SURFACTANT

SURFACE ACTIVE AGENT

In any such system, the boundaries
between the phases may be of primary
importance in determining the
characteristics and behavior of the
system as a whole, although the bulk
characteristics of each phase are, in
theory, unaffected.
Geometrically, it is obvious that only a single
surface can exist between two immiscible. If
three phases are present, only a single line
can be common among the various elements
 Five basic types of interfaces are
encountered:
 solid–vapor (S/V),
 solid–liquid (S/L),
 solid–solid (S/S),
 liquid–vapor (L/V),
 liquid–liquid (L/L)
 The surface tension determines the tendency
for surfaces to establish contact with one
another.

 Therefore, surface tension is responsible for

the shape of a droplet of liquid. If the surface
tension is high, the molecules in the liquid are
greatly attracted to one another and not so
much to the surrounding air.
Because of its lower surface tension, ethanol will
flow and form a larger area of contact (surface)
with a solid than with water. Mercury, with its very
high surface tension, does not flow but breaks into
droplets if given the opportunity.
 Surface active agents interfere with the
ability of the molecules of a substance to
interact with one another and, thereby,
lower the surface tension of the
substance.

 Surfactants used in industrial applications

usually cause a dramatic decrease in
surface tension when used at low
concentration.
Examples that involve interaction of
surfaces include :
• Wetting
• Dispersing
• Emulsification
• Adhesion
• Foaming and defoaming
 Chemically, surfactants are amphipathic
molecules. That is, they have two distinctly
different characteristics, polar and non polar, in
different parts of the same molecule.

 Therefore, a surfactant molecule has both

hydrophilic (water-loving) and hydrophobic
(water-hating) characteristics.
 Since surfactant molecules have both hydrophilic and
hydrophobic parts, the most attractive place for them
in water is at the surface where the forces of both
attraction and repulsion to water can be satisfied.

 One other way that surfactants interact to satisfy

natural forces of attraction and repulsion between
molecules is by formation of micelles.

 Surfactant molecules aggregate in water forming

micelles
 Micelles consist of hydrophobic interior regions,
where hydrophobic tails interact with one another.

 These hydrophobic regions are surrounded by the

hydrophilic regions where the heads of the surfactant
molecules interact with water.
 SELF-ASSEMBLY OF SURFACTANT
MOLECULES

 Concentration of a soluble surfactant in water increased

gradually the surface concentration increases
and reaches a max level at a spesific bulk concentration
 Beyond this concentration, surfactant monomers begin to
aggregate with their hydrophilic tails pointing inward
away from the water
 The concentration at which aggregation occurs critical
micelle concentration (CMC)
 At very low concentration in water, surfactant
molecules are unassociated.
 At higher concentration of surfactant in water,
micelles form.
 The concentration at which micelles form is called the
critical micelle concentration (CMC).
 A low cmc is favoured by increasing the molecular
mass of the lipophilic part of the molecule, lowering
the temperature, and adding electrolyte.
Types (Classes) Of Surfactants
According to the nature of the hydrophilic group:

• anionic: hydrophilic head is negatively charged;

• cationic: hydrophilic head is positively charged;
• nonionic: hydrophilic head is polar but not fully
charged;
• amphoteric: molecule has both potential
positive and negative groups;

charge depends on pH of the medium.

 ANIONIC
SURFACTANT
 Anionic surfactants are the most widely used of the four classes.

 Important types of anionic surfactants are :

carboxylates ------> soaps, only effective in alkaline medium
sulfonates ------> effective in acid and alkaline medium
sulfates ------> excellent foaming agent - shampo
phosphates ------> excellent emulsifier under strongly alkaline
conditions

C12H23OH + CISO3H ---- C12H23OSO3H

Lauryl alcohol chlorosulfonic acid lauryl sulfate
 NONIONIC SURFACTANT

 Of the several types of nonionic surfactants, the

polyoxyethylenated alkylphenols and the polyoxyethylenated linear
are the most common

 The hydrocarbon group is the hydrophobic part of the surfactant

while the chain of ethylene oxide groups is the hydrophilic part of
the molecule.

 They are good dispersing agent in many cases

 Nonionic surfactants, like most ethylene
oxide derivatives, exhibit inverse
solubility characteristics and may
precipitate with increase in temperature
of their solutions.

 The temperature at which precipitation

occurs is called the “cloud point” of
surfactant
 The relative amounts of hydrophilic and
hydrophobic character may be expressed as
the hydrophilelipophile balance (HLB) of the
surfactant.

 Matching the HLB values of substance to be

emulsified and the surfactant is a good starting
point for selection of an appropriate surfactant
 As a general rule, surfactants with good oil
solubility produce water in oil (w/o) emulsions
while more water soluble surfactant produce oil
in water (o/w) emulsions.
 Emulsification behavior should be predictable
from HLB values.

Just rough guide to surfactant selection

 In many cases, a mixed surfactant system will

produce better emulsification than a single
surfactant
CATIONIC SURFACTANT
 Cationic surfactants are important as corrosion inhibitors,
fuel and lubricating oil additives, germicides and hair
conditioners.

 Two common types of cationic surfactants

are long chain amines and quarternary amine salts.

 They are soluble in strongly acidic medium but become

uncharged and insoluble in water at pH greater than 7
The presence of surfactant at an
interface change :
 Surface and interfacial tensions
 Contact angle
 Wettability
 Surface charge
 Surface rheology
CONTACT ANGLE AND WETTING

 Wettability is the tendency of one fluid to spread on

or adhere to a solid surface in the presence of other
immiscible fluids.
 Wettability refers to interaction between fluid and
solid phases.
 Reservoir rocks (sandstone, limestone, dolomite,
etc.) are the solid surfaces
 Oil, water, and/or gas are the fluids
 Porous media in a petroleum reservoir can be water-
wet or oil wet depending on the chemical
composition of the solids and the crude oil.
 This figure shows how the wettability of a water wet
solid surface in contact with an oil droplet can change
when surfactant molecules adsorb on to it.

 The solid surface has some negative sites where

cationic surfactants can be adsorbed, the hydrophobic
tails of these molecules will point towards the oil thus
making the solid surface more wettable by the oil droplet