Chapter

1 ‐ Introduction

Chapter 1 - Introduction

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 26

Chapter 1 ‐ Introduction

1.1Philosophy

It is a wide spread area of knowledge in which the definition of knowledge itself

is one of the subjects investigated. It spans the nature of the universe, the mind, the body;

the relationships between these three, and among people. In other words Philosophy is a

field of research – the pursuit of wisdom; the predecessor and complement of science,

developing the issues which underlying science and also beyond the scope of science.

The essence of philosophy is the study and development of fundamental ideas,

concepts and methods that are not adequately addressed in sophisticated disciplines, such

as a broad area of science. Philosophy provides the foundations upon which all belief

structures of scientific inventions and fields of knowledge are based upon. It determines

the definitions of many scientific inventions and their approaches used to develop the

theories of diverse fields of science. Philosophy has a rich literary heritage, including the

writings and teachings of profound thinkers from many cultures throughout history of

science. In order to understand the principles that underlie all knowledge and being

philosopher developed methods of thinking, including logic, introspection, and meditation

and applying these methods, they investigate the most fundamental questions, such as

"What is the nature of the universe?" (Metaphysics), "What do we know, and how do we

know it?" (Epistemology), etc. 'Philosophy' translates literally from the original Greek

language as 'love of wisdom'. In short philosophy is thinking about thinking. In the

analytic tradition of modern world philosophy has reinvented itself with a new set of

techniques. It concentrates on logic and conceptual analysis. Topics at its centre include

the theory of knowledge, ethics, the nature of language, and the nature of mind. Earlier

philosophy placed more emphasis on the study of the arts and science of life: a general

theory and a commendation of way of life. In this sense, philosophy is concerned with

the practical bits of how to live rather than a theoretical attempt to understand.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 27

Chapter 1 ‐ Introduction

Science and technology in general and chemistry or chemical technology in

particular is deeply penetrated in modern human life. In other words the human life is

enriched by the series of novel concepts, novel inventions and products based on that.

This is the output of innovative research in the field of science and technology. Among

the subject areas studied under the headline of chemical science, surface chemistry or

more precisely “Surfactant chemistry” has dominated the modern human life style. The

formation of biological membranes and functions in living cell to the applications such as

wetting the fuel tank wall in cryogenic engines, the surfactant chemistry has encompassed

every surface and interfacial interaction. As we get up in the morning till the time we go

to sleep, our every activity is balanced on an oriented monomolecular interfacial film only

because of the presence of lung surfactants in the form of phospholipids which regulates

the surface tension of cytoplasm of the cell of alveoli and facilitates the breathing

mechanism.

Even though the surfactant science is about a century old, only in the last few

decades it has emerged rapidly in terms of its industrial applications and theoretical

findings. Academic researchers working in the field of surfactant science have mainly

concentrated on the preparation of high quality surface active materials as with respect to

purity the choice of surface active agent is very limited. On the other hand the industrial

as well as commercial research is basically result oriented towards studies of surface

active materials.

Emulsion and emulsion technology inevitably occupies a ruling position in the

vast domain of applied subject areas covered under the headline of colloids as they are the

profit making subject of major commercial enterprises in chemical industry business.

Emulsion and emulsion technology is also considered as the most suitable and valuable

candidate for academic research due to their complex nature and wide spread

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 28

Chapter 1 ‐ Introduction

applications. If the natural emulsions are taken into considerations the emulsions are in
1
the use for thousands of years. As per the formal definition given by Paul Becher the

emulsion is “A heterogeneous system consisting of at least one immiscible liquid

dispersed in the form of droplets, whose diameter, in general exceeds 0.1 mm. Such

systems possesses minimal stability, which may be accentuated by the additives such as

surface active agents, finely divided solids, etc.”

In simple words emulsion is also defined as,

“Emulsion is a two phase system consisting of two immiscible liquids, the one

being dispersed as finite globules in the other. The dispersed, discontinuous or internal

phase is the liquid which is broken up into globules. The surrounding liquid is known as

continuous or external phase.2 The industry has broadened this definition of emulsion to

include colloidal dispersions or solublization as well as solid dispersions where at least

one phase either dispersed or continuous is liquid as shown in able 1.1

Table 1.1 - Types of emulsions.

Type Dispersed Phase Continuous Phase

Emulsion Liquid Liquid

Foam Gas Liquid

Aerosol Liquid Gas

Solid suspension Solid Liquid

Emulsions are extensively used in various industrial applications due to following

reasons,

1. To dilute an expensive and vital ingredient by an inexpensive and immiscible

diluents.

2. To introduce an insoluble ingredient into the system.

3. To control parameters such as odor, taste, dose, toxicity or reactivity of material.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 29

Chapter 1 ‐ Introduction

4. To obtain an even distribution of active ingredient with smaller quantities.

5. To control the physical and aesthetic properties of formulation.

The commercial as well as economical value of emulsions has long been

recognized in terms of milk which is the most prevalent natural emulsion. The other

examples are rubber latex an industrial natural emulsion, crude oil, etc.

Despite the wide range of applicability, no comprehensive theory of emulsion

preparation and its stabilization has yet been formulated, except in very few specialized

cases. Though the large volumes of experimental results are presented, no generally

acceptable theoretical approach has yet appeared. Present dissertation work is about the

emulsification of edible / non-edible vegetable oils using a blend of surfactants and to

explore the process as well as green chemistry potential of reaction systems with single or

mixed surfactants. Amongst the emulsion systems studied so far, vegetable oil based

emulsions have been neglected as compared to hydrocarbon emulsions despite the

advantages such as non-toxicity, biodegradability, greener oil isolation technique and low

cost compared to hydrocarbons. Simply, vegetable oils come with all their natural

goodness and they are considered as the reservoirs of many natural vital ingredients and

products. However due to the multitude of molecular moieties present in vegetable oil

their emulsification is extremely difficult than hydrocarbon based products. One can find

a very few dissertations in this topic after looking into literature. Few monographs

published remarks the difficulties in vegetable oil emulsification and stabilization.

Therefore, we contemplated this to be an area of research investigations. The wide spread

industrial applications of emulsions are depicted in figure 1.1.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 30

 duction
Chaptter 1 ‐ Introd

Studies in Mixed Surfactant

S Sy
ystems and Vegetable oil Emulsions 31
3
Chapter 1 ‐ Introduction

1.2 Emulsions

Emulsions are the metastable colloids essentially prepared from two immiscible

liquids. Among the two immiscible liquids one is dispersed in the other in presence of

surface active compounds. The dispersed emulsion droplets possess all classical

characteristics of metastable colloids such as, Brownian motion, reversible phase

transitions due to droplet interactions and irreversible transisitions that generally involve
3
droplet detruction. The metastability of emulsion is strongly dependent upon the
4, 5
properties and presence of surface active species at the interface. The significant

increase in the life time of these species at the interface makes them a very good

candidate for commercial applications.6 Emulsion possesses a unique ability to solublize

the hydrophilic as well as hydrophobic molecules depending upon the type and

composition of the emulsion. The surface treatment techniques such as painting, paper

coating, road surfing and lubricating are the major customers of emulsion technology.

The ability of active ingredient solublization makes them suitable and efficient carrier for

drugs to the different target organs of the human body. Emulsions based products are

widely used in food and cosmeceutical industry because of their special appearance and

flow properties called as “Rheology”.

1.3 Basic Processes in Preparation of Emulsion

1.3.1 Droplet formation and development of monomolecular film

The formation of globules of dispersed phase is the ultimate aim of the

emulsification which is achieved by the supply of external energy in terms of controlled

agitation. Under the influence of mechanical agitation the interface between the two

immiscible liquids is first deformed to such an extent that the droplets are produced.

Initially these droplets are too large to maintain their free existence and hence they must

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 32

Chapter 1 ‐ Introduction

be further broken into the finer and quite stable droplets. A geometrical series model can

be used for describing the droplet formation. The number of droplets formed (Zn) after ‘n’

divisions is given by,

Zn = 2n (1)

However, this theoretical model is practically valid only for a limited or initial

stages of divisions and its deviation increases further due to practical limitations of

agitation as well as physicochemical properties of phases involved.7

In order to prevent these droplets from reuniting, energy barrier is needed which will

prevent their collision and further fusing to form a layer. Such barrier is created by the

monomolecular layer of surfactant surrounding the dispersed droplet and can be

maintained by the addition of emulsion stabilizers.

The surfactant molecules accumulate at the interface under the influence of

agitation and orient themselves in such a way that their hydrophilic groups projects in to

aqueous phase and hydrophobic groups towards the organic phase. This produces an

interfacial film and it adsorbs additional surfactant molecules if the droplets are further

broken up mechanically until all the droplets are enveloped by a surfactant film.8, 9 The

thickness of interfacial surfactant layer depends upon the type of system and

concentration of surfactant and internal phase. Though a monomolecular layer is expected

to be surrounding the droplets in many cases the multiple layers are built up.10 The

disintegration of dispersed phase into fine droplets is accompanied by the tremendous rise

in globule surface area and consequently interfacial area. This interface determines the

flow behavior of the emulsion product and hence the action of emulsifiers at the interface

acquires decisive importance.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 33

Chapter 1 ‐ Introduction

1.3.2 Work of division

A liquid always tends to reduce its surface area or interface to a minimum thus

increase in the interfacial area is possible only if the external energy is supplied in terms

of agitation or ultrasonication.

dA = µ.dI (2)

The work expended (dA) for droplet formation is proportional to the increase in

the interface area (dI). The proportionality factor is the magnitude of interfacial tension

(µ) between the phases to be emulsified. Thus if the interfacial tension between the two

phases is too high considerable mechanical energy is required for emulsification unless

the emulsifier is added and vice a versa. 11-13

1.3.3 Decrease in interfacial tension

The emulsifier is the most effective agent lowering the interfacial tension at

lowest possible concentration. The decrease in interfacial tension is due to the

accumulation of emulsifier molecules at the interface between the phases to be

emulsified. To achieve this, emulsifier molecule must possess two effects, 14, 15

1. Diffusion effect: Reach the interfacial region as soon as possible from the phase in

which they are initially dissolved.

2. Adsorption effect: To be adsorbed at the interface to minimize the interfacial

tension to lowest possible value.

The area required by the emulsifier molecule in the interfacial film can be

calculated by plotting interfacial tension (µ) (mN/m) against concentration (c) (g/L) using

the Gibbs equation as follows, 16

τ µ (3)

Where,

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 34

Chapter 1 ‐ Introduction

τ = interface adsorption or accumulation in mol/cm2

R = Gas constant

T = Absolute temperature

The area required (A in m2) can be determined using Avogadro’s number (NA) and

interface adsorption (τ)

A (4)
τ.

It is a property of a good emulsifier molecule to occupy the smaller area at the

interface and arrange themselves at right angles to the interface by forming stable film

where the polar hydrophilic emulsifier groups project into aqueous phase and non polar

hydrocarbon groups towards the organic phase.

1.3.4 Marangoni Effect

Figure 1.2 - Emulsification mechanism

The phenomenon of uniform spreading of emulsifier molecules at the freshly

generated interface is called as “Marangoni Effect” and shown in Figure 1.2.17 In case of

the formation of two emulsion droplets from one larger droplet under the influence of

mechanical force or by Brownian motion, the point of droplet rupture is generally to be

free from emulsifier molecules. Such deficiency of emulsifier molecules at the interface

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 35

Chapter 1 ‐ Introduction

develops an interfacial tension gradient between the emulsifier occupied droplet surface

and that with emulsifier unoccupied droplet surface. This interfacial tension gradient must

be stabilized by the adsorption of emulsifier molecules either from the interior of the

droplet or from the solution or by the spreading of emulsifier molecules from the droplet
18
surface itself. The rapid diffusion and spreading facilitates the emulsion formation.

When a droplet ruptures the flow, turbulence effects are produced between the newly

formed droplets. Such effects are intensified by the spreading of emulsifier molecules

already present on the droplet surface. The life of these droplets formed, plays a decisive

role in emulsion formation as well as stability of emulsion. If the surface of freshly

formed droplet is not occupied rapidly by enough emulsifier molecules, they encounter

little resistance while colliding and coalesce again immediately after being formed. This

occurs if the rate of even one of these i.e. diffusion, spreading and adsorption is slow.19

1.3.5 Electric Charge due to the triboelectric effect

In case of the formation of emulsion under the influence of external mechanical

force, the tribolelectric effects produce the potential difference known as “Zeta Potential”

between the dispersed and continuous phase as the oil droplets in o/w emulsions are
20 - 23
having negative charge. The accumulation of surfactant molecules at the droplet

surface results either in additional droplet charging or charge reversing. This effect is

predominant when the ionic surfactants are used. In case of o/w emulsions the anionic

surfactant increases the negative charge on dispersed oil droplet whereas the cationic
24, 25
surfactants causes droplet charge reversal. The increase in droplet charge is favored

as it enhances the emulsion stability against coalescence.

The charging of emulsion droplets involves following steps,

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 36

Chapter 1 ‐ Introduction

1. Dissociation of surfactant molecule and charging emulsion droplet surface by the

negatively charged surfactant anions.

2. Attraction of cations from the solution by the negatively charged droplet surface

resulting in the formation of electrical double layer called as “Helmholtz layer.”

3. Development of “Stern layer” or “diffuse ion cloud” by further extraction of ions

from the neutral solution.

1.4 Surfactants in emulsions

The term “surfactant” which is an acronym derived from the phase “Surface active

agent” encompasses a range of different surface active materials such as, emulsifiers,

detergents, wetting agents, solubilizers, suspending agents, etc. Emulsifiers are further

divided into sub groups depending upon their chemical behavior as ionic and nonionic

emulsifiers. Ionic emulsifiers are further classified as cationic and anionic emulsifiers.

1.4.1 HLB System

The first step in preparation of essentially stable emulsion involves the selection

of suitable surfactant system. It has been observed that the synergistic stability of

emulsions and ease of emulsion formation is achieved with the blend of surfactants over

the use of single surfactant. 26, 27 “Griffin” assigned a dimensionless numbers from 0 to 20

to each emulsifier molecule in order to predict their water as well as oil compatibility.

The close agreement between the HLB number of emulsifier and that of dispersed is

found to be the most important criteria for the formation of stable emulsion. The numbers

from 0 to 9 characterize oil compatible hydrophobic surfactants whereas 11 to 20 are used

for water compatible hydrophilic surfactants. The hydrophilic – lipophilic equilibrium is

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 37

Chapter 1 ‐ Introduction

situated at the centre (10) of this scale. 28 - 30 Table 1.2 shows the HLB number ranges and

their applications in various systems of commercial as well as industrial importance.

Table 1.2 - Influence of HLB on emulsifier performance

HLB Range Appearance / Water Dispersibility Application

1-2 No dispersibility in water -

3-6 Poor dispersibility w/o emulsifier

6-8 Milky dispersion after vigorous stirring Wetting agent

8-10 Stable milky dispersion o/w emulsifier

10-15 Translucent to clear dispersion Detergent

15+ Clear solution Solubiliser

The HLB system gives an approximate indication of compositions where the

surfactants show optimum behavior and performance. Griffin has put forth a series of

equations from which the hydrophilic – lipophilic balance (HLB) number can be

predicted from compositions or analytical data of selected non-ionic surfactants.

For non-ionic surfactants having polyoxyethylene solublizing groups, the HLB was

calculated from the following formula (5) 31

%
HLB (5)

The HLB number of surfactants based upon polyhydric alcohol fatty acid esters such as

glycerol monostearate can be calculated as shown in equation (6) 32

HLB 20 (6)

Where,

S = Saponification number of the ester

A = Acid number of the acid

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Chapter 1 ‐ Introduction

In case of ethoxylated fatty acid esters of polyhydric alcohols such as glycerol and

sorbitol, the following simple formula (7) can be used if the mass fractions of alcohol

(WA) and polyethylene oxide (WE) are known or can be determined. 33

HLB (7)

If the hydrophilic portion of the surfactant consists only of ethylene oxide (WE)

which is known or determined, the HLB values can be calculated by equation (8)

HLB (8)

Davies and Rideal suggested that the HLB numbers could be calculated based

upon group contributions according to the formula (9) 34

HLB 7 ∑ hydrophilic group numbers ∑ hydrophobic group numbers (9)

In case of polyglycol ethers Moore and Bell gave the following equation (10) for

determining the hydrophilic – lipophilic equilibrium (H/L) as,

100 (10)

The HLB value indicates what mass fraction of the surfactant projects into the

aqueous phase in the ideal case. In ideal case, the HLB of surfactant with molecular mass

(M) and a hydrophilic portion (MH) is given by equation (11) as,

HLB 20 (11)

However, in case of ionic surfactants when equation (11) is applied the calculated

HLB number was found to be too low as the ionic surfactants are more hydrophilic than

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 39

Chapter 1 ‐ Introduction

would be expected from the ideal distribution. Therefore, a correction factor ‘C’ is added

in equation (11) 35

HLB 20 C (12)

As a rule the use of mixed surfactants requires smaller amount of surfactant than

used alone.

The HLB of a mixture of emulsifiers A and B is assumed to be an algebraic mean

of the HLBs of the constituent surfactants as shown in equation (13)

HLBmix = fA × HLBA + (1-fA) × HLBB (13)

Where,

‘fA’ is the weight fraction of surfactant ‘A’ in the mixture.

The HLB method has become the most used method since its discovery. However

the HLB system ignores the considerations such as,

1. Temperature effects of ethoxylates causing inverse cloud points.

2. The role of fatty alcohols whether as emulsion stabilizer or the emulsified oil phase

3. Phase volume ratios

4. Ingredient interactions

5. Amount of surfactant to be used.

The temperature at which the o/w and w/o tendencies of surfactant are balanced is

called as “Phase inversion temperature (PIT)” which takes into account all above

considerations. In case of ethoxylated surfactants the water solubility is due to the H-

36 -38
bonding. As the temperature increases, this H-bonding is disturbed reducing their

water solubility which is the reason for the reverse cloud point. The effective HLB

decreases with increase in temperature. For a good emulsion product the PIT should be at

least 20°C higher than the highest storage temperature.

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Chapter 1 ‐ Introduction

1.5 Types of Emulsions

1.5.1 Coarse emulsion

Depending upon the type of internal and external phases involved, they are

subdivided in to four classes such as,

1. Oil in water (O/W) – oil droplets are suspended in aqueous matrix

2. Water in oil (W/O)- water droplets are suspended in oil matrix

3. Water in water (W/W) –consists of aqueous solutions of mixture of incompatible

polymers systems such as, polysaccharides, proteins, etc.

4. Oil in oil (O/O) –comprising of incompatible organic solvents stabilized by co-

polymers with residues of different solubilities in the solvents used.

1.5.2 Multiple emulsions

Multiple emulsions are emulsions in which globules of the dispersed phase

encapsulate smaller droplets, which in most of the cases are identical with continuous

phase. The two major types of multiple emulsions are W/O/W in which internal and

external aqueous phases are separated by an oil layer and O/W/O in which water

separates the two oil phases. Multiple emulsions are thermodynamically unstable

systems. Principal modes of emulsion breakdown involve coalescence of internal or

external droplets, expulsion of internal droplets, and osmotic swelling or shrinking.39

Stability of the multiple systems can be improved by forming a polymeric gel either in the
40
internal or external aqueous phase. Polyaphrons are three liquid-phase dispersions, the

internal phase being stabilized by encapsulation in a thin aqueous soapy film.

Polyaphrons exhibit foam-like character in which the oil-encapsulated cells aggregate to

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 41

Chapter 1 ‐ Introduction

form stable polyhedral structures. Dispersions containing 97% of dispersed oil phase

within a continuous structure that contains only 3% water could be achieved. In another

example, a five phase novel emulsion consists of water, perfluorinated oil and liquid

crystal dispersed in a continuous silicone phase along with coarsely dispersed aqueous gel

phase.

1.5.3 Microemulsions

Microemulsions are stable, transparent (or translucent), dispersions of oil and

water stabilized by an interfacial film of surfactant molecules and having diameter <100

nm. Microemulsion formation usually involves a combination of three to four

components – water, oil, surfactant/s and co-surfactant/s. The surfactants chosen are

generally those in the non-ionic group because of their good cutaneous tolerance and

balanced lipophilic and hydrophilic property. The most important role of co-surfactant in

the formation of microemulsions is to increase interfacial fluidity and to modify the

41
Hydrophilic-Lipophilic Balance (HLB) of surfactant to optimal value. Thus, their

combination is more effective than a single surfactant. Factors affecting stability of

microemulsions include interfacial tension, interfacial curvature, entropy and fluidity. In

microemulsions, the active is solubilized rather than suspended as in the vesicles and is

available for immediate absorption, generally more rapidly and effectively.

Microemulsions are easy to manufacture as they form spontaneously without high shear

equipments. Their optical transparency and low viscosity ensure that they are of good

appearance, easy to handle and pack. Microemulsion containing di-decanoyl glycerol is

used to increase melanin content of melanocytes thereby increasing pigmentation of skin.

Microemulsion containing ascorbyl palmitate effectively prevents UV-A-induced lipid

peroxidation. 42

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Chapter 1 ‐ Introduction

1.5.4 Nanoemulsions

Nanoemulsions consist of very fine oil-in-water (o/w) dispersions, having droplet

diameter smaller than 100 nm. Compared with microemulsions, they are in a metastable

state and are very fragile systems by nature. Their structures depend on the process used

to prepare them. They can be prepared by spontaneous emulsification such as phase

inversion temperature (PIT) emulsification or phase inversion composition, or by using a

high shear device, which allows a better control of the droplet size and large choice of

compositions. The nanoemulsions are easily employed in skin care because of their good

sensorial properties (rapid penetration, merging textures) and their biophysical properties

(especially, hydrating power). They lead to a large variety of products from water-like

fluids to ringing gels. Lotions, transparent milks, crystal-clear gels with different

rheological behaviors, visual aspects, richness and skin feel are blended with

nanoemulsions. 43

1.5.5 Liquid crystals

Liquid crystalline phase is thermodynamically stable and represents a state of

incomplete melting. Liquid crystals are mainly of two classes – thermotropic liquid

crystals (smetic and nematic type) and lyotropic liquid crystals. Liquid crystals exhibit

birefringence and dichromism and hence enhance the product appeal because of the

colored appearance of the preparations into which they are incorporated. Liquid crystals

form multilayer around the emulsion droplets, decreasing the van der Waal’s energy and

increasing the viscosity which increases the emulsion stability. These multilayers act as

rheological barriers to coalescence. Lipophilic materials such as vitamins, incorporated

into liquid crystalline matrix, are protected from both thermal and photo-degradation.

Emulsions containing liquid crystals have been observed to have a rate of active release

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 43

Chapter 1 ‐ Introduction

much slower than those without this stabilizing component. This effect is because of

multilayer structure of liquid crystalline material around droplet, which effectively

reduces the interfacial transport of the dissolved actives from within the droplet e. g.

timed release of vitamin A palmitate containing liquid crystals dispersed in water-based

gel. 44, 45

1.6 Emulsion Stability

While discussing the stability phenomenon of emulsions, it is important to have a

clear idea of the components of emulsion. Breaking of emulsion is initiated by joining of

small emulsion droplets to form a larger droplet, the process is called as coalescence and

it ultimately leads to complete emulsion destabilization by the formation of two distinct

phase layers with respect to their specific gravity. The terminology “Flocculation” is

defined as the natural adhesion of emulsion droplets to form a three dimensional network

without coalescence. “Creaming” is the separation of dispersed droplets from the

continuous phase under the influence of either gravity or external applied force such as,

sonication, centrifugation, etc. If the dispersed medium is less dense than the continuous

phase, the upward creaming takes place on the other hand for the dense dispersed system

the downward creaming occurs. In case of dilute emulsions the creaming usually occurs

mainly due to the difference in the specific gravity of the phases. Irreversible creaming is

a trivial form of emulsion instability hence it is mainly overcome by the addition of

thickener which acts by modifying the rheology of emulsion system. Figure 1.3 shows the

mechanism of emulsion destabilization. In early efforts of stabilizing emulsions,

adsorption of the ionic species from the electrolyte and forming an electrically charged

double layer has retarded the coalescence to some extents. In this regards potassium

thiocyanate showed some positive effect to some extent. Also the adsorption of natural

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 44

Chapter 1 ‐ Introduction

modified gums, starch and protein molecules at the interface have shown a better

performance in stabilizing emulsions. The use of synthetic polymeric materials such as

polyvinyl pyrrolidone, polyacrylic acid, etc have reduced rate of desorption from the

droplet surface by their adsorption at many sites. The adsorption of finely divided clays

such as bentonite, montmerillonite, etc. was also used to achieve the “Pickering

stabilization.” 46

Figure 1.3 - Mechanism of emulsion destabilization.

The lifetime of typical emulsion can be attributed to the phenomenon such as,

Brownian motion, convection currents and random disturbances of the droplets. The

intensity of these three parameters determines the possibility of coalescence in case of

poorly stabilized emulsions. One of the factor affecting long term stability of emulsions is

the “Ostwald ripening” observed in case of crystalline systems i. e. in case of dispersions

containing large size of oil droplets. As the larger droplets are grown at the expenses of

smaller droplets, the differences in the chemical potential of the molecules in larger

droplets and that in smaller droplets is responsible for “Ostwald ripening.” This

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 45

Chapter 1 ‐ Introduction

difference is quantitatively expressed by using Laplace pressure which shows that the

Laplace pressure is inversely proportional to the radius of droplet,

ΔP = 2γ / r (14)

Where,

‘ΔP’ is the Laplace pressure.

‘r’ is the droplet radius.

1.7 Factors affecting emulsion stability

1.7.1 Temperature

Rise in temperature is associated with the increase in the Kinetic energy of

dispersed droplet. This facilitates the coalescence during inter droplet collisions since

under these conditions the protective envelopes of the droplets are more easily penetrated.

However the rise in emulsion temperature favors the stability of sterically stabilized

emulsions. 47

1.7.2 Addition of electrolyte

As the electrical charge of the boundary layer is very sensitive to the addition of
48
foreign ions destabilizes the emulsion. The effect of added electrolyte increases with

increase in its valency.

1.7.3 Removal or destruction of Surfactant

The addition of the substances which displaces the film forming components from

the interface synergistically destabilizes the emulsion. e.g. addition of acids or bases

destroys the hydrolysis sensitive surfactants whereas the addition of cationic compound to

the emulsion stabilized by the anionic surfactant causes rapid breaking by forming and

precipitating sparingly soluble complexes. Addition of adsorption agents such as,

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 46

Chapter 1 ‐ Introduction

activated carbon, silica gel, fuller’s earth for the adsorption of surfactants breaks the

emulsion rapidly. Generation of voluminous precipitate such as iron and aluminum oxide

hydrates in the aqueous phase destabilizes emulsions.49, 50

1.7.4 Mechanical Stress

External mechanical force in terms of pressure, impact or shaking, disturbs the

uniformly formed delicate interfacial film thereby destabilizing the emulsion.51, 52

Breaking of protein film of fat droplets in milk is mechanically destroyed to produce

butter at the same time the foam formation removes some of the proteins from the milk.

1.7.5 Dilution, Evaporation and Freezing

All these parameters affect adversely on the uniform distribution of emulsion

constituents as well as on the optimum composition and hence they spontaneously destroy

the emulsion network. In addition these parameters promote growth of biological culture

such as bacteria and destabilize the emulsion.53

1.8 Emulsion Stability Testing Procedures

1.8.1 Freeze Stability

In order to get an idea about the emulsion stability the emulsion developed is

frozen either in bulk form or in the form of thin microscopic film. In case of o/w

emulsions on freezing the external aqueous phase forms long ice crystals and these

structural changes in the solution force the dispersed oil droplets into a narrow space

between the unfrozen fluids.54 This crystal growth distorts the oil globules to such an

extent that they extend into filaments and eventually make contact with each other. The

magnitude of coalescence in this case is influenced by several factors such as type of

surfactant and its concentration, extent of globule area covered by surfactant and the

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 47

Chapter 1 ‐ Introduction

nature of oil phase incorporated. In case of o/w emulsion of mixture of triglyceride and

paraffin oil or pure triglyceride as an internal phase, the crystallization point of

triglyceride in emulsion state is lowered as compared to its normal phase.55 However, the

magnitude of reduction in crystallization point is influenced by the nature of emulsifier

employed. A prominent crystallization is observed in case of surfactants having same

alkyl chain length as that of triglyceride. This is mainly due to the promotion of

nucleation by setting triglyceride molecules in order near the globule surface. The

stability of o/w emulsions to coalescence is decreased by freezing due to the

crystallization of triglycerides in the dispersed oil globules. The rise in temperature of

such emulsions following freezing causes intense emulsion break-up.56

1.8.2 Elevated temperature stability

A rise in temperature is responsible for the initiation of strong thermal convection

currents in the internal phase leading to destabilization due to the coalescence. It is

believed that the rate of reaction is almost double for each 10 °C rise in temperature. Thus

testing the physical stability of emulsions at elevated temperature has gained extreme

importance in predicting the long term storage stability of emulsion systems. An emulsion

system stable for a period of six months at the 40°C / 75% relative humidity (R. H.) is

normally found to have shelf life stability for two years.57

1.8.3 Centrifugation stability

The emulsion destabilization process in terms of rate of phase separation can be

best determined by subjecting emulsion system to high speed centrifugation. In case of

o/w emulsion centrifugation, leads to the formation of upper coagulated oil layer, bottom

water layer and middle layer of uncoagulated emulsion. For emulsion oil droplets to

remain spherical the large pool of aqueous phase must be held in between the oil droplets,

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 48

Chapter 1 ‐ Introduction

however under the influence of strong gravitational forces the aqueous phase in between

the droplets is removed. Such changes lead to the change in the geometry of oil droplets

from spherical to distorted polyhedron which ultimately increases the oil phase surface

area. If the surfactant concentration is not enough to envelope this increased area,

emulsions lead to destabilization due to the absence of uniform interfacial film over the

entire interfacial region. The centrifugation stability of emulsion system is affected by

several parameters such as, speed and time of centrifugation, purity of surfactant, ratio of

dispersed phase to continuous phase and physico-chemical nature of rheological

additives.58 The accelerated ageing stability of emulsion can be estimated and predicated

by using Stokes law as where the acceleration due to gravity (g) is replaced by “ω2R” as

in equation (15),

ω –
V (15)
η

Where,

ω = angular velocity of the centrifuge,

R = distance of the sample from the centre of rotation.

The long term emulsion stability can be best predicted by this equation as the

value of ‘ω2R’ is increased many times than the value of gravity (g). In case of a typical

emulsion system, the centrifugation at 3750 rpm at a distance of 10 cm from the centre

for 5 hrs may be equivalent to shelf life stability for a period of one year at ambient

temperature conditions.59

1.8.4 Stability in terms of turbidity measurements

The turbidity of emulsion is the function of droplet concentration and size.

Therefore, the change in these parameters alters the turbidimetric properties of emulsion

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 49

Chapter 1 ‐ Introduction

system.60, 61 Thus any change in emulsion turbidity can be considered as a measure of

emulsion destabilization.

1.8.5 Rheological measurements as a novel technique for assessment of emulsion

stability

Rheological parameters of emulsions such as, apparent viscosity, consistency

index and flow behavior index are cumulatively dependent upon the uniformity and

physico-chemical stability. Any minor changes in uniform distribution of constituents

within the emulsion system due to any phenomenon alter the flow behavior of the

emulsion. Therefore, consistent rheological profile of emulsion over the period of time is

considered as a reliable technique to predict stability of the system under study. A novel

technique of measurement of rheological properties at accelerated storage stability

conditions such as elevated temperature and high speed centrifugation, gave a reliable

picture for the long term storage stability of emulsion system. This plays a very important

role in delivering emulsion based products to consumers via transportation, storage and

handling procedures.62 - 65

1.9 Rheology

The term ‘Rheology” came from the Greek word “Rheo’ meaning to flow.

Rheology is defined as “The science of deformation and flow of matter. It describes

mainly the flow properties of the material such as fluid and semi-solid materials.

Rheology is an interdisciplinary property of material used to describe the flow behavior

of oils, oil based products, food supplements, polymeric substances, inks, clays and dyes.

All these materials possess characteristic flow behavior depending upon their

applications. Viscosity usually means the resistance by the material to the flow which is

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Chapter 1 ‐ Introduction

the inverse of fluidity. Rheology mainly describes the consistency of different products

by the two components viscosity and elasticity.

1.9.1 Newton’s law of flow 66

Consider a liquid block consisting of parallel plates of molecules each having an

area ‘A’ cm2 and separated by a distance ‘dr’. If the top layer moves parallel to the

bottom layer at a velocity of ‘du’ cm/sec relative to the bottom layer, a force ‘F’ dynes is

required to maintain the velocity. The velocity gradient is represented as the extent of

deformation and is referred to as the ‘shear rate’ with unit of sec-1. The shearing force per

unit area is the shearing stress and is denoted by ‘τ’. The relationships between the shear

stress and shear rate are used to define the flow properties of the material. Newtonian

fluids exhibit a proportional increase in shear stress as the shear rate is increased,

producing a straight line passing through the origin with a constant slope. The viscosity

and corresponding rheological profiles for different emulsion systems are depicted in

figure 1.4 and 1.5.

Figure 1.4 - Viscosity Profile

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Chapter 1 ‐ Introduction

Figure 1.5 - Rheological Profile

1.9.2 Non-Newtonian flow behavior 67

A) Dilatant: The viscosity as well as shear stress of such systems increases with increase

in shear rate.

B) Plastic: Viscosity decreases with increase in shear rate however a plot of shear stress

v/s shear rate does not pass through the origin and intercepts shear stress axis at a point

called ‘Yield value”.

C) Pseudoplastic: Viscosity decreases with increase in shear rate however a plot of shear

stress v/s shear rate does not pass through the origin.

Zanatta et al showed that the O/W emulsions of buriti oil prepared using

Steareth-2 associated to Ceteareth-5 and to Ceteareth-20 presented pseudoplastic

behavior. These formulations did not show changes in physical stability, pH, or

rheological behavior after accelerated stability tests. Significant stability differences were

observed only after temperature cycling test.68

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Chapter 1 ‐ Introduction

Akhtar et al reported the Newtonian flow behavior of eight different natural oils,

namely olive, coconut, almond, castor, sesame, cotton seed, sunflower, and paraffin

oils.69

The rheological behavior of corn oil coarse emulsions prepared by high pressure

homogenization (HPH) was investigated over a shear range of 0-150 s-1. It showed

macroscopic change in emulsion consistency. Homogenization of emulsions with low oil

concentration (10 g/100 g) resulted in Newtonian behavior for all treatment pressures.

The rheological behavior of emulsions with higher oil concentration (30 g/100 g) was

found to be dependent on casein concentration in the aqueous phase and varied from

Newtonian to shear thinning. Homogenization pressures induced the formation of a gel-

like structure possibly through pressure-induced interactions between caseins surrounding

adjacent droplets. 70

Droplet size distribution and rheological properties of egg yolk-stabilized

emulsions were studied before and after storage (25 °C, 30 days). Replacement of Palm

kernel oil by soybean oil resulted in a significant increase in mean droplet diameters and

decreased rheological properties of the emulsions.71

The possible relationships between the main emulsion components such as Arabic

gum, xanthan gum, and orange oil and the physicochemical properties of orange beverage

emulsion were evaluated by using response surface methodology. The physicochemical

emulsion property variables were considered as response variables. The main effect of

Arabic gum was the most significant (p < 0.05) turbidity loss rate, and increase in

viscosity. The results indicated that combined level of 10.78% (w/w) Arabic gum, 0.56%

(w/w) xanthan gum, and 15.27% (w/w) orange oil was predicted to provide the overall

optimum region in terms of physicochemical properties of emulsions.72

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Chapter 1 ‐ Introduction

Stability of beverage emulsion is measured by the rate at which the emulsion

creams, flocculates or coalesces, and is generally dependent on rheology of water phase,

difference in specific gravities of the two phases, droplet size and distribution of the

emulsion. The effects of weighting agents such as sucrose acetate isobutyrate, brominated

vegetable oil and xanthan gum on modified starch-based emulsions were evaluated.

Emulsion was formed by the addition of 9% coconut oil, in the presence or absence of

weighting agents, into the water phase containing modified starch at 10, 12 or 14%

without or with the addition of 0.3% xanthan gum. Stabilities of emulsions were

evaluated both in the concentrated form used for storage and dilute form used in

beverages. The addition of xanthan gum into the water phase decreased the flow behavior

index (n) from 0.88 down to 0.31 and increased elastic modulus (G′) over 20 times at

elevated frequency (ω = 50 rad/s) and elevated the stability of the emulsion. The xanthan

gum-added emulsion had smaller particle size and demonstrated 14 and 5 times slower

phase separation compared to the emulsions without or with the addition of weighting

agents, respectively. In case of dilute beverage emulsions creaming was observed in the

absence of xanthan gum.73

Optical and rheological properties of beverage cloud emulsions as a function of

water-phase and oil-phase concentrations were investigated by Taherian et al in terms of

specific gravity of phases, particle size distribution and creaming stability of prepared

emulsions in diluted forms. Combinations of emulsions with added starch and oil were

used. The specific gravity of oil phase was adjusted using a constant combination of

weighing agents [sucrose acetate isobutyrate and brominated vegetable oil] and different

levels of coconut oil. Increase in modified starch concentration for all water phases

decreased the flow behavior index while oil phase at any given concentration of coconut

oil contributed to a Newtonian behavior. Increase in viscosity of emulsions was more

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 54

Chapter 1 ‐ Introduction

pronounced with increased oil concentration. Oil added emulsions showed shear thinning

behavior which is associated with droplet flocculation. Dynamic rheological properties of

emulsions revealed that oil added emulsions showed viscous behavior with the delta

degree (G″/G′), greater than at maximum frequency level (50 rad/s) which decreased with

increasing the oil level.74

Bavarri et al reported that decrease in the fat content of food, changes both aroma

release due to partition effects and the viscosity of the food. A series of flavored

emulsions were prepared to control aroma release and viscosity using different aroma, oil,

and hydroxypropyl methyl cellulose (HPMC) contents. Samples were formulated to

deliver the same aroma-release in vitro and in vivo, and their viscosity was measured

using the Kokini oral shear stress parameter. Despite the in vivo aroma release being

constant, there were perceptual differences among the samples, and the flavor intensity

decreased as in-mouth viscosity increased. For these iso release samples, the Kokini oral

shear stress parameter correlated well with the decrease in perception, suggesting that

there may be a viscosity stimulus or that the viscosity affects release of taste and hinders

aroma-taste interactions.75

The stability and rheology of acidified model oil-in-water emulsions of pH 3.6 ±

0.1 were evaluated by Arora et al before and after high-pressure treatments.

Concentration of canola oil (0-50% w/w), whey protein isolate, polysorbate 60, soy

lecithin (0.1-1.5% w/w each), and xanthan (0.0-0.2% w/w) were varied independently. It

has been observed that the exposure to high pressures (up to 800 MPa) for 5 min at 30 °C

did not significantly affect the equivalent surface mean diameter, flow behavior, and

viscoelasticity of the whey protein isolate and polysorbate-60 stabilized emulsions.

Pressure treatments showed a negligible effect on emulsion stability in these systems.

Soyalecithin-stabilized emulsions had larger mean particle size and lower emulsion

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 55

Chapter 1 ‐ Introduction

volume indices than the others indicating potential instability. Application of pressure

further destabilized these emulsions.76

Guerrero et al reported the influence of composition (sucrose ester and oil

concentrations) and temperature on the linear viscoelasticity properties of highly

concentrated o/w emulsions, using a hydrophilic sucrose palmitate as emulsifier.

Different oil-in-water emulsions were prepared using a sucrose palmitate (1-5 wt %) with

a hydrophilic-lipophilic balance of 15, sunflower oil (60-80 wt %) and water. Oscillatory

measurements were carried out in the linear viscoelasticity region. The relaxation time

spectra of the emulsions were calculated using regularization techniques and were fitted

to an empirical model proposed by Madiedo (1996). The results obtained are explained on

the basis of the relationship among linear viscoelasticity properties, droplet size

distribution, and characteristics of the continuous phase. Thus, an increase in sucrose

palmitate concentration produced higher values of the linear viscoelasticity functions and

a broader plateau region in the relaxation time spectrum, which suggests a certain

enhancement in the elastic network.77

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Chapter 1 ‐ Introduction

Vegetable oil

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 57

Chapter 1 ‐ Introduction

1.10 Vegetable oil

Vegetable oils have been cultivated since ancient time. A several species of plant

seed based oils are widely utilized for numerous domestic as well as industrial

applications. Nowadays, manufacturing of bio-based fuel such as biodiesel has acquired

tremendous importance, as the fossil fuel resources are decreasing day by day. Most of

the plant based fatty acids contain an even number of carbon atoms in the straight chain,

fully saturated, or contains one to six double bonds which generally but not always have a

cis configuration. As compared with animal based fatty acids the plant based fatty acids

are more complex and contains several other functionalities such as, hydroxyl, epoxy,

keto, acetylenic bonds, etc. Fat and oils are predominantly trimesters of fatty acids and

glycerol called as “Triglyceride”. The fatty acid groups in triglyceride may be saturated,

unsaturated or polyunsaturated depending upon their constituent fatty acid. In addition to

triglycerides vegetable oil also contains mono-glycerides, di-glyceride, phospholipids,

galactolipids and traces of free fatty acids generated in the reaction of lipases with

substances such as sterols, terpenes, tocopherols and oil soluble vitamins such ass, Vit. A,

D, E and K. Vegetable oils are divided into following categories depending upon the

application.78

A) Edible oils: Soybean, Rapeseed, Sunflower, Sesame, Almond, Safflower,

Palm,Kokum, Rice bran, Coconut, Mustard, Cotton, Peanut, Corn, etc.

B) Non-edible oils: Karanj, castor, Neem, Undi, Mahua, Linseed, Kharaki, Pisa, Nahor,

etc.

C) Minor oils: Oilve, Mango kernel, Poppy, Cocoa beans, Shea, Grape seed, Water

melon, Avacado, etc.

D) Unexplored oils: Jojoba, Crambe, Babassu, Cuphea, Limnathes, etc.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 58

Chapter 1 ‐ Introduction

Vegetable oil derived from plant shares a total of 70% share in the world total oil

production leaving 30% from the animal based fats. About 80% of the world total oils are

utilized as the human food supplements, 14% as a raw material for industries such as

formulation, oleochemicals and 6% is consumed as an animal food. India being

agriculture based country is in the top 10 of world’s largest oil producers. The global

demand of vegetable oil has increased at an average rate of 35% for decade since

1980’s.79 Figure 1.6 indicates the increase in global demand for oil and fat.

Global Oil and Fat Demand
180 164
160
140 Million Metric Ton
120 110
100
82
80
55
60
41
40 32
25
20
0
1950 1960 1970 1980 1990 2000 2010

Figure 1.6 - Global oil and fat demand.

1.10.1 Applications of vegetable oil

Vegetable oils are the most essential nutrients both for human and animals

providing an average energy of 9 kcal/g. They supply essential nutrients as well as acts as

a carrier for the fat soluble nutrients and vitamins. In human diet the plant based

vegetable oils are preferred over the animal based fat as they contain lower levels of

cholesterol and have high proportion of poly-unsaturated fatty acids (PUFA),

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 59

Chapter 1 ‐ Introduction

predominantly linoleic and linolenic acids. More specifically both of these oils are of high

importance as it is very difficult to make an unsaturation in between carbon atoms of 12

and 13 and between 13 and 16 from an oleic acid molecule.

Vegetable oils are extensively used for cosmetic and healthcare applications also.

Oils such as coconut, sesame and castor are widely used for skin nourishment whereas a

combination of tea tree oil and lemon oil with coconut oil has found to be more effective

for hair care treatment. Considering the issue of side effects of synthetic cosmeceutical

the trend has arrived called as green cosmetics, which mainly utilize the herbal resources

such as vegetable oil to formulate the product with desired activity. In case of an oral care

the substituent such as antibacterials and antibiotics are widely replaced by potent

vegetable based oils such as neem and clove oil. The edible oil industry has recently

witnessed a trend called as “Lite oil” which comprises of formulated vegetable oil

containing low cholesterol levels. These combinations being cost efficient and healthier

are accepted worldwide.

Side effects of the uncontrolled use of synthetic agrochemicals have emerged as

one of the major problem for crop protection and storage industries.80

The traces of agrochemicals in human breast milk have forced the scientists to

search for alternative crop and grain protecting agents. The non-edible vegetable oils such

as, neem, karanj and also castor has shown a promising anti insect activity without any

side effect on the ecosystem as well as consumers. The presence of natural gums such as

lecithin, phospholipids plays a very decisive role in the emulsification of vegetable oil.

The ease of emulsion formation and emulsion stability of unrefined oil is superior to that

of the refined oil due to these ingredients. Table 1.3 shows fatty acid composition of

various vegetable oils.

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Table 1.3 - Fatty acid composition of various vegetable oils.*

Constituent Castor Karanj Neem Almond Mustard Palm Safflower
oil oil oil oil oil oil oil
C14:0 0.2- 1.5 0.4 0.5- <1.0
Myristic 2.6 5.9
C16:0 0.8-1.8 3.7-7.9 16-33 3.9 1.5 32-47 2-10
Palmitic
C16:1 2
Palmitoleic
C18:0 0.8-2.0 2.4-8.9 9-24 3 0.4 2-8 1-10
Stearic
C18:1 3-6 44.5- 25-54 60-78 22 34-44 7-42
Oleic 71.3
C18:2 3.5-6.8 10.8- 6-16 10-30 14.2 7-12 72-81
Linoleic 18.3
C18:3 2 6.8 <1.5
Linolenic
C 18:1 82-95
Ricinoleic
C20:0 2.2-4.7 0.8- 0.5 <0.5
Arachidic 3.4
C20:1 <0.5
Gadoleic
C20:4
Arachidonic
C22:0 4.2-5.3 2
Behenic
C22:1 44.2
Erucic
C24:0 1.1-3.5 1
Lignoceric
Eicosenoic 9.5- 7
12.4
Acid value (max) 2 2.5 2.8 0.02 0.25
Iodine value 83-88 65-80 95-105 50-55 135-150
(Hanus)
Saponification 176- 175- 190-200 192- 186-194
value 182 200 209
Specific gravity 0.957- 0.915- 0.910- 0.910- 0.919-
@25°C 0.961 0.922 0.915 0.919 0.924

*CODEX STAN 210-1999

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1.10.2 Vegetable oil oxidation and health aspects

Vegetable oil processing, storage and use are associated with a major problem of

oxidative deterioration. Susceptibility of vegetable oils to oxidation depends upon the

degree of unsaturation.81 In conventional oil processing, some of the steps such as, caustic

refining or bleaching, remove or destroy the oxidized products or factors may initiate or

enhance the oxidative reactions. These oxidative reactions are responsible for the

breakdown of fatty acid chains and give a rancid odor to the oil and reduction in

nutritional value of the vegetable oil.82 – 84

The oxidation products of fats are further

capable of destroying fat soluble vitamins and exerting adverse biological effects.85

Enveloping the oil globule surface by external aqueous phase in the form of an

o//w emulsion system prevents the access to atmospheric oxygen thus reducing the

chances of oxidations such as, auto-oxidation, enzymatic oxidation, photo-oxidation, etc

to a measurable extent.86

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Mixed Surfactant Systems

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Chapter 1 ‐ Introduction

1.11 Mixed Surfactant Systems

1.11.1 Phase Transfer Catalysis (PTC)
Phase transfer catalysis (PTC) is a predominant technique found useful in variety
of industrial processes. This technique has rapidly gained its application track soon after
the discovery of this technology. Many industrial processes such as including
insecticides, herbicides, pesticides, plant growth regulators and plant growth promoters,
pharmaceutical intermediates, specialty chemicals are now a days manufactured
industrially on vast scale using phase transfer catalysis. It has considerably reduced
reaction process time, selectivity towards the intended products and minimized hazardous
operating conditions involved in manufacturing process.87 Depending upon the physical
nature of reaction phases involved the PTC processes are broadly classified as Solid-
Liquid phase transfer catalysis and Liquid-Liquid phase transfer catalysis. We
collectively report such systems as mixed surfactant systems.

1.11.2 Various aspects of PTC

In prior art the multiple researchers have discovered very efficient and
environmentally greener approaches for commercially feasible chemical processes using
a vast number of phase transfer catalysts.88-95 However, collectively liquid-liquid PTC is
found to be faster than Solid Liquid PTC in majority of chemical processes. This may be
because of hardware efficiency of chemical process plant and heat as well as mass
96-105
transfer limitations. Three phase PTC106-109 has gained more importance in
equipments110-115 capable of handling specialty molecules116-122 and with high
precision123-128 of process conditions.129-132

The reactant species which are more compatible towards the water phase due to
their water solubility are carried in to the organic medium by the PTC133-141 where the
chemical transformation takes place predominantly. On the contrary the reverse case
takes place in case of inverse phase transfer catalysis (IPTC)142-146 in which transport of
lipophilic reactant from the organic phase to the aqueous phase and the main reaction
occurs in the aqueous phase.147-150 In modern days the highly versatile and greener
technique was develoed which uses the supercritical carbon dioxide facilitates solvent
free process with the mechanism which is similar to the conventional PTC mechanism.151

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Chapter 1 ‐ Introduction

Where as in a technique called as Capsule membrane PTC the catalysts were grafted onto
the surface of a porous capsule membranes to achieve maximum reaction output. 152-154

1.11.3 General mechanism of S-L PTC

They depend on the location and mechanism of ion exchange reaction and on the
solubility of solid in the organic phase. Two general mechanisms for S-L PTC are
proposed as the homogeneous and heterogeneous solubilization mechanisms.155, 156

Melville and Goddard 157, 158 proposed a conceptual solubilization models for S–L PTC159-
171
.

1.11.4 Homogeneous solubilization172-176

Schematic representation of homogeneous solubilization is shown in figure 1.7.

The steps involved in S-L PTC can be highlighted as,177-184

1. The dissolution of the inorganic reactant in the organic reaction phase

2. Ion exchange of the PTC in the liquid phase with dissolved reactant.

3. Ion exchange of the PTC to give product

Figure 1.7 - Homogeneous PTC mechanism.

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Chapter 1 ‐ Introduction

1.11.5 Heterogeneous solubilization185-189

Figure 1.8 - Heterogeneous solubilization mechanism.

The heterogeneous solublization route mainly differs from homogeneous

solublization in terms of solubility of one of the reactant species involved in the

reactionand the literature reported kinetic models were found to be valid variety of

chemical transformations.190-195 The schematic representation of the heterogeneous

solubilization mechanism is shown in figure 1.8.

1.11.6 Interfacial catalysis

From thermodynamic and kinetic principles, the interface between two immiscible

liquids can have catalytic properties for interfacial charge-transfer reactions. The interface

of two immiscible liquids has been widely used for the fundamental processes of

photosynthesis,196-200 biocatalysis,201 membrane fusion,202 - 204

ion pumping,205-208 and

electron transport reactions.209 It is also possible to shift the redox potential scale in a

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Chapter 1 ‐ Introduction

desired direction by selecting appropriate solvents, thereby permitting reactions to occur

that are highly unfavorable in a homogeneous phase.

The kinetic mechanism underlying the catalytic properties of the liquid/liquid

interface was discussed first by Kharkats and Volkov210, 211 as they introduced a new term

‘‘interfacial catalysis.’’ Bell212 conducted the first experiments on multielectron redox

reactions at the interface between two immiscible liquids such as, the oxidation of

benzoyl-o-toluidide in benzene solution to benzoyl anthranilic acid by a neutral aqueous

solution of potassium permanganate.213 - 218

A system of two immiscible liquids can form six types of structures, as shown in

Figure 1.9.

Figure 1.9 - Various types of structure arising in the oil/water system.

The transitions from one structure to another can occur if concentrations of

surface-active compounds or electrolyte are varied, or if components of the system are

altered by chemical reactions. In the present work we have studied the catalytic potential

of o/w emulsion interface for condensation reaction at ambient conditions.

Danel et al reported the rapid synthesis of amphiphilic sucrose ethers from 1, 2

epoxydodecane and 1, 2 epoxydodecan-3-ol in solvent-water emulsion system than in

Dimethyl sulfoxide (DMSO) alone.219

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Chaudhari et al reported the hydroformylation of 1-octene using a rhodium-based

catalyst and promoter ligand PPh3 in the organic phase with rate enhancement by a factor

of 10-50. Such enhancement of interfacial catalysis in a biphasic system using catalyst-

binding ligands overcomes the problem of catalyst separation in case of homogeneous

catalysis.220

Boyer et al reported excellent influence of surfactant concentration on chalcone

epoxidation using H2O2 in water / heptane system and discussed the two competitive

catalytic processes as, an Inverse Phase Transfer Catalysis (IPTC) and Interfacial

Catalysis (IC).221

Beattie et al reported acceleration in organic reactions when conducted in aqueous

emulsions by the phenomenon such as the protonation of a substrate by water, driven by

the strong adsorption of hydroxide ions at aqueous interfaces with oils.222

Simonyan et al reported an increase in rate by almost two orders of magnitude for

Michael condensation of lipophilic butyl acrylate and hydrophilic diethylamine in

water/heptanes system in presence of catalytic quantity of surfactant.223

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1.12 Statement of Objective

The development of nature based, energy efficient and environment friendly

techniques for formulation as well as synthesis of value added product has been a central

goal of current research in all aspects of chemical sciences and technology. In this

regards, emulsion formulations based on natural actives and efficient utilization of

surfactant as a catalyst are key techniques for achieving these objectives and to bring the

greener touch to the future chemistry.

Apart from development of newer synthetic moieties as an alternative to their

natural counterpart, the retuning and refining of the readily accessible feedstock to more

functionalized products is of particular importance. The increased awareness of customer

toward natural as well as nature based products is the prominently observed in last few

decades. The prime examples for such transformations are nature based cosmeceuticals,

dietary supplements, germ and pest controlling formulations, etc. Such products are found

to be superior in activity and free from adverse effects of their synthetic counterparts.

Hence, nature based formulations with minimum processing cost keeps an excellent

market as well as commercialization potential. In this context well attained nature based

emulsion delivery systems show following added benefits.

 No requirement of sophisticated equipment.

 Easy formulation technique and low cost.

 Excellent aesthetic attributes.

 Better controlled release property and pharmaco-dynamic activity.

 Stability towards air and humidity.

The present work is a prolific attempt to demonstrate our contribution to the area

of “Vegetable Oil Emulsification” using environmentally acceptable protocols using all

possible cheaper processing methodology keeping the end user sophistication in mind.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 69

Chapter 1 ‐ Introduction

The main theme of research work was the development of vegetable oil based task

specific emulsions, novel and greener catalytic methods for the synthesis of commercial

agrochemicals and their novel homologues.

In another aspect of our research we have demonstrated the efficient, highly

selective and accelerated synthesis of using a blend of non-ionic surfactants instead of

conventional catalyst system comprising of quaternary ammonium salts and sterically

hindered expensive amine derivatives. Also, the hydrolysis prone synthesis route of

chlorpyrifos methyl was converted from L-L PTC to efficient and selective S-L PTC and

validated by developing novel kinetic model.

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Chapter 1 ‐ Introduction

1.13Work done is summarized as follows

Chapter Title Constituents oil Surfactants Application
No. (HLB No.)
2. Effect of CMC-Na on Alomnd oil (6.5) Span 80 and Viscosity
the Rheological Tween 80 dependence
Properties of Almond on c(CMC-
Oil in Water Na) and
Emulsions obtained by temperature.
Required HLB
Method.
3. Formulation, Rheology Almond (6.2) Glycerol Low fat food
and Hypolepidemic Safflower (6) monostearate
Activity of Vegetable Soyabean (6) and
Oil based Egg-less and Mustard (6.3) Soyalecithin
Low Fat Food
Emulsions.
4. Formulation and Almond (6.5) Span 80 and Skin care and
Rheology of Vegetable Safflower (7) Tween 80 moisturizing
Oil-based Palm (7.5)
Cosmeceutical Cream
Bases.
5. Storage Stable O/W Karanj (8) Nonyl Phenol 13 Biopesticide
Emulsions of Karanj, Castor (14) and
Castor and Neem Oil Neem (13) Span 80
for Pesticide
Applications.
6. Greener and Selective - Span 20, 40, 60, Interfacially
Chlorpyrifos Synthesis 65, 80,85 and catalyzed
via Interfacial Tween 20, process
Catalysis. 40,60,80
7. Mathematical Model - BTMAC, TEAB, Solid-Liquid
for Solid-Liquid Phase CDMAB, CPB, phase
Transfer Catalyzed HDTMAB transfer
Chlorpyrifos Methyl process.
Synthesis.

Studies in Mixed Surfactant Systems and Vegetable oil Emulsions 71