Ternary Phase Diagrams

It is convenient to construct ternary phase diagrams on a

C
Gibbs Triangle (shown at right). Note that the variables
for these diagrams are only composition and that
pressure and temperature are held constant (that is that
these diagrams are slices through a four dimensional
space with constant T and P).

A B
 Construction of Ternary Phase Diagrams

∆G

α β

2
 Ternary Eutectic Phase Diagrams

C
T above T of the
ternary eutectic, but
below the binary
γ eutectics.

T
L

β+L
α β
γ+β

β+α
α+ γ
γ+β
α+ γ γ +L +L 0 XB 1
+L
L
α+L β+L

α+ β+L

α α+ β β
A B
3
 Ternary Phase Diagrams

Compositions are read as follows:

C
Draw three lines from the composition
point parallel to the composition lines.
Read the compositions off of the three
axes.

Note: Only two mole fractions are

needed (use the third as a check).
Compositions can be mole fractions [33% C, 33% B, 33% A]
or mass fractions.

[30% C, 70% B]

[100% A]

A B
 Ternary Phase Diagrams

Compositions are read as follows:

C
Draw three lines from the composition
[94% C, 3% B, 3% A]
point parallel to the composition lines.
Read the compositions off of the three
axes.

Note: Only two mole fractions are

needed (use the third as a check).
Compositions can be mole fractions [33% C, 33% B, 33% A]
or mass fractions.

[20% C, 20% B, 60% A]

[30% C, 70% B]

[100% A]

A B
 Ternary Phase Diagrams

Compositions are read as follows:

C
Draw three lines from the composition
[94% C, 3% B, 3% A]
point parallel to the composition lines.
Read the compositions off of the three
axes.

Note: Only two mole fractions are

needed (use the third as a check).
Compositions can be mole fractions [33% C, 33% B, 33% A]
or mass fractions.

[20% C, 20% B, 60% A]

[30% C, 70% B]

[100% A]

A B
 Partially Soluble Ternary Systems
If the two phases both have a partial solubility of the other component, then the analysis is
somewhat more complicated:

The difficulty is that now equilibrium data must be obtained for the ternary which relates the
partial solubilities. Equilibrium data can be obtained graphically, or from tables. The ternary
phase diagram is a typical way of representing the equilibrium compositions of the two phases:

Solute

66% EthGly
7% Furfural
27 % Water
A composition where
Ethylene Glycol Water only a single liquid
exists.

50 % EthGly 17% EthGly

50% Furfural 27% Furfural
56 % Water
A composition where
100% Furfural two liquid phases
coexist.
Solvent Carrier
Furfural
 Specification of Liquid-Liquid Equilibrium
For two phase equilibrium (either complete insolubility, or partially solubility):
• the equilibrium is between two liquids phases (π = 2)
• three components (ternary) distribute between the two phases (N = 3)

For the static equilibrium case we can specify 3 variables:

If we specify T and P we are left with one additional variable:
Thus if we specify the concentration of one component in either of the phases this
completely defines the state of the system.

Ethylene Glycol Water

Tie-Lines:
Show the compositions
of the equilibrium phases.

Furfural
 Partially Soluble Ternary Systems
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.

Solvent Feed Extract out

S, XC(S) E, XB (E), XC (E)
Liquid Feed
Raffinate out
F, XA(F), XB
R, XA (R), XB (R)

Ethylene Glycol Water

Furfural
 Partially Soluble Ternary Systems
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.
Step 1: Locate the Solvent and Feed points

Ethylene Glycol Water

F
60 kg EG
140 kg water

S Furfural
300 Kg
 Partially Soluble Ternary Systems
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.
Step 2: Locate the mixing point M:

X (BF ) FA + XB(S ) S 0.3 × 200kg + 0 × 300kg

= = 0.12
F+S 500kg

Ethylene Glycol Water

F 60 kg EG
140 kg water

M
S
300 Kg Furfural
 Partially Soluble Ternary Systems
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.
Step 3: Use the tie-line to get the raffinate and extract compositions.

Extract (4% water, 14%EG, 82% furfural)

Raffinate (87% water, 5%EG, 8% furfural)

Ethylene Glycol Water

F 60 kg EG
140 kg water
M
E
R

S
Furfural
300 Kg
 Partially Soluble Ternary Systems
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.
Step 4: Determine the amount of extract and raffinate (can use lever rule)

( M)
XC − XC( E )
0.63 − 0.82 Extract (4% water, 14%EG, 82% furfural)
Rf = ( R) ( E) = = 0.257
XC − XC 0.08 − 0.82 Raffinate (87% water, 5%EG, 8% furfural)

R = 0.257 × 500kg = 128.4kg

E = (1 − 0.257 ) × 500kg = 371.6kg

Ethylene Glycol Water

F 60 kg EG
140 kg water
M
E
R

S
Furfural
300 Kg
 Partially Soluble Ternary Systems
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.
Step 5: Determine the solvent free extract: Mixtures of E and S.
Extend line from S through E to solvent free point at H.

Solvent free extract H (20% water, 80% EG)

( R)
XB
H =
(F )
XB
Ethylene Glycol Water

F 60 kg EG
140 kg water
M
E
R

S
Furfural
300 Kg
 Partially Soluble Ternary Systems – Group Exercise!
Ex: Consider a feed of 200 kg of 30% ethylene glycol in water. Add 300kg of pure furfural solvent.
Step 1: Locate the Solvent and Feed points (flow, composition):
S =
F =

Step 2: Locate the mixing point M (composition):

X B( F ) FA + X B( S ) S
=
F +S
Step 3: Use the tie-line to get the raffinate and extract compositions.
Extract = ( % water, %EG, % furfural)
Raffinate = ( % water, %EG, % furfural)

Step 4: Determine the amount of extract and raffinate (can use lever rule)
Rf = *Ratio of Furfural in Raffinate
R = kg
E = kg

Step 5: Determine the solvent free extract: Mixtures of E and S.

Extend line from S through E to solvent free point at H.

Solvent free extract H = ?