Differential thermal analysis

& differential scanning

calorigraphy

By wilwin edara
(I/II M.Pharm)
CHIPS
 Thermal Analysis Techniques

 A group of techniques in which a physical property

is measured as a function of temperature.
 The sample is subjected to a predefined heating or
cooling program.
 Types of thermal analysis

 TG (Thermo gravimetric) analysis:

weight

 DTA (Differential Thermal Analysis):

temperature

 DSC (Differential Scanning Calorimetry):

temperature
Differential thermal analysis
Le-Chateliar studied clays & minerals by an
examination of temperature –time curves.

Later Robert Austen improved technique by

introducing thermocouples.

Definition: DTA is a technique in which the

temperature between sample & thermally inert
reference substance is continuously recorded as a
function of temperature /time.
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 .
 DTA Principle

Differential thermal analysis is a

technique in which the
temperature of the substance
under investigation is
compared with the
temperature of a
thermally inert material.
 Differential Thermal Analysis
sample holder
sample and reference cells (Al)

sensors
Pt/Rh or chromel/alumel thermocouples one for the
sample and one for the reference joined to
differential temperature controller

furnace
alumina block containing sample and reference cells

temperature controller
controls for temperature program and furnace
atmosphere

Recording system
DTA Instrument
 Differential Thermal Analysis

advantages:

instruments can be used at very high temperatures

instruments are highly sensitive

flexibility in crucible volume/form

characteristic transition or reaction temperatures can be

accurately determined

disadvantages:

uncertainty of heats of fusion, transition, or reaction

estimations is 20-50%
 Applications of Differential thermal
analysis

Qualitative and Quantitative Identification of Minerals:

detection of any minerals in a sample
Polymeric Materials: DTA useful for the characterization of
polymeric materials in the light of identification of thermo
physical , thermo chemical, thermo mechanical and thermo
elastic changes or transitions.
Measurement of Crystalline: measurement of the mass fraction
of crystalline material in semi crystalline polymers.
Analysis of Biological Materials: DTA curves are used to date
bone remains or to study archaeological materials.
 Differential Scanning Calorimetry

this technique is developed by E.S.Watson and

M.J.O’Neill in 1962.
 introduced commercially at the Pittsburgh
Conference on analytical Chemistry and Applied
Spectroscopy.
First Adiabatic differential scanning calorimeter
that could be used in Biochemistry was developed by
P.L.Privalov in 1964.
 Principle

In DSC the heat flow is measured and plotted against

temperature of furnace or time to get a thermogram. This is the
basis of Differential Scanning Calorimetry (DSC).

The deviation observed above the base (zero) line is called

exothermic transition and below is called endothermic transition.

 The area under the peak is directly proportional to the heat

evolved or absorbed by the reaction, and the height of the curve is
directly proportional to the rate of reaction.
DSC Curve
 Heat Flux DSC
•sample holder
•sample and reference are connected by a low-resistance heat
flow path Al or Pt pans placed on constantan disc
•sensors
chromel®-constantan area thermocouples (differential heat flow)
chromel®-alumel thermocouples (sample temperature)
•furnace
one block for both sample and reference cells
•temperature controller
the temperature difference between the sample and reference is
converted to differential thermal power, dDq/dt, which is
supplied to the heaters to maintain the temperature of the sample
and reference at the program value
Heat flux DSC
 Power Compensation DSC
individual
heaters
controller P

sample holder
sample reference

Al or Pt pans pan pan

sensors inert gas

vacuum
inert gas
vacuum

Pt resistance thermocouples thermocouple T=0

separate sensors and heaters for the sample and reference

furnace
separate blocks for sample and reference cells

temperature controller
differential thermal power is supplied to the heaters to maintain
the temperature of the sample and reference at the program
value
 Applications of DSC
Protien Stability and Folding
Liquid Biopharmaceutical Formulations
Process Development
Protien Engineering
Rank order Binding
Antibody Domain Studies
Characterisation of Membranes,lipids,nucleiec acids & micellar
systems
Assesment of the effects of structural change on a molecules
stabiity
Measurement of Ultra-light molecular interactions
Assesment of biocomparability during manufracturing.
 Applications of DSC

Polymers:
composition of polymers is determined.
Melting point and lass transition temp can be determined
This can show the polymer degradation by lowering the melting
point(Tm).Molecular weight(low grade –low melting point) can be
determained.
Percentage Crytallinity
Thermal degradation and impurities
Liquid crystals

Oxidative Stability: stability & optimum storage conditions

Drug analysis: widely used in Pharmaceutical industry(defining

processing parameters) and polymer industry(curing process.).

General Chemical analysis: Freezing point depression can be

used as a purity analysis tool.

Functional Applications:
Binding Studies
 Of DSC
Binding Sites;
References:

 Instrumental methods of Chemical analysis-GURDEEP

R.CHATWAL ,pg-no;701 to 739.

 Instrumental methods of chemical analysis-B.K.SHARMA,pg-

no;M-390 to 421.

 Instrumental methods of Chemical analysis,H.KAUR.pg.no-919

to 932.

 www.wikipidia.com

 www.microcal.com/technology/dsc.asp