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SURFACTANTS

SURFACTANTS IN
IN
SOLUTION
SOLUTION
Classification of
Surfactants
O
Anionic S - +
O Na
O
Cationic Sodium dodecylsulfate (SDS)
Zwitterionic +
Nonionic N
Br-
Cetylpyridinium bromide
O
O
O OCH2CH2N(CH3)3+
P O-
O
O
Dipalmitoylphosphatidylcholine (lecithin)

O O OH
O O
Polyoxyethylene(4) lauryl ether (Brij 30)
Surfactant Aggregates
Normal micelles
Unimers cylindrical
spherical

Inverted hexagonal phase


Reverse micelles
Bilayer lamella

4 nm
Critical Micelle Concentration

CMC

14
12
10 Below CMC only
8
6
CMC
unimers are present
4
Above CMC there are
2
0 micelles in equilibrium
0 1
Surfactant concentration with unimers
Solution Properties
14 14
12
unimers 12 Osmotic pressure
Concentration

10 10
8 8
6 CMC 6 CMC
4 micelles 4
2 2
0 0
0 Surfactant concentration1 0 Surfactant concentration1

14
Isc12
10 Light scattering
8
6 CMC
4
2
0
0 Surfactant concentration1
Solubilization
Spontaneous transfer of a compound insoluble in
the bulk solvent into solution due to incorporation
into the surfactant micelles

Normal micelles Reverse micelles

non-polar compound polar compound

amphiphilic compound
Solubility Effects

Solubility of a poorly soluble compound increases


as a result of solubilization in the micelles

14
Solubility

12
10
8
6
CMC
4
2
0
0 1
Surfactant concentration
An example of an HLB value
calculation
BRIJ 98 INCI name : oleth-20 is a 20 mole
ethoxylate of oleyl alcohol
calculate the molecular weight of the 20
moles of ethylene oxide ( one mole ETO =44
);
20 x 44 = 880
add this number to the molecular weight of
the oleyl alcohol;
880+ 270 = 1150 ( the mol. wt of BRIJ 98 )
What percentage of 1150 is 880 ?
880/1150 = 76.5%
76.5% divided by 5 = 15.3
15.3 is the HLB value of BRIJ 98
Important to remember !
HLB and Use of Surfactants

Amphiphilic surfactants are characterized by the


hydrophilic-lipophilic balance (HLB): a relative
ratio of polar and non-polar groups in the surfactant
HLB ca. 1 to 3.5: Antifoams
HLB ca. 3.5 to 8: Water-in-Oil Emulsifiers
HLB ca. 7 to 9: Wetting and spreading agents
HLB ca. 8 to 16: Oil-in-Water Emulsifiers
HLB ca. 13 to 16: Detergents
HLB ca. 15 to 40: Solubilizers
Required HLB
HLB needed for emulsification of the oil phase. If there
are several oil ingredients the required HLB is
calculated as a sum of their respective required HLB
multiplied by the fraction of each.
Calculate the required HLB for the oil phase of the following o/w
emulsion: cetyl alcohol 15 g., white wax 1g. Lanolin 2 g,
emulsifier (q.s.), glycerin 5 g. water 100 g.
Required HLB Fraction
(from reference)
Cetyl alcohol 15 x 15/18 12.5
White wax 12 x 1/18 0.7
Lanolin 10 x 2/18 1.1
Total required HLB 14.3
HLB of Surfactant Blend
Surfactant blends are commonly used to obtain
desired emulsifying properties.
Span 60 (HLB = 4.7)
Tween 60 (HLB = 14.9)
Span 80 (HLB = 4.3)
Tween 80 (HLB = 15.0)
What is the HLB of the mixture of 40 % Span 60 (HLB =
4.7) and 60 % Tween 60 (HLB = 14.9)?

Sorbitan monostearate is an ester of


sorbitol and stearic acid (synthetic wax)

Polyoxyethylenesorbitan monooleate;
Sorbitan monooleate ethoxylate

HLB of mixture: 4.7 x 0.4 + 14.9 x 0.6 = 10.8


In what proportion should Span 80 (HLB = 4.3) and Tween
80 (HLB = 15.0) be mixed to obtain required HLB of 12.0?

4.3.(1-x) + 15.x = 12 x = 0.72


72 % Tween 80 and 28 % Span 80
Glycerol Monostearate

HLB value of 3.6~4.2

dissolves in hot grease, paraffine, ethanol, chloroform, acetone


and aether, the material is widely used when producing of chocolate,
margarine, ice cream, skin care balsam, cold cream, hair oil and drug
ointment, also lubricant for plastic processing
Shampoo
Ingredients
Isobutane
Cyclomethicone
Aluminum Chlorohydrate
Propylene Glycol Dicaprylate/Dicaprate
Lichen extract
Fragrance
Quaternium-18
Silica
Dimethiconol
cyclomethicone

Propylene Glycol Dicaprylate/Dicaprate


Facial Cleanser

Aqua/Water
Palmitic acid
Myristic acid
Lauric acid
Stearic acid
Potassium hydroxide
PEG-7 Glyceryl cocoate
PEG-150 Distearate
Glycerin
Sodium laureth sulfosuccinate
Limonene
Linalool
Zinc PCA
Propylparaben
Propylene glycol
Disodium EDTA
NaCl
Propylene glycol

propyl ester of p-hydroxybenzoic acid = propylparaben

zinc salt of 2-Pyrrolidone-5-Carboxylic Acid

PEG-7 Glyceryl cocoate


Polyoxyethylene glycol glyceryl cocoate (monococoate).
PEG-150 Distearate

Polyethylene glycol diester of stearic acid.

Sodium laureth sulfosuccinate


Cream