THERMAL METHODS OF ANALYSIS

INTRODUCTION

Thermal Analysis (TA) is a group of techniques that study the properties of materials as

they change with temperature.

In practice thermal analysis gives properties like; enthalpy, thermal capacity, mass

changes and the coefficient of heat expansion.

Thermal analysis can be used for studying thermal degradation reactions, phase

transitions and phase diagrams.

Thermal analysis is a branch of material science where the properties of materials are studied as they

change with temperature.

When matter is heated it undergoes certain physical and chemical changes. These physical and chemical

changes take place over a wide temperature range.

Physical changes such as melting or boiling may occur at widely varying temperature, depending on

material involve.

Chemical changes such as decomposition or reaction may also take place at very different temperatures.
Thermal analysis includes several different methods. These are distinguished from one another by the

property which is measured.

Thermogravimetric analysis (TGA): mass

Differential thermal analysis (DTA): temperature difference

Differential scanning calorimetry (DSC): heat difference

Pressurized TGA (PTGA): mass changes as function of pressure.

Thermo mechanical analysis (TMA): deformations and dimension

Dilatometry (DIL): volume

Evolved gas analysis (EGA): gaseous decomposition products

Outline

What is thermal analysis?

Principle/ Definitions

Instrumentation

Thermogram

Application

To explain principle of different types of thermal techniques.

To describe instrumentation of different types of thermal techniques

To distinguish between DSC,DTA & TGA

To explain application of thermal method

 Thermo Gravimetric analysis (TGA)
TGA is that method of analysis where change in mass of a substance (or its reaction

product(s)) is measured as a function of temperature when it is subjected to a controlled

temperature programme.

The measured weight loss curve gives information on:

• changes in sample composition

• thermal stability

• kinetic parameters for chemical reactions in the sample

A derivative weight loss curve can be used to tell the point at which

weight loss is most apparent

 Principle of TGA:
• In thermo-gravimetric analysis, the sample is heated in a given environment (air, N2, CO2, as a function of

temperaturHe, Ar, etc.) at controlled rate. The change in the weight of the substance is recorded e or time.

• The temperature is increased at a constant rate for a known initial weight of the substance and the changes

in weights are recorded as a function of temperature at different time interval.

• This plot of weight change against temperature is called thermo-gravimetric curve or thermo-gram, this is the

basic principle of TGA

Basic components of a typical thermobalance

are listed below:

1. Furnace

2. Balance

3. Unit for temperature measurement and

control (Programmer)

4. Recorder

5. Purging unit

Block Diagram of Thermobalance

 Balance: Null point balance
Null point balances: It consist of a sensor which detects the deviation from the null point and restores

the balance to its null points by means of restoring force.

Sample holder :
• The sample to be studied is placed in sample holder or crucible. It is attached to the weighing arm of
microbalance.
• There are different varieties of crucibles used. Some differ in shape and size while some differ in materials
used.
• They are made up from platinum, aluminum, quartz or alumina and some other materials like graphite,
stainless steel, glass etc
A plot of mass change versus temperature (T) is

referred to as the thermogravimetric curve (TG

curve).

TG curve helps in revealing the extent of purity of

analytical samples and in determining the mode of

their transformations within specified range of

temperature.

A Typical TG Curve
In a TG curve of a single stage decomposition, there are two characteristic

temperatures; the initial Ti and the final temperature Tf (see Fig below).

Ti is defined as the lowest temperature at which the onset of a mass change can be

detected by thermo balance operating under particular conditions and Tf as the final

temperature at which the particular decomposition appear to be complete.

The difference Tf – Ti is termed as reaction interval.

TG Curve of Calcium Oxalate in O2 and N2 atmosphere: [ __________N2 ,----------------- O2 ]
Derivative Thermogravimetry (DTG)

If the rate of change of weight with time dW/dT is

plotted against temperature, a derivative

thermogravimetric (DTG) curve is obtained.

In the DTG curve, when there is no weight loss, then dW/

dT = 0.

The peak on the derivative curve corresponds to a

maximum slope on the TG curve.

Factors affecting TGA: The factors which may affect the TG curves are classified into two main groups.:
(1) Instrumental factors:
(a) Furnace heating rate : The temperature at which the compound (or sample) decompose depends
upon the heating rate. When the heating rate is high, the decomposition temperature is also high. A
heating rate of 3.5°C per minute is usually recommended for reliable and reproducible TGA.
(b) Furnace atmosphere :
(2) Sample characteristics includes :
(a) Weight of the sample : A small weight of the sample is recommended using a small weight
eliminates the existence of temperature gradient throughout the sample.
(b) Sample particle size: The particle size of the sample should be small and uniform. The use of
large particle or crystal may result in apparent, very rapid weight loss during heating.
Other factors affecting TGA curve:
• Sample holder
• Heat of reaction
• Compactness of sample
• Previous history of the sample
Advantages of TGA:
• A relatively small set of data is to be treated.
• Continuous recording of weight loss as a function of temperature ensures equal weightage to
examination over the whole range of study.
• As a single sample is analyzed over the whole range of temperature, the variation in the value of the
kinetic parameters, if any, will be indicated.

Limitations of TGA:
• The Chemical or physical changes which are not accompanied by the change in mass on heating are not
indicated in thermo- gravimetric analysis.
• During TGA, Pure fusion reaction, crystalline transition, glass transition, crystallization and solid state
reaction with no volatile product would not be indicated because they provide no change in mass of the
specimen.
 Applications of TGA:
• The purity and thermal stability of both primary and secondary standard can be determined.
• Determination of the composition of complex mixture and decomposition of complex OR composition of
complex systems (In qualitative analysis).
• For studying the sublimation behavior of various substances.
• TGA is used to study the kinetics of the reaction rate constant.
•  Determination of composition of alloys and mixtures
• Oxidative stability of materials.
• Estimated lifetime of a product.
• TGA is often used to measure residual solvents and moisture, but can also be used to determine solubility of
pharmaceutical materials in solvents.
• The effect of reactive or corrosive atmosphere on materials.
• Moisture and volatiles contents on materials.
Application of TG to the analysis of a mixture of Ca2+,
Sr2+ and Ba2+ ions.

These are first precipitated as monohydrated oxalates

(MC2O4.H2O) and then subjected to heating at a rate
of 5°C/min.

The mass loss between 320°C and 400°C corresponds to

the combined ions of water by three anhydrous
salts forming MC2O4.

Mass between 580°C and 620°C corresponds to the

combined mass of the three carbonates (MCO3). The
mass loss in the next two steps represents loss of
C02 by CaC03 (to form CaO) and SrC03 (to form SrO)
respectively.

From this data, we can easily calculate the mass of each

clement present in the sample.
This is the derivative of thermogram shown in Fig. a.

Thus, in the differential thermogram, the three

peaks at 140°C, 180°C and 205°C suggest that the
three hydrates lose moisture at different
temperature, but a single sharp peak at about 405°C
shows that three oxalates lose CO simultaneously.
In study of polymers:
The most important application of TG is found in the study of
polymers.
TG thermogram provides valuable information about their
decomposition mechanisms.
Moreover, each kind of polymer follows a particular characteristic
pattern and hence, TG thermogram can be used for identification
purposes. Fig. below shows the TG thermogram of some common
polymers.
One of the most important applications of thermogravimetry is in
examining the thermal stability of polymers.
Thermogravimetry is also capable of giving information concerning
polymer identity.
Since derivative thermogravimetry (DTG) is able to show the
temperature where the maximum weight change appears to take
place, it is a valuable method for distinguishing polymers.
TG Thermogram Of PVC (polyvinyl chloride), PPMA
(polymethyl methacrylate), LDDE (low-density polythene)
and PTEE (polytetra fluoroethene)
Calculate the percentage mass change (m %) for the following reactions.

(i) Ca(OH)2 (s) CaO(s) + H2O (g)

74 56 18
% loss = (74-56)/74 x 100 = 24.3%

(ii) 6PbO(s) + O2 (g) 2Pb3O4 (s)

223 x 6 686 x 2
1338 1372
% gain = (1372 – 1338)/ 1338 x 100 = 2.4%

iii) NH4NO3 (s) N2O(g) + 2H2O(g)

In this case, both the products are volatile. No solid residue is left. The % loss in this case is 100%
DIFFERENTIAL THERMAL
ANALYSIS (DTA)
 DIFFERENTIAL THERMAL ANALYSIS (DTA)

DTA involves heating or cooling a test sample and an

inert reference under identical conditions, while
recording any temperature difference between the
sample and reference.

This differential temperature is then plotted against

time, or against temperature.

Changes in the sample which lead to the absorption or

evolution of heat can be detected relative to the inert
reference.

CHM 342
DTA may be defined as a technique for recording the difference in temperature between a substance and a
reference material against either time or temperature when both the specimens are subjected to identical
temperature regimes in an environment heated or cooled at a controlled rate.

In differential thermal analysis (DTA), both the test sample and an inert reference material (usually alumina)
undergo a controlled heating or cooling programme which is usually linear with respect to time.

There is a zero-temperature difference between the sample and the reference material, when the sample
does not undergo any chemical or physical change.
But if any reaction takes place, then a temperature difference (⧍T) will occur between the sample and the
reference material.

Thus, in an endothermic change (when the sample melts or is dehydrated), the sample is at a lower
temperature than the reference material. This condition is only transitory because, on completion of the
reaction, the sample will again show zero temperature difference compared with the reference.

In this technique the heat flow to the sample and reference remain the same rather than the temperature.
Principle:

The basic principle involved is:

The difference of temperature (ΔT) between the test sample (TS) and an inert reference sample (TR ) under

controlled and identical conditions of heating or cooling is recorded continuously as a function of temperature or
time.

The heat absorbed and emitted by a chemical system can be estimated or determined.

The changes are of two type; exothermic and endothermic

If endothermic- ΔT = TR – TS = +ve or TS – TR = -ve

If exothermic- ΔT = TR – TS = -ve or TS – TR = +ve

The Shape and size of the peaks can give a large amount of information about the nature of the test sample.

The sharp endothermic peaks often signify changes in crystallinity or fusion processes while broad endotherms arise from
dehydration reactions.

Physical Changes usually result as endothermic curves whereas chemical reactions, particularly those of an oxidative
nature, are predominantly exothermic.

The shape of a DTA peak does depend on sample weight and the heating rate used.

Lowering the heating rate is roughly equivalent to reducing the sample weight; both lead to sharper peaks with improved
resolution.
DTA; Phenomena causing changes in heat /temperature
Physical
Adsorption (exothermic)
Desorption (endothermic)
A change in crystal structure
(endo – or exothermic)
Crystallization (exothermic)
Melting (endothermic)
Vaporization (endothermic)
Sublimation (endothermic)
Chemical
Oxidation (exothermic)
Reduction (endothermic)
Break down reactions
(endo – or exothermic)
Chemisorption (exothermic)
Solid state reactions
(endo – or exothermic)
 DTA PROVIDES INFORMATION ABOUT:
(1) phase transformations
(2) structure inversions
(3) dehydration
(4) decomposition or dissociation
(5) oxidation or reduction
(6) destruction
(7) formation of crystalline lattice structure
(8) multiple transitions in crystalline structure
(9) recrystallization of quenched samples
(10) stress release
(11) reactions due to the presence of impurities
(12) volatilization of liquids, etc.
Fig: Differential thermogram of CaC2 O4 . H2 O in a flowing stream of air
Fig. shows the differential thermogram of calcium oxalate monohydrate in a flowing air (O2 ), obtained by

increasing temperature at a rate of 8ºC/min.

It contains two minima (for endothermic processes), equations for these decomposition reactions are

shown below the maxima. The single maxima indicate that oxidation of CaC2 O4 to CaCO3 and CO2 is

exothermic.

If the differential thermogram of calcium oxalate monohydrate is obtained in an inert atmosphere.

Then maxima changes to minima, since the decomposition reaction under inert condition would be

CaC2O4 CaCO3 + CO

which is an endothermic process. Hence, there will be three minima.

 Summary
Thermal analysis gives information about changes in material properties as
function of temperature.

Combining the two techniques (TGA-DTA) - comprehensive study of a materials thermal behaviour.
► While TG only measures changes caused by mass loss, DTA also register changes in material where no
mass loss occur, e.g. crystal structure changes, melting, glass transistion, etc.
DIFFERENTIAL SCANNING
CALORIMETRY (DSC)
DSC is a technique for measuring the energy necessary to establish a
nearly zero temperature difference between a substance and an inert
reference material, as the two specimens are subjected to identical
temperature regimes in an environment heated or cooled at a
controlled rate.
There are two types of DSC systems in common use.
In power–compensation DSC the temperatures of the sample and
reference are controlled independently using separate, identical
furnaces.
In heat–flux DSC, the sample and reference are connected by a low–
resistance heat–flow path (a metal disc).
The assembly is enclosed in a single furnace.
Enthalpy or heat capacity changes in the sample cause a difference in its
temperature relative to the reference; the resulting heat flow is small
compared with that in differential thermal analysis (DTA) because the
sample and reference are in good thermal contact.
The temperature difference is recorded and related to enthalpy change in
the sample using calibration experiments.

Fig: Heat Flux DSC

4. DSC finds widespread use in calculating enthalpy of transition
such as enthalpy of melting, enthalpy of crystallization, enthalpy
of fusion, etc. of polymeric materials.
DSC also provides a simple and accurate way of determining
melting, boiling and decomposition points for organic
compounds.
Moreover, DSC curves can be used to determine the purity of
drug samples.
For example, Fig. shows the DSC curves for phenacetin having
different purities. Generally, the curves provide purity data within
1% error.

The weight changes monitored by thermogravimetry invariably

involve the absorption or release of energy, hence they can be
measured by either DSC or DTA.
But there are many changes in energy that are not accompanied
by a gain or loss in weight.
For Example: melting, crystallisation, fusion and solid-state
transitions do not involve weight changes.
Thus, TG is often used in conjunction with either DTA or DSC.

Fig: DSC curves for samples of phenacetin of different

purities.