THERMAL

ANALYSIS
 INTRODUCTION

🠶 Thermal analysis is a group of techniques in which a physical property of a

substance and/or its reaction products is measured as a function of
temperature while the substance is subjected to a linear increase in temperature
@ 5 or 10 C.

🠶 In this course, you will study three methods

 Thermo Gravimetric analysis (TGA)
 Differential thermal analysis (DTA)
 Differential Scanning Calorimetry (DSC)
Thermo Gravimetric analysis
(TGA)
Thermogravimetric analysis (TGA) is the most widely used thermal method. It is based on the
measurement of mass loss of material as a function of temperature.
🠶 In thermogravimetry a continuous graph of mass change against temperature is obtained when a
substance is heated at a uniform rate or kept at constant temperature.
🠶 A plot of mass change versus temperature (T) is referred to as the thermogravimetric curve (TG
curve).
🠶 For the TG curve, we generally plot mass (m) decreasing downwards on the y axis (ordinate), and
temperature (T) increasing to the right on the x axis (abscissa) as illustrated in Fig below. Sometime we
may plot time (t) in place of T.
🠶 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 thermogravimetry, the term ‘decomposition temperature’is a complete misnomer.
🠶 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.
 In a dynamic thermogravimetry a sample is subjected to continuous increase in temperature
usually linear with time whereas in isothermal or static thermogravimetry the sample is
maintained at a constant temperature for a period of time during which any change in mass is
noted.

A Typical TG
Curve
 Objectives

After studying this unit, you should be able to:

🠶 explain the principle of TGA
🠶 describe the experimental setup of TGA
🠶 interpret the analytical information from TGA curves
🠶 describe the applications of TGA in qualitative and quantitative analysis of inorganic,
organic and polymer material.
 INSTRUMENTATION
The instrument used in thermogravimetry (TG) is called a Thermobalance. It consists of several basic
components in order to provide the flexibility necessary for the production of useful analytical data in the
form of TGA Curve.
Basic components of a typical thermobalance are listed below:
1. Balance
2. Furnace: heating device
3. Unit for temperature measurement and control (Programmer)
4. Recorder: automatic recording unit for the mass and temperature changes These components may be
represented by simple block diagram as shown in Fig below.

Block Diagram of Thermobalance

1. Balance
The basic requirement of an automatic recording balance are includes accuracy, sensitivity, reproducibility, and capacity.
The different balances used in TG instruments are having measuring range from 0.0001 mg to 1g depending on sample
containers used.

2. Furnace
🠶 The furnace and control system must be designed to produce linear heating at over the whole working temperature range
of the furnace and provision must be made to maintain any fixed temperature.
🠶 A wide temperature range generally -150 °C to 2000 °C of furnaces is used in different instruments.

3. Temperature Measurement and Control

🠶 Temperature measurement are commonly done using thermocouples , chromal – alumel thermocouple are often used
for temperature up to 1100 °C whereas Thermogravimetric Analysis Pt/(Pt–10% Rh) is employed for temperature up to
1750 °C.
🠶 Temperature may be controlled or varied using a program controller with two thermocouple arrangement, the signal from
one actuates the control system whilst the second thermocouple is used to record the temperature.

4. Recorder
Graphic recorders are preferred for meter type recorders. X-Y recorders are commonly used as they plot weight directly
against temperature. The present instrument facilitate microprocessor controlled operation and digital data acquisition and
processing using personal computer with different types recorder and plotter for better presentation of data.
Factors Affecting Thermogravimetric Results
1. Furnace heating rate
🠶 At a given temperature, the degree of decomposition is greater the
slower the heating rate, and thus it follows that the shape of the TG curve
can be influenced by the heating rate.
🠶 For a single stage endothermic reaction it has been found that:
i) (Ti )F > (Ti )S
ii)(Tf)F > (Tf)S
iii)(Tf –Ti )F > ( Tf –Ti )S
where subscripts F and S indicate fast and slow heating rate respectively.
🠶 For example, calcium carbonate would not show any mass loss below 600
°C, when heated in a thermobalance at heating rate of 3 °C per min., and
yet it is known that CO2 is evolved at 250 °C.
🠶 Similarly, polystyrene decomposes 10% by mass when heating rate is 1
°C per min by 357 °C and 10% by mass when heating rate is 5 °C per
min by 394 °C.
🠶 More specifically, it is observed that the procedural decomposition
temperature Ti, and also Tf (the procedural final temperature) will decrease
with decrease in heating rate and the TG curve will be shifted to the left.
🠶 This effect is illustrated in Fig. shown. The appearance of an inflection in a
TG curve at a fast heating rate may well be resolved into a plateau at a
slower heating rate. Therefore, in TGA there is neither optimum no
standard heating rate, but a heating rate of 3 °C per min. gives a TG curve
with maximum meaningful resolution.
 2. Furnace The effect of atmosphere on the TG curve depends on
Atmosphere
(i)the types of the reaction
(ii)the nature of the decomposition products and
(iii)type of the atmosphere employed.
The effect of the atmosphere on TG curve may be illustrated by taking the example
of thermodecomposition of a sample of monohydrates of calcium oxalate in
dry O2 and dry N2 as shown in Fig.
The first step, which is dehydration is reversible reaction.
Ca C2O4.H2O(s) Ca C2O4(s) + H2O (g )
This is unaffected because both gases are equally effective in sweeping the evolved
water vapours away from the sample surface. For the second step,
Ca C2O4(s)(s) CaCO3 (s) + CO (g)
The curve diverges in O2 atmosphere because the oxygen reacts with evolved CO,
TG Curve of Calcium Oxalate in O2 and N2 giving a second oxidation reaction which is highly exothermic and so raises the
temperature of the un- reacted sample. The temperature accelerates the
atmosphere: [ __________N2 ,-----------------
decomposition of the compound more rapidly and completely at a lower
O2]
temperature as shown in the above diagram in dry O2 then in N2 atmosphere . The
third step in decompositionreaction is also reversible reaction.
CaCO3 (s) CaO (s) + CO2 (g)
This step should not be influenced by O2 or N2. However there is a slight difference
in curves for the two gases as shown in diagram. The small difference was due to
the difference in the nature/composition of CaCO3 formed in the two atmospheres.
This is due to the particle size, surface area, lattice defects or due to the other
physical characteristics of CaCO formed.
3. Sample Holder
 The sample holders range from flat plates to deep crucible of various capacities. The shape of the TG curve will vary as the
sample will not be heated in identical condition.
 Generally, it is preconditioning that the thermocouple is placed on near the sample as possible and is not dipped into the sample
because it might be spoiled due to sticking of the sample to the thermocouple on heating. So actual sample temperature is not recorded,
it is the temperature at some point in the furnace near the sample.
 Thus it leads to source of error due to the thermal lag and partly due to the finite time taken to cause detectable mass change. If the
sensitivity of recording mechanism is not enough to record the mass change of the sample then this will also cause error in recording the
weight change of the sample.
 If the composition of the sample contains is such that it reacts either with the sample, or product formed or the evolved gases then this
will cause error in recording the mass change of the sample.

4. Effect of Sample Mass

The sample mass affects the TG curve in following
i. The endothermic and exothermic reactions of the sample will cause sample temperature to deviate from a linear temperature change

ii. The degree of diffusion of evolved gases through the void space around the solid particles
iii. The existence of large thermal gradients throughout the sample particularly, if it has a low thermal conductivity. Thus, it is
preferable to use as small a sample as possible depending on the sensitivity of the balance.

5. Effect of Sample Particle Size

 The particle size will cause a change in the diffusion of the evolved gases which will alter the reaction rate and hence the curve shape.
 The smaller the particle size, greater the extent of decomposition at any given temperature. The use of large crystal may result in
apparent vary rapid mass loss during heating. This may be due to the mechanical loss of part of the sample by forcible ejection from the
sample container, when the accumulated evolved gases within the coarse grains are suddenly released.
 APPLICATIONS OF TERMOGRAVIMETRIC
ANALYSIS
1. Determination Of purity and chemical stability of both primary and secondary standards:

🠶 Thermogravimetry is a valuable technique for assessing the purity of materials. Analytical reagents especially those used in
titrimetric analysis as primary standards (e.g., sodium carbonate, sodium tetraborate and potassium hydrogen phthalate), have
been examined. Many primary standards absorb appreciable amounts of water, when exposed to moist atmospheres. TG data can
show the extent of this absorption, hence the most suitable drying temperature for a given reagent may be determined.
🠶 From TG studies, the thermal stability of EDTA as the free acid and also as the more widely used disodium salt Na2EDTA. 2 H20
have shown that the dehydration of the disodium salt commences at between 110 and 125°C, so Na2EDTA. 2 H20 could be safely
heated to constant weight at 80°C.

2. Investigating the correct drying temperatures and the suitability of various forms gravimetric analysis:

Initially, the most widespread application of thermogravimetry in analytical chemistry has been in the study of the recommended drying
temperatures of gravimetric precipitates. Duval studied over a thousand gravimetric precipitates by this method and gave the
recommended drying temperatures.
3. In qualitative analysis:

A TG curve indicates the “horizontal portions” (which represent no

weight change) and slinting downwards curves (which represent weight
loss, due to dehydration/ rupture/ formation of volatile products).
🠶 Thus, a TG thermogram is a characteristic for a given compound, since
the unique sequence of physico-chemical reactions occurring over
definite temperature ranges are a function of the molecular structure.
🠶 Fig. below shows the thermogram for decomposition of pure calcium
oxalate (CaC2O4 . H20) obtained by increasing the temperature at a rate
of 5°C/min.
🠶 It is thermally stable upto 100°C and water is evolved slightly above
100°C. At about 226°C, a break is obtained in the downward curve at the
stoichiometry corresponding to anhydrous salt (CaC2O4). TG curve for decomposition of CaC2O4 . H20
🠶 The horizontal portion between 226 — 346°C indicates that anhydrous
salt is thermally stable in this range. At slightly above 346°C, it again
starts losing CO is yield CaCO3. Process is complete at about 420°C.
🠶 Beyond 420°C, CaCO3 is stable upto about 660°C. Beyond 660°C,
there is evolution of CO2 to give CaO. At 840°C, this decomposition is
complete. At 840°0 and above, the horizontal portion represents the
stable CaO.
4. Determination of composition of alloys and mixtures:
🠶 Thermogravimetry may be used to determine the composition of binary mixtures. If each
component possesses a unique pyrolysis curve then resultant curve for the mixture will afford a basis
for determining its composition.

🠶 In such an automatic gravimetric determination, the initial weight of the sample need not be known. A
simple example is automatic determination of a mixture of calcium and strontium as their
carbonates. Both carbonates decompose to their oxides with the evolution of carbon dioxide.

🠶 The decomposition temperature for calcium carbonate is in the temperature range 650 — 850°C
whereas strontium carbonate decomposes in the range 950 — 1150°C.

🠶 Hence. the amount of calcium and strontium present in a mixture may be calculated from the weight
losses due to the evolution of carbon dioxide at the lower and higher temperature ranges respectively.

🠶 This method can be extended to the analysis of a three-component mixture, as barium carbonate is
reported to decompose at an even higher temperature (-1300°C) than strontium carbonate.
 A further example is the automatic determination of a mixture of calcium and magnesium and their oxalates.
Calcium oxalate monohydrate has three distinct regions Of decomposition; magnesium oxalate dihydrate has only two :

🠶 A pyrolysis curve for a mixture of these two oxalates would thus show three decomposition steps.
🠶 The final step would be due entirely to the loss of carbon dioxide from calcium carbonate hence the amount
of calcium present in the mixture may be calculated.
🠶 The amount of magnesium in the oxalate mixture may be calculated from the second step. where stages (b)
and (e)
occur.
🠶 This is because the amount of carbon monoxide due to calcium carbonate may be subtracted from the total
observed weight loss, giving the loss of carbon dioxide and carbon monoxide from anhydrous magnesium oxalate.
🠶 Since stages (a) and (d) do not feature in the calculation, the mixture of Calcium and magnesium oxalates
does not require drying before the automatic determination.
 🠶 Fig. below illustrates the application of TG to the analysis of a mixture of
Ca2+, Sr2+ and Ba2+ ions.

🠶 These are first precipitated as monohydrated oxalates (MC2O4.H2 O) 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. Fig. b is the derivative of thermogram shown in Fig. a.

🠶 Thus, in the differential thermogram of Fig. b, 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 450°C shows that
three oxalates lose CO simultaneously.
5. 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

TG Thermogram Of PVC (polyvinyl chloride),
examining the thermal stability of polymers.
PPMA (polymethyl methacrylate), LDDE (low-
density polythene) and PTEE (polytetra
🠶 Thermogravimetry is also capable of giving information concerning fluoroethene)
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.
6. Studying the oxidation of
alloys
🠶 The oxidation of the cobalt-samarium alloy Co5Sm
was examined by thermogravimetry using an air
atmosphere. The results are shown in Fig below.

🠶 The weight increase AB resulted from the oxidation

of Sm to Sm2O3. The increase BC was due to the
oxidation of Co to Co3O4 and to the formation of the
mixed oxide CoSmO3.

🠶 The final weight loss DE was obtained from the

conversion of Co3O4 to CoO. The formation of Sm2O3
and the mixture of Co3O4 and CoSmO3 were
Oxidation of Co5Sm by thermogravimetry in an air
confirmed by X-ray diffraction studies. atmosphere. AB shows oxidation of Sm to Sm2O3 :
BC shows oxidation of Co to Co3O4 and formation of
the mixed oxide CoSmO4 : DE shows the conversion
of Co3O4 to CoO