Thermal Analysis
Thermal Analysis
Thermal Analysis
INTRODUCTION
A Typical TG Curve
In thermogravimetry, the term ‘decomposition temperature’ is a complete misnomer.
In a TG curve of a single stage decomposition, there are two characteristic temperatures; the initial Ti and
the final temperature Tf (see Fig below).
Ti is defined as the lowest temperature at which the onset of a mass change can be detected by thermo
balance operating under particular conditions and Tf as the final temperature at which the particular
decomposition appear to be complete.
The difference Tf – Ti is termed as reaction interval. In a dynamic thermogravimetry a sample is subjected
to continuous increase in temperature usually linear with time whereas in isothermal or static
thermogravimetry the sample is maintained at a constant temperature for a period of time during which any
change in mass is noted.
A Typical TG Curve
Objectives
2. Furnace
The furnace and control system must be designed to produce linear heating at over the whole working temperature range of the
furnace and provision must be made to maintain any fixed temperature.
A wide temperature range generally -150 °C to 2000 °C of furnaces is used in different instruments.
4. Recorder
Graphic recorders are preferred for meter type recorders. X-Y recorders are commonly used as they plot weight directly against
temperature. The present instrument facilitate microprocessor controlled operation and digital data acquisition and processing using
personal computer with different types recorder and plotter for better presentation of data.
Factors Affecting Thermogravimetric Results
1. Furnace heating rate
At a given temperature, the degree of decomposition is greater the slower the
heating rate, and thus it follows that the shape of the TG curve can be influenced by
the heating rate.
For a single stage endothermic reaction it has been found that:
i) (Ti )F > (Ti )S
ii) (Tf)F > (Tf)
iii) (Tf –Ti )F > ( Tf –Ti )S
where subscripts F and S indicate fast and slow heating rate respectively.
For example, calcium carbonate would not show any mass loss below 600 °C, when
heated in a thermobalance at heating rate of 3 °C per min., and yet it is known that
CO2 is evolved at 250 °C.
Similarly, polystyrene decomposes 10% by mass when heating rate is 1 °C per min
by 357 °C and 10% by mass when heating rate is 5 °C per min by 394 °C.
More specifically, it is observed that the procedural decomposition temperature Ti, and
also Tf (the procedural final temperature) will decrease with decrease in heating rate
and the TG curve will be shifted to the left.
This effect is illustrated in Fig. shown. The appearance of an inflection in a TG curve
at a fast heating rate may well be resolved into a plateau at a slower heating rate.
Therefore, in TGA there is neither optimum no standard heating rate, but a heating
rate of 3 °C per min. gives a TG curve with maximum meaningful resolution.
2. Furnace Atmosphere
The effect of atmosphere on the TG curve depends on
(i) the types of the reaction
(ii) the nature of the decomposition products and
(iii) type of the atmosphere employed.
The effect of the atmosphere on TG curve may be illustrated by taking the example of
thermodecomposition of a sample of monohydrates of calcium oxalate in dry O2 and dry
N2 as shown in Fig.
The first step, which is dehydration is reversible reaction.
Ca C2O4.H2O(s) Ca C2O4(s) + H2O (g )
This is unaffected because both gases are equally effective in sweeping the evolved water
vapours away from the sample surface. For the second step,
Ca C2O4(s)(s) CaCO3 (s) + CO (g)
The curve diverges in O2 atmosphere because the oxygen reacts with evolved CO, giving a
second oxidation reaction which is highly exothermic and so raises the temperature of the un- TG Curve of Calcium Oxalate in O2 and N2
reacted sample. The temperature accelerates the decomposition of the compound more atmosphere: [ __________N2 ,----------------- O2]
rapidly and completely at a lower temperature as shown in the above diagram in dry O2 then in
N2 atmosphere . The third step in decomposition reaction is also reversible reaction.
CaCO3 (s) CaO (s) + CO2 (g)
This step should not be influenced by O2 or N2. However there is a slight difference in curves
for the two gases as shown in diagram. The small difference was due to the difference in the
nature/composition of CaCO3 formed in the two atmospheres. This is due to the particle size,
surface area, lattice defects or due to the other physical characteristics of CaCO3 formed.
3. Sample Holder
The sample holders range from flat plates to deep crucible of various capacities. The shape of the TG curve will vary as the sample will not be heated in identical
condition.
Generally, it is preconditioning that the thermocouple is placed on near the sample as possible and is not dipped into the sample because it might be spoiled due to
sticking of the sample to the thermocouple on heating. So actual sample temperature is not recorded, it is the temperature at some point in the furnace near the sample.
Thus it leads to source of error due to the thermal lag and partly due to the finite time taken to cause detectable mass change. If the sensitivity of recording mechanism is
not enough to record the mass change of the sample then this will also cause error in recording the weight change of the sample.
If the composition of the sample contains is such that it reacts either with the sample, or product formed or the evolved gases then this will cause error in recording the
mass change of the sample.
The smaller the particle size, greater the extent of decomposition at any given temperature. The use of large crystal may result in apparent vary rapid mass loss
during heating. This may be due to the mechanical loss of part of the sample by forcible ejection from the sample container, when the accumulated evolved gases within
the coarse grains are suddenly released.
APPLICATIONS OF TERMOGRAVIMETRIC
ANALYSIS
1. Determination Of purity and chemical stability of both primary and secondary standards:
Thermogravimetry is a valuable technique for assessing the purity of materials. Analytical reagents especially those used in
titrimetric analysis as primary standards (e.g., sodium carbonate, sodium tetraborate and potassium hydrogen phthalate), have
been examined. Many primary standards absorb appreciable amounts of water, when exposed to moist atmospheres. TG data can
show the extent of this absorption, hence the most suitable drying temperature for a given reagent may be determined.
From TG studies, the thermal stability of EDTA as the free acid and also as the more widely used disodium salt Na2EDTA. 2 H20
have shown that the dehydration of the disodium salt commences at between 110 and 125°C, so Na2EDTA. 2 H20 could be safely
heated to constant weight at 80°C.
2. Investigating the correct drying temperatures and the suitability of various forms gravimetric analysis:
Initially, the most widespread application of thermogravimetry in analytical chemistry has been in the study of the recommended drying
temperatures of gravimetric precipitates. Duval studied over a thousand gravimetric precipitates by this method and gave the
recommended drying temperatures.
3. In qualitative analysis:
In such an automatic gravimetric determination, the initial weight of the sample need not be known. A
simple example is automatic determination of a mixture of calcium and strontium as their
carbonates. Both carbonates decompose to their oxides with the evolution of carbon dioxide.
The decomposition temperature for calcium carbonate is in the temperature range 650 — 850°C
whereas strontium carbonate decomposes in the range 950 — 1150°C.
Hence. the amount of calcium and strontium present in a mixture may be calculated from the weight
losses due to the evolution of carbon dioxide at the lower and higher temperature ranges respectively.
This method can be extended to the analysis of a three-component mixture, as barium carbonate is
reported to decompose at an even higher temperature (-1300°C) than strontium carbonate.
Fig. below illustrates the application of TG to the analysis of a mixture of
Ca2+, Sr2+ and Ba2+ ions.
The mass loss between 320°C and 400°C corresponds to the combined ions
of water by three anhydrous salts forming MC2O4.
Mass between 580°C and 620°C corresponds to the combined mass of the
three carbonates (MCO3). The mass loss in the next two steps represents
loss of C02 by CaC03 (to form CaO) and SrC03 (to form SrO) respectively.
From this data, we can easily calculate the mass of each clement present
in the sample. Fig. b is the derivative of thermogram shown in Fig. a.
A pyrolysis curve for a mixture of these two oxalates would thus show three decomposition steps.
The final step would be due entirely to the loss of carbon dioxide from calcium carbonate hence the amount of
calcium present in the mixture may be calculated.
The amount of magnesium in the oxalate mixture may be calculated from the second step. where stages (b) and (e)
occur.
This is because the amount of carbon monoxide due to calcium carbonate may be subtracted from the total observed
weight loss, giving the loss of carbon dioxide and carbon monoxide from anhydrous magnesium oxalate.
Since stages (a) and (d) do not feature in the calculation, the mixture of Calcium and magnesium oxalates does not
require drying before the automatic determination.
5. In study of polymers:
The most important application of TG is found in the study of
polymers.
In differential thermal analysis (DTA), both the test sample and an inert reference material (usually ά-alumina) undergo a
controlled heating or cooling programme which is usually linear with respect to time.
There is a zero-temperature difference between the sample and the reference material, when the sample does not
undergo any chemical or physical change.
But if any reaction takes place, then a temperature difference (⧍T) will occur between the sample and the reference
material.
Thus, in an endothermic change (when the sample melts or is dehydrated), the sample is at a lower temperature than
the reference material. This condition is only transitory because, on completion of the reaction, the sample will again
show zero temperature difference compared with the reference.
Principle:
The basic principle involved is: the difference of temperature (∆T) between the test sample(TS) and an inert
reference sample(TR) under controlled and identical conditions of heating or cooling is recorded continuously as
a function of temperature or time.
The heat absorbed and emitted by a chemical system can be estimated or determined.
The changes are two types- exothermic and endothermic
If endothermic- ∆T = TR – TS = +ve or TS – TR = -ve
If exothermic- ∆T = TR – TS = -ve or TS – TR = +ve
INSTRUMENTATION
1. Sample Holder
Sample and reference crucible are generally metallic or ceramic(silica) and may
or may not have a lid, for good results area of contacts b/w sample and crucible is
maximized. Typically 1-10 mg of sample is required for analytical applications.
2. Furnace
Reference and sample should be thermally matched and symmetrically arranged
with the furnace so that both of them are identically cooled or heated, metal block
around the wall acts as a heat sink and by using internal heater temperature of the
heat sink is slowly increased sink in turn heat the sample and reference material.
Schematic Diagram of DTA Apparatus
Lowering the heating rate is roughly equivalent to reducing the sample weight; both lead
to sharper peaks with improved resolution.
The influence of heating rate on the peak shape and disposition can be used to advantage
in the study of decomposition reactions, but for kinetic analysis it is important to
minimise thermal gradients by reducing specimen size or heating rate.
Factors Affecting Thermogravimetric Results
Since DTA is a dynamic technique, a large number of factors can affect the resulting experimental curves.
If the DTA curve is used for quantitative purposes, the shape, position, the area enclosed by the curve are of
great interest.
For specific heat measurements the baseline deviations become important and such conditions as particle size,
system symmetry, sample packing must be taken into account if accurate results are to be obtained.
As with the technique of thermogravimetry, the DTA curve is dependent on two general categories of variables:
instruments factor and sample characteristics.
2. Instrumental parameters
It includes furnace atmosphere, size and shape of furnace, sample holder materials, sample holder geometry,
heating rate, and location of thermocouple in sample chamber, speed and response of recording device.
2. Characteristics of sample
where Tl and T2 are the differential temperatures generated when the apparatus is first run without any sample at all and then with the test
sample in position. H is the heating rate and the constant K" is determined by calibration against standard substances.
APPLICATIONS
1. Qualitative Analysis of materials
A rapid method for the fingerprinting of minerals, clays and polymeric materials was provided by
DTA measurements.
For example, using DTA with a nitrogen atmosphere, chrysolite (white asbestos) was shown to
give a dihydroxylation endotherm at 650ºC and a characteristic crystallisation exotherm at 845ºC.
A sample containing 1% w/ w chrysolite in talc was detected by DTA.
This fast technique does not involve the extensive sample preparation required by competitive
methods.
Polymers can exhibit their own characteristic melting point endotherms. Thus, in a blend containing
seven commercial polymers, each component was readily identified by the endotherm of melting
using DTA.
2. Fig. shows the differential thermogram of calcium oxalate monohydrate in a flowing air (O2), obtained by increasing
temperature at a rate of 8ºC/min.
It contains two minima (for endothermic processes), equations for these decomposition reactions are shown below the
maxima. The single maxima indicate that oxidation of CaC2O4 to CaCO3 and CO2 is exothermic.
Note:
Then maxima changes to minima, since the decomposition reaction under inert condition would be
CaC2O4 CaCO3 + CO
Note:
Glass transition temperature (Tg) may be defined as the temperature at which the constituent
particles begins to have translatory motion.
Alternatively, it is the temperature at which the expansion coefficient of solid exhibits a sharp change.
In terms of configurational entropy model, it is the temperature at which the configurational entropy of
the material is zero.
▪ Enthalpy or heat capacity changes in the sample cause a difference in its temperature
relative to the reference; the resulting heat flow is small compared with that in differential
thermal analysis (DTA) because the sample and reference are in good thermal contact.
▪ The temperature difference is recorded and related to enthalpy change in the sample using
calibration experiments.
INSTRUMENTATION
A DSC apparatus consists of identical components to that of
DTA, except that it contains individual heaters, located as close
as possible to the sample and reference vessels. Modern form of
heat flux DSC is shown in Fig.
A metallic disc (made of constantan alloy) is the primary
means of heat transfer to and from the sample and reference.
The sample, contained in a metal pan, and the reference, an
empty pan, sit on raised platforms in the constantan disc.
As heat is transferred through the disc, the differential heat flow Fig: Heat Flux DSC
to sample and reference is measured by thermocouples formed
by the junction of the constantan disc and chromel wafers,
which cover the underside of the platforms.
These thermocouples, are connected in series and measure the
differential heat flow.
Chromel and alumel wires attached to the chromel wafers
form thermocouples which directly measure the sample
temperature.
Purge gas is admitted to the sample character through an orifice
in the heating block.
With this equipment, it is possible to achieve heating or cooling
rates of 100ºC min-1 down to rates Of 0ºC min-1 (Isothermal).
Fig: Block Diagram of DSC Apparatus
Representation of Data
3. thermodynamic conditions
adiabatic, non-adiabatic;
1. DSC analysis on a blend of synthetic fibres was an early 2. Polymer blends difficult to evaluate by conventional DSC
application. Using an analysis of differential scanning calorimeter, have been successfully analysed by modulated DSC.
a blend, containing Nylon 66, orlon and polyester was determined.
For example, a polymer blend containing poly-ethyl
The ⧍H values per gram of sample were compared with the terephthalate (PET) and acrylonitrile-butadiene-styrene
corresponding ⧍H per-gram of each pure component. (ABS) has been separated and evaluated using DSC.
Hence, the ⧍H values for the crystallisation peaks of nylon and
the polyester were measured together with a cross-linking
exotherm for orlon. 3. Differential scanning calorimetry can be used to study the
number and temperature range of polymorphs, since each
A quantitative analysis was then made on the fibre blend. For
polymorphic transition causes an energy change that may be
example, the ratio of the ⧍H value for the nylon crystallisation
peak in the fibre blend over the ⧍H value for the pure nylon detected by DSC.
multiplied by 100 gave the percentage nylon in the fibre
blend. Various forms of digoxin have been investigated.
DSC also provides a simple and accurate way of determining melting, boiling
and decomposition points for organic compounds.
Moreover, DSC curves can be used to determine the purity of drug samples.
For example, Fig. shows the DSC curves for phenacetin having different
purities. Generally, the curves provide purity data within 1% error.
Note:
The weight changes monitored by thermogravimetry invariably involve the
absorption or release of energy, hence they can be measured by either DSC
or DTA.
Fig: DSC curves for samples of
phenacetin of different purities.
But there are many changes in energy that are not accompanied by a gain or
loss in weight.