DIFFERENTIAL THERMAL

ANALYSIS (DTA)
 INTRODUCTION
 DTA may be defined formally as a technique for recording the difference in temperature between a substance and a
reference material against either time or temperature as the two specimens are subjected to identical temperature
regimes in an environment heated or cooled at a controlled rate.

 In differential thermal analysis (DTA), both the test sample and an inert reference material (usually ά-alumina) undergo
a controlled heating or cooling programme which is usually linear with respect to time.

 There is a zero-temperature difference between the sample and the reference material, when the sample does not
undergo any chemical or physical change.

 But if any reaction takes place, then a temperature difference (⧍T) will occur between the sample and the reference
material.

 Thus, in an endothermic change (when the sample melts or is dehydrated), the sample is at a lower temperature than
the reference material. This condition is only transitory because, on completion of the reaction, the sample will again
show zero temperature difference compared with the reference.
Principle:
The basic principle involved is: the difference of temperature (∆T) between the test sample(T S) and an inert
reference sample(TR) under controlled and identical conditions of heating or cooling is recorded continuously as
a function of temperature or time.
 The heat absorbed and emitted by a chemical system can be estimated or determined.
 The changes are two types- exothermic and endothermic
 If endothermic- ∆T = TR – TS = +ve or TS – TR = -ve
 If exothermic- ∆T = TR – TS = -ve or TS – TR = +ve
 INSTRUMENTATION

1. Sample Holder
Sample and reference crucible are generally metallic or ceramic(silica) and may or
may not have a lid, for good results area of contacts b/w sample and crucible is
maximized. Typically 1-10 mg of sample is required for analytical applications.

2. Furnace
Reference and sample should be thermally matched and symmetrically arranged
with the furnace so that both of them are identically cooled or heated, metal block
around the wall acts as a heat sink and by using internal heater temperature of the heat Schematic Diagram of DTA Apparatus
sink is slowly increased sink in turn heat the sample and reference material.

3. Sensors and recording system

 Pair of matched thermocouple is used; one pair is in contact with the sample while
the other pair is in contact with the reference.
 The output of the differential thermocouple Ts-Tr is sent to the data acquisition
system after amplification.
 Operating temperature for DTA instruments is generally from room temperature
to around 1600 °C.
 Liquid nitrogen cooling accessories is needed for very low sub ambient
temperature. Figure 5 shows instrumentation of DTA.
Block Diagram of DTA apparatus
 Representation of DTA Data:
 In DTA, a plot is made of ∆T against temperature or time, if the heating or cooling
programme is linear with respect to time.
 An idealised DTA curve shown in Fig. Peak I is an exothermic peak and peak 2 is an
endothermic peak.
 The Shape and size of the peaks can give a large amount of information about the nature
of the test sample.
 The sharp endothermic peaks often signify changes in crystallinity or fusion processes
while broad endotherms arise from dehydration reactions.
 Physical Changes usually result as endothermic curves whereas chemical reactions,
particularly those of an oxidative nature, are predominantly exothermic.

Idealised DTA curve : (1) exothermic

Note : peak. (2) endothermic peak
 The shape of a DTA peak does depend on sample weight and the heating rate used.

 Lowering the heating rate is roughly equivalent to reducing the sample weight; both lead
to sharper peaks with improved resolution.

 The influence of heating rate on the peak shape and disposition can be used to advantage
in the study of decomposition reactions, but for kinetic analysis it is important to
minimise thermal gradients by reducing specimen size or heating rate.
 Factors Affecting Thermogravimetric Results
 Since DTA is a dynamic technique, a large number of factors can affect the resulting experimental curves.
 If the DTA curve is used for quantitative purposes, the shape, position, the area enclosed by the curve are of
great interest.
 For specific heat measurements the baseline deviations become important and such conditions as particle
size, system symmetry, sample packing must be taken into account if accurate results are to be obtained.
 As with the technique of thermogravimetry, the DTA curve is dependent on two general categories of variables:
instruments factor and sample characteristics.

2. Instrumental parameters
It includes furnace atmosphere, size and shape of furnace, sample holder materials, sample holder geometry,
heating rate, and location of thermocouple in sample chamber, speed and response of recording device.
2. Characteristics of sample

 It includes particle size of sample, amount of

sample, packing density, swelling or shrinkage
characteristic of sample, degree of crystallinity,
presence of diluents, thermal conductivity and heat
capacity.
 The effect of furnace atmosphere is similar to that
discussed in the thermogravimetry section and is
significant for equilibrium reactions.
 An increase of the heating rate would cause the
spreading of the DTA curve.
 Since the return of the signal to the baseline is a
time function, this will happen at a higher actual
temperature with more rapid heating as shown in
figure.
DTA provides information about:

(1) phase transformations

(2) structure inversions
(3) dehydration
(4) decomposition or dissociation
(5) oxidation or reduction
(6) destruction
(7) formation of crystalline lattice structure
(8) multiple transitions in crystalline structure
(9) recrystallization of quenched samples
(10) stress release
(11) reactions due to the presence Of impurities
(12) volatilization of liquids, etc.
 where m mass of the sample; ∆H = enthalpy of involved reaction; ⧍T = differential temperature; dt = differential operation, g=
geometrical factor of the apparatus; k = thermal conductivity of the sample. The enthalpy ⧍H is given a negative sign for an exothermic
reaction and a positive sign for an endothermic reaction.
For a given species, k' remains constant, provided the variables like heating rate, particle size of the sample and placement of the
thermocouples are closely controlled.
Under these circumstances it is possible to calculate :
i. mass of the analyte from peak areas by determining k' and ⧍H value by calibration
ii. ⧍H for species, when k' and m have been measured.

 It is possible to measure the heat capacity Cp at constant pressure using DTA:

where Tl and T2 are the differential temperatures generated when the apparatus is first run without any sample at all and then with the test
sample in position. H is the heating rate and the constant K" is determined by calibration against standard substances.
APPLICATIONS
1. Qualitative Analysis of materials
 A rapid method for the fingerprinting of minerals, clays and polymeric materials was provided by
DTA measurements.
 For example, using DTA with a nitrogen atmosphere, chrysolite (white asbestos) was shown to
give a dihydroxylation endotherm at 650ºC and a characteristic crystallisation exotherm at 845ºC.
 A sample containing 1% w/ w chrysolite in talc was detected by DTA.
 This fast technique does not involve the extensive sample preparation required by competitive
methods.
 Polymers can exhibit their own characteristic melting point endotherms. Thus, in a blend containing
seven commercial polymers, each component was readily identified by the endotherm of melting
using DTA.
2. Fig. shows the differential thermogram of calcium oxalate monohydrate in a flowing air (O2), obtained by increasing
temperature at a rate of 8ºC/min.

 It contains two minima (for endothermic processes), equations for these decomposition reactions are shown below the
maxima. The single maxima indicate that oxidation of CaC2O4 to CaCO3 and CO2 is exothermic.

Note:
 If the differential thermogram of calcium oxalate monohydrate is obtained in an inert atmosphere.

 Then maxima changes to minima, since the decomposition reaction under inert condition would be

CaC2O4 CaCO3 + CO

which is an endothermic process. Hence, there will be three maxima.

Fig: Differential thermogram Of CaC 2O4. H2O

in a flowing stream of air
3. DTA provide information regarding processes like fusion, 4. DTA provides an accurate way of determining the
dehydration, dissolution, oxidation, reduction, adsorption, melting and boiling points for organic compounds. Fig.
degradation and solid-state reactions. shows the DTA for benzoic acid at:
 One of the applications of DTA is the generation of phase
(a) atmospheric.
diagrams and the study of phase transitions.
 Fig. shows the DTA thermogram for pure sulphur. (b) 200 lb/m2 (psi).
 Peaks at 113ºC, 124ºC, 179ºC and 446ºC corresponds
 The first peak corresponds to the melting point; while
respectively to the solid-phase change from the rhombic to the
monoclinic form, melting point of sulphur, a transition among the second to the boiling point.
three forms of sulphur and the boiling point of sulphur.

DTA Curve for Benzoic Acid

DTA Curve of Sulphur
5. DTA has been widely used to study and characterization of polymers. Fig. is an idealized DTA
curve that illustrate the various type of transitions that may be encountered during heating of a
polymer.

Note:
 Glass transition temperature (Tg) may be defined as the temperature at which the constituent
particles begins to have translatory motion.

 Alternatively, it is the temperature at which the expansion coefficient of solid exhibits a sharp change.

 In terms of configurational entropy model, it is the temperature at which the configurational entropy of
the material is zero.

Fig: Schematic DTA Thermogram of a

polymer
6. DTA can be used for qualitative analysis of polymer mixture.
 Fig shows a DTA thermogram of a mixture containing of polymers.
 Each peak gives the characteristic melting point of one of the polymers.
 PTFE, however, has an additional low temperature peak, due to a crystalline transition.

Thermogram for a mixture containing PTFE (polytetrafluoroethylene); HIPPE [(high-

pressure low-density polyethylene]; LPPE [low pressure (high density polyethylene);
PP (polypropylene): POM (polyoxymethylene); Nylon 6 and Nylon-66.