Differential

Thermal
Analysis
(DTA)
 INTRODUCTION

This is a comparison method

Analytical method for recording the difference in

temperature (∆T) b/w a substance and an inert
reference material as a function of temperature or
time.

Any transformation – change in specific heat or an

enthaply of transition can be detected by DTA
• In DTA both test sample & an inert reference material
(alumina) – controlled heating or cooling programming
• If zero temperature difference b/w sample & reference
material – sample does not undergo any chemical or physical
change.
• If any reaction takes place temperature difference (∆T)
will occur b/w sample & reference material
• A DTA curve can be used as a finger print for identification
purposes, for example,
• in the study of clays where the structural similarity of
different forms renders diffraction experiments difficult to
interpret.
• In Differential Thermal Analysis, the
temperature difference that develops between a
sample and an inert reference material is
measured, when both are subjected to identical
heat - treatments.

• The related technique of Differential Scanning Calorimetry

relies on differences in energy required to maintain the
sample and reference at an identical temperature.
Principle:
The basic principle involved in DTA is the
temperature difference (∆T) between the test sample and an
inert reference sample under controlled and identical conditions
of heating or cooling is recorded continuously as a function of
temperature or time, thus the heat absorbed or emitted by a
chemical system is determined.
• If any reaction takes place in the sample, then the
temperature difference will occur between the sample and
the reference material.
• In an endothermic change (such as melting or
dehydration of the sample) the temperature of the
sample is lower than that of the reference material
(i.e) ∆T = ‒ ve (for endothermic process)
• In an exothermic change or process the sample
temperature is higher than that of the reference
material.
• (i.e) ∆T = + ve (exothermic process)
• The shape and the size of the peak give information about the
nature of the test sample.
(1)Sharp endothermic peaks indicate phase changes (such as
melting, fusion etc.) transition from one crystalline form to
another crystalline form.
(2)Broad endothermic peaks are obtained from dehydration
reactions
(3)Chemical reactions like oxidative reactions are exothermic
reactions.
(4)Physical changes usually result in endothermic curves
 Factors causing change in
heat / temperature
Physical:
 Adsorption(exothermic)
 Desorption(endothermic)
 A change in crystal structure
(endo –or exothermic)
 Crystallization (exothermic)
 Melting(endothermic)
 Vaporization (endothermic)
Chemical :-
 Oxidation (exothermic)
 Reduction (endothermic)
 Break down reactions
(endo or exothermic)
 Chemisorptions
(exothermic)
 Solid state reactions (endo
–or exothermic)
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Instrumentation for DTA/Block Diagram
The DTA apparatus consists of the following components
• Furnace with sample and reference holder and thermocouple
assembly. (Furnace to heat the sample)
• Furnace temperature controller (to increase the furnace
temperature steadily)
• Furnace atmospheric control system (To maintain a suitable
atmosphere in the furnace and sample holder)
• Low level DC amplifier
• Recording device (Recorder)
• Differential temperature sensor (to measure the temperature
difference between the sample and reference material) the
sample and reference holder are kept inside the furnace and
the temperature of the furnace and sample holder is
controlled by using furnace controller.
 INSTRUMENTATION………
 A DTA consists of a
sample holder
thermocouples
a furnace
a temperature programmer
and a recording system

 Thekey feature is the existence of two thermocouples

connected to a voltmeter.

 One thermocouple is placed in an inert material such as

aluminum oxide, while the other is placed in a sample of
the material under study.
12
 1. Sample holder:
The sample holder and reference cells are made up of aluminum.

2. Sensors/thermocouples:
Platinum or chromyl thermocouples one for sample and one for
reference material is joined to differential temperature controller.

3. Furnace:
Alumina block containing sample and reference cells.

4. Temperature controller:
Controls temperature program and furnace atmosphere

5. Recording system:
It is a system where the change in the temperature i.e. differential
temperature is recorded and the enthalpy is recorded 13
Working principle ….
• Heart of the analysis – heating block
• Identical pair of cavities for the sample, ref.
material
• Whole unit is set in an oven- control pressure
• Thermocouple is place directly in contact with the
sample and another in contact with the reference
• Temp.of the block is raised, the temperature of the
sample & reference follow
• Zero temp. difference – no physical or chemical
change
• If any reaction – difference in ∆T
 DTA of calcium oxalate monohydrate
The DTA curve for the decomposition of calcium
oxalate monohydrate (CaC2O4.H2O) is shown in
the diagram

The thermogram shows the decomposition in CO2

atmosphere and in air atmosphere.
 DTA of calcium oxalate monohydrate
• The thermogram of calcium oxalate monohydrate has
three peaks corresponding to the successive
elimination of H2O, CO and CO2.
• These three points of weight loss corresponds to the three
endothermic process.
• Curve (b) represents the DTA diagram for the same compound
in air. The second peak in this curve is sharply exothermic, but
corresponds to the same weight loss as in carbon dioxide
atmosphere.

• This peak represents the exothermic burning of carbon

monoxide in air at the temperature of the furnace.
Factors affecting results in DTA….
There are so many factors that
affects the DTA curve. They are divided
into two;

Sample Instrumental
characteristics factors

18
Instrumental factors:
Furnace
temperature

Thermocouple Furnace size

location and shape

Sample holder
Heating rate material

19
Sample characteristics factors..

Heat
capacity

Swelling
Effect of and
shrinkage
diluents of
sample

Packing Amount
of sample
density
20
Lets see how these factors effect the
DTA curve and the suggestions…..
Factors Effect Suggestions

1. Heating rate Change in the peak Optimum heating rate

size and position
2. Location of Irreproducible curve Standardize
thermocouple thermocouple location

3. Atmosphere Change in the curve Inert gas should be

around the allowed to flow
sample
4. Amount of sample Change in the peak Standardize sample
size and position mass

5. Particle size of Irreproducible curve Use small uniform

sample particle
6. Packing density Irreproducible curve Standardize packing
techniques
7.Sample container Change in peak Standardize container
 Advantages:
1.Instruments can be used at a very high
temperature
2.Instruments are highly sensitive
3.Flexibility in crucible volume/form
4.Characteristic transition or reaction temperature
can be accurately determined

Disadvantages:
Uncertainty in heats of fusion, reaction or transition
estimations is 20% to 50% in DTA

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 Derivative differential thermal analysis (DDTA)

A method for precise determination in thermograms of

slight temperature changes by taking the first derivative
of the differential thermal analysis

Curve (thermogram) which plots time versus differential

temperature as measured by a differential thermo
couple. Also known as DDTA.
 Applications of DTA
• DTA curves for two substances are not identical. Hence they
serve as finger prints for various substances.
• Used to study the characteristic of polymeric material.
• This technique is used for testing the purity of the drug sample
and also to test the quality control of number of substances like
cement, soil, glass,etc.
• Used for the determination of heat of reaction, specific heat and
energy change occurring during melting etc.
• Trend in ligand stability (thermal stability of the ligands) gives
the information about the ligands in the coordination sphere.
To obtain phase diagrams (sulphatriazole-urea solid dispersions,
gresiofulvin-succinic acid solid dispersions) which are useful in
enhancing their dissolution and absorption rates.