Thermal Analysis / Cooling Curves

The graph plotted between the temperature and time is known as a

cooling curve.

During thermal analysis a pure substance is melted to a liquid state
and is allowed to cool slowly

The temperature is noted at definite intervals.

The graphical representation of the rate of cooling will be a
continuous curve on plotting Temperature Vs Time

The following graph represents the cooling curve of a pure substance.

Along line CD the temperature falls rapidly with time

At D , which is the freezing point of pure component, solid substance
starts separating out

The process of crystallisation is exothermic. If the rate of cooling and
rate of crystalisation are same then there is no change in the
temperature till all the crystals separate out. So the graph is parallel to
time axis.
VSG & KY

Page 1

11/21/2014


Along DE the solid cools as per Newtons law of cooling

On adding an impurity, there occurs a decrease in freezing point.
Greater the percentage of impurity greater will be the decrease.

The thermal analysis of a two component system is carried out by
cooling a mixture of two solids, completely miscible in liquid state.

The temperature is noted as before at periodical intervals.

For example let us consider the crystallization of A in presence of B
as an impurity ( lead in presence of tin )

The freezing point of lead (327OC) decreases due to the presence of
tin as impurity in the liquid phase, from which lead crystallises.

But the freezing point of tin will not be affected as lead is already in
solid phase

The first break appears when

solid A (lead) starts crystallising

leaving the impurity B (tin) behind in the liquid

VSG & KY

Page 2

11/21/2014


The temperature will not remain constant with time ( ie the line will
not be parallel to time axis)

The reason for this is , the crystallization of A(lead) leads to an
increase in the percentage of impurity B (tin) , which results in further
decrease in the freezing temperature of A.

This decrease continues till all A solidifies.

After the solidification of A (eutectic temperature) B starts
crystallizing from the liquid.

As there is no other metal in the liquid state , the temperature remains
constant till all of B solidifies

Then the solidified system cools as per Newtons law of cooling
The Following diagram shows the cooling curves of two metals at varying
composition

There are three breaks in the cooling curve of a two component mixture
VSG & KY

Page 3

11/21/2014

(a) First break occurs at the freezing point of the major component (solid A)
(b) Second break occurs at the eutectic point, when the impurity (solid B)
starts crystallising
(c) Third occurs when the mixture gets completely solidified

The following information are obtained from the thermal analysis

From the cooling curve for any mixture of a definite composition, it
is possible to obtain its: (i) freezing point, and (ii) the eutectic
temperature.

The freezing point varies with the composition of the system, but
the eutectic point remains constant for a given system.

Using the information obtained from thermal analysis of varying
composition of two metals ( Solid A + impurity B and Solid B+
impurity A), a phase diagram can be constructed

Eutectic System

VSG & KY

Page 4

11/21/2014

A binary system consisting of two substances, which are miscible in all

proportions in the liquid phase, but do not react chemically is known as
eutectic system.
Ex. Mixture of lead and silver
Uses of Eutectic System
Suitable alloy composition can be predicted with the help of eutectic
systems
Applied in preparing solders which are used for joining two metal
pieces together.

Eutectic mixture

Eutectic mixture is a solid solution of two or more substances having the

lowest freezing point of all the possible mixture of the components.

Eutectic point

The minimum freezing point obtained by the eutectic mixture (lowest

melting point)
Low melting Eutectic mixture finds application in
Safety devices - Fire alarm
Fire sprinklers ( Woods metal)
Fail safe devices in boilers ie pressure release valve safety valve

VSG & KY

Page 5

11/21/2014