Lecture NO.

1 & 2 (Week 01)

1. Introduction to thermal Methods

What are thermal Methods

Thermal methods of analysis have developed out of the scientific study of the changes
in the properties of a sample which occur on heating.

What is calorimetry

Calorimetric methods measure heat changes.

Difference Between Heat and Temperature

Heat and temperature are two different quantities. The basic difference between heat
and temperature is that, Heat is the form of energy that transfers from hot body to
cold body. Its unit is joule. While the temperature is the degree of hotness and coldness
of the body. Its SI unit is Kelvin. Heat is the total energy of molecular motion in a
substance while temperature is a measure of the average energy of molecular motion
in a substance. Heat energy depends on the speed of the particles, the number of
particles (the size or mass), and the type of particles in an object. Temperature does
not depend on the size or type of object. For example, the temperature of a small cup
of water might be the same as the temperature of a large tub of water, but the tub of
water has more heat because it has more water and thus more total thermal energy.

Important points

1. Heat is a form of energy that can transfer from hot body to cold body while
Temperature is the measure of degree of hotness and coldness of a body.
2. Heat is the total kinetic energy and potential energy obtained by molecules in an
object while Temperature is the average K.E of molecules in a substance.
3. Heat flows from hot body to cold body. Temperature depends on heat, it increases
when we heat an object and falls down when an object is cooled down.
4. Heat has a working ability while Temperature does not have the working ability.
5. SI unit for Heat is “Joule”. SI unit For Temperature is “Kelvin”.
6. Heat is measured by the calorimeter while Temperature is measured by the
thermometer.
Dr. Nadia Bashir
7. Heat is denoted by “Q”.Temperature is represented by “T”.
2. Types of changes in sample properties on heating

Some sample properties may be obvious to the analyst, such as colour,shape and
dimensions or may be measured easily, such as mass, density and mechanical
strength. There are also properties which depend on the bonding, molecular structure
and nature of the material. These include the thermodynamic properties such as heat
capacity, enthalpy and entropy and also the structural and molecular properties
which determine the X-ray diffraction and spectrometric behaviour. Transformations
which change the materials in a system will alter one or more of these properties. The
change may be physical such as melting, crystalline transition or vaporisation or it
may be chemical involving action which alters the chemical structure of the material.
Even biological processes such as metabolism, interaction or decomposition may be
included.

Sometimes a change brought about by heating may be reversed by cooling a sample

afterwards. A pure organic substance melts sharply, for example:

Benzoic acid melts at 122°C (forward reaction) and it recrystallizes sharply when
cooled below this temperature (reverse reaction).

Benzoic Acid (s) ⇌ Benzoic acid (g)

Similarly Ammonium chloride dissociates into ammonia and hydrogen chloride

gases when heated (forward reaction), but these recombine on cooling (Reverse
reaction).

NH4Cl (S) ⇌ NH3 (g) + HCl (g)

At high temperature, Calcium carbonate splits up to yield calcium oxide and carbon
dioxide gas (forward Reaction), and these too will recombine on cooling if the carbon
dioxide is not removed (Reverse Reaction). The system reaches an equilibrium state at
a particular temperature.

CaCO3, (s) ⇌ CaO (s) + CO, (g)

Dr. Nadia Bashir

To raise the temperature of a system heat energy must be supplied and when
sufficient energy is available the system will change into a more stable state. The
mechanical properties of a material change as it is heated. Often it expands and
becomes more pliable well below the melting point. These are fundamental, important
changes on a molecular level, and their study enables the analyst to draw valuable
conclusions about the sample, its previous history, its preparation, chemical nature
and the likely behaviour during its proposed use. The temperature at which a
particular event occurs, or the temperature range over which a reaction happens, are
often characteristic of the nature and history of a sample, and sometimes of the
methods used to study it. Sharp transitions, such as the melting point of pure
materials, may be used to calibrate equipment and as the "fixed points" of
thermometry and of the International Practical Temperature Scale (IPTS).

For example, the simple, pure inorganic compound potassium nitrate, KN0 3, is a
white crystalline solid at room temperature, 20°C. To raise its temperature to 30°C at
constant pressure, we must supply an amount of heat depending on the specific heat
capacity, Cp, approximately 1 J K-1 g-1 at this temperature, the mass m of the sample
and the change in temperature. So, for 1 g heated 10°C, we must supply 1O J. To
complicate matters, the heat capacity changes with temperature as well. When the
temperature reaches 128 °C, the crystals change their structure, and this needs more
energy, about 53 J g-1. Then the new crystals are heated, when Cp ≈ 1.2 J K-1 g-1, until
the melting point of 338°C, when more heat must be supplied to melt the sample.
Raising the temperature above the melting point eventually causes the sample to
decompose to form potassium nitrite, KN02, so that the mass of the sample is
decreased by around 16% and oxygen gas is given off.

Dr. Nadia Bashir

Step 1

KNO3 (solid powder) ⇌ KNO3 (solid crystals)------------ 20°C → 128°C

Step 2

KNO3 (solid crystals) ⇌ KNO3 (L) ------------- 128°C→ 338°C (Melting point)

Step 3

KNO3 (L) → KNO2 + O --------------- Decomposition Above melting point

This example illustrates the importance of thermal techniques and measurements.

Calorimetry measures the amounts of heat, while appropriate thermal methods give
the temperatures of phase changes, the temperatures of decomposition and the
products of the reaction. Other methods will show the expansion, mass and colour
changes on heating.

Dr. Nadia Bashir

 3. DEFINITIONS OF THERMAL AND CALORIMETRIC METHODS

Calorimetry is the measurement of the heat changes which occur during a process.
The calorimetric experiment is conducted under particular, controlled conditions, for
example, either at constant volume in a bomb calorimeter or at constant temperature
in an isothermal calorimeter. Calorimetry encompasses a very large variety of
techniques,including titration, flow, reaction and sorption, and is used to study
reactions of all sorts of materials from pyrotechnics to pharmaceuticals.Calorimetric
methods may be classified either by the principle of measurement (e.g. heat
compensating or heat accumulating), or by the method of operation (static, flow or
scanning) or by the construction principle (single or twin cell).

Thermal analysis is a group of techniques in which one (or more) property of a

sample is studied while the sample is subjected to a controlled temperature
programme. The programme may take many forms:

(a) The sample may be subjected to a constant heating (or cooling) rate

(b) The sample may be held isothermally (p = 0).

(c) A “modulated temperature programme” may be used where a sinusoidal or other

alteration is superimposed onto the underlying heating rate.

(d) To simulate special industrial or other processes, a stepwise or complex

programme may be used. For example, the sample might be equilibrated at 25°C for
10 min, heated at 10 K min-’ up to 2OO0C, held there for 30 min and then cooled at 5
K min-l to 50°C.

(e) The heating may be controlled by the response of the sample itself.

Dr. Nadia Bashir

4. Types of thermal methods

S/No Name of Technique Properties

1 Thermo-gravimetric Analysis Mass changes due to
(TGA) evaporation,
decomposition and
interaction with the
atmosphere
2 Differential thermal Analysis and Thermal effects from
Scanning Calorimetry physical and chemical
(DSC, DTA) processes (phase
transitions, reactions);
specific heat
3 Thermo-mechanical Analysis (TMA) deformations,
viscoelastic properties,
4 Dynamic-Mechanical Analysis (DMA) Dimensional changes,
transitions
5 Dielectric Analysis Electrical
(DEA)
6 Evolved gas analysis (EGA) Gases evolved or
reacted: decomposition
7 Dilatometry (DIL) volume

Dr. Nadia Bashir