THERMAL METHODS OF

ANALYSIS
PRESENTED BY
SAIKRISHNA S
S1 PG CHEMISTRY
St. JOSEPHS COLLEGE FOR WOMEN
ALAPPUZHA
 DIFFERENTIAL THERMAL ANALYSIS (DTA)

DTA is a technique in
which the difference in
temperature
between substance and
a reference material is
measured as
a function of
temperature while the
substance and
Reference material is
subjected to a
controlled temperature
programme
INSTRUMENTATION
PRINCIPLE
DIFFERENTIAL SCANNING
CALORIMETRY
(DSC)
WHAT IS DSC ?

DSC is a technique in which the

difference in energy inputs into
a substance and a reference
material is measured as a
function of temperature.
 Two modes depending on the methods of measurement used;
1. Power compensation DSC
2. Heat flux DSC

POWER COMPENSATION DSC

 Here, the energy necessary to establish a zero temperature
difference between the sample and reference material is
measured as a function of temperature or time.
 Eg. Consider an endothermic transition;
Intial zero temperature difference between sample and
reference Heat absorption from the sample  The
temperature difference between sample and reference changes
from zero  Input of energy equivalent to absorbed energy
into the sample  Back to zero temperature difference.
 Since the energy input is precisely equivalent in
magnitude to the energy absorbed in transition,
direct calorimetric measurement of the energy of
transition is obtained.
 On the DSC chart recording ;
Abscissa  transition temperature
Peak area  total energy transfer to or from the
sample.
 INSTUMENTATION
This makes a direct measurement of the
enthalpy change .
Sample and reference materials are supplied
with separate heaters maintained at same
temperature.
When an endothermic reaction occurs, energy
absorbed by the sample is replenished by an
increased energy input into the sample;thus
maintaining the temperature balance.
 The Pt resistance thermometers
are the sensors.

 Separate heaters are provided for

sample and reference pans.
 DTA  Single heat source  Measures temperature difference.
 DSC  Separate heat source  Measures heat flow difference.
 HEAT FLUX DSC
This variant is based on heat flux
measurement.
A single heater is used to heat the sample
and reference.
Allow temperature between the sample and
reference to vary.
The difference in temperature is used to get
the required heat flow.
INSTRUMENTATION WORKING
Consists of a cylindrical silver heating block.
This block gives heat to the specimen via Constantan
thermoelectric disc.
The disc has two raised platforms on which sample
and reference are placed.
A chromel disc is attached underside of each
platforms.
The chromel-constantan thermocouple is used to
measure differential temperature.
The alumel – chromel thermocouple determines
individual temperatures of sample and reference.
Thermocouple embedded in silver block ,acts as
temperature controller for programmed heating cycle.
SCHEMATIC DIAGRAM OF DSC
 WORKING
The Sample and reference are sealed in Al or Cu pan.
The pans are placed adjacent to each other.
A common heating is applied to both.
The heater heats sample and reference at constant rate and
sensor senses temperature.
Now,sample tends to absorb or release heat due to transition
& temperature varies.
To maintain constant temperature, more or less heat supplied
to the sample.
The amount of heat transferred to sample is monitored by pc
and output received in the form of thermogram.
COMPARISON OF POWER
COMPENSATION & HEAT FLUX DSC
POWER COMPENSATION DSC HEAT FLUX DSC

Separate heaters are used. Single heater is used.

Gives better resolution. Less sensitive.
Rapid cooling and Slower heating and
heating. cooling rate.
 DSC CURVE

The area of the peak corresponds to the total energy

which is transferred to or from the sample.
DTA CURVE { for comparison }
FACTORS AFFECTING DSC CURVES
INSTRUMENTAL
FACTORS
 Heating rate
 Geometry of sample
holder
 Location of sensors
 Recorder or chart speed
 Sensitivity of recorder
 Furnace atmosphere
 Material of sample holder
SAMPLE
CHARACTERISTICS
 Amount
 Size of particle
 Nature
 Compactness
 Heat of reaction
 Thermal conductivity
 Solubility of evolved
gases in sample
 APPLICATION OF DSC
 In TG , absorption or release of energy accompanied by
weight change, only is monitored.The changes that isn’t
accompanied by weight change such as melting,
crystallization, fusion, solid state transition etc. can be
monitored using DSC.
DSC along with DTA is used in pharmaceutical chemistry
for investigation of product purity, identification of optical
isomers, polymorphism and eutetic formation.
In food industry, edible fats and oils are characterized by
DSC.
 DSC can be used for the analysis of blends of
synthetic fibres (polymer blends).
 Used in cement industry in the determination of
calcium sulphate hydrates.
APPLICATION OF TG, DTA, DSC
IN THE STUDY OF METAL
COMPLEXES
1.USE OF TG & DSC IN THERMAL ANALYSIS
OF SOME TRANSITION METAL COMPLEXES
 Combined TG-DSC can be used for thermal analysis of
transition metal complexes like [Cu(L2)Cl2] , [Ni (L2)]Cl2 etc.
 From the results:
1. The thermal decomposition took place in two distinct
steps.
2. The reaction is endothermic upto 700°C.
3. The activation energy( E ) , change in Gibb’s free energy
(∆G) , enthalpy change (∆H) can be calculated from
results of TG analysis.
4. Heat capacity is obtained from results of DSC.
2.TG-DSC STUDY OF THERMAL
DECOMPOSITION OF NiMn(C4H4O4)3.6N2H4

 Thermal decomposition of
Nickelmanganesesuccinatohydrazinate can be studied
using differential scanning calorimetry and
thermogravimetry.
 The DSC-TG study of the complex shows that ;
1. The complex decomposes autocatalytically, once
ignited.
2. Decomposition involves two steps – dehydrazination
followed by decarboxylation.
3.ANALYSIS OF ALKALINE EARTH-
NICOTINATES
 Characterization, thermal stability, and thermal
decomposition of alkaline Earth nicotinates
M(C6H5NO2).nH2O
Where M = Mg(II) , Ca(II) , Sr(II), Ba(II).
From the results:
1. Thermal decomposition occurs with formation of
carbonate as intermediate and respective oxides as final
residue.
2. Exception: for magnesium compounds, thermal
decomposition occurs with the formation of oxide,without
formation of carbonate.
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REFERENCES

1. PRINCIPLES OF INSTRUMENTAL ANALYSIS-

BY DOUGLAS SKOOG
F JAMES HOLLER
STANLEY R CROUCH

2. VOGEL’S TEXT BOOK OF QUANTITATIVE CHEMICAL ANALYSIS

THANK YOU