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Thermal Analysis

SSK 4242

APPLICATION OF TERMOGRAVIMETRY (TGA)

INTRODUCTION

 TGA is a quantitative method


 the change in sample mass can be measured accurately
 although the temperature range where the mass change takes place is qualitative in
nature
 because it depends on the nature of the sample and instrument

 TGA is widely used in the following:


 characterization of materials,
 measurement of moisture content
 metallurgy
 studies on paint, ink, ceramics, foods, organic and inorganic chemicals, polymer,
geochemistry, etc.
 TGA may be applied to all processes that involve mass change.
 If the process does not involve mass change, then other methods such as
DTA, DSC and TMA can be used instead.
 If the mass change is very small (< 1%), then evolved gas analysis (EGA)
techniques may be applied to reveal more information about the sample.

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Table 4.1 The mass changes that can be detected by the


TGA technique

Physical Change Chemical Change

Sublimation Solid Gas


Evaporation Solid1 Solid2 + Gas
Absorption Gas + Solid1 Solid2
Adsorption / Desorption Solid1 + Solid2 Solid3 + Gas

Exercise:
• Give examples of reactions/processes for each of the physical
and chemical changes above.
• Write down the chemical equation for the examples given

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APPLICATION OF TGA

Among the application of TGA methods are as follows:

 Thermal decomposition of inorganic, organic and polymeric


materials,
 Metal corrosion in various atmosphere and high
temperature
 Solid state reactions
 Roasting and combustion of minerals
 Pyrolisis of coal, petroleum and woods
 Determination of moisture, volatile materials and ash
contents
 Distillation and evaporation of liquids
 Determination of the rate of evaporation and sublimation

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Application of TGA in Catalysis
TGA can be used to optimise catalytic processes. The
effects of parameters (e.g. the catalyst composition,
temperature, gas flow) on the catalyst can be quickly
studied for its effectiveness before a large scale
production of the catalyst is carried out.
Example: The support
material is soaked in the NiNO3
solution. After dehydration
and decomposition of the
metal salt in the air, the
The effect of heating rate, gas atmosphere is changed to
flow, and the temperature for hydrogen to produce a metal
each step can be varied and their powder that is impregnated on
effects on the development of the surface of the support.
catalyst can easily be studied.

Figure 4.1 TGA application for optimisation of the method for the production of a catalyst.
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Mass change of the catalyst during the heating


process in certain atmosphere may indicate:
 that adsorption of gas is taking place and its relationship with the active sites
that is related to the atmospheric gas molecule/atoms;

 the conditions of the surface area of the support materials that is coated with
the catalyst at the temperature when a mono-layer is formed;

 the catalyst deactivation. Reactions which involve organic materials have


always caused carbon or sulphur deposits on the surface of the catalyst and
this will deactivate (poison) the catalyst;

 reactivation of the catalyst. Reactivation can be carried out if the deactivation


is due to adsorption of water molecules.

Example: TGA and DTA have been used for the preparation studies of the
following:
- for the oxidation of catalyst La1-xMxMnO3 where M is Pb, Ca, Sr or Ba
- for the thermal decomposition and catalytic studies of BaxLn1-xCoO3 where
Ln is La, Nd, Sm and Dy.

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Application of TGA in Clay and Mineral Industries
 Evaluation by characterisation of the raw material deposits,
 Classification and analysis,
 Investigation on the raw materials that have underwent various industrial
processes,
 Technique for solving various problems arising from the changes of the
raw materials, new technologies, and new specifications.

 TGA and DTG can provide accurate information on the quantitative


determination if the stoichiometry of the clay or minerals reaction takes
place within the range of the temperature change.

Example:
 mass loss due to dehydroxylation of the clay may be used for the
determination clay content of a mixture.
 If the curve shows overlapping mass losses of two processes, separation
of the two processes may be carried out by an isothermal heating, such as
in the determination of alunite and kaolinite in the alunitic clay and the
determination of MgCO3 and CaCO3 in dolomite.
See next page … Lecture 5 4-Nov-04 6
Thermal Analysis
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TGA And DTG Curves of Kaolinite Standard.
• Kaolinite is an important clay which is used as filler or mixture in the paper,
ceramics, and rubber industries.
• Available naturally in most countries, clay represents a secondary mineral that is
formed out of the weathering and hydrothermal processes on aluminum silicate,
particularly the feldspar.
• Adsorbed water is
liberated within the
temperature range up to
200 oC with a quantity
0.2 % of the kaolinite
sample mass.
• The hydroxylation
process takes place
within the temperature
range of 400 – 700 oC
causing mass loss of
13.8 %.
• The DTG curve has a
peak shape (similar to a
Figure 4.2
DTA curve) and the
position of the peak may
alter with the change in
the heating rate, sample
particle size, etc.
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Application of TGA in Coal Industries

Figure 4.3

TGA curve for the coal sample


under air and N2 atmosphere.

The sample mass: 22.14 mg.

Under the N2 atmosphere, the


volatile materials and moisture
are removed until the
temperature reaches 1000 oC.

When the atmosphere was


changed to air (O2), the carbon
content was burned completely
leaving ash residue.

From one sample (10 – 30 mg) several parameters such as the moisture content,
volatile materials, carbon, and the ash residue were determined simultaneously.

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Application of TGA in Petroleum Industry
Figure 4.4: TGA of three petroleum products: the crude oil, light oil and
asphalt
The sample was placed in a sample holder with a pin-holed cover.
The light oil (low molecular mass) distilled out at the temperature range of
100 – 330 oC, crude oil 300 – 600 oC, and the asphalt 250 – 650 oC.

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Application of TGA to Inorganic Analysis

TGA may be used for the determination of The figure shows that the
calcium, strontium and barium as a mixture decomposition process of the
of their salts. oxalates are independent to each
other. The water of hydration is
The ions (Ca2+, Sr2+, and Ba2+) are removed at 100 – 250 oC.
precipitated as their oxalates and then
decomposed under N2 atmosphere in a TGA Based on the individual curve of
system. The Ca, Sr and Ba contents are the respective compounds, the
derived directly from the TGA thermogram water content removal from the
(Figure 4.5). oxalates takes place according to
See Figure 4.5 the order of barium, strontium and
calcium. However, in the mixture,
decomposition of the oxalates of
The quantities of calcium, C, strontium, S, and
strontium and calcium take place
barium, B, can be calculated from the data
simultaneously.
extracted from the voltammogram as follows:
The determination error using this
• The amount of Calcium, C = 0.91068 . G technique is about 1 %.
• The amount of Strontium, S = 1.9911 . L
• The amount of Barium, B = 0.58603 . D - 1.9456 . G - 2.5788 . L

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The Application of TGA to the Analysis of Cuprum (II) Acetate

Figure 4.6 shows the TGA and DTA curves for the decomposition of
Cu2(C2H3O2)4 . 2H2O.
The TGA curve shows that two main thermal processes
have taken place, but the DTA curve indicates that the
thermal process is much more complex.

Application of TGA to the Analysis of Cuprum Chloroasetate

See Figure 4.7 for the TGA and DTA of the decomposition of Cuprum
Trichloroacetate 4-dihydrate.

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Application of TGA to the Oxidation


of Pt Groups

Figure 4.8 shows the TGA curves for the oxides of


the Pt metals (atmosphere: O2, pressure: 100 Torr,
and heating rate: 10 oC/min)

Figure 4.9 shows the TGA and DTA curves for the
thermal decomposition and transformation of
rhenium metal oxide: RhOOH (orthorombic) and
RhO2 (tetragonal)

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Thermal Analysis
Application of TGA in Pharmaceutical SSK 4242

• Medication materials normally contain analgesic agents (reduce pain due to organic and/or
psychological confusion).

• Among those analgesics that have been in use are (I) acetylsalicylic acid (aspirin), (II)
salicylamide, (III) phenasetin, and (IV) N-Acetil-p-aminophenol (acetaminophen)

• Aspirin (I) is more effective for relieve from


headache but less effective for toothache
or soar throat.

• N-Asetil-p-aminofenol (II) has the effect of


reducing body temperature and may be
used in place of aspirin when necessary.

• Acetanilide and phenacetin (III) also have


the analgesic and body temperature
reducing effect. Most acetanilides are
metabolised into acetaminophen (IV)
which is the active agent. However, the
compound (III) and (IV) are less toxic than
the acetanilides and the use of acetanilide
compounds are getting less popular.

• The most commonly used analgesics are Figure 4.10


aspirin (I), normally sold in tablet form of
5-grain (325 mg) which contains small
amount of starch or other materials as the
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Figure 4.11(a) dan (b) show the TGA curves of 12 analgesic agents
found in the market

(a) (b)

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Thermal Analysis
Figure 4.12 a and 12b show the TGA curves for antacids (medication for SSK 4242
the treatment of gastric or internal digestion system). Each preparation has
different capacities to neutral acid in the internal digestion system.
The active components of antacids are calcium carbonate, sodium hydrogen carbonate, aluminum hydroxide,
magnesium trisilicate, dihidroxy aluminum aminoacetate, etc.

(a) (b)

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Determination of Pharmaceutical Material Composition

The thermal processes that are useful for the determination of pharmaceutical
material composition are:

• Dehydration: loss of water content or water of crystallization accompanied


by the formation of an intermediate compound of known composition and
structure. This process normally takes place in the range of 60 – 300 oC;
• Decarboxilation: loss of CO2 from a pharmaceutical compound that contains
NaHCO3 (in the range of 60 – 200 oC) or CaCO3 (in the higher range of
temperature: 600 – 800 oC);
• Weight loss: due to reaction between the volatile components of the
mixture;
• Weight loss: due to the formation of reaction intermediate which deviates
the TGA curve;
• Weight loss: due to volatilation, sublimation, and/or combustion of a
component of the pharmaceutical material.

The quantitative determination of the pharmaceutical materials by using TGA and


DTG methods can be carried out quickly, without the need of a calibration or complex
calculations. The results do not depend on the experimental conditions. The relative
errors are normally less than 5 %.
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The use of TGA for Moisture Determination

TGA is one of the thermal analysis techniques used in the determination


of moisture in pharmaceutical substances.

Two types of moisture:


1. Free moisture or surface moisture
2. Hydration water or bound moisture

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