Surfactant

Technology-ii

Tanvir Ahmed Fahim

•
Surface active agents, also known as Surfactant are the substance that reduce the surface or interfacial tension
between 2 liquids or between a solid & a liquid, thereby increasing it spreading & wetting agents properties.
• The surfactant reduces the surface tension by adsorbing at the liquid–gas interface.
• Based on their HLB values, SA may be emulsifying agents, deflocculating agent, wetting agent, solubilizing agent,
detergent & foaming agent.
• Surfacts are amphipathic/amphiphilic, because they contain-
1. a lipophilic region(tail) -
a group with long hc chain, that has little affinity for aqueous solvent.
Surfactant molecules have either one or two hc chain.
2. a hydrophilic region(head)- a group that has affinity for water. The group posses a polar character. E.g.
ion
Example : Sodium stearate (C17H35COONa)
C17H35 COO- + Na+
Lipophilic Hydrophilic Surface inactive ion/counter ion

• Therefore, a surfactant contains both a water-soluble component & a water-insoluble (or oil-soluble)
component. In the surfactant both the hydophilic & hydrophobic region must be balanced, because then both
the parts will be concentrated at an interface & therefore ST will be lowered. For example, when the
hydrophobic group is weaker than the hydrophilic, the surfactant becomes water-soluble & it becomes oil-
soluble surfactant when a lipophilic group is stronger than hydrophilic part.
• Surfactants are soluble in both organic solvent & water.

• There are 4 types of surfactants based on the charge of hydrophilic region-

Types Chracteristics Uses Example Chemical formula

foaming agents, detergents, C17H35------COO-
emulsifiers. Sodium Na+
found in cleaning products such as stearate
hydrophilic region is negatively
Anionic laundry, toothpaste, handsoap
charged, i.e. anion. C H -------SO -
shampoo, body soaps, detergents & Sodium lauryl 12 25 4
other bath products. sulphate Na+

Antiseptic, Antimicrobial agent.

Cetyl
hydrophilic region is positively in household, institutional & trimethyl C16H33------N+(CH3)3
Cationic industrial cleaners.they disrupt cell
charged, i.e. cation ammonium Br-
membranes of bacteria & viruses
bromide
Wetting agent, solubilizing agent
Hydrophilic region is both Dispersing agent.
Amphoto N-deodecyl C12H25------NH2+CH2-
positively & negatively charged. paint & latex products to help them
ric alanine CH2 COO-
Also known as Zwitter ion. dry or coagulate quicker.

Stabilizing agent, Coating agent

Hydrophilic region has no charge
Pharmaceuticals, polishes, cleaners, Polyethylene CH3(CH2)16----
Non- but derives its water solubility
fragrances, & even some food glycol ---CO (OCH2OCH2)40
ionic from highly polar groups e.g.
products. monostearate OH
polyoxyethylene(-OCH2CH2O)
 ❖ Mechanism

• Surfactants are amphiphilic molecules that have hydrophobic & hydrophilic parts. When surfactants are
dissolved in water they orientate at the surface between 2 immiscible liquids, e.g. oil & water; such a way
that the hydrophilic part migrate towars high polarity phase/water & the hydrophobic part migrate towars
the low polarity phase, according to like dissolve like rule.
• Surfactant molecules are initially distributed as small colloidal particles.When the conc. of hydrophilic
molecules in the water is high, the molecules aggregate & form micelles.The point or conc. at which
micelles are formed is called critical micelle concentration(CMC). These make it possible for the molecules
being adsorbed in the water.
• Surface tension is high or low based on how attracted the molecules to each other in a given liquid.
Liquids, like water, have high ST because the molecules attract each other very strongly by means of
strong cohesive forces act upon them.
• The reason for the reduction in the ST when surfactant molecules adsorb at the water surface is that
the surfactant molecules break these strong interactions & replace some of the water molecules in the
surface. This results in reduction of cohesive force. Consequently, the forces of attraction or the
intermolecular forces between surfactant & water molecules are much lower than those between 2 water
molecules & thus surface tension will decrease & stabilize the interface.

❖ Emulsifying function of Surfactant

1. Lower the ST = Higher the SA = reduce tendency of dispersed molecules to coalesce or bond together =
particle spreads more easily = stable/miscible
2. Formation of interfacial film/mechanical barrier : ____________
3. Formation of electric double layer : ____________

❖ Detergent action of surfactant :

One of the most common soap used in today is Sodium sterate- C17H35COONa. Soap or detergent molecules
ionizes in water to form an anion & cation,
C17H35COO- Na+ C17H35COO- + Na+

As many as 70 stearate anions aggregate to form a micelle of colloidal size. The stearate ion has a long hc chain
with a polar COO– group at one end. In the micelle formation, the tails being insoluble in water are directed
toward the center, while the soluble polar heads are on the surface in contact with water.

The detergent anions are made of oil-soluble hc tails & water-soluble polar heads —COO–. When soap solution
is added to a fabric, the tails of the soap anions are pegged into the grease stain.
The polar heads protrude from the grease surface & form a charged layer around it. The grease stain is thus
absorbed into the interior of the micelle which behaves like liquid hc. As the stain is detached from the fabric,
the dirt particles sticking to the stain are also removed.
 ❖ Micelle & CMC

• A micelle is an aggregate of surfactant molecules dispered in a liquid. The process of formation of micelle is
known as Micellization.
• The formation of micelle depends on the conc. of solutes & solution. At low conc., the surfactant
molecules primarily lay at the interface of the water. When more surfactant is added or when surfactant is
dissolved at higher conc. in solvent, the hydrophilic molecules tend to aggregate themselves at the surface
or interface until all surface or interface is being saturated by surfactant & no more space is available to be
occupied there .
• As many as 70-100 hydrophilic molecules aggregate to form a micelle of colloidal size. This make it possible
for the surfactant being adsorbed in the water & reduce the surface tension.
• Most micelles are spherical in shape. In a micelle, the hydrophobic tails flock to the interior in order to
minimize their contact with water & the hydriphilic heads remain on the outer surface in order to maximize
their contact with water.
• CMC : The point or conc. of surfactant at which micelles are formed is called critical micelle concentration.
So, micelles from only when the conc. of surfactant is greater than the CMC.
• The CMC is an important characteristic of a surfactant. Before reaching the CMC, the ST changes strongly
with the conc. of the surfactant. After reaching the CMC, the ST remains relatively constant or changes
with a lower slope.
• Diluting the surfactant solution to below the CMC causes the micelles to disperse or breakup into single or
nonassociated surfactant molecules.

Oil
❖ Factors affecting the CMC & micellar size

1. Structure of the hydrophobic group :

Increase in length of the hc chain results in decrease in CMC.
2. Nature of the hydrophilic group :
Non-ionic surfactants generally have very much lower CMC values & higher aggregation numbers.
Ionic surfactants have lower CMC & higher aggregation numbers.
3. Type of counterion :
Micellar size increases for a particular cationic surfactant as the counterion is changed according to the series
Cl− < Br− < I−, & for a particular anionic surfactant according to Na+ < K+ < Cs+.
4. Addition of electrolytes :
Electrolyte addition to solutions of ionic surfactants decreases the CMC & increases the micellar size.
5. Effect of T :
At T up to the cloud point there is an increase in micellar size & a corresponding decrease in CMC in inoionic
surfactant. T has a comparatively small effect on the micellar properties of ionic surfactants.

https://www.ommegaonline.org/article-details/Surfactants-and-their-role-in-Pharmaceutical-Product-Development-An-
Overview/2601
 ❖ Pharmaceutical application of surfactant

Surfactants are amphipathic substances with lyophobic and lyophilic groups and are critical components in
pharmaceutical products. Surfactants have several uses in pharmaceuticals,

1. Surfactant are used in tablet & capsule formulations as wetting agents to aid dissolution & absorption.
2. Anionic surfactant has antiadherent property that act like a glidant. Used to improve flowability of
powder.
3. Surfact used in formulation of suppositories in combination with other suppository bases to improve the
wetting & water-adsorption properties of the suppositories.
4. Surfactant used as plasticizers in semisolid delivery systems like cold cream, vanishing cream, shaving
cream, lotion. They control the consistency of product by forming a viscoelastic network throughout the
continuous phase of the formulation.
5. Surfactants used in formulation of solution as solubilizing agent which increase drug solubility.
6. Surfactants are used as foaming agent in mouthwashes & dentifrices. They are used because they aid in
the solubilization of flavours & in the removal of debris by providing foaming action.
7. Surfactants used in formulation of suspension to aid dispersion of solid particles in the liquid. Surfactants
can reduce the interfacial tension between the solid particles & the liquid vehicle. Thus improve
wettability & bioavailability of the formulation.
8. Surfactants having HLB between 3-8 are act as good eumulsifying agents for w/o emulsion. Used for
solubilisation of hydrophobic drugs in aqueous media.
9. Cationic surfactants are capable of exerting antibacterial properties by disrupting bacterial cell
membranes.