EXPERIMENT 1

The Thermal Properties of a Binary Eutectic System

A. INTRODUCTION
Cooling Curve and Phase Diagram
Thermal properties, in general, include quantities such as melting points, heat capacities,
phase transition enthalpies, and the other thermodynamic quantities. In this experiment, the
thermal properties and phase diagram of a binary system containing two organic
compounds are studied. Two methods are used to obtain the melting points and enthalpies
of fusion of the system: the cooling curve method (plotting temperature versus time) allows
visual observation of melting or freezing and direct measurement of these temperatures,
while the calorimetry method offers quick determination of melting points and enthalpies.
Binary temperaturecomposition phase diagrams contain rich information on the thermal
properties of the binary system over a range of compositions and/or temperatures. The
phase diagram of a simple eutectic system looks like that in Figure 1a or 1b, depending on
whether the two components, A and B, are partly soluble in each other when they are in
the solid form (Figure 1a) or immiscible in each other as solids (Figure 1b). The system
studied in this experiment is the latter case.

Figure 1. (a) A typical phase diagram for a binary system comprising A and B with partial
solubility. Solids and are solid solutions of B in A and A in B, respectively; (b) A
typical phase diagram for a binary system comprising immiscible solids A and B.

A phase diagram can be constructed by using either the cooling curve or the calorimetry
method. In the cooling curve method, mixtures of varying compositions are heated up to
melt, and the graphs of temperature versus time are plotted. Cooling curves often show two
types of features: thermal arrest and thermal break. Thermal arrest refers to the plateau
(constant temperature) observed during crystallization. It is often observed in single
component systems, as all phase changes for pure substances take place at constant
temperature. It is also observed in a binary liquid at a certain ratio (eutectic composition),
where the two components crystallize simultaneously to form two solids at the eutectic
temperature. The eutectic temperature is the lowest temperature at which a binary system
can be completely liquid. In binary liquids of compositions other than the eutectic
composition, one component will start to crystalize first while the other remains in the
liquid phase. The rate of cooling is thus changed due to the heat released from
crystallization. This change in the slope of the cooling curve is called thermal break.
Thermal arrest and thermal break temperatures correlate to the points on the phase
boundaries in a phase diagram, as shown in Figure 2.

Figure 2. Correlation between the cooling curves and phase diagram for a binary
mixture of two components A and B
A difficulty often encountered in this experiment is "super cooling" when the temperature
of the solution drops below its freezing point before crystals start to separate. It is caused
by a lack of nuclei of crystallization and manifests itself as a dip in the cooling curve. In
such cases, the thermal arrest or break temperature can be obtained by extrapolating the
adjacent sections of the cooling curve which have relatively constant cooling rates.
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Besides the melting (or freezing) temperatures, a phase diagram also gives information on
the other thermal properties, such as the enthalpy of fusion. When a small amount of B is
added to a large amount of A, freezing point depression is shown by the negative slope of
the liquidus curve on the left side. A similar depression is shown when a small amount of
A is mixed with a large amount of B. The equation for the liquidus curve can be derived
by equating the chemical potential of the two phases in equilibrium, with the assumption
that the liquid phase behaves ideally and the enthalpy of fusion is constant in the
temperature range investigated. The temperature at which two phases are in equilibrium at
constant pressure is related to the mole fraction of predominating component in the liquid
as shown in Equation 1.
1

where

A or B 1

is the melting point of the liquid solution,

predominant component when it is pure,

is the melting point of the

is the molar enthalpy of fusion and

is

the mole fraction of the predominant component.

Differential Scanning Calorimetry

Closely associated with measurement of thermal properties are calorimetry techniques such
as differential scanning calorimetry (DSC), differential thermal analysis (DTA) and
thermogravimetric analysis (TGA). In this experiment, DSC will be used as an introduction
to thermoanalytical techniques. The results obtained will be compared with those from the
cooling curves.
In DSC, a sample and a reference are heated together. The difference between the heat
flows from the sample and reference is measured as a function of temperature or time.
Differences in heat flow arise when a sample absorbs or releases heat due to thermal effects
such as melting, crystallization, and chemical reactions. Such differences will be reflected
as peaks on the DSC curve. The sign and magnitude of these peaks, and the temperatures
at which they occur provide useful information on the thermal properties of the sample.
Enthalpy of transition can be obtained by integrating the area under the peak corresponding
to a given transition.
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B. HAZARDS
The chemicals used in these experiments are known to be toxic or irritant.
Contamination of skin and eyes, as well as inhalation of dust particles must be avoided.
Gloves should be worn.

C. PROCEDURE
The following compounds are provided: biphenyl, naphthalene, triphenylmethane, onitrophenol, p-toluidine. Each group will study one binary system comprising two
compounds from this list using both the cooling curve method and the DSC method. Each
group of students will only obtain cooling curves for one half of the phase diagram, and
will exchange their results with another group for the full phase diagram. Analysis of data
will be done for each method separately and the results will be compared.
The lecturer will assign two compounds to each group of students, specifying which
half of the phase diagram they will perform Part 1 of this experiment on. Find out the
structure, molecular mass and melting point of each compound and note them in your
laboratory logbook.

Part 1. Recording the cooling curves of mixtures with varying compositions.

1.

Weigh accurately about 5 g one of the pure compounds (A) and heat it in a boiling
tube fixed with a two-holed rubber bung, one hole for the digital thermometer (only
inserted after the solid has melted to liquid) and the other for the stirrer. Place the
boiling tube in a beaker of water (used as a water bath and temperature to be measured
with a second thermometer), and heat it with a hotplate until the compound is
completely liquefied. The liquid temperature should be at least 5 C above the melting
point to avoid immediate freezing on removing the boiling tube from the water bath.

2.

Remove the water bath (together with the inner tube) from the hotplate. Quickly insert
the inner tube in a larger (outer) tube provided and keep them in the same water bath,
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now with a temperature maintained at 10 C lower than that of the system. Clamp the
inner tube to a retort stand so it is surrounded by a layer of air while inside the outer
tube. The glass of the inner and outer tubes should not be touching. Allow the system
to cool slowly with constant and gentle stirring. Record the temperature at 30 second
intervals until all the liquid has solidified, and continue cooling to about 5 C below
that temperature (this is a complete cooling curve). During this process, adjust the
temperature of the cooling water bath by adding cold water or ice so a constant
temperature difference is maintained at all times.
3.

Next, form a binary mixture by adding accurately about 1 g of the other compound (B)
to the same boiling tube. Obtain the cooling curve as described above, but you may
stop once the temperature drops 5 C below when the first solid was observed (this is
an incomplete cooling curve). Continue to add compound B, about 1 g at a time, and
obtain the cooling curve after each addition. Obtain a total of five cooling curves with
a total amount of B ranging from 0 to 4 g.

4.

Add another 1 g of B to the mixture and obtain one final cooling curve, but this time
obtain a complete one, i.e., stop only when the temperature has dropped 5 C below
the temperature where all the liquid has solidified. In total, you should have a total of
six cooling curves: one complete cooling curve for the pure compound, as well as four
incomplete cooling curves and one complete cooling curve for the mixtures. Dispose
the mixture into the waste container in the fume hood, clean (with acetone and water)
and dry the inner tube.

Part 2. DSC measurement.

For this experiment, you will share your results with other groups of students that perform
DSC measurements on the same pair of compounds. Discuss among yourselves how you
would split the workload so you do not accidentally perform DSC measurements on
mixtures with the same composition as another group.
1.

Prepare a series of binary mixtures of A and B (approximately 0.5 g each) in 25 mL

beakers with compositions equal or close to those used in Part 1. Grind the mixture
with a mortar and pestle so the solids are homogeneously mixed.

2.

Obtain the DSC curve of pure A, pure B and each mixture in air (flow rate: 50 mL
min1) at the heating rate of 10 C min1. Two heating cycles should be used to ensure
all samples have the same thermal history. Only the data from the second heating cycle
will be used for analysis.

3.

Obtain the melting point and the eutectic point, as well as the enthalpy of fusion from
the DSC curves of the samples.

D. ANALYSIS AND DISCUSSION

1.

With data obtained in Part 1, plot the cooling curves and determine the thermal break
and/or arrest temperatures.

2.

Tabulate these temperatures and construct a temperature-composition phase diagram.

(Use mole fraction to represent the composition.)

3.

From the intersection of the liquidus curves of A and B, estimate the eutectic
temperature and the eutectic composition under normal atmospheric conditions.

4.

Model the data (

and

) using Equation 1. Using Microsoft Excel or otherwise,

perform a regression to obtain the fitted parameters of

and

as well as their

uncertainties. Compare them to literature values.

5.

With data obtained from the DSC measurement in Part 2, plot the phase diagram and
estimate the eutectic temperature and composition.

6.

Compare the above values determined using the two methods with the literature values.
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7.

Comment on the use of the two methods with regards to cost, practicality, and data
precision.

8.

Answer the following questions:

i.

Why do the system and the cooling bath need to be at a constant temperature
difference during cooling?

ii.

What are the greatest sources of error in this experiment? How could they be
reduced?

References
Gallus, J.; Lin, Q.; Zumbhl, A.; Friess, S. D.; Hartmann R.; Meister, E. C. J. Chem. Educ.,
2001, 78, 961964.
DAmelia, R. P.; Clark, D.; Nirode, W. J. Chem. Educ., 2012, 89, 548551.
West, A. R. Basic Solid State Chemistry, John Wiley & Sons: Singapore, 1991.