1
CHAPTER-2
Phase Equilibria
Outline
Introduction to intermolecular forces
Phase diagram
Phase rule
Phase Equilibra 07/16/2025
Objectives
2
After this lesson the students are
expected to:
Describe intermolecular forces
between molecules
Discuss phase diagram
Apply phase rule and its application
Phase Equilibra 07/16/2025
Introduction to Intermolecular forces
3
The Forces Between Molecules
All matter is held together by force
The force between atoms within a
molecule is a chemical or Intramolecular
force
The force between molecules is a physical
or intermolecular force
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Cont..
4
Intramolecular forces
It is the force that holds the atoms or ions
together in a compound.
Intramolecular forces are much stronger than
intermolecular forces.
There are three main types of intramolecular
forces:
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Metallic bonding , Ionic bonding & Covalent
Cont..
5
A. Metallic bonding
Occurs when metal atoms bond to each other.
Bond is characterized by delocalized electrons
being shared between atoms.
B. Ionic bonding
unequal sharing or theft of an electron caused
by large differences in electronegativity.
Ionic or electrostatic bond develops
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Cont…
6
Ionic bonds are characterized by cations and anions
which are held together by electrostatic attraction or
forces.
These forces (electrostatic forces) are responsible for
the extremely high melting and boiling points of ionic
compounds and metals.
In ionic bonding, there is complete transfer of an
electron from a low to a high electronegative element.
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Cont..
7
C. Covalent bonding
If the difference between the electro negativities of
the two reacting elements is not large enough, no
electron theft occurs.
Rather than theft, the atoms involved will share
electrons, resulting in the formation of a covalent
bond.
characterized by sharing ofEquilibra
Phase electrons between two
07/16/2025
Cont…
8
Intermolecular forces
forces of attraction that exists between molecules in
a compound.
Non-bonding
These cause the compound to exist in a certain state
of matter: solid, liquid, or gas; and affect the
physicochemical properties of the cpd.
The intermolecular forces are weaker
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than
The Forces Between Molecules
9
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Types of intermolecular forces
10
1. Dipole - Dipole attractions (Keesom forces)
In some of covalently bonded molecules the electrons
may not be equally shared due to difference in their
electronegativity.
The electrons spent most of their time around the
highly electronegative atom.
This creates charge separation within the bond.
This separation is known as a dipole.
The molecule acts as it hasPhase
a positive and negative pole.
Equilibra 07/16/2025
Cont..
11
Molecules that possess a dipole moment are
polar molecules.
Due to electrostatic attraction, dipolar molecules
tend to align themselves with neighboring
molecule so that the negative pole of one
molecule points towards the positive pole of the
next.
This type of attractionPhase
(i.e. due07/16/2025
Equilibra to permanent
Cont..
12
H atom’s electron spends most of
its time around the chlorine &
oxygen atom.
Polar covalent molecules act as
little magnets; they have positive
ends and negative ends which
attract each other.
A strong dipole leads to high
Phase Equilibra 07/16/2025
intermolecular forces.
Cont..
13
2. Dipole-induced dipole (Debye force)
It shows the ability of a permanent dipole
to polarize charge in neighboring nonpolar
molecule.
Inductio
n
Inductive forces arise from the distortion of
the charge cloud induced by the presence of
another molecule nearby.
In Dipole-induced dipole intermolecular forces
permanent dipole induces a transit electric
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Cont..
14
3. Dipole-induced dipole/London forces
In a symmetrical molecule like hydrogen, however, there doesn't
seem to be any electrical distortion to produce positive or negative
parts.
But that's only true on average.
No
interaction
Since the electrons are mobile, and at any one instant
they might find themselves towards one end of the
molecule, making that end δ−.
The other end will be temporarily short of electrons
and so becomes δ+ Phase Equilibra 07/16/2025
Cont..
15
An instant later the electrons may well have
moved up to the other end, reversing the
polarity of the molecule.
This constant "sloshing around" of the
electrons in the molecule causes rapidly
fluctuating dipoles even in the most
symmetrical molecule.
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Temporary induced dipole
Cont..
16
How temporary dipoles give rise to
intermolecular attractions?
Imagine a molecule which has a
temporary polarity being approached by
one which happens to be entirely non-
polar just at that moment.
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Cont..
17
As the right hand molecule approaches, its
electrons will tend to be attracted by the
slightly positive end of the left hand one &
this sets up an induced dipole in the
approaching molecule.
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Cont..
18
An instant later, the electrons in the left hand
molecule may well have moved up the other
end. In doing so, they will repel the electrons
in the right hand one.
The polarity of both molecules reverses, but
you still have δ+ attracting δ-. As long as the
molecules stay close to each other the
polarities will continue to fluctuate in
synchronization so that the attraction is
always maintained. Phase Equilibra 07/16/2025
Cont..
19
As long as the molecules are close together
this synchronized movement of the electrons
can occur over huge numbers of molecules.
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Cont..
20
4. Hydrogen Bonding
H-bonding is a special type of dipole - dipole attraction that is
very strong.
When an electron is hogged by another atom in a polar
covalent bond, a significant fraction of the hydrogen nucleus
becomes uncovered and the bare nucleus desperately seeks
to be covered by electrons from other atoms.
A proton interacting simultaneously with two atoms, which
have strong negative charges, will form a hydrogen bond.
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Cont…
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These occur between polar covalent
molecules that possess hydrogen bonded to
an extremely electronegative element,
specifically - N, O, and F.
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Cont..
22
The high EN(electronegativity) of NH, OH,
and HF bonds cause these to be strong forces
(about 5x stronger than normal dipole-dipole
forces).
With out hydrogen bonds this world would be
much different, as water would boil at a
temperature far below 0oc.
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Cont..
23
5. Ion-dipole
The ion charge interact with dipole
charge.
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Cont..
24
6. Ion-induced dipole
The ion charge interact with polarizable e-
cloud.
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Summary of intermolecular forces
( kJ/mol)
25
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Intermolecular Forces and Physicochemical Properties
26
The properties of matter result from the properties
of the individual molecule (resulting from
chemical bonding) and how the molecules act
collectively (resulting from intermolecular forces).
The magnitude of the attraction between
molecules of any substance determines whether
that substance is a solid (strong attraction), liquid
(medium attraction), or gas (weak attraction).
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Cont..
27
Determines physical properties like melting point,
boiling point, solubility, etc.
The melting point of a compound is the
temperature at which a compound turns from a
solid to a liquid or a liquid to a solid.
The boiling point of a compound is the
temperature at which a compound turns from a
liquid to a gas.
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The stronger the attractions between particles
Phase equilibrium
28
A phase is a homogenous, physically distinct and
mechanically separable portion of the material with a
given chemical composition and structure of components.
The phase rule is an expression of the number of
variables that can be used to describe a system in
equilibrium.
Component - chemically recognizable species
E.g. H2O and Sucrose solution in water
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Phase equilibrium…
29
Phase diagram shows the phase equilibria with respect to
pressure and temperature.
They provide us with the knowledge of phase composition
and phase stability as a function of T, P & composition (C).
It permit us to study and control important processes as:
phase separation
solidification
purification of single crystals for technological and
other applications.
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Phase equilibrium…
30
Phase Rule is concerned merely with those constituents
which take part in the state of equilibrium.
State of matter which is uniform throughout not only
in chemical composition but also in physical state
helps to characterize state of the system
predict equilibrium relations of phases
helps to construct phase diagrams
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Phase equilibrium…
31
Information regarding phase equilibria can be predicted by a
simple rule (“Gibbs phase rule”):
f=c−p+2
c -is the number of components
p -is the number of phases present in the system.
f, or variance is the degrees of freedom, gives the number of
variables (e.g., pressure, temperature, composition, etc.)
that must be given to completely describe the system, or to
locate the state of the system
Phaseon the phase
Equilibra diagram.
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Phase equilibrium…
32
Gas
No matter how many gases commix, there is
only one gas phase.
Solid
Generally, one kind of solid has one phase
No matter how evenly two solid powder
commix, they are still two phases.
Solutions: one phase but what if it is saturated ?
Liquid
Miscible liquids are one phase
Immiscible liquids are two phase
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Phase equilibrium…
33
Heterogeneous and homogeneous systems
Systems with one phase are homogeneous
Water, ice, water vapor, sugar dissolved in
water, gases in general, etc.
Systems with more than one phase are
heterogeneous
A cube of ice in water. (same chemical
compositions but different physical states)
Oil-water mixture
Example: CaCO3(s) ↔CaO(s) + CO2(g)
Phases: P = 2 solid + 1 gas = 3
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Phase equilibrium…
34
Components(C)
The no of Cs is the minimum no of
independent chemical components
participating in the state of equilibrium
needed to form the system or to define all the
phases.
The Cs of a system are not synonymous with
the chemical elements or compounds present.
But only those constituents the
concentration of which can undergo
independent variation in 07/16/2025
Phase Equilibra the different
Phase equilibrium…
35
How many components are there when NaCl(s)
dissolved in H2O?
+ –
Available chemical constituents are: Na , Cl ,
NaCl and H2O
Is it correct to say c = 4 ?
+ –
Because Na and Cl have the same amount
“equal neutrality” as NaCl, then c = 2 and not
4.
CaCO3(s)↔ CaO(s) + CO2(g)
Available chemical constituents07/16/2025
are three.
Phase Equilibra
Phase rule
36
Degrees of freedom of a system (F): the no of the variable
factors, T, P, and Con. of the components, which must be
arbitrarily fixed in order to define the system.
F is related to the number of components (C) and number
of phases(P).
F=C-P+2
The digit 2 stands for the two variables, temperature and
pressure.
Calculate the degree of freedom for (C = 3 - 1 = 2)
CaCO3 (s) ↔ CaO (s) + CO2 (g)
F=C–P+2=2–3+2=1
Therefore only one variable, either temperature or
pressure, can be changed independently.
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Phase rule for condensed system
37
Solid/liquid systems are usually investigated at
constant P, and thus only two variables need to be
considered
– the vapor pressure for such systems can be neglected.
condensed system
A condensed system will be represented by the
following modified phase rule equation: F = C – P +
1
digit 2 is replaced by the digit 1, which stands for
temperature as variable.
Depending on number of components: one, two or
Three component system
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1. One component system,
water
38
How many
components do you
have? One, H2O
In the one-phase
regions, one can vary
either the
temperature, or the
pressure, or both
(within limits)
without crossing a
phase line.
We say that in these
Phase Equilibra 07/16/2025
regions:
One component system,
39
water…
Along a phase line
we have two phases
in equilibrium with
each other, P=2
If we want to stay on
a phase line, we
can't change the T
and P independently.
We say that along a
phase line:
f = c -p +2 = 1-
2+2= 1
Phase Equilibra 07/16/2025
One component system..
40
At the triple point
there are three
phases in equilibrium,
but there is only one
point on the diagram
where we can have
three phases in
equilibrium with each
other.
We say that at the
triple point:
f = c -p+2= 1-3+2= 0
P= 4.58mmHg Phase Equilibra 07/16/2025
One component system..
41
T3 T2 T1
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Critical point
42
Thermodynamic
state in which
liquid and gas
phases can co-
exist in equilibrium
at the highest
possible T.
Above this T, water
can not exist in the
liquid phase.
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Summary for one component system
43
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2. Two component system containing
liquid phases
44
For two component systems, F = 2-P+2 = 4-P
Four phases: invariant
Two components in three phases:
univariant
Two components in two phases: bivariant
Two components existing in only one phase:
tervariant
In addition to the P and T, therefore, a third
variable factor must be chosen.
concentration of the components
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Two component system…
45
Mixture of two liquid systems can be one of
the following:
Miscible
E.g. Ethyl alcohol and water
Partially Miscible
E.g. Phenol and water, Triethylamine and
water, Nicotine and water etc.
Immiscible
E.g. Mercury and water
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Two component system…
46
In cases where partial miscibility occurs under
normal conditions the degree of miscibility is
usually dependent on the T.
Dependency can described by means of phase
diagrams, which are graphs of T vs. Composition
at constant P.
Pressure is kept constant in two component
system in order to represent the system in planar
form.
The partially miscible systems may be divided into
the following types
i.e. phenol rich and waterPhase
richEquilibra 07/16/2025
Systems showing an increase in
miscibility with rise in temperature
47
Phenol and Water
Phase Equilibra 07/16/2025
miscibility with rise in temperature…
48
Upper consulate temperature (critical
solution)
the maximum T at which two phase region
exists
Line b-c drawn across the region containing
two phases is termed as tie line
It is always parallel to the base line
An important feature of two component system
All system prepared on a tie line at equilibrium
will separate into phase of constant
composition.
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These phase are called conjugate phases
miscibility with rise in
temperature…
49
Tie line can be used to determine the weight and
composition of the phases.
Lever rule
Weight of phase A Length of dc
Weight of phase B Length of bd
water-rich phase A
the phenol-rich phase B
The lengths of dc and bd can be measured with a
ruler in centimeters or inches from the phase diagram.
more convenient to use the units of percent weight of
phenol
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miscibility with rise in
temperature…
50
Example 1: at point d
point d = 24%, b = 11%, c = 63%,
the ratio of dc/bd =water-rich phase A/phenol-rich
phase B
phaseA c d 63 24 39 3
phaseB d b 24 11 13 1
For every 10 g of a liquid system in
equilibrium at point d:
Phase A = 7.5 g & Phase B = 2.5 g
Phase Equilibra 07/16/2025
miscibility with rise in
temperature…
51
At point f =50%
fc 63 50 13 1
bf 50 11 39 3
For every 10 g of system f
Phase A = 2.5 g & phase B = 7.5 g
ec 63 37 26
1
be 37 11 26
At Point e = 37 % Equal weight of phase A &
phase B Phase Equilibra 07/16/2025
miscibility with rise in
temperature…
52
Example 2
If 24 g of phenol mixed with 76 g of water, warmed to 50 0C,
the mixture upon separation of the phases at equilibrium :
Contains 25 g of phases A and 75 g of phase B
Calculate the amount of both in each phase
At equilibrium phase A = 75 g & phase B = 25 g
phase A contains 11 % phenol (11 x75/100=8.25g)
Phase B contains 63 % phenol (63 x 25/100 =15.75g of
phenol)
If you calculate the water part , you will find
phase A contains 66.75g of water
Phase B contains 9.25g of water
Phase Equilibra 07/16/2025
Applications of binary mixtures
53
The phase diagram is used in practice to formulate systems
containing more than one component
where it may be advantageous to achieve a single liquid phase
product.
The handling of solid phenol, a necrotic agent, is facilitated
in the pharmacy if a solution of phenol and water is used.
A number of solutions, containing different concentrations of
phenol, are official in several pharmacopeias
Phase Equilibra 07/16/2025
Applications of binary mixtures…
54
If the temperature is given, the compositions of the two
phases are fixed by the points at the ends of the tie
lines, for example, points b and c at 50°C.
The compositions (relative amounts of phenol and
water) of the two liquid layers are then calculated
A number of other binary liquid systems are water-
aniline, carbon disulfide-methyl alcohol, isopentane-
phenol, methyl alcohol-cyclohexane and isobutyl
alcohol-water Phase Equilibra 07/16/2025
Applications of binary mixtures…
55
Example 3
A mixture of phenol and water at 20° C has a
total composition of 50 % phenol. The tie line
at this temperature cuts the curve at points
equivalent to 8.4 and 72.2 per cent w/w
phenol.
What is the weight of the aqueous layer and
of the phenol layer in 500 g of the mixture?
How many g of phenol are present in each of
the two layers?
Phase Equilibra 07/16/2025
Applications of binary mixtures…
56
Solution:
Let Z be the weight in grams of the aqueous layer.
(500- Z) is the weight in grams of the phenol layer.
The sum of the percentages of phenol in the two layers
= 500 X 50/100 = 250 g
Z (8.4/100) + (500 - Z)(72.2/100) = 250
weight of aqueous layer Z = 174 g
weight of phenol layer (500 - Z) = 326 g
The weight of phenol in the aqueous layer 174 X
8.4/100 = 15 grams
The weight of phenol in the phenolic layer 326 X
72.2/100 = 235 grams Phase Equilibra 07/16/2025
Applications of binary mixtures…
57
At 50oC, the concentrations of phenol in the
water-rich phase and the phenol-rich phase
are 11 and 63% w/w (phenol/water),
respectively. Then a total of 120 g of a 35:65
w/w (phenol/water) is mixed.
Calculate the amount of the phenol-rich and
water-rich phases?
Phase Equilibra 07/16/2025
Applications of binary mixtures…
58
Solution:
Let the amount of water-rich phase be S.
Then the amount of phenol-rich phase is 120
– S. Take a mass balance of phenol: 120 g
x0.35 = S x 0.11 + (120 – S) x 0.63
The weight of the water-rich phase = S = 120
x 0.28/ 0.52 = 64.62 g
The weight of the phenol-rich phase = 120 –
64.62 = 55.38 g
Phase Equilibra 07/16/2025
Applications of binary mixtures…
59
Aniline at b
is 8%
Aniline at Aniline at
c is 20% e is 90%
Phase Equilibra 07/16/2025
binary mixtures…
60
Systems showing a decrease in miscibility with rise
in T
liquid mixture that shows no upper consolute
temperature but instead has a lower consolute
temperature below which the components are miscible
in all proportions.
Below T the two liquids are miscible because they can
lc
form weak complexes (internal forces).
As T increases, these weak complexes break up and
immiscible systems is being formed.
Such systems should be stored in cool place.
Example: triethylamine-water & paraldehyde- water
system. Phase Equilibra 07/16/2025
binary mixtures…
61
Phase Equilibra 07/16/2025
binary mixtures…
62
Systems showing upper and lower critical
solution T
Other systems show both an upper and lower
consolute temperatures.
Such systems are known as closed miscibility loops.
Example; nicotine-water system
After the weak complexes have been disrupted, they
show partial miscibility.
The thermal motion at higher temperatures
homogenizes the mixture again.
Phase Equilibra 07/16/2025
binary mixtures…
63
Phase Equilibra 07/16/2025
binary mixtures…
64
Two-Component Systems Containing Solid and
liquid Phases: Eutectic Mixtures:
The two components are completely miscible in the
liquid state and completely immiscible as solids, i.e.
the solid phases consist of pure components. E.g.
salol-thymol and salol-camphor.
The phase diagram for the salol-thymol system :
60%W/W thymol in Salol heated to 500C
i. a single liquid phase > 290C
ii. solid salol and a conjugate liquid phase 25 - 15 0C
iii. solid thymol is in equilibrium with a conjugate liquid
phase at 10 0C Phase Equilibra 07/16/2025
iv. both Components are present as pure solid phases <
binary mixtures…
65
Phase Equilibra 07/16/2025
binary mixtures…
66
At 250 C, system x is composed of a liquid phase, a1
(composition 53% thymol in salol) and pure solid
thymol, b1
The weight ratio of a1 to b1is
(100 - 60)/(60 - 53) = 40/7 = 6.71:1
When the temperature is reduced to 200 C the
composition of the liquid phase is a2 (45% by weight
of thymol in salol), while the solid phase is still pure
thymol, b2
The phase ratio, a2 : b2 = (100 60)/(60 - 45) =
40/16 = 2.67:1.
Phase Equilibra 07/16/2025
At 15 C the composion of the liquid phase 37%
0
binary mixtures…
67
Below 130 C, the liquid phase disappears altogether
and the system contains two solid phases of pure
salol and pure thymol.
Thus, at 100 C, the system contains an equilibrium
mixture of pure solid salol (a4) and pure solid thymol
(b4)
ratio of (100 - 60)/(60 - 0) = 40/60= 0.67:1
As system x is progressively cooled, the results
indicate that more and more of the thymol separates
as solid
At the eutectic point, three phases (liquid, solid salol,
and solid thymol) coexist.Phase Equilibra 07/16/2025
Applications of binary Eutectic
Mixtures
68
Solid Dispersions
facilitating the dissolution, and frequently, therefore,
the bioavailability, of poorly soluble drugs when
combined with freely soluble "carriers" such as urea.
This increase in dissolution rate is achieved by a
combination of effects, the most significant of
which is reduction of particle size
increased wettability of the material, reduced
aggregation and agglomeration, and a likely
increase in solubility of the drug owing to the
presence of the water soluble carrier.
Solid Solution: in which each solid phase contains
Phase Equilibra 07/16/2025
both components
Three-component system (Ternary
system)
69
The addition of a third liquid to a binary liquid
system produce a ternary or three-
component system.
The mutual solubility of the original pair will
be decreased If the third liquid is
soluble in only one of the two original
liquids or
its solubility in the two original liquids is
markedly different.
The addition of a liquid having roughly the same
solubility in both components of the07/16/2025
Phase Equilibra original pair will
result in an increase in their mutual solubility.
Tertiary system…
70
In systems containing three component but
only one phase
F= 3-1+ 2= 4
The four degrees of freedom:
P, T, the concentration of two of the three
components.
If we regard the system as condensed
system(p constant) and hold the T constant
→ F=2
Planar diagram to illustrate the phase
equilibria. Phase Equilibra 07/16/2025
Rules of triangular diagrams
71
Phase Equilibra 07/16/2025
Rules of triangular diagrams
72
1. Each side of the triangle represent 0% of one of
the components and the apex opposite that side
represent 100% of that component.
A point on one of the sides of the triangle will give
the composition of a mixture in which only two
components are present.
while a point within the triangle will represent the
composition of a ternary mixture.
If line is drawn through the apex to a point on the
opposite side, all systems represented by points
on such a line have a constant ratio of two
components. Phase Equilibra 07/16/2025
Rules of triangular diagrams…
73
Any line drawn parallel to one side of the triangle
represent ternary system in which the proportion of
one component is constant.
Every point within the triangle has the property that
the sum of the perpendiculars from that point on the
sides of the triangle is equal to unity (the height of
the triangle).
The composition of a ternary mixture can be represented by
fixing a point within the triangle such that the lengths of the
perpendiculars from the point to the sides of the triangle are
Phase Equilibra 07/16/2025
equal respectively to the fractional amounts of the three
Rules of triangular diagrams…
74
Phase Equilibra 07/16/2025
Tertiary system…
75
Line DC: points on such a line have a constant ratio of
two components, A and B.
Furthermore, the continual addition of C to a mixture
of A and B will produce systems that lie
progressively closer to apex C (100% of component
C)
Note that in all three systems, the ratio of A to B is
constant and identical to that existing in the original
mixture
Line HI
Represents ternary systems in which the proportion
of one component is constant.
Phase Equilibra 07/16/2025
In this instance, all systems prepared along HI will
Tertiary system…
76
Effect of adding a third component (C) to a binary
systems containing A (5.0 g) and B (15.0g)
Phase Equilibra 07/16/2025
Tertiary system…
77
If the 3rd component is soluble in only one of the two
original liquids
Mutual solubility of binary system will be
decreased
alcohol + castor oil , water 3rd component
(soluble in alcohol)
If the 3rd component has roughly the same solubility
in both components, therefore mutual solubility will
Phase Equilibra 07/16/2025
be increased
Tertiary system…
78
Tertiary system a acetic acid ,butanol & water
contains one pair of partially miscible liquids.
Water and butanol are miscible only to a slight
extent and so a mixture of the two produces a two
phase system,
alcohol is completely miscible with both benzene
and water
the addition of alcoholPhase
to a two produce a single
Equilibra 07/16/2025
Applications tertiary system
79
Application of three component system diagram
Surfactant/oil/water system
Flavor/water/alcohol system
Drug/water/propylene glycol system
The pharmacist can pick any combination from
the region miscible depending on safety,
efficacy, stability or cost.
Phase Equilibra 07/16/2025
80
Thank you
Phase Equilibra 07/16/2025