Professional Documents
Culture Documents
Mr. K. K. Mali
Assistant Professor,
YSPM’s Yashoda Technical Campus, Satara
CONTENTS
Introduction of surfactant
Classification of Surfactant
Properties of surfactant
Phase behaviour of Surfactant
INTRODUCTION
Surface active agents
Lowers surface tension of water
Any material that makes a surface contribution to the free energy of
the surface phase of two component system.
Surfactants is a Amphiphilic compound that
Is soluble in at least one phase of system
Forms oriented monolayers at phase interface
Exhibits equilibrium concentrations at phase interfaces higher than those in
the bulk solution & forms micelles at specific concentration.
Exhibits characters- detergency, foaming, wetting, emulsifying, solubilizing
& dispersing
Tail or hydrophobic group this group is usually hydrocarbon (alkyl)
chain
Head or hydrophilic group can be neutral or charged
INTRODUCTION
Their surface activity arises from
adsorption at the solution air interface –
the means by which the hydrophobic
region of the molecule ‘escapes’ from
the hostile aqueous environment by
protruding into the vapour phase above.
Adsorption at the interface between
aqueous and nonaqueous solutions
occurs in such a way that the
hydrophobic group is in the solution in
the nonaqueous phase, leaving the
hydrophilic group in contact with the
aqueous solution.
INTRODUCTION
Surfactants - behavior
SURFACE AND INTERFACIAL TENSION;
SURFACE AND INTERFACIAL FREE ENERGY
‘‘surface’’ is usually reserved for the region between a condensed phase
(liquid or solid) and a gas phase or vacuum.
‘‘interface’’ is normally applied to the region between two condensed
phases.
liquid–gas interface, molecules of the liquid in the boundary can only
develop attractive cohesive forces with molecules situated below and
adjacent to them.
They can develop attractive adhesive forces with molecules of the
gaseous phase.
At the gas–liquid interface, these adhesive forces are quite small.
The net effect is that molecules at the surface of the liquid have potential
energies greater than those of similar molecules in the interior of the
liquid and experience an inward force toward the bulk of liquid.
This force pulls the molecules of the interface together and the surface
contracts.
Thus, the surface of a liquid behaves as if it were in a state of tension—
the surface tension ()—due to the contracting force acting in all
directions in the plane of the surface.
SURFACE AND INTERFACIAL TENSION;
SURFACE AND INTERFACIAL FREE ENERGY
In order to extend the surface of a liquid it is necessary to
bring molecules from the interior to the surface against the
inward pull.
The work required to increase the surface area by unit area is
termed the surface free energy.
At the interface between two condensed phases, the
dissimilar molecules in the adjacent layers facing each other
have potential energies greater than those of similar
molecules in the respective bulk phases.
This is due to the fact that cohesive forces between like
molecules tend to be stronger than adhesive forces between
dissimilar molecules.
The interfacial tension is the force per unit length existing at
the interface between two immiscible or partially miscible
condensed phases.
The interfacial free energy is the work required to increase
the interface by unit area.
SURFACTANT CLASSIFICATION
Depending on their charge characteristics the
surface-active molecules may be
Anionic: SLS
Cationic: QAC
Zwitterionic (ampholytic): N-dodecyl-N,N-
dimethylbetaine
Nonionic: Sorbitan esters, Polysorbates, Poloxamer
SURFACTANT CLASSIFICATION
Examples
GRIFFIN'S SCALE OF HLB
PROPERTIES OF SURFACTANT
Wetting
Emulsification
Detergency
Solubalization
Micellization
PROPERTIES OF SURFACTANT
Wetting
PROPERTIES OF SURFACTANT
Emulsifying Agent
PROPERTIES OF SURFACTANT
Detergency
• Detergents are surfactants used for removal of dirt.
• Detergency involves
Wetting of the dirt particles
as a deflocculated particle or
• Washing
PROPERTIES OF SURFACTANT
Solublisation
Process of preparing clear solution
Microemulsion
Swollen micelle
Ionic Micelle
MICELLIZATION
Micelles Structure
Critical packing parameter
It is easily seen that if we double volume (v) by adding a second alkyl
chain then the value of CPP will exceed 1/3 and nonspherical
structures such as bilayers (CPP = 1) will form in solution, from which
vesicles are formed .
MICELLIZATION
Micelles Structure
Critical packing parameter
The ‘effective’ cross-sectional area of the surfactant molecule is
strongly influenced by the interaction forces between adjacent head
groups in the micelle surface. These forces are decreased by
addition of electrolyte, leading to a decrease of a, an increase of the
CPP, and a change of shape of the aggregate,
MICELLIZATION
Micelles Structure
ionic surfactants consists of:
Hydrophobic core composed of the hydrocarbon chains of the
surfactant molecule
a Stern layer surrounding the core, which is a concentric shell
of hydrophilic head groups with (1 – )N counterions, where is
the degree of ionisation and N is the aggregation number
(number of molecules in the micelle). For most ionic micelles
the degree of ionisation is between 0.2 and 0.3; that is, 70–
80% of the counterions may be considered to be bound to the
micelles
a Gouy–Chapman electrical double layer surrounding the
Stern layer, which is a diffuse layer containing the N
counterions required to neutralise the charge on the kinetic
micelle. The thickness of the double layer is dependent on the
ionic strength of the solution and is greatly compressed in the
presence of electrolyte.
MICELLIZATION
Micelles Structure
ionic surfactants
When concentration increased
converted spherical to
cylindrical
MICELLIZATION
Micelles Structure
Nonionic surfactants
are larger than their ionic counterparts and may sometimes be
elongated into an ellipsoid or rod-like structure.
attributable to the removal of electrical work which must be done
when a monomer of an ionic surfactant is added to an existing
charged micelle.
nonionic micelles are frequently asymmetric due to its size.
have a hydrophobic core formed from the hydrocarbon chains of
the surfactant molecules surrounded by a shell (the palisade
layer) composed of the oxyethylene chains of the surfactant and
entrapping a considerable number of water molecules, which is
highly hydrated.
MICELLIZATION
MICELLIZATION
Importance
Micelles make insoluble material soluble in water.
The structure of the micelles can affect the viscosity of the
solution.
Micelles are reservoirs of surfactants.
MICELLIZATION
1. Nature of hydrophilic group
6. Effect of pressure
MICELLIZATION
Factors Affecting CMC and Micellar size
Nature of hydrophobic group
•Increase in length of the HC results
in:
• decrease in CMC, which for
compounds with identical polar
head groups is expressed by the
linear equation:
log [CMC] = A – Bm
where m is the number of
carbon atoms in the chain and A
and B
are constants for a homologous
series.
• corresponding increase in
micellar size.
•Branching of HC increases CMC
•Unsaturation of HC increases CMC
MICELLIZATION
Factors Affecting CMC and Micellar size
Nature of hydrophobic group
MICELLIZATION
Factors Affecting CMC and Micellar size
Nature of hydrophilic group
Non-ionic surfactants generally have very much lower CMC
values and higher aggregation numbers than their ionic
counterparts with similar hydrocarbon chains.
An increase in the ethylene oxide chain length of a non-ionic
surfactant makes the molecule more hydrophilic and the CMC
increases.
MICELLIZATION
Factors Affecting CMC and Micellar size
Type of Counterion
Micellar size increases for a particular cationic surfactant as the
counterion is changed according to the series Cl < Br < I , and for
− − −
[M ]
Km
[ S ]n
Term in bracket refers molar concentration of species.
MICELLIZATION
Thermodynamics of Micelle Formation
Mass action model
When n is large – the free energy of micellization at the CMC is
[M p ]
K n n p
2
m
[S ] [ X ]
When aggregation number n is large, the free energy of
micellization at or near the CMC reduces to
p
Gm0 2 RT ln[ S ]CMC
n
MICELLIZATION
Thermodynamics of Micelle Formation
Phase –Separation model
considers micelles as a separate phase at CMC.
Hence s and m0 are defined as the chemical potentials [per mol]
of the free surfactant in the aqueous phase and of the associated
surfactant in the micellar phase respectively
At equilibrium s = m0
If activity coefficients are ignored, s is related to the surfactants
standard state s0 by
s s0 RT ln S
MICELLIZATION
Thermodynamics of Micelle Formation
Phase –Separation model
On the other hand, micellar material is in standard state, and m =
m0
The standard free energy of micellization is
Gm0 m0 s0
Phases Best
Example
PHASE BEHAVIOUR
Liquid crystalline
phase
PHASE BEHAVIOUR
Example of ternary
system
PHASE BEHAVIOUR
Factors
Effect of
Chain length temperature
Effect of Effect of
molecular HLB
structure
PHASE BEHAVIOUR
Best example
Tetrachlorom
ethane
Methyl-
octanoate
Caprylic acid
APPLICATIONS