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Thermal Analysis

SSK 4242

Factors Affecting the TGA Thermograms:

1.Instrumental factors
1.Sample factors

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1. The Effects of Instrumental (Balance) Factors


on the TGA Thermogram:

a) The Effects of Heating Rate

 For an endothermic reaction, the Ti and Tf depends on the heating


rate;
 The initial temperature (Ti) becomes higher when the heating rate
is higher compared to the initial temperature when the heating rate
is lower;
 The final temperature (Tf) becomes higher when the heating rate is
higher compared to the final temperature when the heating rate is
lower;
 The temperature range (Tf - Ti) is also larger when the heating rate
is higher compared to the temperature range when the heating
rate is lower;
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a) The Effects of Heating Rate (Cont’d)

 An example of the effect of heating rate on the TGA


thermogram of Ferum(II) Carbonate is shown in Figure 3.17;

 At any temperature range, the decomposition level becomes


higher when the heating rate is lower compared to that when
the heating rate is higher;

 For an exothermic reaction, the sample temperature


becomes higher than the furnace temperature and the
temperature difference between that of the sample and that
of the furnace also becomes bigger;

 When there is a chain of reactions, the heating rate may


become the major factor that will influence whether or not
resolution/separation of the reactions will be achieved.

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b) The Effects of Furnace Atmosphere on the
Thermogram
The effects of atmosphere on the thermogravimetry
curve depends on the following:
1. Type of reactions,
2. Conditions of the decomposition products,
3. Type of the atmosphere used in the experiment.

Three types of reaction that can be • If an inert gas is used as the


studied whether they are reversible or atmosphere, its function is to remove
non reversible are: the decomposition products of
reactions (1) and (2) and to avoid
reaction (3).
1) As(1) Bs(2) + Cg
• If the atmosphere used contains the
2) As(1) Bs(2) + Cg same gas as the released gaseous
products, it will affect the reversible
3) As(1) + Bg(1) Cs(2) + Dg(2) reaction (1) but does not give any
effect on the irreversible reactions (2)
and (3).

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b) The Effects of Furnace Atmosphere on the
Thermogram (Cont’d)
 Examples of the effect of the atmosphere on the reaction thermograms
for reversible and irreversible reactions are given in Figure 3.18.
 In this example, a 500 mg sample of hydrated calcium oxalate was
heated at a rate of 300 oC/hr in the atmosphere of nitrogen and oxygen,
respectively.
Reaction (I) is a dehydration process.
Neither N2 nor O2 used as the
(I) CaC2O4 · H2O(s) CaC2O4(s) + H2O(g) atmosphere will affect the reaction,
hence their role is to remove the
(II) CaC2O4(s) CaCO3(s) + CO(g) liberated water molecules
Reaction (II) proceeds under the N2
(III) CaCO3(s) CaO(s) + CO2(s) atmosphere. When the atmosphere was
changed to oxygen, the O 2 reacts
Reaction (III), theoretically, is not affected by the exothermally with the released CO(g) as a
use of N2 or O2 as the atmosphere. However, secondary reaction which increases the
temperature of the unreacted solid sample,
Figure 3.18 shows that a small change occurred
which in turn increases the rate of
at the step (III) of the thermogram. This is due to
decomposition. Therefore, under the oxygen
the difference in physical properties (in terms of
atmosphere decomposition of calcium oxalate
particle size, surface area, and crystal defects,
takes place at a faster rate and completes at a
etc.) of CaCO3 formed in step (II) when the
lower temperature than that under the N 2
atmosphere was changed from N 2 to O2. Lecture 4 4-Nov-04 5
atmosphere.
Thermal Analysis
SSK 4242

The Effect of Atmospheric Pressure

 In the case of Reaction (III) (reversible reaction), an


increase of atmospheric pressure of the CO 2 in the
furnace atmosphere will increase the initial temperature,
T i. (III) CaCO (s) CaO(s) + CO (s)
3 2

 Remember Le Chatelier Principle !?

 The initial decomposition temperature changes from 400


o
C at lower partial pressure to 900 oC at higher partial
pressure (760 Torr).

 See Figure 3.19.

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The Effect Of Atmospheric Gas Thermal Conductivity
Decomposition of CaCO3 takes place faster in the atmosphere with greater thermal
conductivity, which indicates that the rate of sample decomposition is influenced by
the speed of heat flow in the thermal system. Figure 3.20 shows that the thermal
conductivity of helium, nitrogen and argon are in the order of He > N2 > He.
Therefore, the decomposition rate of CaCO3 in the respective atmospheric gas will
follow the same order.

The Effect of Atmospheric Vacuum Pressure


Under certain conditions: vacuum condition and the sample has a certain mass
and thickness and using certain sample holder, the sample appeared to have
increased in mass (buoyancy effect) during thermal decomposition.

This is observed during dehydration of CaC2O4.H2O (see Figure 3.21)

Figure 3.22 shows the TGA curves of CuSO4·5H2O under high and low
atmospheric pressure and correction for buoyancy.

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The Effect of Sample Holder

Figure 3.23 The effect of sample holder geometry on the TGA curve of
C2O4.H2O under a dynamic CO2 atmosphere. Dotted line:
quartz plate, solid line: porcelain crucible.

Figure 3.24 The TGA curves of CuSO4.5H2O using a crucible and a thin
aluminum plate. Curve (1) (500 mg) obtained using a crucible,
and curve (2) (200 mg) obtained by using a thin plate. Heating
rate 10 oC/min.

Figure 3.25 The effect of heat sink on the TGA curve for lead carbonate (a)
aluminum block, (b) aluminum plate. Heating rate 450 oC/hr.

Figure 3.26 The effect of sample packing and the sample holder geometry on
the removal of water from the CaC2O4 H2O sample.

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2) The Effects of Sample Properties on TGA


Thermograms

a) The Effect of Sample Mass


The mass of the sample may influence the TGA curve in three ways:

1. The extent of exothermic or endothermic reaction that has caused the sample
temperature to depart from a linear change. The larger the sample mass, the
bigger the departure from linearity.

2. The degree of gaseous products absorption through the pores around the
solid sample particles. Under a static atmosphere, the surrounding
atmosphere will soon be influenced by the whole sample.

3. The existence of a large thermal gradient in the sample, especially when the
sample has a low thermal conductivity.

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ro perties
Sa mple P
E ffects of Cont’d)
The ograms (
Therm
a) The Effect of Sample Mass (Cont’d)

 In order to detect the presence of an


intermediate, smaller sample may be used as
shown in the Figure 3.27.

 The presence of an intermediate CuSO4.3H2O


appeared more evidently when the sample mass
was 0.426 mg compared to that when a larger
sample mass (18.00 mg) was used.

A better resolution for the detection of an intermediate reaction is


obtained by using smaller sample mass

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ro perties
Sa mple P
E ffects of Cont’d) a) The Effect of Sample Mass (Cont’d)
The ograms (
Therm

Other examples of the effects of sample mass on the TGA


curve:

Figure 3.28 shows the effect of sample mass on the TGA


curve of CaC2O4. H2O in a static atmosphere and a
heating rate of 300 oC/hr. Sample mass: (a) 126 mg, (b)
250 mg, and (c) 500 mg.

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ro perties
Sa mple P
E ffects of Cont’d) a) The Effect of Sample Mass (Cont’d)
The ograms (
Therm

Other examples of the


effects of sample mass on
the TGA curve:

Figure 3.29 The effect of sample mass on the thermal


decomposition of calcite.

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ro perties SSK 4242
Sa m ple P nt’d)
ts of s (Co
ffe c
The E Thermog
r a m b) The Effect of Particle Size on
A
on TG the TGA Thermogram

 Figure 3.30 shows the effect of different particle sizes on the TGA
thermogram of dehydration of whewellite (CuC2O4.H2O) under vacuum.
Solid line: 150 mesh; dotted line: single crystal.

 The difference in particle size causes differences in the rate of absorption


of the gaseous products, which in turn changes the shape of the
thermogram.

 Decrepitation of large particles may cause the thermogram to show


sudden loss of the sample mass.

 The small and homogeneous particle size enables the changes to be


closer to the equilibrium conditions and more complete decomposition
process.

 Sample with large particle size has a lower surface area to mass ratio that
normally decomposes at higher temperature than that of the sample with
smaller particle size.
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Sources of Errors in TGA Analysis

The various sources of errors in TGA analysis are interrelated to


each other:

 The sample holder air buoyancy


 Convection current and turbulent of heat in the furnace
 Random fluctuation of the balance and recording mechanism
 The effect of furnace induction
 The effect of electrostatics towards the balance mechanism
 The environment of the balance
 Condensation of materials on the balance fulcrum
 Temperature measurement and calibration
 Weighing calibration of the recording balance
 The flow of recording chart paper
 Reaction between the sample and sample holder material
 Temperature fluctuation
 The effect of momentum shift in vacuum conditions

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The Effect of Air Buoyancy
 The gas phase density decreases with temperature increase
 At 300 oC the reduction of gas phase density (and hence the
increase in buoyancy) effect towards the sample increases to
about one and half times higher than that when the temperature
is 25 oC.
 In air atmosphere, this may cause a mass variation of 0.6
mg/cm3.

The changes of gas


Gas density, mg/cm3

(air) density (and


hence the
buoyancy) Figure 3.31.
(mg/cm3) versus
temperature at two
different pressure is
shown in Figure
3.31.
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y
B uo
f
to
ffe c
e E
Th  Buoyancy affects not only the balance system and the sample
holder, but also on the mass changes and the volume of the
sample during the decomposition processes.

 Figure 3.32 shows the effect of buoyancy and the correction


done on the TGA curve of a large CaCO3 sample in the CO2
atmosphere.

 Curve (I): no correction was done on the effect of buoyancy

 Curve (II): correction has been done on the effect of buoyancy


to the crucible and the crucible support

 Curve (III): correction done includes the effect of buoyancy


towards the sample.

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