Analysis of Emulsifiers: Prafulla Kumar Sahu Alliance Institute of Advanced Pharmaceutical and Health Sciences

Analysis of Emulsifiers
Prafulla Kumar Sahu

Alliance Institute of advanced Pharmaceutical and
Health Sciences
Emulsifiers
• Emulsifiers are the surface-active substances
that act at the surface between two media,
e.g. water and oil.
• They might be said to be schizophrenic
molecules in that they are simultaneously
lipophilic and hydrophilic to varying degrees.
Emulsion
• Heterogenous systems of one liquid dispersed
throughout another in the form of droplets
usually exceeding 0.1 micrometre in diameter
• Compositions
– Internal/Discontinuous/Dispersed phase
– External/Continuous phase
– Emulsifying agent
Emulsion Types
1. Oil-in-water (O/W)
2. Water-in-oil (W/O)
3. Water-in-oil-in-water (W/O/W)
4. Oil-in-water-in-oil (O/W/O)
Determination of Emulsion Types
• By phase ratio between oil and water phase
• By order of addition
– slowly add oil into water  O/W
• By type of emulsifier
– Phase that the emulsifier is soluble will most
probably be continuous phase
Tests for Identification of
Emulsion Types
• Dilution test:
– Emulsion can be diluted only with external phase
• Dye test:
• COCl2/filter paper test:
– Filter paper impregnated with COCl 2 and dried (blue)
changes to pink when O/W emulsion is added
• Fluorescence:
– Oils fluoresce under UV light
• Conductivity: (for ionic O/W emulsions)
– O/W emulsions conduct electric current
Emulsion Theory
To explain how emulsifying agents act in promoting
emulsification and in maintaining the stability of
the resulting emulsion
• Surface tension theory (important in initial
formation)
– The force causing each liquid to resist breaking up
into smaller particle is called interfacial tension.
Surfactants promote the lowering of this resistance
• Surface orientation theory
– Emulsifying agent having a greater hydrophilic
character than hydrophobic character will promote an
o/w emulsion
Emulsion Theory
• Plastic or interfacial film theory
– Emulsifying agent surrounding the droplets of the
internal phase as a thin layer of film adsorbed on
the surface of the droplets, prevent the contact
and coalescing of the internal phase
• Rate of coalescence theory
• Phase volume theory
Mechanism
• To form droplets
– surface free energy or surface tension
– system at its lowest free energy is
thermodynamically stable
– emulsions are not thermodynamically stable
• To stabilize droplets (by surfactants or
polymers)
– by reducing the interfacial tension
– by packing of the emulsifier molecules
Emulsifying agents
• must be present at the interface to prevent
coalescence of the internal phase:
1. To reduce the interfacial tension
2. To be interfacial barrier (most influence on
emulsion stability)
– increase viscosity of continuous phase
– energy barrier
• the electric double layer
• the steric repulsion from absorbed polymer
Fact of Emulsifying Agents
• Structure
• Reside at interface
• When the concentration is increased in excess of
CMC (the critical micellization concentration),
micelles is formed
Properties
1. Compatible with the other ingredients
2. Not interfere with the stability or efficacy of
the therapeutic agent
3. Stable and not deteriorate in the preparation
4. Nontoxic
5. Little odor, taste or color
6. Promote emulsification and to maintain the
stability
Emulsifier Classification
• According to ionic composed of an organic
lipophilic group (surface active portion)
• Synthetic and semisynthetic surfactants
– Anionic
– Cationic
– Nonionic
– Amphoteric
• Naturally occurring materials and their
derivativrs
Anionic Surfactants
• Soaps
– Fatty acid + Base  Soaps
– O/W emulsions
– in acidic condition  precipitated FFA
– external use
– combination of soap (TEA stearate) with an oil-soluble
auxiliary emulsifier (cetyl alcohol)  o/w mixed emulsifer
– incompatible with polyvalent cations
– Soap of di/trivalent metal
Cal oleate  W/O emulsions
– Amine soaps: N(CH2CH2OH)3
– neutral pH
– incompatible with acids and high concentration of
electrolytes
Anionic Surfactants
• Sulfated and sulfonated compound:
– SLS
stable over high pH range
o/w emulsions
• fairly resistant to divalent metal ions used in
combination with a nonionic oil-soluble
emulsifying agent or fatty alcohol to produce a
good emulsions
– sodium dioctylsulfosuccinate
– used as wetting agent
Cationic surfactants
• Quaternary ammonium compounds:
Cetyl trimethylammonium bromide
– (Cetrimide) CH3(CH2)15N+(CH3)3Br-
• Used with nonionic, oil-soluble auxiliary
emulsifiers
• Toxicity and irritancy
• Incompatible with anionic surfactants,
polyvalent anions and unstable at high pH
Nonionic surfactants
• Low toxicity and irritancy  oral, parenteral
• High degree of compatibility
• Less sensitive to change pH or to addition of

electrolytes
• Most of them are based on:

• Hydrophobic part: FA or alcohol (C12-18)
• Hydrophilic part: alcohol (-OH) and/or ethylene
oxide (-OCH2CH2)
• Glycol and glycerol esters
– Glyceryl monostearate (a polyhydric alcohol FA ester):
strongly hydrophobic material
produce w/o emulsions
– Self-emulsifying glycerol monostearate
Soap + glyceryl monooleate
diethylene glycol monostearate
propylene glycol monooleate
• Sorbitan esters
– the esterification of 1 or more of the hydroxyl
groups of sorbitan with either lauric, oleic,
palmitic or steraic acid
– tend to form w/o
– used with polysorbates to produce o/w or w/o
• Polysorbates (Tween)
– polyethylene glycol derivatives of the sorbitan ester
– variation in water solubility based on:
• type of FA
• the number of oxyethylene gr. in the polyethylene glycol
chains
– compatible with most anionic, cationic and nonionic
materials
– provide neutral pH and stable to the effects of heat,
pH change and high conc. of electrolytes
– low toxicity
– unpleasant taste
– form complex with preservatives
• Fatty alcohol polyglycol ethers
– condensation products of polyethylene glycol and
fatty alcohols : polyethylene glycol
: monocetyl ether (Cetomacrogol 1000)
– high water solubility
– stable over a wide pH range
– salted out by high conc. of electrolytes
– o/w emulsions (should used with oil-soluble auxiliary
emulsifier: Cetostearyl alcohol)
• Fatty acid polyglycol esters
– stearate esters or polyoxyl stearates
– i.e. polyoxyethylene 40 stearate (40 = the no. of
oxyethylene units)
water-soluble
used with stearyl alcohol to give o/w
• Poloxalkols
– polyoxyethylene/polyoxypropylene Copolymers
– used for i.v. fat emulsions
• Higher fatty alcohol
– saturated aliphatic monohydeic alcohols:
hexadecyl (cetyl), octadecyl (stearyl)
– used as auxiliary emulsifiers according to their
ability to increase viscosity
– i.e.
cetostearyl alcohol + SLS/  o/w
Cetrimide/
Cetomacrogol 1000
Amphoteric surfactants
• charge depending on the pH of the system
low pH  cationic
high pH  anionic
• i.e. lecithin: used to stabilize i.v. fat emulsion
Naturally Occurring Materials
and Their Derivatives
• Disadvantages:
– batch to batch variation
– susceptible to bacterial and mold growth
– susceptible to alcohol, electrolytes
• Polysaccharides
– i.e. acacia, tragacanth, sodium alginate anionic
– stabilize o/w (internal)
– forming a strong multimolecular film (hydrophilic
barrier) round oil globule
• Semisynthetic polysaccharides
– to reduce batch to batch variation
– as o/w emulsifiers or stabilizer
– i.e. MC (nonionic), CMC (anionic)
• Sterol-containing substance
– Beeswax: beeswax-borax
– Wool fat (anhydrous lanolin)
fatty alcohol with FA esters of cholesterol and
other sterols
form w/o
emollient property
water absorbing property
odor: require antioxidant
• Sterol-containing substance (cont.)
– polyoxyethylene lanolin derivatives
water soluble
o/w emulsifier
emollient property
– wool alcohol
cholesterol together with other alcohols
w/o emulsifier
no strong odor (but still require antioxidant)
– Protein substances
i.e. gelatin, egg yolk and casein
o/w emulsifier
gelatin; provide emulsion that is too fluid
Finely Divided Solids
• i.e. bentonite, aluminium magnesium silicate,
colloidal silicon dioxide
– forming a coherent film which physical prevents
coalescence of the dispersed globules
– if the particles are:
preferntially wetted by the aqueous phase 
o/w emulsion
preferntially wetted by the oil phase  w/o
emulsion
Analysis of Emulsifiers

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Analysis of Emulsifiers

Prafulla Kumar Sahu

• High degree of compatibility

• Less sensitive to change pH or to addition of

• Most of them are based on:

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