Contents

1. INTRODUCTION ...................................................................................... 2
1.1 Introduction ............................................................................................. 2
2. THEORETICAL BACKGROUND ........................................................... 2
2.1 Theory ...................................................................................................... 2
3. EXPERIMENTAL PART .......................................................................... 4
3.1 Equipment ................................................................................................ 4
3.2 Experimental Process .............................................................................. 4
3.2.1 Sample preparation ..................................................................................... 4
3.2.2 Program setting ........................................................................................... 4

4. RESULTS................................................................................................... 5
4.1 Sample 1: ................................................................................................. 5
4.2 Sample 2: ................................................................................................. 7
5. Conclusion .................................................................................................. 8
6. QUESTIONS .............................................................................................. 8
7.

REFERENCES ....................................................................................... 9

1. INTRODUCTION
1.1 Introduction
In most cases heating a system (element, compound, mixture) causes physical
and chemical changes, such as change in modification, melting, evaporation,
sublimation, absorption, desorption, and crystallization.
Differential thermal analysis (DTA) is a technique in which the temperature of
the substance under investigation is compared with the temperature of a
thermally inert material. This differential temperature T is then plotted
against temperature or time to get DTA curve.
From the curve, we can get the knowledge of these physical or chemical
changes. Knowledge of these properties and the changes are important for
scientific and practical interest, especially for material preparation,
determination of phase diagrams and phase stability.

2. THEORETICAL BACKGROUND
2.1 Theory
An idealized representation of the two major processes observable in DTA is
illustrated in Fig. (1), where T is plotted on y-axis and T (Temperature) on xaxis. Endotherms are plotted downwards and exotherms upwards. Similarly,
the temperature of the sample is greater for an exothermic reaction, than that of
the reference, for endotherms the sample temperature lags behind that of the
reference.
When no reaction occurs in the sample material, the temperature of the sample
remains similar to that of reference substance. This is because both are being
heated exactly under identical condition i.e. temperature difference T (TsTr)
will be zero for no reaction. But as soon as reaction starts, the sample becomes
either hot or cool depending upon whether the reaction is exothermic or
endothermic. A peak develops on the curve for the temperature difference T
against temperature of furnace or time. Let us consider the DTA curve in Fig.
(1) again, where T along the line AB is zero indicating no reaction but at B
where the curve begins to deviate from the base line corresponds to the onset
temperature at which the exothermic reaction starts and give rise to a peak
BCD with a maximum at point C. Where rate of heat evolution by the reaction
is equal to the difference between the rates of evolution of
heat and inert reference material. The peak temperature C corresponds to the
maximum rate of heat of evolution. It does not represent the maximum rate of
reaction nor the completion of the exothermic process. Thus, the position of C
does not have much significance in DTA experiments.
2

Fig. (10.1): A representation of the DTA Curve showing exotherm, endotherm and
base line changes

At some determinant point the heat of evaluation process is completed and

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

3. EXPERIMENTAL PART
3.1 Equipment

Netzsch GmbH STA 409 DTA device

2 Al2O3 crucibles
Bp210D Sartorius mass measurement device
CaSO4.2H2O powder

3.2 Experimental Process

3.2.1 Sample preparation
Gypsum CaSO42H2O is used as sample material. Gypsum is an important
construction material. It is used in the cement industry, in the building industry
and in the medicine. Due to the low dehydration temperatures gypsum is
suitable for DTA measurements.
Dehydration of Gypsum:
CaSO4.2H2O CaSO4.0.5H2O + 1.5 H2O
CaSO4.0.5H2O CaSO4 + 0.5 H2O

The aluminum-oxide crucible has to be filled two third of its height and to be
weighted. The measurements are done with above described programs in air.
For each measurement new samples are used. After the measurement is done,
the samples are weighted again for controlling the weight reduction.
3.2.2 Program setting
Sample1
Segment
1
2
3
4

Beginning
Temperature (C)
20
300
300
20

Ending Temperature
(C)
300
300
20
20

Heating Rate
(K/min)
5
0
-5
0

Beginning
Temperature (C)
20
300
300
20

Ending Temperature
(C)
300
300
20
20

Heating Rate
(K/min)
20
0
-20
0

Time(min)
10
10

Sample2
Segment
1
2
3
4

Time(min)
10
10

4. RESULTS
4.1 Sample 1:
Heating rate:5K\min,300 C
Sample mass/mg: 167.760
Sample material: Gypsum
Reference material: Al2O3
Reference mass/mg: 448.920
Type of crucible: DSC/TG pan Al2O3
Sample crucible mass/mg: 1380.160
Reference crucible mass/mg: 1376.120

DTA Vs Time & Mass Vs Time

0.05

DTA/(V/mg)

Mass/%

120

0.04
100

0.03
0.02

80

0.01

0.00

60
19
21
23
25
27
29
31
33
35
37
39
41
43
45
47
49
51
53
55
57
59
61
63
65
67

DTA/V/mg

Mass/%

-0.01

40

-0.02
-0.03

20

-0.04
-0.05

Time /Minutes

Figure 10.2: The DTA and Mass against time Curve of sample1

0.05
0.04

DTA Vs Temperature (Sample 1)

DTA/(V/mg)

0.03
0.02
0.01

DTA/V/mg

22
22
22
28
40
59
80
104
116
131
147
160
173
188
202
215
228
240
251
260
269

0
-0.01
-0.02

-0.03
-0.04
-0.05

Temperature /C

Figure 10.3: The DTA against temperature of sample1

4.2 Sample 2:
Heating rate:20K\min,300C
Sample mass /mg: 151.120
Sample material: Gypsum
Reference material: Al2O3
Reference mass/mg: 448.920
Type of crucible: DSC/TG pan Al2O3
Sample crucible mass /mg: 1374.320
Reference crucible mass/mg: 1376.120

DTA Vs Time (Sample 2)

DTA/(V/mg)

Mass/%

0.1

120

0.08

100

0.06
80

DTA/(V/mg)
0.04

60
0.02
40

20

-0.02

-0.04

19

18

18

17

16

15

15

14

13

12

12

11

10

Time (Minutes)

Figure 10.4: The DTA & Mass against time of sample2.

5. Conclusion
It could be observed from the results that Phase Transition take place in our
sample i.e evaporation that caused the decrease of sample mass (See Figure
10.2 & 10.4).
Higher heating rate are used in the experiment than equilibrium that cause the
overlapping of the two succesive phase transition results.
Also during phase transition one can find large difference between the sample
& the refrence which indicates that during phase transition sample temperature
not increase.

6. QUESTIONS
1. Descripe the correlation between uptaking and release of heat and the
corresponding changes of the thermodynamic state of the sample.
During heat process, the material takes the heat and increases its
temperature as long as there is no transition. The change amount of
temperature T can be calculated with this equation.
q = m C T
q is the amount of the heat that we give to the system during heat process.
C is the specific heat capacity constant depends on the conditions. If the
pressure of the system is constant then the heat capacity is defined as C p
and if the volume of the system is constant then it is defined as Cv. Enthalpy
of the system is defined as ;
H = U + PV
U is the internal energy, P is pressure and V is volume of the system. The
change in enthalpy is defined in thermodynamic as;
The change of enthalpy can be calculated with this equation which is
heated from T1 to T2.
The transformation of a substance from one modification to another cause a
change of the enthalpy. The uptake, or absorption of the heat, causes some
of the heat applied is used for the transformation, hence causing the
temperature of the sample reduced. In other hand, the release of the heat to
the system during the transformation, causes additional temperature in the
system and the temperature system is increased.

2. Descripe the different types of phase transitions.

There are two types of phase transitions. First order phase transition and
second order phase transition. If the first derivative of the chemical
potentials are discontinous at the transition point, it is a first order
transition. If the first derivative of the chemical potentials changes
continous and the second derivative changes discontinuous, it is a transition
second order.
Examples of first transition are melting, boiling, and most of the
modification changes. Example of the phase transition of the second order
is the dehydration reaction of CaSO4.2H2O.
3. Descripe the principle of the differential thermal analysis.
The principle of the DTA is measuring the temperatures of a sample and
reference material while heating them in the same conditions in a furnace.
One can measure the phase transition, exothermic and endothermic
reactions with the change of the temperature.
4. Which test conditions can influence the results of the DTA? How are
the results dependent on parameters like heat conductivity,
temperature conductivity, density and geometry of the samples, sample
weight, geometry of the thermocouples and latent heat of the
reactions?
Furnace atmosphere, heating rate and reference substances influence the
test conditions directly. Furnace atmospher changes when after dehydration
of water and increases the pressure of the furnace. Dehydration process will
be more difficult than before so this will influence reactions and the results
of the DTA. Also as we can see from figure 2.1 and figure 2.3 heating rate
influences the rate of the heating explicitly. Reference is the one of the
most important varible which effects the result of DTA directly. Reference
sample should have the similar heat capacity and eat conductivity with the
sample and it should not have phase transition in the measured temperature
range.

7. REFERENCES
1. M110 DTA Lab Manuscript