CHEM 254

EXPERIMENT 8

Phase Diagrams, Solid - Liquid Phase Equilibrium for Two Component

System and Missibility Gap

Solid and liquid phases may both be present in a system at temperatures below the boiling point.
Consider the temperature composition phase diagram for two almost immiscible solids and their
completely miscible liquids shown in Figure 1.

a. b. a1
liquid
a1
a2
liquid cooling
a2
Temperature, T

Temperature, T
a3 a3 B precipitating
b3
liquid + A(s)
liquid + B(s)
e
a4
a4
eutectic freezing

a5 a5 Solid cooling
Solid A and B

0.0 1.0
mole fraction of B, xB time

Figure 1. a. The temperature composition phase diagram b. Cooling curve

During cooling of a sample w/composition (a1 to a5 on Fig. 1a) various phase changes are observed as
temperature decreases the foloowing proceses do occur.

a1  a2: system enters the two phase region liquid (A and B) and solid B. Here B solidifies, and the liquid
is richer in A.

a2  a3: more B solidifies. The relative amounts the solid and liquid can be determined by lever rule. The
liquid phase is richer in A and mole fraction of B in the liquid phase is b 3.

a3  a4 The composition of the liquid is given by e. This liquid freezes to give two phase system of pure A
and pure B.

e is called the eutectic composition. A liquid with the eutectic composition freezes at a single temperature.
A solid with the eutectic composition melts without a change of composition at the lowest temperature of
any mixture. The corresponding cooling curve starting at point a1 down to a5 is shown in Figure 1.b.
Missibility gap:

A mixture of liquids is a homogeneous distribution of two or more substances, whereby all components
have a definite vapour pressure. Two liquids may either be completely miscible or only partly miscible.
When the van der Waal forces between the two components are smaller than those between molecules
of the same type, then an increase in the vapour pressure results. The molecules can leave their
arrangement more easily than with equally large attractive forces. With sufficiently high deviation from
Raoult’s law:

where

The components of a binary system no longer continuously mix, but instead have the tendency to again
unmix. A miscibility gap can be observed. This is a range of concentrations in which the two liquids form
two phases. The molar mixing enthalpy is positive. Unmixing means in this case the transition to a lower
energy condition.

Systems with limited miscibility can be presented as isobars in temperature / mass content and
temperature / quantity diagrams. In these separation curves, the compositions of the two coexisting liquid
phases, which form from the homogeneous mixture when a certain temperature has been reached, are
plotted as functions of temperature. The coexisting liquid phases are described as conjugated solutions.
They are saturated solutions of the one component in the other. The line connecting the coexisting liquids
is designated as the tie line. Normally the mutual solubility of liquid components increases with increasing
temperature. The coexisting solutions are identical at a critical dissolving temperature. Above the critical
dissolving temperature the components are miscible with one another in any ratio. The compositions of
the coexisting solutions at certain temperature are constant and independent of the mass ratios or the two
components.

Lever Rule:

If the mass content w is used as the

concentration variable the mass ratio of the two
liquid phases can be determined using the so-
called rationality law. This states that the
masses of phases a and b are inversely
proportional to the distance of their composition
from the composition of the original mixture c,
from which it follows that

The relationship is shown in Fig.2

Fig.2 Solubility Diagram of Phenol Water Mixture

Purpose: In this experiment, heterogenous equilibrium between solid and liquid phases of a two
component system will be investigated. The method involves the measurement of temperature for
solutions of two components with definite proportions (thermal analysis).

A number of different mixtures of phenol and water are prepared and heated until complete miscibility is
achieved. As the mixtures cool, two-phase systems form at certain temperatures which are recognisable
by the appearance of turbidity. Plotting separation temperatures against compositions of the mixtures
gives the separation curve

Figure 3. Experimental set up

Apparatus and Chemicals

Apparatus: Test tubes (20 mL capacity), thermometer or thermocouple, rubber stoppers, wire stirrer,
constant temperature bath, stop watch. Experimental set-up is shown in Figure 3.
Chemicals: Naphtalene (N) and diphenyl amine (DPA), water, phenol.

Procedure

I. Naphtalene + diphenyl amine

1. Prepare a hot water bath.

2. Place 5.0 g of naphthalene into a test tube.

3. Place the tube into the hot water bath and let it melt completely.

4. Take out the test tube from the hot water bath.
 5. Place thermocouple into the test tube. Record temperature at each 10 seconds until the 6th
measurement below freezing ( Report Sheet Table ).

6. Add 0.50 g diphenyl amine, DPA, into the test tube and repeat steps 3-5.

7. Add 1.0 g DPA into the test tube and repeat steps 3-5 (total amount of DPA is 1.5 g).

8. Add 1.0 g DPA into the test tube and repeat steps 3-5. (total amount of DPA is 2.5 g).

II. Diphenyl amine + naphtalene

1. Repeat procedure given in Part I using diphenyl amine instead of naphthalene and naphthalene
instead of diphenyl amine. record Record temperature at each 30 seconds until the 6th
measurement below freezing (Report Sheet Table ).

III. Missibility gap:

mixture

1 0.5 4.5
2 1 4
3 1.5 3.5
4 2 3
5 2.5 2.5
6 3 2.0
7 3.5 1.5

1. Weigh the respective phenol portions into appropriately numbered test tubes
2. Seal the test tubes with rubber stoppers and heat them in a temperature controlled bath to 90 °C.
3. During heating remove the rubber stoppersfrom time to time to release excess pressure and
shake the mixtures.
4. When clear solutions have formed in all test tubes remove the tubes from the temperature bath
and start the cooling function.
5. Record the temperatures at which the turbidity caused by separation becomes visible.

Caution: DON’T INHALE PHENOL

Treatment of Data

1. Calculate the mole fraction of naphthalene for all mixtures.

2. Plot cooling curve according to the data obtained for all compositions. Find the freezing points.

3. Compare the experimental freezing points of pure naphthalene and pure diphenyl amine with the
theoretical values and discuss the possible sources of errors at the discussion part.

4. According to the experimental freezing point determined and mole fractions, plot the phase
diagram.

5. Find eutectic point and indicate the temperature and composition it found.

6. Calculate for all mixtures

7. Draw solubility phase diagram (misibility gap) for phenol and water mixture by plotting separation
temperatures against the composition of the mixtures as weight percentage

8. Find upper critical temperature.

Questions

1. Discuss the meaning of eutectic point.

2. Explain the meaning of upper critical temperature and discuss the behaviour of the solution above
and below this temperature.
DATA SHEET Experiment 9. Phase Diagrams Solid - Liquid Phase
Equilibrium for Two Component System

Group Number: Date:

Assistant name and signature:

Fill the following tables.

Pure
N + 0.5 g DPA N + 1.5 g DPA N + 2.5 g DPA
naphthalene

Time(s) T(˚C) Time(s) T(˚C) Time(s) T(˚C) Time(s) T(˚C)

10 10 10 10

20 20 20 20

30 30 30 30

40 40 40 40

50 50 50 50

60 60 60 60

70 70 70 70

80 80 80 80

90 90 90 90

100 100 100 100

110 110 110 110

120 120 120 120

 Pure DPA DPA + 0.5 g N DPA + 1.5 g N DPA + 2.5 g N

Time(s) T(˚C) Time(s) T(˚C) Time(s) T(˚C) Time(s) T(˚C)

30 30 30 30

60 60 60 60

90 90 90 90

120 120 120 120

150 150 150 150

180 180 180 180

210 210 210 210

240 240 240 240

270 270 270 270

300 300 300 300

330 330 330 330

360 360 360 360

1. Calculate mole fractions.

2. Fill the following table using experimental data.

Pure naphthalene X naphthalene Freezing point

N + 0.5 g DPA
N + 1.5 g DPA
N + 2.5 g DPA
DPA + 2.5 g N
DPA + 1.5 g N
DPA + 0.5 g N
Pure DPA
 3. Plot cooling curve.

4. Draw phase diagram.

Missibility gap:

1. Fill the following table by using experimental values:

Phenol- water o
T( C)
mixture
1

2. Plot solubility diagram of water-phenol mixture