Thermal Analysis Application No.

UC 212
Thermal Analysis Application
Application published in METTLER TOLEDO Thermal Analysis UserCom 21

Model free kinetics

Introduction
The kinetics of chemical reactions can
be easily determined from DSC or TGA
measurements. The METTLER TOLEDO
e
STAR software offers three different
software options: the classical nth order
kinetics and two so-called model-free
methods.

The nth order kinetics approach assumes

that the activation energy is constant
throughout the entire reaction. The reac-
tion rate, dα/dt, is given by the equation

where α is the conversion, K0 is the

pre-exponential factor, Ea the activation
energy, R the gas constant, T the temper-
ature and n the order of the reaction. An
nth order reaction is therefore completely
described by the parameters n, Ea and K0.
This model is, however, at best only suit-
able for simple reactions.
In more complex reactions in which sev-
eral reaction steps proceed in parallel, or
in which the reaction is not completely
chemically controlled, nth order kinetics
fails. In such cases, model free kinetics
is an excellent alternative to describe the
reaction kinetics.
Figure 1. Procedure for MFK and AMFK analysis: Step 1: Measurement cur ves
at dif ferent heating rates (2.5, 5, 10, 20 K /min); the peak area (DSC meas-
u r e m e nt s) o r t h e s t e p h e ight ( TGA m e a s u r e m e nt s) s h o uld b e c o n s t a nt t o
±10% and ±5% respe ctively. S tep 2: Calculation of t he conversion cur ves.
Step 3: Calculation of the activation energy as a function of the conversion. Step 4: Predic-
tions using MFK or AMFK. The reaction investigated was the curing of an epoxy resin.
This study shows how model free kinet- Basic principles of model free
ics can be used to evaluate DSC and TGA kinetics
meas-urements and make predictions Model free kinetics assumes that the
about the isothermal behavior of reac- activation energy does not remain con-
tions (i.e. determine conversion as a stant during a reaction but changes.
function of time at a certain tempera- Furthermore, it assumes that the activa-
ture, or the time needed at a given tem- tion energy at a particular conversion is
perature to reach a certain conversion). independent of the temperature program
(the “iso-conversion principle”).
 e
In the STAR software, two different ver-
sions of model free kinetics have been
implemented as software evaluation
options: the standard model free kinet-
ics (MFK, Model Free Kinetics) and the
Thermal Analysis Application
advanced model free kinetics (AMFK,
Advanced Model Free Kinetics). The dif-
ference between these two approaches is
to be found in the numerical algorithms
that are used for the evaluation. Further-
more, with standard MFK, only dynamic
heating curves can be evaluated. With
AMFK, however, curves can be evaluated
that have been measured with any tem-
perature program, including isothermal
measurements.
Experimental details
As “raw data”, model free kinetics re-
quires at least three DSC or TGA curves
measured with different temperature
programs.
First of all, it is always best to make a
trial run in order to first get a general
impression of the “reaction profile”,
that is, the temperature range, reaction
enthalpy and mass loss. Relatively slow
heating rates (e.g. 5 K/min) should be
used for materials that release large
amounts of energy during the reaction
(e.g. explosives). For safety reasons it is
advisable to use high-pressure crucibles
and low sample masses (< 5 mg). With
other materials, heating rates of 10 or
20 K/min can be used for the trial run.
For MFK, a minimum of three experi-
ments must be performed at different
heating rates. Four or five measurements
are how-ever recommended to improve
the relia-bility of the calculated predic-
tions. The heating rates used should
increase in large steps such as 1, 2, 5, 10,
and 20 K/min. The use of smaller steps,
for example 5, 6, 7, 8, 9 K/min, reduces
the accuracy of the results. At increasing
heating rates, chemical reactions take
place at higher temperatures. Accord-
ingly, the temperature range must match
the heating rate. Particularly when high
heating rates are used, for example with
curing reactions, (undesired) decompo-
sition reactions frequently occur toward
Figure 2. Comparison of MFK and AMFK: Left: Initial data for MFK and AMFK. Although MFK
and AMFK clearly yield different activation energy curves (above right), the predictions made
with the two procedures do not significantly differ (below right).
the end of the reaction under investiga-
tion. In such cases, lower heating rates
should be used.
As mentioned above, isothermal temper-
ature programs can be used for AMFK. As
a rule, the temperatures used are below
the peak temperature. The reason for
this is that above the peak temperature
the reaction is very rapid, which makes
correct evaluation of the curves difficult.
A fundamental problem with isothermal
DSC experiments is that at the beginning
of the experiment the initial deflection
and chemical reaction overlap. In this
case, the DSC curve of a second run of
the same sample (which should then no
longer show any reaction) measured un-
der otherwise identical conditions can be
used as the baseline. Just as with MFK, at
least three measurements must be made
with different temperature programs for
AMFK. Four measurements are however
also recommended for AMFK; dynamic
measurements can be combined with
isothermal measurements. With AMFK,
the rate at which the measurement
values are recorded should be set to the
maximum value of 10 measurement val-
ues per second.
As far as sample preparation is con-
cerned, it is important to make sure that
all the samples are prepared in exactly
the same way. In particular, the sample
mass should be about the same for all
samples. And obviously the crucibles
used must not react with the sample.
Furthermore, it should be noted that the
size of the hole in the cru-cible lid could
influence reactions in which gases are
liberated.
Evaluations
The typical revaluation procedure used
for MFK and AMFK is illustrated in the
example shown in Figure 1
(for DSC measurements).
Step 1 (Fig. 1 above left): Display of
DSC measurement curves. As already
mentioned, the peak maximum shifts
to higher temperatures at increasing
heating rates. The reaction enthalpy
however is independent of the heating
rate and should therefore be constant
within about ±10%. At first sight, this
does not appear to be the case in the
heat flow curves displayed (the area
under the reaction peak is clearly larger
at high heating rates than at low heat-
ing rates). The reason for this is that
the reaction enthalpy is evaluated from
the curve plotted as a function of time,
whereas in Figure 1 the curves are shown
as a function of temperature. It should
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TA Application No. UC 212 2
 also be noted that the measured reac-
tion enthalpy depends strongly on the
type of baseline used. As far as possible
the same baseline type should be used
for all measurements. If the reaction
Thermal Analysis Application
enthalpy changes in a systematic way,
this could also indicate the overlap of
different processes. The statements made
here about DSC curves, are in the same
sense valid for TGA curves; instead of
the reaction peaks, mass loss steps occur
that should agree within about ±5% with
each other.
Step 2 (Fig. 1, above right): The conver-
sion curves are calculated from the
measured curves using the “DSC/Con-
version” or “TG/Conversion” routines.
Here again, attention must be paid to
the baseline, which should not intersect
the measurement curve at any point.
With TGA measurements, the problem of
baselines is not so serious. Often, instead
of the TGA curve, its first derivative, the
so-called DTG curve, is used. In this
case, the conversion curve is calculated
in the same way as the DSC curve. With
conversion curves, one should make sure
that the curves for the different heating
rates, in particular for low and high
degrees of conversion do not intersect. If
this occurs, it can usually be avoided by
using other limits or another baseline.
If a reaction exhibits several clearly
separated reaction steps (e.g. the de-
composition of calcium oxalate mono-
hydrate), it is better to analyze each step
individually. Such multi-step reactions
make themselves apparent because in
the conversion curves the conversion
stagnates at a certain tem-perature (the
conversion curve runs horizontally).
Step 3 (Fig. 1, below right): The conver-
sion-dependent activation energy is now
calculated from the conversion curves.
Figure 3. DSC curves (above left) with temperature programs consisting of three segments
(below left). In this case, kinetic analysis can only be performed with AMFK. An isothermal
experiment was performed at 25 °C (below right, red dashed curve) in order to check the
predictions made by AMFK (below right, black curves). The figure shows that prediction and
measurement agree very well.
Since the numerical procedures are dif- then calculates the conversion curves at
ferent, evaluations with MFK and AMFK different temperatures as a function of
yield different activation energy curves time and presents the results graphically
(see Fig. 2). The algorithms used for the and in tabular form. If possible, the pre-
calculation of predictions are different dictions obtained should then be checked
for MFK and AMFK. For this reason, ac- by performing another experiment under
tivation energies calculated using AMFK appropriate conditions.
cannot be used to calculate predictions
using MFK. Although MFK and AMFK An example is shown in Figure 3. Here,
yield different activation energies, the temperature programs were used consist-
predictions made by MFK and AMFK do ing of three segments, namely a dynamic
not significantly differ (see Fig. 2, below segment with isothermal segments be-
right). fore and after (see lower left diagram).
Step 4 (Fig. 1, below left): The conver- Using AMFK, the conversion-dependent
sion-dependent activation energy can activation energy (above right) was
now be used to make predictions, for calculated from the three measurement
example for the conversion of a reaction curves (above left) and then finally the
at a particular temperature as a func- predictions (below right) for the degree
tion of time. To do this, the details of the of conversion as a function of time at
desired temperatures and conversions three different temperatures. A com-
are entered in the “Kinetics/Conversion parison of the predictions at 25 °C with
Parameter Settings” or “Kinetics/Iso- a corresponding measured curve shows
Conversion Parameter Settings” menu. very good agreement between the experi-
Using this information, the software ment and the AMFK predictions.
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TA Application No. UC 212 3
 Conclusions
Model free kinetics allows even complex
chemical reactions to be analyzed using
just a few DSC or TGA measurements and
without making any assumptions about
Thermal Analysis Application
of view, the two approaches differ in the
numerical algorithms used.
The main difference for the user is that
MFK can only evaluate heating curves,
activation energies. However, with regard
to predictions, MFK and AMFK give very
similar results.
Publishing Note:

e
a particular reaction model. The STAR but AMFK can in addition evaluate iso- This application has been published in
software has implemented two equivalent thermal or combinations of isothermal the METTLER TOLEDO Thermal Analysis
UserCom No. 21.
procedures (MFK and AMFK software and dynamic measurements. Both pro- See www.mt.com/ta-usercoms
options). From the mathematical point cedures usually yield somewhat different

Mettler-Toledo AG, Analytical www.mt.com/ta

CH-8603 Schwerzenbach, Switzerland For more information
Phone +41-44-806 77 11
Fax +41-44-806 72 60
Internet www.mt.com

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TA Application No. UC 212 4