CHAPTER - 1

INTRODUCTION
1.1 Surfactants

Surfactants or surface active agents are a special class of versatile

amphiphilic compounds that possess spatially distinct polar (hydrophilic

head) and non-polar (hydrophobic tail) group.1 They show interesting

phenomena in solution by modifying the interfacial and bulk-solvent

properties. The unusual characteristic properties of surfactants in solution

especially at the interfaces owe it to the presence of distinct hydrophilic as

well as hydrophobic domains in the same molecule.2,3 In view of its

amphiphilic nature and distinctive capability of lowering the interfacial

tension, surfactant finds applications in almost every aspects of our daily

life directly or otherwise in household detergents and personal care products,

in industrial process as in pharmaceuticals, food processing, oil recovery and

in nanotechnologies, etc.3-8 Detergents, a term often used interchangeably

with surfactants especially the anionic ones, refer to a combination of

synthetic surfactants with other substances - organic or inorganic -

formulated to enhance functional performance specially as cleaning agents.8

Colloids and surface science have emerged as a versatile interdisciplinary

subject, which have made inroads, inter alia, into the study of mimetic

chemistry that play a vital role in understanding a variety of functions in the

living cells and also the intricate life processes.9-11

1.2 Classification of Surfactant

Generally, based on the nature and the type of the surface active moiety

group present in the molecule, surfactants are classified as anionic, cationic

or non-ionic surfactants and in case both cationic and anionic centres are

present in the same molecules, they are termed as zwitterionic (amphoteric)

surfactants.1,3 Figure 1.1 represents a schematic representation of a surfactant

molecule. Anionic surfactants, which are relatively less expensive, are

employed in an extremely wide variety of surfactant based applications.

While anionic surfactants mostly contain carboxylates, sulfonates, sulfates or

phosphates moiety as hydrophilic head group, it is often an amine or

ammonium groups in case of cationic surfactants. On the other hand, non-

ionic surfactants generally have ethylene oxide chains or hydroxyl groups as

polar centre and are less reactive compare to the ionic ones.

Hydrophilic head

Hydrophobic tail
(a) (b)
Figure 1.1: Schematic representation of (a) a typical surfactant molecule, (b) a Gemini
Surfactant

Zwitterionic surfactants contain both cationic and anionic centres, the ionic

behaviour of which is altered according to pH of the solvent. These

surfactants are effectively used in personal care and household cleaning

products beacuse of the excellent dermatological properties of the

surfactants. There is yet another newer class of surfactants known as Gemini

2
(or dimeric) surfactants which are considerably much superior to the

conventional surfactants in many ways.12 Gemini surfactants (Figure 1b)

consist of two hydrophobic tails each attached to a hydrophilic head group

connected at the level of head groups by a spacer group.13-16 The length and

type of this spacer moiety dictates the conformation of the dimeric molecule

having a high diffusion rate, high surface activity, and low CMC.17 In recent

years, studies on Gemini surfactants are being directed towards changes

associated not only with the variation in the length of the spacer group but

also with the introduction of various substituent groups within the spacer.17-19

Some representative surfactants along with their chemical formulae are listed

in Table 1.1.

Table 1.1: Some representative examples of surfactant

Class Examples Molecular structure

- +
Sodium stearate
CH3(CH2)16 - COO Na
Anionic Sodium dodecyl sulfate CH3(CH2)11 - SO4- Na+
- +
Sodium dodecyl benzene
CH3(CH2)10 C6H4 - SO3 Na
sulphonate
+ -
Laurylamine hydrochloride
CH3(CH2)11NH3 Cl
+ -
Cationic Hexadecyltrimethylammonium
CH3(CH2)15N (CH3)3 Cl
bromide
+ -
Tetradecyltrimethylammonium
CH3(CH2)13N (CH3)3 Cl
bromide
Polyoxyethylene(4)dodecanol CH3(CH2)11-O-(CH2-CH2O)4H
Non-ionic Polyoxyethylene(9)hexadecanol CH3(CH2)15-O-(CH2-CH2O)9H
+ -
Dodecyl betaine
C12H25N (CH3)2CH2COO
Zwitterionic + -
Dodecyldimethylammonium
CH3(CH2)11(CH3)2N CH2COO
acetate
+
Gemini Bis (quaternary ammonium
C12H25N (CH3)2-(CH2)8-
bromide) + -
N (CH3)2C12H25 2Br

3
1.3 Micellization

One of the most interesting properties of surfactants in solution is their

ability to self aggregate to form association colloids known as micelles,

accompanied by an overall decrease in the free energy of the system.2,4 At

very low concentration, the surfactant molecules are preferentially adsorbed

at air water interface with its hydrophobic tail pointing away from the water

surface thereby lowering the interfacial tension.3 As the concentration

increases, the adsorption at the air water interface becomes stronger forming

a condensed monolayer, known as Gibb’s monolayer at the interface after

which any further addition of surfactant molecules remain in the aqueous

phase.2,20 When the concentration of the surfactant molecules in the bulk of

the solution exceeds a limiting value, the surfactant molecules self aggregate

to form micelle which is manifested by an abrupt change in many physic-

chemical properties. A schematic representation of surfactants in solution is

shown in Figure 1.2.

Figure 1.2: Diagram showing surfactant monomers at interface

The narrow concentration range over which these changes occur is known as

critical micelle concentration (CMC) and is perhaps the most important

characteristic property of a surfactant.1,21 The CMC may also be considered

4
as the concentration at which micelles first appears in solution and is

determined from the marked changes in the plot of some physico-chemical

properties of the solution against the surfactant concentration. Some of the

most commonly employed techniques in determining the CMC include

surface tension, conductivity, turbidity, osmotic co-efficient, viscosity, density,

spectrophotometer, calorimeter, light scattering, etc.2,22-27 A Schematic

representation of the changes in some physico-chemical properties of sodium

dodecyl sulfate (SDS) is shown in Figure 1.3 .

Critical
concentration

Detergency
Physico- Chemical Property

Density change

Conductivity (H. F)

Osmotic pressure

Interfacial tension

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Surfactant concentration %

Figure1.3: Changes in some Physico-chemical properties of SDS (Ref. 4)

Depending on the concentration of the surfactant, the geometric and

energetic factors, the size and shape of micelles fluctuate in a given system.3

Size of a micelle is expressed in terms of aggregation number i.e. the number

of monomer units present in a micelle. Generally, the aggregation number is

5
between 20 and 100 for single chain ionic surfactants while large aggregation

number of 1000 or more have been reported for non-ionic micelles especially

near the cloud point.3 The shape of micelles however may vary from

spherical to cylindrical, hexagonal, rod and to lamellar structure depending

upon various factors. Micelles are spontaneously formed and addition of

more surfactant leads to formation of more micelles increasing the micellar

concentration or the micellar growth while the surfactant monomers in the

system remain more or less unchanged. The result is a decrease in the

average distance between the micelles and hence an increase in inter-micellar

repulsion. In order to compensate it, the spherical micelles may transform

into worm like micelles thereby increasing the distance between the micelles.

The molecular architecture of a given surfactant determines the type of

aggregate into which a surfactant associates in aqueous solution.

Alternatively, the relationship between the degree of binding of surfactant

monomers to an aggregate and the repulsions between the surfactant

molecules was reportedly important in determining the aggregate shape.8

Of the various structures, the spherical micelle proposed by Hartley2 is

arguably the most successful one for the purpose of rationalization of

observed behaviour of micelles in solution. In a typical spherical micelle, the

hydrophobic tails of the surfactant monomer in aqueous solution are

preferentially associated to form the core of the micelle while the hydrophilic

heads are exposed to the water. Immediate environment of the hydrophobic

6
core that contains the hydrophilic head along with the counterions constitute

the stern layer, which forms the inner portion of the electrical double layer

surrounding the micelle. The Guoy-Chapman layer refers to the more

diffused outer layer containing the remaining counterions. The outermost

boundary of the stern layer constitutes the hydrodynamic shear surface of the

micelle while the core of the stern layer is known as the kinetic micelle. In

the micelles of polyethoxylated based non-ionic surfactants the core is

surrounded by a layer of hydrogen bonded solvent molecules known as

Palisade layer.2,28,29 Figure 1.4 shows a schematic diagram of a spherical

micelle. Generally, un-branched single–tailed surfactants aggregate to form

spherical micelles in aqueous solution above their critical micelle

concentration.3

Figure1.4: Structural representation of a Spherical Micelle

The main driving force behind the formation of surfactant aggregates in

aqueous solution is believed to be the Hydrophobic effect.30-32 The

hydrophobic effect promotes the aggregation of the surfactant molecules

7
while the electrostatic repulsion between the charged head groups opposes

it.33 Aggregation of hydrophobic groups in aqueous solution above a certain

concentration is due to the overlap of hydration shells formed around the

hydrophobic moieties. Water undergoes a structural enhancement in the

hydrophobic hydration shells and upon aggregation, these shells overlaps and

part of the water molecules surrounding the individual solutes is released

thereby de-structuring the water structure. This accounts for the overall

entropy gain upon micellisation.2,3

The tendency of a surfactant to form micelle in solution is largely dependent

on the type and nature of the surfactant.2,34 Surfactants with longer

hydrophobic tail (i.e. more hydrophobicity) generally exhibit greater

tendency towards micelles formation. With increase in the length of the

hydrophobic tail, the hydrophobic effect becomes stronger and consequently

the CMC decreases and larger micelles are formed. The aggregation number

also increases with hydrophobic chain length.35 Besides the chain length,

branching in the surfactant is also known to affect the CMC and the

aggregation number. The CMC of the branched surfactant has been shown to

be higher and the aggregation number lower than those of their linear

chain.36

1.4 Counterion Variation

Counterions also have a large influence on the aggregation of the surfactant

molecules in solution mainly through changes in the ionic strength of the

8
solution.34,36 In addition, the valency of the counterion also influences the

CMC to a larger extent. The degree of the counterion binding is due to the

balance between the electrostatic forces which pull the counterion towards

the oppositely charged head group of micelles and the hydration forces

which tends to inhibit the binding.37 The CMC value normally decreases as

counterion binding increases. Counterions or ions with opposite charge to

that of the surface active moiety of the surfactant are known to have an

additional specific effect. For example, sodium bromide was found to induce

the growth of micelles of the cationic surfactant cetyl pyridinium bromide

whereas sodium chloride did not.38 Aromatic counterions like benzoate,

tosylate, salicylate, because of their strong binding at the micellar surface

lower the CMC while increasing the counterion binding.39 Salicylate in

particularly is effective in inducing micellar growth. The counterion binding

also increases with increasing counterion hydrophobicity enhancing the

micelle formation.40 Hydrophobic counterions are interesting as charge

carrier or quencher in biomembranes and membrane photochemistry.41

Addition of cationic surfactant to SDS is a special case of hydrophobic

counterion interaction. The CMC of a mixture of anionic and cationic

surfactant in aqueous solution is considerably lower than that of the

individual surfactants due to the synergistic interaction between the

surfactant molecules and they exhibit properties superior to their constituent

single surfactant in many surfactant applications.42

9
1.5 Solvent Effect on the Aggregation of Surfactant

The formation of micelles and its stability is considerably solvent dependent.

Solvent polarity and its ability to form H-bond in solution are of considerable

interest in understanding the micellar behavior of surfactant. Besides water,

micelle formation has been observed in solvents which are analogous to

water. There has been report of micelle formation in solvents such as

hydrazine, formamide, glycerol, which have high degree of hydrogen

bonding.43-51 The ability of the solvent to form hydrogen bonding was

considered to be a prerequisite for the micellisation to occur.52 However,

micelle formation also occurs in solvents which has little or no hydrogen

bonding, for examples in solvents like acetone, acetonitrile and dimethyl

sulfoxide where the hydrogen bonding ability is minimal.53,54 Formation of

micelles of SDS and cetyl triethyl ammonium bromide in dimethyl sulfoxide

and N,N- dimethyl formamide has also been reported.55 More than the H-

bond or the electrostatic forces criteria, changes in the solvent

hydrophobicity are expected to play a role in determining the micellar

behaviour. Besides the hydrophobicity of the surfactant molecule,

hydrophobicity of the solvent media also plays a critical role in micellisation

process.45,56-59 The more hydrophobic the solvent media, lesser is the

tendency of the surfactant molecules to form micelle. In non polar solvents

which offer environment similar to the hydrophobic part of the surfactant,

the self-aggregating tendency of the surfactant is reduced.60 Addition of small

amount of an organic solvent has been known to produce marked changes in

10
the CMC thereby highlighting the importance of co-solvent in the

micellisation process.56,61 The micellar behaviour is greatly influenced by

the presence of co-solvent due to the tendency of the added organic solvent

either to break or make the water structure through solvation of the

hydrophobic tail of the surfactant by the hydrocarbon part of the organic

solvent.45 It is reported that the presence of ethylene gylcol delayed the

micelle formation in SDS.45 Ethylene gylcol acts as the water structure

breaker and in the aqueous phase it disrupts the water structure enforced by

the dissolved hydrophobic group thereby decreasing the entropy increase on

micellisation. The tendency to form micelles in non polar solvents (reverse

micelle) like benzene, carbontetrachloride, decreases in general with increase

polarity of the solvent.60 The solvent effect on the micellar behavior in case

of sodium 2,6-di-n-dodecylnapthalene-l-sulphonates in benzene and n-

decane has been reported by Heilweil62 highlighting the role of co-solvent

and its importance in understanding the phenomenon of formation of

micelles.

1.6 Thermodynamics of Micellization

The primary reason for the formation of the molecular aggregates is the

overall decrease in the free energy of the system resulting from the

preferential self association of the hydrophobic hydrocarbon chains of the

surfactant molecules accompanied by desolvation. The formation of micelles

disrupts the iceberg structure of water surrounding the non polar segment of

11
the surfactant with a resultant gain in entropy and heat content. The process

of micellization has mostly been treated theoretically either by applying the

Law of Mass Action63 to the equilibrium between monomers and aggregates

or by considering the micelles as a separate but soluble phase, the so called

pseudo phase separation model.64

-/+
According to Mass Action principle, micellization of ionic surfactants (S )

along with counter ion (I +/-) can be represented as

nS − / + + mI + / − = M ( n − m) −or ( n − m) + (1.1)

where n is the aggregation number and m is the number of counterions that

associate with the ionic micelle. Neglecting charges on the surfactant and the

counterion, the equilibrium constant or micellization constant can be written

as
[M ]
KM = (1.2)
[ S ]n [ I ]m

The free energy of micelle formation expressed per mole of monomer unit

(ΔG0) is then given by

∆G 0 = RT ( −1 / n ln[ M ] + ln[ S ] + m / n ln[ I ]) (1.3)

At CMC, [S] = [I] = CMC and since n is large 1/n ln[M] may be ignored (for

very small fraction of surfactant ions form micelles), then we have

∆G 0 = (1 + f ) RT ln CMC (1.4)

where f = m/n is the fraction of counterion bound to the micelle.

12
The Mass Action treatment predicts increase in the monomer concentration,

although at much reduced rate above CMC. However, it fails to account for

the variations in aggregation numbers and is generally not applicable to

multicomponent micelles and systems in solubilizates.

In Pseudo-Phase Separation Model, the micelles are considered to form a

separate phase (pseudo phase) within the system at and above the critical

micelle concentration. The increase of the surfactant concentration above the

CMC results into formation of micelles while the monomer concentration

remains constant. Above the CMC, both the micelles and the monomers are

present and the two phases are in equilibrium:

Monomer Phase I Micelle Phase II (Pseudo Phase)

Since the two phases are in equilibrium, their chemical potential must be
equal,
µm = µM (1.5)

where, µm is the chemical potential of the monomer in solution and µM is the

chemical potential of the micelles in pseudo phase. Then,

µ0m + RT ln am = µ0M + RT ln aM (1.6)

where, µom and µoM are the standard chemical potentials of the monomer and

micelles with activities am and aM respectively.

13
The monomer concentration in the micellar solution which is assumed to be

constant is equal to the CMC and for the pseudo phase, aM =1. The standard

free energy of micellization can be written as

∆GM
o
= (1 + f ) RT ln X cmc (1.7)

The Pseudo Phase Model, besides its simplicity, has the added advantage of

treating micelles containing number of components including mixed

micelles.

The two models have been shown to merge asymptotically with increasing

micellar aggregation number giving similar expression for GMo . The enthalpy

and the entropy of micellization are given by the relations

δ (ln X CMC )
∆H M0 = (1 + f ) RT 2 [ ] (1.8)
δT
and
∆H M
0
− ∆GM
0
∆S M
0
=[ ] (1.9)
T

Neither the mass action model nor the phase separation model is rigorously

correct and the computed thermodynamic functions of micellization will

depend to a larger extent on the model and the approximations used.

However, the models described above are significant enough to be applied to

the systems under investigation and for the evaluation of the associated

thermodynamic parameters.

14
1.7 Dye and its Self Aggregation

Dyes are important class of organic compounds which contain

chromophores, delocalized electron system with conjugated double bonds

and auxochromes, electron withdrawing substituent that cause or intensify

the colour of the chromophores.65 One of the important features of dye is

their ability to self aggregate in solution. Despite having similar charges the

dye molecules undergo spontaneous aggregation in solution leading to

formation of dimers and other higher aggregates.66-68 The aggregation of dye

in solution is of extreme importance from fundamental as well as applied

viewpoints especially in biological, colloid, surface, textile, photographic

and analytical chemistry since the photophysics and photochemical

properties are largely dependent on the aggregation of dye.69-73 The

aggregation of dye is accompanied by the changes in the absorption spectra

of the dye compared to the individual monomeric molecules.72,74 Hence the

spectrophotometric method is most commonly employed in the study of the

aggregation phenomena of dyes as a function of concentration.75-76 The dye

molecules possess strong intermolecular van der Waals like attractive forces

between them which favors the dye molecules to aggregate.74 The presence

of dye molecules causes disruption in the H-bonded water structure and the

high dielectric constant of water causes a reduction in the electrostatic

repulsion between the charged dye molecules, thus facilitating the

aggregation of dye. Besides, the water structure and the hydrophobic

interactions are the predominant factors which enhance the aggregation of

15
dye.68,77 Aggregation of dyes is strongly affected by dye concentration and its

structure, ionic strength, temperature and presence of organic solvent or

surfactants.70,78 It may increase with an increase of dye concentration or ionic

strength and decrease with raising the temperature or adding organic

solvents.

Aggregation of dyes also occurs in mixed solvents and in heterogeneous

media including micelles.79-82 Aggregation of dyes can be induced by

surfactants at low concentrations below the CMC.72 Changes in the local

microenvironment of the dye in solution can produce measurable spectral

shifts. The spectral behavior of the dye vis-a-vis its aggregation is greatly

influenced by the nature of the solvent media and exhibits either a

bathochromic or hypsochromic shifts in solvents of different polarity.83,84

From the aggregation behavior of a large number of synthesized squaraine

dyes in aqueous and mixed aqueous-organic solution, Chen et al85 reported

the importance of hydrophobic effects in the aggregation process by

observing that the tendency for aggregation increases as the length of the

hydrophobic chain of the dye increases while squaraines with quaternary

ammonium head groups exhibited less tendency for aggregation. Wurthner et

al87 reported the occurrence of dimeric aggregates from the concentration

dependence of the dipole moment of some polar merocyanine dyes. From the

studies on the dimerization of polar merocyanine dyes they also concluded

that hydrophobic effect is one of the major driving forces behind the dye

aggregation, which is again controlled by changes within the microstructure

16
of water around the solute. The solvent dependence of the aggregation

behavior of the merocyanine is again confirmed by Ashwell87 who reported

that the formation of dimeric aggregates is favored in less polar solvents.

Goni et al88 quantified the monomer and dimer components of the

merocyanine 540 using curve fitting techniques and showed that the

maximum absorption wavelength of the monomer band was sensitive to

polarity changes in the chromophore region and a blue shift indicating a

more polar environment. Tatikolov et al89 studied the spectral and

fluorescence properties of the heterogeneous aggregates formed by some

cation-anionic polymethine dyes in weakly polar and non polar solvent

media. From a large number of fluorescence and absorption studies on the

carbocyanine, thiazine and azo dyes, it has been found that the aggregation

behavior of the dye have been very sensitive to solvent polarity.68,90 Patil et

al69 studied the aggregation of thazine dyes in aqueous and mixed media

highlighting the importance of hydrophobic effects in the aggregation

behavior of the dye. Recently the effect of the poly electrolytes on the

dimerisation of methylene blue had been studied by Ghasemi et al91 who

reported that the addition of the inorganic salts increases the ionic strength of

the solvent media promoting the dye molecules to aggregate.

1.8 Dye Surfactant Interactions

Dye surfactant interactions are of great interest in dyeing and photographic

industries, in biological and medicinal photosensitization, designing of

17
supramolecular nanostructures, etc.92-95 In various dyeing industries, the dye

surfactant interaction is important because surfactants are used as solubilizers

for various water insoluble dyes.96 The sensitivity of dyes to the polarity of

the medium in which they are dissolved makes them suitable for studying the

spectral changes of dyes in presence of hydrophobic microdomains in

aqueous solution.97 Dyes are often used for determining the critical micelles

concentration (CMC) of surfactants since presence of surfactants affect the

electronic spectra of many dyes.98,99 For example, Pinacyanol chloride is

used to determine the critical micelle concentration of ionic surfactants.100

Successive addition of small concentration of surfactant changes

dramatically the absorption spectrum of a dye and upon increasing the

surfactant concentration, dye spectrum shifts from that in aqueous solution to

a spectrum of the dye similar to that in apolar solvents when micelles are

present since solubilisation of the aggregates occurs into the surfactant

micelles.101,102 The interactions of dyes with the surfactant either decreases or

increases its CMC depending on the nature of the dyes, the surfactant and

their aggregation behavior.103 Mukherjee and Mysel104 observed lowering in

the CMC value in dye surfactant systems. Rio et al105 also reported lower

CMC value of SDS in SDS - crystal violet system than the one obtained by

conductivity method. Presence of surfactant above or below the CMC

dramatically changes the solution properties of the dye resulting into changes

in the absorption spectra of the dye due to the formation of dye surfactant

premicellar aggregates.106-108 The micelle/water interface favors complex

18
formation due to absorption of dye from solution and increases the

concentration of complexes.109 Although neutral dyes can induce the

formation of submicellar aggregates, they are commonly formed when the

charges of the ionic groups of the surfactant and dye are opposite.110,111 The

dye can participate in the formation of these aggregates through its charged

groups which compensate the repulsion forces between ionic surfactant

molecules bearing the same charge. Hydrophobic and specific interactions

between the hydrophobic alkyl chains of surfactants with the hydrophobic

portion of the dye have also been reported to govern dye induced premicellar

aggregate formation.112,113 However, the electrostatic repulsion forces

facilitate the interaction between the similarly charged dye and surfactant,

and hence, the complexion between such system was found to be lower by

two to three orders as compared to systems with oppositely charged dyes and

surfactant molecules.114 When two surfactants are present in aqueous dye

solution, preferential interaction between the surfactants impact a decrease in

the degree of binding of either surfactants to dye molecules.113

Many investigations on dye surfactant interactions in aqueous system have

been studied in the last few decades of which the peculiar behavior in

absorption spectra were attributed to the formation of a continuum of dye

surfactant aggregates.112-120 The formation of these dye surfactant aggregates

have been understood in terms of hydrophobic effect.118,119 Models of

interactions have been proposed in which the observed changes were

19
attributed to the change in the microenvironment of the dye resulting from its

incorporation inside the micelle.120 Estelrich and co-workers121,122 studied

the behavior of pinacyanol dye in the presence of surfactant at different

solvent media and found that the transfer of pinacyanol from a polar aqueous

medium to a relatively non polar site in the micellar environment or to

organic phases affects its spectral properties leading to bathochromic shift.

The Menger micelle model123 also predicts the distribution of cationic dye in

a large region surrounding the relatively small hydrophobic core. The

spectral resolution of overlapping bands for quantitative analysis was studied

by Karukatis et al124,125 to characterize multiple sites for aromatic

chromophore within aqueous and reverse micelles.

1.9 The Molecular Exciton Model of Dye Aggregation

Absorption spectra of dye aggregates usually show large differences when

compared with individual monomeric species. From the spectral shift,

various aggregation patterns of the dye in different solvent media have been

proposed. These differences in the spectral behavior have been explained in

terms of molecular exciton coupling theory based on the coupling between

the transition dipole moments of the individual dye molecules.65,126According

to this theory, the dye molecule is regarded as a point dipole and the

excitonic state of the dye aggregate splits into two levels through the

interaction of the dipoles.127 The spectral shift from the monomer peak

position is a function of the magnitude of the transition dipole moment, the

20
distance between the dipoles, and the slip angle between the chromophore

axes and the chromophore center-to-center line.12 7 The chromophores should

preserve their individual characteristics in the aggregates, i.e. it is assumed

that there is negligible overlap of respective molecular orbitals. Moreover,

the transition moment of the electronic transition is assumed to be localized

in the center of the chromophore and its polarization axis parallel to the long

axis of the chromophore. The angle between the line of centres of a column

of dye molecules and the long axis of any one of the parallel molecules is

called the angle of slippage (θ). Large molecular slippage results in a

bathochromic shift and when θ is less than 32°, hypsochromic shift results.

Figure 1.5: Schematic representation of the exciton splitting of the excited state of
dye aggregates in a parallel (left) and head-to-tail (right) fashion.

Dye molecules can aggregate either in a parallel (H-aggregation) or in a

head-to-tail (J-aggregation) fashion leading to hypsochromic (blue) and

bathochromic (red) shifts respectively.127 A schematic representation of the

exciton splitting of dye aggregates is shown in Figure 1.5. In the case of

parallel dye aggregation, transition dipoles can either be aligned in a parallel

21
or in an antiparallel fashion. The former situation leads to an excited state

that is higher in energy than the excited state in the monomer due to

electrostatic repulsion between the transition dipole moments whereas when

the transition dipoles are in a head-to-tail orientation, it leads to a decrease in

the excited state energy. The absorption band caused by the dimer consisting

of parallel dye dimers will be blue-shifted with respect to that of the

monomeric dye. A red shift is observed for the dye dimer consisting of J-

aggregates compared to that of the monomer. If the arrangement of the two

chromophores is neither in-line nor in parallel, both states are allowed and

can be seen in the spectrum as two separate bands or as a broadened band

depending on the interaction energy.

1.10 Scope and Objective of the Present Study

One of the most important features of surfactants, as briefly highlighted

above, is their tendency to form micelles in solution, which is generally

understood in terms of CMC and other associated thermodynamic

parameters. Since surfactant forms micelles in solution, understanding the

behavior of the surfactant solutions in different mixed media is of

considerable relevance not only from fundamental but from applied view

points also. A perusal of literature reveals that though the behavior of

surfactant solutions has been widely studied both in aqueous and mixed

aqueous media, the role of solvent hydrophobicity in the micellization

process of surfactant in mixed media including the mixed aqueous organic

22
solvent has not been adequately appreciated. A proper understanding of the

role of the solvent hydrophobicity on the micellar behavior is, therefore, of

fundamental importance in designing and characterizing a surfactant and in

surfactant based applications.

As discussed earlier, the distinct behavior of the surfactant in solution was

clearly understood in terms of hydrophobic effect. With increase in the

hydrophobicity of the solvent media, the formation of the micelle is likely to

be delayed, which would decrease the CMC of the surfactant due to

interaction between the hydrophobic part of the solvent and the hydrophobic

tail (hydrocarbon chain) of the surfactant. In mixed aqueous organic solvent

media, the presence of co-solvent can significantly affect the micellization of

surfactant due to their tendency either to make or break the water structure. It

is known that -CH2 group attached immediately adjacent to the polar group

of a solvent contribute less to the hydrophobic character. However, with

more and more such groups, the hydrophobicity gradually increases that can

effectively perturb the water structure and hence delay the micelle formation

leading to an increase in CMC. It was observed that the hydrophobic group

of ethyl acetate or ethylene glycol solvated the hydrophobic part of an ionic

surfactant through hydrophobic interactions thereby causing an increase in

CMC. Similarly, Emerson et al128 observed increased in CMC from studying

the stability of the SDS micelle in aqueous acetamide solution. The

inhibitory effect of acrylamide on micelle formation is less in comparison

23
with that of the ethyl acetate at similar mole fraction and temperature, which

clearly showed the importance of the solvent hydrophobicity. With increase

in the alkyl chain in alcohol, the CMC was found to increase further

indicating the role of solvent hydrophobicity on the micellization

process.47,129

Currently, in absence of predictive theoretical approaches towards

understanding the solvent hydrophobicity and its effect on the micellar

behavior of surfactant, selection of solvent of different hydrophobicity are

rather purely on the trial and error research. In view thereof, the study of

micellization in solvent media of different hydrophobicity would help in

integrating the role of the solvent media and its hydrophobicity towards

development of a more comprehensive and predictive fundamental approach

in the micellization process besides enriching the contemporary

understanding of the micellar behavior. With a view to critically analyzing

the role of the solvent hydrophobicity on the self-aggregating systems like

surfactants or dyes, it has been considered worthwhile to undertake a

systematic investigation on the self-aggregating behavior of some

representative ionic surfactants or dyes in aqueous and mixed aqueous

organic solvent media of different hydrophobicity.

The addition of electrolyte, for example NaCl, imparts an increase in the

dielectric constant of the solvent media and hence enhances the dye

24
aggregation whereas presence of organic solvent of low polarity inhibits the

aggregation process of the dye and a reduction in the formation of dye and

surfactant aggregates. Though the dye molecules of similar charges are

believed to be associated through H- bonding, van-der-Waals forces and

other short range forces, the exact nature of the origin of the dye aggregate is

still not clearly understood. From a number of studies on the dimerisation of

the certain dyes such as cyanine, thiazine, azo dye, etc. and its interactions

with the surfactant, it has been reported that water structural effects and the

hydrophobic interactions are the major factors behind the self aggregation of

the dye and their binding onto a surfactant. In view of the importance of the

water structural features and the solvent hydrophobicity on the aggregation

of the dye and its interactions with surfactant, the study on the role of the

solvent polarity including the solvent hydrophobicity on the aggregation of

not only the self-aggregation of the surfactant or the dye alone but their

interactions also in the mixed media would assume greater relevance.

Apparently, there has not been enough approaches towards understanding the

effective role of solvent hydrophobicity vis-a-vis the hydrophobic effect in

the stabilization of the aggregates in solution. With a view to critically

analyzing the role of the solvent hydrophobicity, it was considered

worthwhile to undertake a systematic investigation on the formation of dye

surfactant complex in mixed aqueous media containing some organic

solvents with different hydrophobic groups.

25
An attempt has also made to investigate the iodine iodide equilibrium and

the formation of tri-iodide in aqueous and mixed aqueous organic media

including polymers like HPC, PEO. The formation of tri-iodide may also be

assumed to be formation of aggregates in solution. To the best of our

knowledge, no systematic investigation has been carried out to understand

how the tri-iodide formation is influenced by change in the hydrophobicity of

the solvent media or in presence of a surfactant. Keeping in view the

importance of the solvent hydrophobicity in the micellisation process and

surfactant based systems including iodine complexes, it was considered

worthwhile to investigate the effect of either anionic or non ionic surfactants

on the self-aggregation of iodine into tri-iodide in the mixed aqueous organic

solvent media.

The thesis, in short, is an embodiment of the results of such investigations

towards re-emphasizing the importance of hydrophobic interactions in some

self aggregation systems like surfactant, dye including their interactions and

also formation of tri-iodide aggregates. We have undertaken a systematic

investigation on the self aggregation behavior of some chosen ionic

surfactants and also the pinacyanol chloride in mixed solvent media having

different hydrophobicity. The interactions of PC dye with an anionic

surfactant in different mixed aqueous organic solvent media have also been

investigated. A modest attempt has also been made to study the effect of the

solvent hydrophobicity on the iodine-iodide equilibrium in presence of an

26
anionic as well as a nonionic surfactant in presence of some water soluble

polymer such as HPC or PEO at very low concentration. We sincerely hope

that the results will enrich the contemporary understanding of the self-

aggregating systems in different solvent media while highlighting the

importance of the solvent hydrophobicity in such systems.

27
Reference
1. M. J. Rosen, Surfactants and Interfacial Phenomena, John Wiley and Sons,
Inc. 3rd Ed, New Jersey, 2004
2. Y. Moroi, Micelle, Theoritical and Applied Aspects, Plenum Press, New
York and London, 7, 1992
3. L. L. Schramm, Surfactants: Fundamentals and Applications in Petroleum
Industry, Cambridge University Press, Cambridge, 2000
4. L. L. Schramm, E. N. Stasiuk, D. Gerrard Marangoni, Annu. Rep. Prog.
Chem., Sect. C, 99, 3, 2003
5. K. Holmberg, B. Jonsson, B. Kronberg, B. Lindman, Surfactants and
Polymers in Aqueous Solution, 2nd Ed., John Wiley and Sons, New York,
2002
6. C. C. Ruiz, J. Aguiar, Langmuir, 16, 7946, 2000
7. U. Bazylinska, R. Skrzela, K. Szczepanowicz, P. Warszynski, K. A. Wilk,
Soft Mater, 7, 6113, 2011
8. L. Wattebled, Oligomeric Surfactants as Novel Type of Amphiphiles:
Structure – Property Relationships and Behaviour with Additives, Ph. D
Thesis, University of Potsdam and Fraunhofer Institute for Applied
Polymer Research, Potsdam, 2006 (available in the net).
9. J. Xi, R. Guo, J. Soln. Chem., 37, 107, 2008
10. S. R. Koti, N. Periasamy, J. Mater. Chem., 12, 2312, 2002
11. J. H. Fendler, Membrane Mimetic Chemistry, Wiley Interscience, New
York , 1982
12. Y. Li, P. Li, C. Dong, X. Wang, [Link], H. Yan, R. K. Thomas, Langmuir,
22, 42, 2006
13. C. K. Baig, J. Duhamel, S. Wettig, Langmuir, 27, 7, 3361, 2011
14. F. M. Menger, J. S. Keiper, Angew. Chem., 112, 1980, 2000
15. P.A. Fitzgerald, T. W. Davey, G. G. Warr, Langmuir, 21,7121, 2005
16. C. Groth, M. Nyden, K. Holmberg, J. R. Kanicky, D. O. Shah, J. Surfact.
Deterg., 7, 3, 2004
17. S. D. Wettig, C. Wang, R. E. Verrall, M. Foldvari, Phys. Chem. Chem.
Phys., 9, 871, 2007
18. S. Chavda, K. Kuperkar, P. Bahadur, J. Chem. Eng. Data, 56, 5, 2647,
2011
19. T. Lu, F. Han, G. Mao, G. Lin, J. Huang, X. Huang, Y. Wang, H. Fu
Langmuir, 23, 6, 2732, 2007
20. A. W. Adamson, A. P Gast, Physical Chemistry of Surfaces , 6th Ed., John
Wiley & Sons, New York, 1997
21. E. Pramauro, E. Pelizzetti, Surfactants in Analytical Chemistry:
Applications of Organized Amphiphilic Media, Elsevier, Amsterdam, 1996
22. T. Kawaguchi, T. Hamanaka, Y. Kito, J. Phys. Chem., 95, 3837, 1991
23. S. Shimizu, P. A. R. Pires, W. Loh, O. A. El Seoud, Colloid Polym. Sci.,
282, 1026, 2004
24. G. B. Ray, I. Chakraborty, S. Ghosh, S. P. Moulik, R. Palepu, Langmuir,
21, 10958, 2005
25. S. Alila, S. Boufi, M. N. Belgacem, D. Beneventi, Langmuir, 21, 8106,
2005

28
26. P. R. Majhi, S. P. Moulik, Langmuir,14, 3986, 1998
27. Md. E. Haque, A. R. Das, S. P. Moulik. J. Phys. Chem., 99, 14032, 1995
28. S. P. Moulik, Current Science, 71, 368, 1996
29. L. Mikael, A. Michael, J. Bengt, J. Phys. Chem., 96, 950, 1992
30. C. Tanford, The hydrophobic effect: Formation of Micelles and Biological
Membranes, 2nd Ed.; Wiley, New York, 1980
31. D. J. Michel, D. J. Cleaver, J. Chem. Phys., 126, 034506, 2007
32. F. Grieser, M. Lay, P. J. Tbistletbwaite, J. Phys. Chem., 89, 2065, 1985
33. M. R. Bohmer, K. K. Luuk, J. Lyklema, J. Phys. Chem., 95, 9569, 1991
34. B. Lindman, H. Wennerstrom, Micelles Amphiphile Aggregation in
Aqueous solution, Spinger Verlag, New York, 1980
35. S. P. Moulik, M. E. Haque, P. K. Jana, A. R. Das, J. Phys. Chem., 100, 701,
1996
36. A. Goldsipe, D. Blankschtein, Langmuir, 21, 9850, 2005
37. S. Berr, R. R. M. Jones, J. S. Johnson Jr., J. Phys. Chem., 96, 5611, 1992
38. G. Porte, J. Appell, Y. Poggl, J. Phys. Chem., 84, 3105, 1980
39. K. Bijma, J. B. F. N. Engberts, Langmuir, 13, 4843, 1997
40. S. Manet, Y. Karpichev, D. Bassani, R. K. Ahmad, R. Odo, Langmuir, 26,
10645, 2010
41. M. Almgren, S. Swarup, J. Phys. Chem., 87, 876, 1983
42. S. Puvvada, D. Blankschtein, J. Phys. Chem., 96, 5567, 1992
43. A. Callaghan, R. Doyle, E. Alexander, R. Palepu, Langmuir, 9, 3422, 1993
44. M. Ramadan, D. F. Evans, R. Lumry, S. Philson, J. Phys. Chem., 89, 3405,
1985
45. K. Gracie, D. Turner, R. Palepu, Can. J. Chem., 74, 1616, 1996
46. R. Jha, J. C. Ahluwalia, J. Phys. Chem., 95, 7782, 1991
47. M. Almgren, S. Swarup, J. E. Lofroth, J. Phys. Chem., 89, 21,1985
48. I. Rico, A. Lattes, J. Phys. Chem., 90, 5870, 1986
49. a. A. Ray, Nature, 231, 313, 1971
b. A. Ray, G. Nbmethy, J. Phys. Chem., 75, 809, 1971
50. S. E. Friberg, Y. C Liang, Colloid Surf., 24, 325, 1987
51. D. F. Evans, A. Yguchi, G. J. Wei, V. A. Bloomfield, J. Phys. Chem., 87,
3537, 1987
52. A. Beesley, D .F. Evans, R.G. Langhlin, J. Phys. Chem., 92, 791, 1988
53. R. Gopal, J. R. Singh, J. Phys. Chem., 71, 1973, 1973
54. R. Gopal, J. R. Singh, Kolloid ZZ Pollym., 239, 699, 1970
55. H. N. Singh, S. M. Saleem, R. P. Singh, K. S. Birdi, J. Phys. Chem., 84,
2191, 1980
56. R. Palepu, H. Gharibi, D. M. Bloor, E. W. Jones, Langmuir, 9, 110, 1993
57. M. S. Bakshi, Bull. Chem. Soc. Jpn., 69, 2723, 1996
58. N. Alizadeh, H. Gharibi, M. Shamsipur, Bull. Chem. Soc. Jpn., 68, 730,
1995
59. H. Gharibi, B. M. Razavizadeh, A. A. Rafati, Collids Surf. A, 136, 123, 1998
60. H. F. Eicke, Surfactants in Non-polar Solvent, Aggregation and
Micellisation, Spinger Verlag, New York, 1980
61. F. Jalali, M. Shamsipur, N. Alizadeh, J. Chem. Thermodynamics, 32, 755,
2000

29
62. I. J. Heilweil, J Colloid Sci, 19, 105, 1964
63. K. Shinoda, E. Hutchinson, J. Phys. Chem., 66, 577, 1962
64. M. J. Blandamer, P. M. Cullis, L. G. Soldi, J. B. F. N. Engberts, A.
Kacperska, N. M. Vanos, M. C. [Link], Adv. Colloid and Inter. Sci., 58,
171, 1995
65. A. Hassanzadeh, A. Z. Isfahani, M. H. Habibi, Spectrochimica Acta Part A,
64, 464, 2006
66. L. Anotonov, G. Gergov, V. Petrov, M. Kubista, J. Nygren, Talanta, 49, 99,
1999
67. J. B. Ghasemia, M. Miladib, [Link]. Soc., 56, 459, 2009
68. K. Patil, R. Pawar, P. Talap, Phys. Chem. Chem. Phys., 2, 4313, 2000
69. M. Dakiky, I. Nemcova, Dyes Pigm., 40, 141, 1999
70. A. K. Chibisov, G. V. Zakharova, H. Gorner, Phys. Chem. Chem. Phys., 3,
44, 2001
71. B. Armitage, J. Retterer, D. F. O. Brien, J. Am. Chem. Soc., 115, 10786,
1993
72. A. Navarro, F. Sanz, Dyes Pigm., 40, 131, 1999
73. C. Ouyang, S. Chen, B. Che, G. Xue, Colloids and Surfaces A:
Physicochem. Eng. Aspects, 301, 346, 2007
74. A. K. Chibisov, G. V. Zakharova, H. Gorner, Y. A. Sogulyaev, I. L.
Mushkalo, A. I. Tolmachev, J. Phys. Chem., 99, 886, 1995
75. R. F. Khairutdinov, N. Serpone, J. Phys. Chem. B, 101, 2602, 1997
76. B. Neumann, P. Pollmann, Phys. Chem. Chem. Phys., 2, 4784, 2000
77. H. C. Junqueira, D. Severino, L.G. Dias, M. S. Gugliotti, M. S. Baptista,
Phys. Chem. Chem. Phys., 4, 2320, 2002
78. D. Sarkar, P. Das, A. Girigoswami, N. Chattopadhyay, J. Phys. Chem. A,
112, 9684, 2008
79. F. L. Arbeloa, T. L. Arbeloa, E. G. Lage, I. L. Arbeloa, F. C. D. Schryver, J.
Photochem. Photobiol. A, 56, 313, 1991
80. V. K. Kelkar, B. S. Valalulikar, J. T. Kunjappu, C. Manohar, J. Photochem.
Photobiol., 52, 717, 1990
81. J. C. Mialocq, P. Hebert, X. Armand, R. Bonneau, J. Morand, J. Photochem.
Photobiol. A, 56, 323,1991
82. M. D. Deumie, P. Lorente, D. Morizon, J. Photochem. Photobiol. A, 89,
239, 1995
83. R. Sabate, M. Gallardo, J. Estelrich, J. Colloid Interface Sci., 233, 205, 2001
84. R. Sabate, J. Estelrich, Spectrochimica Acta Part A, 70, 471, 2008
85. H. Chen, M. S. Farahat, K. Y. Law, D. G. Whitten, J. Am. Chem. Soc., 118,
2584, 1996
86. F. Wurthner, S. Yao, Angew Chem., Int. Ed., 39, 1978, 2000,
87. G. J. Ashwell, K. Skjonnemand, G. A. N. Paxton, D. W. Allen, J. P. L.
Mifflinb, X. Lib, J. Mater. Chem., 11, 1351, 2001
88. P .Kaschny, F. M. Goni, Eur.J. Biochem., 207, 1085, 1992
89. A. S. Tatikolov, G. Ponterini, Zh. A. Krasnaya, Inter. J. Photoenergy, 2, 17,
2000
90. K. Murakami, Dyes Pigm., 53, 31, 2002
91. J. B. Ghasemi, M. Miladi, J. Chin. Chem. Soc., 56, 459, 2009

30
92. Md. F. Nazar, S. S. Shah, Md. A. Khosa, J. Surfact Deterg., 13, 529, 2010
93. S. Tunc, O. Duman, Fluid Phase Equilib., 251, 1, 2007
94. N. Hashemi, G. San, Ind. Eng. Chem. Res, 49, 8347, 2010
95. H. V. Berlepsch, S. Kirstein, R. Hania, C. Didraga, A. Pugzlys, C.
Bottcher, J. Phys. Chem. B, 107, 14176, 2003
96. C. Kartal, H. Akbas, Dyes Pigm., 65 ,191, 2005
97. R. V. Wandruszka, CRC Crit. Rev. Anal. Chem., 23, 187, 1992
98. S. E. Sheppard, A. L. Geddes, J. Chem. Phys., 13, 63, 1945
99. J. W. Ledbetter, J. R. Bowen, Analytical Chemistry, 41, 10, 1345, 1969
100. a. S. K. Hait, P. R. Majhi, A. Blume, S. P. Moulik, J. Phys. Chem. B, 107,
3650, 2003
b. M. L. Corrin, W. D. Harkins, J. Am. Chem. Soc., 69, 679, 1947
c. M. E. Ginn, J. C. Harris, J. Am. Chem. Soc., 62, 1554, 1958
101. R. T. Buwalda, J. M. Jonker, J. B. F. N. Engberts, Langmuir, 15, 1083,
1999
102. P. Mukerjee, K. J. Mysels, J. Am. Chem. Soc., 59, 2937, 1955
103. S. Shah, M. S. Khan, H. Ullah, M. A. Awan, J. Colloid Interface Sci., 186,
382, 1997
104. P. Mukerjee and K. J. Mysels, J. Am. Chem. Soc., 59, 2937, 1955
105. L. Garcia-Rio, P. Hervella, J. C Mejuto, M. Parajo, Chem. Phys., 335, 164,
2007
106. S. E. Sheppard, A. L. Geddes, J. Chem. Phys., 13, 63, 1945
107. J. K. Weil, A. J. Stirton, J. Phys. Chem., 60, 899, 1956
108. E. L. Colichman, J. Am. Chem. Soc., 73, 3385, 1951
109. S. Basu, S. De, B. B. Bhowmik, Spectrochimica Acta Part A, 66, 1255,
2007
110. K. Ogino, T. Kasuya, M. Abe, Colloid Polym. Sci., 266, 539, 1988
111. B. Simoncic, J. Span, Dyes Pigm., 36(1):1-4 ,128, 1998
112. R. Fabios, M. D. Sicilia, S. Rubio, D. P. Bendito, Anal. Chem., 75, 6011,
2003
113. B. Simoncic, M. Kert, Dyes Pigm., 54, 221, 2002
114. M. Bielska, A. Sobczynska, K. Prochaska, Dyes Pigm., 80, 201, 2009
115. S. Bracko, J. Span, Dyes Pigm., 45, 97, 2000
116. M. N. Khan, A. Sarwar, Fluid Phase Equilib., 239, 166, 2006
117. P. F. Tavcer, J. Span, Text. Res. J., 69, 278, 1999
118. B. Gohain, P. M. Saikia, S. Sarma, S. N. Bhat, R. K. Dutta, Phys. Chem.
Chem. Phys., 4, 2617, 2002
119. S. A. Shapovalov, V. L. Koval, T. A. Chernayaa, A.Y. Pereverzev, N. A.
Derevyankoc, A. A. Ishchenko, N. O. M. Petrossyan, J. Braz. Chem. Soc.,
16, 2, 232, 2005
120. a. M. Dakiky, I. Nemacova, Dyes Pigm., 40, 141, 1999
b. M. Dakiky, I. Nemacova, Dyes Pigm., 44, 181, 2000
121. R. Sabate, J. Estelrich, J. Phys. Chem. B, 107, 4137, 2003
122. R. Sabate, M. Gallardo, A. de la Maza, J. Estelrich, Langmuir, 17, 6433,
2001
123. F. M. Menger, D.W. Doll, J. Am. Chem. Soc., 106, 1109, 1984

31
124. K. K. Karukstis, A. A. Frazier, D. S. Martula, J. A. Whiles, J. Phys.
Chem., 100, 11133, 1996
125. K. K. Karukstis, A. A. Frazier, C. T. Loftus, A. S. Tuan, J. Phys. Chem.
B, 102, 8163,1998
126. G. B. Behera, P. K. Behera, B. K. Mishra, J. Surface Sci. Technol., 23, 1-
2, 1, 2007
127. H. Yao, T. Isohashi, K. Kimura, J. [Link]. B, 111, 176, 2001
128. M. F. Emerson, A. Holtzer, J. Phys. Chem., 71, 3320, 1967
129. M. Almgren, S. Swarup, J. Colloid Interface Sci., 91, 256, 1983

32