EMULSIFIERS – DEFINITION, CLASSIFICATION,

PROPERTIES, MECHANISM OF ACTION AND

APPLICATIONS PERMITTED LEVELS AND TOXIC
EFFECTS
INTRODUCTION
 Food products are generally multiphase systems in which
solids, liquids and air are finely distributed during
manufacture to give the finished products the desired
structure and shelf life.
 As many of these phases are not miscible, substances
required to facilitate phase distribution during manufacture
and particularly to ensure stability and prevent separation
during storage.
 Emulsifiers are used for this purpose because of their
amphiphillic molecular structure they are deposited at the
phase interface and help to stabilize the phases
EMULSIFICATION
 Oil and water produce emulsion by stirring, however, the
emulsion starts to break down immediately after stirring is
stopped.
 The purpose of emulsification is to stabilize emulsion state by
preventing break down which occurs due to creaming
aggregation and coalescence.
 To solve these issues, decreasing size of dispersed particles,
reducing the density different of dispersion and protecting the
surface of oil droplets are effective.
 There are two types of emulsion, O/W emulsion or oil droplets
in water, which can be found in ice cream and or milk, and
W/O emulsion or water droplets in oil, found in butter and
margarine.
DEFINITION

 A food emulsifier, also called an emulgent, is a surface-active

agent that acts as a border between two immiscible liquids
such as oil and water, allowing them to be blended into stable
emulsions.
 Emulsifiers also reduce stickiness, control crystallization and
prevent separation.

These multiple type emulsions not only make low calorie items
such as cream which contain less oil, but also stabilize the
emulsion by dissolving the unstable substance present in the
deepest region of water droplets. Taste can also be enhanced by
injecting seasonings and flavors into the water droplets.
• Emulsifiers create two types of emulsions: either droplets of oil
dispersed in water or droplets of water dispersed in oil.
• Within the emulsion, there is a continuous and dispersed phase. In
an oil-in-water emulsion, the continuous phase is the water and the
dispersed phase is the oil; conversely, in a water-in-oil emulsion,
the oil is the continuous phase.
 The emulsifier molecule has at least one group with polar
affinity (hydrophilic range) and one group with non polar
affinity.
 With food emulsifiers the lipophilic range consist almost
exclusively of edible fatty acids, while the hydrophilic, water
soluble range can be extremely varied.
 Apart from glycerol and condensed polyglycerol, there is
propylene glycol, sorbitol, sucrose or lactic acid with
hydroxyl groups and form esters with fatty acids.
 Through a subsequent reaction by the esters with organic
acids like acetic, citric or tartaric acid or phosphoric acid, the
hydrophilic component of the emulsifier can be further
increased. The hydrophilic effect can also be improved
through neutralization of the free acid group with Na/K/Ca
salts.
MECHANISM OF ACTION OF EMULSIFIERS
 The presence of hydrophilic and lipophilic groups in the
molecule, emulsifiers interact with water as well as with fats
and oils.
 The emulsifier is oriented at the phase interface with the
hydrophilic component going toward the water and the
lipophilic component toward the oil.
 This causes a monomolecular film formation which increases
the surface area and the interfacial tensions.
 The interfacial tensions can be greatly reduced by the
emulsifiers. Depending on the ratio of hydrophilic and
lipophilic components, the emulsifier is more readily soluble
in one or other of the phase.
FUNCTIONS OF EMULSIFIER
Dispersion
 Water-insoluble fine powder like cocoa is difficult to disperse
because small lumps tend to form on the surface of interface.
Powders gradually aggregate and precipitate even after
dispersing by shaking. Maintaining suspension of water-
insoluble fine powder is called dispersion. When the dispersing
material is liquid, we call it emulsion.
 Cocoa is produced by dispersing cocoa powders in water (O/W
type emulsion), while chocolate is made by dispersing them in
oil (W/O type emulsion).
Foaming
 Foaming ability is one of the major characteristics of
emulsifiers. When a solution containing an emulsifier is
stirred, the emulsifier is adsorbed on the surface of the
produced foam to make a mono-molecular layer and the foam
outside of the solution makes a bimolecular layer of the
emulsifier.
 The film coating a bubble is about 100 times thicker than a
bimolecular layer, but a bubble breaks off as soon as migration
of liquid trapped between bimolecular films occurs.
 The addition of emulsifier enables foaming and stabilizes
emulsion state of products, thus, smooth texture and expanded
volume can be obtained.
 Typically, emulsifier for ability above is used for cakes, ice
cream, moose, whipped topping, etc.
Anti-foaming / Defoaming
 Emulsifier also has anti-foaming and defoaming ability. Anti-
foaming or defoaming agents are used in food production
where undesirable foaming may occur in the presence of
protein, starch etc.
 Anti-Foaming/Defoaming Agents Characteristics:

water insoluble
• floatable on the surface because of its small specific gravity
• small surface tension and easy spreading on liquid surface
 These characteristics lower the surface tension, and the foam
will get thinner. As these agents spread on the liquid surface,
all foam will be diminished.
W ater

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CATEGORIES OF FOOD EMULSIONS

 Lecithin and lecithin derivatives

 Glycerol fatty acid esters

 Hydroxy carboxylic acid and fatty acid esters

 Lactylate fatty acid esters

 Polyglycerol fatty acid esters

 Ethylene or propylene glycol fatty acid esters

 Sorbit*an fatty acid esters

 Miscellaneous derivatives
LECITHIN
 It is one of the widely used emulsifiers is lecithin which is
found in milk, egg and soya bean.
 Lecithin keeps in milk the butter fat and water phases more or
less uniform.
 Commercial vegetable lecithin is obtained principally from
soya bean which has about 1 to 3% of it.
 The term Lecithin is used to describe both phosphatidlycholine
and mixtures of phospholipids.
 Lecithin is employed in the preparation of cocoa butter and
chocolate candy.
 The texture and keeping qualities of bread and other fermented
baking products are improved by the use of lecithin.
 It is an effective emulsifying agent in combination with mono
glyceryl stearate and ascorbic acid.
 A number of mono and diglycerides and their derivative are
good emulsifying agents.
 In these cases, the ester groups make the molecule fat
soluble, which the alcohol group lends water solubility to
another portion of the molecule.
 As a result, the molecule can serve as a bridge to keep fat
molecules suspended in water.
 Synthetic Emulsifiers: There are about 1, 50,000 – 2, 00,000
of emulsifiers of which mono, diglycerides and their
derivatives account for the largest part i.e., about 75%.
 Ex: Di acetyl tartaric acid ester of monoglyceride (DATEM),
Sorbitol monostearate, Sorbitol tristearate, Stearyl
monoglyceride, Sodium oleate and Potassium oleate
EMULSIFIER EFFECT ON EMULSION FORMATION

 Polar or water soluble emulsifiers form an oil in water

emulsion, while non polar oil soluble emulsifiers form a
water in oil emulsion.
 One of the main criteria when selecting an emulsifier is thus
the HLB (Hydrophilic - Lipophilic Balance), which indicates
the relationship between the hydrophilic and lipophilic
components.
 Emulsifiers are also employed to exploit the interaction
between fats, proteins and carbohydrates as they produce
many beneficial effects.
EMULSIFIER - LIPID INTERACTION
 Triglycerides can occur in different crystal forms. When
melted fat cools, the alpha form occurs initially giving the
product a waxy structure.
 Through slow cooling the major beta form occurs. Its
microscopy reveals crystalline clusters.
 It is most stable form for some fats, other fats can transform
into block shaped beta crystals of 75 ± 25 mm size imparting
the food product an unwelcomed sandy texture.
 Thus due to different crystalline forms, the organolepticity
differs.
 Fat containing whipped desserts, ice creams and pastries
require no alpha and beta crystals for stability.
 Lipophilic emulsifiers with low HLB value usually inhibit or
decelerate the formation of stable beta forms.
 In margarines, diglycerides delay the crystalline growth of
fats, in chocolates sorbitan tristearate slows down the fat
bloom.
 Emulsifier – carbohydrate interaction: Amylose can
crystallize out of the aqueous helix structure causing white
bread to go stale.
 The fatty acid remnant in many emulsifiers can have a
stabilizing effect by enclosing the helix structure, thereby
keeping the bread soft far longer.
 The emulsifier also binds water soluble starch and improves
the texture of starchy products like noodles or mashed
potatoes.
 Emulsifier – protein interaction: The hydrophilic
component of emulsifier can interact with proteins as a result
of ionic charges or through hydrogen bridges, thereby
improving the structure of many food products.
 In yeast risen baked goods, the gas retaining capability of the
wheat gluten is improved making far better volume and
crumb structure.
EMULSION
 An emulsion can also be defined as a heterogeneous system
consisting of one immiscible liquid intimately dispersed in another
in the form of drop lets whose diameter in general exceeds 0.1 µ.
 Food emulsions should have the appropriate appearance (color and
opacity), texture (viscosity, plasticity and oiliness) and flavour for
acceptance.
 Visual appearance of an emulsion depends on the droplet diameter.
 Food emulsions are important for food quality as oil in water
emulsion helps the incorporation of fat soluble flavoring and
coloring matter or vitamins.
 The opacity of a fluid product can be created by dispersing droplets
of very small size (0.05 to 1.0 µ) in the continuous phase.
 A high degree of plasticity can be achieved by raising the
concentration of the dispersed liquid to about 60% or above. Oil
can be introduced into a system without imparting an oily sensation.
 Formation of emulsion: The most common method of
preparing an emulsion is by mechanically dispersing one
liquid phase in another.
 Formation of small droplets takes place from a beater blade
or from passage of the coarse emulsion through a
homogenizer.
 A stable emulsion is not formed by a mere mixing of the
liquids. When the emulsion is left to stand, droplets in the
dispersed phase coalesce due to surface tension.
 An emulsifier added to the system would reduce the
interfacial tension, enhance the formation of small droplets
and reduce the rate at which the droplets coalesce.
 Properties of emulsions: The opacity of an emulsion is
determined by the droplet size, droplet concentration and
difference in the refractive indices of the two phases.
 An emulsion is transparent when the refractive indices of two
liquids are the same or when the droplet diameter is 0.05 µ or
less.
 An increase in the size of the droplets results in opaqueness
which reaches a maximum when the size is 0.05 to 1.0 µ.
 The sedimentation rate depends on the droplet diameter and
hence micro droplets are more stable.
 The viscosity of the continuous phase is a major factor in
governing the properties of an emulsion.
 In many food emulsions, gums are added to continuous phase
to enhance the viscosity and stability of the emulsion.
 Gum stabilizes an emulsion by being absorbed at the oil-water
interface to form a hydrated film and by increasing the
viscosity of the continuous phase.
 When the volume of the dispersed phase exceeds 74% of the
emulsion, the droplets are distorted and the emulsion has high
degree of plasticity.
MECHANISM OF EMULSION DESTABILIZATION
 Emulsion destabilization can be due to one or more of the five
possible mechanisms –
 Flocculation: The adherence of droplets to form aggregates or
clusters and the buildup of these aggregates is referred to as
flocculation. It occurs when the attractive forces between
droplets exceeds that of the repulsive forces without a
breakdown in the structural integrity of the interfacial film
surrounding the droplets.
 Coalescence: When aggregates or flocculants of the dispersed
phase combine to form a single and large drop, the
phenomenon is referred to as coalescence. It reflects the
nature of the interfacial film on the surface of the droplets. A
strong and stable film on the surface of the droplet due to the
addition of correct concentration of the appropriate emulsifier
will minimize this destabilization.
 Changes in droplet concentration: Droplet concentration can
increase preferentially in either the top or bottom portion of the
emulsion depending on the relative density of the two phases.
Reducing the average droplet size and adding an emulsifier will
substantially reduce the rate at which this phenomenon occurs in
foods.
 Ostwald ripening: If the two phases forming the emulsion are not
totally immiscible and there are differences in the droplet size
within the emulsion, larger droplets will form at the expense of
smaller droplets due the process called Ostwald ripening. The
driving force of Ostwald ripening is the difference in the chemical
potential between droplets of difference sizes.
 Phase inversion: The viscosity of an emulsion will gradually
increase as more and more of given phase is added until critical
volume is reached. If more of the same phased is added,
exceeding the critical volume, the emulsion will invert – that is,
the discontinuous phase will become the continuous phase.
 CMC (Critical Micelle Concentration):
 CMC is a function of emulsifier concentration above which
the emulsifier aggregates, reversibly to give spherical micelle,
changing surface tension slightly.
 CMC is a characteristic value of the emulsifiers which
decreases as the hydrophobic part of the molecule increases.
It is generally influenced by temperature, pH and electrolytic
imbalance.
 The temperature at which the solubility of an emulsifier
reaches the CMC is called critical micelle temperature (T c).
 Crystals, micelles and the dissolved emulsifiers are in
equilibrium at the Tc and an emulsifier cannot form micelles
below the Tc.
 Emulsifiers are lyotrophic mesomorphs depending on water
content and temperature.
FUNCTION OF EMULSIFIER
Functions Products
Emulsification, water in oil emulsion Dressings, margarine
Emulsification, oil in water emulsion Mayonnaise
Control viscosity Molten chocolate
Aeration and Whippability Whipped toppings
Inhibition of fat crystallization Ice creams, margarine, candies
Improved wetting ability Instant soups
Inhibition of sugar crystallization Panned coatings
Softening Candies
Fat stabilizer Food oils
Antispattering agent Margarine, frying oils
Antisticking agent Caramel candy
FUNCTION OF EMULSIFIER
Functions Products
Foam prevention Jam
Foaming Pastries, ice creams, desserts
Freeze thaw stability Whipped toppings
Defoaming agent Sugar production
Lubrication Extruded products, separators
Protein interaction, improvement of loaf volume, Bread
reduction of shortening requirement and antistaling
Dough conditioner Bread dough
Protective coating Fresh fruits and vegetables
Surfactant Molasses
Stabilization of flavor oils Flavor emulsion
Humectant and Plasticizer Cake icings
Promotion of ‘dryness’ Ice cream
Solubilization Flavorings, drinks
Splash protection Margarine
Starch complexing Bread, noodles, instant potatoes
Thickening Nut pastes
Viscosity reduction Chocolates
Wetting Soups