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Determination of the adiabatic Time to Maximum Rate by DSC for thermal safety
assessment / UserCom Thermal Analysis No. 40

Chapter · June 2014

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 resources of fossil fuels, global warm- trometer. The results yield information Reference
ing or accidents in nuclear power sta- about the composition (moisture, ash, [1] Thomas Bührke, Roland Wen-
genmayr: Erneuerbare Energien-
tions. Biomass is recognized as an im- carbon) of the biomass and the type of Konzepte für die Energiewende,
portant renewable energy source. gases that are produced during the py- Wiley-VCH, 3. Auflage 2011.
rolysis. This information allows the po-
Applications

Biomass can be easily characterized tential of a particular biomass material

by TGA/DSC coupled to a mass spec- as an energy source to be estimated.

Determination of the adiabatic Time to Maximum

Rate by DSC for thermal safety assessment
Dr. Samuele Giani

The identification and assessment of possible hazards and risks in chemical processes is of major practical
importance. It is essential for developing and controlling chemical reactions both on the laboratory scale
and in an industrial environment. Frequently chemical accidents are due to loss of control and incorrect han-
dling. The result of this is often a so-called runaway reaction that can lead to an explosion.

Introduction mal behavior under any temperature scenario [1, 2, 3] is on the one hand de-
The earliest possible identification of profile. This procedure can be applied for scribed by means of the adiabatic tem-
possible hazards and risks is of major the risk analysis of chemical compounds perature increase ∆Tad . Alternatively,
importance for product development. or processes. The most important objec- the so-called “Time to Maximum Rate
DSC measurements are very useful for tive is to ensure safe working conditions under adiabatic conditions” (TMR) pro-
this because only small amounts of and to minimize possible risks. vides information about the probability
sample are needed to quickly measure of a thermal risk.
the enthalpies and rates of chemical re- Risk assessment can be carried out to
actions. introduce methods and measures to TMR indicates the time it takes for a
ensure that a specified level of safety is reaction mass to reach the maximum
In this connection, the maximum adia- maintained and that control strategies rate of heat release for a given starting
batic temperature increase and the Time are implemented. temperature. In an adiabatic system,
to Maximum Rate (TMR) are important no heat exchange occurs between the
quantitative criteria. They describe the Risk profiles mostly serve as the basis for material under investigation and the
conditions under which a substance or a classifying acceptable scenarios versus surroundings; this means that the total
process becomes thermally unstable or a unacceptable situations. Such profiles heat generated remains in the system
thermal runaway, for example an explo- are generally described and are linked and increases its temperature.
sion, could occur. to severity and probability.
The formula for the adiabatic tempera-
Kinetic descriptions of chemical reac- Thermal safety with regard to severity in ture increase is given in equation 1 and
tions can be used to estimate their ther- connection with an exothermic runaway for TMR in equation 2.

20 METTLER TOLEDO UserCom 40

'Tad= 'h
Figure 1.
Adiabatic reaction
cp (1) profile of an exo-
thermic reaction.

Here ∆Tad is the adiabatic temperature

increase, ∆h the specific enthalpy of re-
action, and cp the specific heat capacity
at constant pressure.

TMR= §dT ·
© dt ¹max
(2)

The reaction rate is given in equation 3 and

is determined from kinetic calculations.

dD =K(T) · f(D) (3)

dt
Figure 2.
Dynamic DSC
The rate of the adiabatic temperature measurement of the
increase is given by equation 4. decomposition of
benzoyl peroxide
dissolved in dibutyl
dT ='T dD (4) phthalate. A sample
dt ad dt
mass of about
|OIYCUWUGF
in a high-pressure
Different calorimetric methods are used crucible.
to measure these values. DSC experi-
ments are particularly suitable for de-
termining cp, ∆h, and reaction kinetics
at an early stage of product development
[4].

A further advantage is that only a few

milligrams of substance are needed.
The reaction rate can be described by
means of kinetic analysis and corre-
sponding parameters (for example, see and illustrates the concept of TMR. Case study: the decomposition
reference [5]). The upper diagram (black curve) dis- of benzoyl peroxide
plays the adiabatic development of an The thermal decomposition of benzoyl
Adiabatic profile exothermic reaction for a given starting peroxide (synonym: dibenzoyl peroxide)
The adiabatic course of a reaction can temperature, T0. dissolved in dibutyl phthalate is used
be calculated using data from a dy- as a case study to illustrate the deter-
namic DSC experiment. Integration of As the reaction proceeds, the tempera- mination of the TMR. This reaction is
the heat flow signal yields the reaction ture increases more and more rapidly frequently used for comparison purpos-
enthalpy, and cp is determined by means and reaches a maximum temperature es; see reference [7] and the references
of a DSC measurement [6]. given by ∆Tad. listed in it.

Kinetic evaluation of one or more DSC The rate of change of temperature has its Figure 2 displays a dynamic DSC mea-
measurements allows reaction behavior maximum at the point of inflection of surement of the thermally induced de-
to be predicted with regard to time and the curve. The lower diagram (red curve) composition reaction at a heating rate
temperature. shows the first derivative of the adiabatic of 10 K/min.
temperature increase; the curve displays
The typical course of an adiabatic tem- the rate of self-heating. The time to the The measurement curve shows that the
perature increase is shown in Figure 1 maximum of the peak corresponds to TMR. reaction begins at about 80 °C. It takes

METTLER TOLEDO UserCom 40 21

 place over a temperature range of 80 K ent starting temperatures. As expected, cause up until this time an intervention
and generates an exothermic enthalpy the higher the adiabatic starting tem- (e.g. cooling or quenching) can still
of reaction of 1365 J/g. Assuming a con- perature, the shorter the TMR. successfully prevent an uncontrolled re-
stant specific heat capacity of 2 J/(g K), action.
the adiabatic temperature increase, TMR is the basis for determining safety-
Applications

∆Tad, is calculated to be 682.5 °C – a relevant data values. For example, if the Another important quantity is TD24.
value that is so high that the material production of heat exceeds the cooling This corresponds to the temperature at
would completely decompose. rate, an exothermic reaction can lead to which TMR is 24 hours. It is a frequently
a thermal runaway. used safety criterion and means that
Kinetic analysis yields the three param- an intervention is still possible within
eters shown in Figure 2 which describe This means that failure of the cooling 24 hours.
the reaction behavior for an activation system followed by adiabatic condi-
energy E A of 127 kJ/mol. The curves dis- tions presents a worst case scenario. If In this particular example, TD24 cor-
played in Figure 3 were calculated using an emergency cooling system is to cope responds to a starting temperature of
these values. with an imminent runaway reaction, 36.5 °C. Temperatures above this value
then it must be effective within a time must therefore be avoided.
They show the adiabatic temperature shorter than the TMR. This time span is
behavior of benzoyl peroxide for differ- also known as the intervention time be- Thermal safety diagram
Figure 4 displays a thermal safety dia-
Figure 3.
Change in the gram for the reaction investigated. It
sample temperature was constructed using values obtained
of a decomposition
from Figure 3.
reaction of benzoyl
peroxide calculated
under adiabatic The diagram shows the relationship
conditions for start-
ing temperatures of
between TMR and the process tempera-
30, 35, 36.5 and ture, T 0. For situations with tempera-
|Œ% tures above 36.5 °C, the process can be
looked on as inherently unsafe. It is
therefore not acceptable in a production
environment.

In this case, changes must be made to

the process or the process will have to
be completely redesigned. Further infor-
mation must be obtained and the pos-
sibility of additional measurements, for
example using the METTLER TOLEDO
Figure 4. RC1 reaction colometer, should be con-
Variation of the sidered.
adiabatic TMR and
the starting tem-
perature, T0. Conclusions
The risk of a reaction runaway can in
principle be estimated from DSC mea-
surements of the adiabatic temperature
increase, ∆Tad, and the Time to Maxi-
mum Rate (TMR).

The classification is somewhat difficult

because there is no direct quantitative
relationship between the measured val-
ues of ∆Tad and TMR and the probability
and severity of an event. A generally ac-
cepted order of magnitude is that pro-
posed by Stoessel [8] given in Table 1.

22 METTLER TOLEDO UserCom 40

 'Tad in K
It is important to emphasize that the Table 1.
Risk / Factor TMR in h
Assessment criteria
TMR must be estimated with the utmost High >200 <8 for the severity and
50 < 'Tad <200
caution (worst-case scenario). probability of run-
Medium 8 < TMR <24
away reactions [8]
Low <50 a >24 using ∆Tad, TMR, or
If for any reason increased risk is ex- a both quantities.
Condition: the boiling point is not exceeded.
pected, it is imperative to take addition-
al measures to clarify the situation. mal safety: simple experimental [7] Y.-H. Huang et al., Thermal runaway
access by means of the catalytic reaction evaluation of benzoyl per-
References decomposition of H2O2, J. Loss Pre- oxide using calorimetric approaches,
[1] D. Townsend et al., Thermal hazard vent. Proc. (2003), 289–296. J. Therm. Anal. Calorim. (2003),
evaluation by an accelerating rate [4] R. Riesen, Rapid investigation of 595–598.
calorimeter, Thermochim. Acta, thermally hazardous substances, [8] F. Stoessel, Thermal Safety of Che-
(1980), 1–30. UserCom 33, 6–9. mical Processes: Risk Assessment
[2] T. Grewer, Thermal hazards of che- [5] Safety Investigations with Model Free and Process Design, John Wiley &
mical reactions, Elsevier (1994). Kinetics, UserCom 10, 11–12. Sons (2008), 64–67.
[3] K. Hungerbühler et al., The runaway [6] Measuring specific heat capacity,
scenario in the assessment of ther- UserCom 7, 1–6 .

METTLER TOLEDO UserCom 40 23

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