) Effect of urea, guadinium chloride, and dioxane
on the CMC of branched-chain nonionic detergents. J. Colloid Sci., 20, 46472.
Shetevi, B.B. Ph.D. Dissertation, University of Bath, UK (1975).
Shinoda, K. Yamaguchi, T. and Hori, R. (1961) The Surface Tension and the critical
Micelle Concentration in aqueous solution of -D-alkyl glucosides and their
mixtures. Bull. Chem. Soc. Japan,34(2), 23741.
Shinoda, K. Yama-Guchi, T. and Hori, R. Bull. Chem. Soc. Jpn. 34, 237 (1961).

104 | P a g e

KINETIC STUDIES OF SOME ESTERS AND AMIDES IN PRESENCE OF MICELLES

Tanford, C. (1980) The Hydrophobic Effect.Wiley, New York.


Tauer, K. and Kosmella, S. (1993) Synthesis, Characterisation and Application of
surface active initiators. Polym. Int., 30, 253.
Van Hook, J.P. and Tobolski, A.V. (1958) The thermal decomposition of 2,2_ azoisisobutyronitrile.J. Am. Chem. Soc., 80, 77982.
Vidal, F., Guillot, J. and Guyot, A. (1995) Surfactants with transfer agent properties in
styrene emulsion polymerization. Colloid Polym. Sci., 273, 9991007.
Winterborn, I.K. (1972). Ph.D. Thesis, University of Bath, U.K.
Zuidema, H.H., G.W. Waters, (1941). A Ring Method for Determination of Interfacial
Tension. Industrial and Engineering Chemistry, Analytical Edition, 13: 312.

105 | P a g e