BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI

Pilani Campus, Chemistry Department

Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

Experiment: 8

DIFFERENTIAL SCANNING CALORIMETRY AND THERMOGRAVIMETRY

BASED EXPERIMENTS

Differential Scanning Calorimetry Instruments

INTRODUCTION:

Thermal methods are the group of the methods in which some physical property of the sample
is continuously measured as a function of temperature, while the sample is subjected to a
controlled temperature change. DSC is one of the thermal analysis methods.
The effect of heat can be wide ranging & cause changes in many properties of a sample.
Measurement of energy changes form the basis of differential scanning calorimetry and thus it
can tell us if that reaction is exothermic or endothermic. It shows, generally, an endotherm on
melting and exotherm on freezing.
DSC differs from DTA (Differential Thermal Analysis) in that instead of allowing a
temperature difference to develop between the reference and sample materials, DSC measures
the energy that must be applied to keep the temperatures same.

The Device Diagram and Instrumentation

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

When a material undergoes a change in its physical state, or when it reacts chemically, heat is
either absorbed or liberated. This corresponds to endothermic or exothermic changes,
respectively. Fusion process is endothermic while adsorption is generally exothermic in nature.
But crystalline transitions may be either endothermic or exothermic. This is also true of
chemical decompositions.
In DSC, the instrument keeps sample (S) and reference (R) at the same temperature. The
amount of heat that must be supplied to S or R to achieve this equivalence in temperature is
continuously measured over the temperature range employed. This recorded heat flow gives a
measure of the amount of energy absorbed or evolved in a particular transition, and hence gives
calorimetric measurements directly. S & R are provided with their own separate heaters and
temperature sensors so that both are maintained at identical temperature by controlling
electrically the rate at which the heat is transferred to them.

The instrument consists of the following components:

1. Sample holder assembly (incorporating sample and reference containers mounted in a
suitable holder)
2. Furnace or heating device (incorporating temperature sensor)
3. Temperature programmer (with control system)
4. Recording device
5. Atmosphere control, Nitrogen supply to ensure inert atmosphere
6. Cooling control

DSC CURVES

These curves record the differential heat input to the sample (expressed as a heat flow dH/dt
in mJs-1 or mcal s-1) on the ordinate, against temperature (T) or time (t) on the abscissa. An
idealized representation (for a polymer) of three major processes observable by DSC is given
below. Normally exotherm is plotted upwards and endoderm downwards.

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

Glass transition temperature, Tg:

This is the point at which, on heating, an amorphous polymer changes from being hard, brittle
and glass like to being a soft rubber like substance. In a way, this is analogous to a percolation
threshold. As the polymer is cooled, molecules have less freedom and become bonded to each
other. As the percentage of bonded molecules increases, there comes a point at which long-
range connectivity occurs (the “percolation threshold”) and the polymer reverts to a glass like
phase again. This point may be identified as a dip on a graph of heat flux versus increasing
temperature, this is due to the molecule having a greater degree of freedom and absorbing
energy to maintain the same rate of heating as the reference. It can then be concluded that glass
transition is an endothermic process. Unlike a transition from a solid to a liquid, or liquid to
gas, the energy change involved in glass transition (a second order phase change) is quite small.
Fully crystalline polymers have no glass transition and their structure remains intact until the
melting point.

Temperature of crystallisation, TC:

Continuing to heat a polymer past its Glass transition temperature eventually leads to another
transition. Before this point in the thermal analysis, the molecules are arranged in a random
fashion and are coiled around each other in an unfavorable manner. A transition occurs when
molecules acquire enough freedom to move into a more energetically stable phase, i.e. a
crystalline state. This would indicate that the phase following the glass transition is metastable
and when sufficient energy is supplied, its molecules adapt a more stable (lower energy)
arrangement. Because the molecules in a crystalline solid have less freedom than those in a
flexible rubbery one, the transition between these two states is exothermic and may be seen as
a brief upward “jump” in the graph.

Temperature of melting, Tm:

This is the point at which the (now crystalline) polymer molecules have gained enough
vibrational freedom to break free from the solid binding forces and form a liquid. Due to the
increased freedom of these molecules, the DSC graph should take a sudden dip at this
temperature to indicate the endothermic nature of the process, which is a first order transition.
The melting point of any substance can be given by:
∆
𝑇 = ∆

ΔHm is the melting temperature and ΔSm is the change of entropy involved in the melting phase
(entropy of fusion).

Degradation Temperature, Td:

The final transition on a DSC graph is the degradation temperature, TD. At this point in the
heating cycle, individual bonds between atoms start to break as the vibrations become more
and more fierce until eventually, individual polymer molecules decompose into their
components. Depending on the nature of the substance under investigation, this process can be
either endothermic or exothermic

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

Analysis:
When the enthalpy changes (H) for a reaction is greater than zero, the sample heater in DSC
is energized and a corresponding signal obtained. For an exothermic change (H<0) the
reference heater is energized to calibrate the sample and reference temperatures again and
restore T to zero. This gives a signal in the opposite sense. Since these energy inputs are
proportional to the magnitude of the thermal energies involved in the transition, the records
give calorimetric measurements directly.
Peak areas are proportional directly to the thermal effects experienced by the sample as it is
subjected to the temperature program.
Peak area (A) =  H m k
Where H = sample enthalpy change
m = sample mass
k = proportionality constant
From this equation we can determine the enthalpy changes for a reaction directly from peak
area.
When a sample is subjected to heating program, the rate of heat flow into the sample is
proportional to its heat capacity (Cp). DSC is particularly sensitive to such changes, which may
be detected by the displacement of the baseline from one near horizontal position to another.
The value of Cp may be determined at a particular temperature by measuring the displacement
(D) that is basically the heat flow .

ℎ𝑒𝑎𝑡 𝑓𝑙𝑜𝑤 𝑑𝐻
𝐶 = = 𝑑𝑡
𝐻𝑒𝑎𝑡𝑖𝑛𝑔 𝑟𝑎𝑡𝑒 × 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑑𝑇
𝑑𝑡 × 𝑚

Thus, DSC curves provide us valuable physical data of the sample.

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

Thermogravimetric Analysis Instruments

INTRODUCTION:

The effect of heat can be wide ranging & cause changes in many properties of a sample. TGA
measures the change in weight of the sample as a function of temperature under an inert
atmosphere. Using this technique, we can get information about the different physical and
chemical properties of the material, such as phase transition, absorption, adsorption,
desorption, chemisorption, thermal decomposition, and oxidation-reduction reactions.
TGA differs from DTA (Differential Thermal Analysis) and DSC (Differential
Scanning Calorimetry) such that in DSC and DTA use a reference and measure the difference
of heat or energy while in TGA, the sample is heated on a pan without any reference, and the
weight loss or gain is measured.

The Device Diagram and Instrumentation

Since we measure the change in weight, the balance plays a critical role. The balance generally
operates on a “null-balance” principle. At the zero or “null” position, equal amounts of light
shine on the two photodiodes (shown in 2nd picture). If the balance moves out of the null
position, an unequal amount of light shines on the two photodiodes. In this condition, a current
is applied to the meter movement to return the balance to the null position. The amount of
current applied is proportional to the weight loss or gain.

Once the initial weight is recorded, then with the increase in temperature, weight change will
occur depending on the sample.

The instrument consists of the following components:

1. Balance system
2. Furnace or heating device (incorporating temperature sensor)
3. Temperature programmer (with control system)
4. Recording device or a detector

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

5. Atmosphere control, Nitrogen supply to ensure an inert atmosphere

6. Cooling control

TGA CURVES

The curves record the mass change of the sample (generally expressed in %weight loss) on the
ordinate, against temperature (T) or time (t) on the abscissa. An idealized representation of
TGA for the decomposition of calcium oxalate monohydrate is given below. The plot also
shows the derivative curve.

The derivative curve is plotted as dM/dT to find the point of inflection, i.e., the point at which
the maximum weight change occurs.

By analyzing the nature of the TGA curve, we can know what is happening to our sample. For
example, as shown in the figure, if we consider the case (ii), then it can be interpreted as the
loss of water molecules if this type of curve is obtained around 110-120 oC.

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

Applications of TGA
TGA has a wide range of applications. We can study the thermal stability of materials. As
explained in the above section, by the nature of the curve of thermogram, we can easily
interpret the thermal stability of a compound. Oxidative stability of the given sample can be
studied by oxidation of the sample in air instead of an inert atmosphere. Composition of multi-
component systems can be evaluated by studying the nature of thermogram of the sample.
Sufficiently different behavior on the temperature scale can be identified and reaction
mechanism can be formulated. Lifetime of a product can also be estimated using TGA.

References:

I. https://photometrics.net/thermogravimetric-analysis-
tga/#:~:text=Principle%20of%20Operation,loss%20of%20a%20volatile%20component.
II. https://www.slideshare.net/bknanjwade/thermal-analysis-42770949
III. https://www.iitk.ac.in/che/pdf/resources/TGA-DSC-reading-material.pdf
IV. https://www.slideshare.net/sureshselvaraj108/thermogravimetric-analysis
V. Images taken from: https://sites.google.com/a/iastate.edu/laboratory-10-
thermogravimetric-analysis/experimental-
methods?tmpl=%2Fsystem%2Fapp%2Ftemplates%2Fprint%2F&showPrintDialog=1
VI. https://www.researchgate.net/publication/257761811_Cobalt_Ferrite_in_YSZ_for_Use_a
s_Reactive_Material_in_Solar_Thermochemical_Water_and_Carbon_Dioxide_Splitting_
Part_I_Material_Characterization/figures?lo=1

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 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI
Pilani Campus, Chemistry Department
Instrumental Methods of Analysis, CHEM F313, Semester I, 2023 - 24
Laboratory Manual

Overall Experiment:
A hydrated metal salt will be provided to you. With the help of DSC and TGA study, the
following objectives need to be carried out:
(a) Find out the temperature ranges and the corresponding enthalpy changes
(endothermic/exothermic) of the processes (put the DSC curve and the TGA curve in a
single figure)
(b) Show the stepwise mechanism of the dehydration processes under heating of the
example and correlate the processes with the TGA weight loss and the corresponding
enthalpy changes
(c) Calculate the Cp of the sample.
(d) Calculate the number of water molecule associated with the inorganic salt from TGA
curve.

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