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SSK 4242
1.Instrumental factors
1.Sample factors
Lecture 4 4-Nov-04 1
Thermal Analysis
SSK 4242
Lecture 4 4-Nov-04 3
Thermal Analysis
SSK 4242
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.
Lecture 4 4-Nov-04 4
Thermal Analysis
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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
Lecture 4 4-Nov-04 6
Thermal Analysis
SSK 4242
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.
Figure 3.22 shows the TGA curves of CuSO4·5H2O under high and low
atmospheric pressure and correction for buoyancy.
Lecture 4 4-Nov-04 7
Thermal Analysis
SSK 4242
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.
Lecture 4 4-Nov-04 8
Thermal Analysis
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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.
Lecture 4 4-Nov-04 9
Thermal Analysis
A
on T G SSK 4242
ro perties
Sa mple P
E ffects of Cont’d)
The ograms (
Therm
a) The Effect of Sample Mass (Cont’d)
Lecture 4 4-Nov-04 10
Thermal Analysis
A
on T G SSK 4242
ro perties
Sa mple P
E ffects of Cont’d) a) The Effect of Sample Mass (Cont’d)
The ograms (
Therm
Lecture 4 4-Nov-04 11
Thermal Analysis
A
on T G SSK 4242
ro perties
Sa mple P
E ffects of Cont’d) a) The Effect of Sample Mass (Cont’d)
The ograms (
Therm
Lecture 4 4-Nov-04 12
Thermal Analysis
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.
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.
Lecture 4 4-Nov-04 13
Thermal Analysis
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Lecture 4 4-Nov-04 14
Thermal Analysis
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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.
Lecture 4 4-Nov-04 16