Unit 8 Thermal Methods of Analysis

UNIT 8

THERMAL METHODS OF
ANALYSIS

Structure
8.1 Introduction 8.6 Factors Affecting TG Curve

Expected Learning Outcomes 8.7 Applications of

Thermogravimetric Analysis
8.2 Thermogravimetric Analysis
8.8 Summary
8.3 Instrumentation
8.9 Terminal Questions
8.4 Sources of Error in TGA
8.10 Answers
8.5 Interpretation of TG Curve

8.1 INTRODUCTION
In the preceding blocks you have studied various chromatographic methods.
These methods are commonly used to separate mixtures. We now turn our
attention to other analytical methods which are based on the determination of
changes in chemical or physical properties of material on heating. These
analytical methods are known as thermal methods. These have been
developed based on the scientific study of changes in the properties of a
sample which occur on heating. You may be familiar will the facts like, when
ice is heated, it melts at 0 oC and then boils at 100 oC, when sugar is heated; it
first melts, and then forms brown Caramel. In your undergraduate Organic
Chemistry lab you may have used melting points of organic solids in assessing
the purity and characterization of organic compounds. Melting points are
independent of experimental conditions whether we were using an oil bath or a
heating block. Basically in this process we are subjecting the organic sample
to a heating procedure and measuring a physical property (melting point) by
observing the physical change of the material, as it is heated. In fact, every
material behaves in a characteristic way when heated. The thermal methods
of analysis are based on the determination of change in chemical or physical
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Block 3 Thermal and Electroanalytical Methods

properties of material as a function of temperature in a controlled atmosphere.

These methods are good analytical tools to measure:

 thermal decomposition of solids and liquids;

 solid-solid and solid-gas chemical reactions;

 material specification, purity and identification;

 adsorption behaviour of material;

 phase transitions.

These informations help us in the characterization of organic and inorganic

chemicals, polymers, metals, semiconductors and other common classes of
materials. Not only this, thermal methods also help us in understanding the
likely behaviour of chemicals and materials with change of temperature during
reactions, transport and storage. On that basis, one can suggest to take
possible precaution in handling the particular chemical or material.

Here we have summarized the variety of materials which can be usefully

studied by the thermal methods.

1. Organic and Inorganic compounds

2. Pharmaceuticals

3. Polymers and Plastics

4. Textiles and Fibers

5. Minerals, Soils and Clays

6. Ceramics and Glass

7. Building materials such as cement and concrete

8. Catalysts

9. Biological Materials e.g. kidney stone

10. Explosives

11. Fats, oils, soaps and waxes

12. Flame retardants

13. Foodstuffs and additives

14. Liquid crystals

15. Metals and alloys

The more frequently used thermal methods of analysis are shown in Table1,
with the brief names commonly used for them.
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Unit 8 Thermal Methods of Analysis

Table 8.1: Thermal methods

Technique Abbreviat Property Uses
ion

Thermogravimetry or TG Mass Decompositions

(Thermogravimetric TGA Oxidations
analysis)
Differential thermal DTA Temperature Phase changes,
analysis difference reactions
Differential scanning DSC Power difference Heat capacity,
calorimetry or heat flow phase changes,
reactions
Thermometric Titration TT Enthalpy Acid-base and Non-
aqueous systems

Though in this unit our focus will be on thermogravimetric analysis, but a brief
description these techniques is given below.
TGA: This is a technique in which weight of a material is measured as a
function of temperature in controlled conditions. This technique provides
information regarding weight change of a material on heating and enables the
stoichiometry of the reaction involved during process. When we heat a
sample there may be two situations, sample either loses weight or gain weight,
which are shown below:
Sample (Solid) Product (Solid) + Gas (Loss of weight)
Gas + Sample (Solid) Product (Solid) (Gain of weight)

DTA & DSC: In DTA techniques, the difference in the temperature (  T)

between the material and an inert reference material is measured as function
of temperature under control conditions. DSC is very similar to DTA as both
shows an endotherm on melting and an endotherm (or exotherm) when
decomposition of material occurs. DSC differs from DTA in that instead of
allowing a temperature difference to develop between the sample and
reference, DSC measures the energy that has to be applied to keep the
temperature same. Beside these techniques thermometric titrations have
many applications in analytical chemistry. In such titrations we plot a graph of
change in temperature (  T) against the volume of titrant added. These
titrations are used for quantitative analysis.

Instrumentation for thermal methods

The modern instrumentation used for any experiment in thermal methods is

usually consists of five major parts:

 The sample and a container or holder,

 Sensor to detect and measure a particular property of the sample and to

measure temperature,

 An encloser within which the experimental parameters such as

temperature, pressure, gas atmosphere may be controlled,
9
Block 3 Thermal and Electroanalytical Methods

 A programmer to control the experimental parameters, such as the

temperature programmer,

 Recorder to collect the data from the sensors and to process the data to
produce meaningful results

Basic components of an instrument used for thermal methods are shown

schematically below.

Schematic of a typical instrument used to measure thermal properties

Expected Learning Outcomes

After studying this unit you should be able to:

 describe the basic thermal methods of analysis;

 explain the principle of TGA;

 describe the experimental setup of TGA;

 interpret the analytical information from TGA curves; and

 describe the applications of TGA in qualitative and quantitative analysis

of inorganic, organic and polymer materials.

8.2 THERMOGRAVIMETRIC ANALYSIS

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. 8.1. 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.

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.
8.1). Ti is defined as the lowest temperature at which the onset of a mass
10 change can be detected by thermo balance operating under particular
Unit 8 Thermal Methods of Analysis

conditions and Tf as the final temperature at which the particular

decomposition appears to be complete. Although Ti has no fundamental
significance, it can still be a useful characteristic of a TG curve and the term
procedural decomposition temperature has been suggested. 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. Now we will take up the instrumentation
commonly used to obtain TG Curve.

Fig. 8.1: A Typical TG Curve

8.3 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 as shown in Fig. 8.4.

Basic components of a typical thermobalance are listed below:

i) Balance

ii) Furnace: heating device

iii) Unit for temperature measurement and control (Programmer)

iv) Recorder: automatic recording unit for the mass and temperature
changes

These components may be represented by simple block diagram as in Fig. 8.2

Fig. 8.2: Block diagram of a Thermobalance. 11

Block 3 Thermal and Electroanalytical Methods

Balance

The basic requirements of an automatic recording balance are accuracy,

sensitivity, reproducibility, and capacity. Recording balances are of two types,
null point and deflection type. The null type balance, which is more widely
used, incorporates a sensing element which detects a deviation of the balance
beam from its null position. The sensor detects the deviation and triggers the
restoring force to bring the balance beam back to the null position. The
restoring force is directly proportional to the mass change. Deflection
balance of the beam type involve the conversion of the balance beam
deflection about the fulcrum into mass – change curves identified by (a)
photographic recoding i.e. change in path of a reflected beam of light
available of photographic recording, (b) recording electrical signals generated
by an appropriate displacement measurement transducer, and (c) using an
electro- mechanical device. The different balances used in TG instruments are
having measuring range from 0.0001 mg to 1 g depending on sample
containers used.

Furnace

The furnace and control system must be designed to produce linear heating
rate over the whole working temperature range of the furnace and provision
must be made to maintain any fixed temperature. A wide temperature range
generally from ambient temperature to 2000 °C of furnaces is used in
different instruments manufacturers depending on the models. The range of
furnace basically depends on the types of heating elements are used.

Temperature Measurement and Control

Temperature measurement are commonly done using thermocouples ,

chromel – alumel thermocouple are often used for temperature up to 180°C
whereas Pt/(Pt–8% 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.

Recorder

Graphic recorders are preferred to 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 of
recorder and plotter for better presentation of data.

In Fig. 8.3, we have shown a schematic diagram of the specific balance and
furnace assembly as a whole to better understand the working of a
thermobalance. In this diagram you can clearly see that the whole of the
balance system is housed in a glass to protect it from dust and provide inert
atmosphere. There is a control mechanism to regulate the flow of inert gas to
provide inert atmosphere and water to cool the furnace. The temperature
sensor of furnace is linked to the programme to control heating rates, etc. The
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Unit 8 Thermal Methods of Analysis

balance output and thermocouple signal may be fed to recorder to record the
TG Curve.

Fig. 8.3: Schematic diagram of a typical balance and furnace assembly.

Thermogravimatic Curves

So far we have discussed the instrumentation of TG now we turn our attention

to quantitative aspects of TG. As discussed earlier TG curves represent the
variation in the mass (m) of the sample with the temperature (T) or time (t).
Normally, we plot mass loss downward on the ordinate (y) axis and mass gain
upwards as shown in Fig. 8.4.

Fig. 8.4: TG Curve. Note the plateau of constant weight (region A), the mass loss
portion (region B), and another plateau of constant mass (region C)
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Block 3 Thermal and Electroanalytical Methods

Sometime we also record derivative thermogravimetric (DTG) Curves. A DTG

curve presents the rate of mass change (dm/dt) as a function of temperature,
or time (t) against T on the abscissa (x axis) as shown in Fig. 8.4 when
substance is heated at uniform rate. In this figure, the derivative of the Curve
is shown by dotted lines.

SAQ 1
List the different components of a thermobalance.

8.4 SOURCES OF ERRORS IN TGA

There are a number of sources of error in TGA, and they can lead to
inaccuracies in the recorded temperature and mass data. Some of the errors
may be corrected by placing the thermobalance at proper place and handling it
with great care. For understanding we are discussing some common source of
errors during operation of a thermobalance.

i) Buoyance effect: If a thermally inert crucible is heated when empty

there is usually an apparent weight change as temperature increases.
This is due to effect of change in buoyancy of the gas in the sample
environment with the temperature, the increase convection and possible
effect of heat from the furnace in the balance itself. Now, in most modern
thermobalances, this effect is negligible. However, if necessary, a blank
run with empty crucible can be performed over the appropriate
temperature range. The resultant record can be used as a correction
curve for subsequent experiment performed in the same condition.

ii) Condensation on balance suspension: Condensation of the sample

will also affect the mass of the sample and consequently the shape of
TG curve .This can be avoided by maintaining a dynamic atmosphere
around the sample in the furnace so that all the condensable product
may be driven by the flowing gases.

iii) Random fluctuation of balance mechanism

iv) Reaction between sample and container

v) Convection effect from furnace

vi) Turbulence effect from gas flow

vii) Induction effect from furnace

Errors of type (iii) can be avoided by proper placing of balance in the

laboratory and error (v) can be avoided by sensible choice of sample
container. Last three errors (v-vii) have to be considered in the design of the
furnace, the balance and its suspension system. By avoiding excessive
heating rate and proper gas flow rate some of above mentioned errors may be
avoided.

In the light of above discussion it is necessary to calibrate thermobalance

14 before to use.
Unit 8 Thermal Methods of Analysis

Calibration of thermobalance for the measurement of mass: It can be

done by adding known mass of the sample container and noting the reading of
the chart.
Temperature calibration: ferromagnetic standards are used for this purpose.
In a magnetic field these substances show detectable mass changes. The
ferromagnetic standards are quite suitable for the temperature range from 242
to 771° C.

SAQ 2
What are common source of errors in thermogravimetric analysis?

8.5 INTERPRETATION OF TG CURVES

TG curves of a pure compound are characteristic of that compound. Using TG
curve we can relate the mass changes to the stoichiometry involved. This can
often lead us directly to the quantitative analysis of samples whose
quantitative composition is known. To further illustrate, let’s consider the
example of TGA curve of CaCO3, (Fig. 8.5.) This curve indicates that CaCO3
decomposes in a single step between 600° C and 900° C to form stable
oxide CaO and the gas carbon dioxide. This can be explained the chemistry of
CaCO3 when it is heated:

CaCO3 (s)  CaO (s) + CO2 (g)

… (8.1)
Mr 100.1 56.1 44

Where Mr is relative mass. Now again consider the Fig. 8.5 (c), it indicates the
% mass lost by the sample is 44 (100.1–56.1) between 600 and 900° C. This
exactly corresponds to the mass changes calculations based on stoichiometry
of the decomposition of CaCO3 expressed by the chemical Eq. (8.1). As in this
case, percentage weight loss of CaCO3 will be
M
m

r (CO 2 )
M

% 100 … (8.2)
r (CaCO3 )

44×100
= = 44
100.1

o o
Fig. 8.5: TG and DTG Curve of CaCO3 at various heating rates (b =8 C, c = 3 C)
(DTG = Rate of Change of mass, dm/dt) curve. 15
Block 3 Thermal and Electroanalytical Methods

We have seen above how TG Curves is related to stoichiometry (quantitative

interpretation). Now we see in next example how it can be used to compare
thermal stability of materials (qualitative interpretation). Such information can
be used to select material for certain end-use application, predict product
performance and improve product quality. Fig. 8.6 gives TG Curves of some
polymers. TG Curves clearly indicate that polymer (PVC) is the least thermally
stable and polymer (PS) is most thermally stable. Polymer (PS) looses no
weight at all below about 500o C and then decomposes abruptly by about 600 o
C. The other three polymers have all decomposed by about 450 o C. Polymers
(PMMA) decomposes more slowly overall than the others as indicated by
slopes of TG curves. TG curve of polymer (PMMA) has less slope than the
others.

Fig. 8.6: TG Curves of some polymers: PVC = polyvinyl chloride; PMMMA =

polymethyl methacrylate, LDPE = low density poly ethylene; PTFF =
ploytetra fluoroethylene; and PS = polystyrene.

SAQ 3
Calculate the percentage mass change (m %) for the following reactions.
Δ
i) Ca(OH)2 (s) 
Heat
 CaO(s)+H2O(g)

Δ
ii) 6PbO (s) + O2 (g)  2Pb3O4 (s)

Δ
iii) NH4NO3 (s)  N2O(g) + 2H2O(g)

Δ
iv) CuSO 4 .5H2O  CuSO4 .4H2O +H2O

Δ
v) CuSO 4  CuO + SO3

SAQ 4
A thermogram of a magnesium compound shows a loss of 91.0 mg from a
total of 175.0 mg used for analyte. Identify the compound either as MgO,
MgCO3, or MgC2O4.

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Unit 8 Thermal Methods of Analysis

8.6 FACTORS AFFECTING TG CURVE

In the beginning of this units we talked about the lowest temperature, Ti at
which the onset of a mass change can be detected by the thermobalance
operating under particular conditions and Tf is the final temperature at which
the decomposition completed. We may like to call this as decomposition
temperature, which is not correct. Actually in TGA experiments, both Ti and Tf
do not have fundamental significance, but they can still be a useful
characteristic of a TG curve and the termed procedural decomposition
temperature. It is often used for the temperature at which mass change
appears to commence. This indicates us that procedural decomposition
temperature does not have a fixed value, but depends on the experimental
procedure employed to get it. Similar to this there are many factors which
influence a TGA curve. These factors may be due to instrumentation or nature
of sample. We have listed the main factors which affects the shape, precision
and accuracy of the experimental results in thermogravimetry.

1. Instrumental factors:

i) Furnace heating rate.

ii) Recording or chart speed

iii) Furnace atmosphere

iv) Geometry of Sample holder/ location of sensors

v) Sensitivity of recording mechanism.

vi) Composition of sample container.

2. Sample Characteristics:

a) Amount of sample

b) Solubility of evolved gases in sample.

c) Particle size

d) Heat of reaction

e) Sample packing

f) Nature of sample

g) Thermal conductivity.

Now we will take up some important factors in some detail.

a) 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

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Block 3 Thermal and Electroanalytical Methods

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, 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.
8.5. 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.

b) Recording or Chart Speed

The chart speed on the recording of the TG curve of rapid or slow

reaction has pronounced effect on the shape of the TG curves. For a
slow decomposition reaction low chart speed is recommended for
recording the TG curve because at high chart speed the curve will be
flattened and it will not show the sharp decomposition temperature. For
a slow reaction followed by a rapid one at the lower chart speed the
curve will show less separation in the two steps than the higher chart
speed curve. For fast-fast reaction followed by slower one similar
observation was observed in shorter curve plateaus.

c) Furnace Atmosphere

The effect of atmosphere on the TG curve depends on (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. 8.7.

Fig. 8.7: TG Curve of Calcium Oxalate in O2 and N2

atmosphere: [ N2 ,----------------- O2]

18
The first step, which is dehydration is reversible reaction.
Unit 8 Thermal Methods of Analysis

Ca C2O4.H2O(s) Ca C2O4 (s) + H2O (g ) ... (8.3)

This is unaffected because both gases are equally effective in sweeping

the evolved water vapours away from the sample surface. For the
second step,

CaC2O4(s) CaCO3 (s) + CO (g) ... (8.4)

The curve diverges in O2 atmosphere because the oxygen reacts with

evolved CO, giving a second oxidation reaction which is highly
exothermic and so raises the temperature of the un-reacted sample.
The temperature accelerates the decomposition of the compound more
rapidly and completely at a lower temperature as shown in the above
diagram in dry O2 than in N2 atmosphere. The third step in
decomposition reaction is also reversible reaction.

CaCO3 (s) CaO (s) + CO2 (g) ... (8.5)

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
CaCO3 formed.

d) 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.
e) Effect of Sample Mass

The sample mass affects the TG curve in the following circumstances:

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. 19
Block 3 Thermal and Electroanalytical Methods

Thus, it is preferable to use as small a sample as possible depending on

the sensitivity of the balance.
f) 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 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.

g) Effect of Heat of Reaction

The heat of reaction will affect the extent to which sample temperature
proceeds or succeeds the furnace temperature. This depends on
whether the reaction is exothermic or endothermic and consequently the
extent of decomposition will also be affected.

The other sample characteristics such as sample packing, nature of the

sample and its thermal conductivity will also affect the shape of TG
curves. If the sample is packed loosely then the evolved gases may
diffuse more easily than if the sample packed tightly.

If the sample reacts with the sample container on heating then it will not
give the mass of the product formed so the sample will change. We can
avoid this effect by a sensible choice of sample container.

SAQ 5
What are the common instrumental factors affecting TG curves.

8.7 APPLICATIONS OF TERMOGRAVIMETRIC

ANALYSIS
In the previous section we have seen how TGA can be used to understand the
chemistry of decomposition of a particular compound. TGA also provides
information about the temperature range over which a particular sample
appears to be stable or unstable. We have also interpreted TG curves
qualitatively. Beside these there are many other applications of
thermogravimetric analysis. Some are listed below:

i) Purity and thermal stability.

ii) Solid state reactions.

iii) Decomposition of inorganic and organic compounds.

iv) Determining composition of the mixture.

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Unit 8 Thermal Methods of Analysis

v) Corrosion of metals in various atmosphere.

vi) Pyrolysis of coal, petroleum and wood.

vii) Roasting and calcinations of minerals.

viii) Reaction kinetics studies.

ix) Evaluation of gravimetric precipitates.

x) Oxidative and reductive stability.

xi) Determining moisture, volatile and ash contents.

xii) Desolvation, sublimation, vaporizations, sorption, desorption,

chemisorptions.

It is not possible to discuss all these applications at this level; it is worth to

describe some of the applications which are more common.

Analysis of Inorganic and Organic Mixtures

We have already seen that single and pure compound gives characteristic TG
curves. Now, we will see how TG Curves can be used in predicting relative
quantities of the components of a mixture.

Binary mixtures

Consider a mixture of two compounds AB and CD having characteristic TG

Curves which are different from each other as shown in Fig. 8.8

Fig. 8.8: (a) Thermogravimetric curves of two compounds AB and CD and (b)
their Mixture.

The decomposition of pure compound AB and CD occur at T1, and labeled as

bc and temperature T2, and labeled as fg respectively, as illustrated in
Fig. 8.8 (a). The TG curve of mixture of AB and CD together is shown in
Fig. 8.8 (b). You can see in this figure, the plateaus (corresponding to the
regions of constant mass) commence at about the same temperature as they
21
Block 3 Thermal and Electroanalytical Methods

do in the TG Curves for the pure compounds AB and CD. You can also notice
that the mass loss overall up to T1 is x mg and from T1 to T2 it is an additional y
mg. By measuring these two quantities x and y from the TG curves of Fig. 8.8
(b), we can determine the relative quantities of AB and CD in the original
binary mixture. To understand further consider the mixtures of calcium and
magnesium carbonates.

i) Analysis of a mixture of calcium and magnesium carbonates

A typical TG curve of a mixture of calcium and magnesium carbonates is

shown in Fig. 8.9. You can notice that a significant mass loss occurs
before 28° C. This is due to the moisture present in the mixture. Another
mass loss at about 480° C is due to the following reaction:

MgCO3 (s)  MgO(s) + CO2 (g) … (8.6)

Earlier we mentioned that CaCO3 decomposes at about 800 °C. In Fig.

8.8 mass loss between about 600 °C and 900 °C can be interpreted due
to decomposition of CaCO3.

CaCO3 (s)  CaO (s) + CO2 (g) … (8.7)

Portion of the curve ab represents a mixture of MgO and CaCO3 and cd

represents a residue of the mixture of MgO and CaO. Both these
plateaus ab and cd represent weight m1 and m2, respectively. In fact
mass m1 is due to CaCO3 + MgO.

Fig. 8.9: TG curve of mixture of calcium and magnesium carbonate.

22
Unit 8 Thermal Methods of Analysis

Thus, m1 – m2 is the loss of CO2 between 600° C and 900° C due to the
decomposition of CaCO3. Using TGA curve we can relate the mass of
different components formed during TGA experiment.

The mass of CaO (m3) formed can be calculated using following Eq. (8.8)

m3 = 1.27 (m1 – m2) … (8.8)

This equation can be obtained as follows:

The CaO is formed by the evolution of CO2 on the decomposition of

CaCO3,

CaCO3 (s)  CaO(s) + CO2 (g)

Mr 100.1 56.1 44

From the above equation 1mole of CaCO3 gives 1 mole of CO2 and
(m - m2 )
1mole of CaO. Thus, moles of CO2 in the given examples = 1
Mr (CO2 )
and this is equal to moles of CaO formed

(m1 - m2 )
Thus the amount of CaO must be, m3 = × Mr (CaO)
44

where, Mr(CaO) is the relative molar mass of CaO.

(m1 - m2 )
m3 = ×56.1 g
44

m3 = 1.27(m1 – m2) g

We know the mass of residue left, i.e., m2, the mass of MgO (m4) can be
calculated.

m4 = m2 – m3

Here m3 is the mass of CaO formed, which is equal to 1.27 (m1 – m2).
Thus

m4 = m2 – 1.27 (m1 – m2)

Mass of the Ca (mca) in the original sample can also be related to m1 and
m2 by the following formula

mca = 0.91 (m1 – m2)

This can be obtained as follows:

You know amount of Ca in CaCO3 and CaO will be equal in moles,

therefore amount of Ca in

Ar(Ca) Ar(Ca)
mCa = m3 × = 1.27 (m1 - m2 )×
Mr(CaO) Mr(CaO)

where, Ar(Ca) and Mr (CaO) are the relative atomic mass and relative
molar mass of Ca and CaO, respectively. Thus,
23
Block 3 Thermal and Electroanalytical Methods

= 1.27 (m1 – m2) × 40/56.1 = 0.91 (m1 – m2)

Similarly, mass of magnesium in the original sample can be related to m1

and m2:

Thus, the mass of Mg in original sample (mMg)

Ar (Mg)
= (mass of residue – mass of CaO)×
Mr (MgO)

Ar (Mg) 24.3
mMg = (m2 - m3 )× = (m2 - m3 )×
Mr (MgO) 40.3

mMg = 0.60 (m2 – m3)

ii) Mixture of calcium and magnesium oxalates

Calcium oxalate monohydrate is unsatisfactory weighing form for

determining calcium as oxalate because its tendency to retain excess
moisture even at 110 °C, co-precipitated ammonium oxalate remain un-
decomposed. The anhydrous calcium oxalate is hygroscopic but CaCO3
is excellent weighing form if heated to 500 ± 25 °C as can be seen in
TG curve of CaC2O4.H2O. Above 635 0C the decomposition of CaCO3
commences to become significant under usual laboratory conditions and
completely converted to CaO at 900 °C. Thus, calcium oxalate
monohydrate decomposes in three steps, first dehydration, second
removal of CO and formation of CaCO3 then third step CaCO3
decomposes to CaO (see Fig. 8.10).

CaC2O4.H2O → CaC2O4 + H2O at about 135-220 °C

CaC2O4 → CaCO3+CO at about 400-480 °C

CaCO3 →CaO+ CO2 at about 635-900 °C

But magnesium oxalate dihydrate decomposes in two steps instead of

three steps. First, dehydration then removal of CO and CO2
simultaneously and forming MgO, there is no horizontal corresponding to
MgCO3 as it is thermally unstable at this temperature.

MgC2O4.2H2O → MgC2O4+2H2O at about 135-220 °C

MgC2O4 → MgCO3 + CO→MgO+CO2 at about 500 °C

The TG curve for the mixture of CaC2O4.H2O and MgC2O4.2H2O shows

two mass losses up to 500 °C, first at about 200 °C due to loss of water
and the second mass loss occurs in the 390-500 °C range which is due
to decomposition of both calcium and magnesium oxalates. Thus, at
500°C, the composition of the mixture will be CaCO3 and MgO. Third
mass loss after 500 °C is due to only the decomposition of CaCO3. If m1
and m2 are the mass of the mixture at 500 °C and 900 °C then similar to
the previous example we can calculate the amount of calcium and
magnesium in the original sample.
24
Unit 8 Thermal Methods of Analysis

Fig.8.10: DTG/TG curve of calcium oxalate.

Organic Mixtures
TGA also provides quantitative information on organic compound
decompositions and is particularly useful for studying polymers. For example
TGA can be used in the determination of the amount of vinyl acetate in
copolymers of vinyl acetate and polyethylene. When vinyl acetate is heated it
looses acetic acid at about 340 °C. TG curves shown in Fig. 10.11 for several
vinyl acetate polyethylene copolymers are clearly indicating the loss of acetic
acid at about 340 °C due to the decomposition of vinyl acetate. Each mole of
vinyl acetate losses one mole of acetic acid. The amount of vinyl acetate in the
polymers can be calculated.

Fig. 10.11: TG curve of vinyl acetate copolym

SAQ 6
A mixture of CaO and CaCO3 is analysed by TGA. The result indicates that
mass of the sample decreases from 250.6 mg to 190.8 mg only between
600°C and 900°C. Calculate the percentage of calcium carbonate in the
mixture.
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Block 3 Thermal and Electroanalytical Methods

8.8 SUMMARY
Thermogravimetric Analysis (TGA) technique has been described for its basic
principle, instrumentation and applications. The interpretation of results and
applications are discussed by taking different examples. The elementary
calculation are included to elaborate the topics. The probable cause of errors,
their remedies, interpretation of result are also discussed.

8.9 TERMINAL QUESTIONS

1. Formulate the solid state reaction of sodium bicarbonate when heated. It
decomposes between 80 and 225 °C with evolution of water and carbon
dioxide. The combined loss of water and carbon dioxide totaled 36.6%
by mass whereas the mass loss due to carbon dioxide alone was found
to be 25.4 %. Explain.

2. What types of standard are required to calibrate the mass variation

obtained with a TGA equipment?

3. What type of standards is required for temperature calibration of any

TGA?

4. A mixture of CaCO3 and CaO is analysed using TGA technique. TG

curve of the sample indicates that there is a mass change from 145.3 mg
to 115.4 mg between 500–900 °C. Calculate the percentage of CaCO3 in
the sample.

5. A 250 mg hydrated sample of Na2HPO4 decreases to a mass of 145.7

mg after heating to 150 °C. What is the number of water hydration in
Na2HPO4.

6. Draw a labeled diagram of the TG curve obtained by heating a mixture of

80 mg of CaC2O4.H2O and 80 mg of BaC2O4.H2O to 1200 °C. Calculate
the amount of all mass losses.

8.10 ANSWERS
Self Assessment Question
1. Balance; furnace; unit for temperature measurements and control; and
recorder.

2. Common source of error in thermogravimetric are listed in Sec. 8.3.

Δ
Ca(OH) 2  CaO  H 2 O
3. i)
Mr 74.1 56.1 18

Percentage loss =
 74.1- 56.1 = 24.3%
74.1

ii) 6PbO (s)  O 2 (g)  2Pb 3 O 4 (s)

26
Unit 8 Thermal Methods of Analysis

Mr 223.2 × 6 685.6 × 2

1339.2 1371.2

1371.2  1339.2 
  100
So, percent gain 1339.2
 2. 4 %

Δ
iii) NH 4 NO 3 (s)  N 2 O (g)  2H 2 O (g)

In this case, both the products are volatile when NH4NO3 is heated
at 300°C no solid residue is left. The percentage loss in this case is
80%.
Δ
iv) CuSO 4 .5H 2 O  CuSO 4 .4H 2 O  H 2 O

Mr 249.7 231.7 18

249.7  231.7  18
percen loss  100   100
249.7 249.7
 7. 2 %

Δ
v) CuSO 4  CuO  SO 3

Mr 231.7 151.7 80

231.7 - 151.7
%m × 100
231.7

80
%m  100  34.5%
231.7

4. Decomposition reaction of the MgO, MgCO3 and MgC2O4

MgO → No reactive

MgCO3 → MgO + CO2

MgC2O4 → MgO + CO2 + CO

44
% mass loss for MgCO3 = 100  52.2%
84.3

44  28 
% mass loss for MgC2O4 = 100  64.3%
112.3

91.0
% mass loss of the sample = 100  52%
175

Therefore, this compound is MgCO3.

5. Instrumental factors: Furnace heating rate, recording chart speeds,

furnace atmosphere, geometry of sample, holder/location of sensors,
sensitivity of recording mechanism, composition of sample container,
etc.
27
Block 3 Thermal and Electroanalytical Methods

6. The possible decomposition in the mixture may be written as

CaCO3 (s) → CaO (s) + CO2 (g)

Mr 100.1 56.1 44.0

Mass loss in the mixture is due to the formation of CO2 (g). We can
calculate the m moles of CO2, i.e. (250.6 – 190.8) mg/44 =1.359 mmol.
From the above chemical equation, 1 mole of CaCO3 give 1 mole of CO2.
Therefore the amount of CaCO3 in the mixture must be 1.359 mmol. This
will equal to = 1.359 × 100.1 mg = 135.9 mg.
135.9
So percentage of CaCO3 in the sample will be 100  54.2% by
250.6
mass.

Terminal Questions
1. Reaction proceed in following steps

Above 60 °C, it gradually decomposes into sodium carbonate and water

and carbon dioxide.

2NaHCO3 → Na2CO3 + H2O + CO2

Total calculated mass loss should be 36.9, dehydration is 8.71 and

decarbonylation is 26.19 . The observed mass loss is quite similar i.e.
total 36.6, dehydration 11.2 and decaroxylation is 25.4%.

2. There are no standards available for TGA calibration. It is only possible

to calibrate the balance using calibrated masses. However, it is possible
to use some materials with known mass variations, such as copper
sulphate pentahydrate or calcium oxalate, to check for good operation of
the thermobalance. The latter materials are generally agreed as working
standards but do not use the first mass loss, corresponding to the first
hydrate.

3. Temperature calibration of the TGA requires the use of a metal that is

99.99% pure and magnetic. A magnet has to be adjusted on the TGA
furnace.

4. Write the decomposition reaction of CaCO3

CaCO3 → CaO + CO2

Mr 100.1 56.1 44.0

This equation indicates that one mole of CaCO3 produces one mole of
CaO and one mole of CO2. Therefore,

m moles of CO2 = m moles of CaCO3

m moles of CO2 = mg lost/Mr (CO2)

= (145.3 – 115.4) mg/44.0

= 29.9/44.0
28
Unit 8 Thermal Methods of Analysis

= 0.682 m moles

A mount of CaCO3 in sample = m moles of CaCO3 × Mr (CaCO3)

= 0.682 × 100.1 mg

= 68.2 mg

68.2
% of CaCO3 = 100.  46.9 %
145.3

5. Molar mass of hydrated Na2HPO3 is 215.9. We can calculate mass loss

corresponding to each mole of hydrated water (n).

m % loss 8.8 16.7 25.0 33.3 41.7

n 1 2 3 4 5

250  145.7 
In this problem % mass loss =  100
250

= 41.7%

This corresponds to a mass loss of 5 moles of water of (hydration).

Therefore given sample must be of Na2HPO3.5H2O).

6. Table the help of Fig.8.12 to draw a labeled diagram of the TG curve for
mixture of CaC2O4.H2O and BaC2O4.H2O.

Total mass loss = 49.3 (CaC2O4.H2O) + 29.6 (BaC2O4.H2O)

= 78.9 mg.

29