Unit 7.

Thermal Analysis-I
7.1 Thermal Analysis

Thermal method of analysis monitors property of a sample as a function of temperature change.

OR

Thermal analysis monitors temperature change as a function of a chemical reaction.

In thermal analysis, a wide range of temperature provided to substances, during which it

undergoes some physical or chemical changes, react with the constituents of atmosphere, water
of crystallization may be removed or the sample may undergo fragmentation etc. All these
changes are accompanied by the absorption or release of heat energy.

As fact substances have many properties which could be monitor, so many types of thermal
analysis are possible. The major classes of thermal analysis are;

7.1.1 Types of thermal Analysis

There are various types of thermal analysis,

a. Thermogravimetry

In this method mass of the sample is measure as a function of increase in temperature. Through
this method we can determine thermal stability, rate of reaction, reaction process, and sample
composition.

b. Differential Thermal Analysis (DTA)

In this method the temperature difference between sample and non-reactive reference substance
is monitored as a function of controlled temperature of one of the two substances. Though this
method we can determine heat of reaction, kinetics, heat capacities, phase transition, thermal
stabilities, sample composition and purity, critical points, and phase diagrams.

c. Differential Scanning Calorimetry (DSC)

In this technique of thermal analysis, the difference in heat which goes to the sample and that
which goes to the reference substance is monitored as a function of temperature. This is similar
to DTA.

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7.2 Thermogravimetric Analysis (TGA)

Thermogravimetry (TG) involves continuously measuring the mass of a sample as a

function of its temperature. Plot of mass versus temperature are called
Thermogravimetric curves or TG curves.
7.2.1 General Description
Suitable sample for TG are solid that undergo one of the following reactions.
Reactants (s) → Product (s) + Gas
Gas + Reactants (s) → Product (s)
The first reaction involves a mass loss, whereas the second involve a mass gain. Process
occurring without change in mass cannot be studied by thermogravimetry such as melting
of a substance. Generally change in mass occurs due to volatile component present in
sample, for example H2O is a major concern. In this technique decomposition and
dissolution are frequently monitored. The change in mass can be used for quantitative
analysis and the temperature at which the change take place is useful for qualitative
analysis.

7.2.2 Instrumentation of Thermogravimetric Analysis (TGA)

TGA instrumentation should made of the following components.
(a) A balance
(b) A heating device
© A unit for temperature measurement and control
(d) A mean for automatically recording the mass and temperature
(e) System to control the atmosphere around the sample.
The combination of these apparatus which simultaneously heat the sample and measure
the change in mass is called thermobalance.

(a) Balance
Balance must remain precise, accurate under extreme temperature and atmospheric
conditions and should deliver a signal for continuous recording. The electro balance

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 is largely used. This device providing an electrical force to restore the beam to its
original position as the mass of the sample change.
(b) Heating device
The sample can be heated by resistance heaters by infrared or microwave radiation or
by heat transfer from hot liquid or gases. Usually the sample is heated inside the
furnace by above mentioned sources. Furnace should be designed to heat the sample
uniformly and systematically and also the furnace should be designed so that the heat
generated should localize on the sample.
(c) Temperature measurement and control
The initial, final temperature and rate of temperature increase between the initial and
final temperature can be controlled on some instrument by dials located on the control
panel of the instrument.
The temperature of the instrument is normally monitored by thermocouples which
placed near but not contact with the sample.
(d) Recording the signal
Electrical signal from the balance and from the measuring thermocouples is fed into
recording potentiometer, or a strip chart-recorder or x-y recorder may also be used.
(e) Controlling the atmosphere
The composition of the atmosphere around the sample can have large and
advantageous effect. The instrument is equipped with a system whose function is
continuously purging the furnace and sample with a gas. Nitrogen or argon is largely
used.

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 Figure 7.1 A diagram of thermobalance

7.2.3 Mode of operation of thermobalance

The sample is placed in the sample boat on the single pan of the balance. Counterweights are

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used on the opposite arm of the balance. The beam of the balance is constructed from quartz and
attached to a metallic arm housed between the poles of an electromagnet. Change in mass
through heating is accompanied with the volatization or some time due to decomposition to
cause the balance to move. Motion of the balance is detected by observing the deflection of a
light beam on a photosensitive null detector which is attached to the beam of the balance. A
deflection of the beam is automatically compensated by a change in current flow through the
electromagnet which restores the beam to its original position. The current that flows through the
electromagnet is monitored and is displayed on the read out device. The electrical signal is
basically related to the sample mass. Although sample as large as 1 g can be studied with some
instrument. Sample with masses between 5 and 25 mg are used for most studies.

Thermobalance can be operated in two different ways. One is isothermally (temperature

constant) and other is temperature program study. In each case curve will be obtain between
change in mass and temperature or time. Typically the heating rate is adjusted between 5 and 25
o
C/min. Generally dark colored substances absorb thermal energy more readily than white
substances.

7.2.4 Analytical calculation

Thermogravimetry can be used for both qualitative and quantitative analysis.

Qualitative analysis:-
The onset temperature can be used for qualitative analysis. It is the temperature on which change
in mass occurs. It is measured by extrapolating to intersection the linear portion of the thermal
curve recorded prior to and during the mass loss. The onset temperature can be compared to
values for standards that were measured under identical experimental conditions for qualitative
analysis. Often a single sample has several consecutive mass losses and onset temperature.

Quantitative analysis:-
The mass change ∆m is measured from thermal curve which can be used for quantitative
analysis. The ∆m is obtained from the linear vertical portion of the TG curve between the
horizontal portion prior to and after the mass loss.

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Figure 7.2 A diagram illustrating measurement of the onset temperature Tonset from a thermal
curve

7.2.5 Application of Thermogravimetry

Thermogravimetry can be used for qualitative and quantitative analysis. On feature of the TGA
curve is the onset temperature which is used for qualitative analysis and other is the change in
mass (∆m) which is used for quantitative analysis.
A few interesting applications of thermogravimetry are given below.

1. Mixture of divalent cation oxalate can be analyzed successfully with a high degree of
precision. A mixture of calcium, strontium and barium oxalate monohydrate wills loss all its
water of hydration between 100 oC and 250 oC. The three anhydrous oxalate will decompose
simultaneously between 360 oC and 500 oC and the carbonate will finally decompose to
oxides in the following order.
Calcium 620 to 860 oC (240 oC)
Strontium 860 to 1100 oC (240)
Barium 1100 to onward
2. Thermogravimetry can also be used to determine the temperature range within which a
precipitated reaction product can be dried during a gravimetric analysis and to study some
chemical reaction at elevated temperatures.

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3. Thermal curve are often used to characterize polymeric materials such as polyvinyl chloride
and polyethylene.
4. In oxidizing atmosphere (oxygen or air purge gas) oxidation product of the sample can form,
as an example, while using oxygen as the purge gas, FeS is converted to Fe2(SO4)3, causing a
mass gain rather than a mass loss. Fe2(SO4)3 is further oxidized to Fe2O3. Thus gain in mass
instead of loss can also be analyzed using thermogravimetry.

7.3 Differential Thermal Analysis (DTA

Differential thermal analysis (DTA) is the analytical technique in which the temperature
difference between the sample and a non-reactive reference material is monitored while the two
substances are subjected to the identical heating program. The thermal curve is a plot of the
temperature difference as a function of the temperature of one of the two substances. Normally
the temperature difference is recorded as a function of the temperature of the reference
substance.

7.3.1 General Consideration

Difference in temperature between sample and inert material can be measured if changes occur
in some basic properties, such as heat of reaction, phase change or structural changes occurs in
the sample. Thermal curves obtained with DTA show peaks corresponding to processes in which
the temperature of the sample is increased or decreased relative to the temperature of the
reference substance. Upward deflections usually correspond to exothermic reaction and
downward deflections to endothermic reaction. Figure 7.3 shows the DTA curve for exothermic
and endothermic process.

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Figure 7.3 DTA curve showing exothermic and endothermic process.

DTA curve is useful both for qualitative and quantitative analysis. The temperature at which the
peaks are observed in the thermal curve can be used for qualitative analysis by comparison with
curve recorded under similar conditions with known materials. Peak area or peak heights are
used for quantitative analysis.

7.3.2 Instrumentation of DTA

DTA instrument consists of the following parts;
a. A circuit for measuring difference in temperature
b. A heating device and temperature controlled unit.
c. An amplifying and recoding apparatus.
d. An atmosphere controlled device.

These parts will be discussed in detail below.

Temperature measurement:-
Thermocouples are the most reliable device for measuring temperature. The temperature
measurement of sample and reference material largely depends on the size of the sample and
packing. Thus the size should be as small as possible and the packing should be uniform.

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 Thermocouples may be embedded in the sample or may be physically separated from
sample and reference. In any case the thermocouples of sample and reference should be matched
in temperature and the geometrical arrangement of the sample and reference thermocouples
should be symmetrical with the oven.

Heating and Temperature Control:-

Heating and temperature control units are very similar to that of thermogravimetry (TG). Ovens
are used for heating which should be constructed in such a way to avoid electrical interferences
with the thermocouples. For this purpose most instruments have an inner chamber for sample
and reference to act as an electrical shield and to minimize thermal fluctuations.

Recording the Signal:-

Signal amplification and recording is done in much the same way as that of TG, but replacing the
signal for mass change with the potential difference between the thermocouples.

Figure 7.4 Schematic of the entire DTA setup

7.3.3 Applications of DTA

DTA curves are use both for quantitative as well as qualitative analysis.

Qualitative application:-

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Including qualitative applications using DTA curve we can determine rate of reaction, activation
energy and heat capacity of substance.

i. Heat capacity determination

Heat capacity can be determined using DTA curve. First reference and sample of known heat
capacity is run and baseline is obtained. Then a baseline with sample of unknown heat capacity
is obtained. The baseline for two is not always the same, but there is a shift after the peak of the
sample baseline. From comparison of this shift of the sample known and unknown heat capacity
we can easily estimate the heat capacity of the unknown sample.

ii. Polymer determination

Under control careful condition, the shape of the heating curve indicates both the type of
polymer and the method use to prepare it. There are commonly two peaks one for the reaction of
crystalline part and other for the reaction of non-crystalline part. The magnitudes of these peaks
are used to estimate percent crystalinity.

Quantitative application:-

DTA can also be used for quantitative analysis.

i. The analysis of soil and clay can also be brought by DTA.

ii. Analysis of biological materials such as leaves, cell culture, and tissue culture can also be
brought by DTA.

Best of Luck

Dr. Muhammad Naeem Khan

Assistant Professor
Department of Chemistry
Allama Iqbal Open University
Islamabad

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