Dnyanasadhana College, Thane.


hhh

Department of Chemistry

T.Y.B.Sc. Analytical Chemistry

Paper-IV Sem-VI

DIFFERENTIAL THERMAL analysis

Dr.Bhagure G.R.
1
 Contents
• 4.1.3 Differential Thermal Analysis (DTA):
Principle,
• Instrumentation –balance,
• Thermocouple
• Reference material used in TA (MgO,Al2O3,SiC),
• DTA curve
• Applications : DTA of CaC2O4.H2O and
CuSO4.5H2O, Difference between TGA and
DTA.
• DTA is a technique in which the
temperature difference between the
sample and the reference material
(thermally inert ) is continuously
recorded as a function of temperature or
time.
• The sample and reference material are
subjected to a controlled temperature
programme

• A graph of ∆T Vs.
temperature is plotted
 Principle of DTA
• When a graph of ∆T Vs.
temperature is plotted, the maxima
and / or minima due to exothermic
and/ or endothermic processes.
• Maxima and minima are called as
peaks.
• Maxima = exothermic process in
which heat is evolved from the
sample causing temperature to
increase.
• Minima = endothermic process in
which heat is absorbed by the sample
causing temperature to decrease.
Peak area (A) is corrected to the mass of the analyte (m) as

A = KGm∆H
= K’ m ∆ H

G = calibration factor related to sample geometry

K = constant related to thermal conductivity of sample
K’ = constant related to heating rate, particle size,
placement of sample etc.

The mass of a particular analyte can be determined if

K’ and ∆ H can be known by calibration.
 MELTING

Vaporization

Boiling
Endothermic
Desolvation

Solid–solid phase
transitions

Chemical
degradation
 Crystallization

Oxidative
decomposition
EXOTHERMIC
REACTIONS
Solid state
reactions

Chemisorption
DIFFERENTIAL THERMAL ANALYSER

1.Sample holder

2.Furnace.
Instrumentation
3.Temperature
programmer

4.Recording
system
SCHEMATIC DIAGRAM OF DTA
INSTRUMENT

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 • The sample holder assembly consists of a
thermocouple each for the sample and
1.Sample reference, surrounded by a block to ensure
holder an even heat distribution.
• sample containers made from ceramic or
metallic block.

• Furnace consist of electrical heating

systems. Electrical heating coils are made
2.Furnace from Nichrome wire windings & platinum
wire windings.
or heating • Furnace should provide uniform hot &
device linear heating rate one
• Should have cooling facility for rapid
return to ambient temperature
 • Thermocouple are used as temperature
sensors.
• Thermocouples are made from Chromel
P Alumel wires (both made of Nickel-
chromium alloys) are used to measure
temperature upto 11000C.
• Thermocouples are made of pure
Platinum and Platinum-Rhodium are used
to measure temperature above 11000C.
3. • While selecting thermocouples as
THERMOCOUPLES temperature sensors, the following points
should be consider,
• Temperature interval
• Thermoelectric coefficient
• Chemical compatibility with the sample
• Chemical gaseous environment
• Reproducibility
• Availability
• Cost
4.Differntial • The thermocouples served as the
temperature sensor .The voltage signal
Temperature produced dependence on the
Detector temperature different, ∆T between two
junctions of the thermocouples

• It Consist of an amplifier to
magnify signals coming from
5.Recorder temperature sensor (T) &
differential temperature sensor
(∆T) of the thermocouples
 • A Facility for flushing the sample
& reference assembly with
6.Atmpospheric selected gas is provided.
Control & • There is also cooling facility to
Cooling cool the assembly to ambient
Controls: temperature .
• Liquid Nitrogen is used in a
special low temperature assembly.
 Reference material used in DTA
(MgO,Al2O3,SiC

MgO

Reference
material used Al2O3
in DTA

SiC
 Should not under go
thermal events over
the operating
temperature

It should be inert
Characteristic of the
towards sample
Reference material
holder or
used in DTA
thermocouple
Thermal
conductivity & het
capacity should be
similar to that of
sample
 Sample
characteristics

Factors
2. Instrumental
affecting DTA
characteristics
curve

3.Environment
l factors
 Amount of Sample:
Small size sample give best
peak which can be easy for
resolution.

Particle size:
Sample Finely powdered sample size
sample give best peak. Particles
characteristics having bigger size increases the
peak area.
Sample packing:
It is regular practice to mix Sample
with inert material like glass like
alumina. The degree of crystallinity of
sample and compactness also affect on
DTA curve.
 Sample holder
Sample holders made up from high thermal conducting material gives sharp
exothermic peak but relatively flat endothermic peak.
Generally very small sample holders made from glass or ceramic re used.
Sometimes shallow metallic pans are used.

Thermocouples:
Position of Thermocouples affect on DTA curve.
If Position of Thermocouples is not varies reproducible results can be
obtained

Instrumental Furnace characteristics: The type of winding on furnace shows direct effect
on DTA curve.
characteristics
The grooved muffled core furnace are preferred because it gives uniformity in
windings.

Heating rate:
Heating rate has great influence on DTA curve. Generally ,heating rate of
100c to 200c is preferred for sharper peak .

Recorder:
DTA curve also effect by type, chart speed, and pen response of recorder.
 Static gaseous
atmosphere: Studies
in Static gaseous
atmosphere are not
precise.
3.Environmentl
factors
Dynamic gaseous
atmosphere: The
results obtained in
Dynamic gaseous
atmosphere re more
precise & accurate
 Clay
Qualitative
analysis
Reaction
products
 DTA peaks re
proportional to total het
of reaction which is
equivalent to wt. of the
sample

Analysis of Polymers
Quantitative analysis

Ceramic & metal

Industry

Phase transitions
Ex.Sulphur
•DTA
Curves
 DTA curve of CaC2O4.H2O in the
presence of O2. Heating rate = 80C/min
Calcium oxalate monohydrates gives two
endotherms
1.
Aroun
• CaC2O4.H20CaC2O4 +H20
d
200 Oc
2.
Aroun
d • CaCO3.CaO +C02
800 Oc
Calcium oxalate monohydrates gives one
exotherms

1.
Intermediat
e • 2CaC2O4O+O2CaCO3+CO2
Exotherm • (In Air)

• In Nitrogen atmosphere the above

process is endothermic
 DTA curve of CuSO4.5H2O in the presence of
O2. Heating rate = 80C/min

∆T

100 200 250 300 

 DTA curve of CuSO4.5H2O gives three
endotherms

1. • CuSO4.5H2O CuSO4.3H2O
81-96 Oc

2. • CuSO4.3H2OCuSO4.2H2O
111- 120 Oc

3.
• CuSO4.2H2OCuSO4.H2O
220-250 Oc
DIFFERENCE BETWEEN TGA & DTA
TGA
 Change in mass of sample
with increase in temperature
 Plots a graph of change in
mass Vs. T
 Change in mass gives
information about
• Change in sample
composition
• Change in thermal stability
• Change in kinetic
parameter
DTA
 Measure the temperature
difference between sample
and reference with increase
in temperature.
 Plots a graph of ∆T Vs.
T
 maxima and minima gives
information about
exothermic and endothermic
processes associated with
sample
 Instruments can be
used at very high
temperatures

Instruments are highly

Advantages
sensitive

Characteristic
transition or reaction
temperatures can be
accurately determined.