Journal of Loss Prevention in the Process Industries 13 (2000) 7–17

www.elsevier.com/locate/jlp

Comparison of different methods for estimating TMRad from

dynamic DSC measurements with ADT 24 values obtained from
adiabatic Dewar experiments
Jörg Pastré a, Udo Wörsdörfer b, Andreas Keller a, Konrad Hungerbühler a,*

a
Safety and Environmental Technology Group, Chemical Engineering Department, ETH Zentrum, CH 8092 Zürich, Switzerland
b
Aventis Research and Technologies (former Hoechst AG), Frankfurt a. M., Germany

Abstract

Recently, a method for estimating the time to maximum rate under adiabatic conditions (TMRad) from non-isothermal DSC
measurements was presented by Keller, A., Stark, D., Fierz, H., Heinzle, E., & Hungerbühler, K. (1997). J. Loss. Prev. Process.
Ind., 10, 31–41. The method was tested on the basis of isoperibolic data only, because data from adiabatic experiments were not
available. In this study we used results from 180 Dewar vessel experiments with an adiabatic shield and the corresponding dynamic
DSC measurements provided by Aventis Research and Technologies (former Hoechst AG) to test the estimation method suggested.
The data were obtained for reaction mixtures, bottom residuals, reaction residuals, and products. We found that in all cases the
predicted TMRad at a given temperature was shorter than the experimental value determined from adiabatic measurements. This
result shows that the TMRad estimation method is useful as a screening tool for the assessment of thermal risk. Furthermore, the
estimation method introduced by Keller et al., is more on the safe side than other common and often applied estimation methods
like the so-called 100 degree rule or the 50 degree rule. We also describe how to derive adiabatic induction times for different
temperatures by using a minimum number of adiabatic experiments.  1999 Elsevier Science Ltd. All rights reserved.

Keywords: Safety screening; DSC; Adiabatic Dewar experiments; Time to maximum rate

1. Introduction The German “TAA”-Guideline TAA-GS-05 (German

In industrial chemical production it is important to
have information about safe working, handling and stor-
age temperatures for a given process. Many technical
accidents in a chemical plant can be directly linked to a
chemical runaway incident.
The adiabatic temperature increase ⌬Tad describes the
severity in a runaway scenario. The probability for a run-
away scenario can be described by the time to maximum
rate under adiabatic conditions (TMRad). To describe the
hazard potentials of a runaway reaction, commonly
thermo-kinetic models are used together with data sets
from calorimetric methods. Various methods to derive
kinetic parameters are outlined in the literature
(Townsend, Ferguson & Kohlbrand, 1995; ANSI/
ASTM, 1979; Gimzewski & Audley, 1993; Grewer, 1994).
* Corresponding author: Fax: +41-1-632-1053.
E-mail address: hungerb@tech.chem.ethz.ch (K. Hungerbühler)
guidelines, 1994) suggests three methods for defining a
safe maximum handling temperature for substances and
reaction mixtures. One is the common 100 degree rule
which defines a handling temperature as safe if it is 100
degrees below the onset temperature of a DSC measure-
ment with a heating rate between one and 10°C/min
(Grewer, Klusacek, Löffler, Rogers & Steinbach, 1989).
Hofelich and Thomas (1989) found that this rule does
not fit in all cases. Furthermore, in some laboratories a
less stringent 50 degree rule is used. This means that
handling temperatures 50°C below the DSC onset are
regarded as safe.
Keller, Stark, Fierz, Heinzle and Hungerbühler (1997)
presented a model based (zeroth order reaction) esti-
mation method for TMRad from non-isothermal DSC
measurements but tested this method on the basis of iso-
peribolic data only, since data from adiabatic experi-
ments were not available. In this study we used more
than 180 adiabatic Dewar experiments and the corre-
sponding dynamic DSC measurements to test the method

0950-4230/00/$ - see front matter  1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 5 0 - 4 2 3 0 ( 9 9 ) 0 0 0 6 1 - 3
8 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17

Nomenclature
ADT 24 Temperature at which TMRad is 24 h derived from adiabatic measurements [K]
c Concentration [mol m⫺3]
cp Heat capacity [J kg⫺1 K ⫺1]
cp,cor Corrected Heat capacity [J kg⫺1 K ⫺1]
cp,sample Heat capacity of sample [J kg⫺1 K ⫺1]
Dewarcor Correction for Dewar vessel [J K ⫺1]
DSC Differential Scanning Calorimetry
Ea Arrhenius activation energy [J mol⫺1]
⌬hR Specific Enthalpy of reaction [J kg⫺1]
k0 Preexponential factor
m Mass of sample [kg]
q̇ Heat release rate [W kg⫺1]
q̇0 Heat release rate at T0 [W kg⫺1]
q̇onset Heat release rate at Tonset [W kg⫺1]
R Universal gas constant [J mol⫺1 K ⫺1]
T Temperature [K]
⌬Tad Adiabatic temperature rise [K]
T0 Temperature at which TMRad is calculated [K]
TMRad Time to maximum rate at adiabatic conditions [s]
Tonset Temperature were heat release rate signal can be differentiated from baseline [K]
To,24 Temperature at which TMRad is 24 h derived from dynamic DSC measurements [K]
Tq̇=0.1 W/kg Temperature at which q̇=0.1 W/kg [K]
Tq̇=0.5 W/kg Temperature at which q̇=0.5 W/kg [K]
Texo Temperature which is concerned as safe in the German guidelines (1994) [°C]
t Time [s]

suggested. The data were provided by Aventis Research
and Technologies and comprise reaction mixtures, bot-
tom residuals, reaction residuals, and products. We also
used experimental data measured by Grewer and Klais
(1988, 1992), which were obtained for pure substances.
1.1. Estimation of TMRad from dynamic DSC
measurements
Many decomposition reactions can be described by an
Arrhenius model. Assuming a zeroth order reaction, the
following expression for TMRad can be derived (Frank-
Kamenetzkii, 1969; Townsend & Tow, 1980):
cp·R·T 20
TMRad⫽
q̇0·Ea
where T0 [K] is the start temperature, q̇0 [W kg⫺1] the
corresponding heat release rate, Ea [J mol⫺1] the Arrhen-
ius activation energy, R [J mol⫺1 K ⫺1] the gas constant,
and cp [J kg⫺1 K ⫺1] the specific heat of the reaction
mass. In this model the concentration decrease is neg-
lected, so that the calculated TMRad is always shorter
than the real adiabatic value and, thus, is on the con-
Usually the value of Ea is unknown. One possibility
to estimate an activation energy is by measuring the heat
release rate at different temperatures in a number of isop-
eribolic DSC measurements. The logarithmic heat
release rate has then to be plotted against the correspond-
ing inverse temperature to derive the activation energy
as the slope of the resulting line (Grewer & Klais, 1988).
Instead of using this procedure, a very conservative esti-
mation of Ea,m=50 kJ/mol was used in this study. This
is a rather low value for a decomposition reaction. To
obtain the heat release rate q̇0 at a certain initial tempera-
ture T0, the conditions at the onset (q̇onset and Tonset) of
a dynamic DSC curve are used. The temperature of the
onset point Tonset is defined as the temperature where the
(1) heat rate signal can first be differentiated from the base-
line temperature reading by visual inspection. Keller et
al. (1997) assumed that the heat release rate at the onset
point q̇onset is of the order of 20 W/kg (Townsend &
Tow, 1980). This minimal detectable heat release rate
depends on the sensitivity of the instrument and on the
curvature of the baseline. The conversion at the onset
point is negligibly small, so it can be neglected. By
using q̇onset (20 W/kg) and assuming an Arrhenius model

冉 冊
servative side. To calculate TMRad not only the heat
release rate q̇0 but also an Arrhenius activation energy Ea
q̇⫽k0·exp ⫺ ·f(c)·(⫺⌬hR) (2)
Ea are needed. RT
 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 9

it is possible to estimate the heat release rate q̇0 at any

temperature T0:

q̇0⫽q̇onset·exp 冉冉
Ea 1
⫺
1
R Tonset T0 冊冊 (3)

Using this value for q̇0 and an estimated value for the
activation energy it is possible to calculate TMRad using
Eq. (1). The resulting estimated TMRad is a conservative
value, because the extrapolation is based on a zeroth
order Arrhenius model and a low activation energy
which leads to an overestimated value of q̇0 (Keller et
al., 1997). Inserting Eq. (1) into Eq. (3) a temperature
with a time to maximum rate of more than 24 h can be
defined, referred to as To,24:

To,24⫽ 冉 1 R
⫺ · ln
Tonset Ea 冉 T 2o,24·R·cp
Ea·TMRad·q̇onset 冊冊 −1
(4)

The parameter To,24 (determined by DSC) has a corre-

spondent referred to as ADT 24 in the German “TAA”-
Guideline TAA-GS-05 (German guidelines, 1994). ADT
24, the adiabatic decomposition temperature, which will
lead to a runaway in 24 h, is determined by an adia-
batic experiment.
A linear regression is done to express To,24 as a func-
tion of Tonset:
To,24[K]⫽0.65·Tonset[K]⫹50 (5)

The resulting correlation factor is 0.9998. At this point

it should be mentioned that Keller et al. (1997) used the
above mentioned estimation method only as a second
step in a complete safety check procedure. The full pro-
cedure is shown in Fig. 1. Generally a previous selection
of autocatalytic reactions is done. In the following pres-
entation we will test the model based estimation method,
Eq. (5), without screening for autocatalytic reactions and
compare it with the common 100 and 50 degree rules,
mentioned here as Eqs. (6) and (7).
To,24ⱖTonset⫺100 (6)
To,24ⱖTonset⫺50 (7)

2. Experimental

The DSC measurements were done using a conven-

tional DSC apparatus from Mettler Toledo. The reaction
mixture was heated with a heating rate of 3°C per
minute. When possible the samples were heated in
closed glass containers. In some cases stainless steel
containers were used to avoid chemical reactions with
the container material.
For the adiabatic experiments the improved Dewar
Fig. 1. Flowsheet of the thermal risk assessment procedure as defined
by Keller et al. (1997).
method was used (Grewer & Klais, 1988). The improved
Dewar technique is one of the common adiabatic test
methods to study the thermal stability of a substance.
Because the heat loss of a Dewar vessel is similar to that
10 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17
of a technical apparatus with a volume of about 1 to 5
m3 (Grewer et al., 1989), the Dewar test can simulate in
a very easy way the thermal behaviour of large sample
mass. This means that the results can be transferred
directly to the plant conditions without substantial cor-
rection of the experimental data.
This method uses a massive autoclave around the
Dewar flask. An aluminium block oven with electrical
heaters produces a homogeneous temperature distri-
bution resulting in an adiabatic shield (Fig. 2) around
the Dewar flask. The top of the vessel is closed with an
insulating lid. A magnetic stirrer is used for the investi-
gation of heterogeneous liquids.
The storage temperature of the adiabatic experiments
and the inserted mass are determined using the former
DSC results like onset temperature and heat of reaction.
Normally about 200 g of the test substance is the start
material in the Dewar vessel. The sample- and oven tem-
perature and the pressure are measured and recorded
using a computer. The external heat flow leads to a tem-
perature equilibrium between the autoclave and the sam-
ple. If self heating is registered after reaching the storage
temperature, the oven temperature follows the sample
temperature with less then 0.3 K difference. The appar-
atus is able to determine heat production rates of 100
mW/kg.
2.1. Evaluation procedure
2.1.1. Determination of ADT 24
In this chapter we present the method of evaluating
the ADT 24 at Aventis by using an example (Figs. 3–
5). The first step is to carry out a DSC measurement of
a sample (Fig. 3) to decide which amount of substance
(derived from specific heat of reaction) and which stor-
age temperature (derived from the onset temperature)
should be used in the Dewar experiment. A detailed dis-
cussion on how to determine the onset temperature is
Fig. 2. Experimental set up of a Dewar test with an adiabatic shield.
given below. The next step is to measure the adiabatic
pressure and temperature profiles of the sample and the
corresponding oven temperature. Then the differential
temperature (dT/dt) and pressure (dp/dt) increases are
plotted against inverse temperature to obtain information
on the reaction rate and the amount of gas which is pro-
duced at a certain temperature.
The last step is the extrapolation of the experiment to
a storage temperature at which TMRad will be 24h (ADT
24) as shown in the following example, in which the
evaluation of the Pressure increase is not discussed,
because this information is not needed to obtain ADT
24 values.
Temperature and pressure profiles of adiabatic experi-
ments normally look as shown in Fig. 4. The reaction
mass reaches the oven temperature very slowly because
of the isolation of the Dewar. This temperature is called
storage temperature T0, which is 160°C in this example.
The time-span in going from the oven temperature to
runaway is called induction time or time to maximum
rate. It is important that the time span of the adiabatic
temperature rise is sufficient for allowing observation of
the kinetic behaviour. The induction time should be
between 10 and 40 hours. This is necessary since extra-
polation is more robust when regression is done over a
longer time period. On the other hand, if adiabatic induc-
tion time takes too long there is a possibility that the
reaction mixture is heated up very slowly by an unin-
tended heat input caused by a controller.
In Fig. 5 the logarithm of dT/dt is plotted against
inverse temperature Eq. (8) in a typical Arrhenius dia-
gram.
dT ⬘ Ea
ln ⫽k 0⫺ (8)
dt R·T
The lowest self heating rate can be observed at storage
temperature. Below this temperature the sample is heated
resulting in a larger dT/dt than at the storage tempera-
ture. The measurement is reliable and extrapolations are
allowed if a straight line describes the behaviour
between ln dT/dt and the inverse temperature is visible.
In this simple example the plot shows a linear depen-
dency between 160°C and 260°C. A zeroth order kinetic
model is fitted to the linear part as shown in Fig. 5. This
kinetic model is on the safe side because the reaction is
not becoming slower at higher degrees of conversion. It
is also possible to fit a first order kinetic model to the
data when the curve of temperature increase versus
inverse temperature flattens for higher temperatures.
From the slope of the straight line a value for the acti-
vation energy can be calculated.
Finally, a simulation of heat production q̇ is done by
multiplying the rate of temperature increase with the cor-
rected specific heat of the sample cp,cor.
 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 11

Fig. 3. A dynamic DSC measurement with well defined onset temperature.

Fig. 4. Representative courses of oven temperature (grey line), sample temperature (black line) and pressure (dashed line) as a function of time
in an adiabatic Dewar experiment corresponding to Fig. 3.

dT istic for each Dewar vessel used. The specific heat

·c ⫽q̇ (9) cp,sample of the reaction mass m can be calculated from
dt p,cor
the specific heat of reaction ⌬hR [J kg⫺1] determined in
the DSC experiment and the adiabatic temperature rise
The corrected specific heat is derived considering the ⌬Tad obtained from the adiabatic experiment.
Dewar correction Dewarcor.
⌬hR
cp,cor⫽冉Dewarcor+cp,sample·m
m 冊 (10)
cp,sample⫽
⌬Tad
(11)

After having completed all of the above mentioned

The value for Dewarcor is determined from former heat evaluation steps, the consistency of the measurement is
loss experiments of the Dewar vessels and is a character- checked. Then it is possible to extrapolate the induction
12 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17

Fig. 5. Semi-logarithmic plot of temperature increase versus inverse temperature (䉬) corresponding to Fig. 3. Simulation of the heat production
(grey line) and a fit of zeroth order kinetics (black line) are shown. A Celsius scale is included for easier reading.

time to the maximum heat production under adiabatic TMRad⬀e(Ea)/(R·T) (12)

conditions for different temperatures as shown in Fig. 6.
A ADT 24 is normally used to compare different
measurements. This value is generated by plotting the
logarithm of the induction time against the inverse tem-
perature. A straight line should be obtained, because the
induction time is a kinetic quantity and its temperature
dependence should follow an Arrhenius-type equation
(Grewer, 1994):
The resulting slope is Ea/R. The initial point chosen for
plotting the time scale is the point where the sample tem-
perature equals the oven temperature. Afterwards for
each temperature the corresponding time to maximum
rate is plotted. Then a linear regression is done (Fig. 6)
in the temperature region where a linear dependence is

Fig. 6. Semi-logarithmic plot of the induction time (䉬) versus the inverse temperature corresponding to Fig. 3. Straight line: Extrapolation of
the induction time to lower temperatures. A Celsius scale is included for easier reading.
 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17
observed. In the example shown in Fig. 6 linear behav-
iour can be observed between 160 and 200°C. The point
of intersection of the line representing an induction time
of 1440 min (dashed line in Fig. 6) and the extrapolated
line yields the temperature where TMRad is 24 h, which
is 158°C for the chosen example.
Another check to decide whether the chosen model
(zeroth or first order) is consistent and an extrapolation
is possible is the following one: The activation energy
which results by multiplying the slope of the linear part
of Fig. 6 by R should be of the same order of magnitude
as the activation energy obtained by the model determ-
ined in Fig. 5. The results obtained for the example are
given in Table 1.
The determination of ADT 24 is only allowed if the
earlier described kinetic fitting is feasible and if the adia-
batic time to maximum rate is of the order of one day
or at least greater than 600 minutes.
2.1.2. Determination of Tonset
For the determination of the onset temperature a tem-
perature programmed DSC plot is used and the onset of
the first exothermic reaction is visually determined. A
typical example is shown in Fig. 3.
When different choices for the baseline exist, the read-
ing of the onset temperature becomes more difficult as
shown in Fig. 7. When an endothermic process occurs
before the exothermic decomposition reaction it will
generally be difficult to decide when the exothermic pro-
cedure starts. In our example the onset is chosen to be
145°C because the exothermic process is separated from
the endothermic process. If a separation of these two
processes was not possible we always used the minimum
of the endotherm in order to be on the safe side.
There are samples which may lead to difficulties when
calculating ADT 24 from dynamic DSC curves, namely
those with an additional exotherm before the main exo-
thermic process as shown in Fig. 8. For our kinetic
evaluation we often chose the onset of the main
Table 1
Parameters characterising the example shown in Figs. 3–6
Experimental data
Storage temperature 161.0°C
Induction time 1200 min
20 h
Max. temperature 374°C
Adiabatic temp. rise 213 K
Max. pressure 17 bar
Gas production 8.7 l at room temp.
124 l/kg substance
Free gas volume in autoclave 0.5 l
Specific heat of substance 1700 J/kg/K
Corrected specific heat 3843 J/kg/K
13
exotherm because in most cases the first exothermic pro-
cess has a rather small reaction heat and often the adia-
batic measurement has to be done at temperatures above
the onset of the first process, so that the kinetic behav-
iour of the first process is not visible in the adiabatic
measurement. In dubious cases it is important to use the
first exotherm to be on the safe side. In the next chapter
we will discuss what happens when the different onsets
are chosen.
3. Results and discussion
In Fig. 9 the ADT 24 values obtained from 180 adia-
batic experiments are plotted versus the onset tempera-
tures of the corresponding DSC measurements. Two dif-
ferent data sets are shown. The open symbols represent
data measured and evaluated by Grewer and Klais
(1992). The closed symbols represent measurements
done at Aventis in the last three years and are presented
above. In the plot three straight lines are shown which
represent the model based estimation method, the 100
degree rule, and the 50 degree rule given in Eqs. (5)–
(7), respectively. The slope of the line which represents
the estimation method Eq. (5) is smaller than the slope
of the two other parallel lines. At onset temperatures
over 170°C the suggested estimation method Eq. (5)
gives a much more conservative prediction of ADT 24.
Below onset temperatures of 170°C this behaviour is dif-
ferent. At low temperatures the 100 degree rule Eq. (6)
is more conservative than the estimation method Eq. (5).
For a reliable prediction ADT 24 values derived from
estimation rules must be smaller than values derived
from adiabatic experiments. This means that all data
points should lie above the lines representing the rules.
This requirement is not fulfilled by the 50°C rule Eq.
(7) in many cases (Fig. 9).
Also the condition Tonset minus 100°C Eq. (6) will lead
to ADT 24 values which in some cases are not safe
Kinetic data (Fig. 5)
0th Order reaction (Evaluation 170–280°C
range)
Activation energy Ea (0th) 163 kJ/mol
Frequency factor k0 (0th) 3E+17 l/min
From simulation of heat production derived values (Fig. 5)
0.1 W/kg at a temperature of: 146°C
0.5 W/kg at a temperature of: 161°C
From extrapolation of the induction time against 1/T derived values
(Fig. 6)
ADT 24 159°C
Activation energy 153 kJ/mol
14 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17

Fig. 7. A dynamic DSC measurement with an endothermic process preceding an exothermic process. Possible choices of onset temperatures
are shown.

Fig. 8. A dynamic DSC measurement with a small exotherm before the main exotherm. The resulting data points derived by using different
onsets are shown in Fig. 9.

enough. Eight points lie under the line representing the
100 degree rule and quite a few points are situated very
close to that rule, especially at higher temperatures. On
the other hand, the suggested model based estimation
method fulfils the requirement for all samples. For the
data investigated in this study it would not always be
appropriate to use the 100 degree rule even though the
onsets of the first exotherm were used.
From Fig. 9 some remarkable measurements can be
identified. One is acroleine, which is from the data set
compiled by Grewer and Klais (1992). In that special
case the onset is at 70°C while the sample could be
stored for 24 hours at 110°C until the runaway occurs.
We think this behaviour is due to a polymerisation.
Another substance measured by Grewer and Klais
(1992) produces the highest onset of all. It is sodium
 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 15

Fig. 9. The ADT 24 values are plotted against the corresponding onset temperatures (䉬: new data; 䉫: data of Grewer & Klais, 1988, 1992). The
100 degree rule (grey line) (Cronin, Nolan & Barton, 1987; Hofelich & Thomas, 1989), the 50 degree rule (dashed line) and the model based
estimation method (black line) as given in Eq. (5) of Keller et al. (1997) are shown.

azide with an onset temperature of 420°C. It is remark-

able that this solid substance deviates far from the 100
degree rule but that the new estimation method Eq. (5)
gives a safe prediction. The other points which do not
fit into the 100 degree rule are mostly bottom or reaction
residuals of chloroanilines.
We tried to find some qualitative correlation between
chemical structure and DSC onset temperatures, ADT 24
or the deviation from the 100 degree rule. But for the
investigated substances, reaction mixtures and residuals
no correlation could be found.
A direct comparison can be done between To,24 values
derived from dynamic DSC measurements using the esti-
mation method of Keller et al. (1997) and ADT 24
values derived from adiabatic measurements shown in
Fig. 10. The same results from both methods are located
on the straight line. The estimation method can be con-
sidered as being safe if all data points are situated in the
lower right corner. This means To,24 values are always
Fig. 10. Comparison between the estimated To,24 (derived from a
smaller than values given by an adiabatic measurement.
dynamic DSC measurements) and the ADT 24 (derived from an adia-
batic measurements).
3.1. Using the wrong onset

To show what happens when the wrong onset is used, reaction. The two possible onsets are marked in Fig. 9.
we plotted an adiabatic measurement using different When the onset of the first exotherm is used the corre-
onset temperatures of the DSC. The DSC plot in Fig. 8 sponding experimental ADT 24 values are further away
shows a small exotherm before the main decomposition from the estimation methods and, thus, move on the safe
16 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17

side. Therefore, it is important, to use the first exother-

mic onset that is accessible, if safety is an important con-
cern and when only a DSC measurement is available. In
that case it is important to test for autocatalytic reaction
mechanisms as is described by Keller et al. (1997).

3.2. Outlook

For a prediction of a safe handling temperature differ-

ent methods are used. They should be replaced by gener-
ally accepted guidelines and technical rules similar to
the German “TAA”-Guideline (German guidelines,
1994).
In these guidelines three methods are mentioned,
which describe the maximum safe working temperature
Texo, where no decomposition takes place in a long time
period (German guidelines, 1994; Berufsgenossenschaft
der chemischen Industrie, 1996). In the technical guide-
lines two other rules are mentioned besides the 100
degree rule:
I) ADT 24 [°C]⫺10⫽Texo [°C]
II) Tq̇=0.1 W/kg [°C]⫺10⫽Texo [°C]
I) One is to extrapolate the results of adiabatic
measurements as shown above, to obtain a cer-
tain storage temperature ADT 24 at which a
sample needs 24 h to reach the runaway. The
safe working temperature Texo results after sub-
tracting 10°C.
II) The other method uses the temperature
Tq̇=0.1 W/kg at which the heat of reaction is 0.1
W/kg. The safe working temperature can be cal-
culated by subtracting 10°C.
It is also interesting to compare the ADT 24 with the
temperature Tq̇=0.1 W/kg mentioned in the TAA guidelines.
We are aware of the fact that our comparison and the
following results will apply only to the Dewar system
used or a technical apparatus with a volume of about 1
to 5 m3 (Grewer et al., 1989). After fitting of the kinetic
data of the decomposition reaction we did in some cases
simulate the heat production (Fig. 5). From the simul-
ation results we recognised that the temperature at which
the heat release rate is 100 mW/kg is significantly lower
than the determined ADT 24. This is shown in Fig. 11.
Here the temperature corresponding to a certain heat
release rate is plotted versus the ADT 24. Safe working
temperatures obtained from both methods should fall
onto a straight line, as shown in Fig. 11. The closed
symbols describe the temperature for a heat release rate
of 0.1 W/kg while the open symbols correspond to a
heat release rate of 0.5 W/kg. We believe that a value
of 0.1 W/kg would lead in most of the cases to a rather
Fig. 11. Temperatures with the heat release rates of 0.5 (䉫) and 0.1
(䉬) W/kg are plotted against ADT 24 values. The straight line signifies
equal values for ADT 24 and temperatures with a certain heat
(13) release rate.
(14)
conservative estimation of the ADT 24. A value of 0.5
W/kg, however, results in good agreement with the
determined ADT 24 values shown in Fig. 11. Since the
Dewar experiment is similar to a technical apparatus it
is important to conduct further research on this question.
4. Conclusions
On the basis of the 180 data sets investigated we were
able to confirm the reliability of the TMRad-estimation
method of Keller et al. (1997) which was based on a
single dynamic experiment. The rule was successfully
applied without a previous identification of autocatalytic
reactions and proved by using adiabatic measurements
(Fig. 10). The 100 degree rule Eq. (6) was not as reliable
as the model based estimation method especially at
higher temperatures (Fig. 9). The 50 degree rule Eq. (7)
was found not to be reliable. This rule completely breaks
down at higher temperatures (Fig. 9). From the results
presented in this study we conclude that handling tem-
peratures below those resulting from the model based
estimation method will lead to TMRad longer than 24
hours.
We tried also to show that there is a correlation
between the ADT 24 and a temperature with a certain
heat release, in our case 0.5 W/kg (Fig. 11).
Acknowledgements
The authors would like to thank Dr. O. Klais, Dr. U.
Fischer, Dr. O. Kut and M. Graedel for their many
 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17
suggestions, valuable discussions and corrections. We
also would like to thank D. Mank and F. Ernst for their
help in making data available.
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