Phase Rule: 3 Component Systems

For three component liquid systems, there are three possibilities:

1) Liquids are completely miscible with each other

2) Liquids are completely immiscible with each other
3) Liquids are partially miscible with each other

For liquids which are partially miscible with each other, three types of systems are
possible:

One pair of partially miscible liquids:

At given temp. and pressure, consider a pair of liquids B and C which are partially
miscible.

If both B and C are mixed, some of C will dissolve in B and vice versa. Composition
of two layers is shown by ‘a’ and ‘b’.

If we add small amount of A, it will distribute between two layers. A will increase
the miscibility of B and C.

The increase in miscibility depends on amount of A added and amount of B, C.

When A is added, composition of two ternary solutions is given by points ‘a1’ and
‘b1’.
The line joining ‘a1’ and ‘b1’ is called tie line.

Again when more A is added, composition of two ternary solutions is given by

points ‘a2’ and ‘b2’ and so on.

When more A is added, composition of two ternary solutions starts becoming

more similar. Tie line becomes shorter.

When sufficient A is added, two points of tie line merge into one point ‘D’. It is
known as ‘critical or plait point’.

At this point, two layers form a single homogeneous phase.

Curve aDb is called ‘Binodal curve’.

Acc. to phase rule for 3 component system: F=5-P. For constant temp. & pressure,
F=3-P. Outside the curve aDb, P=1 so F=3-1=2.

Examples : (1) Acetic acid, chloroform and water,

(2) Acetone, water and phenol

Two pairs of partially miscible liquids:

At given temp. and pressure, consider pairs of liquids A, B and A, C which are
partially miscible. Here, pair B,C is completely miscible.

If both A and B are mixed, some of A will dissolve in B and vice versa. Composition
of two layers is shown by ‘a’ and ‘b’.

If we add small amount of C, it will distribute between two layers. C will increase
the miscibility of A and B.

By adding more amount of C, curve aDb is obtained for composition of pair A, B

containing C.

Similarly, curve cFd is obtained for composition of pair A, C containing B.

Plait points are at D and F.

Outside binodal curves aDb and cFd, two layers form a single homogeneous
phase.

Acc. to phase rule for 3 component system: F=5-P. For constant temp. & pressure,
F=3-P. Outside the curve aDb and cFd, P=1 so F=3-1=2.

The binodal curve changes its position with temperature. If we lower

temperature, curve ‘abcd’ shown in below fig. is obtained.

Examples : (1) Water-phenol-aniline,

(2) Water-ethyl acetate- n-butanol

Three pairs of partially miscible liquids:

At given temp. and pressure, consider pairs of liquids A, B and B,C and A, C which
are partially miscible.

If both A and B are mixed, some of A will dissolve in B and vice versa. Composition
of two layers is shown by ‘a’ and ‘b’.

If we add small amount of C, it will distribute between two layers. C will increase
the miscibility of A and B.

By adding more amount of C, curve aDb is obtained for composition of pair A, B

containing C.

Similarly, curve cFd is obtained for composition of pair A, C containing B.

Similarly, curve eEf is obtained for composition of pair B, C containing A.

Plait points are at D, F and E.

Outside binodal curves aDb, cFd and eEf, a single homogeneous phase is
obtained.

If we lower temperature, phase diagram shown in below fig. is obtained.

Here, for any point in the area shown by ‘2’, two liquid layers are present.

So, F=5-P, F=5-2 =3.

Here, for any point in the area shown by ‘1’, single liquid layer is present.

So, F=5-P, F=5-1 =4.

Here, for any point in the area shown by ‘3’, three liquid layers are present.

So, F=5-P, F=5-3 =2.

Example: Succinic nitrile-water-ether

Q.: Define: Quintuple point.

Number of phases can be maximum when value of ‘F’ is minimum.

F= C-P+2

0= 3-P+2

P=5.

For a three component non-variant system, five phases are in equilibrium state.
This point is known as “Quintuple” point.