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Analytical solution for the Kissinger equation
Pere Rouraa) and Jordi Farjas
Grup de Recerca en Materials i Termodinamica (GRMT), Department of Physics,
University of Girona, Campus Montilivi, E17071 Girona, Catalonia, Spain
An analytical solution for the Kissinger equation relating the activation energy, E, with
the peak temperature of the reaction rate, Tm, has been found. It is accurate (relative error
below 2%) for a large range of E/RTm values (from 15 to above 60) that cover most
experimental situations. The possibilities opened by this solution are outlined by applying
it to the analysis of some particular problems encountered in structural relaxation of
amorphous materials and in kinetic analysis.
J. Mater. Res., Vol. 24, No. 10, Oct 2009 © 2009 Materials Research Society 3095
P. Roura et al.: Analytical solution for the Kissinger equation
ATm 1 are accurate enough to be used in theoretical analyses
xm ¼ Ln þ Ln : ð5Þ involving the Kissinger equation. Some examples are
b xm
given in Sec. III.
A plot of xm versus Ln(ATm/b) (inset of Fig. 1) reveals
a quasilinear dependence with a slope close to 1 for the
useful xm range of most solid state reactions (i.e., 15 < III. SOME APPLICATIONS
xm < 60). This simple dependence arises because of the The first two examples concern structural relaxation
reduced variation of xm when ATm/b spans over many processes in amorphous materials. These processes can-
orders of magnitude (see inset of Fig. 1). Consequently, not be directly described by Eq. (1), because they are not
an approximate analytical solution of Eq. (4) can be governed by single activation energy. Consequently,
written as analysis of the transformation temperature shift with the
ATm 1 heating rate through the Kissinger equation can lead to
xm ¼ Ln ; ð6Þ erroneous interpretation of the activation energy.14
b xm0
It is usually accepted that structural relaxation involves
where xm0 is a particular value between 15 and 60. The a distribution of independent defects that relax to a lower
accuracy of this solution has been tested for several energy state.15 A particular kind of defect is identified
values of xm0 and the relative error in the whole range by its activation energy and many analyses consider that
has been plotted in Fig. 1. Relative errors below 2% are the pre-exponential rate constant is the same for all
achieved with xm0 = 20. These are also the relative errors defects.16,17 Therefore, structural relaxation can be formal-
of the activation energy, when Eq. (6) is solved for E: ly described by the superposition of a continuum of trans-
formations characterized by a distribution of activation
ATm 1
E ¼ RTm Ln ; ð7Þ energies, N(E). Any particular transformation will follow
b xm0
Eq. (1) and will obey the Kissinger equation.13 Under
and, when solved for Tm, these assumptions, a simple relationship can be found
between the peak temperature of a given transformation
1 R AE 1
¼ Ln ; ð8Þ within the distribution and its activation energy. The de-
Tm E b R xm0 2 rivative of Eq. (7) in Tm leads to
the relative errors are twice those of E, because xm0 now dE=R
appears squared. Of course, the accuracy can be im- dTm ¼ ¼ BdE ; ð9Þ
proved if the range of xm is restricted and xm0 is chosen Ln ATm 1
b xm0 þ1
inside the range. The accuracy achieved for E is higher
than that obtained from most experiments. In addition, it where B is almost constant (almost independent of Tm)
is similar to the accuracy of the Kissinger equation itself for a given heating rate. In other words, although for
when applied to the analysis of non-first-order kinetics.9 relaxation experiments at a constant heating rate it is
Consequently, although Eqs. (6)–(8) are not exact, they more natural to describe the defects by the distribution
of peak temperature; this distribution has a shape that is
nearly identical to the distribution of activation energies.
Additionally, B has a smooth dependence on the heating
rate. For the particular case of structural relaxation of
a-Si (take A 1013 s1, the Debye frequency),16 B in-
creases by 20% when b increases from the usual values
of conventional differential scanning calorimetry (1 K/s)
to the high values of nanocalorimetry (104 K/s).18
Concerning the activation energy of the defects in the
distribution, we will show that, for constant A, it is
almost proportional to the peak temperature. Without
any further approximation, application of Eq. (7) to
(E1, Tm1) and (E, Tm) leads to:
E1 1 Tm E1
E¼ Tm 1 þ Ln T ; ð10Þ
Tm1 xm1 Tm1 Tm1 m
where the last expression is obtained because xm1>>1.
FIG. 1. Relative error in the activation energies delivered by the Of course, the higher xm1 the better the proportionality
analytical solution [Eq. (7)] with a single value of xm0 for the entire between Tm and E. Thanks to this relationship, we have
range of interest of xm. Inset: exact solution of the Kissinger equation. shown in Ref. 13 that, when A is constant, the logarithmic
variations with time of selected properties during the depend on C0 through the pre-exponential constant A.
isothermal relaxation of amorphous materials have a When the initial concentration changes from C01 to C02,
slope proportional to the annealing temperature. the shift of the peak temperature can be deduced, as we
The next two examples have a general interest in have done for the previous application and we obtain
kinetic analysis. First of all, we will derive a relationship
1 LnðC02 =C01 Þ
that allows calculating the shift of Tm when the heating Dð1=Tm Þ : ð17Þ
rate is increased from b1 to b2. From Eq. (8) we obtain Tm1 2 þ xm1
the exact formula (xm0 replaced by xmi): This last formula has been applied in Ref. 13 to show
1 1 R that in amorphous materials structural relaxation cannot
Dð1=Tm Þ ¼ ½Lnðb1 =b2 Þ be described by a superposition of second-order recom-
Tm2 Tm1 E
bination processes.
þ 2Lnðxm1 =xm2 Þ : ð11Þ
Since, as commented previously, xm has a variation IV. CONCLUSIONS
smoother than that of b (in fact bR/AE), we can expand
the logarithm of xmi around xm1/xm2 = 1 (i.e., around To conclude, we can say that during the past 50 years,
Tm2/Tm1 = 1). We obtain the Kissinger equation has been widely used for the anal-
ysis of experiments concerning the kinetics of structural
R Dð1=Tm Þ transformations. Despite this success, the particular func-
Dð1=Tm Þ ¼ Lnðb1 =b2 Þ 2 : ð12Þ
E 1=Tm1 tional dependencies on E and Tm make it difficult to use
the equation for general analytical predictions. Instead,
Solving for D(1/Tm) leads us to the desired result: predictions involve solving the equation numerically for
1 Lnðb1 =b2 Þ particular conditions. We hope that the analytical solu-
Dð1=Tm Þ : ð13Þ tion obtained in this work will broaden the range of
Tm1 2 þ xm1
applications of the Kissinger equation.
A similar, less accurate relationship was published
several decades ago.19 Numerical analysis of our ap-
proximate relationship reveals that, as expected, its ac- ACKNOWLEDGMENT
curacy improves when xm becomes higher. Consider This work was supported by the Spanish Programa
the particular case of a process with peak temperature Nacional de Materiales under Contract No. MAT2006-
Tm = 500 K and activation energy of 83.1 KJ/mol 11144.
(xm = 20). When the heating rate is increased by a
factor of 100, Eq. (13) predicts a shift of the peak
temperature of 132.4 K, which is very close to the REFERENCES
exact result of 130.6 K. 1. D.W. Henderson: Thermal-analysis of nonisothermal crystalliza-
Finally, we will consider second-order kinetics. This tion kinetics in glass forming liquids. J. Non-Cryst. Solids 30, 301
is the kinetics governing defect recombination in crys- (1979).
talline materials. Their concentration, C, diminishes 2. J. Farjas and P. Roura: Modification of the Kolmogorov-Johnson-
Mehl-Avrami rate equation for non-isothermal experiments and
according to a bimolecular reaction: its analytical solution. Acta Mater. 54, 5573 (2006).
dC 3. J. Farjas and P. Roura: Simple approximate analytical solution for
¼ kC C2 ; ð14Þ nonisothermal single-step transformations: Kinetic analysis.
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where kC is thermally activated. With the definition of 4. H.E. Kissinger: Reaction kinetics in thermal analysis. Anal.
Chem. 29, 1702 (1957).
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C0 C and desorption properties of Ni-dispersed carbon nanotubes.
a ; ð15Þ Appl. Phys. Lett. 88, 143126 (2006).
C0 6. E. Jona, P. Simon, K. Nemcekova, V. Pavlik, G. Rudinska, and
E. Rudinska: Thermal properties of oxide glasses. Part II. Activa-
where C0 is the initial concentration, we arrive to the tion energy as a criterion of thermal stability of Li2O2SiO2nTiO2
particular form of Eq. (1) for a second-order reaction glass systems against crystallization. J. Therm. Anal. Calorim. 84,
da 673 (2006).
¼ ðkC C0 Þð1 aÞ2 ; ð16Þ 7. A.P. Srivastava, D. Srivastava, and G.K. Dey: A study on micro-
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that, compared with Eqs. (1) and (2), leads to the conclu- tion of Fe40Ni38B18Mo4 metglass. J. Magn. Magn. Mater. 306,
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Kissinger equation [Eq. (8)], the peak temperature will some recent studies. Chem. Phys. Lipids 3, 304 (1969).
9. P. Budrugeac and E. Segal: Applicability of the Kissinger equation in 15. M.R.J. Gibbs, J.E. Evetts, and J.A. Leake: Activation-energy
thermal analysis revisited. J. Therm. Anal. Calorim. 88, 703 (2007). spectra and relaxation in amorphous materials. J. Mater. Sci. 18,
10. H. Yinnon and D.R. Uhlmann: Applications of thermoanalytical 278 (1983).
techniques to the study of crystallization kinetics in glass-forming 16. J.H. Shin and H.A. Atwater: Activation-energy spectrum and
liquids. 1. Theory. J. Non-Cryst. Solids 54, 253 (1983). structural relaxation dynamics of amorphous-silicon. Phys. Rev.
11. S. Vyazovkin and N. Sbirrazzuoli: Isoconversional kinetic analy- B 48, 5964 (1993).
sis of thermally stimulated processes in polymers. Macromol. 17. W. Deceuninck, G. Knuyt, H. Stulens, L. Deschepper, and
Rapid Commun. 27, 1515 (2006). L.M. Stals: Determination of the attempt frequency for relaxation
12. S.K. Padhi: Solid-state kinetics of thermal release of pyridine and phenomena in amorphous metals. Mater. Sci. Eng., A 133, 337
morphological study of [Ni(ampy)2(NO3)2]; ampy = 2-picolyla- (1991).
mine. Thermochim. Acta 448, 1 (2006). 18. J-F. Mercure, R. Karmouch, Y. Anahory, S. Roorda, and
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second-order processes: Application to pure amorphous silicon. phous silicon on implantation temperature. Phys. Rev. B 71,
Acta Mater. 57, 2098 (2009). 134205 (2005).
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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca
Short communication
a r t i c l e i n f o a b s t r a c t
Article history: The Šesták–Berggren equation, representing a powerful tool for the description of kinetic data by the
Received 20 February 2011 model-fitting methods, is analyzed. It is discussed that the exponents in the conversion function are non-
Received in revised form 14 March 2011 integer in general and that the conversion function may not have a mechanistic interpretation. Within the
Accepted 23 March 2011
framework of single-step approximation, the Šesták–Berggren equation enables to describe the kinetics
Available online xxx
of complex condensed-state processes without a deeper insight into their mechanism.
© 2011 Elsevier B.V. All rights reserved.
Keywords:
Šesták–Berggren equation
Single-step approximation
Model-fitting method
Mechanistic interpretation
Kinetics of the processes in condensed phase is frequently The exponents a and b in Eq. (3) may differ from those m and n
described by the so-called general rate equation representing the introduced in Eq. (2).
reaction rate d˛/dt as a product of two mutually independent func- Eq. (3) can be encountered in the literature published before
tions: 1971. Erofeev and Mitskevich in 1961 [3] pointed out that the
d˛ expansion and rearrangement of the differentiated form of the
= k(T )f (˛) (1) Yerofeev equation lead to Eq. (3). As early as in 1940, Akulov
dt
reported Eq. (3) where the constants a and b called the “constants of
The temperature function, k(T), depends solely on temperature T homogeneity” [4]. Eq. (3) is also quite frequently cited in the liter-
and the conversion function, f(˛), depends only on the conversion ature as an extended form of the Prout and Tompkins autocatalytic
of the process, ˛. The temperature function is prevailingly inter- equation [5], for example in [6–9]. Nonetheless, Eq. (3) is generally
preted as the rate constant and the conversion function is believed considered a transformation of Eq. (2) so that it is equally called the
to reflect the mechanism of the process. SB equation.
Fourty years ago, a paper by Šesták and Berggren [1] appeared Eq. (3) is widely applied to the study of not only isothermal,
in this journal introducing in Eq. (1) a three-parameter conver- but also non-isothermal processes; mathematical correctness of
sion function for a generalized description of reaction kinetics. The either description was justified in [10]. Later it was shown [11]
equation is often named after their authors, i.e. the Šesták–Berggren that this two-parameter model retains its physical meaning only
equation (habitually abbreviated as the SB equation): for a ≤ 1. Málek pointed out that the classical nucleation-growth
d˛ equation (often abbreviated as JMAYK) is actually a special case of
= k(T )˛m (1 − ˛)n [−] (2) this two-parameter SB model and thus SB equation represents a
dt
plausible alternative description for the crystallization processes
where m, n, and p are the (generally non-integer) exponents. Later taking place in non-crystalline solids [12]. The increasing value of
on, Gorbachev [2] demonstrated that, for isothermal conditions, Eq. the exponent a indicates a more important role of the precipitated
(2) can be transformed into three invariant expressions with two phase on the overall kinetics. It also appears that a higher value
exponents only. Among them, the following form is the one which of the second exponent (b > 1) indicates increasing reaction com-
is most frequently employed: plexity; however, the temptation to relate the values of a and b to
d˛ a reaction mechanism can be doubtful and should be avoided [12]
= k(T )˛a (1 − ˛)b (3) without complementary measurements [13,14].
dt
Due to its ability to describe variety of kinetic data both of
organic and inorganic origin [9], the SB equation attracts much
∗ Tel.: +421 2 59325530; fax: +421 2 52926032. attention. It was believed that it can be considered a univer-
E-mail address: peter.simon@stuba.sk sal expression for kinetic models [15]. For certain combinations
0040-6031/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tca.2011.03.030
Please cite this article in press as: P. Šimon, Fourty years of the Šesták–Berggren equation Thermochim. Acta (2011), doi:10.1016/j.tca.2011.03.030
ARTICLE IN PRESS
G Model
TCA-75649; No. of Pages 2
2 P. Šimon / Thermochimica Acta xxx (2011) xxx–xxx
Please cite this article in press as: P. Šimon, Fourty years of the Šesták–Berggren equation Thermochim. Acta (2011), doi:10.1016/j.tca.2011.03.030
Solid State lonics 63-65 (1993) 245-254
SOLID
North-Holland STATE
IONICS
and
J i l l M~tlek
Joint Laboratory of Solid State Chemistry of the Academy of Sciences of the Czech Republic,
and Universityof Chemical Technology, ~s. Legil sq. 565, 532 I0 Pardubice. Czech Republic
Kinetic models of solid-state reactions are often based on a formal description of geometrically well defined bodies treated
under strictly isothermal conditions; for real processes these prepositions are evidently incorrect. It can be equally useful to find
an empirical function containing the smallest possible number of constants. In such a case the models of heterogeneous kinetics
can be assumed as a distorted (fractal) case of the simpler homogeneouskinetics and mathematically treated by multiplying by
an "accommodation" function. In addition, the conventional thermoanalytical (TA) studies apply intentionally the experimental
conditions with constant heating and/or cooling where the model's validity must again be investigated. The general method of
kinetic data evaluation is proposed to include two-step evaluation: first, determining the activation energy, E, from a set of TA
curves at different heating rates, and second, using the pre-establishedE to search for the reaction mechanism by analyzing the
entire course of the singleTA curve. In this respect the possibilityof a simultaneous determination of all kinetic data is discussed.
The computer method is recommended to be based on the evaluation of two specific functions available for a direct derivation
from experimental data.
Table 1
The kinetic models.
Model Symbol f( a )
Johnson-Mehl-Avrami A. n(l-ol)[-ln(1-e~)]l-'/"
2D reaction R2 ( 1- a ) '/2
3D reaction R3 ( l - - a ) 1/3
2D diffusion D2 l/[-ln(1-a)l
Jander equation 9 3 ( l - c~)2/3/[ t - ( 1-c~) 2/3]
Ginstling-Brounshtein Da 3 [(1--O:)-L/3-- l]
J. ,~estdk,J. Mdlek / Phenomenological models of heterogeneous reactions 247
E increases slightly with increasing Xp for diffusion is confined to the interval 0 < o~M< OLpand it can be
models (i.e. D2, D3 and D4). On the other hand, the used to determine the apparent kinetic exponent ra-
ratio EapJE decreases with increasing Xp for the A, tio [13]
model as corresponds to the following equation [ 13 ]:
map p _ aM (9)
Eapp -- n-1 + 1, (5) nap p I -- OLM
E xo~(Xp)
It should be stressed that any change of the value
where n is the true kinetic exponent of the A, model of the apparent activation energy leads to a different
and 7r(x) is the approximation of the temperature value of the ratio mapp/n,pp. Therefore both appar-
integral in the form [ 14 ] ent kinetic exponents are mutually interdependent.
x 3 + 18x z + 8 8 x + 9 6 A characteristics napp versus mapp dependence can be
~ ( x ) = X 4 + 20x3_t_ 1 2 0 x Z + 2 4 0 X + 120 " (6) found for each true kinetic model. These plots (full
lines) calculated using eqs. (7) and (9) are shown
It is noteworthy that the empirical relationship E a p p / in fig. 2. The dashed lines correspond to the different
E = 1 . 0 5 E - 0 . 0 5 found by Criado et al. [11] cor- values of the maxima of the function yapp((~). An
responds to the general equation (5) for Xp= 38.3. important feature of the napp-mapp plot is that it is
The limiting values o f the parameters napp and characteristic for the true kinetic model. Neverthe-
E~pp/E are summarized in table 2 for the kinetic less, it can be seen that these plots are identical for
models discussed. the D3 and R3 models. There is also one c o m m o n
curve corresponding to the An model regardless of
3.2. The Sestdtk-Berggren model the values of the true kinetic exponent, n. Similar be-
havior was observed also for other types of reference
The ratio of the apparent and true activation ener- plots [ 15,16 ]" see fig. 2.
gies can be expressed for the SB model in the fol- Many works are concerned with the kinetic anal-
lowing form [ 12 ]: ysis of a single TA curve. However, these methods
are somewhat problematic because of the apparent
EaPp- f(aP) ( r/app - mape'] (7)
kinetic models. For example, the popular Freeman
E f'(ap) 1-ap ap }"
By rewriting eq. ( 1 ) for an apparent activation en- *~ It is evident that if the kinetic exponent, m, is equal to zero
(i.e. for the RO model), then a M = 0 . On the other hand Eapp
ergy we obtain:
should not be negative. Therefore it follows from eq. ( 7 ) that
Yapp( a ) = (dot/dt) exp (Eapp/R T). (8) o<M has to be lower than a w
Table 2 R2
The values of apparent parameters (Xv~OO) for the RO model. D,~_
DI
True model napp E,,pr,/ E
and Carroll method [ 17] was derived for the RO mental TA curve. This problem can be solved, how-
model. Therefore, this method always gives apparent ever, if the true activation energy is known. Then the
parameters napp and Eap p corresponding to the RO most probable kinetic model can be determined and
model regardless of the true kinetic model. Similarly, subsequently the pre-exponential term is calculated.
it must be borne in mind that the non-linear or mul- The method of kinetic analysis is described in the
tiple linear regression methods can lead to incorrect following sections.
results because any TA curve can be interpreted
within the scope of several apparent kinetic models 5.1. Calculations of the activation energy
(RO or SB) depending on the value of the apparent
activation energy. The calculation of the activation energy is based
On the other hand, if the true activation energy is on multiple scan methods where several measure-
known, the SB kinetic model can be found very use- ments at different heating rates are needed. Probably
ful in real heterogeneous systems [6,18,19], where the most popular in this family is the Kissinger
other kinetic models cannot be successfully used for method [25] based on the equation derived from
a quantitative description of the experimental data. the condition for the maximum rate on a TA curve.
A very similar method of calculation of activation
energy is the Ozawa method [ 26 ].
4. Correlation of the kinetic parameters An alternative method of calculation of the acti-
vation energy is the Isoconversional method which
Both the activation energy and the pre-exponen- follows from the logarithmized form of the kinetic
tial factor in eq. (1) are mutually correlated [20]. equation ( 1 ):
This correlation can be expressed by the following
equation (see Appendix): In (dc~/dt)= l n { A f ( t ~ ) } - E / R T . (11)
lnA=a+bE, (10) The slope ofln (dc~/dt) versus 1/ T f o r the same value
of a gives the value of the activation energy. This
where a and b are constants. Any change in the ac-
procedure can be repeated for various values of ct.
tivation energy is, therefore, "compensated" by the
So it easily allows one to check the invariance of E
change of In A as expressed by eq. (10). From this
with respect to c~, which is one of the basic assump-
point of view, it seems that the methods of kinetic
tions in kinetic analysis. Hence, the isoconversional
analysis aiming to ascertain all kinetic parameters
method can be recommended for the calculation of
from only one experimental TA curve are somewhat
the E.
problematic. Similarly, as in the preceeding Section,
On the other hand, we cannot recommend the
we have to realize that this problem cannot be solved
Freeman-Carroll method [17] because it was de-
even using the most sophisticated non-linear regres-
rived for the RO (n) model and, therefore, due to the
sion algorithms unless the kinetic models or at least
mutual correlation of kinetic parameters, this method
one kinetic parameter is a priori known.
always gives apparent kinetic parameters napp and
The value of E can further consist of the elemen-
Eap p corresponding to the RO (napp), regardless of the
tary parts arising from the partial reaction steps [21 ],
true kinetic model.
i.e. nucleation, interface chemical reaction and di-
fussion, which became particularly important in the
analysis of glass crystallization [22,23 ]. 5.2. Determination of the kinetic model
data. These functions can be formulated as follows tivation energy is decisive for a reliable determina-
[27,28]: tion of the kinetic model because of the correlation
of kinetic parameters.
y(a) = (da/dt)e x , (12) Similarly we can discuss the mathematical prop-
z(a) =n(x) (da/dt)T/fl. (13) erties of the function z ( a ) . It is fairly easy to de-
monstrate (see Appendix, eq. A.10)) that the func-
The function y ( a ) is proportional to the function tion z ( a ) has a maximum at 0% for all kinetic
riot). Thus by plotting the y ( a ) dependence, nor- models summarized in tables 1 and 2. This param-
malized within the interval (0, 1 ), the shape of the eter has characteristic values [ 13 ] for basic kinetic
function f ( a ) is obtained. The function y ( a ) is, models as summarized in table 4. It is interesting that
therefore, characteristic for a given kinetic model, as the a~° practically does not depend on the value of
shown in fig. 3, and it can be used as a diagnostic the activation energy used to calculate the function
tool for kinetic model determination. The mathe- z ( a ) (in fact it varies within 1% of the theoretical
matical properties of the y ( a ) function for basic ki- value). An important fact is that a ~ is invariant with
netic models are summarized in table 3. The func- respect to the kinetic exponent for the JMA(n)
tion y ( a ) has a maximum aM ~ (0, ap) both for the model. On the other hand, for both the R O ( n ) and
HMA (n > 1 ) and SB (m, n) model (see Appendix SB (m, n) models, the parameter a ~ depends on the
eqs. (A.13) and (A.14)). values of the kinetic exponents as shown in fig. 4.
It should be stressed that the shape of function It is evident that the shape of the function y ( a )
y ( a ) is strongly affected by E. Hence the true ac- as well as the maximum, a ~ , of the function z ( a )
can be used to guide the choice of a kinetic model.
Both parameters aM and a ~ are especially useful in
JMA(3) this respect. Their combination allows the determi-
nation of the most suitable kinetic model, as shown
by the scheme in fig. 5. As we can see, the empirical
SB (m, n) model gives the best description of TA data
i f a ~ ~0.632 and aM ~ (0, ap). According to our ex-
perience, these conditions are fulfilled for some solid-
state processes [29,30].
0.8
0.o°°, ......
c(
0.7
0.6
Table 3
Properties of the function y ( a ) for basic kinetic m o d e l s
0.5
Model y (a )
0,4
JMA(n) concave, for n < 1
linear, for n = 1
~-~ SB(0.8, n)
m a x i m u m , for n > 1 0.3
R2 convex 0.3 0.8 1.3 18 2.3 2.8 3 3 38
TI
R3 convex
D2 concave
Fig. 4. The d e p e n d e n c e of the m a x i m u m of the function z ( a ) ,
D3 concave
a ~ , on the kinetic exponent, n, for the R O ( n ) and S B ( m , n)
D4 concave
kinetic models.
J. ~est6k, J. MMek / Phenomenological models of heterogeneous reactions 251
_-_9 ~M = 0 D3 ap = 0.704
RO(n>l)
7:q
JMA(n<I)
> SB(m,n)
5.4. Calculation of the pre-exponentialfactor dict the behaviour of the studied system under iso-
thermal conditions.
Knowing the value of the activation energy and
the kinetic model, the pre-exponential factor is cal-
culated using the following equation [28]: 7. Conclusions
A=
•Xp
T f ' ( ~ p ) exp(xp) . (20) It was shown that both activation energy and pre-
exponential factor are mutually correlated. As a con-
sequence of this correlation any TA curve can be de-
scribed by an apparent kinetic model instead of the
appropriate one for a certain value of apparent ac-
6. Software for kinetic analysis tivation energy. Therefore, the kinetic analysis o f TA
data cannot be successful unless the true value o f the
It is rather surprising that the mutual correlation activation energy is known.
of kinetic parameters as well as the apparent kinetic Taking into account these facts, a new method of
models are very often ignored even in the commer- kinetic analysis of TA data has been proposed. This
cially available kinetic software. This is why a new method allows the determination of the most suit-
software package TA-system was developed, based able kinetic model and calculation of the meaningful
on the method of kinetic analysis of TA data de- kinetic parameters of the general kinetic equation.
scribed above. It is possible to draw benefit in TA kinetics from
The TA-system runs under MS DOS operating its easiness and rapidity, provided that relatively low
system on any IBM or compatible computer with at gradients are kept in the sample, which evidently re-
least 512 kB RAM and EGA or VGA graphics card. quires as small a charge as possible. In the case that
The system is very simple to use and it features flex- the sample must be larger, and if the reaction pro-
ible and interactive graphics capabilities which will duces gaseous products, the technique of controlled
present the results in an optimal way required by the rate thermal analysis (CRTA) [23] can provide
user. Both data and graphs can be exported into most more reliable results.
graphical and spreadsheet software packages.
The software package includes programs to cal-
culate the activation energy from several sets of ki- Appendix. The integral kinetic equation
netic data at various heating rates. This value of ac-
tivation energy is used by another program to
If the temperature rises at a constant rate, fl, then
calculate both y(c~) and z(c~) functions, The shape
we obtain after integration of eq. ( 1 ) the equation:
of these functions enables the proposal of the most
probable kinetic model. Then the pre-exponential
g(a)=
f f ~da- ) AE
_ ~-~ e - x -
~(x) (A.l)
factors and kinetic exponents are calculated. This • X
procedure is repeated for all heating rates. There- 0
A. 1. The condition for the m a x i m u m o f the TA Hence the value o f a ~ also corresponds to the max-
curve i m u m of a hypothetical DSC or D T A peak for x p - - . ~ .
Differentiating eq. (1) with respect to time, the A.4. The m a x i m u m o f the y(a) function
following equation is o b t a i n e d [ 19 ]:
C o m p a r i n g eqs. ( i ) and ( 6 ) , the function y ( a )
d 2 a / d t 2 = [fl/ Trc(x) ]2f( a )g( a ) [ f ' ( a )g( a )
can be expressed as follows:
+xn(x) ] . (A.3)
y(a) =Af(a). (A.12)
The condition for the m a x i m u m o f the TA curve is
Therefore, the condition for the m a x i m u m o f the
obtained by setting eq. (A.3) equal to zero:
function y ( a ) can be written a s f ' ( a ) = 0 . Analyz-
-f'(ap)g(ap) =XpTt(Xp) . (A.4) ing this condition we can find that the D2, D3, D4
and R O ( n ) kinetic models have a m a x i m u m at
A.2. Correlation o f kinetic parameters aM = 0. It can also be shown that there is a m a x i m u m
o f the function y ( a ) at 0 < a M < a p for both the
Substitution o f e q . (A.1) into eq. (A.4) gives eq. J M A ( n ) and SB(m, n) models that d e p e n d s on the
(A.5): value o f the kinetic exponents. The condition for a
m a x i m u m o f the J M A ( n > 1) model is given by
-f ' (ap)Ae .... flRx~/ E . ( A.5 ) equation:
Eq. (A.5) can be rewritten after converting it to log- aM = 1 - e x p [ ( 1 - n / n ) ] . (A.13)
arithms in the following form:
Similarly, the condition for a m a x i m u m o f the SB (m,
lnA=a+bE , (A.6) n) model is expressed as follows:
where b = 1/RTp and a = l n [ --flXp/Tf'(ap)]. aM = m / ( m + n ) . (A.14)
d o t / d t = [ f l / T n ( x ) ]f( a ) g ( ot) . (A.7) [ 1] J. ~esVik, ed., in: Reaction kinetics by Thermal Analysis,
Special issue of Thermochim. Acta 203 ( 1992 ).
After a rearrangement o f eq. (A.7) the following [ 2 ] J. ~est~ik,J. Thermal Anal. 16 ( 1979 ) 503; 33 ( 1988 ) 1263.
equation can be written for z ( a ) : [3] J. ~esuik, Thermophysical Properties of Solids, Their
Measurements and Theoretical Thermal Analysis (Elsevier,
z(a)=n(x)(da/dt)T/fl=f(a)g(a) . (A.8) Amsterdam, 1984).
[4] J. ~est~ikand G. Berggren, Thermochim. Acta 3 ( 1971 ) I.
Differentiating eq. (A.8) with respect to a we obtain [ 5 ] V.M. Gorbatchev, J. Thermal Anal. 18 (1980) 194.
eq. (A.9): [6] J. M~llekand V. Smr6ka, Thermochim. Acta 186 (1991)
153.
z'(a) =f'(a)g(a) + 1. (A.9) [7] J. ~est~ik,J. Thermal Anal. 36 (1990) 1977.
By setting eq. ( A . 9 ) equal to zero, we get the equa- [ 8 ] J. M~ilekand J.M. Criado, Thermochim. Acta 175 ( 1991 )
305.
tion (A. 10) that must be fulfilled by a ~ at the max-
[9 ] J. ~est~ik,in: Thermal Analysis,Proc. 2nd ESTAC,Aberdeen,
imum of z(a): ed. D. Dollimore (Wiley, London, 1981 ) p. 115.
[ 10] T. Kem6ny and J. ~est~ik,Thermochim. Acta 110 (1987)
-f (a o )g(ap )=1. (A.10) 113.
An identical result is obtained from eq. (A.4) when [ 11 ] J.M. Criado, D. Dollimore and G.R. Heal, Thermochim.
Acta 54 (1982) 159.
Xp is infinite because in this case
[12] N. Koga, J. ~est~tkand J. M~ilek, Thermochim. Acta 188
lim [ X p T ~ ( X p ) ] = 1 . (A.1 1) (1991) 333.
xla~ [ 13 ] J. M~llek,Thermochim. Acta 200 ( 1992 ) 257.
254 J. ~estdtk, J. M~lek / Phenomenological models of heterogeneous reactions
[ 14 ] G.I. Senum and R.T. Yang, J. Thermal Anal. 11 (1977) 445. [25 ] H.E. Kissinger, Anal. Chem. 29 (1957) 1702.
[ 15 ] J.M. Criado, J. M~ilek and A. Ortega, Thermochim. Acta [26] T. Ozawa, J. Thermal Anal. 2 (1979) 301.
147 (1989) 377. [27] J.M. Criado, J. Malek and A. Ortega, Thermochim. Acta
[ 16 ] J. M~ilek and J.M. Criado, Thermochim. Acta 164 (1990) 147 (1989) 377.
199. [ 28 ] J. M~ilek, Thermochim. Acta 138 ( 1989 ) 337.
[ 17 ] E.S. Freeman and B. Carroll, J. Phys. Chem. 62 ( 1958 ) 394. [29] J. M~ilek and V. Smr?zka, Thermochim. Acta 186 (1991)
[ 18 ] L. Tich~' and P. Nagels, Phys. Status Solidi A87 ( 1988 ) 769. 153.
[ 19] J. M~ilek, J. Non-Cryst. Solids 107 (1989) 323. [30] J. M~ilek, J. Non-Cryst. Solids 107 (1989) 323.
[ 20 ] N. Koga and J. ~est~ik, Thermochim. Acta 182 ( 1991 ) 201. [31 ] V. ~atava, Thermochim. Acta 2 ( 1971 ) 423.
[ 21 ] J. ~est/ik, Phys. Chem. Glasses 15 (1974) 137. [ 32 ] J. M~ilek, J.~est~ik, F. Rouquerol, J. Rouquerol, J.M. Criado
[22] J. ~est~ik, Thermochim. Acta 98 (1986) 339. and A. Ortega, J. Thermal Anal. 38 (1992) 71.
[23] N. Koga and J. ~est~ik, J. Thermal Anal. 37 ( 1991 ) 1103.
[24] J. M~llek, J.M. Criado, J. ~est~lk and J. Militk~,, Thermochim.
Acta 153 (1989)429.