THERMAL METHODS OF ANALYSIS

A
PROJECT REPORT

FOR ELECTIVE SUBJECT

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SUBMITTED TO THE
HEMCHANDRACHARYA NORTH GUJARAT UNIVERSITY, PATAN

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IN PARTIAL FULFILLMENT OF
THE REQUIREMENT FOR THE DEGREE OF
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BACHELOR OF PHARMACY

SUBMITTED BY
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TARANG B. VORA
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DEPARTMENT OF PHARMACEUTICAL CHEMISTRY

SHREE S.K. PATEL COLLEGE OF
PHARMACEUTICAL EDUCATION AND RSEARCH.
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GANPAT VIDYANAGAR
KHERVA-GUJARAT

2004-2005
 Certificate

This is to certify that the Project Work for elective subject entitled Thermal

Methods of Analysis represents the bona fide work of Tarang B. Vora,

carried out under my guidance and supervision at the Department of

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Pharmaceutical Chemistry, Shree S.K. Patel College of Pharmaceutical

Education and Research, Ganpat Vidyanagar, during Academic Year 2004-05.

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He has collected the literature very sincerely and methodically. This work is

up to my satisfaction.

_______________
Teacher-In-Charge
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I/c Principal
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Mr. P.U. Patel Dr. N.J. Patel
Asst. Prof. (H.O.D.) M.Pharm, Ph.D.
Dept of Pharm. Chem. of Shree S.K. Patel College of
Shree S.K. Patel College of Pharmaceutical Education and
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Pharmaceutical Education and Research Research

Ganpat Vidyanagar Ganpat Vidyanagar
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Kherva Kherva
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Date:
Place: Ganpat Vidyanagar
 ACKNOWLEDGEMENT

This thesis is on Thermal Methods of Analysis has been prepared for fulfillment of
the academic requirement leading to the bachelor degree in pharmacy. Numerous
people have been instrumental in enabling me to give a concrete shape to my thesis.
Constraints of time and space preclude the mention of all of them here. However, I

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must mention the name of few people who have made of catalytic impact on the
development of thesis.

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First and foremost, I would like to acknowledge to continuous encouragement and
help extended to me by Mr. P.U. Patel for preparing this thesis. Right from the day, I

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started working on it till it was completed; he has been my sole guide, philosopher
and friend throughout the period of my work. But for the spontaneous support and
expert guidance provided by him. This project would not have seen the light of the
day in its present form. His extensive knowledge of subject and way he imparted the
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same to me, enabled one to develop the thesis in a cohesive manner and has kindled
within me a passion for the subject.
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I take this opportunity to place on record my indebtedness to Mr. K. Molvi, Mr. M.B.
Patel, Mr. J.R. Patel, Mr. S.A. Patel and all the other faculty members who have also
contributed a lot, at various stages of my academic career in the institute, in terms of
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valuable knowledge inputs.

I also express my profound gratitude to Dr. N.J. Patel, our principle who has been a
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constant source of inspiration to steer me forward throughout the four years of my

study. I am also thankful to the members of my family not only for their support and
encouragement in my work but also for patiently tolerating my long and irregular
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working hours during the hectic period in which this work was under preparation. I
owe a special thanks to my sister, whose help has been invaluable at various stages,
and especially during the finalization of the thesis. Lastly, I wish to thank my friends
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in the college, as well as the administrative staff for their kindness and support during
the course of my studies.

Tarang B. Vora
 Contents
1. Introduction 1-3

2. Thermogravimetry (TG) 4-15

2.1. Principle 4
2.2. Methodology 6

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2.3. Instrumentation 9
2.4. Application 15

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3. Differential thermal analysis (DTA) 16-26
3.1. Principle 16
3.2. Instrumentatio 21

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3.3. Application 26

4. Differential Scanning Calorimetry (DSC) 27-34

4.1. Principle 27
4.2. Instrumentation
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4.3. Application 34
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5. Thermomechanical analysis (TMA) 35-41
5.1. Principle 35
5.2. Instrumentation 36
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5.3. Application 41

6. Dynamic mechanical analysis (DMA) 42

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6.1. Principle 42
6.2. Application 42

7. Thermometry titration (TET) 43-49

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7.1. Principle 43
7.2. Methodology 43
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7.3. Instrumentation 45
7.4. Application 48
 8. Pyrolysis-gas chromatography & Evolved gas analysis (EGA) 50-53
8.1. Principle 50
8.2. Instrumentation 51
8.3. Application 53

9. Thermomicroscopy (hot-stage microscopy) 54-57

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9.1. Principle 54
9.2. Instrumentation 55
9.3. Application 56

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10. Dielectric analysis 58

11. Microcalorimetry 59

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12. Bibliography 60

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1.
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Introduction
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 Introduction

1. Introduction

Thermal analysis is a method includes a group of techniques in which specific

physical properties of material are measured as a function of temperature. Thermal
analysis instruments measure physical properties like mass, temperature, dimensions,
enthalpy, mechanical properties, optical property, magnetic property, electrical property,

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acoustic property, evolution of gas & particles. There is substantial number of sample
properties on which the effect of heat has been studied, which has to lead to the
development of a number of recognized techniques for which the appropriate

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instrumental is available.

Here are the various methods for thermal analysis.

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Technique Property
Mass Thermogravimetry (TG)

Temperature
e Derivative Thermogravimetry (DTG)
Differential thermal analysis (DTA)
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Enthalpy Differential scanning calorimetry (DSC)
Dimensions Thermodilatometry
Mechanical properties Thermomechanical analysis (TMA)
(thermomechanometry)
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dynamic mechanical analysis (DMA)

Optical properties Thermoptometry or thermomicroscopy
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Magnetic properties Thermomagnetometry (TM)

Electrical properties Thermoelectrometry
Acoustic properties Thermosonimetry & thermoacoustimetry (TS)
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Evolution of radioactive gas Emanation thermal analysis

Evolution of particles Thermoparticulate analysis
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Thermal Methods of Analysis 1

 Introduction

Thermal events are usually studied by recording the change in thermal property
as the temperature is varied to give thermal analysis curve or thermogram. Thermal
events give information about detailed structure and composition of different phases of
given sample.

Thermal analysis is useful in both quantitative & qualitative analysis.

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Quantitative results are obtained from changes in weight and enthalpy as the sample is
heated. The temperature of phase changes and reactions as well as heats of reaction is

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used to determine the purity of materials.

In thermal analysis microprocessor is used to enhance & simplified the

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techniques. Sample is heated at a programmed rate in the controlled environment of the
furnace. Changes in selected properties of a sample are monitored by specific
transducers; which generate voltage signals. These signals are then amplified, digitized,
and stored on a magnetic disk. Data may be displayed or plotted in real time. The
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microprocessor is used to t process the data with a library of applications software
designed for thermal analysis techniques. Multitasking capabilities of some computer
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system allow a single microcomputer to operate several thermal analyzers simultaneously
and independently.
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Thermal Methods of Analysis 2

 Introduction

Here is the schematic diagram of thermal analysis.

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Transducer:

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Thermocouple
Balance
Displacement transducer
Gas detector
Amplifier

Recorder/
Plotter
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Storage

Data
Analysis
Sample
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Sample
Temperatur
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Temperature
controller
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Thermal Methods of Analysis 3

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2.
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Thermogravimetry
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 Thermogravimetry

2. Thermogravimetry

Thermogravimetry also known as thermogravimetric analysis (TGA). Thermogravimetric

analysis is usually of two types.
1) Dynamic TGA: In this type of analysis the sample is subjected to conditions of
continuous increase in temperature usually linear with time.

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2) Isothermal or Static TGA: In this type of analysis, the sample is maintained at a
constant temperature for a period of time during which any changes in weight are
noted.

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2.1 Principle:

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It is based on the very simple principle of monitoring the change in weight of a
sample as the temperature is varied. The result is expresses in the form of a thermogram,
which is a plot of weight versus temperature. By controlling the atmosphere, e.g. with O2
or N2, it may be possible to encourage or suppress oxidation reactions, thus controlling to
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some extant the nature of the thermal events occurring. When sample is heated over the
rang of temperatures, ambient to approximately 1000oC, may materials undergo weight
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changes giving characteristic curves. Where changes can be linked to a particular thermal
event, such as oxidation, or loss of water of crystallization, the size of the step in the
curve can be used for quantitative analysis.
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Some times thermograms are complex, or where changes are subtle, derivative curves
(DTG) can be valuable in interpretation.
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Figure 2.1.1 shows a thermogram of calcium oxalate. And figure 2.1.2 shows a more
complex thermogram & its derivative curve.
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Thermal Methods of Analysis 4

 Thermogravimetry

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Fig.2.1.1

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Fig.2.1.2

Thermal Methods of Analysis 5

 Thermogravimetry

2.2 Methodology:

Samples are placed in a crucible or shallow dish that is positioned in a furnace

on a quartz beam attached to an automatic recording balance.
Above figure shows a TG instrument that contains a taut-band suspension
electromechanical transducer.

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The horizontal quartz beam is maintained in the null position by the current
flowing through the transducer coil of an electromagnetic balance.
A pair of photosensitive diodes acts as a position sensor to determine the

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movement of the beam.
Any change in the weight of the sample causes a deflection of the beam ,
which is sensed by one of the photodiodes.

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The beam is then restored to the original null position by a feedback current
sent from the photodiodes to the coil of the balance.
The current is proportional to the change in weight of the sample.

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Linear heating rates from 5 to 10C/min are typical.
Sample size range from 1 to 300 mg.
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Computer software allows the computation of w/ t, which is important in
kinetic interpretations of reaction and processes.
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Thermal Methods of Analysis 6

 Thermogravimetry

Factors affecting Thermogravimetry analysis

There are two types of factors which affect TGA
Instrumental factors
Sample characteristics

Instrumental Factors

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1. Heating rate:
If the heating rate is fast a narrow region of constant weight might be recorded.

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And very slow rate is employed; time taken for recording a thermogram will
become very long. In practice, an optimum heating rate of 5-10oC/min is
employed.

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2. Furnace atmosphere:
The nature of the atmosphere surrounding the sample in the furnace can have a
marked effect upon the temperature of the decomposition stage. For example;
decomposition of Calcium Carbonate occurs at a higher temperature in a
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carbondioxide atmosphere rather than when a nitrogen atmosphere is employed.
3. Crucible geometry:
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The geometry of the crucible can alter the slope of the thermogravimetric curve.
Generally, a flat shaped crucible is preferred to a cone one because the diffusion
of any gases is easier with the former type.
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Sample characteristics

Thermogravimetric results are governed by the weight-particle size and

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the mode of preparation the sample. Large volume of sample can often create a
deviation from linearly if the temperature rises. A large volume in crucible can
impede the evolved gases through the bulk of the solid large crystals. Other
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samples may swell, foam and even bubble. In practice, a small sample weight is
desirable for thermogravimetry.
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Method of preparation

Method of preparation of sample is also affect the shape of TG curve.

For example Mg(OH)2 obtained by naturally occurring and also prepared by
precipitation method. Both have different temperature of decomposition.

Thermal Methods of Analysis 7

 Thermogravimetry

Disadvantage:

Limited to samples which undergo weight changes, thus melting, crystal

phase changes etc. cannot be studied. Complex thermal traces are often difficult to
interpret.

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Thermal Methods of Analysis 8

 Thermogravimetry

2.3 Instrumentation for Thermogravimetry

The principles of TG are based on the fact that the sample be continuously
weighed as it is heated to elevated temperatures. The sample is continuously weighed by
an instrument, called a thermobalance. Both manual and automatic recording balances
have been built, but for practical reasons the automatic balance is preferred.

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An automatic thermogravimetric analyzer consists of the following parts:
1. a sensitive analytical balance

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2. a furnace
3. a furnace temperature controller & the programmer
4. a recording device

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Fig.2.3.1

Schematic diagram of an automatic thermogravimetric analyzer.

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Thermal Methods of Analysis 9

 Thermogravimetry

Criteria for a good thermobalance are as follows:

It should be capable of continuously registering the weight change of the sample

as a function of temperature.
The temperature should be recorded to an accuracy of better than 1C.
Furnace should reach the maximum desired temperature.

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The rate of heating should be linear and reproducible.
Sample holder should be in the hot zone of furnace & this zone should be of
uniform temperature.

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It should cover a wide range of temperature even up to 2000C or more.
It should have facilities for the provision of variable heating rates.

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Balance mechanism should be protected from the furnace & from effect of
corrosive gases.
Balance should be sufficient sensitive for studying small sample weights.
It should have a high degree of electronic and mechanical stability.
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Criteria for a good furnace:
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Furnaces which operate at maximum temperature up to 2000C have been
described. They are constructed as to allow easy access to the sample holder and
also to cool down rapidly after the completion of a run.

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Furnace design and control must be able to provide a suitable smooth input so that
it can maintain either a linear heating programme or fixed temperature.
Nichrome winding and Pt-Rh windings have been found to permit a temperature of
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1000C and 1450C respectively. Higher temperature can also be obtained using a
graphite tube furnace, but difficulty arises in the control and measurement of the
temperature.
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Thermocouple
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Thermocouple is used for measuring temperature. A cromel-alumel thermocouple

is suitable for temperature measurement up to 1100C. For temperature up to 1750C,
thermocouples made of Pt alloys and rhodium is used. For still higher temperature
tungsten and rhenium thermocouples are suitable.

Thermal Methods of Analysis 10

 Thermogravimetry

Furnace temperature programmer and controller:

Various heating rates have been employed in TGA work, from 0.5 to several
hundred C per minute. Generally a heating rate of 5Cper minute is preferred which
should bee linear w.r.t. time.
There are more than 15 manufacturers of thermobalance and some of them

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produce several models. The weighing mechanism may be modification of a single or
double pan balance, an electronically self balancing device, a torsion balance, or a simple
spring balance.

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Thermal Methods of Analysis 11

 Thermogravimetry

Types of recording thermo balances

Recording thermobalance are two types:
1) Deflection type. 2) Null type.
Deflection balances:
Are further divided in to four important categories.

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a) Beam type:-
In these balances, a conversion of beam deflection about the fulcrum into a
suitable identifiable weight change curve takes place by either of the following.

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1) By photographic recorded trace
2) By recorded signals generated by suitable displacement measuring
transducers

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3) Electromechanically drawn curves

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Fig.2.3.2
Schematic diagram of the components of the beam type thermo balance.

Thermal Methods of Analysis 12

 Thermogravimetry

b) Helical type:-
In these balances, an elongation or contraction of the spring takes place as
a result of weight change. Transducers are used for recording this change in length
of the springs. Quartz fiber is most widely used as a fiber, because it avoids
fatigue problems as well as anomalous results expected by change in temperature.
c) The cantilever beam type:-

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In these balances, one end is kept fixed and other end is free to undergo
deflection and it contains the sample. The deflection measurements are similar to

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beam type balance.
d) Torsion wire:-
In these balances, the beam is attached to a taunt wire acting as the

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fulcrum. This wire is firmly fixed at any end or at both the ends and deflections in
the beam is thus proportional to weight changes in the sample. A metallic ribbon
may also be used instead of taunt wire. In such a case detection devices are similar
to those used in beam type instrument.
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Null point balances:
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These balances are however, more commonly used. In these balances, a sensor is
employed to detect the deviation of the beam from its null point position. A restoring
force of electrical or mechanical weight load is then applied to the balance beam in order
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to restore its null point position from the horizontal or vertical norm. The weight change
is proportional to this restoring force, which can be recorded directly or by making use of
a transducer.
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Thermal Methods of Analysis 13

 Thermogravimetry

Sample holder

Geometry, size and material of the sample holder or crucible have a marked
influence on the shape of a TG curve. The nature of the sample, its weight and maximum
temperature range to be studied depend upon the size and shape of the sample holder,
which may be constructed from glass, quartz, alumina, stainless steel, platinum, graphite,

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metals and various alloys.

There are mainly four types of sample holder.

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1) Shallow pans:-
This type of sample holder is suitable where it is necessary to eliminate diffusion
as the rate controlling step. This is due to as a result of decomposition of a sample,

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volatile material in the form of gas or other volatile matter is formed throughout the
pyrolysis and so it should diffuse to the surface instantaneously to escape so that
weight loss may be recorded immediately. In such reactions, where side reaction
occur. For example in case of polymers, the sample is arranged in thin layers, so that
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volatile matter formed may escape freely.
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2) Deep crucibles:-
These crucibles are successfully employed in the following cases.
a) In the study of industrial scale calcinations
b) In surface area measurement
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c) In partial equilibrium reactions

d) In reactions where side reactions are desired
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3) Loosely covered crucibles:-

These crucibles are suitable when rate of weight loss and not the exact
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temperature is taken into consideration, as in case of self-generated atmosphere

studies.
4) Retort cups:-
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These cups, which resemble alchemist retorts, are suitable in boiling

point studies.

Thermal Methods of Analysis 14

 Thermogravimetry

2.4 Application

Automatic gravimetric analysis.

New weighing compositions in analysis and determination of their thermal
stability ranges.
Weighing substance which is unstable at ambient temperatures such that those

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which absorb CO2 & H2O from air.
Determination of the composition of complex mixture.
Determination of the purity and thermal stability of analytic reagents, including

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primary and secondary standards.
Correction of errors in gravimetric analysis.

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For studying the sublimation behavior of various substances.
For deciding whether or not a precipitate should be dried or ignited.
Discovery of new method of separation.
For the evaluation of various filtration techniques, such as ignition of filter paper.

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For the study of properties of materials in relation on the methods useful for their
preparation.
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For the determination of the composition of complex materials such as carbon-
black.
For the evaluation of suitable standards in analytical chemistry by combined TG
studies with infra red absorption spectrophotometric studies.
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TG has been used in the kinetic analysis of polymer stability, compositional

analysis of multicomponent materials, atmospheric analyses and corrosion
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studies, moisture and volatiles determinations, and accelerated tests of aging.

Thermogravimetric analysis has also been used in sample purity testing.
By making use of DTA in conjugation with TGA and using a derivatography, a
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large number of organic compounds have been studied in order to get various
results.
Thermogravimetric analysis is used for study of drying and ignition temperatures.
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Thermal Methods of Analysis 15

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Differential
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Thermal Analysis
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 Differential thermal analysis

3. Differential thermal analysis (DTA)

Differential thermal analysis is also known by thermography.

3.1 Principle:
Differential thermal analysis is based on the principle of monitoring of the
temperature between a sample and a thermally inert reference material as they are heated

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uniformly. In differential thermal analysis the difference in temperature between sample
and thermally inert reference material is measured as the function of temperature. In
differential thermal analysis usually alumina, silicon carbide or glass beads are used as

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reference compound.

In differential thermal analysis temperature of sample and reference compound both are

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increased at constant rate. If the sample does not undergo any physical or chemical
change then there is no temperature difference between the sample (S) and reference (R).
If there is a physical or chemical change takes place, and then the temperature of the
sample will be different from that of the reference resulting in a temperature difference T.
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if the sample absorbs heat, then the temperature of the reference (TR) will be higher than
that of the sample (TS), so TS- TR will be negative which indicates Endothermic reaction.
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In other hand, if the sample emits heat, the temperature of the sample of the sample (TS)
will be the higher than that of reference (TR), so TS-TR will be positive which indicates
exothermic reaction.
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A typical DTA curve is shown as below.

Figure: 3.1.1
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Thermal Methods of Analysis 16

 Differential thermal analysis

The maxima and minima such as those appearing in this figure are termed
peaks. Those appearing above zero on the ordinate scale are the consequences of
exothermic processes, whereas those peaks below zero correspond to endothermic
processes. These heat changes may be the result of physical or chemical phenomena.
(1) Physical processes such as crystalline rearrangement, solid-phase transitions, fusion,
vaporization, sublimation, and dehydration give rise to endotherm.

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(2) Physical processes like adsorption and crystallization give rise to endotherm.
(3) Chemical reactions can give rise to exotherms or endotherms. Oxidation reaction,

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however, give rise to exotherms only.
(4) Among endotherms, sharp endotherms are indicative of crystalline rearrangements-
fusion and/or solid state transitions. Broader endotherms usually result from

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dehydration or melting of polymers.
(5) Among exotherms, narrow exotherms indicate crystallizations, while broad
exotherms denote chemical reactions or polymerizations.
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Thermal Methods of Analysis 17

 Differential thermal analysis

Factors Affecting Differential Thermal Analysis:

The DTA curve of a substance is not strictly reproducible, probably due to the
factors caused by the instruments and those depending upon the characteristics of the
sample. The factors caused by instrument are furnace atmosphere, size, shape of the
furnace, sample holder geometry, heating rate, speed and response of recording device

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and thermocouple location in the sample chamber. Particle size, thermal conductivity,
heat capacity, packing density, amount of sample, swelling or shrinkage of the

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sample, effect of diluents and degree of crystallinity are the other factors which
depend upon the sample characteristics

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Furnace atmosphere:
The DTA technique is very sensitive to the gaseous environment around the
sample. The gaseous atmosphere may react with the sample, and as a result, extra
peaks are expected to be obtained in the curve. For example, Oxygen of the air may
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cause oxidation giving rise to an exothermic reaction peak.
The gaseous atmosphere in DTA may either be static gaseous atmosphere or dynamic
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gaseous atmosphere.

Geometry of the sample holder:

The resolution, size and shape of the DTA curve peaks are greatly influced
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by the geometry and material used in the preparation of the sample holder.

Thermal conductivity and resistance:

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If the wires used in temperature sensing devices are much thick, more
distortion of the peak heights and peak temperatures are expected to take place, while
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reverse is the case if thin wires are used for the same purpose. A compromise is made
here because of the fact that thin wires have much higher resistance and they are also
not suitable in impedance matching.
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Thermal conductivity and hence the rate of flow of heat os clearly influenced by
packing density.

Thermal Methods of Analysis 18

 Differential thermal analysis

Position of temperature measuring and differential thermocouple:

The intensity of the peak, shapes of the peaks and base line are greatly
influenced by the position of the temperature measuring and differential
thermocouples. Best results are obtained by plotting differential temperature against
the sample temperature.

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The base line is greatly affected by non-uniformed winding used in the furnace. The
commercially available instruments employ machine wound furnace windings and so
this problem is much solves there.

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Heating controller:
In order to get a constant heating rate for DTA, on-off type controllers are

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not used. Because considerable noise may occur, partially at temperatures above
700oC. Motor driven variac in conjugation with a proportional position adjusting type
controller is most suitable for this purpose.
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Heating rate:
DTA curve is also influenced by heating rate. Higher heating rate, higher the
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peak temperature and deeper the peaks. The most appropriate rate is 10o-20o per
minute.

Effect of diluents:
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The area of DTA peak is greatly change if the sample is diluted with some
inert substance.
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Effect of recorder:
DTA curve also influenced by the type, span, chart speed and pen response
of a recorder. The DTA peaks get flattened out on case of faster chart speeds. For
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transient heat effects a rapid pen response is desirable.

Particle size:
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Particle size of the sample also affects the packing density and thermal
conductivity of the sample. The peak area has been found to decrease with increases
generally, as the particle size increases.

Thermal Methods of Analysis 19

 Differential thermal analysis

Quantity of sample:
Peak area also depends upon the quantity of the sample. But in case of
cylindrical sample holders and fixed location of thermocouple, no increase in peak
area is observed with an increase in the amount of the sample.
Peak intensity as well as temperature increase with increasing weight of the sample.
In case of similar amount of sample, the resolution is greatly influenced.

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Similarly, other factors, such as degree of crystallinity of the sample, chemical
reactivity of the sample, the thermocouple material, the ambient gaseous environment

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etc greatly influence the DTA peaks.

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Disadvantages:

Small sample sizes are often required to minimize thermal conductivity problems.
Less satisfactory than DSC with regard to resolution of thermal traces and
quantitative data.

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Difficulty of linking the thermal changes shown on the thermogram with the
actual thermal process taking place.
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Thermal Methods of Analysis 20

 Differential thermal analysis

3.2 Instrumentation DTA

The apparatus required for DTA consists of the following components:
(1) Furnace
(2) Furnace temperature control system
(3) Furnace atmosphere control

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(4) Amplifier
(5) Recorder as
(6) Sample holder

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A typical Differential Thermal Analyzer is shown in Figure 3.2.1

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Figure: 3.2.1

Thermal Methods of Analysis 21

 Differential thermal analysis

The essential instrumentation for DTA involves a single furnace containing both
the sample and reference which are heated at the same rate. The temperatures of the
sample and reference are measured separately by individual thermocouples. A
thermogram is then plotted of the difference in temperature between sample and
reference against overall furnace temperature.
In below figure 3.2.2 DTA apparatus is shown:

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Figure: 3.2.2

Thermal Methods of Analysis 22

 Differential thermal analysis

The most commonly used temperature detecting device is the thermocouple

which is constructed from chromel vs. alumel, copper vs. platinum-10-13% rhodium
and others. Thermopiles, thermistors and resistance thermometers have also been
employed for the same purpose. The choice of temperature detection device also
depends upon the maximum temperature desired, chemical reactivity of the sample,
sensitivity of D.C. amplifier and recording instrument. For temperature up to 1500 C,

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a platinum couple is most satisfactory; for fairly low temperatures, up to 300 C,
copper couple is recommended and for general purposes up to 1000 C, a chromel

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alumel couple is suitable.

The choice of furnace geometry and heating element also depends upon the

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temperature range to be studied. The furnaces which cover the range from-190 to
2800 C have been in use and they can be heated by a resistance element, infra red
radiation, high frequency r, f, oscillator or by a coil of tubing through which a heated
or cooled liquid or gas is circulated. Resistance elements, made of such material as
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Nichrome, platinum, rhodium, globar, molybdenum and tungsten have widely been
employed.
bn
In the first the sample and reference are heating block (Figure 3.2.3). This arrangement is
known as a classical DTA instrument. In the second arrangement, the sample and
reference pans are placed on separate heating blocks or heat sinks, with the temperature
fli

of the block being measured, rather than the sample itself (Figure 3.2.4). Such an
arrangement comprises a calorimetric or Boersma DTA instrument.
in
u.
gn

Figure: 3.2.3 Figure: 3.2.4

Classical apparatus Calorimetric or Boersma apparatus

Thermal Methods of Analysis 23

 Differential thermal analysis

The temperature rise of the furnace is usually controlled by either increasing

the voltage through the heater element by a motor driven variable transformer or by a
thermocouple. The most commonly used rate is 10 to 15 per minute.

Strip chart recorders or galvanometric recorders or an X-Y recorder is used for

recording the amplifier T signals as a function of temperature or time.

in
Sample holder:

Various containers have been used to contain the sample and reference material.

c.
They are usually made of alumina, borosilicate glass, fused quartz, zirconia, beryllia,
stainless steel, nickel, platinum, silver, aluminum, graphite and the sample it self. The

t.a
choice of the material depends upon the sample and temperature range to be studied.
There should be no reaction between sample and container during pyrolysis. When three,
four, five or six samples are to be studied simultaneously, multiple sample holders have
been employed.
e
Some common types of sample holders are illustrated in figure: 3.2.5
bn
fli
in
u.
gn

Thermal Methods of Analysis 24

 Differential thermal analysis

Figure: 3.2.5

in
c.
e t.a
bn
fli
in
u.
gn

Thermal Methods of Analysis 25

 Differential thermal analysis

3.3 Applications

The combination of exotherms and endotherms will be unique to a particular

sample composition. Thus the pattern of the thermogram can be used as finger
print for qualitative analysis, whilst the areas under the curve may be used for
quantitative analysis. These principles can be widely applied to samples of very

in
different types, e.g. Minerals, inorganic compound, pharmaceuticals, polymers,
foodstuffs and biological specimens. Typical samples sizes are from 1 mg
upwards allowing, where necessary, for measurements to be made on small

c.
samples.
DTA may be used effectively in simple characteristics of a specimen. On the

t.a
other hand much more complex systems may be usefully studied.
Study of inorganic substances: DTA has been widely used for studying the
thermal behaviour of inorganic compounds such as silicates-ferrites, clay, oxides,
ceramics and glasses.

e
Study of organic compounds: DTA provides a simple and accurate method for the
determination of the melting point, boiling point and the decomposition points for
bn
organic compounds.
Study of polymers: DTA thermograms can be used in the characterization of
polymeric materials.
As a control technique, it can be used to distinguish between raw materials
fli

quickly and easily in those cases where the treatment of the material must be
modified if slight changes in the material are noticed.
in

For the investigation of various solid phase reactions, phase transformation, and
investigation regarding kinetics and phenomena associated with polymeriszation,
thermal and oxidative degradation, solvent extraction can be elegantly carried out
u.

by using differential thermal analysis.

Thermograms of typical explosives and propellants provide useful information
regarding the manufacture, storage and application of these high energy materials.
gn

Determination of moisture content of powdered substances.

Formation of derivatives of organic compounds is also possible in a DTA sample
chamber.

Thermal Methods of Analysis 26

 in
c.
e t.a
bn
fli

4.
in

Differential
u.

Scanning Calorimetry
gn
 Differential scanning calorimetry

4. Differential Scanning Calorimetry (DSC)

4.1 Principle

Sample and an inert reference heated separately, with the power supply to the
sample heater variable so that the temperature difference can be maintained at zero even
when endothermic or exothermic changes occur. The difference in power supplied to the

in
two heaters is monitored as the analytical signal (E). Alternatively, the difference heat
flow to sample and standard when they are heated from the same source is monitored. A
schematic representation of the variation of power supply to the sample and reference in

c.
DSC in Fig: 4.1.1 and DSC curve in Fig: 4.1.2

t.a
Figure: 4.1.1

e
bn
fli
in
u.
gn

Thermal Methods of Analysis 27

 Differential scanning calorimetry

Figure: 4.1.2

in
c.
e t.a
bn
fli

In this technique, the sample and reference materials are subjected to a precisely
programmed temperature change. When a thermal transition (a chemical or physical
in

change that results in the emission or absorption of heat) occurs in the sample, thermal
energy is added to either the sample or the reference containers in order to maintain both
the sample and reference at the same temperature. Because the energy transferred is
u.

exactly equivalent in magnitude to the energy absorbed or evolved in the transition, the
balancing energy yields a direct calorimetric measurement of the transition energy. Since
DSC can measure directly both the temperature and the enthalpy of a transition or the
gn

heat of a reaction, it is often substituted for differential thermal analysis as a means of

determining these quantities except in certain high-temperature applications.

Thermal Methods of Analysis 28

 Differential scanning calorimetry

Arrangement of temperature sensors in DSC are shown in the following figures.

in
c.
Figure: 4.1.3
e t.a Figure: 4.1.4

In the figure 4.1.3 temperature sensors are placed in the sample holder while in
bn
figure 4.1.4 temperature sensors are placed at the bottom of the sample holder.

The change in enthalpy, H, of the sample is equal to the difference between the heat
flow to or from the sample, QS, and the heat flow to or from the reference material, Qr
fli

(H is used to indicate that the heat flow is the change in enthalpy.):

H = Qs Qr
in

According to the thermal analog of Ohms law,

Q = T2 T1 Rth
The heat flow is proportional to the driving force (the temperature difference between
u.

temperatures T1 and T2) and inversely proportional to the thermal resistance, Rth.
combining the preceding relationships yields
H = Qs Qr = Tc Ts / Rth Tc Tr / Rth
gn

Where Ts is a constant temperature external to the sample and reference, Ts is the sample
temperature, and Tr is the reference temperature. The system is so designed that the two
Tc and two Rth values are identical. Thus Equation 2.3 reduces to
H = Ts Tr / Rth

Thermal Methods of Analysis 29

 Differential scanning calorimetry

The measured signal is the voltage from the thermocouple or thermopile, which is
proportion to the temperature difference, Ts Tr .

Integration of the area under a DSC curve provides a direct measurement of H for
thermally induced transitions according to the equation
A = -kmH

in
Where A is the area; k the instrument constant, which is independent of the temperature;
m the mass; and H the enthalpy of the reaction or transition.

c.
Pressure DSC

The ability to control the pressure of the atmosphere above the sample is often

t.a
useful in DSC analysis. Applications of this technique include studies of pressure
sensitive reactions, evolution of catalysts and resolution of overlapping transitions.

Disadvantage:
e
Usually limited to small sample sizes. Thermogram is often complex and thus
bn
difficult to interpret fully.
fli
in
u.
gn

Thermal Methods of Analysis 30

 Differential scanning calorimetry

4.2 Instrumentation DSC

A DSC instrument contains sample and reference crucibles with separate

heaters. Thermocouples with feedback to sample heater so that the power is varied to
maintain T = 0. Data output equipment to provide E vs. temperature curves, derivative
curves and peak integration. Facility to vary atmosphere of sample.

in
A typical DSC cell uses a constant (Cu-Ni) disk as the primary means of
transferring heat to the sample and reference positions and also as one element of the

c.
temperature-sensing thermoelectric junction. The sample and a reference are placed in
separate pans sit on raised platforms on the disk. Heat is transferred to the sample and
reference through the disk. The differential heat flow to the sample and reference is

t.a
monitored by the chromel/constant thermocouples formed by the junction of the constant
disk and the chromel wafer covering the underside of each platform. Chromel and alumel
wires connected to the underside of the wafers from a chromel/alumel thermocouple,
which is used t directly monitor the sample temperature. Constant calorimetric sensitivity
e
is maintained by computer software, which linearizes the cell-calibration coefficient.
DSC provides maximum calorimetric accuracy from -170 to 750 oC. sample sizes range
bn
from 0.1 to 100 mg.
In the figure DSC cell cross section is shown in figure: 4.2.1
fli
in
u.
gn

Figure: 4.2.1

Thermal Methods of Analysis 31

 Differential scanning calorimetry

For power DSC

The equipment for power-compensated DSC involves two parallel temperature
measurement systems. Sample (ca. 50mg) and reference in small pans are placed on the
separate blocks (figure 4.2.2). Each block is provided with a separate heater and
thermocouple with feedback to the heaters so that the power supply can be varied as
necessary to ensure that T = 0 at all times as the temperature is raised overall. A

in
thermogram is then generated by monitoring the difference in power supplied to the two
heaters (E) and plotting this against the overall temperature. Data presentation at its

c.
simplest may be on a chart recorder, but increasingly microcomputers or microprocessors
are used to give added flexibility to the presentation. Built into the system will be a
facility to control the atmosphere of the sample. For heat flux DSC the sample and

t.a
reference in separate containers are placed on separate platforms which sit on a heated
metal (Cu/Ni alloy) disc. Thermocouples are placed to monitor the heat flow from the
disc to the sample and standard. The differential heat flow will then reflect the different
thermal behavior of the sample and standard. A plot of this against overall temperature
e
produces a graph analogous to those from power-compensated DSC. Calibration is by use
of standards (e.g. indium) with accurately known thermal characterization.
bn
Figure: 4.2.2
fli
in
u.
gn

S = sample
R = reference

Thermal Methods of Analysis 32

 Differential scanning calorimetry

Precise determinations require enlargement of the thermogram for accurate area

measurements and a time base display rather than the temperature-based thermogram.
Also, precise quantitative heat capacity measurements are typically made at high
sensitivity settings. The data stored on disks are recorded at maximum sensitivity.
Thermogram can be replotted over a temperature range and on a scale selected by the
operator. Temperature expansion to 0.2 C /cm is possible. When this feature is

in
combined with a high calorimetric sensitivity of 0.01 mW/cm, thermal occurrences that
produce very small amounts of heat can be recorded. For maximum accuracy, a baseline

c.
id obtained and subtracted from the sample thermogram to determine the heat capacity
Heats of transitions are calculated from stored data by the applications software of the
microcomputer.

e t.a
bn
fli
in
u.
gn

Thermal Methods of Analysis 33

 Differential scanning calorimetry

4.3 Applications

Widespread study of thermal properties in an extensive range of sample types.

Qualitative and quantitative analysis. Relative precision is very variable, at best
ca. 1% but can be poorer.
DSC essential studies the same thermal phenomena as DTA, albeit using a

in
different principle. Thus DTA and DSC provide very much the same information
and their applications are similar. Reference back to the section on the
applications of DTA will suffice to indicate the scope of DSC. Some difference

c.
in the quality of the information obtained sometimes exist however, leading to a
preference for one technique over the other for particular purpose.

t.a
DTA and DSC

The experimental set up for heat flux DSC is very similar to that for calorimetric
or Boersma DTA. Thus heat flux DSC will have the same freedom from the
e
thermal properties of the sample and slower response times associated with
Boersma DTA. DSC will generally have better resolution. Finally, by measuring
bn
the power different, DSC is making a direct measurement of enthalpy changes
and is thus the more satisfactory tool for thermodynamic measurements.
fli
in
u.
gn

Thermal Methods of Analysis 34

 in
c.
e t.a
bn

5.
fli

Thermomechanical
in

Analysis
u.
gn
 Thermomechanical analysis

5. Thermomechanical analysis (TMA)

5.1 Principle:
Measurement of the effect of heat on the mechanical properties of a sample, e.g.
expansion, compression, penetration, extension and resonant frequency of oscillation as

in
function of temperature. As shown in figure the core is coupled to the sample by means
of a quartz probe that contains a thermocouple for measurement of the sample
temperature. Any movement of the sample is translated into a movement of the

c.
transformer core and results in an output that is proportional to the displacement.

e t.a
bn
fli
in
u.
gn

Thermal Methods of Analysis 35

 Thermomechanical analysis

5.2 Instrumentation

A TMA analysis will need to measure accurately both the temperature of the
sample, and very small movements of a probe in contact with the surface of the sample.
A typical analyzer, as illustrated in figure 5.2.1 and figure 5.2.2

in
c.
e t.a
bn
fli

Fig: 5.2.1
in
u.
gn

Thermal Methods of Analysis 36

 Thermomechanical analysis

in
c.
e t.a
bn
fli
in
u.
gn

Fig: 5.2.2

Thermal Methods of Analysis 37

 Thermomechanical analysis

The typical apparatus, diagrammed in fig.5.2.1 & 5.2.2 is a probe connected

mechanically to the core of a linear variable different transformer (LVDT). The core
is coupled to the sample by means of a quartz probe that contains a thermocouple for
measurement of the sample temperature. Any movement of the sample is translated
into a movement of the transformer core and results in an output that is proportional
to the displacement. The temperature range is from that of liquid nitrogen to 850 C.

in
In the penetration and expansion modes, the sample rests on a quartz stage

c.
surround by the furnace. Under no load, expansion with temperature is observed. The
thermal coefficient of linear expansion is calculated directly from the slope of the
resulting curve. A weight tray attached to the upper end of the probe allows a

t.a
predetermined force to be applied to the sample to study variations under load. Probes
with a small tip diameter and a loaded weight tray are used when the sensitive
detection of softening temperatures, heat-diameters and zero loading are used in the
expansion mode when coefficients of expansion and dimensional changes due to
e
stress relief are the objects of investigation. Sample down to a few micrometers are
observable.
bn
For the measurement of samples in tension, the sample stage and probe are
replaced by a sample holder system consisting of stationary and movable hooks
constructed of fused silica. This permits extension measurements on films and fibers.
fli

Holes about 0.6 cm apart are punched into injection-molded pieces or solution-cast or
extruded films; also a fiber fused into a loop can be used for this test. The double-
in

hook probe is designed to grasp a pair of aluminum spheres that are crimped on to
either end of a fiber sample. Measurements made with these probes are related to the
tensile modulus of a sample.
u.

Volume-expansion characteristics of samples are measured by placing the

sample in quartz cylinder fitted with a flat-tipped quartz probe in a cylinder-piston
gn

arrangement. Sample volume changes are translated into linear motion of the piston.

Thermal Methods of Analysis 38

 Thermomechanical analysis

Uses of quartz probe containing a thermocouple for temperature measurement,

and is coupled to the core of a linear variable differential transformer (LVDT). Small
movements at the sample surface are transmitted to the core of the LVDT and converted
into an electrical signal. In this way samples ranging from a few microns to centimeter
thicknesses may be studied with sensitivity to movements of a few microns. For studying
different mechanical properties the detailed construction of the probe will vary as is

in
illustrated in figure 5.2.3

c.
e t.a
bn
fli

Figure: 5.2.3
in
u.
gn

Thermal Methods of Analysis 39

 Thermomechanical analysis

Quartz probes fitted with thermocouples to measure the temperature and follow
the movement of the sample. Linked transducer, i.e. a linear variable density transformer
to sense the probe movement and produce a related electrical signal. Sample furnace,
programmers and various output devices.

Disadvantage

in
Information is restricted largely to mechanical properties and cannot easily be
related to the actual composition of a sample.

c.
.

e t.a
bn
fli
in
u.
gn

Thermal Methods of Analysis 40

 Thermomechanical analysis

5.3 Applications

TMA has mainly been used in the study of polymers. The mechanical properties
study may be used to characterize a polymer as well as to assess its mechanical
utility. There is an obvious application to quality control. The ability to study
small specimens gives the technique a distinct advantage over more traditional

in
methods of mechanical testing if sample size is limited.
Investigation of the mechanical properties of a range of materials, especially

c.
polymers, and their change with heating over the range -100C to 1000C.
Quality control of mechanical properties.
The ability to study small specimens gives the technique a distinct advantage over

t.a
more traditional methods of mechanical testing if sample size is limited.

e
bn
fli
in
u.
gn

Thermal Methods of Analysis 41

 in
c.
e t.a
bn
fli

6.
in

Dynamic
u.

Mechanical Analysis
gn
 Dynamic mechanical analysis

6. Dynamic mechanical analysis

6.1 Principle:
An associated technique which links thermal properties with mechanical ones is
dynamic mechanical analysis (DMA). In this, a bar of the sample is typically fixed into a
frame by clamping at both ends. It is then oscillated by means of a ceramic shaft applied

in
at the centre. The resonant frequency and the mechanical damping exhibited by the
sample are sensitive measurements of the mechanical properties of a polymer which can

c.
be made over a wide range of temperatures. The effects of compositional changes and
methods of preparation can be directly assessed. DMA is assuming a position of major
importance in the study of the physico-chemical properties of polymers and composites.

t.a
6.2 Application

DMA is helpful in determining the effectiveness of reinforcing agents and

e
fillers used in thermoset resins.
Also used to determine physical properties important in production of
bn
multilayer printed circuit boards.
DMA is used in the study of the physico-chemical properties of polymers and
composites.
fli
in
u.
gn

Thermal Methods of Analysis 42

 in
c.
e t.a
bn
fli
in

7.
u.

Thermometry
gn

Titration
 Thermometry titration

7. Thermometry titration

7.1 Principle
Thermometric enthalpy titrations (TET) and direct injection enthalpimetry
(DIE) are the two main types of enthalimetric analysis. Since practically all chemical
reactions are accompanied by heat effect, the course of a reaction can be easily

in
followed by observing the heat liberated. Thus in thermometric titrations once utilizes
heats of reaction to obtain titration curves. The latter are obtain by plotting changes in
solution temperature against volume of titrant.

c.
7.2 Methodology

t.a
Contrary to various types of potentiometric titrations that depend solely on the
equilibrium constant, K, and therefore on the free energy of the reaction, G, or
-G = RT ln K
e
where R is the gas constant and T is the Kelvin temperature of the reaction, thermometric
titrations depend only on the enthalpy of the reaction, H, or
bn
H = G T S

Where S is the enthalpy of the reaction. Thus a thermometric titration may be feasible
when all free energy methods fail. This point is clearly illustrated in figure 7.2.1 where
the thermometric titration curves for HCL and H3BO3 are shown. In contrast to the
fli

potentiometric curve, the thermometric titration curve has a well-defined end point for
the weak acid. The change in temperature of the titration curve is dependent on the heat
in

of reaction of the system, according to the equation

T = N H/ Q

Where N represents the number of moles of water formed in the neutralization, H is the
u.

molar enthalpy of neutralization, and Q is the heat capacity of the system. In practice, H
and Q are constant throughout the reaction so that T is proportional to N.
gn

Thermal Methods of Analysis 43

 Thermometry titration

in
c.
Figure: 7.2.1
e t.a
On the thermometric titration curve shown in figure 7.2.1 point A occurs at the
beginning of the temperature readings, and line AB is a trace of the temperature of the
bn
solution before the addition of titrant. If the line AB shows a marked slope, it is an
indication of excessive heat transfer between the solution and its surroundings. At point B
the addition of titrant begins; line BC shows the gradual evolution of heat of the reaction.
Point C is the end point. Line CD may slope either up or down. The linear portions of the
fli

curves are extrapolated to give the initial and equivalence points, and the distance
between them is measured along the volume (or time) axis of the graph to determine the
in

volume of titrant consumed in the reaction. The vertical line BB is the temperature
difference (T) used to evaluate the enthalpies.
u.

A typical direct-injection enthalpimetry thermogram is shown in fig. By measuring the

difference in the temperature of the solution before and after the injection of an
appropriate reagent, this technique can determine the heat evolved or absorbed by the
gn

reaction and hence the amount of analyte present in the solution.

Thermal Methods of Analysis 44

 Thermometry titration

7.3 Instrumentation thermometry titration:

The equipment consists of following parts:

1) Reagent addition system (motor-driven, automated burette)
2) An adiabatic reaction cell
3) Stirring device

in
4) Thermistors
5) Wheatstone bridge circuit
6) A recorder or other output device.

c.
In the blow schematic diagram of apparatus is given in figure 7.3.1

t.a
Figure: 7.3.1
e
bn
fli
in
u.
gn

Thermal Methods of Analysis 45

 Thermometry titration

To minimize heat transfer between the solution and its surroundings, the
titrations are performed under as near adiabatic conditions as possible in an insulated
beaker or Dewar flask of 100- to 250-mL capacity that is closed with a stopper
provided with holed for the burette tip, a glass stirrer, and the thermistors. The titrant
is delivered at flowrates of 0.1-1.0 mL/min. To obviate volume corrections and to
minimize temperature variations between the tyrant and sample, the titrant

in
concentration is usually 100 times greater than that of the reactant. Amounts of the
sample are selected so that a volume of titrant not exceeding 1-3 mL is required.

c.
Because the temperature changes during a titration range between 0.1 and 0.2 C, the
accuracy of the temperature measurement must be about 10-4 C. For a thermistors
that has a resistance of 2k and a sensitivity of -0.04 ohm ohm-1 deg-1 Celsius in the

t.a
25 C temperature range, a change of 0.01 C corresponds to an imbalance potential
of 0.157 mV. A Wheatstone bridge circuit is shown in the figure 7.3.2

Figure: 7.3.2 Wheatstone bridge circuit

e
bn
fli
in
u.
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Thermal Methods of Analysis 46

 Thermometry titration

Temperatures of the titrant and sample should be within 0.2 C before a

titration is begun. A small heating element, located inside the titration vessel, can be
used to warm the sample to the temperature of the titrant or as a calibrating device
when estimating the heats of reaction or mixing.

In a differential thermometric apparatus, temperature-sensing elements are placed in

in
both the sample and blank (pure solvent plus titrant) solutions. The sensitivity is
improved and extraneous heat effects, such as stirring and heats of dilution, are
minimized.

c.
For conventional liquid-phase DIE, it is important to introduce the reagent
instaneously as a single plug. Since the injected reagent is usually in excess and the

t.a
heat capacity of the system is easily determined after each injection, precise volume
measurements are not required. Thus a manually operated syringe is adequate. The
same adiabatic conditions required for thermometric enthalpy titrations are necessary
for direct-injection enthalpimetry.
e
bn
fli
in
u.
gn

Thermal Methods of Analysis 47

 Thermometry titration

7.4 Applications
The application of TET and DIE to the determination of an analyte is contingent
upon the knowledge of two fundamental quantities, the stoichiometry of the reaction with
thermometric enthalpy titrations and the heat of the reaction with DIE.

Determination of the concentration of an unknown substance, the reaction

in
stoichiometry, and the thermodynamic quantities G, H, and S. The first
application is perhaps the most useful to the analytical chemist. Precision and

c.
accuracy of measurement depend largely on the enthalpy of the reaction involved
and range from 0.2 % to 2%. About 0.0001M is the lowest limit of concentration
that can be successfully titrated in the more favorable cases.

t.a
All acids with Ka 10-10 can be titrated thermometrically in 0.01M solution with
a precision of 1% if the heat of neutralization is 13 3 kcal/mole. The extension
to acids too weak to titrate potentiomentrically is clearly demonstrated by the
curves in fig. Good end points are obtained for other weak acids and bases, even
e
in emulsions and thick slurries.
Nonaqueous systems are well suited for thermometric titrations, although
bn
attention must be paid to the heat of mixing of solvents and dilution. The lower
specific heat of many organic solvents introduces a favourable sensitivity factor.
Under strictly anhydrous conditions, even diphenylamine, urea, acetamide, and
fli

acetanilide are readily titratable with perchloric acid in glacial acetic acid. Lewis
bases, such as dioxane, mrpholine pyridine, and tetrahydrofuran, have been
titrated with the Lewis acid SnCl4 in the solvents CCl4, benzene and nitrobenzene.
in

Thermometric titrations are very useful in titrating acetic anhydride in acetic acid-
sulfuric acid acetylating baths, water in concentrated acids by titration with
fuming acids, and free anhydrides in fuming acids. In fact, methods based on the
u.

heats of reaction offer one of the few approaches to the analysis of concentrated
solutions of these materials.

gn

Good results are obtained in precipitation and ion-combination reactions such as

the halides with silver or mercury (II) and cations such Mn(II) with EDTA and
oxalate. Silver titration of halides has been done at elevated temperatures in
molten salts.

Thermal Methods of Analysis 48

 Thermometry titration

Enthalpimetric analysis has been used in enzyme assay and immunological

determinations as well as in the analysis of alkaloid drugs such as codeine
phosphate and morphine sulfate.
When the titration reaction is appreciably incomplete in the vicinity of the
equivalence point, actual titration curves exhibit a curvature from which
equilibrium constants and corresponding free energies can be calculated.

in
The temperature rise that occurs during an exothermic reaction can be used to
determine constituents. For example, benzene has been determined rapidly and

c.
with good precision in the presence of cyclohexane by measuring the heat of
nitration when a standard nutrating acid mixture is added to the sample; the
temperature rise is a direct function of the benzene present.

t.a
In a similar manner, heats of reaction are used to estimate the heats of successive
steps in the formation of metal-ammine complexes, the heats of chelation, and the
heats of reaction in fused salts under virtually isothermal conditions.
e
bn
fli
in
u.
gn

Thermal Methods of Analysis 49

 in
c.
e t.a
bn

8.
fli

Pyrolysis-gas
in

chromatography &
u.

Evolved gas Analysis

gn
 Pyrolysis-gas chromatography & Evolved gas analysis

8. Pyrolysis-gas chromatography & Evolved gas analysis (EGA)

8.1 Principle:
Controlled Pyrolysis of small samples followed by GC separation of the
products and identification by MS or FT-IR.

in
Evolved gas analysis (EGA) is based on the study of gases or volatile breakdown
products emitted by a sample on heating. The identity and properties of the volatile
materials emitted serve as a basis for the analysis of the sample. One particular technique

c.
of EGA which has attracted substantial attention is Pyrolysis-gas chromatography (Py-
GC). As the name suggests this technique uses gas chromatography to separate the
breakdown products of the sample which have been produced by carefully controlled

t.a
Pyrolysis. The pyrogram thus obtained will generally show a complex pattern of peaks
which may be used for both qualitative and quantitative analyses. Identification of the
peaks present in the program has been carried out for some time by standard GS-Ms
e
procedures. However, more recently, with the development of FT-IR instruments, GC-
FT-IR is also being exploited in this way.
bn
Disadvantage :
Relatively poor reproducibility because of the dependence on accurately
fli

reproduced heating profiles and the use of very small samples.

in
u.
gn

Thermal Methods of Analysis 50

 Pyrolysis-gas chromatography & Evolved gas analysis

8.2 Instrumentation

The essential instrumentation is divided into three parts:

(a) The pyrolyser
(b) The gas chromatograph and
(c) The MS or FT-IR instruments.

in
Furnace, Curie-point or heated filament pyrolysers linked to packed column or
capillary column gas chromatograph. GC-MS or GC-FT-IR interfaces.

c.
It has been recognized that best results are obtained when the temperature of the sample
is raised rapidly and reproducibly to the Pyrolysis temperature and then held closely at
that temperature for the desired Pyrolysis time. One obvious way of achieving this aim is

t.a
by the use of an electrically heated microfurnace.
A design of modern furnace is shown in figure 8.2.1

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Figure: 8.2.1

Thermal Methods of Analysis 51

 Pyrolysis-gas chromatography & Evolved gas analysis

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Figure: 8.2.2
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An alternative approach has been to use Curie-point pyrolysers. The Curie point
is used for accurately reproducing a temperature. In a slightly different way the Curie
point can be used for accurately reproducing Pyrolysis conditions with the added
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advantage that the rise time is only about 0.4s. The sample, typically 50 g, is either
placed on or encapsulated in the end of a Pyrolysis wire composed of the appropriate
ferromagnetic alloy.
Induction heating can then be used t raise the temperature rapidly to the Curie
point where it can be accurately maintained until the induction coil switched off.

Thermal Methods of Analysis 52

 Pyrolysis-gas chromatography & Evolved gas analysis

Heating profile of Curie-point pyrolysers is constructed with that for a typical

microfurnace in Figure: a and the construction of a pyrolysis unit in Figure: b with typical
pyrolysis wores shown in figure 8.2.3

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Figure: 8.2.3
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A third type of pyrolyser sometimes utilizes a filament heated by its own
electrical resistance. The most effective pyrolysers of this type use an initial pulse of
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heating at a high voltage to produce a high current and rapid heating to the Pyrolysis
temperature, i.e. 700C in 12 ms, followed by reduction to an accurately controlled
maintenance voltage to maintain the Pyrolysis temperature.
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8.3 Applications

Potentially applicable to a wide range of organic materials. Most use has been
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made in the analysis of polymers and oils. Essentials a qualitative technique with
poor precision for quantitative measurements.
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Thermal Methods of Analysis 53

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9.
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Thermomicroscopy
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 Thermomicroscopy (hot-stage microscopy)

9. Thermomicroscopy (hot-stage microscopy)

9.1 Principle

Thermomicroscopy (TM) or hot-stage microscopy (HSM) is a thermo-

optical technique and has been extensively used in the characterization of solid-state

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properties of drug compounds. In the early development steps of drug substances (e.g.
preformulation, salt selection, etc.) when only a few milligrams of a drug candidate
are available, this method is particularly valuable because only minute quantities are

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required to quickly provide important data, such as melting points, thermal stability,
purity (qualitative), as well as the existence of different crystal modifications.

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Advantages:

Hot-stage microscopy not only benefits from the features of the hot stage but
also the quality and accessories of the microscope. It is obvious that this technique
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also needs some fundamental knowledge of chemical and optical microscopy. In this
context, it should be noted that the advantage of hot stages that combine the features
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of differential thermal analysis (DTA) and optical microscopy are questionable since
both the sensitivity of the DTA signal and the microscopic preparation features suffer
much from this combination.
In order to understand the results obtained by other thermal analytical
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techniques (e.g. DSC or TGA), it is highly recommended to perform also

thermomicroscopic investigations. Visual images are very convincing and contain
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often much more information than any plotted curve. This may finally save a
considerable amount of time and additional experiments, but like most microscopy
techniques, TM requires also some experience and patience.
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Thermal Methods of Analysis 54

 Thermomicroscopy (hot-stage microscopy)

9.2 Instrumentation

This simple and rather inexpensive method requires basically a hot stage
attached to a suitable polarized-light microscope.

The hot stages available provide basically different features. The classic and
most inexpensive Kofler hot stage is less accurate in temperature (0.5 C) and lacks

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the feature of linear heating. However, because of the ease of access to the sample, a
large number of experimental possibilities exist, which are extremely valuable in hot-

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stage microscopy. Owing to a small vertical temperature gradient, the sublimations
behavior can be readily observed during heating, which is important for decisions
concerning the sample preparation with other thermal analytical technique such as

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DSC.

Another widely used hot stage is that of by the Mettler company (e.g.
Mettler FP82) where the sample preparation with where the sample ( on a glass slide )
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is heated from both the top and bottom. This sandwich heating provides a good
temperature control (0.1 C) as well as accurate heating programmes and
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encompasses most of the needs in solid-state characterizations.

The Linkam Company offers a large assortment of hot and cold stages for a
wide variety of applications. The specimen is inaccessible and locked within the stage
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but can be cooled with liquid nitrogen, purged with gases or optionally evacuated.
This type of hot stage also permits observation of freeze drying processes and can be
used in combination with IR and Raman microscopes.
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For documentation purposes and to overcome the disadvantage of subjective

results by the investigator, hot-stage microscopes are nowadays commonly equipped
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with 35 mm or digital photographic cameras or video systems (monitor, camera,

recorder, and video text overlay for recording the temperature signal).
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Thermal Methods of Analysis 55

 Thermomicroscopy (hot-stage microscopy)

9.3 Application:

Thermo-optical technique and has been extensively used in the

characterization of solid-state properties of drug compounds. In the early
development steps of drug substances (e.g. preformulation, salt selection, etc.)
when only a few milligrams of a drug candidate are available, this method is

in
particularly valuable because only minute quantities are required to quickly
provide important data, such as melting points, thermal stability, purity
(qualitative), as well as the existence of different crystal modifications.

c.
The application field of hot-stage microscopy in pharmaceutical analysis is
broad and crosses almost the entire range of materials. Table summarizes

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some applications of Thermomicroscopy related to properties of small
molecules.
Typical photomicrographs of crystal forms that have been crystallized from
the supercooled melt in film preparations (between glass slide and cover slip).

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The forms can be readily distinguished by their different appearances in the
polarized light (e.g. shape, pattern, and birefringence colours).
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Thermal Methods of Analysis 56

 Thermomicroscopy (hot-stage microscopy)

Following table summarizes some application of Thermomicroscopy related to small

molecules.
Table 9.1 Hot-stage microscopy applications

Melting point determination Melting range (purity)

Equilibrium melting point
Instantaneous melting point (for thermally

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unstable compounds)
Incongruent melting (polymorphism)

Sublimation Quick estimate of the vapour pressure

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Micropurification by sublimation
Sublimation to polymorphic forms
(morphology)
Epitaxy studies

Crystallization (film preparation)
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Transformation phenomena
(Crystal film, single crystals)
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Crystallization of polymorphs from the melt
(liquid, supercooled)
Crystal growth characteristic (melt, solution)
Crystal growth kinetics
Morphology of crystals
solid-solid transformations (spontaneous, slow,
reversible, irreversible, nucleation and growth
characteristics, solvent effects)

Desolvation reactions Change to a polycrystalline aggregate upon

(hydrates, solvates) desolvation (pseudomorphosis) or melting and
crystallization phenomena
Detection of the solvent using lipophilic oil
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(bubbles)
Desolvation kinetics (single crystals)
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Special phenomena Grain growth

Plastic crystals
Liquid crystals
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Thermal characterization of Eutectics

binary systems including Peritecics
racemates contact
preparation method)
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Thermal Methods of Analysis 57

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10.
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Dielectric Analysis
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 Dielectric analysis

10. Dielectric analysis

Dielectric analysis (DEA), or dielectric spectroscopy, measures the response

of a material to a time-varying voltage signal and detects subtle differences in the
electrical properties of the sample. DEA can detect phase transitions not detected by
DSC or dynamic mechanical thermal analysis (DMTA). DEA measures capacitance

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and conductance versus time, temperature, and frequency. Capacitance, the ability to
store an electrical charge, dominates the electrical responses for a rigid material (e.g. a
polymer below its glass-transition temperature Tg). Conductance, the ability to

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transfer charge, is important when a heated material becomes less rigid (e.g.
amorphous material, a polymer above Tg , or a melt). Charges in capacitance and
conductance provide molecular or structural-state information of a sample. Parameters

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monitored by dielectric analysis are ( permittivity), which measures the degree of
molecular dipole alignment to an applied electrical field and (loss factor), which
reflects the alignment of dipoles or ions and the energy needed to align them. DEA is
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particularly useful for mixtures and characterization of dipole and/or ionic phases in
mixtures.
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Thermal Methods of Analysis 58

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11.
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Microcalorimetry
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 Microcalorimetry

11. Microcalorimetry

Microcalorimetry is an extremely sensitive technique that determines the

heat emitted or adsorbed by a sample in a variety of processes. Microcalorimetry can
be used to characterize, heats of reaction, heats of dilution, and heats of adsorption.
Isothermal Microcalorimetry has been used to investigate drug-excipient

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compatibility. Pikal and co-workers have used isothermal Microcalorimetry to
investigate the enthalpy of relaxation in amorphous material. Isothermal
Microcalorimetry is useful in determining even small amounts of amorphous content

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in a sample. Solution calorimetry has also been used to quantitate the crystallinity of a
sample. Other aspects of isothermal Microcalorimetry may be obtained from a review
by Buckton.

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Thermal Methods of Analysis 59

 Bibliography

12. Bibliography

Willard, Merritt, Dean, Settle, Instrumental Methods of Analysis, CBC,

Seventh Edition.
F.W. Fifield and D. Kealey, Principle and Practice of Analytical Chemistry,
Blackwell Publishing, Fifth Edition.

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S.Usharani, Analytical Chemistry, Macmillan Publishing.
David C. Lee and Michael Webb, Pharmaceutical Analysis, Blackwell
Publishing.

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D. Kealey and P.J. Haines, Analytical Chemistry, Viva Publishing.
B.K. Sharma, Instrumental Method of Chemical Analysis, Goel Publication,
23rd Edition.

Web sites:

www.e-thermal.com
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www.acdlabs.com
www.rsc.org
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www.alibris.com
www.thermal-instruments.com
www.tainstruments.com
www.chembio.uoguelph.ca.
www.thermalmethodsgroup.org.uk
www.ssci-inc.com
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www.anasys.co.uk
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Thermal Methods of Analysis 60