Thermoanalytical Methods

Definition : a group of techniques in which a physical property of a substance or /and its

reaction products is measured as a function of temperature , while the substance is subjected to a
controlled temperature program.
(Or)
A group of methods used to obtain the analytical information on properties ( mass, heat of the
reaction and volume) as a function of temperature are called Thermal or Thermoanalytical,
Thermometric Methods.

Commonly used thermal methods

Sl. Instrument
Thermal Methods Parameter measured
No. employed

Change in mass w.r.t.

1. Thermogravimetric analysis (TGA) Thermobalance
temperature

Derivative Thermogravimetric analysis

Rate of change of
2. (DTG) Thermobalance
mass with temperature

Heat content change

3. Differential Thermal Analysis (DTA) DTA apparatus
with temperature

Differential Scanning Calorimetry Heat Flow w.r.t.

4. DSC Calorimeter
(DSC) temperature

Change in temperature
5. Thermometric Titration (TT) Calorimeter
w.r.t. volume
Thermogravimetric analysis (TGA)

 An instrumental technique used to show, how the mass of a substance is altered due to changes
in temperature.

 It deals with one branch of thermal analysis, which investigates the change in weight for a
substance as function of time or temperature.

 The analyte mass difference is a results of

⁕ Degradation / Decomposition of sample material

⁕ Removal of moisture or solvents
⁕ Oxidation of Components
Analysis of TG Curves

1. Mass loss and Residue 2. Onset and endset temperature

T1 - initial temperature (onset)

Mass (mg)
T2 - final temperature (endset)

T1 T2

Temperature (°C)

3. Decomposition peak Temperature

Mass (mg)

Td - Decomposition temperature of the substance

Td

Temperature (°C)
Interpretation of TG Curves

A. No mass change over entire range of temperature

B. Desorption/ Drying. (Mass loss is large followed by

mass plateau)

C. Single stage Decomposition

D. Multistage Decomposition

E. Similar to D but either due to faster heating rates or

due to no intermediaries

F. Atmospheric Reaction, ( Increase in mass, reactions

like surface oxidation)

G. Similar to curve F, but product decomposes at higher

temperature
Calcium Oxalate Decomposition
TGA of Calcium Oxalate Monohydrate
Schematic representation of TG System
Components of TGA
1. Sample Holder/ crucible :
 The sample to be studied is placed in sample holder or crucible.
 They are made from platinum, aluminum, quartz, alumina or some other material like
graphite, stainless steel, glass.
 There are different type of crucibles
 Shallow Pans
 Deep Crucibles
 Loosely covered crucibles
 Retort Cups

2. Microbalance:
 The sample holder or furnace is linked to a microbalance , that monitors changes in mass of
substance or sample.
 Two types of microbalances
 Deflection type instruments(Deflection balances): Beam type, Helical type, Cantilever type,
Torsion type
 Null type instruments (null point balances)

Null point balances

Deflection type balances

3. Furnace:
 Furnace should be designed such a way that it produces linear heating rate
 It should have a hot zone which hold the sample and crucible and its temperatures
corresponding to the furnace.
 Furnace is connected to a purge gas system. Nitrogen or argon gas released within the furnace
to prevent the sample from oxidizing as the thermal analysis is taking place.
4. Temperature Measurements:
 Temperature measurement is done with the help of temperature sensors (thermocouples).
 The position of the thermocouples relative to the sample is important.

5. Recorder:
 The output from the microbalance and furnace are recorded using the chat recorder or
microcomputer.
 In microcomputer, we get a plot of mass change versus temperature or time.
Types of TGA

1. Dynamic TGA: In this method , temperature of the sample will be increasing continuously at a
specific heating rate. Therefore, temperature of the sample varies linearly with time.

2. Static or Isothermal TGA: In this method, sample is allowed to be maintained at constant

temperature condition for a fixed internal of time. During this time period , the mass change that
occurs in the sample will be recorded.

3. Quasistatic TGA: In this method, sample is heated to a constant weight at each of a series of
increasing temperature.
Factors affecting TG curves
 Instrumental factors:

1. Heating Rate

Shift in decomposition temperature with heating rate

Shift in onset with heating rate
Time to complete degradation
Influence of heating rate on resolution
2. Furnace atmosphere
theoretical

• Usually the entire furnace compartment is vacuum air

flushed with an inert gas , Nitrogen. So as

carbon
to achieve accurate decomposition dioxide
temperature and hence reproducible
thermogram.

3. Crucible geometry
 Sample characteristics:
1. Sample mass

Large sample mass increases the decomposition temperature

2. Sample morphology

PET- Polyethylene terephthalate

 A larger volume of sample or sample with high packing density in the crucible can impede the diffusion
of evolved gas through the bulk of the solid large crystal and sample may swell, foam and even bubble.
So, smaller sample weight is describe for TG
Applications of TGA
What TGA can tell you?

 Thermal Stability and Purity of Materials:

 Oxidative stability of Material

Carbon black filler content: PET

Comparison of Filled and Un-filled PET
 Composition of Multi-component/mixture/alloys systems:

EVA (Ethylene-vinyl acetate) Copolymer

Composite

(Polytetrafluoroethylene)
 Moisture an volatile content of Materials:
Advantages of TGA

⁕ Easy to set up
⁕ When the individual decomposition steps occur at well –separated
temperatures, quantitative information for each step can be obtained
Limitations of TGA

⁕ Complex thermal scans with broad weight losses

⁕ Overlapping weight losses: Multiple peaks/shoulders
 Derivative Thermogravimetry (DTG)

 When the rate of change of mass with temperature plotted against temperature,
the curve obtained is called the derivative thermogravimetric curves.

 The DTG finds its application in the complicated decomposition of sample where
mass changes occurs at close temperatures
Decomposition of copper sulphate pentahydrate
Questions??
1. In the TGA of 0.250 gm of Ca(OH)2 , the loss in weight at different temp was
(i) 0.018 gm at 100-150 °C (loss of hydroscopic water)
(ii) 0.038 gm at 550-560 °C (dehydration)
(iii) 0.0229 gm at 900-950 °C (dissociation)
Determine the composition of Ca(OH)2
2. The TG curve of 125.7 mg sample that contain CaC2O4.H2O (mol. Wt. 146) and a thermally stable
salt exihibited a weight loss of 6.98 mg at a temperature of 140°C corresponding to loss of water.
Determine the percentage of CaC2O4.H2O in sample.
3. In the TGA analysis of the mixture of calcium oxalate and magnesium oxalate the weight loss was
found to be 34.6 mg between 400-500 °C and 13.9 mg between 650-850 °C. Find the weight
percentage of calcium oxalate and magnesium oxalate in the mixture.
4. From an examination of the weight change versus temperature curve of a substance, information can
be obtained regarding;
(a) Thermal stability and composition of the original material
(b) Thermal stability and composition of the intermediate compounds
(c) Composition of the final product or residue
(d) All of the above are correct

5. The property measured in derivative thermogravimetric analysis (DTG) is

(a) Change in weight
(b) Rate of change in weight
(c) Heat evolved or absorbed
(d) Change in temperature

6. In TGA, the weight loss curve depends on the following instrumental factors
(a) Furnace heating rate
(b) Recording or chart speed
(c) Furnace atmosphere
(d) All of the above

7. The most important requirements of a suitable recording the thermobalance are

(a) accuracy
(b) reproducibility
(c) insensitivity to ambient temperature changes
(d) All of the above
 Differential Thermal Analysis (DTA)

The heat absorbed or liberated in a chemical change is observed by

measuring the temperature difference between the sample and an inert
reference sample (such as alumina, SiC or glass beads) as the
temperature of both are raised at a constant rate. This method of analysis
is called the differential thermal Analysis (DTA)

(Or)
Analytical method for recording the difference in temperature (T)
between a sample and an inert reference material as a function of
temperature or time, when both are subjected to identical heat treatment.
∆𝑻 = 𝑻𝑺 - 𝑻𝑹

If T = 0, Sample does not undergo any chemical or physical change.

If T  0, Sample does undergo any chemical or physical change.

 Any transformation – change in specific heat or an enthalpy of

transition can be detected by DTA.
∆𝑻 = 𝑻𝑺 - 𝑻𝑹  0

 If T = +ve, Exothermic change (𝑻𝑺 >𝑻𝑹 )

 If T = -ve, Endothermic change (𝑻𝑺 <𝑻𝑹 )

 Instrumentation of DTA / Block Diagram

AC S R F

𝑻𝑺 𝑻𝑹

A V
DTA apparatus consists of the following components

1. Sample holder comprising thermocouples (TS, TR),

sample and reference container (S, R)
2. Furnace
3. Furnace control (F)
4. Atmosphere Control (AC)
5. Amplifier (A)
6. Recorder (V)
 Working Principle

 Furnace is heated at a linear rate

 If there is any temperature difference between sample and
reference , then a potential difference developed between two
thermocouple
 The potential is fed into the amplifier and the output is recorded
on the Y-axis of the recorder.
 The temperature of the furnace is measured by a separate
thermocouple(T) which is connected to the X-axis of the recorder
 Factors affecting the DTA curve

Instrumental factors
 Size and Shape of the sample holder
 Material from which sample holder is made
and its corrosive attack
 Heating rate
 Furnace Atmosphere
Sample characteristics
 Amount of the Sample
 Particle size of the sample
Decomposition of Calcium oxalate
Interpretation of Differential Thermal Analysis (DTA) Curves

 BCD is exothermic reaction peak

 EFG is endothermic reaction peak.
 The baselines of exothermic curve AB and DE , both are
different levels above X-axis. This is due to the fact that heat
capacity of the sample has changed as a result of exothermic
process. Similar explanation after endothermic curve.
 Peak area provides quantitative information regarding mass of
sample (m), heat of reaction( enthalpy change, H) and factors such
as sample geometry and thermal conductivity.

 𝐴 = ± Δ𝐻 𝑚𝐾

Where, + ve sign for endothermic reaction (Δ𝐻 > 0) and –ve sign for
exothermic reaction (Δ𝐻 < 0).
K is Calibration factor / calibration constant, which is temperature
dependent. So, it can be determine by calibrating DTA with some
standard.
 The change in heat capacity Δ𝐶𝑝 may be determined at a particular
temperature by measuring the difference in base lines (d)
 Δ𝐶𝑝 = 𝑑
𝑑𝑇
ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑟𝑎𝑡𝑒( )×𝑚
𝑑𝑡
 Phenomenon causing change in temperature

1. Physical process such as crystalline rearrangement, solid phase transitions,

fusion , vaporization, sublimation and dehydration give rise to endotherm.

2. Physical process like adsorption and crystallization give rise to exotherms

3. Chemical reactions can give endotherm or exotherm. Oxidation reactions

give exotherms only.

4. Sharp endothermic peaks indicate phase changes (such as melting, fusion

etc.), transition from one crystalline form to another crystalline form. Broad
endothermic peak are obtained from dehydration reaction

5. Among exotherms, narrow exotherms indicate crystallization, while broad

exotherms denote chemical reactions, or polymerization
 Applications of DTA

We will now discuss some application of DTA which are of particular interest to chemist

Physical Chemistry: Heat of reaction, Heat capacity

Analytical Chemistry:

 Identification of substance: We know that DTA curve for two substances

are not identical. They serve as finger prints for various substance.

 Identification of products: The products are identified by their specific

DTA.
This technique has been termed reaction DTA

 Melting Points: As m.p. can easily determined by DTA. It means that this
technique can be used as direct check of the purity of the compounds

 Quantitative analysis: mass, heat of reaction, Crystallinity of the polymer

etc.
Application in polymer analysis
 Quality control : DTA technique has been widely used for the quality
control of a large number of substance like cement, glass, soil, textiles,
resins etc.
 Study of inorganic Substances

 used for studying the thermal behaviour of inorganic compounds such as silicates-
ferrites , clays, oxides, ceramics and glass
 Provides information about processes such as fusion , dehydration, oxidation ,
reduction, adsorption etc.
 Help in construction of phase diagram.

 113 degree Celsius corresponds to a

solid –phase change from rhombic to
monoclinic form
 124 degree Celsius corresponds to
the melting point of sulphur.
 Peak at 179 degree Celsius apparent
involves a transition among liquid
sulphur
 The peak at 446 degree Celsius
corresponds to the boiling point of
sulphur.
 Study of organic Substances

 DTA provides a simple and accurate method for the determination of

the M.P. , B.P. and decomposition points for organic compounds.

 The data appear to be more consistent and reproducible than those

obtained with other method (capillary bath).

 DTA of Benzoic acid consists of two sharp endotherms at 122 and 249
degree Celsius, which corresponds to M.P. and B.P., respectively.