THE CASE FOR A GENERIC DEFINITION OF

DIFFERENTIAL SCANNING CALORIMETRY

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INTRODUCTION material are subjected to a controlled temperature program.

(Note: This definition is that approved by the International
Since the introduction of the first commercial (temperature Confederation for Thermal Analysis in August 1977.)
servo) device for quantitatively measuring heat flow into (or
out of) a sample as it undergoes a transition, there has been All DSC instruments possess similar features which differentiate
considerable confusion about what name should be used them from classical Differential Thermal Analyzers (DTA) with
to describe this analytical measurement (1). A wide variety which they are sometimes confused.
of labels has been applied including Quantitative Differential
Thermal Analysis (QDTA) (1,2,3), Dynamic Differential • They use temperature sensors as their primary
Calorimetry (DDC) (4), Dynamic Enthalpic Analysis (DEA) transducer. There is no such device as a “heat flow”
(5,6,7,8) and, of course, Differential Scanning Calorimetry transducer. All DSC instruments use temperature
(DSC) (1,9,10). DSC has been the most accepted name sensors as the primary transducer. In all cases the
largely because instrument manufacturers have used the heat flow output to the recorder is derived from the
term. With the introduction of other commercial devices, differences in temperature between sample and
which also measure differential heat flow (11,12) but reference taken from these temperature sensors. In
are not based on the temperature servo approach (13), differential temperature type devices, the sensors are
the confusion has increased. This confusion has been thermocouples or thermopiles. Since thermocouples
aggravated by the instrument manufacturers themselves are also used in DTA devices, it is often implied that
who have often claimed unspecified advantages for their DSCs which use thermocouples are really QDTA
particular instrument. The manufacturer of the original instruments. In temperature servo systems, the sensors
commercial device, understandably, has attempted to limit are platinum resistance thermometers.
the DSC definition exclusively to his design. He continues to
claim that his instrument is the only “true DSC”. • They have their temperature sensors located external
to the sample. Boersma, in his famous theoretical
We believe that DSC should be defined in terms of what is paper, points out that this is a condition which must
measured (i.e., heat flow) rather than how a particular type of be met in order to make calorimetric measurements
instrument makes the measurement. In this sense we believe (14). Non-calorimetric classical DTA, in which the
that DSC is generic in definition. This is the position recently temperature sensor is imbedded in the sample, can
adopted by the International Confederation of Thermal be made semi-quantitative simply by separating
Analysis (40). TA Instruments, almost all of the instrument the thermocouple from the sample. This can be
manufacturers, and the vast majority of thermal analysis easily demonstrated with the TA Instruments High
users have chosen to define DSC in the generic sense. The Temperature DTA cell which is capable of operating
former position, we believe, is very much like the makers of in either mode. With no sample cup liners it performs
front wheel drive automobiles claiming that only front wheel as a classic, non-quantitative DTA, but with liners (and
drive automobiles are “true automobiles” because some of consequently removal of the thermocouple from the
the first models operated in that fashion. In practice it makes samples) accuracies and precision of calorimetric
little difference whether the vehicle is front or rear wheel measurements of ±5% can be obtained (41). These
driven. What is important is how it makes the trip. levels are insufficient to qualify this device as a DSC,
however, since DSC devices characteristically provide
We intend to show that a generic definition of DSC is the calorimetric accuracies and precision better than
only acceptable definition. This position will be supported by ±1%.
equivalency of results obtained, general usage in the open
literature, by comparison of temperature excursions of the While removing the temperature sensor from the
sample, and by comparison to classical calorimetry. sample is a necessary condition for DSC (and
quantitative calorimetry), removal of the temperature
sensor alone is insufficient to produce a quantitative
DEFINITION OF DSC
device. Advocates of the temperature servo definition
of DSC have seized on this point and disparagingly
In a generic sense then, Differential Scanning Calorimetry is
refer to all devices whose thermocouple temperature
a technique in which the difference in energy inputs into a
sensors are external to the sample as “Boersma DTA’s”
substance and a reference material is measured as a function
regardless of their calorimetric performance.
of temperature while the substance and the reference

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 • They have an instrument output proportional to heat
flow (i.e. power). All DSC instruments display heat flow
as their primary output. This is a condition for DSC and
is met by all instruments carrying the DSC label.

For some DSC devices, the calorimetric sensitivity

changes with temperature and thus a calibration
constant (which is a function of temperature) must
be applied to each calorimetric measurement. For
such devices the output from the DSC is expressed as
voltage to the recorder and an empirically determined
calibration factor is applied to obtain heat flow data.
Such instruments, while increasing the amount of
effort required to obtain calorimetric data, are still Figure 1: DSC Cell cross-section
calorimetrically quantitative and properly part of the
generic DSC family.
When a sample is programmed at a constant heating rate
• It is desirable then, but not a necessary condition through its melting point, the heat capacity of the sample
for a DSC instrument to have constant calorimetric increases to infinity (in theory) and the sample temperature
sensitivity. In instruments possessing this capability the becomes essentially invariant; thus,a ΔT is developed between
calibration constant is not a function of temperature it and the constantly rising reference temperature. This ΔT
permitting the instrument output to be directly signal is proportional to the heat flowing into the sample as
calibrated in heat flow units of milliwatts. part of this transition. (The mathematical verification of this
fact is provided in the “Theory” section of this paper). When
the amplified and scaled signal presented to the computer
OPERATION
in milliwatts is integrated over time, a value for the heat in
millijoules associated with the transition is obtained.
As discussed above, Differential Scanning Calorimeters
operate on one of two principles—differential temperature
The inherent simplicity of this design affords the scientist an
measurement and temperature servo measurements. Let
easy grasp of its operating principles. Several manufacturers
us first examine the TA Instruments DSC 910 System as an
offer DSC devices based on this principle including TA
example of the differential temperature type DSC.
Instruments and Mettler.
A cross sectional diagram of the DSC cell is shown in Figure
Let us now turn our attention to the second type of
1. The cell employs a constantan disc as its primary means of
instrument, that of the temperature servo system shown in
heat transfer to the sample and reference positions, and as
Figures 2 and 3 (9). In this design the sample and reference
one element of the temperature measuring thermoelectric
pans are placed in close contact with platinum resistance
junctions. The sample of interest and a reference are placed
thermometers which are used to measure their temperature
in pans which sit on raised platforms on the constantan disc.
at any given moment. In addition, the unit has two individual
Heat is transferred through the disc and up into the sample
heaters which control the heat flow to these samples.
and reference via the sample pans. The differential heat
flow to the sample and reference is monitored by chromel-
constantan area thermocouples formed by the junction of
the constantan disc and a chromel disc which covers the
underside of each platform. The ΔT output from these series
opposed sample and reference thermocouples, is fed to a
variable high gain amplifier where the signal is amplified,
electronically scaled to read directly in heat flow units and
finally displayed on one Y-axis. Chromel and alumel wires are
connected to the underside of the chromel disc, and the
resultant chromel-alumel thermocouple is used to directly
monitor the sample temperature.

Figure 2: Temperature Servo Cell Schematic Diagram

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 thermometers used in the instrument in question do not
generate a voltage output themselves, their response
depends upon the 23 mA current (i) passing through them
and the temperature sensitivity (R). R can be obtained from
standard tables; a value of 0.24% /K at 157°C, (the calibration
temperature of most DSC instruments) can be used (18).

Using this value, 0.5 mV/cm for G, and an amplifier gain of

2500 we get:

Figure 3: Temperature Servo Schematic Diagram

At maximum sensitivity of 21mW/cm (0.01 mcal/sec in),
each centimeter of chart deflection corresponds to 0.23
When a sample is temperature programmed through millikelvin difference in temperature between sample and
its melting point and the sample temperature becomes reference. Put in other words, a modern, second generation
essentially invariant, the ΔT signal developed between it and temperature servo type DSC generates an 11 millikelvin
the reference is amplified, scaled and displayed as the output sample temperature excursion for each milliwatt of heat
from the device, as shown in Figure 3 (9, 13). In addition, flow. (In traditional units this is 0.046 degrees per mcal/s).
differential power is supplied back to the sample heater This is despite the attempts of the system’s temperature servo
attempting to reduce the temperature difference between to minimize this temperature excursion. This temperature
the sample and reference. The operating principle of a servo difference between sample and reference is easily verified
system, however, requires the restoring signal (here a voltage by measurement with a differential thermocouple pair.
signal to the differential heater) to be proportional to the
offset (here the temperature difference). If the temperature We can compare this error signal with that of the TA
difference is really zero, no differential power could be Instruments DSC 910 for which G is also 0.5 mV/cm and A
supplied by the servo system. An actual zero temperature is 30,000. The value for E for chromel/constantan of 71,µV/K
difference can exist only if the servo amplifier gain is infinite, can be obtained from the same source as that above (19).
which, of course, it is not.

SAMPLE TEMPERATURE DIFFERENCE

Many users believe, that the temperature servo system

reduces the temperature differences between sample and This comparison points out that at maximum sensitivity the
reference to zero during a transition (1,15). The very nature temperature servo instrument and the TA Instruments DSC
of a servo system belies this. Indeed, the recorder output is 910 generate approximately the same sample temperature
directly proportional to the temperature difference between excursion per centimeter of chart deflection. Most DSC work
sample and reference as can be seen in both the patent is not done at maximum sensitivity, however, and values 1000
covering such devices shown in Figure 3, and electronic times greater are likely to be encountered in ordinary work.
schematic of such instruments (13,16). The manufacturer For example, O’Neill has published scans for real life indium
states “....(the temperature difference between sample and samples in which the maximum heat flow during freezing
reference) is never really zero, because in any such control was 71 mW (19). This value, multiplied by the instrument
system there must always be some small ‘error signal’” (17). differential temperature sensitivity calculated above, yields,
Let us examine how small this error signal really is. for this so-called temperature null device, a peak temperature
excursion of 0.8 kelvin (0.8°C). While this value is not large, it is
The error signal (S, in K/cm of chart) can be calculated from certainly not zero and certainly is not isothermal.
the maximum sensitivity of instrument output (G, in mV/cm of
chart), the ΔT amplifier gain (A) and the differential response It is clear from the comparison above, that practical
of the transducer (E, in mV/K change in temperature). temperature servo type instruments do not maintain the
sample and reference materials at the same temperature
even if the instrument is of high sensitivity.

COMPARISON TO CLASSICAL CALORIMETRY

Since the 13 ohm (at room temperature) platinum resistance Calorimetry is the scientific field dealing with the

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measurement of the heat or energy content of various “It is not possible by inspection of an unlabeled thermal
chemical and physical reactions. In a typical classical analysis peak to determine which sort of apparatus was
adiabatic calorimetric experiment, a chemical reaction may used....”(17). Moreover, there are almost no applications
be carried out in a sealed container insulated from heat where one instrument obtains data and the other does not.
losses to the outside world. From the known heat capacity Articles abound in the open literature on the ability of a variety
(Cp) of the insulated container and its contents, and the of equipment, based on differing operating principles, to
small measured change in temperature (ΔT) of that system, make equivalent measurements (21,22,23,24). Outstanding
the heat content of the chemical reaction (ΔH) can be research (21,23,25) has testified to the equivalency of results
calculated: obtained on instruments of both types. In addition, such
respected institutions as the Drug Standards Laboratory and
American Society for Testing and Materials (ASTM) have
stated the equivalency of results obtained on both instrument
The experiment is usually designed so that the change in types (22,26,27).
system temperature is kept small, usually several Kelvin. Under
such conditions Cp is a constant. GENERIC USE OF DSC

Such experiments have given rise to the definition of the Despite attempts to limit the definition of DSC to devices
calorie as the unit of measurement for heat content or based on the temperature servo technique, DSC is used
energy: calorie— the amount of heat necessary to raise the in the open scientific literature as a generic phrase. All
temperature of 1g of water at 15°C, 1°C. other titles have faded into historical interest although one
occasionally still sees QDTA used. C. B. Murphy’s biennial
In DSC, the temperature excursion of a sample seldom review of thermal analysis uses the phrase DSC generically
exceeds a few tenths of a degree. It is clear, then, that DSC without differentiating the type of instrument used and
instruments operate well within the conditions of classical includes DSC under the DTA heading as a quantitative
calorimetry from which thermodynamic data is almost technique (28,29,30,31,32).
exclusively obtained.
Virtually all thermal analysis manufacturers who make
This comparison of DSC to classical calorimetry needs one quantitative calorimetric measurements, market their
other amplification. In classical adiabatic calorimetry, heat instruments under the title of Differential Scanning Calorimetry
losses from the sample to the environment are kept to a even though operating under different principles. These
minimum. This concept is most nearly met in differential include: TA Instruments, Mettler, Perkin-Elmer, and others.
temperature DSC instruments since the sample is totally
surrounded by a uniform temperature environment. It is the SUMMARY
temperature of this environment which is programmed during
the course of the experiment. Thus the sample “sees” only We have shown that all Differential Scanning Calorimeters,
an environment whose temperature is very near that of its regardless of method of measurement, measure the same
own, thereby reducing to a minimum emissivity, atmosphere quantity, namely, heat flow into (or out of) a sample. It follows
thermal conductivity, and other potential heat losses. This that the name should be used generically and applied
produces the remarkably stable baseline performance of to all measurements of this type rather than limited to
the instruments of this type. measurements made on a particular instrument.This position
is supported by:
On the other hand, temperature servo instruments suffer from
thermal conductivity and emissivity losses, thermal gradients • equivalence of measurement
and thermal atmosphere convection because the sample • general usage in the open literature
chamber (in which the sample and reference materials • similar temperature excursions of the sample
are located) is thermostated at constant temperature (20). • comparison to classical calorimetry
This means that the sample sees a constantly changing
environmental gradient during the course of an experiment.
Obviously this is far afield from the standard adiabatic
calorimeter and can lead to poor baseline performance
of temperature servo instruments if not corrected for by
electronic baseline compensation.

EQUIVALENCY OF RESULTS

Perhaps no stronger claim can be made for a generic

definition of DSC, than the fact that results from instruments of
the temperature servo type and instruments of the differential
temperature type are indistinguishable from each other. This
has been pointed out in a previous treatise on the subject;

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REFERENCES The essential parts of the DSC are a sample at temperature
TS, its container at temperature TSH, and a temperature
1. E. S Watson, M. J. O’Neill, J. Justin, and N. Brenner, Anal. programmed source at temperature TB. Heat will flow
Chem., 36, 1233 (1964). between these positions at a rate di/dt depending on
2. A. P. Gray, Am. Lab., 3, 43 (1971). the temperatures involved and the thermal resistances
3. H. E. Bair, Polym. Eng. Sci., 10, 247 (1970). connecting the positions. The sample and its container
4. S. M. Ellerstein, Anal. Calor., R. S. Porter and J. F. Johnson have a heat capacity CS. Since the calorimeter operates
(eds.), Plenum, 279 (1968),. differentially, a similar description can be developed for the
5. R. F. Schwenker and J. C. Whitwell, Anal. Calor., R. S. Porter reference side of the cell. Figure 4 illustrates this description
and J. F. Johnson (eds.), Plenum, 249 (1968). schematically.
6. V. Crescenzi and F. Delbin, Intern. J. Protein Res., 3,
57(1971).
7. B. Miller, J. Appl. Poly. Sci., 11, 2343 (1967).
8. G. Beech, J. Chem. Soc., (A), 1903 (1969).
9. W. W. Wendlandt, Thermal Methods of Analysis, John
Wiley 193 (1974).
10. T. C. Daniels, Thermal Analysis, John Wiley 122 (1973).
11. R. A. Baxter, Thermal Analysis, R. F. Schwenker, Jr., and P. D.
Garn (eds.), Academic Press, 65 1969.
12. D. J. David, Anal. Chem., 36, 2162 (1964).
13. E. S. Watson and M. J. O’Neill, U. S. Patent 3,263,484 (1966).
14. S. L. Boersma, J. Am. Ceramic Soc., 38, 281 (1955).
15. J. L. McNaughton and C. T. Mortimer, Thermochemistry
and Thermodynamics, H. A. Skinner (ed), Butterworth, 1
(1975).
16. Perkin-Elmer DSC-2 Manual.
17. Perkin-Elmer, Thermal Analysis Newsletter No.9 (1970).
18. H.F. Stimson, J.F. Swindells and R.E. Wilson, American Figure 4: Calorimetric Schematic
Institute of Physics Handbook, D. E. Gray (ed), McGraw-
Hill, 4-1 1963.
19. M. J. O’Neill, Anal. Chem.,47, 630 (1975). If we make the simplifying assumptions that the calorimeter
20. P. L. Privalov, V. V. Plotnikov, and V. V. Filimonov, J. Chem. is symmetrical and that thermal resistances are identical on
Thermodynamics, 7, 41 (1975). the reference and sample sides at any given temperature;
21. A. Doelman, A.R. Greggs, E.M. Barrall II, Paper No. that the temperatures of the sample, reference, and their
77, American Chemical Society National Meeting, containers are uniform; and that the flow of heat from sample
September 1, 1976. to reference can be neglected, then the response of the
22. L. T. Grady, S. E Hays, R. H. King, H. R. Klein, W. J. Mader, D. K. calorimeter can be described with the aid of heat balance
Wyatt and R. O. Zimmerer, J. Pharm. Sci., 62, 456 (1973). equations and thermal ohm’s law relationships.
23. E.F. Palermo and J.Chiu, Thermochim. Acta, 14, 1 (1976).
24. W.J. Miller, W.H. Foester and F.E. Freeberg, J. Am. Oil Chem. If we assume a sample undergoing an exothermic transition
Soc., 46, 341 (1969). giving up heat energy at a rate dH/dt, then the appropriate
25. B. Wunderlich, Physical Methods of Chemistry, A. equations are:
Weissberger (ed), Vol. 1, Part 5, John Wiley, 427 (1971).
26. ASTM Method D-3417 “Measurement of Heats of Fusion
and Crystallization of Polymers by Thermal Analysis.”
27. ASTM Method D-3418 “Measurement of Transition
Temperatures of Polymers by Thermal Analysis.”
28. C. B. Murphy, Anal. Chem., 48, 341 R (1976).
29. C. B. Murphy, Anal. Chem., 46, 451R (1974).
30. C. B. Murphy, Anal. Chem., 44, 513R (1972).
31. C. B. Murphy, Anal. Chem., 42, 268R (1970).
32. C. B. Murphy, Anal. Chem., 40, 380R (1968).

APPENDIX THEORY

The theoretical basis for the TA Instruments DSC 910 is well

documented in Baxter’s work on the subject (11). A portion
of his work is reproduced and expanded here for the sake of Equation (4) indicates that the heat evolved by the sample
completeness: goes either into heating the sample or is dissipated to the
surroundings.

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We can combine equations (2) and (3), and (1) and (4)

Substituting the temperature values from equations (1) and

(2) for the individual heat flow yields:

The equation for the reference side (5) is subtracted from

that for the sample side (6) to obtain: The temperature difference sensed by the detectors is directly
proportional to the difference in heat flow into or out of the
sample and reference.

Since

Solving equation (8) for dTS/dt and substituting into (7) yields:

Figure 5: Idealized Thermogram

Since the quantity measured is the difference in temperature
between the sample and reference holders, not the sample
and reference themselves, this equation can be modified by
Prepared by Roger L. Blaine
the relationships in equations (1) and (2).
For more information or to place an order, go to
http://www.tainstruments.com to locate your local sales
office information.

The final relationship is arrived at by combining Equations (9)

and (10) to obtain:

Equation (11) indicates that the rate of heat evolution is

made up of three terms (Figure 5):

1. The instrument response divided by a constant which

is proportional to the difference in heat flow between
sample and reference.

2. A constant term depending on the heat capacity of

the sample and the heating rate.

3. A term involving a time constant and the rate of

change of the recorded quantity.

It is useful to define a term Δq to be the difference in heat flow

to the sample and reference as illustrated in Figure 4.

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