31

Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
UNIT 11 DIFFERENTIAL THERMAL
ANALYSIS, SCANNING
CALORIMETRY AND
THERMOMETRIC TITRATIONS
Structure
11.1 Introduction
Objectives
11.2 Differential Thermal Analysis (DTA)
Principle
Characteristics of DTA Curves
Instrumentation
Factors Affecting DTA Curves
Sources of Errors
Interpretation of DTA Curve
Applications
11.3 Differential Scanning Calorimetry
Principle
Instrumentation
Factors Affecting DSC Curves
Sources of Errors
Interpretation of DSC Curve
Applications
Advantages of DSC
11.4 Thermometric Titrations
Principle
Instrumentation
Applications
11.5 Summary
11.6 Terminal Questions
11.7 Answers
11.8 Further Readings
11.1 INTRODUCTION
In the previous Unit we discussed thermagravimetric analysis and its applications.
You have learnt that TGA has many applications, but they are limited to the reactions
where mass change should have occurred. Now we will consider two similar thermal
techniques, differential thermal analysis (DTA) and differential scanning calorimetry,
both these techniques have much wider applications than TGA. In the last section of
this unit, thermometric titrations and their applications have been briefly discussed.

As defined earlier, in DTA, the heat changes within a material are monitored by
measuring the difference in temperature (T) between the sample and the inert
reference. This differential temperature is then plotted against temperature or time to
get DTA curve (see Fig. 11.1). In differential scanning calorimetry (DSC), the initial
temperatures of the sample and the reference are kept same. The amount of heat that
has to be supplied to the sample or reference to achive this equivalence in temperature
is constantly measured over the temperature range employed. This basically measures
of the amount of energy absorbed or evolved in a particular transition, and hence gives
calorimetric measurements directly. Similar to DTA Curve, DSC Curve can be
obtained by plotting differential heat input to the sample (expressed as a heating rate
dH/dt) against temperature and time (t) (see Fig. 11.2). With this background, now we
will consider the instrumentation and applications of DTA technique.



32
Thermal Methods
Objectives
After studying this unit, you should be able to:
explain the principle of DTA, DSC and thermometric titration,
describe the experimental setup of DTA, DSC and thermometric titration,
interpret the analytical information from DTA and DSC curves and
enthalpogram,
describe the applications of DTA, DSC and thermometric titration, and
distinguish between thermometric and classical titrimetry.
11.2 DIFFERENTIAL THERMAL ANALYSIS (DTA)
Differential thermal analysis is the most widely used and is probably a very suitable
method for the identification and estimation purposes especially in the case of soils
(clays) and minerals. The chemical or physical changes which are not accompanied by
the change in mass on heating are not indicated in thermogravimetric but there is a
possibility that such changes may be indicated in DTA.

Fig. 11.1: Typical DTA Curve Fig. 11.2: DSC Curve
11.2.1 Principle
Differential thermal analysis is a technique in which the temperature of the substance
under investigation is compared with the temperature of a thermally inert material
such as -alumina and is recorded with furnace temperature as the substance is
heated or cooled at a predetermined uniform rate. The range of temperature
measurable in the course of DTA is much larger than TG determination. Thus, during
TG, pure fusion reactions, crystalline transition, glass transition and crystallization and
solid state reactions with no volatile product would not be indicated because they
provide no change in mass of the specimen. However, these changes are indicated
during DTA by endothermal or exothermal departure from the base line. Since DTA is
a dynamic method, it is essential that all aspects of the technique be standardized in
order to obtain reproducible results. These include pretreatment of specimen, particle
size and packing specimen, dilution of the specimen and nature of the inert diluent.
The principle of method consists in measuring the change in temperature associated
with physical or chemical changes during the gradual heating of the substance.
Thermal changes due to fusion, crystalline structure inversions, boiling, dissociation or
decomposition reactions, oxidation and reduction reactions, destruction of crystalline
lattice structure and other chemical reactions are generally accompanied by an
appreciable rise or fall in temperature. Hence, all these are accounted in DTA.
Generally speaking, phase transitions, dehydration, reduction and some decomposition
reactions produce endothermic effects whereas crystallization, oxidation and some
decomposition reactions produce exothermic effects.

In DTA a sample of material under investigation (specimen) is placed by the side of
thermally inert material (the reference sample) usually calacite or - alumina in


33
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
suitable sample holder or block. The temperature difference between the two is
continuously recorded as they are heated. The block is heated in an electric furnace
i.e. both are heated under identical conditions.
11.2.2 Characteristics of DTA Curves
An idealized representation of the two major processes observable in DTA is
illustrated in Fig. 11.3, where T is plotted on y-axis and T on x-axis. Endotherms are
plotted downwards and exotherms upwards. Similarly, the temperature of the sample
is greater for an exothermic reaction, than that of the reference, for endotherms the
sample temperature lags behind that of the reference.

Fig. 11.3: A representation of the DAT Curve showing exotherm, endotherm and base
line changes
When no reaction occurs in the sample material, the temperature of the sample
remains similar to that of reference substance. This is because both are being heated
exactly under identical condition i.e. temperature difference T (T
s
T
r
) will be zero for
no reaction. But as soon as reaction starts, the sample becomes either hot or cool
depending upon whether the reaction is exothermic or endothermic. A peak develops
on the curve for the temperature difference T against temperature of furnace or
time. Let us consider the DTA curve in Fig. 11.3 again, where T along the line AB
is zero indicating no reaction but at B where the curve begins to deviate from the
base line corresponds to the onset temperature at which the exothermic reaction starts
and give rise to a peak BCD with a maximum at point C. Where rate of heat
evolution by the reaction is equal to the difference between the rate of evolution of
heat and inert reference material. The peak temperature C corresponds to the
maximum rate of heat of evolution. It does not represent the maximum rate of
reaction nor the completion of the exothermic process. Thus, the position of C does
not have much significance in DTA experiments.

At some determinant point the heat of evaluation process is completed and after this
point heat evaluation goes on decreasing up to D. The usefulness of the method arises
from the fact that peak temperature is normally characteristic of the material in the
sample. Area of the peak BCD is proportional to the amount of reacting material. For
endothermic reaction the peak EFG will be obtained as shown in the idealised curve.
This peak shows that the T i.e. (T
s
T
r
) will be negative because heat is absorbed and
consequently T
s
will be smaller than T
r
. Note the levels of base lines of extotherm
curve, AB and DE. Both are at different levels above x-axis. This is due to the fact that
heat capacity of the sample has changed as a result of the exothermic process. Similar
explanation can be given for the difference in levels of base lines of endotherm curve
i.e. DE and GH. DTA curves are not only help in the identification of materials but
their peak areas provide quantitative information regarding mass of sample (m), heat
of reactions (enthalpy change, H) and factors such as sample geometry and thermal


34
Thermal Methods
conductivity. If latter two factors are expressed by a factor K called calibration factor,
then peak area can be express as follows.
Peak area (A) = H m K (11.1)
We will use +ve sign for endothermic reaction (H > 0) i.e. when the temperature of
the sample will lag behind the that of the reference, and negative sign for exothermic
reaction (H < 0) the temperature of the sample will exceed that of reference, factor
K is called calibration constant which is temperature dependent. It can be
determined by calibrating DTA with some standard. Once we know the value of K at a
particular temperature, the peak area can be used for quantitative analysis to determine
the mass of sample or energy (enthalpy changes) of a reaction. Beside this DTA curve
also helps in estimating heat capacity of a sample. As you can see in Fig. 11.3 that
there is always a difference in the base lines. The changes in heat capacity ( C
p
) may
be determined at a particular temperature by measuring the difference in base lines i.e.
displacement (d) since:
m m
d
C
1
or
rate heating
p

=
(dT/dt)
d
(11.2)
SAQ 1
Write an expression, which relate the peak area with the amount of the sample. Give
the unit of calibration factor, K
r
.
...
...
...
...
...
11.2.3 Instrumentation
In Fig. 11.4 is shown a block diagram of a differential thermal analyzer. It consists of
following basic components:
1. Furnace Assembly
2. Sample and reference holder with temperature detector
3. Temperature programmer
4. Amplifier and recorder
5. Atmosphere control equipment for furnace and sample holder
The instrument measures the differential temperature of the sample as a function of
temperature or time where the temperature rises at a constant linear rate.
Source of Uniform heating:
Nichrome (nickel and chromium alloy) furnace can be used up to 1300 C, platinum
and its alloys up to 1750 C and molybdenum (Mo) for higher range up to 2000 C. A
special type of higher frequency induction heating may be used for higher
temperatures.
Temperature regulating System:
Uniform rate of heating of the furnace is ensured through electronic temperature
regulators.
If area (A) is measured in
cm
2
and unit of H is
J g
1
, the unit of K will be
cm
2
J
1
.
1
J
2
cm
1
g J g
2
cm

=

= K

In DTA/DSC C
p
is
commonly expressed in
mJ g
1
C
-1
. Though in
the SI units, it is
expressed as J mol
-1
K
-1
.

SI units of change in
enthalpy, H, is kJ mol

1
. It is also express as kcal
mol
1


1 calorie = 4.2 J


35
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations

(a)

(b)
Fig. 11.4: Schematic diagram of a differential thermal analyzer (a) complete layout (b)
furnace part sharing continuous heating of sample and standard
Specimen Holder
It is designed to accommodate even a small quantity of material and to give maximum
thermal effect. It can be of Pt, Ni, stainless steel, Ag and alloy such as Pt-Rh. Certain
ceramic materials such as sintered alumina , silica, fire clay, heat resistant glass and
even graphite have been recommended as material specimen holder for the sample
under investigation and reference material like (-alumina).
Measurement of Temperature
Rare metal alloy such as Pt- (Pt-10-13% Rh) are commonly used as thermocouple for
measuring the temperature. For higher temperature up to 2000
0
C W-Mo thermocouple
may also be used. Very thin thermocouple is inserted in the sample and reference
holder.
Temperature Recording System
Visual galvanometric observations, though inconvenient can also be used when only a
few samples are to be investigated. Nowadays automatic pen and ink electronic
recorder have been found to be more convenient.
Direct recording of the heating curve
When a sample is heated at a constant rate, the temperature function T, is linear up to
the moment when the sample undergoes change, its slope represents the rate of heating
which remains constant.



36
Thermal Methods
At the moment, when an exothermic or endothermic change takes place, the shape of
curve changes as shown in Fig. 11.3. An exothermic reaction causes an increase in
heating rate while endothermic reaction causes a decrease in heating rate. The main
disadvantage of this method is its sensitivity, because small changes in the temperature
causes small deviation in linearity of the curve which some times are not observable.
So, small temperature changes occurring in the sample are generally not detected by
this method. Since detector thermocouples are opposed to each other, small difference
between T
s
and T
r
can be detected after suitable voltage amplification (Fig.11.4). Thus
very small sample size may be used in this method.

Thus recording of the differential curve is advantageous because it can record the
small change in enthalpy that is not accompanied by a change in weight.
11.2.4 Factors affecting DTA curves:
DTA is a dynamic temperature technique. Therefore, a large number of factors can
affect the resulting experimental curves. Similar to TGA curves, these factors can be
divided into the two groups:
i) Sample factors, and
ii) Instrumental factors
The Instrumental factors such as size and shape of sample holder, sample holder
material, heating rate of the sample, sensitivity of recording system, location of
thermocouple in the sample and atmosphere around sample. Most of these factors are
associated with instrumental design. We have very little control on these factors.
Sample characteristics includes amount of sample, particle size, packing density, heat
capacity and thermal conductivity, degree of crystallinity, dilutes of diluents, swelling
and shrinkage of the sample. In following lines we will concentrate on some of the
important factors in some detail.
1. Amount of Sample: In DTA analysis, peak area of DTA Curve is proportional
to the mass of the sample. Certainly this assumption is valid only over a certain
range of amount of the sample. Generally in DTA experiments, a few mg of
powdered solid sample is used.
2. Particle Size: In DTA experiments, Samples in the form of fine powers are
generally preferred except polymers, in which case we might have to use plastic
fragments or chopped fibers. When we are comparing between two materials,
their sample should have similar particle size.
3. Sample packing: Packing density of sample influences the shape of DTA
Curve. Tight packing influences the escape of volatiles and interaction of
sample with atmosphere of furnace due thermal experiments. Therefore, a
reproducible method of packing the sample is desirable.
4. Heating rate: It is observed that an increase in heating rate increases, the
procedural peak temperature, and some time it also increases peak area. Often
high heating rate results in poor resolution of fine peak in DTA curve. Therefore
slower heating rate is preferred for DTA experiments. Heating rate of 10 C
min
-1
and 5 C min
-1
are commonly preferred.
5. Atmosphere around sample: Similar to DTG, a flowing gas is preferable to a
static atmosphere as in static atmosphere. There is a possibility of change of
atmosphere around sample on its degradation or decomposition especially in
case of a volatile sample. In such a case we generally use flowing gas technique.
Flowing gas sweeps away volatile by products and keeps homogenous
atmosphere around sample. In Table 11.1, we have summarized the major factor
which can affect the DTA curve.


37
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
Table 11.1: Factors that influence DTA Curve
Factor Effect Suggestions
1. Heating rate Change in peak size and
position
Use a low heating rate
2. Location of
thermocouple
Irreproducible curve Standardise thermocouple
location
3. Atmosphere around
sample
Change in the curve Inert gas should be allowed to
flow
4. Amount of sample Change in peak size and
position
Standardise sample mass
5. Particle size of
sample
Irreproducible curves Use small, uniform particle size
6. Packing density Irreproducible curves Standardise packing technique
7. Sample container Change in peak Standardise container

Rather empirical nature of the method gives rise to many difficulties originating from
small differences in technique e.g. the peak temperature normally used for reporting
differential thermal results as well as for identification is variable depending upon
the rate of heating, amount of active material, packing of specimen, type of specimen
holder etc. Thus standardization of technique is essential. In general, it is essential that
each apparatus should be calibrated from the mineral expected to be the sample under
investigation.
SAQ 2
List the main factors which affect DTA curves.
...
...
...
11.2.5 Sources of Errors
There are a number of sources of errors in DTA, and they can lead to inaccuracies in
the recorded temperature and weight data. Some errors may be eliminated by placing
the thermocouple at proper place and handing it with the care. For understanding we
discuss some common sources of errors during operation of a DTA.
i) Buoyance effect: If a thermally inert crucible is heated when empty there is
usually an apparent mass change as temperature increases. This is due to effect
of change in buoyancy of the gas in the sample environment with the
temperature, the increase convection and possible effect of heat from the furnace
in the balance itself. Now, in most modern instruments, this effect is negligible.
However, if necessary, a blank run with empty crucible can be performed over
the appropriate temperature range and calibrate the base line through mentioned
procedure by individual instruments . The resultant record can be used as a
correction curve and results for subsequent experiment performed in the same
condition.
ii) Condensation on Temperature Sensor: Condensation of the sample will also
affect the sensitivity of a thermocouple for temperature measurement. This can
be avoided by maintaining a dynamic atmosphere around the sample in the
furnace so that all the condensable products may be driven by the flowing gases.
iii) Fluctuation of thermostats.
iv) Reaction between sample and container


38
Thermal Methods
v) Convection effect from furnace
vi) Turbulence effect from gas flow
vii) Induction effect from furnace
It may noted that errors of type (iii) may be eliminated by properly placing balance in
the laboratory and maintaining constant power supply and error (v) can be avoided by
sensible choice of sample container. Last three types of errors (v-vii) have to be
considered in the design of the furnace, the balance and its suspension system. By
avoiding excessive heating rate and proper gas flow rate some of above mentioned
errors may be eliminated. To further minimize errors, DTA equipment should be
calibrated both for temperature and peak area determination with appropriate
standards. For temperature substances like KNO
3
, In, Sn, SiO
2
, BaCO
3
, etc. are used
depending upon the temperature range used for the experimental condition. For area
calibration indium is often employed as a standard, but as calibration factor K in case
of DTA is temperature dependent, therefore, dependium upon the temperature range of
the experimental condition other standard are also used.
11.2.6 Interpretation of DTA Curve
DTA curves of a pure compound represent characteristic of that compound for
physical chemical changes. Using DTA curve one can co-relate the changes in energy
because of thermophysical and chemical change occurring in a compound because of
heating the material. This can often provide us directly to the temperature at which
the physico- chemical transition are occurring and which is also used to identify the
presence of respective elements or compounds qualitatively. The change in DTA curve
further gives information about the thermophysical changes associated with mass
change e.g. melting point, glass transition temperature, crystallization temperature etc.

To further illustrate, lets consider the example of CaC
2
O
4
.H
2
O for which DTA curve
is shown in Fig. 11.5. This curve indicates that out of three DTA peaks first is
endothermic in nature, second is exothermic and third one is again endothermic in
nature. The correlates the TGA results and confirms that the nature of reactions
occurring in the endothermic are because of desolvation and decarboxylation while
exothermic is due to decomposition followed by oxidation and finally formation of
stable oxide CaO with evolution of carbon dioxide gas. This can be explained by the
chemistry of decomposition of CaC
2
O
4
.H
2
O when it is heated.

Fig. 11.5: DTA curve of CaC
2
O
4
.H
2
O in the presence of O
2



39
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
DTA curves are useful both qualitatively and quantitatively. Similar to TGA, the
position and shapes of the peaks (curve) can be used to determine the composition of
the sample. As discussed earlier, Eq. 11.1 can be used to relate peak area with the heat
of the reaction and amount of sample used for analysis. But before using this equation
we should know the value of calibration constant, K, at the temperature concerned.
This can be achieved by the calibration of instruments with known standards.
However, the value of the calibration factor, K, may be eliminated from the
quantitative calibration by comparison of peak area of unknown sample with the
known sample under identical condition. For example if A
1
is the peak area of known
mass (m
1
) and A
2
is the peak area of unknown sample having mass equal to m
2
, then
using Eq. 11.1 we can write.
2
1
2
1
A
A
m
m
=
or
|
|

\
|
=
1
2
1 2
A
A
m m (11.4)
Similarly, the heat of reaction of a unknown sample can also be calculated by
comparison with a sample of known heat of reaction. One thing keep in mind that the
calibration factor, K, in Eq. 11.1 is temperature dependent in DTA situation, therefore
both known and unknown sample should be run at identical temperature.

You may have noticed in Fig 11.3 and 11.6 that the initial and final baselines of peaks
do not coincide. Therefore, determination of the area under the peak may be subject to
ambiguity. To resolve this problem a method for determination of the peak area is
illustrated in Fig. 11.6. Both baselines are extended to a perpendicular line drawn from
the maximum of the curve and the area under the two halves of the curve are
determined and added to give the total area.

Fig. 11.6: Illustration depicting the determination of DTA peak areas. The difference in
the initial and final base indicates a change in heat capacity
The heat of reaction observed in DTA can be further used to calculate molar enthalpy
of reactions by using the formula:
H
m
= H
r
M
r
/ m (11.3)
where, H
m
= molar enthalpy of reaction, H
r
= enthalpy of reaction, M
r
= related
molar mass of the compound, m = Mass of substance used for analysis.
Determination of Heat Capacity
The DTA curve is conveniently used to measure the heat capacity (specific heat). For
this purpose first a DTA curve is recorded for an empty container and then for the
sample placed in container is recorded in identical condition. The absolute change in
temperature (T
x
) has been measured and put in the equation for calculations:


40
Thermal Methods
mH
T T
K C
1 2
p

= (11.5)
where C
p
is the heat capcity at temperature T, T
1
and T
2
are diffenrential temperature
generated when the instrument is first run without any sample at all and then with the
test sample in position, H is the heating rate (dT/dt) and K is calibration factor. It can
be determined by calibration against standard substance of known enthalpy change.

Construction of Phase Diagram:
The Melting point can be recorded by DTA curve for a eutectic mixture of different
sample with variable composition. These melting points can be used to construct a
phase diagram The critical temperature of organic compounds can be determined by
DTA if sealed sample holder is used. The determination is used of cooling curve, a
discontinuity is observed at the critical temperature T
c
. Curie point temperature
making a sudden change at this point can also be determined by this technique . The
specific heat increases gradually upon the curie point e.g 357
o
C for nickel,
observed simply by ploting dQ/dT or dT against temperature .
Estimation of Transition temperature:
The precise determination of a transition temperature (e.g. M. P. and B.P.) up to a
precision of 0.3
o
C over a wide range of heating rate. The temperature estimated for
M.P. T
m
or B.P. T
B
, were most often selected from the portion peak as shown in Fig.
11.7. In this figure first a base line meeting low and high temperature sides of the peak
is drawn where A is the intersection of extrapolated straight line portion of the low
temperature side of the peak with the base line. Further, point B is the inflection point
of low temperature side of the peak and point C is the extrapolated peak, while D is
the extrapolated return to the base line. Melting point T
m
is measured by the using
sample is closest to the temperature of point C for sample and temperature at B for
reference. In exceptional cases it may closer to point D.

Fig. 11.7: The different temperature of DTA curve.
SAQ 3
Compound X has a relative molar mass of 98.4 K and heat of fusion ) (
x
H of
6.85 kJ mol
1
. Compound Y has a relative molar mass of 64.3 and having same
melting point as X. 500 gm samples of each yield DTA peak areas of 60.0 cm
2
and
45.0 cm
3
for X and Y, respectively. Calculate the heat of fusion of Y.
...
...


41
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
11.2.7 Applications
Now we study in some more examples to understand how DTA is used in chemical
identification of a material (qualitative interpretation) comparing and for thermal
stability of materials. Such informations can be used to select material for certain end-
use application, predict product performance and improve product quality.
Qualitative and Quantitative Identification of Minerals
For the detection of any minerals in a sample, it is essential that it undergoes
measurable energy changes in the temperature range used. Since most of the minerals
undergo such changes, choice of an appropriate temperature range should have
priority. However, assuming a suitable range variation occurring in the minerals
themselves may frequently lead to difficulties in the interpretation of curves. Another
complication arises from the fact that certain minerals give reasonably characteristic
thermal effect, sometimes clays do not show similar result. Other difficulties may arise
by the presence of organic matter.

Oxidation of organic materials if present masks the thermal effect of substance.
Consequently the analysis of such cases should preferentially be carried out in inert
atmosphere or in vacuum. Organic material some times be removable by a suitable
solvent or may be oxidized by treating with H
2
O
2
. When clays or ore contain organic
material then a broad exothermic peak appears between 200 600
0
C. Thus the
appearance of a broad exothermic peak between 200-600
0
C indicates the presence of
organic material in a given sample.

In practice however, difficulties do arise in a case where peak areas for two distinct
samples of same mineral give peaks at two different temperatures. It is, therefore,
necessary for qualitative work to know the peak area given by pure mineral identical
to that in the sample under investigation. This, however, is not possible. Another
limitation in the quantitative work in the occurrence of overlapping of peaks e.g. when
Kaolinite and Illite are present in the same sample almost completely overlapping
takes place. A representative DTA curve of some minerals are shown in Fig. 11.8. It
may be observed that none of these miners show an exothermic peak in the range 200-
600 C corresponding to organic material as mentioned above.

Fig. 11.8: DTA curves for (A) : kaolinite, (B): Mortmonillonite, (C): Illite


42
Thermal Methods
Polymeric Materials
DTA is a very useful technique for the characterization of polymeric materials in the
light of identification of thermophysical , thermochemical, thermo mechanical and
thermo elastic changes or transitions. It provides important parameters for polymer
processing and its end use. The DTA also provides useful information about
quantitative aspect, degree of fusion, crystallinity, phase equilibrium, heat of
polymerization, degree of curing etc. A typical DTA curve of a polymer is shown in
Fig. 11.9 with labeled four transitions: glass transition, crystallisation, melting and
oxidation, abbreviated as T
g
, T
c
, T
m
and T
d
respectively.

Fig.11.9. DTA curve of a typical polymeric sample
The DTA technique is also used for analyzing a polymeric mixture qualitatively and
quantitatively. The individual polymers exhibit their own characteristic peaks. The
Fig. 11.9 is differential thermal curve of seven components polymeric mixture for
their melting points: Polytetrafloroethylene (PTFE), High Pressure (high dencity)
Polypropylene (LPPE), Low Density Polypropylene (LPPE), Polypropylene (PP),
Polypropylene POM, Nylon 6, Nylon 66.

Fig. 11.10: DTA curve of a typical polymeric mixture
It is shows characteristics peaks of all the polymers and hence confirm the presence of
individual polymers in the analyzed sample. The area under the peak is related to the
heat of reaction and related to the quantity of material present in the mixture. The
DTA graph of ethylene propylene block copolymer indicates two peaks for ethylene
and propylene. On comparing areas under the peaks it is found that 51 % ethylene and
49 % propylene present in the analysed block copolymer . The peak height technique
has been also employed to measure the quantity of polysebacic anhydride in a epoxy
resin- sebacic anhydride mixture.

Another important parameter determined from by DTA is glass transition (T
g
), a
second order transition caused by relaxation of chain segment in the amorphous
portion of a polymer. The first evidence that a glass transition could be detected by
DTA was provided in (1957), where a transition at 28 C was shown but not


43
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
interpreted. As such this transition is not associated with latent heat but rather a
sudden change in specific heat to bring a liquid into the glassy state. The necessary
condition is to cool it rapidly to approximately two third of its melting point.
T
g
/T
m
=0.66
The glass transition of a polymer can be obtained using number average molecular
mass M ranging from 8 10
3
to 3 10
6
from expression:
T
g
= [ ( 96.5 +/- 1.0 ) ( 2.8 +/- 0.1)] 10
3
/ M
The deduction about the slope of the glass transition as depicted by DTA curve:
a) The slope of the curve T surface temperature should be sigmoidal.
b) The maximum value of T at the glass transition temperature should be
linearly dependent on the heating rate.
c) The inflection point Tg should rise in temperature with the heating rate. It has
been shown that glass transition is associated with a sudden shift in base line.
The T
g
depends on heating rate, volume fraction and molar mass. The DTA results
provide important information about polymerization reaction , mainly about heat of
polymerization, degree of curing, effect of catalysts, decomposition reaction and
radiation effects.
11.2.8 Measurement of Crystallinity:
A common application of DTA is the measurement of the mass fraction of crystalline
material in semi crystalline polymers. The method is based upon the measurement
of the polymers heat of fusion , H
f
, and the plausible assumption that this
quantity is proportional to the crystalline content . If by some process of
extrapolation the heat of fusion , H
f*
, of a hypothetical crystalline sample is known
then the mass fraction of a crystallinity is
Mass fraction =
*
f
f
H
H

Thus, crystallinity of a polymer sample (X) can be determined by measuring the total
energy absorbed by the sample per gram ( H ) and subtracting the amount of
energy which would be absorbed by one gram of totally amorphous material
[ (a)
f
H ] in the temperature interval, and then dividing by the heat of fusion of one
gram of a perfectly crystalline sample [ (c)
f
H ], as expressed by following
equation.
X = H H
f
(a)/ H
f
(c)
Another method for the determination of polymer crystallinity is based upon the
ability of the instrument to cool a molten sample rapidly and reproducibility to a
selected temperature where isothermal crystallization is allowed to occur. A number
of crystallization curves may be obtained at different temperatures. The difference in
crystallinity may be caused by branching, nucleation and molecular effect.
Degree of Polymerisation:
The area observed in DTA curve is directly related to heat of polymerization and
can be expressed in terms of per mole or per g. Consider the DTA graph of
polymerization process of trialkylcyanurate and triallylisocyanurate. Samples were
prepared by mixing two parts Al
2
O
3
, one part monomer 0.1 part catalyst as a 50 %
paste in tricresyl phosphate and heating the mixture at a rate of 8
0
C per minute.
Typical values of heat of polymerization as estimated from the peak area, are given in
Table 11.1.


44
Thermal Methods
Table 11.2: Estimated Heat of Polymerization
Materials heat of polymerization (H
1
) heat of polymerization (H
2
)
trialkylcyanurate 35 107
triallylisocyanurate 56

Further the area (size) of peak appears in DTA curve had a great value in assessing
the degree of curing. This is done by the residual cure remaining in a polymer system
after various treatments. This approach has been applied for estimation of degree of
curing in an unsaturated polyester-styrene copolymer cured at ambient temperature .
The variation in the size of the curve represents the percentage of curing in 2 hours
63 % , 3 hours 68.6 % 4 hours 74.3% , 5 hours 77.0 % and 6 hours 78.2%. Similarly
the relative change in the heat of reaction measured by DTA also gives information
regarding role of catalyst , degree of crystallinity and decomposition of polymer
samples.
Analysis of Biological Materials
DTA has been widely used in the determination of thermal characteristics of bio-
organic molecules, the main constituent of body of living being. The bio materials are
having heterogenity as a significant feature. This describes it as
multicomponent, molecular non homogenous materials, in which component exist as
continuous , separate and inter mixed structures. Biological systems present
complexity even in static state and then difficulty in obtaining meaningful results and
establishing correlation between thermal characteristics and other physical chemical
properties. However, the investigations carried out under variable experimental
condition indicate that DTA curve should be of value as fingerprint of biological
materials. The thermal characteristics of a number of biological materials such as fresh
biological materials and decomposed materials determined under different
atmospheric condition have been studied.

Fresh biological material consists of materials of active body of plants and animals. It
is always difficult to elucidate the chemical constituents of the plant materials.
Information obtained from the study of the simple molecules can not be necessarily
applied directly to heterogeneous system . In the study of such system indirect
method has been applied e.g. complete combustion, dilution effect, environmental
effect etc. The DTA curves of four leave samples of different plant in oxygen exhibit
two pronounced exothermic effect in the range 240-270
0
C region. The first peak is
invariably smaller than second one at least in height always not in area apart from
variation in peak temperature. The general similarity in these curves may be inferred
that leaves of the plants have at least same micro-chemical composition.

The DTA curves for some plant materials have also been obtained in a static or air
or dynamic oxygen atmosphere, since it is difficult to distinguish between
decomposition and oxidation effects, which may overlap. Endothermic reaction such
as dehydration or volatilization while exothermic accompany combustion under inert
atmosphere condition, with oxidation reaction suppressed, such endothermic effect can
be detected. Similarly the analytical method is useful for analysis of high energy
materials, explosives, ceramic, cement and pharmaceuticals.
SAQ 4
List the melting point of individual polymer samples from the DTA curve of
Fig. 11.10.
...
...


45
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
11.3 DIFFERENTIAL SCANNING CALORIMETRY
In previous section we have studied DTA techniques in these methods, thermal
reactions are observed by measuring the deviation of the sample temperature from that
of the reference material. This deviation effects the DTA curve and decreases the
sensitivity. There is another technique called Differential Scanning Calorimetry (DSC)
which have the advantage of keeping the sample and reference at the same
temperature and heat flow into sample and reference is measured. This can be
achieved by placing separate heating devices in the sample and reference chambers.
This is in contras to the DTA scheme, where both sample and reference are heated by
the same source.
11.3.1 Principle
In DSC the heat flow is measure and plotted against temperature of furnace or time to
get a thermogram. This is the basis of Differential Scanning Calorimetry (DSC). The
curve obtained in DSC is between dH/dt in mJ s
-1
or mcal s
-1
as a function of time or
temperature. A typical DSC curve is shown in Fig. 11.11. The deviation observed
above the base (zero) line is called exothermic transition and below is called
endothermic transition. The area under the peak is directly proportional to the heat
evolved or absorbed by the reaction, and the height of the curve is directly
proportional to the rate of reaction. Therefore Eq. 11.1 is equally valid for DSC
scheme also. The only difference is the calibration factor K in case of DSC is
independent of temperature. This is a major advantage of DSC over DTA.

Fig. 11.11: A typical DSC Curve
11.3.2 Instrumentation
The block diagram of a DSC instrument as shown in Fig. 11.12a, essentially works on
the temperature control of two similar specimen holder assembly. The left half of the
block diagram represents the circuit for differential temperature control while right
hand side indicates that for average temperature control. In the average temperature
control circuit, the temperature of the sample and reference are measured and averaged
and the heat output of the average heater is automatically adjusted so that the average
temperature of the sample and reference increases at a linear rate. The differential
temperature use control circuit monitors the difference in temperature between the
sample and reference and automatically adjust the power to either the reference or
sample chambers to keep the temperatures equal. For getting a thermogram, the
temperature of the sample is put on the x-axis and the difference in power supplied (in
terms of J s
-1
or cal. s
1
) to the two differential heaters is displayed on the y-axis.

Fig. 11.12 b illustrates the heating arrangement in sample and reference compartments.
Here the sample and reference compounds are provided with their own separate
heaters, as well as their own temperature sensors so that both S and R are maintained
at identical temperature by controlling electrically the rate at which heat is transferred
to them.



46
Thermal Methods
In DSC, samples for analysis range in size from 1 to 100 mg are placed in a sealed
sample container. A wide range of heating rate (0.5 to 80C/min) can be used, DSC
instruments are generally sensitive energy detect heat evolution or absorption at a rate
less than one millicalories per second. Electrical signals are amplified and recorded
similar to TGA and DTA.


Fig. 11.12: (a) Block diagram of a DSC instrument (b) Heating arrangement in DSC
compare this with Fig. 11.4 b
During thermal process reactions either liberate or absorb heat. Thus, when H is
positive (endothermic reaction), the sample heating device is energized and a positive
signal is obtained; when H is negative the reference heating device is energized and
a negative signal is obtained. An idealized representation of the three major processes
observable in DSC is given in Fig. 11.13. The peak area in DSC are proportional to the
amount of sample, the heat of reaction and similar to DTA peak area can be expressed
by following equation.


47
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations

Fig. 11.13: An idealized representation of the three processes observed in DSC
Peak area (A) = HmK (11.6)
where H represents sample enthalpy change and m is the mass of sample and K is a
constant called calibration factor. Unlike DTA it is independent of temperature. Using
above Eq. 11.6, we can determine enthalpy change for a reaction directly from peak
area, if we known the value of K. We can also determine enthalpy change by
comparing the H of the sample with the known H of the standard. i.e.,
s s
S k k
s
m A
H m A
H

= (11.7)
where H
s
is the enthalpy change for sample, H
k
is the enthalpy change for known
standard, m
s
and m
k
are masses of sample and known standard respectively, and A
s

and A
k
represents the area of peaks of sample and standard materials, respectively.

DSC technique is not only sensitive for the determination of H, but it is also very
sensitive for the determination of heat capacities (C
p
). when a sample is subjected to a
heating programme is DSC, the rate of heat flow into the sample is proportional to its
heat capacity. This may be detected by the displacement of the base line as illustrated
in Fig. 11.13. The value of C
p
may be determined at a particular temperature by
measuring this displacement (d). :
m
d
C

=
rate heating
p
(11.8)
m
t T
t H
1
) d / d (
) /d d (
=
(11.9)
Using Eq. 11.9, we can deduce the unit of C
p
. In DSC curve displacement (d) will be
measured in mJ s
1
. If heating rate is in C s
1-
and m is expressed in g, then,
1 1
1
1
p
C g mJ
s C
1
g
s mJ

= =
o
C
C
p
can also be expressed in term of mcal. as
1 1
C g mCal

[conversion factor for J
and Cal. is: 1 calorie = 4.2 J].

In practice we normally measure the base line shift by reference to a base line obtained
for empty sample and reference pans. To further minimize experimental error we
usually determine heat capacity of the sample by comparing with the known heat
capacity of the standard.



48
Thermal Methods
( )
dt
d
p 1 2
T
mC H H K = (11.10)
or
dt
d
d
p
T
mC K =
where, H
1
and H
2
are differential heat generated when the instruments is first run
without any sample at all and then with the test sample in position (in DSC curve
(H
2
H
1
) is expressed as displacement, d). K is calibration factor, it can be
determined by calibration against standard substance. However, K from the Eq.
11.10 can be eliminated, if a material with a known heat capacity is used to calibrate
the instrument.

Once of the commonly used standard is -aluminium oxide (Al
2
O
3
) or synthesized
sapphire for which specific heat has been determined to five significant figures in the
temperature range 0 to 1200 K. After the base line and sample program, a third
program is run with a weighed sapphire structure. At any temperature T, following
equation applies:
K d =
dt
d
p
T
C m (11.11)
d K =
dt
d
p
T
C m (11.12)
where d and d are ordinate deflections (displacements) due to the sample and the
standard respectively,
P
C m are mass and heat capacity of the standard. Dividing the
Eq. (11.11) by (11.12) we get
m d
m d
C
C
C
C
m
m
d
d

=

=

p
p
p
p
or (11.13)
Thus the calibration requires only the comparison of the two displacement values at
the same temperature . We can easily calculate value of Cp on putting the rest values
in the Eq. 11.13. The basic components of DSC are quite similar except the
differential energy measuring system. In DSC, two principle works: one based on
power compensation and other heat flow method. In power compensation method
smaller secondary heater are attached two equalize the generated energy difference
between sample and reference materials. While in heat flow technique heat flux
passing through sample and reference are evaluated and their difference is related
energy consumed or released in the thermal reactions.
SAQ 5
Write the essential differences between a DTA and DSC.
...
...
...
...
11.3.3 Factors Affecting DSC Curve
In the beginning of this block we talked about the lowest temperature, T
i
at which the
onset can be detected by the instrument operating under particular conditions. We
may like to call this as transition temperature, which is not correct. Actually in a DSC
experiment, both T
i
, T
f
and T
c
(the final temperature at which the decomposition is


49
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
completed) do not have fundamental significance, but they can still be a useful
characteristic of a DSC curve. The term procedural thermogram, often used for the
temperature at which temperature change appears to commence. This indicates that a
start of thermal reaction, temperature does not have a fixed value, but depends on the
experimental procedure employed to get it. Similar to this there are many factors
which influence a DSC curve. These factors may be due to instrumentation or nature
of sample. We have listed the main factors which affect the shape, precision and
accuracy of the experimental results:

1. Instrumental factors:
a) Furnace heating rate.
b) Recording or chart speed
c) furnace atmosphere
d) Geometry of sample holder/ location of sensors
e) Sensitivity of recording mechanism.
f) Composition of sample container.
2. Sample Characteristics:
a) Amount of sample
b) Solubility of evolved gases in sample.
c) Particle size
d) Heat of reaction
e) Sample packing
f) Nature of sample
g) Thermal conductivity.
Some of these factors we have are already described in sec.11.2.4 in detail.
11.3.4 Sources of Error
There are a number of sources of error in DSC, and they can lead to inaccuracies in the
recorded data of heat. Some of the errors may be corrected by placing the thermo
balance at proper place and handing it with the care. For understanding we are
discussing some common source of errors during operation or common as discussed in
DTA except the in accuracy caused by secondary heaters and thermostats.

Errors can be avoided by proper placing of instrument in the laboratory, maintaining
operating temperature, and constant power supply. By avoiding excessive heating rate
and proper gas flow rate other errors can be also avoided.

To further minimize the errors during experiments, similar to DTA, DSC instruments
are also be calibrated for the temperature and peak area measurements with suitable
standards. The only difference is that calibration constant in DTA situation is
temperature dependent to a significant degree. Therefore in DTA measurement, we
should calibrate peak areas using a standard which provide a reference peak in a same
temperature range as the test sample. In DSC situation, K is independent of
temperature. Therefore, it requires simple steps for the calibration of the instrument.
For peak area calibration we require standard of high purity and accurately known
enthalpy of fusion (
f
H ) are required. Few examples of calibration standards are
indium (In), benzoic acid, tin, lead, silver, gold, etc.


50
Thermal Methods
SAQ 6
DTA and DSC, which method you will prefer for quantitative purposes and why?
...
...
...
...
11.3.5 Interpretation of DSC Curve
DSC curve of a pure compound is a fingerprint of that compound in the context of
transition temperature as well as heat required for that transition. Therefore, DSC
curve can be used to infer about the presence of a particular compounds and its
thermal behaviour. The peaks observed shifting of base line either up or down. A
typical DSC curve is shown in Fig 11.11. The peak above the base line is exothermic
while down the base line is endothermic.

We have seen above how area under DSC Curves is related to the amount of energy
released or absorbed in a physico-chemical change. It has been shown that under
certain conditions the area under the peak is proportional to the amount of heat
evolved in a reaction.

So this area under the curve is used for stochiometric ratio of analyzed compounds
(quantitative interpretation). Now we see in next example how it can be used to
compare thermal stability of a material for physical state and chemical states .This can
be used for chemical identification of a material (qualitative interpretation). Such
information can be used to select material for certain end-use application, predict
product performance and improve product quality. DSC Curves of a polymeric
mixture and probable transitions are shown in Fig. 11.14 for illustration about
probable change in behaviour of a polymer sample.

Fig. 11.14: Change in Behavior of Polymeric Materials in DSC
The DSC technique is more sensitive than DTA and it provides clear presence of a
thermal events occurring during course of heating of time ageing of material . Thus,
the information acquired by DSC is more realistic. The technique is used for the
presence of polymorphism, degree of crystallinity, curing fraction etc. Curves clearly
indicate that Fig. 11.13is showing the peaks for the glass transition, ordering, melting
and decomposition of individual polymers. The ratio of areasunder the curve by
dividing the enthalpy of heat of decomposition, provides the ratio of individual
monomers in a analysed copolymer sample .

The heat of reaction (H
r
) observed in DSC can be further used to calculate molar
enthalpy of reactions by using following formula:


51
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
H
m
= H
r
M
r
/m
Where, (H
m
= molar enthalpy of reaction ,
M
r
= relative molar mass of analysed compound,
m = Mass of substance used for analysis.
11.3.6 Applications
Differential scanning Calorimetry (DSC) used to measure energy changes as a
function of temperature or time. A typical graph is shown in Fig. 11.13. Using this
technique it is possible to observe a number of characteristic properties of a sample
like fusion, crystallization, glass transition temperatures (T
g
) as well as other thermo
chemical reactions. DSC can also be used to study oxidation, as well as other chemical
reactions. Glass transitions may occur as the temperature of an amorphous solid is
increased. These transitions appear as a step in the baseline of the recorded DSC
signal. This is due to the sample undergoing a change in heat capacity; no formal
phase change occurs. As the temperature increases, an amorphous solid will become
less viscous. At some point the molecules may obtain enough freedom of motion to
spontaneously arrange themselves into a crystalline form. This is known as the
crystallization temperature (T
c
). This transition from amorphous solid to crystalline
solid is an exothermic process and results in a peak in the DSC signal. As the
temperature increases the sample eventually reaches its melting temperature (T
m
). The
melting process results in an endothermic peak in the DSC curve. The ability to
determine transition temperatures and enthalpies makes DSC an invaluable tool in
producing phase diagrams for various chemical systems. The technique is widely used
across a range of applications, both as a routine quality test and as a research tool. The
equipment is easy to calibrate, using low melting indium for example, and is a rapid
and reliable method of thermal analysis. The few notable specific applications of DSC
are:

The result of a DSC experiment is a curve of heat flux versus temperature or time.
There are two different conventions: exothermic reactions in the sample shown with a
positive or negative peak. This curve can be used to calculate enthalpies of transitions.
This is done by integrating the peak corresponding to a given transition. It can be
shown that the enthalpy of transition can be expressed using the following equation:

H = KA

where H is the enthalpy of transition, K is the calorimetric constant, and A is the area
under the curve. The calorimetric constant will vary with the instrument and can be
determined by analyzing a well-characterized sample with known enthalpies of
transition.

Most of well known spectroscopic methods of great value in the qualitative and
quantitative chemical analysis are based on our ability to measure energy
absorption or emission caused by transition from one energy state to another. The
great potential of thermal spectroscopy for quantitative analysis was not realized in
the past because of the absence of a suitable, fast scanning, the calibration run for
the synthetic compounds and the base line technique used in the area measurement
and can be used for the quantitative analysis of constituents present in the fiber
blend.

Many materials can exist in two or more different crystal line forms. The chemical
reactivity and physical properties of different forms vary frequently one to another.
Technological handling requires one of the perfect suitable form, hence the
phenomenon is of great importance in chemistry and conveniently studied by
DSC.



52
Thermal Methods
DSC may also be used in the study of liquid crystals. As matter transitions between
solid and liquid it often goes through a third state, which displays properties of both
phases. This anisotropic liquid is known as a liquid crystalline or mesomorphous state.
Using DSC, it is possible to observe the small energy changes that occur as matter
transitions from a solid to a liquid crystal and from a liquid crystal to an isotropic
liquid.

DSC curves may also be used to evaluate puriting of a drug and polymer. This is
possible because the temperature range over which a mixture of compounds melts is
dependent on their relative amounts. This effect is due to a phenomenon known as
freezing point depression, which occurs when a foreign solute is added to a solution.
(Freezing point depression is what allows salt to de-ice sidewalks and antifreeze to
keep your car running in the winter.) Consequently, less pure compounds exhibit a
broadened melting peak that begins at lower temperature than a pure compound. DSC
is used widely for examining polymers to check their purity and composition. Melting
point and glass transition temperature for most polymers are available from standard
compilations, and the method can show up possible polymer degradation by the
lowering of the expected melting point, Tm. It depends on the molar mass of the
polymer, so lower grades will have lower melting points than expected.

In pharmaceutical industry it is necessary to have well-characterized drug compounds
in order to define processing parameters. For instance, if it is necessary to deliver a
drug in the amorphous form, it is desirable to process the drug at temperatures below
those at which crystallization can occur. The above mentioned transition are well
observed in DSC curve and used in industry regularly

There are two important criteria for characterization of waxes and fats by DSC:
1. Although melting peak shape of wax and wax formulations can be quite
complex , they are much less sensitive than fats to variation in the
crystallization condition.
2. The crystallization of waxes is easily nucleated with the result that solidification
occurs readily with little or no super cooling. In fact the crystallization peak for
most waxes is virtually mirror image to its melting point. Although reading of
DSC thermogram and applying to these criterion, we can easily make
statement whether the supplied material is wax or fat.
Using differential scanning calorimetry to study the oxidative stability of samples
generally requires an airtight sample chamber. Usually, such tests are done
isothermally (at constant temperature) by changing the sample atmosphere. First, the
sample is brought to the desired test temperature under an inert atmosphere, usually
nitrogen or organ. Then, oxygen is added to the system. Any oxidation that occurs is
observed as a deviation in the baseline. Such analysis can be used to determine the
stability and optimum storage conditions of a compound

A more specific application of DSC where DTA cannot be employed is the detection
of magnetic transition in the materials. The magnetic transition are of second order
with H=0 but with the a maximum heat capacity at the transition temperature.
Technique is sensitive to detect these minor variations. A typical DSC curve for a
magnetic transition is shown in Fig. 11.15. Similarly glass transition can be detected
easily with DSC.


53
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations

Fig 11.15: A Typical magnetic transition observed in DSC
11.3.7 Advantages of DSC
1. Small sample size 1 to 10 mg.
2. Simple and rapid procedure of analysis, typically 15 to 30 min. per
determination.
3. Ideal for comparison of sample purity for example in quality control.
4. Does not require high absolute temperature accuracy ( in contrast with melting
point depression method.
5. Does not require calibration with known impurity levels, cryoscopic constant
is obtained simultaneously.
6. The use of melting rather than a freezing curve avoid problems associated
with super cooling of sample , poor crystallizability from melt , instability in
the melt etc.
11.4 THERMOMETRIC TITRATIONS
In the earlier section you have learnt about thermogravimertric analysis (TGA),
different thermal analysis (DTA) and differential Scanning Calorimetry (DSC)
methods. We hope that you have clearly understood the principle of TGA, DTA and
DSC its analytical applications. We assume that you can apply the knowledge of TGA,
DTA and DSC to derive analytical information about simple and complex compounds.

In this section we will introduce you to thermometric titration and familiarize you with
the instrumentation including experimental details. At the end we will discuss some
typical analytical applications of thermometric titration methods.
11.4.1 Principle
Similar to the case of thermogravimetry, basic principle of thermometric titrations is
based on the change in temperature with the addition of titrant and determine the end
point from a plot of temperature vs. volume of titrant. The titrant is added to an
isothermal titrate in an adiabatic titration calorimeter. In most instances there occurs a
change in enthalpy concomitantly, yielding a corresponding heat of reaction. As a
result these are also called enthalpy titrations and the titration curves are called
enthalpograms. It can be exothermic or endothermic. In thermometric titration,
change in temperature occurs only when titration is in progress and sample reactant is
present. Thus, start and end point of a titration are readily observed and the number of
moles titrated is calculated as in regular titration. By determining the heat capacity of
the system under study, heat of reaction can be readily determined. In addition,
equilibrium constant can be evaluated under appropriate experimental conditions.


54
Thermal Methods

Fig. 11.16: Tupical Enthalpogram for (a) exothermic reaction and (b) endothermic
reaction, showing start of titration, progress of titration, end point and excess reagent line
Typical shapes of enthalpogram are shown in Fig. 11.16 a and b. On both
enthalpograms, the base line represents temperature-time blanks recorded prior to the
start of the actual titration, B corresponds to the beginning of addition of titrant, C is
the end point and CD the excess reagent line. Thus BC is the titration branch proper of
the enthalpograms. In cases where H <0, it has an ascending slope shown in as Fig.
11.16 a whereas for H >0, it has a descending slope as showing Fig. 11.16 b both
cases the excess reagent branches of the enthalpograms (CD) are drawn with
ascending slope because the dilution of most titrants is an exothermic process. In order
to minimize variations in heat capacity during titration, it is customary to use titrants
50-100 times more concentrated than the unknown titrated. Thus the volume of titrate
solution is maintained virtually constant, but the titrants are diluted appreciably. The
heat of dilution can be corrected for conveniently by the linear back extrapolation CB.
Under these conditions, the extrapolated ordinate height BB represents a measure of
the change of temperature. T, due to the titration reaction, as well as of integral heat,
Q, evolved or absorbed viz.,:
BB T
T =
K
H N.
K
Q
= (11.14)
where K denotes the effective heat capacity and N is the number of moles reacted in
the titration. From Eq.(11.14), it is evident that the quantity BB can be used for
obtaining the following informations;
Heat of titration reaction, H, whenever a known amount of titrate is used.
Concentration of an unknown titration, whenever H is known (T is
proportional to concentration and independent of tirate sample size).
Quantity of an unknown in a known volume of titrate.


55
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
Nomenclature
Operationally enthalpograms are thermometric titration curves, where temperature is
experimentally observable variable upon addition of titrant. The basic property which
determines the shape of an enthalpogram is change in enthalpy. This accounts for the
designation Thermomatic titration (TT) and enthalpy titration used in literature.
Other similar terms include Calorimetric titration, thermochemical titration, thermal
titration, similar to the usage for potentiometric/amperometric techniques.

Another type of thermometric titration includes direct injection enthalpimetry (DIE)
which yields a plot of temperature vs the time following injection of the titrant. In this
case end point is not obtained but the magnitude of the temperature change is
proportional to the concentration. The speed of analysis is enhanced and processes
with equilibrium unfavourable for titration are readily studied by using a large excess
of one reagent.
SAQ 7
What does enthalpogram represent and what type of information it provides?
...
...
...
...
11.4.2 Instrumentation
Experimental setup of TT consists of a reagent delivery system (motor driven
automated buret), an adiabatic reaction cell (such as Dewar flask with stirring device),
an electronic temperature sensing system and an amplifying and data processing
system. A typical experimental assembly and adiablatic cell are illustrated in Fig 11.17
and 11.18 respectively. In TT temperature control is most important and depends upon
the results required. Often, it is possible to obtain and paint in titrations simply by
bringing both the sample and the titrant to rooms temperature. However, for precise
calorimetric results the titrant and sample must be close to the same temperature as far
as possible and this is achieved by a thermostat.

Fig. 11.17: Schematic layout for thermometric titration assembly and bridge circuit


56
Thermal Methods

Fig. 11.18: An efficient adiabatic cell for thermometric titrations
A. Delivery Pump: A constant delivery pump permits the time axis of a strip chart
recorder to be used as the volume of titrant axis. Typically a syringe driven by a
synchronous motor which drives the screw is used and solution is delivered at a
constant rate ranging down to few dm
3
per min.

In DIE the syring is rapidly emptied at the start of the experiment to deliver the
titrant instantaneously into the sample cell.

B. Adiabatic Cell: These have widely varying designs ranging from an insulated
beaker to a Dewar flask type cell (Fig. 11.18). All the cells are designed to
minimize the heat transfer from the cell to the environment thus maximizing the
temperature change observed. When only titration end point is of interest, the
simple cell is sufficient. However, if quantities such as heat of reaction,
equilibrium constant or kinetic parameters are sought, it becomes essential to
use better cells which have thin walls to minimize the heat capacity and
maximize the speed of response to temperature change.

C. Calibration Unit: In order to bring the cell quickly to thermal equilibrium, it is
essential to use calibration heater. It has two purposes, to determine the heat
capacity of the system and to control the temperature in the cell itself. The heat
evolved or absorbed is calculated from the temperature change using the
relationship.
Q = TC
p
(11.15)
Where C
p
is the heat capacity of the system which is measured as the amount of
heat necessary to raise the cell temperature by an unit.
D. Temperature Sensing System : It is the heart of thermometric titrator. The
principal temperature sensor is a thermistor which is temperature sensitive
semiconductor whose resistance obeys the Eq. 11.16.
R
T
= A
B/T
e (11.16)



57
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
where A and B are constants whose values depend on the nature of the
thermistor. A thermistor has the advantage of being small size, fast response to
temperature change and chemical resistance.

E. Amplification and Recording: It is often advantageous to amplify the signal
obtained from the thermistor. ADC amplifier is used to obtain good signals for
temperature changes of the order of 10
-4
C or less. For still lower temperature
changes of the order of 10
-6
C, and AC, Wheatstone bridge with a lock in
amplifier is used. The two most popular data acquisition systems are the strip
chart recorder the digital data storage system.

Fig. 11.19: Idealized representation of the four major regions of the TT curve. With a
constant-delivery pump, the x-axis can be in units of time or moles of titrant
Experimental Considerations: An idealized thermometric titration curve is
represented in Fig.11.19 showing four region: region 1 is the baseline which is ideally
horizontal but in practice it always has finite slope due to frictional heat added by
stirring, resistive heat added by the thermistor and the transfer of heat from the cell to
the thermostat. If heating due to friction and resistance are constant and equal to W,
the slope of region I is represented by
W C(Tc-Te)
d
d
+ =
t
T
(11.17)
where c = the heat leak modulus, T
c
= the temperature of the cell, T
e
= the temperate of
the environment.

In case of Region 2 slope is due to similar effects as a in Region 1 and following
cases; temperature change generated by the reaction, the heat of dilution of the
reactants H
d
) and the difference in temperature where between titrant and sample
after the start of titration (T
r
), It is represent by
k T
C
H
t
n
C
H
W T T C
t
T
r
p
D
p
e c
d
d
p
) (
d
d
+
|
|

\
|

+
|
|

\
|
|
|

\
|

+ + = (11.18)


58
Thermal Methods
where k is a constant and n
p
is the fraction product. In Region 3, equivalence point has
been passed and the slope of the curve is described by
r
p
d
T
C'
H
W ) T C(T
dt
dT
+ + + =
e c
(11.19)
After this no more titrant in added and the slope in Region 4 obeys Eq. (11.17). In real
titration, however, a rounding is observed at the equivalence point and this case is
dealt separately.

The Eq. 11.17-11.19 can be combined to obtain the heat of reaction H and if the
production of product (n
p
) is equilibrium, controlled, equilibrium constant K of the
reaction can be calculated as-
G = RT In K = H + TS ... .(11.20)
Analytical Calculations: Knowing the concentration of either the titrant or the
sample, concentration of unknown may be calculated from the volume added to reach
the end point. Heat of reaction is, in general, obtained from the Eq. 11.17 - 11.19.
However, in practice a graphical method is followed. Heat capacity at the mid point of
the curve is obtained by extrapolating the part of the curve in Region III back to region
II and thus measuring Q from the baseline to the extrapolated line at the mid point of
titration (see Example 2 and Fig.11.18)
SAQ 8
What are the essential components of the experimental setup for carrying out
thermometric titration.
...
...
...
...
SAQ 9
Explain why reaction cell should be adiabatic and continuous stirring is required when
the reaction is in progress?
...
...
...
...
11.4.3 Application
Since heat of reaction is the most general property of chemical processes,
thermometric titrations have a wide range of applicability in quantitative analysis. It
includes the determination of the concentration of an unknown substance, the reaction
stoichiometry, equilibrium constant and the thermodynamic quantities G, H and
S. These have been applied successfully to all types of titration processes including
acid-base (neutralization) reactions, redex reactions, precipitation reactions, and
complexometric reactions in media ranging from aqueous at room temperature to
molten salt at 350C. Precision and accuracy of measurements depends largely on the
enthalpy of the reaction involved ranging from 0.2%. Lowest limit of concentration
that can be successfully titrated is 10
-4
M. The main limitation of the method is that it


59
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
is non selective. The nature of information derived from the judicious mathematical
analysis of thermometric titration curves is summarized in Table.11.2.
Example 1
A classical example of thermometric titration is in the titration of boric acid
(K
a
= 6.4 10
-10
) with a strong base (such as NaOH) which is otherwise very difficult
to perform.
Table 11.2: Summary of Application of Thermometric Titrations
Type of Application Information Obtained Procedure

Fundamental
Analytical
Heat of reaction
Free energy of reaction
Entropy of reaction

Reaction Stoichiometry
Concentration of
unknown
From extrapolated ordinate heights
From curvature in equivalence pt.
Region.

From the modynamic equation
End point determination
Direct enthalpimettry

As an illustration, Fig.11.20 shows comparision of potentiometric (pH) and
thermometric titration curves for HCl and H
3
BO
3
with NaOH in dilute Aqueous
solution. The potentiontiometric curves of the two acids (fig.11.20 a) are very different
yielding a large end point inflexion for the HCl (K
a
~ ) and virtually none for boric
acid. However, corresponding enthalpograms (Fig.11.20 b) are strikingly similar,
because the heats of neutralization of the two acids are comparable, -13.5 kcal/mole
for HCI and 10.2 kcal/mole for H
3
BO
3
. As a result H
3
BO
3
can be determined with
better precision and accuracy by thermometric titration compared to potentiometric
method. In the enthalpogram for H
3
BO
3
and NaOH

(Fig.11.20 b), AB represents a
trace of the temperature of the solution before the addition of titrant and C is the end
point. Line BC shows the gradual evolution of heat of reaction. Linear portions of the
curves are extrapolated to give the initial and equivalence points and the vertical
distance between them (BB) gives temperature difference (T) used to evaluate
enthalpy [Eq.(11.14)].

(a) (b)
Fig. 11.20: Comparision of (a) potentiometric and (b) thermometric titration curves for
HCl and H
3
BO
3
with NaOH solution



60
Thermal Methods
Thermometric titraions possess extraordinary potentiality for determining heat of
reaction in a dilute solution rapidly and conveniently so that H values can be set
virtually equal to the ideal thermodynamic parameters corresponding to infinite
dilution.

Non aqueous systems are well suited for thermometric titrations though heat of mixing
of solvent and dilution pose a problem. The lower specific heat of many organic
solvents introduces a favorable sensitivity factor. Under strictly anhydrous conditions,
even diphenylamine, urea, acetamide and acetanilide are readily titrated with
perchloric acid in glacial acetic acid. Lewis bases such as dioxane, morpholine,
pyridine and tetrahydrofuran may be titrated with a Lewis acid such as SnCl
4
in CCl
4
,
benzene and nitrobenzene. TT is very useful for titrating acetic anhydride in acetic
acid Sulfuric acid acetylating bath water in conc. acids by dilution with fuming acids
and free anhydrides in fuming acids.

Analysis of mixtures is possible when the two species have different equilibrium
constants and heats of reaction with the titrant. For example, in the titration of mixture
of calcium and magnesium with EDTA. Calcium (K
f
= 10
11
) reacts first and
exothermally (H = 5.7 kcal/mole) and then magnesium (K
f
= 10
9.1
) reacts
endothermally (H = 5.5 kcal/mole) as illustrated in Fig. 11.21.

Fig. 11.21: Typical curve for thermometric titration of a mixture of Ca
2+
and Mg
2+
with
EDTA
Precipitation and ion-recombination reactions by TT also yield good results. For
example, halide reacts with silver or mercury (II), and cations such as Mn(II) with
EDTA and oxalate. Titration of silver with halide can be carried out at elevated
temperatures in molten state.

Example 2 : To Determine equilibrium constant of complex formation by
thermometric titration. Equilibrium constant of complex formation reaction may be
estimated from enthalpograms when there is distinct curvature near the equivalence
point as shown in (where is Fig. 11.22) Let us consider the reaction.
A + B AB


61
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations

Fig. 11.22: Equilibrium curvature of enthalpograms, illustrating parameters h and h
t

used to estimate equilibrium constants
where equilibrium concentrations [A] and [B] can be calculated using analytical
concentration (A) and (B). Thus we have
[ ] ) ( AB
t
A
h
h
=
[A] = (A) - [AB]
[B] = (B) - [AB] (11.21)

These concentrations are then used to calculate quilibrium constant (K) using the
expression
[ ]
[ ][ ] [ ] [ ] [ ] [ ] AB ) ( AB ) (
) (
B A
AB
t

= =
B A h
A h
K
(11.22)


Consider the reaction between a metal (M) with a ligand (L) to form a complex ML
Initial concentrations for both are given to be 0.015 M. It gives an enthalpogram
similar to Fig. 11.22 where h and h
t
were measured to be 58.2 and 67.9 (0C, cm, mV
or in any other units) respectively wherefrom stability constant of the complex can be
estimated as described in following lines.

At the end point, following relationship holds.
C
L
= 0.0015 = [ML] + [L]
and C
M
= 0.0015= [ML] + [M]
but [ ]
)
`

=
)
`

=
t
L
t
M
ML
h
h
C
h
h
C
[L] = [M] = C
M
- [ML] = C
L
- [ML]
Thus stability constant may be calculated as
[ ]
[ ][ ]
[ ] ( ) ( ) [ ]
3
2 2
M t
M
10 8 . 2
9 . 67 / 2 . 58 015 . 0 015 . 0 9 . 67
2 . 58 015 . 0
ML
L M
ML
=

= =
C h
h C
K

When dilute solutions are used, it may be safely assumed that the measured
thermodynamic parameters are essentially the same as in standard state of infinite
dilution (H
mean
H

).


62
Thermal Methods
SAQ 10
What is the chief limitation of thermometric titrations.
...
...
...
...
SAQ 11
Even after the equivalence point, an increase in temperature is observed. Why?
...
...
...
...
11.5 SUMMARY
In this unit, basic principles, instrumentations and applications of differential
thermal analysis (DTA), differential scanning calorimetry (DSC) techniques and
thermometric titrations are described.
The applications of DTA and DSC are discussed by taking different examples
related to different properties e.g. quantitative and qualitative analysis,
polymorphism , crystallinity, physico chemical transitions etc. The elementary
calculations are discussed to elaborate the topics.
The probable cause of errors, their remedies, interpretation of result and
comparison of DTA and DSC has been discussed keeping the identical
objective of both the techniques.
Thermometric titrations are based on the change in temperature with the
addition of titrant where two quantities are plotted to yield an enthalpogram
involving the determination of heat of reaction used for quantitative
determination of an unknown.
Experimental setup of thermometric titration consists of a reagent delivery
system, an adiabatic reaction cell and an amplifying and data processing system.
Thermometric titrations can be used for studying all types of reactions such as
neutralization, redox, precipitation and complelxometric. It can also be used for
the determination of reactions toichiometry and thermodynamic quantities G,
H, and S.
Non aqueous systems are well suited for thermometric titrations.
In TT, precision and accuracy of the measurements range from 0.2% to 2% with
lowest limit of concentration being 10
-4
M.
11.6 TERMINAL QUESTIONS
1. Calculate the change in entropy for melting of Indium metal at 157.6
o
C the
heat absorbed is 13.6 Cal per gram.


63
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
2. All the thermal analysis instruments have features in common. Discuss these
common features and the way in which the individual techniques differs form
others
3. Estimate the purity of a materials which melts during DSC melting endotherm.
Describe the procedure.
4. What type of standard do you need for the calibration of heat and temperature
of DSC?
5. How DSC can be used for measuring the heat capacity of solid samples. Is a
particular standard required?
6. Explain how thermometric titrations are different than classical titrations.
Discuss their advantages.
7. Why is it essential to calibrate the thermometric titration unit. How is it done?
8. What are the various heat terms involved in different stages of an enthalpogram.
Derive an expression to determine S for a reaction.
9. In a thermometric titration of acid A with a base B, the slopes of four regions
were found to be 1.0x10
-5
, 8.0x10
-4
, and 0.5x10
-5
C/sec respectively. The
overall temperature change was 0-100C and heat capacity of the cell was
determined to be 1.00 cal/C. The titration rate was 6.0 x 10
-8
moles B/sec. And
the titration of B into pure water gave a slope of 2.0 x 10
-5
C/sec. Calculate the
heat of reaction.
11.7 ANSWERS
Self Assessment Questions
1. The relationship is given by Eq. 11.1
A = HmK
where K is the calibration factor. The unit of K can be calculated as:
H m
A
K

=
If A is in cm
2
, m in g and H is J g
1
, then unit of K are given by
1 2
1
2
J cm
g J g
cm

=
2. Important factors are listed in Table 11.1.
3. Using Eq. 11.1 we can get following equation.
|
|

\
|
|
|

\
|
=
x
y
x
y
x y
m
m
A
A
H H
Before substituting m
x
and m
y
, they should be converted in molar quantities.
m
x
= 500/98.4 moles, m
y
= 500/64.3 moles
Therefore, |

\
|
|

\
|
=
4 . 98 / 500
3 . 64 / 500
0 . 60
0 . 45
85 . 6
y
H
= 7.85 kJ mol.
4. PTFE melts 350 C
HPPE melts 100 C


64
Thermal Methods
LDPP melts 125 C
PP melts 175 C
POM melts 210 C
Nylone 6 160 C
Nylone 66 300 C
5. i) In DSC, the sample and reference materials are provided with their own
heating arrangements, as well as their own temperature sensor. In DTA
scheme both sample and reference are heated by the same source.
ii) Calibration factor in DTA is temperature dependent, on the other hand in
DSC, it is independent of temperature in DTA.
6. DSC is preferred for quantitative methods. In DTA, the calibration constant K, is
temperature dependent, therefore, it require extra calibration steps. Further, DSC
is more sensitive technique.
7. Enthalpogram is a titration curve which represents a plot between the volume of
titrant added on x-axis and change in temperature on y-axis.
It provides information as the star and end point of a titration. With its help we
can determine heat of reaction, equilibrium constant of the reaction and kinetic
parameters.
8. Experimental set up of thermometric titration consists of an adiabatic cell
(Dewar flask), delivery pump, and recording unit including ADC amplifier.
9. An adiabatic with negligible or minimum heat transfer losses is required for
accurate determination of heat of reaction and other parameters. It started
maximize the temperature changes as quickly as possible.
10. Thermometric titrations are not suitable for all types of titrations except where a
change in temperature occurs.
11. In most cases dilution of titrant in an exothermic process. Hence after the end
point, if excess amount of reagent is added then it gets diluted resulting in
increase in temperature.
Terminal Questions
1. Entropy change = 13.6 /157.6 =86.29 cal per gram per C.
2.

TGA DTA DSC
Measures thermal effect Measures thermal effect Measures thermal effect
Provide range thermal
stability of materials
Provide range thermal
stability of materials
Provide range thermal
stability of mat
erials
Contains : furnace ,
temperature measuing unit,
atmosphere control unit
and recorder
Contains : furnace ,
temperature measuing unit,
atmosphere control unit
and recorder
Contains : furnace ,
temperature measuing unit,
atmosphere control unit
and recorder


65
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
Dissimilarity
TGA DTA DSC
Measures thermo
Chemical effect
Measures thermo physical
thermo Chemical effect
Measures thermo
physical thermo
Chemical effect with
more sensitively
Provide range thermal
chemical stability of
materials
Provide range thermal:
physical and chemical
stability of materials
Provide range thermal
physical and chemical
stability and also transition
temperature e.g Curie
tempraure.
Contains Thermbalance Contains : Thermocouple
for measuring T
Contains : Seacodary
heater for measure H

3. The heat of fusion H
f
and temperature during melting are measured and a
curve is plotted, the slope gives the melting point, depression (T) due to
presence of impurities in sample and Zero intercept represents the melting point
of a theoretical sample without impurity (T
o
).

Depression of melting point ( T ) can be expressed as

s
f
2
o
T x
H
RT

=
where ,
y
H is the heat of fusion in mol
1
, T
o
is the melting point of the pure
solvent system (substances) in Kelvins and, R is the gas constant and x
s
is the
mole fraction of solute (impurity). This expression can be used to calculate %
impurity in the sample.
Mole % impurity = T
RT
H
2

|
|

\
|

o
f
100
Area under DSC curve gives heat of fusion for the sample.
4. It is recommended to use pure metal standards (99.999% pure) for the
temperature and heat calibration of DSC and DTA. According to the
manufacturers of thermal analysis equipment, one or more standards are needed.
Indium (In) is the commonly used standard for the calibration of temperature
and peak area.
5. For such a measurement sapphire has to be used as a standard. The C
p

determination using DSC requires a run of three different tests as follows: 1-
two pans empty, 2- one pan with the sample, the reference pan remaining empty,
3- one pan with the standard, the reference pan remaining empty. The pans need
to have the same mass, and an identical heating rate has to be used for the three
runs.
6. Thermometric titrations can be performed only for the systems where heat is
evolved or absorbed. In other words these involve change in enthalpy. Further,
these do not require any indicator for the detection of end point. However,
classical titration through require an indicator but these are good for all kinds of
reaction i.e. neutralization, precipitation, redox, complexometric etc. It has the
added advantage that equilibrium constant of reaction can be determined.


66
Thermal Methods
7. It is essential to calibrate the thermometric titration unit so that its heat capacity
may be determined. Further it helps in the earliest of cell temperature.
8. In an enthalpogram represents primarily change in enthalpy and temperature due
to the titration reaction. However, it also involves internal heat evolved or
absorbed.
As per eq. (11.20) RT ln K = S T H + . which as rearrangement gives

T
H
K R
T
H K RT
S

+ =
+
= ln
ln

9. Use Eq. (11.17) and correct Fig. 11.19

The slope in Region 1 corresponds to because T
c
=T
e
. Same equation applies to
Region 4. In this case, however, constant C can be evaluated since w and (T
c
-
T
e
) are known. Value of c is found to be 1.5 10
-4
sec
1
. Heat of dilution factor
in eqn. (11.19) is the difference between the slope f the titration of B into pure
water and the slope in Region 1.
sec / C 10 0 . 1 10 0 . 1 10 0 . 2
5 5 5
P
D
o

= =

C
H

Thus Eq. (11.19) can be solved for T
R
and a value of 1.210
4
sec
1
is obtained.
Finally, are the above information is used in Eq. (11.18) to obtain.

4 P
P
10 1 . 8
d
d

= |

\
|

t
H
C
H

The term
dt
d
P
H
is equal to the titration rate as
P
C is already given. Thus heat of
reaction is
mol / kcal 5 . 13 or mole / cal 10 5 . 13
10 0 . 6
10 1 . 8
3
8
4
=

H
Ans: H = -13.5 Kcal/mole
11.8 FURTHER READING
1. H.H.Willard , L.L.Merrit Jr., J.A. Dean , F.A.Settle Jr., Instrumental Method
of Analysis, Wadsworth Publishing company , USA, 1986.
2. M.E. Brown, Introduction to Thermal Analysis, Kluwer Academic Publisher ,
London, 2001.
3. P.D.garn, Thermoanalytical Methods of Investigations, Academic Press , New
York , 1965.
4. W.W. Wandlandt, Thermal Analysis, Wiley, New York, 1986.
5. A.Blazek, Thermal Analysis, Van Nostrand Reinhold, London,1972 .
6. H.Kmaber , P.D.Garn , Thermal Analysis: Comparative studies on Materials,
John Wiley & Sons, New York, 1974.


67
Differential Thermal
Analysis, Scanning
Calorimetry and
Thermometric
Titrations
7. H.Gunzzler and A.Williams, Hand Book of Analytical Techniques, Wiley
VCH , Weinheim , Vol -2, 2001.
8. G.W.Ewing, Analytical Instrumentation Handbook, Marcel Dekker Inc, New
York, 1990.
9. J.Jiordan, J.Chem. Education, 40, A5(1963)
10. J. Batethel, Thermometric titrations, John Wiley, New York, 1975.
11. N. Jespersen in Instrumental Analysis Eds. H.H.Bauer, G.D.Christian, and
J.E.O Reilly, Second Edn.Allyn and Bacon. Inc. Boston, 1986,p.523.
12. H.H. Willard, L. L. Meritt, J. A. Dean and F.A. Settle, Instrumental Methods of
Analysis, Seventh Edn, Wadsworth Publishing company, Belmont, 1988.
13. R.A. Meyer, Encyclopedia of Analytical Chemistry, John Wiley & Sons Ltd ,
Vol 15, 2000.
14. R.C. Mackenzie, Differential Thermal Analysis, Academic press London, 1970.
15. Skoog, Douglas A., F. James Holler and Timothy Nieman, Principles of
Instrumental Analysis. Fifth Edition. New York. 1998..
16. Dean, John A., The Analytical Chemistry Handbook. New York. McGraw Hill,
Inc. 1995.