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Emulsions and
Surfactants

1 fine
Dispersed phase -> substance which is
dispersed as very particles

Dispersion - > substance

medium present in larger quantity

Disperse systems
T 101
G109
M 106
k 103
d 10-
C 10-2
M 10-3
-
M10
N 10-9

P 10-12 Tolloid : a mixture in which

of
one substance consisting
microscopically dispersed
insoluble particles is

suspended throughout another

substance

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Deptt of Pharmaceutics, COP, SAU, Al-

November 4, 2023 kharj

Deptt of Pharmaceutics, COP, SAU, Al-

November 4, 2023 kharj

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Deptt of Pharmaceutics, COP, SAU, Al-

November 4, 2023 kharj

Deptt of Pharmaceutics, COP, SAU, Al-

November 4, 2023 kharj

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[Link]
chemistry/[Link]

THEORY OF EMULSIFICATION

What happens when 2 immiscible liquids are agitated together?

One of the liquids is dispersed as small droplets in the other.
But after a while !
The liquids separate rapidly into
two clearly defined layers
WHY?
❑A fine dispersion of oil and water leads to an enormous
increase in the interfacial area.
❑This is associated by an increase in the interfacial free energy
also known as surface free energy.
❑This phenomenon leads to the system is thermodynamically
unstable.
❑The high interfacial free energy favors a reduction of
interfacial area by causing droplets to coalesce. Therefore
separation of phases takes place.

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Coalescence and breaking lead to large bodies of oil separating from
the water and essentially result in the emulsion separating
completely. To reverse this process the emulsion must be remade
and this will require a lot of energy. Emulsions are all
thermodynamically unstable, meaning that they will eventually
separate however, they can be stabilised and in some cases they
can remain intact indefinitely. Both coalescence and flocculation are
more likely if the surface energy between the two phases is high and
if the surface area to volume ratio is high (i.e. the oil droplets are very
small). However, emulsions of small droplets are easier to stabilise

making something
homogeneous (uniform in
composition)

Deptt of Pharmaceutics, COP, SAU, Al-

November 4, 2023 kharj

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CLASSIFICATION OF EMULSIONS
❑Based on nature of dispersed phase
➢Oil in Water (O/W): Oil droplets dispersed in water.
➢Water in Oil (W/O): Water droplets dispersed in oil.
❑Based on size of dispersed phase /droplets.
➢>1000 nm Macroemulsions
➢10 – 200 nm Microemulsions
❑Based on Number of dispersed phase: Multiple emulsion
❖W/o/w (water in oil in water): Small water droplets are enclosed
within larger oil droplets which are themselves then dispersed in
water
❖O/w/o (oil in water in oil): Small oil droplets are enclosed within
larger water droplets which are themselves then dispersed in oil
phase

Deptt of Pharmaceutics, COP, SAU, Al-

November 4, 2023 kharj

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THEORY OF EMULSIFICATION:
Emulsifier – The Stabilizer

Lipophilic Tail & Hydrophilic Head

Lipophilic tails align with oil

Hydrophilic heads align with water
Emulsifying agents stabilize emulsions by 3 mechanisms:
1. Reduction of interfacial tension.
2. Formation of a rigid interfacial film-
mechanical barrier to coalescence

3. Formation of an electric double layer-

electric barrier to approach of particles.

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THEORY OF EMULSIFICATION: How Emulsifier Work?

1. Reduction of interfacial tension.
2. Formation of a rigid interfacial film-mechanical barrier to
coalescence.
If the concentration of the emulsifier is high enough, it forms a
rigid film between the immiscible phases, which hinders
mechanically the coalescence of the emulsion droplets.
3. Formation of an electric double layer- electric barrier to coalescence

In case of an ionic surfactant, the

hydrocarbon tail is dissolved in the oil +
++
+
droplet, while the ionic heads are + +
facing the continuous aqueous phase. + +
++ +
+ +
As a result, the surface of the droplet is ++
charged. This creates a repulsive effect
between the oil droplets and thus
hinders coalescence.
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Emulsions in daily life

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Typical food emulsions

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Typical food emulsions

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Oil in Water – O/W

◼ Dispersed phase / Internal phase = OIL
◼ Dispersion medium/ continuous phase /External phase = WATER
◼ Advantages
◼ Easiest to formulate
◼ disperses more easily
◼ has consistent pH
◼ Least expensive
◼ Best feel – cooling effect
◼ Disadvantages
◼ Less oil delivered
◼ Not as effective for dry skin

◼ Not water-resistant
Examples: Hair conditioners, Sunscreen, vanishing cream, Wrinkle
Creams, Mayonnaise, milk, and cream.
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Water in Oil – W/O

Dispersed phase / Internal phase = WATER
Dispersion medium/ continuous phase /External phase=oil
◼ Advantages
◼ Waterproofing possible
◼ Most effective for dry skin

◼ Better stability

◼ Disadvantages
◼ Oily, tacky feel
◼ More expensive
Examples: COLD CREAMS

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Multiple Emulsions
◼ Multiple phases
◼ Oil in Water in Oil (O/W/O)
◼ Water in Oil in Water (W/O/W)
◼ Advantages
◼ More effective than Oil in Water
◼ Less greasy than Water in oil
◼ Time release, active delivery possible
◼ Disadvantages
◼ Difficult to manufacture
◼ Not always stable

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Formulation aspects:
Elements of the Formula
◼ Formula Components
◼ Oil Phase
◼ Hydrophobic materials: Oils, fats, lipids
◼ Affects viscosity, spread,

◼ Aqueous phase
◼ Extracts, colorants
◼ Humectants

◼ Thickeners

◼ Emulsifiers
◼ Holds it all together

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Destabilizing effects on emulsions

Ostwald ripening

❖ Coalescence – two drops merge into one.

❖ Flocculation – the small spheres of oil stick together to form clumps or flocs
which act as if they are larger drops.
❖ Creaming – difference in the density between the drop and the medium result
in concentration of drops in the top or bottom of the container.
❖ Breaking – combined coalescence and creaming, the two phases separate
completely forming a continuous layer.
❖ Ostwald ripening – diffusion of droplet’s molecules through the medium causes
small droplets to decrease in size and disappear while large
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Emulsion stabilizer agents

If oil and water are mixed and small oil
A. Surfactants (adsorbs strongly at the droplets are formed and dispersed
interface between two immiscible throughout the water, eventually the
droplets will coalesce to decrease the
phases) amount of energy in the system. However, if
solid particles are added to the mixture,
they will bind to the surface of the interface
B. Simple inorganic electrolytes (such as and prevent the droplets from coalescing
potassium thiocyanate KCNS) thus causing the emulsion to be more
stable.
These additives are believed to cover the
system in such a way that long loops and
C. Macromolecular stabilizers (proteins, tails extend out into solution.
polysaccharides and some synthetic
polymers)

D. Finely divided solids (adhere to the

interface due to surface energy
effects)

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Surfactants
❖ A surfactant (emulsifier) molecule consists of
water soluble hydrophilic part and water-
insoluble, oil-soluble lipophilic part within it.

❖ When a surfactant is added to a mixture of

water and oil, the surfactant is arranged on
the interface, anchoring its hydrophilic part
into water and its lipophilic part into oil.

❖ The hydrophilic part and the lipophilic part are

adsorbed and arranged around the interface.
The interfacial tension is reduced by the
emulsifier.
❖
That is, the force to separate the oil and water
is thus weakened, resulting in the easily mixing
of oil and water.
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Classification of surfactants
❖ Anionic – The surface-active portion bears a
negative charge
❖ Alkane carboxylic salts (soap)
❖ Alkane sulfonic salts (detergents)
❖ Alkyl-aromatic sulfonic salts
❖ Others: Phosphates, phosphoric salts
❖ Cationic – The surface-active portion bears a
positive charge
❖ Amine salts
❖ Quaternary ammonium salts
❖ Amphoteric – The surface-active portion bears both
charges
❖ Long-chain amino acid salts
❖ Betaines
❖ Nonionic – The surface-active portion contains no
charge
❖ Long chain ethers
❖ Fatty acid esters
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Hydrophilic-Lipophilic Balance (HLB) System

▪ The hydrophilic-lipophilic balance (HLB) number indicates the polarity of
the molecules in a range of 1-40, with the most commonly used
emulsifiers having a value between 1 and 20.
▪ The HLB number increases with increasing hydrophilicity.

Function HLB Range

Antifoaming agent 1-3

Emulsifier, (w/o) 3-6

Wetting agent 7-9

Emulsifier, (o/w) 8-18

Detergent 13-15

Solubilizer 15-18

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Emulsion HLB ranges and

usages

The higher surfactant HLB value, the more

0 - totally oil soluble hydrophilic it is.
20 - totally water soluble ➢The lower surfactant HLB value, the more
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lipophilic it is.
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HLB system
 All compounds that have
hydrophilic parts and lipophilic
parts are not always useable as
an emulsifier. When
hydrophilicity is too great, such
compounds disperse into water
and the ones with great
lipophilicity would disperse into
oil.

 When the hydrophilicity and

lipophilicity are well-balanced,
the emulsifier exhibits sufficient
effects.

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Examples of Surface active agents on HLB scale

❖ Spans are sorbitan fatty acid esters having low HLB

values ranging from 1.8 to 8.6.

❖ Tweens are polyoxyethylene derivatives of spans.

So, they are more hydrophilic having higher HLB
values ranging from 9.6 to 16.7

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Commonly Used Emulsifiers And Their HLB

Values

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Group Numbers for Calculating

HLB Values- Davies' method
In 1957, Davies suggested a method based on
calculating the HLB value based on the
chemical groups of the molecule. The
advantage of this method is that it takes into
account the effect of strongly and less strongly
hydrophilic groups.

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Examples

HLB for : (C11H23COONa) would be:

HLB= 7 + 19.1 -11(0.475) = 20.9

-OSO3O-Na+

(11) CH3 and CH2 -CH2CH2O-

CH3(CH2)11(OCH2CH2)nOSO3Na

HLB = 7+(0.33+38.7)-(12*0.475)=40.33

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Calculating HLB for

emulsifiers combination

❖ What is the HLB value of an emulsifier mixture containing 10 gm Span® 20

(HLB = 8.6) and 10 gms Tween® 21 (HLB = 13.3)?
❖ The HLB value of a combination of different emulsifiers can be calculated as
follows:

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What is the HLB value of a surfactant

system composed of 10g Span 60
(HLB=4.7) and 20g Tween 60 (HLB=14.9)?

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Examples

• How many grams of Span 80 (HLB 4.3) and how many grams of
Tween 20 (HLB 16.7) should be used to make 5 grams of a
mixture having a HLB value of 12 ? Determine by using

a) Formula below:

b) Allegation method.

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HLB for mixtures: Method (1)

The total weight of S and T is 5 :

S +T = 5 …1

4.3 * S + 16.7 * T
= 12 …2
5

Solving (1 and 2) for S and T we get :

T=3.1 gm and S=1.9 gm

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HLB for mixtures: Method (2)

Allegation Method
Step 1 (minus) Step 4 (solve)
Tween 16.7 7.7 12.4/5 = 7.7/T
12.4/5 = 4.7/S
12 Step 3 (add)
Span 4.3 4.7 T = 3.1gm
S = 1.9gm
Step 2 (minus) --------
12.4 gm

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a) HLB

b)

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a) Mineral oil

HLB =

b)

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Determination of the Required HLB values

and Blending of Surfactants

❖ ➢Oils used in the formulation of emulsions require a

certain HLB value to be formulated as w/o emulsion or
o/w emulsion.

❖ For the same oil, the required HLB value for O/W
emulsion is higher than the required HLB value for W/O
emulsion.

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❖ Calculation of the required HLB for a mixture of oils, fats or waxes

❖ 1. Multiply the required HLB of each ingredient by its fraction from the total oily
phase.
❖ [Link] the obtained values to get the total required HLB for the whole oily phase.
❖ Example:
❖ Liquid paraffin 35%
❖ Wool fat 1%
❖ Cetyl alcohol 1%
❖ Emulsifier system 7%
❖ Water to 100%

❖ Solution
❖ The total percentage of the oily phase is 37 and the proportion of each is:

❖ Liquid paraffin 35/37 x 100 = 94.6%

❖ Wool fat 1/37 x 100 = 2.7%
❖ Cetyl alcohol 1/37 x 100 = 2.7%

❖ The total required HLB number is obtained as follows:

❖ Liquid paraffin (HLB 10.5) 94.6/100 X 10.5 = 9.93
❖ Wool fat (HLB 10) 2.7/100 x 10 = 0.3
❖ Cetyl alcohol (HLB 15) 2.7/100 X 15 = 0.4
❖ Total required HLB = 10.63 43

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Calculation of ratio of emulsifier to produce a

particular required HLB value

➢The HLB of the mixture of surfactants, consisting of

fraction x of A and (1-x) of B is assumed to be the
algebraic mean of the two HLB numbers, i.e.:

HLB mixture = x HLBA + (1-x) HLBB

➢ Rearrangement the above equation in percent (%) form will be

A = 100 (X-HLBB) / (HLBA – HLBB)

B = 100 – A

Where X is the required HLB of the surfactant (oil) mixture

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Problem
❖ What is the HLB value of a mixture
consisting of 40% span60 (HLB 4.7) and
60% Tween 60 (HLB 14.9).
❖ Solution

❖ Assuming

❖ A: tween 60 , B: span 60

❖ A = 100 (X – HLB B) / (HLB A – HLB B)

❖ 60 = 100 (x – 4.7) / (14.9 – 4.7)
❖ 60 = 100x – 470 / 10.2
❖ X = 10.82

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❖ Problem
❖ A mixture of two surface active agents having an
HLB value of 13.5, calculate the percent of each if it
consists of Brij35 (HLB 16.9) and span80 (HLB 4.3).
Solution
Assuming
A: Brij35 , B: span 80

A = 100 (X – HLB B) / (HLB A – HLB B)

A = 100 (13.5 – 4.3) / (16.9 – 4.3)

A = 920 / 12.6
A = 73.01 %

B = 100 – A
B = 100 – 73.01
B = 26.98 %
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Worked example
❖ A formulator is required to formulate an o/w emulsion of the basic
formula:
❖ Liquid paraffin 50 g
❖ Emulsifying agents (required HLB 10.5) 5 g
❖ Water to 100 g
❖ Calculate the fraction of Tween 80 (HLB of 15) and Span 80 (HLB of 4.3)
used to produce a physically stable liquid paraffin emulsion.

❖ Solution
❖ Assume that Tween 80 is A and Span 80 is B. So,

❖ A = 100 (x-HLBB) / (HLBA-HLBB)

❖ = 100 (10.5-4.3) / (15-4.3)
❖ = 57.9%

❖ B = 100 – A
❖ = 100- 57.9 = 42.1 %

❖ A = 57.9/100 × 5 = 2.89 g
❖ B = 5 – 2.89 = 2.11 g
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❖ Stearyl alcohol 8%
❖ Cetyl alcohol 1%
❖ Lanolin anhydrous 1%
❖ Emulsifier 4%
❖ preserved water ad. 100%

❖ a)Calculate the RHLB of the oil phase where RHLB sterayl alcohol 15, RHLB
for cetyl alcohol is 15, and RHLB for lanolin anhydrous is 10.

❖ b) How many grams of span 80(HLB 4.3) and how many grams of tween
❖ 60 (HLB 14.9) should be used in formulating 1000 gms of this product

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Stearyl alcohol 80/100 x 15 = 12

Cetyl alcohol 10/100 x 15 = 1.5
Lanolin anhydrous 10/100 x 10 = 1
Total RHLB 14.5

A: Tween 60 and B: Span 80

A = 100 (x-HLBB) / (HLBA-HLBB)
A= 100 (14.5 – 4.3)/(14.9 – 4.3)
A = 96.22% So, B = 100 – A = 3.78%

Because of the total amount of emulsifier in formula: 4%

So, A = 96.22/100 x 4 = 3.85% → 3.85 g and
B = 3.78 /100 x 4 = 0.15% → 0.15 g
• Note that he asked about amount for 1000 gms of the product but the given formula for only 100 gms.
• So, the required amounts in grams must be multiplied by Factor (1000/100).
For 1000 grams:
A = 3.85 x 10 = 38.5 g B = 0.15 x 10 = 1.5 g 49

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Ways to break an
emulsion
 Disrupt the water or break the emulsifier film:
◦ Surface dry or freeze
 Increase water surface tension
◦ Salt
 Mechanical agitation
 Denature the emulsifier
◦ Heat
 Precipitate the emulsifier
◦ Acid/Alkali
 Attack the emulsifier
◦ Enzymes

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