PHILIPPINE NORMAL UNIVERSITY

The National Center for Teacher Education

College of Graduate Studies and Teacher Education

Research
Science Education Specialization
Taft Avenue cor. Ayala Blvd.
Manila, Philippines

A Module

Presented to
Sir Nelson Garcia
Professor

In Partial Fulfillment in the course requirements in

CHEM503: Techniques in Analytical Chemistry

Presented by
Villie S. Alas
M.A. Science Education in Chemistry
April 4, 2015

TABLE OF CONTENTS
Title page i
Academic Integrity Pledge ... ii
Table of Contents .. iii
Acknowledgment ... iv
I. INTRODUCTION ... 1-2
OBJECTIVES .... 2
III. PRE-TEST .... 3
IV. DISCUSSION
Principles of Differential Thermal Analysis 4-5
Instrumentation of Differential Thermal Analysis .. 6-10
Application of Differential Thermal Analysis ...... 11
V. SUMMARY . 12
VI. POST-TEST ...... 13-14
VII. ANSWER KEY .... 15-16
VII. REFERENCES .... 17

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ACADEMIC INTEGRITY PLEDGE

I, Villie S. Alas, taking Master of Arts in Science Education major in

Chemistry and enrolled in CHEM503: Techniques in Analytical Chemistry,
hereby pledge that the submitted work abides by the guidelines set by the
Code of Conduct and is my own thoughts and ideas. This includes proper
citations, proofreading, studying, originality, integrity and honesty to the
University and the individual professors standards. I have neither given
nor received unauthorized assistance on this work.

Signature over Printed name

iii

Acknowledgement
This module would not be possible without the help and guideline of some respected persons, who deserve the authors greatest heartfelt gratitude. The completion of this module gives the authors much pleasure.
I would like to thank Ms. Gail Macapagal, for giving her insights on the
proper contents of this module throughout numerous conversations thru her at
Facebook (a social networking site) and for giving me the email address of our
Dear Professor.
In addition, a thank you to Professor Nelson Garcia who introduced us to
this alternative requirement in CHEM503: Techniques in Analytical Chemistry.
I also place on record, my sense of gratitude to one and all, who directly or
indirectly, have lent their hand in the completion of this project.
Above all, thank you to our Almighty God, for guiding and giving me the
courage, patience and wisdom for me to be able to finish and come up with this
kind of requirement.
Again, thank you very much!

Sincerely,
VSAThe Author
iv

INTRODUCTION
Analytical chemistry is the science of obtaining, processing, and communicating
information about the composition and structure of matter. According to David (2000),
analytical chemistry is often described as the area of chemistry responsible for characterizing the composition of matter, both qualitatively (what is present) and quantitatively
(how much is present).
Analytical chemistry is not a separate branch of chemistry, but simply the application of chemical knowledge. In other words, according to ACS (2015), it is the art
and science of determining what matter is and how much of it exists. In 2012 (salary
survey data), analytical chemistry was the most popular field of work for ACS
(American Chemical Society) chemists.
Analytical chemists use their knowledge of chemistry, instrumentation, computers, and statistics to solve problems in almost all areas of chemistry and for all kinds
of industries. For example, their measurements are used to assure the safety and quality of food, pharmaceuticals, and water; to assure compliance with environmental and
other regulations; to support the legal process; to help physicians diagnose diseases;
and to provide measurements and documentation essential to trade and commerce.
Analytical chemists often work in service-related jobs and are employed in industry,
academia, and government. They conduct basic laboratory research; perform process
and product development; design instruments used in analytical analysis; teach; and
work in marketing and law. Analytical chemistry can be a challenging profession that
makes significant contributions to many fields of science.
In analytical analysis, chemist used an analytical technique for different types of
research. According to Wikipedia (2014), analytical technique is a method that is used
to determine the concentration of a chemical compound or chemical element. There
are a wide variety of techniques used for analysis, from simple weighing (gravimetric
analysis) to titrations (titrimetric) to very advanced techniques using highly specialized
instrumentation. The most common techniques used in analytical chemistry are listed
below:
Titrimetrybased on the quantity of reagent needed to react with the analyte;
Electroanalytical methods, including potentiometry and voltammetry;
Spectroscopybased on the differental interaction of the analyte along with
electromagnetic radiation;

Chromatographyin which the analyte is separated from the rest of the sample
so that it may be measured without interference from other compounds;
There are many more techniques that have specialized applications, and within
each major analytical technique there are many applications and variations of the general techniques.
According StrataMark Dynamic Solutions (2014), the selection of appropriate
analytical techniques is crucial in designing effective marketing research that will lead
to clear insights and recommendations to your research studies. The suitability of each
type of analysis to a particular study design is determined by your specific objectives
and needs.
One of the advancement in analytical techniques is the Thermal Analysis (TA).
According to Tarasov (2012), it is a group of physicalchemical methods which deal
with studying materials and processes under conditions of programmed changing's of
the surrounding temperature. In other words, it is a group of techniques that study the
properties of materials as they change with temperature.
In practice thermal analysis gives properties like; enthalpy, thermal capacity,
mass changes and the coefficient of heat expansion. Moreover, in solid state chemistry
it is used for studying reactions in the solid state, thermal degradation reactions, phase
transitions and phase diagrams, according to Frberg (?). Thus, this analytical technique has major contribution in the science field.
Thermal analysis includes several different methods. These are distinguished
from one another by the property which is being measured. This module will focus on
thermal analytical technique specifically with Differential Thermal Analysis.

OBJECTIVES
At the end of this module, the students should be able to:
1. Explain the principles of the Differential Thermal Analysis;
2. Describe the thermogram or temperature vs. time graph of a sample DTA
result; and
3. Recognize the importance of its application in coal mining industries.
2

Lets get it started!

PRE-TEST
Direction: Underline the words on the puzzle grid that are listed below. The words
can be forwards, backwards, vertical, horizontal and diagonal.
thermogram

reference

endothermic

thermocouple

exothermic

temperature

sample

furnace

transition

inert

Differential Thermal
Analysis
According to Britannica dictionary (2015), DTA is a special type of thermoanalytical technique which is used for measuring, identifying and quantitatively analyzing the chemical composition of substances, by observing the thermal behavior of
a sample as it is heated caused due to the variation of applied temperature.
Note: As a substance is heated, it undergoes reactions and phase changes that involves the absorption (endothermic) and emission (exothermic) of heat.
The difference in temperature between the sample and a thermally inert reference material is measured as a function of temperature (usually the sample temperature). Any transition that the sample undergoes results in liberation or absorption of
energy by the sample with a corresponding deviation of its temperature from that of
reference.
It is the most common as well as popular thermal analysis method that provides lots of essential information to the experimenters regarding the sample materials. In this module, we will talk about the principle of DTA, instrumentation used for it,
and its applications in different fields.
Below is a table that shows different types of thermal analysis.
TECHNIQUES
Thermogravimetric analysis (TGA)
Differential scanning calorimetry
(DSC)
Differential thermal analysis (DTA)

QUALITY MEASURED
Weight change
Heats and temperature of transitions and reactions
Temperatures of transitions and
reactions

Table 1: Thermal analysis technique

Principles of Differential Thermal

Analysis
The analysis involves TWO distinct materials:
The sample (s) which is to be tested
The inert reference (r). According to Britannica dictionary (2015), the term
inert is used to describe a substance that is not chemically reactive. The noble
gases were previously known as inert gases because of their perceived lack of
participation in any chemical reactions. In other words, an inert reference in
DTA is a substance that is not chemically reactive with the programmed temperature.
Both of these materials are subjected to a restricted temperature program (T)
where the applied temperature goes up linearly with time. This results in a temperature difference (T) between those two materials which is determined by DTA.
The difference between the temperature of the sample (Ts) and that of the reference (Tr) is measured by the differential thermocouple, and the output signal (Ts
Tr) is termed as T. This output is then magnified to some extent and transferred to

Self

CHECK
Complete the sentence below:
Differential Thermal Analysis, also known as DTA is a
that analyzes chemical composition of a
substance. These substances are comprises of a
, which is to be tested and a
, which is chemically inactive with respect to
. The change in temperature indicates that the substance undergoes
that results from absorption and
of heat.

Instrumentation of Differential
Thermal Analysis
This DTA uses a dumbbell-shaped detector. A
temperature controller, gas flow adjuster, and transmission interface have all been incorporated into a slim, 173
cm-wide body. A high-temperature DSC function is also
included.
High Temperature (ambient to 1500C) heat-flux Differential Thermal Analyzer
Temperature range: Room temperature to 1500C
Measurement range: 0.2 to 1000 V (from 0.2
mW)
Heating speed: 0 to +50C/min
http://www.barascientific.com/
products/shimadzu/analytical/
physical/eng/TA/DTA-50.php

Figure2: Differential Thermal

Analyzer

High Temperature Heat Flux DTA, Provides Quantitative Calorimetric Measurements Quick Response and
High Sensitivity Accurate Temperature Control High
Temperature DSC Type Performance Rapid Atmos-

The various component of a

DTA apparatus are as following:
Furnace- this is device for
heating the sample.
Sample holder- this is used to
contain the sample as well as
the reference material.
DC amplifier- generally a low
level DC amplifier is employed.
Differential Temperature Detector- the function of this dehttp://www.pharmatutor.org/articles/drug-excipienttector is to measure differential compatibility-studies-using-thermal-methods?page=0,3
temperature.
Figure3: Internal Schematic diagram of differential
thermal analyzer

Recorder- this is to record the DTA curve.

Control Equipment- its function is to maintain a suitable atmosphere in the
furnace & sample holder.
Thermocouple-a temperature-measuring device consisting of two dissimilar
conductors that contact each other at one or more spots, where a temperature
differential is experienced by the different conductors (or semiconductors).
DTA data are accurate of all thermal techniques, because the thermocouple is
inserted into the sample and only the temperature of transition and not the amount of
heat can be measured from a DTA curve.

ON THE OPERATION
How it works
The basic configuration is the two thermocouples are connected in a differential arrangement and connected to a high
gain low noise differential amplifier. One thermocouple is placed
in an inert material such as Al2O3, while the other is placed in a
sample of the material under study. As the temperature is increased, there will be a brief deflection of the voltage if the sample is undergoing a phase transition. This
occurs because the input of heat will raise
the temperature of the inert substance, but
be incorporated as latent heat in the material changing phase.
In order to perform it successfully, we need
certain advanced tools and equipment. At
first, we need to prepare the sample (s)
and the reference sample (r) properly.
Note: Matters that do not change in the measurement temperature range (usually alumina) are used as reference.
http://www.hitachi-hightech.com/global/products/
science/tech/ana/thermal/descriptions/dta.html/

Figure4: The furnace and its component

PROPERTIES OF MATERIALS
Raw materials should be of high purity.
Fine -grained powder should be used to achieve greater contact
area and better equilibrium conditions.
The time at any temperature must be sufficiently long in order to permit completeness of reactions.
When the furnace heating begins, the reference and the sample begin heating
with a slight delay depending on their respective heat capacity, and eventually heat up
in accordance to the furnace temperature.
We need to take two aluminum containers for keeping the sample as well as reference in them. Thermocouples are connected to each of the material for measuring
their temperature, and heat is applied to them under cautiously regulated conditions.
The sample material has gone through certain chemical reaction or physical transformation, its temperature will change significantly due to the change in its enthalpy' or
heat content. However, the temperature of the reference material will remain unchanged. There would be temperature changes (T) until a static state is reached after
the heating begins, and after
achieving stability, reaches a
set amount compliant with the
difference in heat capacity between the sample and the reference. The signal at the static
state is known as the baseline.
The difference between
the temperature of the sample
(Ts) and that of the reference
(Tr) is measured by the differential thermocouple, and the
output signal (Ts Tr) is
http://www.hitachi-hightech.com/global/products/science/tech/
termed as T. This output is
ana/thermal/descriptions/dta.html/
then magnified to some extent
Diagram1: A thermogram
Graph (a) shows the temperature change of the furnace, the reference
and transferred to the data acand the sample against time. Graph (b) shows the change in temperaquisition system in order to obture difference (T) against time detected with the differential thermotain it as a function of Ts, or
couple. T signal is referred to as the DTA signal.
Tr, or time.
8

When the temperature rises and melting occurs in the sample, for example,
the temperature rise stops as shown in graph (a) and the T increases. When the
melting ends, the temperature curve rapidly reverts to the baseline.
Refer to diagram 1, at this point, the T signal reaches the peak, as shown in
graph (b). From this, we can detect the samples transition temperature and the reaction temperature from the T signal (DTA signal or thermogram).
In graph (b), the temperature difference due to the samples endothermic
change is shown as a negative direction and the temperature difference due to the
samples exothermic change is shown as a positive direction.

No phase transition but there is a

change in temperature

Lets take another

example of thermogram
from a scientific research
entitled Spontaneous
Combustibility Characterisation of the
Chirimiri Coals, Koriya
District, Chhatisgarh,
India by Durga Shankar
Pattanaik, Purnananda
Behera and Bijay Singh.

The thermogram
reveals that phase transformation due to dehydration of the coal samples
of the Sonawani seam
and Karakoh seam numbered as So/1, So/3,
Kk/2, Kk/4 and Kk/6
showed endothermic
peaks in tempera-ture
range of 104C to 116C,
but the coal samples of
the Kaperti seam and the
Duman seam numbered
Diagram2: A thermogram of different caol seams in India
as Ka/1, Ka/3, Du/1, Du/3
and Du/4 showed peak maxima be-tween 100C and 106C.
9

A close scrutiny of the thermograms shows that there is gradual variation in the
bulging nature of these endothermic peaks vis-a-vis the stratigraphic sequence. The
bulging in case of Sonawani and Karakoh is greater compared to those of Kaperti and
Duman seams. The second endothermic peaks are due to the combustion of volatiles
or degasification. For Sonawani and Karakoh, the peak maxima are found between
400C and 415C, whereas for the samples of the Kaperti and the Duman, the peak
maxima are in between 390C and 410C. The exothermic peaks due to the combustion of fixed carbon are found in the temperature range of 455C to 490C in the samples of Sonawani seam and the Karakoh seam whereas for the samples of Kaperti and
the Duman seams, the peaks range from 455C to 495C.

CHECK YOUR
UNDERSTANDING

Direction: Write a short inference given a DTA thermogram below.

http://article.sapub.org/10.5923.j.pc.20120206.01.html

10

A closer LOOK
DTA has become an integral part of the engineering industry. There are many application of this analytical procedure.
Some of them are listed below:
1. Producing and determining phase diagrams and identifying phase conversions
because offers a wide spectrum of useful investigations related to reaction kinetics, polymerization, solvent retention, phase-transformations, solid-phase
reactions and curing or drying properties of a product, heat change measurements and decomposition in various atmospheres.
2. Finding the change in enthalpy (H) in the entire procedure.
3. Fingerprinting certain materials such as DTA curves may be used to date bone
remains or to study archaeological materials..
4. Verifying decomposition temperatures of various organic composites in characterizing pharmaceuticals, food/biological industries, organic chemicals and thermal stabilities inorganic compounds.
5. Analyzing a physical mixture of commercial polymers qualitatively. The DTA
technique is widely used for identifying minerals and mineral mixtures, may be
used in cement chemistry, mineralogical research and in environmental studies.
In short, Differential Thermal Analysis can be extremely helpful in almost each
and every aspect of the engineering industry.

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IN the
Nut
shell

Differential Thermal Analysis is a thermal analysis

technique that is used to identify and quantitatively analyze
the chemical composition of substances by observing the
thermal behaviour of a sample as it is heated. Hence, the
quality that is being measured is the temperatures of transitions and reactions of a substance.
The difference in temperature between the sample
and a thermally inert reference material is measured as a
function of temperature (usually the sample temperature).

Both materials are subjected to a restricted temperature program (T) where the applied temperature goes up linearly with time. This results in a temperature difference (T) between those two materials which is determined by DTA known as thermogram.
The various component of a DTA apparatus are furnace, sample holder, DC
amplifier, differential temperature detector, furnace temperature programme,
recorder, and control equipment.
The curves provide data on the transformations that have occurred such as
glass transitions, crystallization, melting or sublimation. Under the DTA peak, the
area can be measured wherein enthalpy change is not affected by the heat capacity
of the substance.
DTA is used in rapid identification of the compositions of mixed clays, studying
the thermal stabilities of inorganic compounds, critically examining in a specific reaction whether a new compound is actually formed, and it offers a wide spectrum of
useful investigations related to reaction kinetics, polymerization, solvent retention,

12

After a comprehensive discussion of the principles and instrumentation of the differential thermal l analysis, its time to check what you have
learned from this module. GOODLUCK!
A. Direction: Fill-out the puzzle given the description below of it.

5
1
0
7

8
6
3

HORIZONTAL
1. basis for temperature
2. material to be tested
3. a temperature measuring device

DOWN
5. a heating device
6.a thermal analyzer
7. temperature vs. time graph

4. an endothermic phenomena

8. emission of heat
9. a chemically nonreactive substance
10. absorption of heat

13

B. Direction: Briefly discuss the given diagram below based from the principles and
instrumentation of differential thermal analysis.

http://www.friedli.com/research/PhD/Dsc/chap3.html

C. Direction: Write a short inference regarding the thermogram below.

http://article.sapub.org/10.5923.j.pc.20120206.01.html

14

ANSWER KEY
PRE-TEST

E
X
O
T
H
E
R
M
I
C
D
S
C

M
C
E
O
S
T
S
T
R
E
N
I
O

A
V
R
Y
A
R
E
X
E
S
M
N
U

R
F
U
R
N
A
C
E
F
R
M
E
P

G
D
T
F
U
R
R
S
E
P
E
R
L

O
I
A
O
N
M
R
H
R
I
S
S
E

M
E
R
T
C
F
T
R
E
L
S
A
D

R
T
E
A
D
O
A
A
N
L
E
M
D

E
I
P
I
D
L
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T
C
I
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I

H
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E

T
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E
B

A
D
T
N
O
I
T
I
S
N
A
R
T

SELF-CHECK
Differential thermal analysis; sample, inert reference; temperature; phase transitions; emission

SELF-CHECK
Students answer may vary

15

1.

5.

E F

R E N

E
10
.

E
7.

R
N

T
H

9.

N S

I T
N

O N
D

2.

S A M P L E
C
R
E
M

E
R
T

O
T
H

8.

6.

D
3.

T
A

H E R M O C O U P L
A
T
M
H
E
R

E M
I
C

4.

M E
I
C

N G

B. Students answer may vary

The two thermocouples are connected in a differential arrangement and connected to a high gain low noise differential amplifier. One thermocouple is placed in
an inert material while the other is placed in a sample of the material under study.
When the furnace heating begins, the reference and the sample begin heating with a
slight delay depending on their respective heat capacity, and eventually heat up in
accordance to the furnace temperature. As the temperature is increased, there will be
a brief deflection of the voltage if the sample is undergoing a phase transition.
The difference between the temperature of the sample (Ts) and that of the reference (Tr) is measured by the differential thermocouple, and the output signal (Ts
Tr) is termed as T. This output is known as thermogram.
C. Students answer may vary

16

REFERENCES

Differential thermal analysis (DTA). Retrieved from http://www.britannica.com/

EBchecked/topic/162962/differential-thermal-analysis-DTA on February 15, 2015.
Beckett A.H., Stenlake J.B., Practical Pharmaceutical Chemistry 4th edition 2004, in
two parts, published by CBS publisher & distribution, New Delhi, p. no. 69-74
Canalytical Instruments for Science and Industry. (2015). Retrieved from http://
canalytical.com/instruments/physical-testing/thermal-analysis/ dated on April 3, 2015
Research solutions. Analytical Techniques. StrataMark Dynamic Solutions. (2014).
Retrieved from http://www.stratamarkds.com/researchsolutions/
AnalyticalTechniques.aspx dated on April 2, 2015
Wikipedia. (2014). Retrieved from http://en.wikipedia.org/wiki/Analytical_technique
dated on April 2, 2015.
Careers. Analytical Chemistry. (2015). Retrieved from https://www.acs.org/content/
acs/en/careers/college-to-career/areas-of-chemistry/analytical-chemistry.html dated
on April 1, 2015.
Scientific Research. International Journal of Geosciences. (2011), 2, 336-347
doi:10.4236/ijg.2011.23036 Published Online August 2011 Retrieved from (http://
www.SciRP.org/journal/ijg) dated March 21, 2015.

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