Differential thermal analysis and differential scanning calorimetry: A History

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 DIFFERENTIAL THERMAL ANALYSIS (DTA)

• Differential thermal analysis, DTA, is the simplest and most widely used thermal analysis technique.
• Differential thermal analysis (DTA) is a technique in which the difference in temperature, ΔT, between the
sample and an inert reference material is measured as a function of temperature or time while the
temperature of the sample, in a specified atmosphere, is programmed.
• Both sample and reference material must be heated under carefully controlled conditions.
• If the sample undergoes a physical change or a chemical reaction, its temperature will change while the
temperature of the reference material remains the same.
• DTA is capable of measuring the same changes measured by TGA, plus many additional changes that TGA
cannot measure because no mass change occurs.

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• A DTA plot or thermal curve has ΔT on the y-axis and T (or time) on the x-axis.
• The x-axis temperature can be the temperature of the heating block, the temperature of the sample or the
• temperature of the reference, or it can be time.
• By convention, exothermic changes are plotted as positive, and the peaks point up, while endothermic changes are
plotted as negative, and the peaks point down.
• Some changes, such as the glass transition, do not result in a peak, but only a step change in the baseline. 4
 DTA Instrumentation
• The sample is loaded into a crucible, which is
then inserted into the sample well (marked S).
• A reference sample is made by placing a
similar quantity of inert material (such as
Al2O3) in a second crucible. This crucible is
inserted in the reference well, marked R. The
reference material should have the following
characteristics: (i) It should undergo no
thermal events over the operating
temperature range. (ii) It should not react with
the sample holder or thermocouple, (iii) Both
the thermal conductivity and the heat capacity
of the reference should be similar to those of
the sample. Alumina, and carborundum, SiC,
have been extensively used as reference
substances for inorganic samples, while for
organic compounds, especially polymers, use
has been made of octyl phthalate and silicone
oil. 5
 DTA Instrumentation

• The dimensions of the two crucibles and of

the cell wells are as nearly identical as
possible; furthermore, the weights of the
sample and the reference should be virtually
equal. A standard experiment might involve a
sample of about 10-20 mg of powder.

• The sample and reference should be matched

thermally and arranged symmetrically with
the furnace so that they are both heated or
cooled in an identical manner. The metal
block surrounding the wells acts as a heat
sink.
• The temperature of the heat sink is slowly
increased using an internal heater. The sink in
turn simultaneously heats the sample and
reference material. Heating rates between 0
and 100 K/min are used, but the normal rate
is about 10 K/min. 6
• Modern DTA instruments have the ability to change atmospheres from inert to reactive gases.

• As is the case with TGA, the appearance of the DTA thermal curve depends on the particle size of the
sample, sample packing, the heating rate, flow characteristics inside the furnace, and other factors. Both
solid samples and reference materials are usually used in powdered form.

• Thermal matching between the sample and the reference is often improved by diluting the sample with the
inert reference, keeping the total masses in each crucible as close to each other as possible.

• Sample crucibles are generally metallic (Al, Pt) or ceramic (silica). Best results are obtained when the area of
contact between the sample and the pan or crucible is maximized.

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• A pair of matched thermocouples is used. One pair is in contact with the sample or the sample
container (as shown); the other pair is in contact with the reference. The output of the differential
thermocouple, Ts -Tr or ΔT, is amplified and sent to the data acquisition system.

• This allows the difference in temperature between the sample and the reference to be recorded as a
function of either the sample temperature, the reference temperature or time.

• If there is no difference in temperature, no signal is generated, even though the actual temperatures of
the sample and reference are both increasing.
• Operating temperatures for DTA instruments are generally room temperature to about 1600 oC. To
reach the very low sub ambient temperatures, a liquid nitrogen cooling accessory is needed. Some low
temperatures may be reached with electrical cooling devices or with forced air-cooling.

• When a physical change takes place in the sample, heat is absorbed or generated. For example, when a
metal carbonate decomposes, CO2 is evolved. This is an endothermic reaction; heat is absorbed and the
sample temperature decreases. The sample is now at a lower temperature than the reference.

• The temperature difference between the sample and reference generates a net signal, which is
recorded. 8
• The DTA experiment is performed under conditions of constant pressure (usually atmospheric pressure).

• Under constant pressure, the change in heat content of a sample (the change in enthalpy) is equal to the
heat of reaction, ΔH.

• Any chemical or physical change that results in a change in ΔH gives a peak in the DTA thermal curve.
There are some types of changes that do not result in a peak in the thermal curve but only a change in the
baseline. These types of changes do not undergo a change in ΔH, but a change in their heat capacity, Cp.

• The most common process that gives rise to a change in baseline but not a peak in the DTA is a “glass
transition” in materials such as polymers or glasses.

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A glass resembles a solid in many of its physical
properties, e.g. rigidity, but differs in that the
constituents do not show the regular (lattice)
arrangement of a crystalline solid.

Glasses are thus examples of non-crystalline

solids, do not melt at a sharply-defined
temperature, but soften over a temperature
interval. This transition from the rigid glassy
state to a more flexible form is known as the
glass transition and the temperature interval
over which this change occurs, known as the
glass transition temperature, Tg, is of
tremendous importance in the practical use of
polymers.

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The peak area in DTA is related to the enthalpy change, ΔH, to the mass of sample used, m, and to a large
number of factors like sample geometry and thermal conductivity.

These other factors result in the area, A, being related to the mass and ΔH by an empirically determined
calibration constant, K:

Unfortunately, K is highly temperature-dependent in the DTA experiment, so it is necessary to calibrate

the peak area in the same temperature region as the peak of interest. This may require multiple
calibration standards and can be time consuming.

As we shall see, the calibration constant K for DSC is not temperature dependent; therefore DTA is usually
used for qualitative analysis, while DSC is used for quantitative measurements of ΔH and heat capacity.

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 Analytical Applications of DTA
• The main use of DTA is to detect thermal processes and characterize them as exothermic or endothermic,
reversible or irreversible, but only qualitatively.

• DTA thermal curves can be used to determine the order of a reaction (kinetics), and can provide the
information required to construct phase diagrams for materials.

• DTA can be used for characterization of engineering materials, for the determination of the structural and
chemical changes occurring during sintering, fusing, and heat treatments of alloys to change
microstructure, identification of different types of synthetic rubbers, and determination of structural
changes in polymers.

• The physical properties, such as strength, flexibility and solubility of a polymer depend (among other
things) on its degree of crystallinity. The degree of crystallinity in the semicrystalline polymer can be
calculated from the heat of fusion (the area under the crystallization exotherm), but quantitative
measurements of this sort are usually performed by DSC because DSC is more accurate than DTA for
quantitative analysis.

• Qualitative identification of materials is done by comparing the DTA of the sample to DTA thermal curves
of known materials. DTA thermal curves serve as fingerprints for materials.
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Schematic DTA thermal curves for the totally amorphous polymer structure and the semicrystalline
polymer structure shown in Fig. Both show Tg; only the semicrystalline polymer has a crystallization
exotherm.

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 DIFFERENTIAL SCANNING CALORIMETRY

Differential scanning calorimetry, or DSC, is a thermoanalytical technique in which the difference in heat flow
to a sample and to a reference is monitored against time or temperature while the temperature of the
sample, in a specified atmosphere, is programmed. In practice, the heat is supplied to the sample contained
in the pan, and similarly, to the reference in its pan. The difference in heat flow is a difference in energy; DSC
is a calorimetric technique, and results in more accurate measurement of changes in enthalpy and heat
capacity than that obtained by DTA.

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 DSC Instrumentation
The DSC measurement requires a sample and a reference, as does DTA. Modern DSC sample and reference
pans are usually made of Aluminium. Sample size is generally 1–10 mg.

Often the reference pan is left empty, but an inert reference material such as is used in DTA may be used.
Commercial DSC equipment can operate at temperatures from -180 oC to 700oC. The DSC must be able to be
heated and cooled in a controlled manner. To achieve the very low end of the temperature range, a special
liquid nitrogen cooling accessory is needed; for other cooling applications, electrical cooling or forced air
cooling is used.

In heat flux DSC, the temperature is changed in a linear manner while the differential heat flow into the
sample and reference is measured.

The sample and reference pans sit on the heated thermoelectric disk, made of a Cu/Ni alloy. The differential
heat flow to the sample and reference is monitored by area thermocouples attached to the bottom of the
sample and reference positions on the thermoelectric disk.

The differential heat flow into the pans is directly proportional to the difference in the thermocouple signals.
The sample temperature is measured by the alumel/chromel thermocouple under the sample position. This
temperature is an estimated sample temperature because the thermocouple is not inserted into the sample
itself. 17
The accuracy of this temperature will depend on the thermal conductivity of the sample and its container,
the heating rate, and other factors. As shown in Fig. the sample and reference pans both have lids and the
reference pan is an empty pan.

A schematic of a power compensated DSC is presented in Fig. The major difference in power compensated
DSC instruments is that two separate heating elements are used for the sample and the reference.

A change in temperature between the sample and the reference serves as the signal to “turn on” one of
the heaters so that the sample and the reference stay at the same temperature.

When a phase change, reaction, glass transition, or similar event occurs in the sample, the sample and
reference temperatures become different. This causes extra power to be directed to the cell at the lower
temperature in order to heat it. In this manner, the temperatures of the reference and sample cells are
kept virtually equal (ΔT =0) throughout the experiment.

The power and temperature are measured accurately and continuously. The temperatures of the sample
and reference are measured using Pt resistance sensors, shown in Fig.

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Since an endothermic peak involves the absorption of more power by the sample, one convention plots endothermic peaks
upwards. This does cause some confusion, and so, we shall adopt the 'DTA' convention throughout, while indicating the
sign of heat flow on the y axis. The difference in power input is plotted vs. the average temperature of the sample and
reference. Power compensation provides high calorimetric accuracy, high precision, and high sensitivity. This permits
analysis of very small samples.
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Applications of DSC

DSC is used to study all of the types of reactions and transitions that can be studied using DTA, with the
added advantage of accurate quantitative measurements of ΔH and ΔCp.
Polymer chemists use DSC extensively to study percent crystallinity, crystallization rate, polymerization
reaction kinetics, polymer degradation, and the effect of composition on the glass transition
temperature, heat capacity determinations, and characterization of polymer blends.

Materials scientists, physical chemists, and analytical chemists use DSC to study corrosion, oxidation,
reduction, phase changes, catalysts, surface reactions, chemical adsorption and desorption
(chemisorption), physical adsorption and desorption (physisorption), fundamental physical properties
such as enthalpy, boiling point, and equilibrium vapor pressure.

DSC instruments permit the purge gas to be changed automatically, so sample interactions with reactive
gas atmospheres can be studied.

The heat of fusion is a useful measure of the percent crystallinity of polymers.

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The resultant thermal curve is similar in appearance to a DTA thermal curve, but the peak areas are accurate
measures of the enthalpy changes. Differences in heat capacity can also be accurately measured and are
observed as shifts in the baseline before and after an endothermic or exothermic event or as isolated baseline
shifts due to a glass transition.
Because DSC provides accurate quantitative analytical results, it is now the most used of the thermal analysis
techniques. A typical DSC thermal curve for polyethylene terephthalate, the polymer used in many soft drink
bottles, is shown in Fig. 16.22.

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The experimental set up for heat flux DSC is very similar to that for DTA. DSC will generally have better
resolution.
Finally, as has been discussed earlier, by measuring the power differential, DSC is making a direct
measurement of enthalpy changes and is thus the more satisfactory tool for thermodynamic
measurements.

Comparison of DSC and DTA for CuSO4.5H2O.

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 THERMOMETRIC TITRIMETRY
Thermometric titration is a calorimetric technique, depends on measuring the heat generated during a
chemical reaction. Usually the reactions take place at room temperature under conditions such that no heat
enters or leaves the titration cell except that brought in by introduction of the titrant.

In this procedure a titrant of known concentration is added to a known volume of sample. The titration
reaction follows the generalized chemical equation

For any particular reaction, a mole of A titrated with a mole of B will generate a fixed quantity of heat,
which is the heat of reaction.
If there is half a mole of A present, half as much heat is generated, even if there is an excess of B. Heat is
generated only while A and B react with each other; an excess of either one does not cause generation of
heat.

The reaction is usually set up in an insulated beaker, a Dewar flask, or a Christiansen adiabatic cell. This
ensures a minimum of heat loss from the system during titration.
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In practice, the temperature of the system is measured as the titrant is added to the sample. A thermometric
titration plot generally has ΔT on the y-axis and volume of titrant on the x-axis.

Representative thermometric titration plot. The endpoint is denoted by an abrupt change in the slope of
the curve. The thermometric titration plot for HCl (a strong acid) with NaOH would look virtually identical
to the thermometric titration plot for boric acid (a very weak acid) with NaOH because the ΔH of reaction is
almost the same for both acids. 25
The sample solution and the titrant are initially at room
temperature. As titrant is added and the exothermic reaction
occurs, the temperature of the solution increases. It can be seen
that the temperature of the mixture increases until approximately
4.5 mL of titrant have been added to the sample. This is the
equivalence point of the titration.

Further addition of titrant causes no further reaction, because the

entire sample A has been consumed. The temperature of the
mixture steadily decreases as the cooler titrant is added to the
warm mixture. The endpoint can therefore be determined as the
abrupt change in slope that occurs at the equivalence point. In
these circumstances it is not necessary to add exactly the
stoichiometric amount of titrant. Any excess added does not result
in an increase in temperature, and is therefore not a source of error
as it is in conventional volumetric analysis.

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Apparatus and setup for automated thermometric titrimetry

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Modern automated thermometric titrators consist of a constant delivery pump for the titrant, a
temperature control system for the titrant, an insulated cell, calibration circuitry, electronic
temperature sensing, and a data processing system. Most modern instruments are totally
computerized, so different methods can be programmed and run unattended.

The titrant is delivered with a motorized syringe pump. This permits the volume of titrant to be
calculated from the rate of delivery. These pumps are able to deliver rates of flow down to microliters
per minute with high precision.

The temperature control system, usually a thermostatted bath for the titrant and a heater for the
sample cell, is used to bring the titrant and the sample to exactly the same temperature. This is
required for high precision measurements of heat capacity and enthalpy. Modern thermostats can
maintain the temperature to within 0.001 oC.

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For precise measurements of reaction parameters such as rate constants, equilibrium constants, and
enthalpies, a well-designed insulated titration cell is required.

The cell should have minimum heat loss to the surroundings. It should have as small a mass as possible to
minimize the contribution of the cell to the total heat capacity and to maximize the response of the system
to temperature changes.

The calibration circuitry is used to determine the heat capacity of the system, which must be known if
accurate heats of reaction are to be measured.

Thermistors, which are temperature-sensitive semiconductors, are used as the temperature sensors in these
systems due to their small size, fast response, and sensitivity.

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Applications for thermometric titrimetry are drawn from the major groupings, namely:

Acid-base tritration
Redox titration
Precipitation titration
Complexometric titration

Because the sensor does not interact electrically or electrochemically with the solution, electrical
conductance of the titrating medium is not a pre-requisite for a determination.

Titrations may be carried out in completely non-conducting, non-polar media if required.

Further, titrations may be carried out in turbid solutions or even suspensions of solids, and titrations
where precipitates are reaction products can be contemplated.

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 Applications of Thermometric Titrimetry

A major use of thermometric titrimetry is for the titration of very weak acids or bases. As the acid
becomes weaker, the change in pH near the equivalence point decreases until the equivalence point
becomes too shallow to detect by potentiometric titration.

For example, the weak acid boric acid, with pK1 = 9.24 and pK2 = 12.7, does not give a good end point in a
potentiometric titration with NaOH because the inflection is too small.

However, in a thermometric titration with NaOH, boric acid gives a sharply defined end point, and is easily
determined, because the ΔH for the boric acid neutralization is large. It is very similar in magnitude to that
for neutralization of HCl by NaOH.

Thermometric titrations can be used for quantitative analysis using neutralization reactions, oxidation-
reduction reactions, and complexation reactions, as well as to determine heats of mixing and to
determine equilibrium constants.

In thermometric titration it is assumed that the rate of reaction is relatively fast and that the endpoint will
occur as soon as a small excess of titrant is added. This assumption is not valid if the reaction is slow. The
position of the endpoint will be distorted and the results will be inaccurate. 33