Phase Equilibrium-Ternary System

Ternary System
A three-component (or ternary) system has
𝑓 =𝑐 −𝑝 +2=3 −𝑝 +2=5 − 𝑝
For a single-phase system, , there are degrees of freedom.
To make a two-dimensional plot of this system, two variables (T and P) must

be fixed:
𝑓 =3 −𝑝=3 − 1=2
The two independent variables are taken as and , the mole fractions of
components A and B, with as the dependent mole fraction of component C.
𝑥𝐶 =1− ( 𝑥 𝐴 + 𝑥 𝐵 )
For multiphase systems, and will be taken as the overall mole fractions of
components A and B in the system.
If more convenient, we can use weight fractions instead.
We could use a rectangular plot with and as the variables on the two
axes. However, Gibbs suggested the use of an equilateral-triangle plot, and
this has become standard for ternary systems.
Mole Fractions of a Three-Component System Plotted in an Equilateral
Triangle with both 𝑇 and 𝑃 held fixed:
A theorem of plane geometry asserts that

for any point inside the triangle:
𝐷𝐸 + 𝐷𝐹 + 𝐷𝐺=h
where is the height of the triangle
If the size of the triangle is chosen
so that this sum equals unity, these
three perpendicular distances can
represent the three mole fractions.
𝑥 𝐴 + 𝑥 𝐵 + 𝑥 𝐶 =1
Each vertex of the triangle

represents a pure component.
Triangular coordinate system
used in ternary phase
diagrams
The point marked with a dot

represents 50 mole % C, 25
mole % A, 25 mole % B.
Once and are fixed, the

location of the point in the
triangle is fixed as
the intersection of the two
lines corresponding to the
given values of and .
Along edge AC, the % of B
present is zero; points on AC
correspond to the binary
system A + C.
At vertex A, we have 100 %

A. At this point, the distance
to the side opposite vertex A
is a maximum.
Ternary liquid–liquid equilibrium
Consider the system acetone–water–diethyl ether at 1 atm and 30°C.
Under these conditions,

• water and acetone are completely miscible with each other
• ether and acetone are completely miscible with each other, and
• water and ether are partly miscible.
Addition of sufficient acetone to a two-phase mixture of water and ether

will produce a one-phase solution.
Ternary system with 1 partially miscible pair
Acetone–water–diethyl
ether system at 1 atm
and 30°C.
Complete miscibility Curve CFKHD is also known as
The region above the saturation curve, also solubility
binodal curve CFKHD envelope
is a one-phase area.
Partial miscibility
A point in the region
below this curve
(biphasic region),
represents a system
consisting of two
liquid phases
coexisting in
equilibrium.
The locations of the
tie lines are
determined by
chemical analysis of
pairs of phases in
equilibrium.
The lines in the 2-phase
region are tie lines whose
endpoints give the
compositions of the two
phases in equilibrium.
A system of overall composition G
consists of a water-rich, ether-poor phase a
of composition F and an ether-rich, water-
poor phase b of composition H.
The slope of the tie line FGH shows that phase a has a smaller
acetone mole fraction than phase b.
Point K, the limiting point approached
by the tie lines as the two phases in
equilibrium become more and more
alike, is called the plait point or the
isothermal critical point.
It is characterized by the fact that the

two phases have identical compositions.
At point K, the tie-line converge in a

point and the two phases become only
one phase.
Partition coefficient for acetone between the
two phases at F and H can be calculated
from the locations of F and H and the
densities of the phases at F and H.
Lever rule in ternary systems
𝑛
𝛼
( 𝑥 𝛽𝐵 − 𝑥 𝐵 )
𝛽
= ⇐𝑙𝑒𝑣𝑒𝑟 𝑟𝑢𝑙𝑒 𝑓𝑜𝑟 2 𝑝h𝑎𝑠𝑒 𝑠𝑦𝑠𝑡𝑒𝑚𝑠
𝑛 ( 𝑥𝐵 − 𝑥𝐵)
𝛼
where:
• and are the total number of moles of all species in phases and
• , , and are the overall mole fraction of B, the mole fraction of B
in phase , and the mole fraction of B in phase
𝑙𝛼 𝑛 𝛽
𝛽
= 𝛼
𝑙 𝑛
where and are the tie-line lengths to the points that give the compositions of
phases and
𝑛
𝛼
( 𝑥 𝛽𝐵 − 𝑥 𝐵 )
𝛽
=
𝑛 ( 𝐵 𝐵)
𝑥 − 𝑥 𝛼
𝑙
𝛽
( 𝑥 𝛽𝐵 − 𝑥 𝐵 )
𝛼
=
𝑙 ( 𝐵 𝐵)
𝑥 − 𝑥
𝛼
The solubility envelope for the same ternary system is going to change at
different temperatures and pressures, since different equilibria are present
among the components.
When the process design of a ternary
system requires the use of graphical
methods, the use of the right triangular
diagrams could be more convenient since
in this case the drawing of perpendicular
lines and heights could result a lot easier.
Problem. Ternary phase diagram
For the system water (1) plus ethyl acetate (2) plus acetone (3) at and
1 atm, mole-fraction compositions of pairs of liquid phases and in
equilibrium are:
where the last set of data gives the isothermal critical solution point.
(a) Plot the ternary phase diagram including tie lines. (b) Suppose 0.10
mole of acetone, 0.20 mole of ethyl acetate, and 0.20 mole of water are
mixed at and 1 atm. Find the mass of each component present in each
phase at equilibrium.
Ternary system consisting of 1 liquid and 2 solids
Concentration–concentration phase diagram of lithium sulfate, ammonium

sulfate, and water at and 1 atm.
Pure lithium sulfate
and ammonium
sulfate are
solid at this
temperature.
lithium sulfate-ammonium sulfate-
water system at and 1 atm.

Phase Equilibrium-Ternary System

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Ternary System

A three-component (or ternary) system has

To make a two-dimensional plot of this system, two variables (T and P) must

If more convenient, we can use weight fractions instead.

A theorem of plane geometry asserts that

Each vertex of the triangle

The point marked with a dot

Once and are fixed, the

At vertex A, we have 100 %

Under these conditions,

Addition of sufficient acetone to a two-phase mixture of water and ether

It is characterized by the fact that the

At point K, the tie-line converge in a

Concentration–concentration phase diagram of lithium sulfate, ammonium

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