THERMAL ANALYSIS

1
No. CONTENTS
No. Page

INTRODUCTION
1 Definition and history……………………… 5
2 Thermal analysis instruments……………… 6
3 Types of measurement…………………….. 8
4 The main techniques……………………….. 8
THERMAL EVENTS
1 The solid state……………………………… 10
2 Reactions of solids…………………………. 12
THERMOGRAVIMETRY (TG-DTG)
1 The balance………………………………… 17
2 Heating the sample………………………… 18
3 The atmosphere……………………………. 21
4 The sample………………………………… 23
5 Temperature measurement and calibration... 24
6 Temperature programmers………………… 27
7 Interpretation of TG and DTG curves……... 27
8 Factors affecting the TG curve…………….. 31
9 Applications……………………………….. 35

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 CONTENTS
No. Page
DIFFERENTIAL THERMAL
ANALYSIS (DTA)
1 Principle…………………………………… 40
2 Characteristics of DTA curves…………….. 42
3 Instrumentation……………………………. 46
4 Factors affecting DTA curves……………... 51
5 Interpretation of DTA curve………………. 55
6 Determination of heat capacity……………. 60
7 Construction of phase diagram…………….. 60
8 Estimation of transition temperature………. 61
9 Applications……………………………….. 63
DIFFERENTIAL SCANNING
CALORIMETRY (DSC)
1 Principle…………………………………… 74
2 Instrumentation……………………………. 76
3 Factors affecting DSC curve………………. 81
4 Sources of error……………………………. 83
5 Interpretation of DSC curve……………….. 84
6 Applications……………………………….. 87
7 Advantages of DSC………………………... 94

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 CHAPTER I

INTRODUCTION

4
 INTRODUCTION

1. Definition and history

What do bread and chocolate, hair and finger-nail
clippings, coal and Egyptian papyri have in common?
Many interesting answers could probably be suggested,
but the connection wanted in this context is that they all
undergo interesting and practically important changes on
heating.
The study of the effect of heat on materials obviously
has long history, form’s earliest attempts at producing
pottery, extracting metals (~8000 BC) and making glass
(~3400 BC) through the philosophical discussions of the
alchemists on the elements of fire, air, earth and water, to
early work on the assaying of minerals (~1500 AD),

followed by the development of thermometry and

calorimetry. Only in the late 19th century did experiments
on the effect of heat on materials become more controlled
and more quantitative. Much of this work depended upon
the development of the analytical balance which has its
own interesting history.
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 It has been suggested that the definition of thermal
analysis should be extended to allow for rapid heating of
sample to some elevated temperature, followed by
measurements of the property with time under isothermal
conditions, i.e. at zero heating rate.

2. Thermal analysis instruments

All thermal analysis instruments have features in
common. These are illustrated in Figure 1. The variety of
the techniques to be discussed stems from the variety of
physical properties that can be measured and the variety
of transducers that can be used to convert these properties
into electrical signals.
Measurements are usually continuous and the heating
rate is often, but not necessarily, linear with time. The
result of such measurements is a thermal analysis curve
Figure 1.

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Fig. 1. Generalized thermal analysis instrument and
thermal analysis curve.

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3. Types of measurement
Absolute values of the sample property may be
recorded or the difference in the property of the sample
compared to the some property of a reference material
may be more convenient to measure, or the rate of change
of the sample property with temperature may be of interest
(derivative measurements).

4. The main techniques

The main sample properties used and the associated
techniques are listed in Table 1. All of these techniques
may be combined with evolved gas analysis and it is often
possible to carry out simultaneous measurements of more
than one property.

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Table 1. The main thermal analysis techniques

Property Techniques Abbreviation

Mass Thermogravimetry TG
Derivative
thermogravimetry DTG
Temperature Differential thermal DTA
analysis
Enthalpy Differential scanning
calorimetry DSC
Mechanical Thermomechanical TMA
properties analysis
Dynamic mechanical DMA
analysis
Optical, Thermomicroscopy
Magnetic and Thermomagnetometry TM
Electrical Thermoelectrometry
properties
Acoustic Thermoacoustimetry TS
properties
Evolution of Emanation thermal ETA
radioactive gas analysis
Evolution of Thermoparticulate TPA
particles analysis

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 THERMAL EVENTS
1. The solid state
The main characteristic feature of the solid state in the
relatively ordered arrangement of the constituent atoms,
molecules or ions. Just as the concept of an “ideal gas” is
useful in describing the behavior of real gases, the concept
of a “perfect solid” or “prefect crystal” is useful as
reference point for real solids. A perfect (crystalline) solid
has a completely ordered arrangement of its constituents,
while real solids have imperfection of many kinds. When
the order present is marginally is sometimes referred to as
a (non-crystalline solid). When liquids composed of
complex molecules or ions are cooled rapidly a glass may
be formed. A glass resembles a solid in many of its
physical properties, e.g. rigidly, but differs in that the
constituents do not show the regular (lattice) arrangement
of crystalline solid. Glasses are thus example of non-
crystalline solids. They do not melt at a sharply-defined
temperature, but soften over a temperature interval. This
transition from the rigid glassy state to a more flexible

10
from is known a the glass transition temperature, Tg is of
tremendous importance in the practical use of polymers.
Crystalline solids, may be classified according to the
dominant forces between the constituents in the crystal,
i.e. as molecular, covalent, ionic or metallic crystals.
In molecular crystal, the identity of each individual
molecule is preserved. The Van Der Waals attractive
forces between molecules, which give the solid its
coherence, are molecule. On heating, most molecular
solids melt without chemical changes of the constituents.
In covalent crystal, each constituent atoms is lined to
its neighbours through directed covalent bonds. The
crystal structure is determined by the arrangement in
space of these bonds. Such solids are hard and have high
melting points, e.g. diamond, silicon carbide, etc.
In ionic crystal, ions of opposite charge. Because of
the non-directional nature of electrostatic forces, the
structures adopted are determined by: (i) the relative
numbers of cations and anions, (ii) the relative sizes of
positive and negative ions and (iii) the ionic chapes.

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Molecules of water (or solvent) of crystallization, may be
incorporated in the crystal structure.
Metal (and alloys) are usually close-packed
arrangements of similar sized spheres. Each atom has a
high coordination number. The valence electrons from
each atom have freedom to migrate in an applied field so
that metals are good conductors of electricity, e.g. copper,
iron, lead, etc.

2. Reactions of solids
When a sample pure solid substance, A, is heated in an
inert atmosphere, the resultant increase in molecular,
atomic or ionic motion may lead to changes in crystal
structure, sintering, melting or sublimation. If the
intramolecular forces are weaker than the intermolecular
forces, the substance may decompose forming new
molecular fragments, some or all of which may be volatile
at the temperatures reached. Numerous examples of such
decompositions exist, e.g.

BaCl2.2H2O(s) → BaCl2(s) + 2H2O(g)

CaCO3(s) → CaO(s) + CO2(g)
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NH4Cl(s) → NH3(g) + HCl(g)
BaN6(s) → Ba(s) +3N2(g)
More complicated reactions result when the initial
solid can react with the surrounding atmosphere, e.g.

2Ag(s) + ½ O2(g) → Ag2O(s)

CuO(s) + H2(g) → Cu(s) + H2O(g)
Ni(s) + 4CO(g) → Ni(CO)4(g) + H2O(g)
C(s) + O2(g) → CO2(g)

When more than one solid substance is present

initially, there are correspondingly more possibilities for
interaction on heating and new phases, such as solid
solution and eutectic mixture, may from as well as new
compounds formed by addition or double decomposition
reaction e.g.

Fe2O3(s) + MgO(s) → MgFe2O4(s)

NaCl(s) + AgBr(s) → AgCl(s) + NaBr(s)

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Table 2. The main thermal events on heating a signal
solid (A) in an inert atmosphere

The reaction Nomenclature H Sign Mass

A(s) structure 1 → Phase transition yes + or - no
A(s) structure 2
A(s) → A(l) Melting yes + no
A(glass) → Glass transition no no no
A(rubber)
A(s) → A(g) Sublimation yes + yes
A(s) → B(s) + Thermal yes + or - yes
gas or gasses decomposition

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 CHAPTER II

THERMOGRAVIMETRY (TG-DTG)

15
 THERMOGRAVIMETRY (TG-DTG)
Measurements of changes in sample mass with
temperature are made using a thermobalance. This is a
combination of a suitable electronic microbalance with a
furnace and associated temperature programmer. The
balance should be in a suitably enclosed system so that the
atmosphere can be controlled (Figure 2).

Fig. 2. A schematic thermobalance.

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1. The balance
The sensitivity of thermobalance and the maximum
load which it can accept, without damage, are related.
Typical values are maximum loads of 1 g and sensitivities
of the order of 1 µg. Use can be made of alternative
suspension points on the balance beam to increase the
maximum load.
The output signal may be differentiated electronically
to give a derivative thermogravimetryic (DTG) curve. In
addition to conventional TG studies, much use has been
made of microbalances in studying the kinetics of
reactions of solids under isothermal conditions. Studies of
decomposition reactions pose some special problems.
Many decompositions are reversible if a supply of the
gaseous products of reaction is maintained. Such studies
thus require careful control of the surrounding atmosphere
and should include runs at reduced pressures. Reducing
the pressure, through worsens the heat exchange, causing
problems in temperature measurement. In an attempt to

17
overcome some of these problems, the use of quartz
crystal microbalance has been suggested.
Use of the piezoelectric effect in certain crystal
(usually quartz) for measuring the mass of material
deposited or condensed on the a crystal face is well
documented. There are basically two ways in which such
crystal can be used in TG studies. The sample may be
deposited on a crystal face and the sample plus crystal may
be heated as required, or the sample may be heated
separately in one part of a reaction chamber and all or
some of its gaseous decomposition products may be
condensed on the initially clean face of a crystal which is
held at a suitably low temperature. Changes in the amount
of material deposited on the crystal surface show up as
changes of frequency of oscillation of the crystal, which
is usually excited in a conventional series resonance
circuit.
2. Heating the sample
In the more conventional thermobalances, there are
three main variation in the position of the sample relative

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to the furnace as shown in Figure 3. The furnace is
normally an electrical resistive heater and many as shown,
be within the balance housing, part of the housing, or
external to the housing. It should: (i) be non-inductively
wound, (ii) be capable of reaching 100 to 200oC above the
maximum desired working temperature, (iii) have a
uniform hot-zone of reasonable length, (iv) reach the
required starting temperature as quickly as possible and
(v) not affect the balance mechanism through radiation or
convection.
For DTA the sample and the reference are placed in
cylindrical Teflon or silica containers. The absorption
coefficient for microwaves varies from one substance to
another and also varies markedly with temperature, thus
making matching of the sample with a suitable reference
difficult. As with classical DTA, the sample is often mixed
with an excess of inert reference material, such as Al2O3
or TiO2 which have high absorption coefficient. The
higher the absorption coefficient, the greater the heating
rate possible.

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Fig. 3. Alternative arrangements of furnace, sample and
housing.
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3. The atmosphere
Thermobalances are normally housed in glass or metal
systems and to allow for operation at pressures ranging
from high vacuum ( 10-4 Pa) to high pressure ( 3000
kPa), of inert, oxidizing, reducing or corrosive gases. One
correction, which may have to be made, is for buoyancy
arising from lack of symmetry in the weighing system. If
the asymmetry can be measured in terms of a volume V,
the mass of displaced gas (assuming ideal gas behavior) is
m= pM V/RT (where p is the pressure and M the molar
mass). The buoyancy thus depends not only on the
asymmetry V, but also on the pressure, temperature and
nature of the gas. Attempts may be made to reduce V to
zero, or correction may be calculated, or an empirical
correction may be applied by heating an inert sample
under similar conditions to those to be used in the study of
the sample of interest.
The sample may be headed in a small container with a
restricted opening. Decomposition then occurs in a self-
generated atmosphere of gaseous decomposition products.

21
The inhibiting or catalytic effects of these products on the
decomposition can then be studied.
At atmospheric pressure, the atmosphere can be static
or flowing. A flowing atmosphere has the advantages that
it: (i) reduces condensation of reaction products on cooler
parts of the weighing mechanism; (ii) flushes out
corrosive products; (iii) reduces secondary reactions; and
(iv) acts as a coolant for the balance mechanism. The
balance mechanism should, however, not be disturbed by
the gas flow. It is possible for the balance mechanism to
be protected by an inert gas atmosphere, while a corrosive
gas or vapour is passed over the sample (e.g. H2O vapour
for dehydration studies).
The use of dense carrier gases at high pressures in hot
zones with large temperature gradients gives the most
noise. Vibrations in the flow rate of the gas do not affect
the noise level much, but may shift the weighing zero.
Noise levels also increase as the radius of the hangdown
tube increase. A series of closefitting convoluted baffles
(Figure 4).

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 Fig. 4. Reduction of convection effect by use of baffles
in the hangdown tube.
Sample containers should be of low mass and made of
inert material (e.g. platinum containers may catalyze some
reactions). Sample should generally be thinly spread to
allow for ready removal of evolved gases. Results should
be checked for sample-holder geometry effects.
4. The sample
Although solid samples may be nominally of the same
chemical composition, there may be considerable
differences in their behavior on heating. These differences
arise from structural differences in the solid, such as the
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defect content, the porosity and the surface properties,
which are dependent on the way in which the sample is
prepared and treated after preparation. For example, very
different behavior will generally be observed for single
crystals compared to finely ground powders of the same
compound. In addition to the influence of defects on
reactivity, the thermal properties of powders differ
markedly from those of the bulk material.
As the amount of sample used increase, several
problems arise. The temperature of the sample becomes
non-uniform through show heat transfer and through
either self-heating or self-cooling as reaction occurs. Also
exchange of gas with the surrounding atmosphere is
reduced.
5. Temperature measurement and calibration
The sample temperature, Ts, will usually lag behind the
furnace temperature, Tf, and Ts cannot be measured very
readily without interfering with the weighing process. The
lag Tf - Ts, may be as much as 30oC, depending upon the
operating conditions. The lag is marked when operating in

24
vacuum or in fast-flowing atmospheres and with high
heating rates. Temperature measurement is usually by
thermocouple and it is advisable to have separate
thermocouples for measurement of Ts and for furnace
regulation.
An ingenious method of temperature calibration for
small furnaces makes use of the Curie points of a range of
metals and alloys. On heating a ferromagnetic material, it
loses its ferromagnetism at a characteristic temperature
known as the Curie point. If a magnet is positional below
the sample of ferromagnetic material, as shown in Figure
5 (a), the total downward force on the sample, at
temperature below the Curie point, is the sum of the
sample weight and the magnetic force. At the Curie point
the magnetic force is reduce to zero and an apparent mass
loss is observed (Figure 5 (b)). By using several
ferromagnetic materials, a multi-point temperature
calibration may be obtained (Figure 5 (c).

25
Fig. 5. Curie point method of temperature calibration.
26
6. Temperature programmers
A wide variety of fully-electronic temperature
controllers and programmers is available commercially.
Temperature sensors are either platinum resistance
thermometers or thermocouples. Heating rates offered
range from fractions of a degree per minute to nearly
1000oC, with facilities for isothermal operation. In a small
thermal analysis laboratory, one programmer may serve
several instruments.

7. Interpretation of TG and DTG curves

Actual TG curves obtained may be classified into
various types as illustrated in Figure 6.

27
Fig. 6. Main types of thermogravimetric (TG) curves.
28
Possible interpretations are as follows:
Type (i) curves. The sample undergoes no
decomposition with loss of volatile products over the
temperature range shown. No information is obtained,
however, on whether solid phase transitions, melting,
polymerization or other reactions involving no volatile
products have occurred.
Type (ii) curves. The rapid initial mass loss observed
is characteristic of desorption or drying. It could also arise,
when working at reduced pressures, from effects such as
thermomolecular flow or convection. To check that the
mass loss is real, it is advisable to rerun the sample, which
should then product a type (i) curve, unless the carrier gas
contained moisture or was very readily reabsorbed on the
sample at the lower temperature.
Type (iii) curves. These represent decomposition of
the sample in a single stage. The curve may be used to
define the limits of stability of the reaction, to determine
the stoichiometry of the reaction and to investigate the
kinetics of reaction.

29
 Type (iv) curves. These indicate multi-stage
decomposition with relatively stable intermediates.
Again, the temperature limits of stability of the reactant
and of the intermediates can be determined from the curve.
together with the more complicated stoichiometry of
reaction.
Type (v) curves. These also represent multi-stage
decomposition, but in this example stable intermediates
are not formed and little information on all but the
stoichiometry of the overall reaction can be obtained. It is
important to check the effect of heating rate on the
resolution of such curves. At lower heating rates, type (v)
curves may tend to resemble type (iv) curves more
closely, while at high heating rates both type (iv) and type
(v) curves may resemble type (iii) curves and hence the
detail of the complex decomposition is lost.
Type (vi) curves. These show a gain in mass as a result
of reaction of the sample with the surrounding
atmosphere. A typical example would be the oxidation of
a metal sample.

30
 Type (vii) curves. These are not often encountered.
The product of an oxidation reaction decomposition again
at higher temperature (e.g. 2Ag + 1/2O2 → Ag2O → 2Ag
+ 1/2O2).

8. Factors affecting the TG curve

Many factors influence the form of the TG curve, both
sample and instrument related, some of which are
interactive. The primary factors are heating rate and
sample size, an increase in either of which tends to
increase the temperature at which sample decomposition
occurs, and to decrease the resolution between successive
mass losses. The particle size of the sample material, the
way in which it is packed, the crucible shape, and the gas
flow rate can also affect the progress of the reaction.
Careful attention to consistency in experimental details
normally results in good repeatability. On the other hand,
studying the effect of deliberate alterations in such factors
as the heating rate can give valuable insights into the
nature of the observed reactions.

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 TG has been applied extensively to studying analytical
precipitates for gravimetric analysis. One example is that
of calcium oxalate monohydrate, as shown below (Figure
7). This material has become popular for demonstrating
thermobalance performance, as it gives three distinct
weight losses over a wide temperature range.

Fig. 7. TG-DTG curves of calcium oxalate monohydrate.

The plot also shows the derivative of the TG curve, or

the DTG curve, which is often useful in revealing extra

32
detail, such as the small event around 400oC, which would
not have been seen on the TG curve itself. The DTG curve
is sometimes used to determine inflection points on the
TG curve, to provide reference points for weight change
measurements in systems where the weight losses are not
completely resolved.
The measured losses above agree well with the
theoretical losses, according to the usual scheme

CaC2O4.H2O → CaC2O4 → CaCO3

apart from that due to decomposition of the anhydrous

oxalate to calcium carbonate around 500oC. The curve
gives a value of 18.7% lost, as compared to the theoretical
value of 19.2%. This is due to the disproportionation of
carbon monoxide into carbon dioxide and carbon. CO2 has
been seen to evolve in parallel with CO by evolved gas
analysis. The residual calcium oxide from an experiment
such as that above is pale grey, due to the carbon
deposited. Changing the atmosphere in the thermobalance
to air after the decomposition of the carbonate around

33
700oC would initiate a weight loss due to the oxidation of
this carbon. The extent to which the disproportionation
reaction occurs is influenced by several factors including
the nature and cleanliness of the material from which the
sample container is made, and it is difficult to obtain
reproducible results for this reaction step. It is therefore
unwise to use this material as a weight change standard,
as has been sometimes suggested, when operating in inert
atmosphere. Even in an oxidizing atmosphere, difficulties
may arise in obtaining a reproducible result. In this case,
the CO produced on decomposition is oxidized
quantitatively to CO2, in a strongly exothermic process.
The heat generated raises the sample temperature, and
accelerates the reaction, resulting in a sharper DTG peak.
The sharpness of the peak however depends on the
catalytic activity of the sample holder material.
The absence of a grey residue after running calcium
oxalate in an inert atmosphere would probably be due to
traces of air in the system. A good test of the inert
atmosphere quality in a thermobalance is to hold a sample
of carbon black at 1000oC, and measure the rate of weight
34
loss. A well-made instrument, after thorough initial
purging with inert gas, should be able to give a result of
below 1m g/min. For the best results with highly sensitive
materials (e.g. finely-powdered metals) it may well be
necessary to deliver the inert gas via metal pipes, and to
use an oxygen scrubber.

9. Applications
The ability of TG to generate fundamental quantitative
data from almost any class of materials, has led to its
widespread use in every field of science and technology.
Key application areas are listed below:
- Thermal Stability: related materials can be compared
at elevated temperatures under the required
atmosphere. The TG curve can help to elucidate
decomposition mechanisms.
- Kinetic Studies: a variety of methods exist for
analyzing the kinetic features of all types of weight loss
or gain, either with a view to predictive studies, or to
understanding the controlling chemistry.

35
- Material characterization: TG and DTG curves can be
used to "fingerprint" materials for identification or
quality control.
- Corrosion studies: TG provides an excellent means of
studying oxidation, or reaction with other reactive
gases or vapours.
- Simulation of industrial processes: the thermobalance
furnace may be thought of as a mini-reactor, with the
ability to mimic the conditions in some types of
industrial reactor.
- Compositional analysis: by careful choice of
temperature programming and gaseous environment,
many complex materials or mixtures may be analyzed
by selectively decomposing or removing their
components.

36
 CHAPTER III

DIFFERENTIAL THERMAL ANALYSIS

(DTA)

DIFFERENTIAL THERMAL ANALYSIS

(DTA)
In the previous unit we discussed thermagravimetric
analysis and its applications. You have learnt that TGA
has many applications, but they are limited to the reactions
37
where mass change should have occurred. Now we will
consider two similar thermal techniques, differential
thermal analysis (DTA) and differential scanning
calorimetry, both these techniques have much wider
applications than TGA. In the last section of this unit,
thermometric titrations and their applications have been
briefly discussed.

As defined earlier, in DTA, the heat changes within a

material are monitored by measuring the difference in
temperature ( T) between the sample and the inert
reference. This differential temperature is then plotted
against temperature or time to get DTA curve (see Figure
8 (a)). In differential scanning calorimetry (DSC), the
initial temperatures of the sample and the reference are
kept same. The amount of heat that has to be supplied to
the sample or reference to achive this equivalence in
temperature is constantly measured over the temperature
range employed. This basically measures of the amount of
energy absorbed or evolved in a particular transition, and
hence gives calorimetric measurements directly. Similar
38
to DTA curve, DSC curve can be obtained by plotting
differential heat input to the sample (expressed as a
heating rate dH/dt) against temperature and time (t) (see
Figure 8 (b)). With this background, now we will consider
the instrumentation and applications of DTA technique.

(a) (b)
Fig. 8. DTA and DSC curves.

1. Principle

Differential thermal analysis is a technique in which

the temperature of the substance under investigation is
compared with the temperature of a thermally inert
material such as α-alumina and is recorded with furnace

39
temperature as the substance is heated or cooled at a
predetermined uniform rate. The range of temperature
measurable in the course of DTA is much larger than TG
determination. Thus, during TG, pure fusion reactions,
crystalline transition, glass transition and crystallization
and solid state reactions with no volatile product would
not be indicated because they provide no change in mass
of the specimen. However, these changes are indicated
during DTA by endothermal or exothermal departure from
the base line. Since DTA is a dynamic method, it is
essential that all aspects of the technique be standardized
in order to obtain reproducible results. These include
pretreatment of specimen, particle size and packing
specimen, dilution of the specimen and nature of the inert
diluent. The principle of method consists in measuring the
change in temperature associated with physical or
chemical changes during the gradual heating of the
substance. Thermal changes due to fusion, crystalline
structure inversions, boiling, dissociation or
decomposition reactions, oxidation and reduction
reactions, destruction of crystalline lattice structure and
40
other chemical reactions are generally accompanied by an
appreciable rise or fall in temperature. Hence, all these are
accounted in DTA. Generally speaking, phase transitions,
dehydration, reduction and some decomposition reactions
produce endothermic effects whereas crystallization,
oxidation and some decomposition reactions produce
exothermic effects.
In DTA a sample of material under investigation
(specimen) is placed by the side of thermally inert material
(the reference sample) usually calacite or α-alumina in
suitable sample holder or block. The temperature
difference between the two is continuously recorded as
they are heated. The block is heated in an electric furnace
i.e. both are heated under identical conditions.

2. Characteristics of DTA curves

An idealized representation of the two major processes
observable in DTA is illustrated in figure 9, where T is
plotted on y-axis and T on x-axis.

41
 Fig. 9. A representation of the DAT curve showing
exotherm, endotherm and base line changes.

Endotherms are plotted downwards and exotherms

upwards. Similarly, the temperature of the sample is
greater for an exothermic reaction, than that of the
reference, for endotherms the sample temperature lags
behind that of the reference.

42
 When no reaction occurs in the sample material, the
temperature of the sample remains similar to that of
reference substance. This is because both are being heated
exactly under identical condition i.e. temperature
difference T (Ts-Tr) will be zero for no reaction. But as
soon as reaction starts, the sample becomes either hot or
cool depending upon whether the reaction is exothermic
or endothermic. A peak develops on the curve for the
temperature difference T against temperature of furnace
or time. Let us consider the DTA curve in figure 9 again,
where T along the line AB is zero indicating no reaction
but at B where the curve begins to deviate from the base
line corresponds to the onset temperature at which the
exothermic reaction starts and give rise to a peak BCD
with a maximum at point C. Where rate of heat evolution
by the reaction is equal to the difference between the rate
of evolution of heat and inert reference material. The peak
temperature C corresponds to the maximum rate of heat of
evolution. It does not represent the maximum rate of
reaction nor the completion of the exothermic process.

43
Thus, the position of C does not have much significance
in DTA experiments.
At some determinant point the heat of evaluation
process is completed and after this point heat evaluation
goes on decreasing up to D. The usefulness of the method
arises from the fact that peak temperature is normally
characteristic of the material in the sample. Area of the
peak BCD is proportional to the amount of reacting
material. For endothermic reaction the peak EFG will be
obtained as shown in the idealized curve. This peak shows
that the T (Ts-Tr) will be negative because heat is
absorbed and consequently Ts will be smaller than Tr. Note
the levels of base lines of extotherm curve, AB and DE.
Both are at different levels above x-axis. This is due to the
fact that heat capacity of the sample has changed as a
result of the exothermic process. Similar explanation can
be given for the difference in levels of base lines of
endotherm curve i.e. DE and GH. DTA curves are not only
help in the identification of materials but their peak areas
provide quantitative information regarding mass of
sample (m), heat of reactions (enthalpy change, H) and
44
factors such as sample geometry and thermal
conductivity. If latter two factors are expressed by a factor
K called calibration factor, then peak area can be express
as follows.

Peak area (A) = ± H m K …(1)

We will use +ve sign for endothermic reaction ( H >

zero) i.e. when the temperature of the sample will lag
behind the that of the reference, and negative sign for
exothermic reaction ( H < zero) the temperature of the
sample will exceed that of reference, factor K is called
calibration constant which is temperature dependent. It
can be determined by calibrating DTA with some
standard. Once we know the value of K at a particular
temperature, the peak area can be used for quantitative
analysis to determine the mass of sample or energy
(enthalpy changes) of a reaction.

3. Instrumentation

45
 In Figure 10 is shown a block diagram of a differential
thermal analyzer. It consists of following basic
components:
1. Furnace Assembly
2. Sample and reference holder with temperature detector
3. Temperature programmer
4. Amplifier and recorder
5. Atmosphere control equipment for furnace and sample
holder

The instrument measures the differential temperature

of the sample as a function of temperature or time where
the temperature rises at a constant linear rate.

46
3.1. Source of uniform heating:
Nichrome (nickel and chromium alloy) furnace can be
used up to 1300°C, platinum and its alloys up to 1750°C
and molybdenum (Mo) for higher range up to 2000°C. A
special type of higher frequency induction heating may be
used for higher temperatures.

3.2. Temperature regulating system:

Uniform rate of heating of the furnace is ensured
through electronic temperature regulators.

47
Fig. 10. Schematic diagram of a differential thermal
analyzer (a) complete layout (b) furnace part sharing
continuous heating of sample and standard.
48
3.3. Specimen holder
It is designed to accommodate even a small quantity of
material and to give maximum thermal effect. It can be of
Pt, Ni, stainless steel, Ag and alloy such as Pt-Rh. Certain
ceramic materials such as sintered alumina, silica, fire
clay, heat resistant glass and even graphite have been
recommended as material specimen holder for the sample
under investigation and reference material like (α-
alumina).

3.4. Measurement of temperature

Rare metal alloy such as Pt- (Pt-10-13% Rh) are
commonly used as thermocouple for measuring the
temperature. For higher temperature up to 2000oC W-Mo
thermocouple may also be used. Very thin thermocouple
is inserted in the sample and reference holder.

3.5. Temperature recording system

Visual galvanometric observations, though
inconvenient can also be used when only a few samples
are to be investigated. Nowadays automatic pen and ink

49
electronic recorder have been found to be more
convenient.

3.6. Direct recording of the heating curve

When a sample is heated at a constant rate, the
temperature function T, is linear up to the moment when
the sample undergoes change, its slope represents the rate
of heating which remains constant.
At the moment, when an exothermic or endothermic
change takes place, the shape of curve changes as shown
in figure 9. An exothermic reaction causes an increase in
heating rate while endothermic reaction causes a decrease
in heating rate. The main disadvantage of this method is
its sensitivity, because small changes in the temperature
causes small deviation in linearity of the curve which
some times are not observable. So, small temperature
changes occurring in the sample are generally not detected
by this method. Since detector thermocouples are opposed
to each other, small difference between Ts and Tr can be
detected after suitable voltage amplification (Figure 10).
Thus very small sample size may be used in this method.
50
 Thus recording of the differential curve is
advantageous because it can record the small change in
enthalpy that is not accompanied by a change in weight.

4. Factors affecting DTA curves

DTA is a dynamic temperature technique. Therefore, a
large number of factors can affect the resulting
experimental curves. Similar to TGA curves, these factors
can be divided into the two groups:
i) Sample factors, and
ii) Instrumental factors

The Instrumental factors such as size and shape of

sample holder, sample holder material, heating rate of the
sample, sensitivity of recording system, location of
thermocouple in the sample and atmosphere around
sample. Most of these factors are associated with
instrumental design. We have very little control on these
factors. Sample characteristics includes amount of
sample, particle size, packing density, heat capacity and
thermal conductivity, degree of crystallinity, dilutes of

51
diluents, swelling and shrinkage of the sample. In
following lines we will concentrate on some of the
important factors in some detail.
a) Amount of Sample. In DTA analysis, peak area of
DTA curve is proportional to the mass of the sample.
Certainly this assumption is valid only over a certain
range of amount of the sample. Generally in DTA
experiments, a few mg of powdered solid sample is
used.
b) Particle Size. In DTA experiments, samples in the
form of fine powers are generally preferred except
polymers, in which case we might have to use plastic
fragments or chopped fibers. When we are comparing
between two materials, their sample should have
similar particle size.
c) Sample packing. Packing density of sample
influences the shape of DTA curve. Tight packing
influences the escape of volatiles and interaction of
sample with atmosphere of furnace due thermal
experiments. Therefore, a reproducible method of
packing the sample is desirable.
52
d) Heating rate. It is observed that an increase in heating
rate increases, the procedural peak temperature, and
some time it also increases peak area. Often high
heating rate results in poor resolution of fine peak in
DTA curve. Therefore slower heating rate is preferred
for DTA experiments. Heating rate of 10°C min-1 and
5°C min-1 are commonly preferred.
e) Atmosphere around sample. Similar to DTG, a
flowing gas is preferable to a static atmosphere as in
static atmosphere. There is a possibility of change of
atmosphere around sample on its degradation or
decomposition especially in case of a volatile sample.
In such a case we generally use flowing gas technique.
Flowing gas sweeps away volatile by products and
keeps homogenous atmosphere around sample. In
Table 3, we have summarized the major factor which
can affect the DTA curve.

Table 3. Factors that influence DTA curve

Factor Effect Suggestions
53
 Heating rate Change in peak Use a low heating
size and position rate
Location of Irreproducible Standardize
thermocouple curve thermocouple
location
Atmosphere Change in the Inert gas should be
around sample curve allowed to flow
Amount of Change in peak Standardize sample
sample size and position mass
Particle size of Irreproducible Use small, uniform
sample curves particle size
Packing density Irreproducible Standardize packing
curves technique
Sample container Change in peak Standardize
container

5. Interpretation of DTA curve

54
 DTA curves of a pure compound represent
characteristic of that compound for physical chemical
changes. Using DTA curve one can co-relate the changes
in energy because of thermophysical and chemical change
occurring in a compound because of heating the material.
This can often provide us directly to the temperature at
which the physico- chemical transition are occurring and
which is also used to identify the presence of respective
elements or compounds qualitatively. The change in DTA
curve further gives information about the thermophysical
changes associated with mass change e.g. melting point,
glass transition temperature, crystallization temperature
etc.

To further illustrate, let's consider the example of

CaC2O4.H2O for which DTA curve is shown in Figure 11.

55
Fig. 11. The DTA curve of CaC2O4.H2O in presence O2.

This curve indicates that out of three DTA peaks first

is endothermic in nature, second is exothermic and third
one is again endothermic in nature. The correlates the
TGA results and confirms that the nature of reactions
occurring in the endothermic are because of desolvation
and decarboxylation while exothermic is due to
decomposition followed by oxidation and finally
formation of stable oxide CaO with evolution of carbon
56
dioxide gas. This can be explained by the chemistry of
decomposition of CaC2O4.H2O when it is heated.
DTA curves are useful both qualitatively and
quantitatively. Similar to TGA, the position and shapes of
the peaks (curve) can be used to determine the
composition of the sample. As discussed earlier, Eq. (1)
can be used to relate peak area with the heat of the reaction
and amount of sample used for analysis. But before using
this equation we should know the value of calibration
constant, K, at the temperature concerned. This can be
achieved by the calibration of instruments with known
standards. However, the value of the calibration factor, K,
may be eliminated from the quantitative calibration by
comparison of peak area of unknown sample with the
known sample under identical condition. For example if
A1 is the peak area of known mass (m1) and A2 is the peak
area of unknown sample having mass equal to m2, then
using Eq. (1) we can write:

m1/m2 = A1/A2 or m2 = m1(A2/A1) ...(2)

57
 Similarly, the heat of reaction of a unknown sample
can also be calculated by comparison with a sample of
known heat of reaction. One thing keep in mind that the
calibration factor, K, in Eq. (1) is temperature dependent
in DTA situation, therefore both known and unknown
sample should be run at identical temperature.

You may have noticed in Figure 9 and Figure 12 that

the initial and final baselines of peaks do not coincide.
Therefore, determination of the area under the peak may
be subject to ambiguity. To resolve this problem a method
for determination of the peak area is illustrated in Figure
12. Both baselines are extended to a perpendicular line
drawn from the maximum of the curve and the area under
the two halves of the curve are determined and added to
give the total area.

58
Fig. 12. Illustration depicting the determination of DTA
peak areas. The difference in the initial and final base
indicates a change in heat capacity.

The heat of reaction observed in DTA can be further

used to calculate molar enthalpy of reactions by using the
formula:

Hm = Hr x Mr/ m ... (3)

where, Hm = molar enthalpy of reaction, Hr = enthalpy

of reaction, Mr = related molar mass of the compound, m
= mass of substance used for analysis.
59
6. Determination of heat capacity
The DTA curve is conveniently used to measure the
heat capacity (specific heat). For this purpose first a DTA
curve is recorded for an empty container and then for the
sample placed in container is recorded in identical
condition. The absolute change in temperature ( Tx) has
been measured and put in the equation for calculations:

Cp = K …(4)
where Cp is the heat capcity at temperature T, T1 and T2
are differential temperature generated when the
instrument is first run without any sample at all and then
with the test sample in position, H is the heating rate
(dT/dt) and K is calibration factor. It can be determined by
calibration against standard substance of known enthalpy
change.

7. Construction of phase diagram

The Melting point can be recorded by DTA curve for a
eutectic mixture of different sample with variable
composition. These melting points can be used to

60
construct a phase diagram. The critical temperature of
organic compounds can be determined by DTA if sealed
sample holder is used. The determination is used of
cooling curve, a discontinuity is observed at the critical
temperature Tc. Curie point temperature making a sudden
change at this point can also be determined by this
technique. The specific heat increases gradually upon the
curie point e.g 357oC for nickel, observed simply by
ploting dQ/dT or dT against temperature.

8. Estimation of transition temperature

The precise determination of a transition temperature
(e.g. M.P. and B.P.) up to a precision of ± 0.3oC over a
wide range of heating rate. The temperature estimated for
M.P. Tm or B.P. Tb, were most often selected from the
portion peak as shown in Figure 13. In this figure first a
base line meeting low and high temperature sides of the
peak is drawn where A is the intersection of extrapolated
straight line portion of the low temperature side of the
peak with the base line. Further, point B is the inflection
point of low temperature side of the peak and point C is
61
the extrapolated peak, while D is the extrapolated return
to the base line. Melting point Tm is measured by the using
sample is closest to the temperature of point C for sample
and temperature at B for reference. In exceptional cases it
may closer to point D.

Fig. 13. The different temperature of DTA curve.

62
9. Applications
Now we study in some more examples to understand
how DTA is used in chemical calorimetry and identifi-
cation of a material (qualitative interpretation) comparing
and for thermalstability of materials. Such informations
can be used to select material for certain endues
application, predict product performance and improve
product quality.

9.1. Qualitative and quantitative identification of

minerals

For the detection of any minerals in a sample, it is

essential that it undergoes measurable energy changes in
the temperature range used. Since most of the minerals
undergo such changes, choice of an appropriate
temperature range should have priority. However,
assuming a suitable range variation occurring in the
minerals themselves may frequently lead to difficulties in
the interpretation of curves. Another complication arises
from the fact that certain minerals give reasonably

63
characteristic thermal effect, sometimes clays do not show
similar result. Other difficulties may arise by the presence
of organic matter.

Oxidation of organic materials if present masks the

thermal effect of substance. Consequently the analysis of
such cases should preferentially be carried out in inert
atmosphere or in vacuum. Organic material some times be
removable by a suitable solvent or may be oxidized by
treating with H2O2. When clays or ore contain organic
material then a broad exothermic peak appears between
200-600oC. Thus the appearance of a broad exothermic
peak between 200-600oC indicates the presence of organic
material in a given sample.

In practice however, difficulties do arise in a case

where peak areas for two distinct samples of same mineral
give peaks at two different temperatures. It is, therefore,
necessary for qualitative work to know the peak area given
by pure mineral identical to that in the sample under
investigation. This, however, is not possible. Another
limitation in the quantitative work in the occurrence of
64
overlapping of peaks e.g. when Kaolinite and Illite are
present in the same sample almost completely overlapping
takes place. A representative DTA curve of some minerals
are shown in Figure 14. It may be observed that none of
these miners show an exothermic peak in the range 200-
600°C corresponding to organic material as mentioned
above.

Fig. 14. DTA curves for (A) : Kaolinite, (B):

Mortmonillonite, (C): Illite.
65
9.2. Polymeric materials

DTA is a very useful technique for the characterization

of polymeric materials in the light of identification of
thermophysical, thermochemical, thermo mechanical and
thermo elastic changes or transitions. It provides
important parameters for polymer processing and its end
use. The DTA also provides useful information about
quantitative aspect, degree of fusion, crystallinity, phase
equilibrium, heat of polymerization, degree of curing etc.
A typical DTA curve of a polymer is shown in Figure 15
with labeled four transitions: glass transition,
crystallisation, melting and oxidation, abbreviated as Tg,
Tc, Tm and Td respectively.

The DTA technique is also used for analyzing a

polymeric mixture qualitatively and quantitatively. The
individual polymers exhibit their own characteristic
peaks. The Figure 16 is differential thermal curve of seven
components polymeric mixture for their melting points:
Polytetrafloroethylene (PTFE), High Pressure (high
dencity) Polypropylene (LPPE), Low Density
66
Polypropylene (LPPE), Polypropylene (PP),
Polypropylene POM, Nylon 6, Nylon 66.

Fig.15. DTA curve of a typical polymeric sample.

Fig. 16. DTA curve of a typical polymeric mixture.

It is shows characteristics peaks of all the polymers and
hence confirm the presence of individual polymers in the
67
analyzed sample. The area under the peak is related to the
heat of reaction and related to the quantity of material
present in the mixture. The DTA graph of ethylene
propylene block copolymer indicates two peaks for
ethylene and propylene. On comparing areas under the
peaks it is found that 51% ethylene and 49% propylene
present in the analyzed block copolymer. The peak height
technique has been also employed to measure the quantity
of polysebacic anhydride in a epoxy resin-sebacic
anhydride mixture.

Another important parameter determined from by

DTA is glass transition (Tg), a second order transition
caused by relaxation of chain segment in the amorphous
portion of a polymer. The first evidence that a glass
transition could be detected by DTA was provided in
(1957), where a transition at 28°C was shown but not
interpreted. As such this transition is not associated with
latent heat but rather a sudden change in specific heat to
bring a liquid into the glassy state. The necessary

68
condition is to cool it rapidly to approximately two third
of its melting point.

Tg/Tm = 0.66

The glass transition of a polymer can be obtained using

number average molecular mass M ranging from 8 x 103
to 3 x 106 from expression:
Tg = [ ( 96.5 +/- 1.0 ) -( 2.8 +/- 0.1)] x 1 3 / M
The deduction about the slope of the glass transition as
depicted by DTA curve:
a) The slope of the curve T surface temperature should
be sigmoidal.
b) The maximum value of T at the glass transition
temperature should be linearly dependent on the
heating rate.
c) The inflection point Tg should rise in temperature with
the heating rate. It has been shown that glass transition
is associated with a sudden shift in base line.
The Tg depends on heating rate, volume fraction and
molar mass. The DTA results provide important
information about polymerization reaction , mainly about
69
heat of polymerization, degree of curing, effect of
catalysts, decomposition reaction and radiation effects.

9.3. Measurement of crystallinity

A common application of DTA is the measurement of

the mass fraction of crystalline material in semi crystalline
polymers. The method is based upon the measurement of
the polymer's heat of fusion, Hf, and the plausible
assumption that this quantity is proportional to the
crystalline content. If by some process of extrapolation the
heat of fusion, Hf *, of a hypothetical crystalline sample
is known then the mass fraction of a crystallinity is mass
fraction = Hf / Hf *.

9.4. Analysis of biological materials

DTA has been widely used in the determination of
thermal characteristics of bio- organic molecules, the
main constituent of body of living being. The bio
materials are having heterogenity as a significant feature.
This describes it as multicomponent, molecular non
homogenous materials, in which component exist as
70
continuous, separate and inter mixed structures.
Biological systems present complexity even in static state
and then difficulty in obtaining meaningful
re1establishing correlation between thermal
characteristics and other physical chemical properties.
The thermal characteristics of a number of biological
materials such as fresh biological materials and
decomposed materials determined under different
atmospheric condition have been studied.
Fresh biological material consists of materials of active
body of plants and animals. It is always difficult to
elucidate the chemical constituents of the plant materials.
Information obtained from the study of the simple
molecules can not be necessarily applied directly to
heterogeneous system. In the study of such system indirect
method has been applied e.g. complete combustion,
dilution effect, environmental effect etc. The DTA curves
of four leave samples of different plant in oxygen exhibit
two pronounced exothermic effect in the range 240-270oC
region. The first peak is invariably smaller than second
one at least in height always not in area apart from
71
variation in peak temperature. The general similarity in
these curves may be inferred that leaves of the plants have
at least same micro-chemical composition.
The DTA curves for some plant materials have also
been obtained in a static or air or dynamic oxygen
atmosphere, since it is difficult to distinguish between
decomposition and oxidation effects, which may overlap.
Endothermic reaction such as dehydration or
volatilization while exothermic accompany combustion
under inert atmosphere condition, with oxidation reaction
suppressed, such endothermic effect can be detected.
Similarly the analytical method is useful for analysis of
high energy materials, explosives, ceramic, cement and
pharmaceuticals.

72
 CHAPTER IV

DIFFERENTIAL SCANNING
CALORIMETRY (DSC)

DIFFERENTIAL SCANNING
CALORIMETRY (DSC)

In previous section we have studied DTA techniques

in these methods, thermal reactions are observed by
measuring the deviation of the sample temperature from

73
that of the reference material. This deviation effects the
DTA curve and decreases the sensitivity. There is another
technique called differential scanning calorimetry (DSC)
which have the advantage of keeping the sample and
reference at the same temperature and heat flow into
sample and reference is measured. This can be achieved
by placing separate heating devices in the sample and
reference chambers. This is in contras to the DTA scheme,
where both sample and reference are heated by the same
source.

1. Principle
In DSC the heat flow is measure and plotted against
temperature of furnace or time to get a thermogram. This
is the basis of differential scanning calorimetry (DSC).
The curve obtained in DSC is between dH/dt in m J s-1 or
m cal s-1 as a function of time or temperature. A typical
DSC curve is shown in Figure 17. The deviation observed
above the base (zero) line is called exothermic transition
and below is called endothermic transition. The area under
the peak is directly proportional to the heat evolved or
74
absorbed by the reaction, and the height of the curve is
directly proportional to the rate of reaction. The only
difference is the calibration factor K in case of DSC is
independent of temperature. This is a major advantage of
DSC over DTA.

Fig. 17. A typical DSC Curve.

2. Instrumentation
The block diagram of a DSC instrument as shown in
Figure 18, essentially works on the temperature control of
two similar specimen holder assembly. The left half of the
block diagram represents the circuit for differential
temperature control while right hand side indicates that for

75
average temperature control. In the average temperature
control circuit, the temperature of the sample and
reference are measured and averaged and the heat output
of the average heater is automatically adjusted so that the
average temperature of the sample and reference increases
at a linear rate. The differential temperature use control
circuit monitors the difference in temperature between the
sample and reference and automatically adjust the power
to either the reference or sample chambers to keep the
temperatures equal. For getting a thermogram, the
temperature of the sample is put on the x-axis and the
difference in power supplied (in terms of J s-1 or cal s-1) to
the two differential heaters is displayed on the y-axis.

76
 Fig. 18. Block diagram of a DSC instrument.

Figure 19 illustrates the heating arrangement in sample

and reference compartments. Here the sample and
reference compounds are provided with their own separate
heaters, as well as their own temperature sensors so that
both S and R are maintained at identical temperature by
controlling electrically the rate at which heat is transferred
to them.
In DSC, samples for analysis range in size from 1 to
100 mg are placed in a sealed sample container. A wide
range of heating rate (0.5 to 80°C/min) can be used, DSC
77
instruments are generally sensitive energy detect heat
evolution or absorption at a rate less than one millicalories
per second. Electrical signals are amplified and recorded
similar to TGA and DTA.

Fig. 19. Heating arrangement in DSC.

During thermal process reactions either liberate or absorb

heat. Thus, when H is positive (endothermic reaction),
the sample heating device is energized and a positive
signal is obtained; when H is negative the reference
heating device is energized and a negative signal is
obtained. An idealized representation of the three major
processes observable in DSC is given in Figure 20. The

78
peak area in DSC are proportional to the amount of
sample, the heat of reaction and similar to DTA peak area
can be expressed by following equation:

Peak area (A) = ± H m K …(5)

Fig. 20. An idealized representation of the three

processes observed in DSC.
where H represents sample enthalpy change and m is
the mass of sample and K is a constant called calibration
factor. Unlike DTA it is independent of temperature.
Using above Eq. (5), we can determine enthalpy change
for a reaction directly from peak area, if we known the
79
value of K. We can also determine enthalpy change by
comparing the H of the sample with the known H of
the standard i.e.

…(6)

where Hs is the enthalpy change for sample, Hk is the

enthalpy change for known standard, ms and mk are masses
of sample and known standard respectively, and As and Ak
represents the area of peaks of sample and standard
materials, respectively.
DSC technique is not only sensitive for the
determination of H, but it is also very sensitive for the
determination of heat capacities (Cp). when a sample is
subjected to a heating programme is DSC, the rate of heat
flow into the sample is proportional to its heat capacity.
This may be detected by the displacement of the base line
as illustrated in Figure 19. The value of Cp may be
determined at a particular temperature by measuring this
displacement (d):

80
 …(7)

Using Eq. 7, we can deduce the unit of Cp. In DSC curve

displacement (d) will be measured in m J s-1. If heating
rate is in °C s-1 and m is expressed in g, then Cp can also
be expressed in term of m cal as m cal g-1 C-1 [conversion
factor for J and cal is 1 calorie = 4.2 J].
In practice we normally measure the base line shift by
reference to a base line obtained for empty sample and
reference pans. To further minimize experimental error
we usually determine heat capacity of the sample by
comparing with the known heat capacity of the standard.
3. Factors affecting DSC curve
In the beginning of this block we talked about the
lowest temperature, Ti at which the onset can be detected
by the instrument operating under particular conditions.
We may like to call this as transition temperature, which
is not correct. Actually in a DSC experiment, both Ti , Tf
and Tc (the final temperature at which the decomposition
is completed) do not have fundamental significance, but
they can still be a useful characteristic of a DSC curve.
81
The term procedural thermogram, often used for the
temperature at which temperature change appears to
commence. This indicates that a start of thermal reaction,
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 DSC curve.
These factors may be due to instrumentation or nature of
sample. We have listed the main factors which affect the
shape, precision and accuracy of the experimental results:
3.1. Instrumental factors:
a. Furnace heating rate
b. Recording or chart speed
c. furnace atmosphere
d. Geometry of sample holder; location of sensors
e. Sensitivity of recording mechanism
3.2. Sample characteristics:
a. Amount of sample
b. Solubility of evolved gases in sample.
c. Particle size
d. Heat of reaction

82
 e. Sample packing
f. Nature of sample
g. Thermal conductivity
4. Sources of Error
There are a number of sources of error in DSC, and
they can lead to inaccuracies in the recorded data of heat.
Some of the errors may be corrected by placing the thermo
balance at proper place and handing it with the care. For
understanding we are discussing some common source of
errors during operation or common as discussed in DTA
except the in accuracy caused by secondary heaters and
thermostats.
Errors can be avoided by proper placing of instrument
in the laboratory, maintaining operating temperature, and
constant power supply. By avoiding excessive heating rate
and proper gas flow rate other errors can be also avoided.
To further minimize the errors during experiments,
similar to DTA, DSC instruments are also be calibrated
for the temperature and peak area measurements with
suitable standards. The only difference is that calibration

83
constant in DTA situation is temperature dependent to a
significant degree. Therefore in DTA measurement, we
should calibrate peak areas using a standard which
provide a reference peak in a same temperature range as
the test sample. In DSC situation, K is independent of
temperature. Therefore, it requires simple steps for the
calibration of the instrument. For peak area calibration we
require standard of high purity and accurately known
enthalpy of fusion ( Hf) are required. Few examples of
calibration standards are indium (In), benzoic acid, tin,
lead, silver, gold, etc.
5. Interpretation of DSC curve
DSC curve of a pure compound is a fingerprint of that
compound in the context of transition temperature as well
as heat required for that transition. Therefore, DSC curve
can be used to infer about the presence of a particular
compounds and its thermal behaviour. The peaks
observed shifting of base line either up or down. The peak
above the base line is exothermic while down the base line
is endothermic.

84
 We have seen above how area under DSC curves is
related to the amount of energy released or absorbed in a
physico-chemical change. It has been shown that under
certain conditions the area under the peak is proportional
to the amount of heat evolved in a reaction.
So this area under the curve is used for stoichiometric
ratio of analyzed compounds (quantitative inter-
pretation). Now we see in next example how it can be used
to compare thermal stability of a material for physical
state and chemical states. This can be used for chemical
identification of a material (qualitative interpretation).
Such information can be used to select material for certain
end-use application, predict product performance and
improve product quality. DSC curves of a polymeric
mixture and probable transitions are shown in Figure 21
for illustration about probable change in behaviour of a
polymer sample.

85
 Fig. 21. Change in behavior of polymeric materials in
DSC.
The DSC technique is more sensitive than DTA and it
provides clear presence of a thermal events occurring
during course of heating of time ageing of material. Thus,
the information acquired by DSC is more realistic. The
technique is used for the presence of polymorphism,
degree of crystallinity, curing fraction etc. Curves clearly
indicate that Figure 20 is showing the peaks for the glass
transition, ordering, melting and decomposition of
individual polymers. The ratio of areasunder the curve by
dividing the enthalpy of heat of decomposition, provides

86
the ratio of individual monomers in a analyzed copolymer
sample .
The heat of reaction ( Hr) observed in DSC can be
further used to calculate molar enthalpy of reactions by
using following formula:
…(8)

Where, ( Hm = molar enthalpy of reaction, Mr = relative

molar mass of analyzed compound, m = mass of
substance used for analysis.
6. Applications
Differential scanning calorimetry (DSC) used to
measure energy changes as a function of temperature or
time. Using this technique it is possible to observe a
number of characteristic properties of a sample like
fusion, crystallization, glass transition temperatures (Tg)
as well as other thermo chemical reactions. DSC can also
be used to study oxidation, as well as other chemical
reactions. Glass transitions may occur as the temperature
of an amorphous solid is increased. These transitions
appear as a step in the baseline of the recorded DSC signal.

87
This is due to the sample undergoing a change in heat
capacity; no formal phase change occurs. As the
temperature increases, an amorphous solid will become
less viscous. At some point the molecules may obtain
enough freedom of motion to spontaneously arrange
themselves into a crystalline form. This is known as the
crystallization temperature (Tc). This transition from
amorphous solid to crystalline solid is an exothermic
process and results in a peak in the DSC signal. As the
temperature increases the sample eventually reaches its
melting temperature (Tm). The melting process results in
an endothermic peak in the DSC curve. The ability to
determine transition temperatures and enthalpies makes
DSC an invaluable tool in producing phase diagrams for
various chemical systems. The technique is widely used
across a range of applications, both as a routine quality
test and as a research tool. The equipment is easy to
calibrate, using low melting indium for example, and is a
rapid and reliable method of thermal analysis. The few
notable specific applications of DSC are:

88
 The result of a DSC experiment is a curve of heat flux
versus temperature or time. There are two different
conventions: exothermic reactions in the sample shown
with a positive or negative peak. This curve can be used
to calculate enthalpies of transitions. This is done by
integrating the peak corresponding to a given transition. It
can be shown that the enthalpy of transition can be
expressed using the following equation:
H = KA
where H is the enthalpy of transition, K is the
calorimetric constant, and A is the area under the curve.
The calorimetric constant will vary with the instrument
and can be determined by analyzing a well-characterized
sample with known enthalpies of transition.
Most of well known spectroscopic methods of great
value in the qualitative and quantitative chemical analysis
are based on our ability to measure energy absorption or
emission caused by transition from one energy state to
another. The great potential of thermal spectroscopy for
quantitative analysis was not realized in the past because
of the absence of a suitable, fast scanning, the calibration
89
run for the synthetic compounds and the base line
technique used in the area measurement and can be used
for the quantitative analysis of constituents present in the
fiber blend.
Many materials can exist in two or more different
crystal line forms. The chemical reactivity and physical
properties of different forms vary frequently one to
another. Technological handling requires one of the
perfect suitable form, hence the phenomenon is of great
importance in chemistry and conveniently studied by
DSC.
DSC may also be used in the study of liquid crystals.
As matter transitions between
solid and liquid it often goes through a third state,
which displays properties of both phases. This anisotropic
liquid is known as a liquid crystalline or mesomorphous
state. Using DSC, it is possible to observe the small
energy changes that occur as matter transitions from a
solid to a liquid crystal and from a liquid crystal to an
isotropic liquid.

90
 DSC curves may also be used to evaluate puriting of a
drug and polymer. This is possible because the
temperature range over which a mixture of compounds
melts is dependent on their relative amounts. This effect
is due to a phenomenon known as freezing point
depression, which occurs when a foreign solute is added
to a solution. (Freezing point depression is what allows
salt to de-ice sidewalks and antifreeze to keep your car
running in the winter). Consequently, less pure
compounds exhibit a broadened melting peak that begins
at lower temperature than a pure compound. DSC is used
widely for examining polymers to check their purity and
composition. Melting point and glass transition
temperature for most polymers are available from
standard compilations, and the method can show up
possible polymer degradation by the lowering of the
expected melting point, Tm. It depends on the molar mass
of the polymer, so lower grades will have lower melting
points than expected.
In pharmaceutical industry it is necessary to have well-
characterized drug compounds in order to define
91
processing parameters. For instance, if it is necessary to
deliver a drug in the amorphous form, it is desirable to
process the drug at temperatures below those at which
crystallization can occur. The above mentioned transition
are well observed in DSC curve and used in industry
regularly
There are two important criteria for characterization of
waxes and fats by DSC:
1. Although melting peak shape of wax and wax
formulations can be quite complex, they are much
less sensitive than fats to variation in the
crystallization condition.
2. The crystallization of waxes is easily nucleated
with the result that solidification occurs readily
with little or no super cooling. In fact the
crystallization peak for most waxes is virtually
mirror image to its melting point. Although reading
of DSC thermogram and applying to these criterion,
we can easily make statement whether the supplied
material is wax or fat.

92
 Using differential scanning calorimetry to study the
oxidative stability of samples generally requires an
airtight sample chamber. Usually, such tests are done
isothermally (at constant temperature) by changing the
sample atmosphere. First, the sample is brought to the
desired test temperature under an inert atmosphere,
usually nitrogen or organ. Then, oxygen is added to the
system. Any oxidation that occurs is observed as a
deviation in the baseline. Such analysis can be used to
determine the stability and optimum storage conditions of
a compound.
A more specific application of DSC where DTA
cannot be employed is the detection of magnetic transition
in the materials. The magnetic transition are of second
order with H = zero but with the a maximum heat
capacity at the transition temperature. Technique is
sensitive to detect these minor variations. A typical DSC
curve for a magnetic transition is shown in Figure 22.
Similarly glass transition can be detected easily with DSC.

93
Fig. 22. A typical magnetic transition observed in DSC.

7. Advantages of DSC
1. Small sample size 1 to 10 mg
2. Simple and rapid procedure of analysis, typically 15 to
30 min per determination
3. Ideal for comparison of sample purity for example in
quality control
4. Does not require high absolute temperature accuracy
(in contrast with melting point depression method)
5. Does not require calibration with known impurity
levels, cryoscopic constant is obtained simul-taneously

94
6. The use of melting rather than a freezing curve avoid
problems associated with super cooling of sample,
poor crystallizability from melt, instability in the melt
etc.

95
FURTHER READING
1. H.H. Willard, L.L. Merrit Jr., J.A. Dean, F.A. Settle Jr.,
Instrumental Method of Analysis, Wadsworth
Publishing company, USA, 1986.
2. P.D. garn, Thermoanalytical Methods of
Investigations, Academic Press, New York, 1965.
3. H. Gunzzler and A. Williams, Hand Book of
Analytical Techniques, Wiley - VCH, Weinheim, Vol
2, 2001.
4. G.W. Ewing, Analytical Instrumentation Handbook,
Marcel Dekker Inc., New York, 1990.
5. J. Jiordan, J. Chem. Education, 40, A5 (1963).
6. J. Batethel, Thermometric titrations, John Wiley, New
York, 1975.
7. N. Jespersen in Instrumental Analysis Eds. H.H.
Bauer, G.D. Christian, and J.E. O'Reilly, Second Edn.
Allyn and Bacon. Inc. Boston, p. 523, 1986.
8. H.H. Willard, L.L. Meritt, J. A. Dean and F.A. Settle,
Instrumental Methods of Analysis, Seventh Edn,
Wadsworth Publishing company, Belmont, 1988.

96
9. R.A. Meyer, Encyclopedia of Analytical Chemistry,
John Wiley & Sons Ltd, Vol. 15, 2000.
10.R.C. Mackenzie, Differential Thermal Analysis,
Academic press London, 1970.
11.Skoog, Douglas A., F. James Holler and Timothy
Nieman, Principles of Instrumental Analysis. Fifth
Edition. New York. 1998.
12.Dean, John A., The Analytical Chemistry Handbook.
New York. McGraw Hill, Inc. 1995.
13.M.E. Brown, Introduction to Thermal Analysis,
Kluwer Academic Publisher, London, 2001.
14.W.W. Wandlandt, Thermal Analysis, Wiley, New
York, 1986.
15.A. Blazek, Thermal Analysis, Van Nostrand Reinhold,
London,1972.
16.H. Kmaber, P.D. Garn, Thermal Analysis:
Comparative studies on Materials, John Wiley & Sons,
New York, 1974.

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