completed) do not have fundamental significance, but they can still be a useful Differential Thermal

characteristic of a DSC curve. The term procedural thermogram, often used for the Analysis, Scanning
temperature at which temperature change appears to commence. This indicates that a Calorimetry and
start of thermal reaction, temperature does not have a fixed value, but depends on the Thermometric
Titrations
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:

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.
f) 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.

Some of these factors we have are already described in sec.11.2.4 in detail.

11.3.4 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 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 ( ∆ H f ) are required. Few examples of calibration standards are
indium (In), benzoic acid, tin, lead, silver, gold, etc.

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Thermal Methods SAQ 6
DTA and DSC, which method you will prefer for quantitative purposes and why?

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11.3.5 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. A
typical DSC curve is shown in Fig 11.11. The peak above the base line is exothermic
while down the base line is endothermic.

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 stochiometric ratio of analyzed compounds
(quantitative interpretation). 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 Fig. 11.14 for illustration about
probable change in behaviour of a polymer sample.

Fig. 11.14: 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 Fig. 11.13is 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 the ratio of individual
monomers in a analysed copolymer sample .

The heat of reaction (∆Hr) observed in DSC can be further used to calculate molar
enthalpy of reactions by using following formula:

50
 ∆Hm = ∆Hr × Mr /m Differential Thermal
Analysis, Scanning
Where, (∆Hm = molar enthalpy of reaction , Calorimetry and
∆Mr = relative molar mass of analysed compound, Thermometric
m = Mass of substance used for analysis. Titrations

11.3.6 Applications
Differential scanning Calorimetry (DSC) used to measure energy changes as a
function of temperature or time. A typical graph is shown in Fig. 11.13. 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. 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 (T m). 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:

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 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.

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