this slides include ohase behaviour of surfactant in binary &ternary ststem

1. A
Seminar on
Phase Behaviour of surfactant in Binary & ternary system
Prepared By:-Mayuri A.Sawant.
Guided By:-Mr.U.C.Galgatte
Roll No:-PH111
Modern college of Pharmacy Nigadi pune 44

2. SURFACTANT
 Hydrophillic:-Water loving/oil hating
 Hydrophobic:-Water Hating/Oil loving
 Surfactant are Amphiphilic molecule composed of a
hydrophilic/Polar moiety known as Head
&Hydrophobic or nonpolar moiety Known as Tail.
 Alcohols, Amines Acids Changes from hydrophilic
to Lipophilic as Carbon atoms increasing in their
Alkyl Chain.

3. TYPES OF SURFACTANT :-
 IONIC:-
a)Anionic:-
1)Fatty Acid Salts(Soaps)
2)Sulphates:-Sodium dodecyl Sulphate(SDS)
Ammonium Lauryl Suphate (SDS)
Sodium lauryl ether sulphate
3)Ether Suphate:-Alkyl ether Sulphate
4)Phosphate esters
5)Sulphonates:-Alkyl Benzene Sulphonates
b)Cationic:-
1)Amine Salt:-Alkyl amine salt, Alkyl Diamine Salt
2)Ammonium Salt:-Alkyl trimethyl ammonium salt
3)Benzalkonium chloride(BAC)

4. c)Zwitterionic(amphoteric):-
1)Quaternary amine group & Carboxy group
Containing Surfactant:-Alkyl betaine
Alkyl imidazoline
2)Quaternary amine group & sulfonic group
containing surfactant:-Alkyl Sulphobetaine
3)Phospholipid Surfactant:-
Phosphatidyl serine
Phosphatidyl choline
Phosphatidyl ethanolamine
4)Carbohydrate Based Surfactant:-
Alkyl polyglucoside
Alkyl Glucamide

5. d)Nonionic:-
• Alkyl Ethoxylate
• Nonylphenolethoxylate
• Amine Ethoxylate
• Alkyl poly(ethylene oxide)
HLB SYSTEM:-
• HLB VALUE
• HIGH
• MORE POLAR/MORE HYDROPHILIC
• E.g.polyoxyethelene erivative of spans &
tweens(9.6-16.7)

6. • HLB VALUE
• LOW
• MORE NON POLAR/MORE LIPOPHILIC
• E.g:-Sorbitan esters(spans)(1.8-8.6)

7. Adsorption Phenomenon of Surfactant:
1)Adsorption at liquid-liquid interface:-
2)Adsorption at liquid-gas interface:-

8. CRITICAL MICELLE CONCENTRATION(CMC)
 The concentration of monomer at which micelles
are start to form in solvent at particular tempreture.
 Micelles are divided into three groups:-
1)Monomeric micelles:-
 Individual surfactant molecules that are in the
system but are not part of a micelle are called
“monomers”.

9. 2)Reverse micelle:-
 In a non polar solvent, the lipophilic tails of
surfactant molecules have less contact with water .
 Therefore,the head groups are pull at centre with
tails extending out is called as inverse/Reverse
micelle(water in oil micelle).

10. 3)In polar Solvent:-
 The hydrophilic “heads” of surfactant molecules are
always in contact with the sequestering solvent&
hydrophobic tail region in micelle centre called
Normal micelle(oil in water micelle)

11. PHASE BEHAVIOUR OF SURFACTANT
 The phase diagram of the ternary micellar system
is represented by a triangle (A: water,B: oil and C:
surfactant).
 The oil surfactant (B-C) binary mixture is
characterized by an upper critical solution
temperature(UCST); i.e., it phase separates upon
cooling.
 The water-oil (A-B) binary mixture is also
characterized by a UCST behavior but is mostly
phase separated (water and oil do not mix).
 water-surfactant (A-C) binary solution is more
complex and is characterized by a UCST behavior
at low temperatures and a closed loop
immiscibility island at high temperatures; i.e., it
phase separates both upon cooling and upon
heating.

12.  Phase separation proceeds along tie lines and produces a phase rich in the
A component (left side) and a phase rich in the C component (right side).
 The A-C binary phase diagram shows three critical points.
 Note that the UCST may lie below the freezing point of the mixture.
The water/surfactant (A-C) binary phase diagram.

13. PHASE DIAGRAM FOR THE TERNARY SYSTEM
 The critical condition for the ternary mixture is referred to as the “plait”
point (equivalent to ‘critical” point for binary mixtures).
 Type I corresponding to a 2-phase region where the surfactant is dissolved
mainly in the water phase, Type II corresponding to a 2-phase region where
the surfactant is dissolved mainly in the oil phase ,Type III to a 3-phase
region where the surfactant forms a phase of its own between the (bottom)
water phase and (top) oil phase.

15. THE THREE-PHASE REGION
 when the surfactant becomes more amphiphile or when the oil becomes
more hydrophobic. The slope at the inflection point becomes steeper till it
becomes horizontal. This corresponds to a so-called “tricritical”
condition. Beyond that,the critical points line breaks which leads to the
formation of a 3-phase region.
Fig:-Variation of the critical points line with increasing
amphiphile character of the surfactant and/or increasing the
hydrophobic nature of the oil.

16.  The 2-phase regions at low temperature and high temperature are almost
unchanged but a 3-phase region appears at intermediate temperature.
Representation of the prism phase diagram
when a 3-phase region is present.

17.  The surfactant is transferred continuously from the water-rich phase to the
oil-rich phase as temperature is increased.
 Consider a triangle phase diagram at a temperature for which a 3-phase
region exists. The 1-phase region is close to the surfactant corner. The 2-
phase regions are on each of the three sides of the 3-phase region. The 3-
phase region itself is a triangle within the triangle. The 3-phase triangle
size varies depending on the ternary system used and on the temperature
considered.
 Consider a vertical cut MC (referred to as the
“isopleth” line) through the ABC triangle. Representing
the phase diagram along the MC cut gives the
“fish” phase diagram.

18. The triangle delimiting the 3-phase region.

19. THE FISH PHASE DIAGRAM
 The “fish” phase diagram is obtained when an MC cut is taken across the
ABC triangle phase diagram.
 This cut corresponds to increasing the surfactant concentration but keeping
the amount of water and oil constant.
 Representation of the temperature/ surfactant concentration phase diagram
comprises the m-phase region at high surfactant concentration, two 2-
phase regions (at low and high temperatures) and a 3-phase region at
intermediate temperatures.

20. Fig:- The fish phase diagram.

21.  The m-phase region is the region of micelle formation and micelles are of
nanometer size.
 The m-phase region is rich in mesophases (with various morphologies).
It contains spherical, cylindrical (also called wormlike) and lamellar
micelles depending on the temperature range.
 Structures for these mesophases correspond to cubic (spherical micelles),
hexagonal (cylindrical micelles) and lamellar symmetry respectively.
Note also that the “microemulsion” is also called bicontinuous phase.
Moreover, oil-in-water micelles are obtained at low temperature and
“reverse” (water-in-oil) micelles are obtained at high
temperatures.

22. References:
1)M. Kahlweit and R. Strey, “Phase Behavior of Ternary Systems of the
Type H2O-Oil-Nonionic Amphiphile (Microemulsions)”, Angewandte
Chemie International Edition in English 24, 654–668 (1985).
2)K. Mortensen, “Structural Studies of Aqueous Solutions of PEO-PPO-
PEO Triblock Copolymers: Their Micellar Aggregates and Mesophases; A
SANS Study” J. Phys.;Condensed Matter 8, A13 (1996).
3)Physical pharmacy and pharmaceutical science,Martin,third eddition page
no85.

23. Thank You!!!!