EXPERIMENT – 5

AIM
Construction of the phase diagram of simple eutectic like cinnamic
acid – benzoic acid using cooling curves method.

APPARATUS REQUIRED
Thermometer, test tubes, clamp, stand, stirrer, conical flask, spatula,
test tube holder, 50 mL titration flask, Bunsen burner.

CHEMICALS REQUIRED

Cinnamic acid and benzoic acid.

THEORY
Phase rule is a qualitative treatment of systems in equilibrium. It
enables us to predict in general the conditions that must be satisfied
to a given system to be in equilibrium and the variation that may be
expected among the variables defining its state.

PHASE RULE-
It states that for systems in complete equilibrium in which the
phases can exchange material, heat and pressure-volume work the
following relation holds good
F+P= C+2
P= number of phases
C= number of components
F= degrees of freedom
2 is included to account for the fact that the two intensive variables-
temperature and pressure must be specified to describe the state of
equilibrium.
THERMAL ANALYSIS-
It is a convenient method to study solid- liquid equilibrium. In this
method solid mixture of different components are melted above
their melting point. The resulting liquid melt is cooled slowly and the
cooling curve is constructed by plotting temperature(y-axis) against
time(x-axis). A break in cooling curve indicates crystallization of the
solid whereas a horizontal portion in the curve represents separation
of a second solid and temperature remains constant at this point
indicating the presence of three phases that is- two solids and one
liquid and at this point, F=0 that is the degrees of freedom of the
components is zero. Once the solidification is complete, the
temperature falls gradually giving a smooth curve again.

Cooling curve of a pure component.

 Cooling curve for a liquid mixture of two components

Cooling curve of a liquid mixture of two components in

which supercooling has occurred

EUTECTIC MELTING POINT-

It is the lowest temperature at which the liquid can exist and if the
liquid is cooled below this temperature, both the components
separate out, simultaneously because the composition of solid phase
is same in all cases.
PROCEDURE
1. Set the apparatus (clamp the 50 mL titration flask on the
stand).
2. Take a clean and dry test tube and transfer atleast 4g of
cinnamic acid to it. Melt cinnamic acid on the burner along with
stirring it with thermometer and simultaneously observe its
temperature. Once the temperature on thermometer reaches
between 140-150°C, remove test tube from burner.
3. Immediately transfer the test tube to an already clamped
titration flask and as the liquid cools down note down the
temperature readings after each 20sec (or as directed by
teacher) till the point where solid forms again while stirring it
continuously.
4. Repeat the same procedure with pure benzoic acid. Plot the
phase diagram for both and determine their melting points.
5. Repeat the same procedure for different compositions (e.g.
20%, 40%, 60% and 80% urea) of cinnamic acid-benzoic acid.

Composition of Mass of Mass of benzoic

cinnamic acid ( % of cinnamic acid/g acid/g
cinnamic acid)
20 0.8 3.2
40 1.6 2.4
60 2.4 1.6
80 3.2 0.8

NOTE: Place the lower melting component at the bottom of the test
tube and above it the higher melting component.

6. To get the phase diagram curve plot a graph between

temperature readings (y-axis) and percentage composition (x-
axis). Mark the break and halt in each curve. Using these halts
and breaks plot eutectic phase diagram for the system.
OBSERVATION
Table 1

Composition of Mass of Mass of benzoic

cinnamic acid ( % of cinnamic acid/g acid/g
cinnamic acid)
20 0.8 3.2
40 1.6 2.4
60 2.4 1.6
80 3.2 0.8

Table 2

Time/s Temperature /°C

Composition of cinnamic acid-benzoic acid system (%
of cinnamic acid)

0 20 40 60 100
0
20
40
60
-
-
-
-

Table 3

Composition of
cinnamic acid-benzoic Break/°C Halt/°C
acid system (% of
urea)
0
20
40
60
80
100

RESULT
Eutectic temperature = °C

Eutectic composition = % of cinnamic acid

PRECAUTIONS
1. Place the lower melting component at the bottom of the test
tube.
2. Stir the contents in the test tube generously while observing
the temperature.