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 O 2 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 TG Thermogram Of PVC
(polyvinyl chloride), PPMA
maximum weight change appears to take
(polymethyl methacrylate), LDDE
place, it is a valuable method for
(low-density polythene) and
distinguishing polymers. 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 (∆T) between the test sample (T S) 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- ∆T = TR – TS = +ve or TS – TR = -ve
If exothermic- ∆T = 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 Chemical
Adsorption (exothermic) Oxidation (exothermic)
Desorption (endothermic) Reduction (endothermic)
A change in crystal structure Break down reactions
(endo – or exothermic) (endo – or exothermic)
Crystallization (exothermic) Chemisorption (exothermic)
Melting (endothermic) Solid state reactions
Vaporization (endothermic) (endo – or exothermic)
Sublimation (endothermic)
DTA PROVIDES INFORMATION ABOUT:
(1) phase transformations (generation of phase diagrams)
(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 CaC 2O4. H2O 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 CaC2O4 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 Fig: Heat Flux
related to enthalpy change in the sample using 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.
Fig: DSC curves for samples of
Thus, TG is often used in conjunction with
phenacetin of different
either DTA or DSC.
purities.
