PHASE DIAGRAMS OF BINARY SYSTEMS

Liquid-Liquid Phase Diagrams

Key Points:

(a.) Phase separation of partially miscible liquids may occur when the temperature is below the
upper critical solution temperature or above the lower critical solution temperature; the
process may be discussed in terms of the model of the regular solution.
(b.) The upper critical solution temperature is the highest temperature at which phase
separation occurs. The lower critical solution temperature is the temperature below which
components mix in all proportions and above which they form two phases.
(c.) The outcome of a distillation od a low-boiling azeotrope depends on whether the liquids
become fully miscible before the boil or boiling occurs before mixing is complete.

(A) PHASE SEPARATION

 The temperature-composition diagram for

hexane and nitrobenzene at 1 atm.
 The region below the curve corresponds to
the compositions and temperatures at which
the liquids are partially miscible.
 The upper critical temperature, Tuc, is the
temperature above which the two liquids are
miscible in all proportions.

Example: Interpreting a liquid-liquid phase diagram

A mixture of 50 g of hexane (0.58 mol C 6H14) and 50 g of nitrobenzene (0.41 mol C6H5NO2) was
prepared at 290K. What are the compositions of the phases, and in what proportions do they
occur? To what temperature must the sample be heated in order to obtain a single phase?

The composition of the two-phase region is:

 One phase is 35% nitrobenzene (65%

hexane), the phase which is richer in
hexane
 The other phase, is 83% nitrobenzene
(17% hexane), the phase which is richer in
nitrobenzene

APPLYING LEVER RULE:

nα I α 0.83−0.41
= = =7
n β I β 0.41−0.35
 Heating the sample to 292 K takes it into
the single-phase region.
(B) CRITICAL SOLUTION TEMPERTURES

 The upper critical solution temperature, Tuc

(or upper consolute temperature), is the
highest temperature at which phase
separation occurs.
 Above the upper critical temperature, the
two components are fully miscible.

 Some systems show a lower critical

solution temperature, Tlc (or lower
consolute temperature), below which they
mix in all proportions and above which
they form two phases.

 Some systems have both upper and lower

critical solutions temperatures.

(C) THE DISTILLATION OF PARTIALLY MISCIBLE LIQUIDS

The figure shows the phase diagram for two components that
become fully miscible before they boil.

 Distillation of a mixture of composition a1 leads to a

vapour of composition of b1, which condenses to the
completely miscible single-phase solution at b 2.

 Phase separation occurs only when this distillate is

cooled to a point in the two-phase liquid region, such as
b3.
 PHASE DIAGRAMS OF BINARY SYSTEMS
Liquid-Solid Phase Diagrams

Key points:

(a) A phase diagram summarizes the temperature-composition properties of a binary system

with solid and liquid phases; at the eutectic composition the liquid phase solidifies without
change of composition.
(b) The phase equilibria of binary systems in which components react may also be summarized
by a phase diagram.
(c) In some cases, a solid compound does not survive melting.

SOLID-LIQUID PHASE DIAGRAMS

- Knowledge of the temperature-composition diagrams for solid mixtures guides the design of
important industrial processes, such as the manufacture of liquid crystal displays and
semiconductors.

(A) EUTECTICS  The temperature-composition phase diagram for

two almost immiscible solids and their completely
miscible liquids.

 The isopleth through e corresponds to the eutectic

composition, the mixture with the lowest melting
point.

a1: components A and B exist as liquid (melt)

a2: solid A appears, liquid component = ZB

a3: more solid A forms, liquid is richer in component B

(lesser in A since more A solidifies)

a4: 3 phases exist [pure solid A, pure solid B and liquid

(last trace of liquid freezes)]

a5: 2 phases exist: pure solid A and pure solid B

 One technologically important eutectic is solder,

which in one form has mass composition of about
67% tin and 33% lead and melts at 183oC.
(B) REACTING SYSTEMS

 The phase diagram for a system in which A and B

react to form a compound C=AB

 Constituent C is a true compound, not just an

equimolar mixture

1. CONGRUENT MELTING
- Melting without change in composition
- The compound formed melts normally
2. INCONGRUENT MELTING
- The compound formed melts into its
components and does not itself form a liquid
phase