Thermogravimetric Analysis(TGA)

The Change in weight is plotted against temperature.

Thermogravimetric curve

Mechanism of Wt change in TGA

Weight loss : (i) Decomposition
(ii) Evaporation
(iii) loss of volatile components
(iv) Desorption
Weight gain: (i) oxidation
(ii) Absorption or Adsorption
Derivative Thermogravimetric Analysis(DTA): Rate of change
of weight is plotted against temperature.
No wt loss → dw/dt is zero
Maximum wt loss → Peak

Methods of obtaining Thermogram

1. Actual wt loss is plotted against temperature
2. Percentage wt loss is plotted against temperature
3. dw/dt ( rate of change of wt) is plotted against temperature
TGA of CuSO4.5H2O
CuSO4.5H2O → CuSO4.3H2O + 2H2O at 100oC
CuSO4.3H2O → CuSO4.H2O + 2H2O at 250oC
CuSO4.H2O → CuSO4 + H2O at 300oC at 3000C
CuSO4 →CuO + SO2 + 1/2 O2 at 7000C to 8000C
CuO →Cu2O + 1/2 O2 at 10000C to 11000C
Instrumentation
1. Precision Balance
2. Heating Device
3. Sample cup
4. Temperature control device
5. Atmosphere control device
6. Recorder
•Characteristics of a Good Thermobalance
1. It should be accurate, sensitive and stable
2. It should be able to respond rapidly to change in wt
3. It should be operative over a wide range of
temperature ( upto 2000oC)
4. Heating rate should be linear and reproducible.

•Heating and Temperature measurement

Heating rate : 4-5oC
Small furnace : cools very quickly, so difficult to control
linear heating rate
Large Furnace : Suitable to maintain linear heating rate
but slowly attains target temperature
Temperature is measured by Thermocouple.
Problems of thermocouple :
(i) risk of catalytic decomposition
(ii) Contamination error
• Sample Cups
Architecture of Sample Cup:
(i) Shallow Pans : used when volatile products are
obtained
(ii) Deep Crucible : used for calcination and surface area
study
(iii) Covered Cup : used to study reactions with self-
generated atmosphere
(iv) Retort Cups: used to study melting points

Material of Sample Cup

(i) Alumina Pan : inert upto 1700oC
(ii) Platinum: Good thermal conductivity but not always
inert due to catalytic activity

•Atmosphere Control : Flushing the whole balance with

an inert gas gives reproducible result.
•Recorder

Factors Affecting TGA:

1. Heating Rate :
When the heating rate is high, decomposition
temperature is also high
Time to complete Degradation:

Time required for complete decomposition increases for

higher heating rate.

2. Furnace atmosphere:
Even a small change in composition of atmosphere can
affect the thermogram. It is therefore necessary to flush
the thermobalance with inert gas.
3. Sample characteristics:
(i) Wt of the sample: A small wt is preferred.
(ii) Compactness of the sample: Compact sample
decomposes at higher temperature
(iii) Particle size: Smaller particles decompose at lower
temperature.
(iv) Previous history of the sample
4. Heat of reaction
TGA Instrument
Technique of quantitaive analysis of a mixture of Ca and
Mg-salts in mixture
ab = Mixture of
cd = mixture of
(m1 - m2) =
Amount of CaO(m3) =
Amount of MgO (m4) =
Amount of Ca =
Amount of Mg =
Thermal Decomposition of CaC2O4.2H2O and MgC2O4.2H2O
Applications of TGA
1. Determination of Purity and Thermal Stabilty of a
compound
2. Determination of correct drying temperature
3. Analysis of Mixture
4. Determination of Curie point
5. Analysis of Alloy
6. Kinetic study
7. Measurement of surface area
8. Characterization of polymer, soil, clay, glass etc.

Source of Error in TGA

1. Buoyance effect
2. Condensation on balance
3. Reaction between sample and container
4. Convection effect from furnace
5. Turbulence effect from gas flow
Problem 1. On heating a sample of 25 mg of hydrated
compound (molar mass = 250) in thermogravimetric analysis ,
16 mg of dehydrated compound remains. The number of
water molecules lost per molecule of hydrated compound is
_______________. GATE 2019

Problem 2. The use of dynamic inert atmosphere in TGA

(i) decreases decomposition temperature
(ii) increases decomposition temperature
(iii) decreases wt loss
(iv) decreases rate of decomposition
CSIR NET JUNE 2014
Problem 3. Decomposition Temperature of CaCO3 in TGA will
be highest in dynamic atmosphere of
(i) N2
(ii) synthetic gas
(iii) 1:1 mixture of O2 and CO
(iv) water gas CSIR NET JUNE 2016
Problem 4. A solid sample of Na[Fe(EDTA)(H2O)] showed 5.6%
wt loss at 120oC in TGA experiment. Identify the complex left
after wt loss
(i) Na[Fe(EDTA)(H2O)]
(ii) Na[Fe(EDTA)]
(iii) Na[Fe(EDTA)(H2O)2]
(iv) Na[Fe(EDTA)(H2O)3] CSIR NET Dec 2018

Problem 5. The TGA curve of 125.7 mg of sample that

contained a mixture of CaC2O4.H2O( mol wt 146) and a
thermally stable salt exhibited a wt loss of 6. 98 mg at a
temperature of 140oC corresponding to the loss of water.
Determine the percentage of CaC2O4.H2O in the sample.

Problem6. In the thermogravimetric analysis of the mixture

of calcium oxalate and magnesium oxalate , the wt loss was
found to be 34.6 mg between 400-500oC and 13.9 mg between
650-850oC. Find the wt % of calcium oxalate and magnesium
oxalate in the mixture.
Differential Thermal Analysis

Phenomena causing changes in heat/temperature

Physical:
1. Adsorption(Exothermic)
2. Desorption(Endothermic)
3. Change in Crystal Structure(Exothermic/Endothermic)
4. Crystallisation(Exothermic/(Endothermic)
5. Melting(Endothermic)
6. Sublimation(Endothermic)
7. Vaporisation(Endothermic)
Chemical
1. Oxidation(Exothermic)
2. Reduction(Endothermic)
3. Decomposition(Exothermic/(Endothermic)
4. Solid state reaction(Exothermic/(Endothermic)
5. Chemisorption(Exothermic)

Problem 6 Identify the correct statement from the following:

a) Area of DTA peak is proportional to the amount of sample
b) Area DTA curve is proportional to mass loss
c) Phase transmission cannot be studied with DSC
d) Simultaneous determination of two metal ions is possible in
TGA
i) a, b and d
ii) a, b and c
iii) b, c and d
iv) a, c and d CSIR NET June 2017