EMULSIONS
by Ali K. Alobaidy
EMULSIONS
• An emulsion is a dispersion in which the dispersed
phase is composed of small globules of a liquid
distributed throughout a vehicle in which it is
immiscible.
• In emulsion terminology, the dispersed phase is the
internal phase, and the dispersion medium is the
external or continuous phase.
:Types of emulsions
1. O/W emulsions: in this type the oil droplets (internal
phase) are dispersed throughout the aqueous phase
(external phase).
2. W/O emulsions: in which the water (internal phase) is
dispersed throughout the oil phase (external phase).
Factors that affect the type
:of emulsions
1. The ratio of phases or relative phase volume:
This means the phase in small volume will be the dispersed phase
while the phase present in large volume is called the dispersion
medium.
2. Emulsifying agent (EA):
It is very important to keep emulsion stability. Most of emulsifying
agents prefer one type of emulsion, like acacia prefer o/w emulsion.
3. Order of mixing or method of preparation.
• Note : The type of emulsion depend on the solubility of EA in the
external phase.
Tests for identification of
emulsion type
1. Miscibility test: In this test the emulsion is mixed with a liquid
that is miscible with the continuous phase.
• e.g. Dilution of emulsion with water, if no destruction occurs,
this indicates its o/w, while if destruction occurs, this means the
emulsion is w/o.
2. Conductivity test: Emulsions with aqueous continuous phase will
readily conduct electricity, while emulsions with oily continuous
phase will not.
3. Staining test: In this test we use water soluble dye. If the
continuous phase is colored , this means that the emulsion is o/w
emulsion.
Requirement for good emulsion
1. All equipment used must be clean and dry.
2. A primary emulsion should be prepared first, which is thick, stable
emulsion.
3. A suitable emulsifying agent should be chosen.
4. All water-soluble components should be dissolved in part of water
forming an aqueous phase. Also, all oil soluble components should
dissolve in oil phase.
5. If there is any waxy material or semisolid surfactant, the phases
should be warmed and the temperature of the aqueous phase should be 2-
3 ºC above that of the oily phase to prevent crystallization of the waxy
material which will affect the stability of the emulsion.
6. Additives – like strong electrolytes may affect the stability of emulsion
so these should be added after finishing the primary emulsion to prevent
interaction with the emulsifying agent.
:Calculation of primary emulsions
• The amount of the emulsifying agent needed for preparation of
primary emulsion depend on the type and the amount of the oil
present in the prescription.
E.A .Ratio of Oil :Water :E.A
Fixed oil except Volatile oil and
liquid petrolatum liquid petrolatum
and linseed oil and linseed oil
Acacia or 3:2:1
4:2:1
2:2:1
Tragacanth
40:20:1 or 30:20:1
20:20:1
• Note: If more than one oil is to be incorporated, the quantity of
E.A for each is calculated separately and the sum of quantities
used.
• Examples of volatile :Examples of volatile and fixed oils:
Volatile oils (essential Fixed oils
oils)
Turpentine oil Castor oil
Clove oil Lard oil
Camphor oil Olive oil
Caraway oil Almond oil
Menthol Cod liver oil
Anethol Theobroma oil
Orange oil Cotton seed oil
Anise oil Linseed oil
Lemon oil Maize oil
Rose oil Sesame oil
Cinnamon oil Sunflower oil
Nutmeg oil
Thyme
Peppermint oil
Sandal wood oil
Terebene
Methods of preparation of emulsions
A.Dry gum method
B.Wet gum method
C.Nascent soap method
D.Electrical method (Using electrical
homogenizers)
Dry gum method
1. Measure the oil in a dry measuring cylinder.
2. Triturate the oil with acacia powder in a dry mortar.
3. Measure water for primary emulsion and immediately add all of
the water and stir continuously and vigorously (in the same
direction) until the mixture thickens and the primary emulsion is
formed. This is characterized by crackling sound.
4. Gradually dilute the primary emulsion with small volumes of the
vehicle.
5. Gradually add any other ingredients.
6. Transfer to a measuring cylinder and make up to a final volume
with the vehicle.
Wet gum method
• 1. Water is added to the acacia gum and quickly triturated until
the gum dissolve, to make mucilage.
• 2. Oil is added to this mucilage in small portions drop by drop,
triturating the mixture thoroughly after each addition (in the same
direction) until a thick primary emulsion is obtained.
• 3. Gradually dilute the primary emulsion with small volumes of
the vehicle.
• 4. Gradually add any other ingredient.
• 5. Transfer to a measuring cylinder and make up to final volume
with the vehicle.
Differences between wet and
dry gum method
• Emulsifying agent is mixed with the oil in dry gum method while
it is mixed with water in wet gum method.
• The addition of water will be all at once in dry gum method,
while the oil is added drop by drop in wet method.
• The crackling sound is heard higher in wet method than in dry
method.
Nascent soap method (Bottle method)
• This method involves placing the oil phase with an
equal amount of alkali solution (NaOH, KOH,
Mg(OH)2) in a suitable bottle that is closed firmly,
and mixture is shaken vigorously, a reaction takes
place between the free fatty acids in oil and alkali
solution that will form the emulsifying agent which is
the soap (nascent soap).
• Notes:
• Nascent soap method requires an oil rich in free fatty acids as
olive oil or linseed oil.
• The type of emulsion produced by nascent soap method
depend on the type of alkali.
• FFA + NaOH = monovalent soap (Form o/w emulsion)
• FFA + Mg (OH)2 = Polyvalent soap (Form w/o emulsion)
Rx1
Castor oil 20 ml
Acacia Q.S.
Water Q.S. 40 ml
Calculations:
Oil= 20 ml
Water= 2/4 *20= 10 ml
Acacia= 1/4 *20 = 5 g
Rx2
Oil of turpentine fƷii
Purified water Q.S. f ℥i
Ft. emulsion
Sig. as directed
Calculations (primary emulsion)
1 fƷ (fluidrachm) = 4 ml
2*4= 8 ml oil of turpentine
½ *8 = 4 g acacia
Amount of water =8 ml
Note: Oil of turpentine is rubefacient for muscle spasm.
Rx3
Castor oil fƷii
Bismuth carbonate gr x
Purified water Q.S. f℥ i
Ft. emulsion
Sig. f℥ss o.n
Calculations (primary emulsion)
2*4 = 8 ml of oil
¼ *8 = 2 g of acacia
½ *8 = 4 ml of water
Notes:
• Castor oil is used internally as cathartic and externally as emollient.
• Bismuth carbonate is used for mild irritant skin, duodenal ulcer.
• Bismuth carbonate (insoluble diffusible solid) is added or spread on
the surface of the primary emulsion with continuous trituration.
Rx4
Almond oil fƷii
Ferric ammonium citrate gr x
Water Q.S. f℥i
Ft. emulsion
Calculations (primary emulsion)
2*4= 8ml of oil
¼ *8 =2 g acacia
1/2 *8 = 4 ml water
Method:
Put the acacia in dry mortar then add oil phase all at once with trituration, then add water at
once with trituration until you have a crackling sound of primary emulsion, dissolve ferric
ammonium citrate in part of water to get a solution then add the remaining water or dilution
(gradually also with trituration then add ferric solution gradually also with trituration)
Notes:
• Almond oil is used as nutritive.
• Ferric ammonium is used for iron deficiency anemia.
• This prescription is used as tonic.
Rx5
Oil of turpentine fƷ i
Arachis oil fƷ i
Purified water Q.S. f℥ I
Calculations (primary emulsion)
1*4= 4 ml of each oil
½ *4 = 2 g acacia for oil of turpentine
¼ *4 = 1 g acacia for arachis oil
Total amount of acacia = 3 g
½ * 4 = 2 ml water (for arachis oil)
1*4 = 4 ml water (for oil of turpentine)
Total amount of water = 6 ml
Notes:
• Turpentine oil is used as emollient and counterirritant.
• Almond oil is used as emollient and nutrient.
Rx 6
Castor oil 10 ml
Oleic acid 5 ml
Ca(OH)2 q.s 30 ml
Ft. emulsion
Procedure:
By nascent soap method
Ca(OH)2+ oleic acid = Ca oleate (E.A.) to prepare w/o emulsion
Rx7
Liquid paraffin 10 ml
Oleic acid 5 ml
Sodium hydroxide Q.S. 30 ml
Ft. Emulsion
Procedure:
We take 10 of liquid paraffin with 5 ml of oleic acid with 15 ml sodium
hydroxide in a bottle, then we shake for few seconds and an emulsion is
formed.
Notes:
• Sodium hydroxide with oleic acid leads to formation of sodium oleate
(soap) which is the emulsifying agent and will form o/w emulsion.
• Liquid paraffin used internally as a laxative and externally as emollient to
the skin.
Concentrated Peppermint emulsion
Rx8
Peppermint oil 20 ml
Polysorbate 20(tween 20) 1ml
Double strength chloroform water 500 ml
Purified water Q.s. 1000 ml
Ft. emulsion
M.ft. 50 ml
Procedure:
1. Shake the peppermint oil with polysorbate 20
2. Gradually add double strength chloroform water and shake
well after each addition.
3. Add sufficient water to produce 1000 ml.
HLB System
• The most important property for the effective emulsifying agent is
to undergo strong adsorption at the interface between oil and
aqueous phase. This requires a good balance between the
hydrophilic and hydrophobic properties in the molecule and this
value is called the (HLB value).
• The HLB value has been expressed as numerical scale that
extends from (1 to 50) but practically the values are taken from (1
to 18).
• 8-16 → ↑HLB →↑ Hydrophilicity → ↑miscibility with water
→ o/w
• 3-6 → ↓ HLB → ↑ Lipophilicity → ↓ miscibility with water
→ w/o
Required HLB
• Is the HLB that must be provided by emulsifying agent to
produce a stable emulsion for a specific oil and each oil has two
required HLB once for w/o and for o/w emulsion.
• The required HLB value may vary according to:
• 1. Source of the material.
• 2. Required concentration.
• 3. Method of preparation.
Rx9
Mineral oil 25 g
E.A. (span 80 + tween 80) 2g
Preservative 0.2 g
Purified water q.s. 100 g
The required HLB for the mineral oil = 11 and the HLB for span 80 = 4.3 and
the HLB for tween 80 = 15
How much span 80 and tween 80 required to produce a stable emulsion?
FS * HLB s + FT * HLB T = required HLB of the oil
Let fraction of span =X
Let fraction of tween = 1-X
X*4.3 + (1-X)*15 = 11
10.7 X= 4
X= 0.37 fraction of span
Amount of span = 2 g * 0.37 = 0.74 g
1-X = 0.63 fraction of tween
Amount of tween = 2* 0.63 = 1.26 g
Rx10
Petrolatum 25 g
Cetyl alcohol 20 g
E.A. (S+T) 2g
Preservative 0.2 g
Purified water 100 g
Percent of oil in oil phase Fraction of oil
25/45 *100 = 56%0.56
20/45 *100 = 44%0.44
The required HLB for petrolatum = 8
The required HLB for cetyl alcohol =15
F oil 1 * required HLBfor oil 1+ F oil 2 * required HLBfor oil 2 = HLB oil phase
0.56*8 +0.44 *15 =11.08
Let fraction of span =X and fraction of tween = 1-X
Fs *HLBs +FT *HLB T = HLB oil
X *4.3 + (1-X)*15 =11.08
Fraction of span = X = 0.366 and amount of span = 0.73 g
Fraction of tween = 1-X= 0.634 and amount of tween = 1.26 g
• Notes:
• The advantages of mixing the emulsifying agent:
1. Provide the proper HLB
e.g: Lecithin → o/w E.A.
cholesterol → w/o E.A.
Mixing them in certain ratio gives either emulsion.
• 2. To establish stable film at the interface. e.g: Na oleate
emulsion is improved by addition of cetyl alcohol.
• 3. Give the required consistency. e.g: Addition of the thickening
agent to prevent the creaming in acacia emulsion.
Rx11
Liquid paraffin 35 g
Wool fat 1g
Cetyl alcohol 1g
Emulgent 7g
Water 100 g
HLB of liquid paraffin = 12
HLB of wool fat = 10
HLB of cetyl alcohol = 15
35+ 1+1= 37 g of oil phase
35/37 *100 = 94% w/w of liquid paraffin
1/37 *100 = 2.7% w/w of wool fat
1/37 *100 = 2.7% w/w of cetyl alcohol
0.94 *12 + 0.027*10 + 0.027*15 =12.1 required HLB for the oil phase
HLB of span 80 = 4.3
HLB of tween 80 = 15
Suppose that the fraction of span = X
Fraction of tween =1-X
4.3 *X + 15 (1-X) = 12.1
X =0.27 fraction of span
7* 0.27 =1.89 g amount of span
1-0.27 = 0.73 fraction of tween
7 *0.73 = 5.11g amount of tween
Procedure
1. Mix the liquid paraffin with wool fat with cetyl alcohol and span. Heat the mixture on water bath at 70 ºC.
2. Mix water and tween, heat the mixture on water bath at 75ºC.
3. Add the oil phase to water phase gradually with mixing using stirrer.
4. Transfer to suitable bottle.
