J Therm Anal Calorim (2013) 113:15271541

DOI 10.1007/s10973-012-2882-5

Ozawas kinetic method for analyzing thermoanalytical curves

History and theoretical fundamentals
Nobuyoshi Koga

Received: 1 November 2012 / Accepted: 11 December 2012 / Published online: 16 January 2013
 Akademiai Kiado, Budapest, Hungary 2013

Abstract By reviewing the history of thermal analysis and

its application to the kinetic analysis of the solid-state processes, we investigate the theoretical basis and historical
perspective of Ozawas kinetic method for analyzing thermoanalytical curves. Ozawas nonisothermal kinetic method
is demonstrated using thermoanalytical data for the thermal
decomposition of sodium hydrogencarbonate and the crystallization of anhydrous magnesium acetate glass as examples. Through investigating recent theoretical advancements
in nonisothermal kinetic analysis in view of the theoretical
fundamentals of Ozawas kinetic method, it is indicated that
they are in line with Ozawas kinetic theory. On the basis of
the above investigations, we discuss the role of Ozawas
kinetic theory in advancing the analysis of complex reaction
kinetics.
Keywords Thermal analysis  Kinetic calculation 
Ozawas method  Isoconversional relationship 
Experimental master plot

Introduction
Thermal analysis deals with measuring changes in physical
properties of materials on heating or cooling as a function of
time and it is extremely useful for the characterization of a
certain class of materials. As early as 1887, Le Chatelier
Dedicated to the late Dr. Takeo Ozawa with the authors profoundest
condolences.
N. Koga (&)
Chemistry Laboratory, Department of Science Education,
Graduate School of Education, Hiroshima University, 1-1-1
Kagamiyama, Higashi-Hiroshima 739-8524, Japan
e-mail: nkoga@hiroshima-u.ac.jp

[1, 2] recorded a type of thermometric curve by heating clay

minerals and observing the thermal effect of the change in
heating rate. In 1899, Roberts-Austen [3, 4] introduced
differential measurements, an epoch-making concept. He
performed differential thermal analysis (DTA), i.e., he
recorded the temperature difference between a sample and
reference material as a function of time and temperature. In
the mid-20th century, DTA became common and commercially available [5]. Numerous experimental studies were
performed using DTA apparatus and the interest shifted to
the correspondence of the area of DTA peak to the enthalpy
change associated with a transformation [6]. Several problems in the quantitative treatment of the DTA peak were
pointed out experimentally and they were analyzed theoretically by Boersma [7] in 1955 using the Fourier equation
of thermal conduction. On the basis of the theoretical analysis, he concluded that it is inherently impossible to quantify
the enthalpy change by DTA. After approximately 10 years,
Ozawa performed a similar theoretical study on DTA with a
new arrangement of the measuring head that stated the
construction of a heat-flow sensor [8]. His efforts produced a
simple quantitative relationship between the DTA peak area
and enthalpy change associated with a transformation, and it
was the basis for heat-flux differential scanning calorimetry
(DSC).
In 1915, Honda developed an instrument of thermogravimetry (TG), i.e., Hondas thermobalance [9], which
was independent of the development of DTA and DSC.
This instrument consisted of an analytical balance, a
heating chamber, and temperature measuring and optical
reading systems. He recorded mass-change traces for
thermal dehydration and decomposition of inorganic solids
under stepwise isothermal heating. The instrument recorded high resolution of reaction steps and demonstrated
acceptable quantification of the respective mass-changes.

123

1528

From the thermoanalytical curves, he also calculated the

average rate of the reactions within a restricted temperature
region.
Through the above review on the establishment of the
major thermoanalytical technique, we present potential
usefulness of thermal analysis inherent in the methodology
of measuring the changes in the physical properties of
materials as a function of time and temperature [10, 11]. At
first, thermal analysis aimed to qualitatively identify thermally induced transformation and determine the transformation temperature. Subsequently, instrument improvement
based on experiments and theoretical analysis enabled to
quantitatively determine the changes in the physical properties, such as enthalpy change and mass-change. In addition,
from the methodology of tracing the transformation process
as a function of time and temperature, thermal analysis is a
powerful tool for recording the kinetic rate data of thermally
induced chemical and/or physical processes. On the other
hand, if we apply the inverse methodology, the transformation process can be quantitatively controlled; Rouquerol and
Paulik brothers later proposed this methodology as the
controlled rate thermal analysis (CRTA) or sample-controlled thermal analysis (SCTA) [12].
Many researchers have tried to apply thermal analysis to
the kinetic characterization of thermally induced processes
in various materials [13]. Among them, the contribution of
Dr. Takeo Ozawa, see Fig. 1, is distinguished. He established the theoretical basis of thermoanalytical kinetics
under nonisothermal conditions and developed a reliable
kinetic analysis method, known as Ozawas method. In this
article, we review Ozawas contribution from the historical
prospective of development of nonisothermal kinetics. The
theoretical fundamentals is investigated by applying the
practical procedures of Ozawas kinetic analysis to the
thermal decomposition of sodium hydrogencarbonate
(SHC) [14] and crystallization of anhydrous magnesium
acetate glass (AMAG) [15] as examples. The impact of
Ozawas kinetic theory on the field of thermal analysis and
its role in the future advancements of our field are discussed on the basis of the investigations.

Development of nonisothermal kinetics

Ten years after the development of Hondas thermobalance, Kujirai and Akahira measured a series of isothermal mass-loss traces for the thermal degradation of six
different fibrous insulating materials [16], to evaluate the
effect of temperature on the deterioration of these
materials. For the kinetic analysis of the mass-loss data at
different temperatures, they found the following empirical expression of the Arrhenius-type equation for the
reactions.

123

N. Koga

Fig. 1 The late Dr. Takeo Ozawa (February 14, 1932October 2nd,
2012)

log t

Q
 F w;
T

where Q and w are the process constant and mass-loss

fraction, respectively. This equation indicates that at fixed w,
the data points of the mass-loss data at different temperatures
form a straight line when plotting the logarithm of the
reaction time against reciprocal temperature. Using the
currently using symbols, the equation can be rewritten as
Ea
A
log t
;
2
 log
g a
2:303RT
where Ea, A, and g(a) are the apparent activation energy,
Arrhenius pre-exponential factor, and kinetic model function expressed using the fractional reaction a, respectively.
In Fig. 2, this relationship was reproduced using a series
of the isothermal mass-loss data for the thermal decomposition of SHC. At different a, the plots of log t against the
reciprocal temperature are straight lines with a slope that is
practically constant in all plots, Fig. 2a. The Ea values calculated from the plots at different a are practically constant in
a wide range of a, 0.1 B a B 0.9, Fig. 2b. The observations
demonstrate that Kujirai and Akahira successfully applied
the isoconversional kinetic analysis to a series of isothermal
mass-loss traces as early as 1925.
In addition, they evaluated the value of F(w) in Eq. (1)
at different mass-loss fractions from the intercept of the
respective isoconversional plots. The experimentally
determined value of Q and F(w) were used to predict the
lifetime of the fibrous insulating materials. The methodology of kinetic analysis and its application to lifetime
prediction are the same as those used today.
In 1928, Akahira [17] derived the differential kinetic
equation from their integral equation, Eq. (1).


Zw
dw
Q
dw
C exp 
f w with expF w C
dt
T
f w
0

Ozawas kinetic method for analyzing thermoanalytical curves

(a)

2.5

1529

temperatures by an integral method. In this way, the

nonisothermal kinetics was first developed in Japan [19].

= 0.9

log (t/min)

2.0

Isoconversional plot for nonisothermal data:

the ozawa plot

1.5

= 0.1

1.0

0.5
2.48

2.50

2.52

2.54

2.56

2.58

T 1/kK1

Ea/(kJ/mol)

(b)

150
125
100
75
50
0.0

0.2

0.4

0.6

0.8

1.0

Fractional reaction

g a

Fig. 2 Kinetic analysis of isothermal mass-loss data of the thermal

decomposition of sodium hydrogencarbonate by the isoconversional
method: a isoconversional plots at different a from 0.1 to 0.9 in steps
of 0.1 and b the a-dependence of the Ea value evaluated from the
slope of the isoconversional plots

This equation is equivalent to the fundamental kinetic

equation in differential form in present-day.


da
Ea
A exp 
f a;
4
dt
RT
where f(w) and f(a) are the kinetic model functions in
differential form. Akahira pointed out that the differential
equation can be applied to the kinetic rate data under
varying temperatures. He simulated the kinetic rate data
recorded by applying temperature jumps between two
different temperatures repeatedly with a period of cycle s
and defined the equivalent constant temperature, Te, as
Te 

Q
 t
:
 
R
log 1s exp  QT dt

In the mid-20th century, basic thermal analysis instruments

such as DTA and TG became commercially available, and
thermoanalytical measurements were applied to a variety
of chemical and/or physical processes of materials. The
kinetic analysis of processes using the thermoanalytical
curves was also one of the subjects at that time. Because
the most widely applied temperature program was that
under linearly changing temperatures as is still today, the
analysis for the kinetic rate data under linear nonisothermal
conditions was preferred. In this case, the differential
kinetic equation derived by Akahira [17], Eqs. (3) and (4),
can be applied directly, but the derivation of the integral
kinetic equation requires an approximation of the exponential temperature integral. Using the approximation
function of the temperature integral, p(x) with x = Ea/RT,
the integral kinetic equation is expressed as [2024]

With this expression, he showed Te depends only on the

time integral of exp(-Q/T) and can be used to characterize the
kinetic behavior under varying temperatures. Furthermore, he
published a table of numerical values of exponential
temperature integral [18], which is necessary for the
analysis of the kinetic rate data under linearly changing

Za
0

da
AEa

f a
bR

Z1

expx
AEa
p x;
dx
x2
bR

where b is the heating rate.

Several kinetic analysis methods using thermoanalytical
curves under linear nonisothermal conditions have been
proposed based on Eqs. (4) and (6). These methods can be
classified into differential and integral methods on the basis
of the analytical form of the kinetic equation and also into
single-run and multiple-run methods on the basis of the
procedures. Considering the performance of the thermoanalytical instruments and the data recorded by the analog
pen recorders at that time, differential kinetic analysis was
not preferred because the reliability issues with the kinetic
rate data recorded by thermal analysis and difficulty in
performing numerical differentiation without a PC. For the
integral method of kinetic analysis, several analytical
forms of the integral kinetic equation were derived using
different p(x) functions. For example, Coats and Redfern
derived the following equation [25]:



g a
AEa
2RT
Ea
ln 2 ln
1
7

T
Ea
bR
RT
using
p x



expx
2
1

x2
x

At a constant b, Eq. (7) suggests that the plot of the

logarithmic term on the left-hand side of the equation

123

1530

N. Koga

against the reciprocal temperature should be a straight line

if the correct g(a) is employed and the approximation of
2RT/Ea \\ 1 is satisfied. Then, the Ea and A values can be
calculated from the slope and intercept of the plot,
respectively, by selecting the most appropriate kinetic
model function in view of the linearity of the plot.
Accordingly, the Coats and Redfern method is classified as
a single-run method.
Ozawa employed the following p(x) function of empirical linear interpolation proposed by Doyle [26]
log p x a bx

where a and b are constants determined by linear

interpolation within the practical range of x, for example
a = -2.315 and b = -0.4567 for 20 B x B 60. Therefore,
the integral kinetic equation derived by Ozawa is [27]



AEa
bEa
log b log
a
gaR
RT

10

According to Eq. (10), the data point at fixed a of a

series of nonisothermal rate data at different b form a
straight line when plotting logb against the reciprocal
temperature. This methodology is equivalent to that
proposed by Kujirai and Akahira for the kinetic analysis
of the isothermal mass-loss data using Eq. (2). This
procedure requires a series of the kinetic rate data at
different temperatures with the Kujirai and Akahira method
or at different b with the Ozawa method, so that it is
classified as a multiple-run method. Because the
relationships in Eqs. (2) and (10) are realized for fixed a,
the kinetic plots are sometimes called isoconversional
plots. On the basis of this approach, Ea values are evaluated
at different a. By comparing Eqs. (2) and (10), we note that
Ozawa elegantly solved the problem of the extension of the
kinetic equation to linear nonisothermal conditions just by
replacing the reaction time in Eq. (2) with the heating rate,
the most characteristic parameter in thermal analysis.
Flynn and Wall derived an equation similar to Eq. (10) and
reported it 1 year after Ozawa did [28].
In Fig. 3, the above two methods of kinetic calculations,
i.e., Coats and Redfern method and Ozawa method, are
shown using the kinetic rate data for the thermal decomposition of SHC at different b, Fig. 3a. The Coats and
Redfern plot is drawn for the kinetic rate data at fixed b,
Fig. 3b. The Ozawa plot is drawn among the kinetic rate
data at different b for the data points at fixed a, Fig. 3c.
Probably because of the less laborious thermoanalytical
measurements and quick evaluation of all the kinetic
parameters, the single-run method of Coats and Redfern
was widely used. However, the problems inherent in the
methodology of single-step kinetic calculations became
apparent in practical applications. The values of the

123

Arrhenius parameters sometimes change systematically

depending on b. The Coats and Redfern plots using several
different kinetic model functions indicate comparable
straight lines; therefore, the selection of the most appropriate kinetic model function is not an easy task. When an
inappropriate kinetic model function is selected, the calculated Arrhenius parameters deviate from the true values
[29], indicating the mutual correlation between the values
of Ea and A [3033]. In reality, the single-step kinetic
approach does not provide a rigorous check system to
evaluate the reliability of the kinetic results.
The Ea values at different a are evaluated from Ozawa
plots. Figure 3d shows an example of the a-dependence of
Ea, where Ea is practically constant during the course of the
reaction. In view of the fundamental kinetic equation,
Eq. (4), the constant Ea during course of reaction is one of
the prerequisites. In practice, we sometimes encounter
a-dependent variation of Ea. The variation should be interpreted on the basis of two different viewpoints. One is the
reliability of the kinetic rate data in the calculations based on
Eqs. (2) and (10). Because the isoconversional relationship is
derived according to the assumption that the kinetic process
is controlled by a single rate-limiting step and can only vary
depending on temperature with Arrhenius-type dependence,
any possible factors that influence the ideal isoconversional
relationship should be eliminated when measuring the
kinetic rate data by thermal analysis. The sample and measurement conditions that satisfy the requirements are often
very limited and vary depending on the characteristics of the
kinetic process under investigation. When the kinetic process is complex, as in the cases of multistep reactions and
accompanying variations in which the physical conditions of
the reactants vary as reaction advances, the variation of Ea is
superficial and results from the application of inappropriate
kinetic equations. For such processes, the refinement of the
kinetic model expressed by the kinetic equation is required.
In a strict sense, the calculated values of Ea indicating the adependent variation cannot be the apparent activation energy
defined in Eq. (4). Earlier, Ozawa pointed out [27] and
repeatedly stated [34] that isoconversional methods have
such a check system for the reliability of the kinetic rate data
and validity of the applied kinetic equation.

Generalized time and experimental master plot

Although the isoconversional relationship in integral form
formalized by Ozawa has been widely applied to the
kinetic analysis of the thermoanalytical data for a variety of
chemical and/or physical processes, the so-called Ozawa
plot is only a part of his kinetic analysis theory. On the
basis of the constant Ea during the course of a reaction, he
derived another important kinetic equation in integral form

(a)

1531

(a)

0.8

/K min1
1
2
3

0.6
0.4

/1011 min

Fractional reaction

1.0

0.2

1.5

1.5

1.2

1.2

0.9

0.9

0.6

0.6

0.3

0.3

0.0
380

390

400

420

410

440

430

450

460

(d /d )/1011 min1

Ozawas kinetic method for analyzing thermoanalytical curves

T/K
0.0

12

(b)

0.0
0.0

0.2

0.4

In{[g()/T 2]/K2}

g( ) = 1(1)

1.0

Fractional reaction

= 2 K min1
13

0.8

0.6

1/2

(b)

0.05 0.95

0.6
0.5

14

(d /d )

0.4

15

0.3
0.2

16
2.4

2.3

2.5

0.1

2.6

T 1/kK1
0.0
0.0

0.6

0.8

1.0

1.0

log [ /(K

Fig. 4 Experimental master plots for the thermal decomposition of

sodium hydrogencarbonate: a integral and differential forms and
b multiplied form

0.8
0.6

0.4
0.2

0.8
0.6

0.0

0.2

T 2.
1
/k
K

2.5
2.6

0.0

on

ti
ac

0.4

2.3

(d)

0.4

Fractional reaction

min1 )]

(c)

0.2

1.0

by employing the time integral of the exponential term in

the Arrhenius equation as [27]

l re

na

o
cti

Fr

g a

Za
0

125

da
A
f a

Zt



Ea
exp 
dt Ah
RT

11

Ea/(kJ/mol)

with
100

Zt



Ea
exp 
dt;
RT

12

75

50
0.0

0.2

0.4

0.6

0.8

1.0

Fractional reaction

Fig. 3 Kinetic analysis of nonisothermal TG curves of the thermal

decomposition of sodium hydrogencarbonate: a TG curves at
different b, b typical Coats and Redfern plot, c Ozawa plots at
different a, and d the a-dependence of the Ea value evaluated from the
slope of the Ozawa plots

where h was termed as the reduced time, and the

terminology was changed later to generalized time [35]
to avoid the confusion with the conventional reduced time,
t/t0.5, used in the isothermal kinetic analysis. h is
interpreted as the hypothetical reaction time calculated by
extrapolating the reaction time at real temperatures to
infinite temperature according to the Arrhenius equation. It
is noted that the time integral of the Arrhenius exponential
term already appeared in the definition of Te by Akahira

123

1532

N. Koga

[17], Eq. (5). The values of h at different a are calculated

using Eqs. (12) and (13) for the kinetic rate data under
isothermal and linearly changing temperature conditions,
respectively [27, 35].


Ea
h t exp 
13
RT
Ea
h
bR

Z1

expx
Ea
p x
dx
x2
bR

14

Equation (11) is similar to the conventional kinetic

equation at constant temperature: g(a) = kt. Once more,
Ozawa succeeded in obtaining a kinetic expression for
nonisothermal data by replacing t and k at a constant
temperature with h and A, respectively.
Similarly, Ozawa also derived the corresponding differential equation. Time differentiation of Eq. (12) gives
[36, 37]


dh
Ea
exp 
15
dt
RT
Combining Eqs. (15) and (4), we obtain
 
da da
Ea
exp
Af a
dh dt
RT

16

Equation (16) is also analogous to the differential kinetic

equation at a constant temperature: da/dt = kf(a), formalized by replacing t and k with h and A, respectively.
In Fig. 4, the kinetic relationships expressed by Eqs. (11)
and (16) are shown for the thermal decomposition of SHC.
Figure 4a shows the plots of h and da/dh against a.
Applying Eqs. (11) and (16) to the kinetic rate data calculated from the measured rate data by extrapolating to infinite temperature, the A value is determined and the most
appropriate kinetic model function is selected, as is the case
of the isothermal kinetic analysis for determining k by
selecting g(a) or f(a). At the same time, by combining the
kinetic data extrapolated to infinite temperature with the Ea
value assumed to calculate the data, the kinetic behavior at
any temperature conditions can be predicted. In addition,
the most appropriate kinetic model function is selected
graphically by reducing h and da/dh to h/h0.5 and (da/dh)/
(da/dh)0.5, respectively, and mathematically by applying the
nonlinear regression analysis. Accordingly, the calculated
rate data in Fig. 4a can be called the experimental master
plot. Ozawa established the multistep kinetic analysis for
the kinetic rate data recorded by thermal analysis under
nonisothermal conditions by consecutively using the Ozawa
plot to the isoconversional relationship and the experimental master plots formalized using h to the isothermal
relationship. In addition to the single-step chemical process,
Ozawa indicated the applicability of the theoretical basis of

123

the above kinetic analysis to the physical process controlled

by diffusion [38].
Later, Malek et al. derived an alternative equation
[3941], that is the product of Eqs. (11) and (16).
da
h f aga
dh

17

In this equation, the Arrhenius pre-exponential factor is

canceled; therefore, the experimental master plot is directly
correlated to the kinetic model function. Figure 4b shows the
plot of (da/dh)h against a obtained by multiplying the
experimental master plots in Fig. 4a. Furthermore, Malek
investigated the detailed conditions of a at the maximum of the
plots, f(a) and f(a)g(a) against a, for the different types of
kinetic model functions for solid-state reactions [41]. It was
suggested that the a values of the peak maximum of these plots
are characteristic of the respective kinetic model functions and
the most appropriate kinetic model function can be selected by
investigating the peak positions of the corresponding
experimental master plots, da/dh and (da/dh)h against a, of
the process under investigation. This diagnostic tool also
distinguishes the process that is not described by the
conventional kinetic model functions because of the
complex geometry of sample particles and the movement of
reaction interfaces and also those distributions [42, 43]. For
describing the rate behavior of such processes, the application
of empirical kinetic model functions with non-integral or
fractional dimensions [4446] and the more powerful Sestak
Berggren model [47] with two kinetic exponents has also been
proposed [48]. The method has been successfully applied
to the crystallization [4951] and thermal decomposition
[45, 52] of inorganic materials. The experimental master plots
based on Eqs. (16) and (17) are sometimes called Maleks y(a)
and z(a) master plots, respectively.
Equations (11) and (17) have found limited use to the
kinetic rate data under isothermal and linear nonisothermal
conditions, because of the temperature integral of the
exponential term under nonisothermal conditions. This
limitation was eliminated by the introduction of computerbased data acquisition systems in thermal analysis. Because
h in Eq. (12) is defined as the time integral of the exponential
term, the h value at different a is calculated under any temperature conditions by numerical integration; therefore, all
the three experimental mater plots are universally applicable
to the kinetic rate data under any temperature conditions, if
the constant Ea value has been previously determined.

Isoconversional method in differential form and further

In 1964, Friedman [53] proposed the differential isoconversional method. The analytical form of the method can
be derived by taking the logarithm of the fundamental

Ozawas kinetic method for analyzing thermoanalytical curves

1 ]

In[(d /dt)/s

Although the equation is applicable to the kinetic rate

data under any temperature changes as mentioned by
Akahira, the differential method did not find wide use
because of the difficulty in reading the kinetic rate data that
were recorded on paper at that time. This problem was
solved in the 1980s by the development of computer-based
data acquisition systems and the kinetic analysis using the
Friedman plot, ln(da/dt) against T-1 at fixed a, was applied
to the practical study [54]. Figure 5 demonstrates the
kinetic analysis by Friedman plots for the thermal
decomposition of SHC. As in the case of the Ozawa plot,
for a fixed a, the data points of the series of the kinetic rate
data recorded at different b form a line when plotting ln
(da/dt) against T-1, Fig. 5a. For the ideal single-step
reaction, the slopes of the Friedman plots at different a are
invariant during the course of the reaction and the Ea values
evaluated from the respective Friedman plots at different a
indicate a constant value independent of a, Fig. 5b. It is
also noted that the intercept of the Friedman plot is the
logarithm of da/dh; therefore, the experimental master plot
of da/dh against a is directly obtained from the change in
the intercept of the Friedman plots at different a, see Eqs.
(16) and (18).
In 1986, Ozawa pointed out [37] that the Friedman plot
has wider applicability than the Ozawa plot because no
approximation of the exponential temperature integral is
required and there is no restriction to the temperature
profile of the kinetic rate data. Using the Friedman method,
the two-step kinetic approach to the processes, i.e., the
kinetic characterization of the isoconversional and subsequent isothermal relationship, is universally applied to
the kinetic rate data under isothermal and nonisothermal
conditions. This idea can be extended to the kinetic analysis of the data under nonlinear nonisothermal conditions
[55, 56]. The application of the Friedman method to such
nonlinear nonisothermal data was demonstrated when the
programed linear heating was distorted by significant selfcooling during the course of the reaction [52] and for the
data recorded by SCTA [57]. As described above, the
subsequent kinetic analysis of the isothermal relationship
using the experimental master plots based on h was performed by calculating h from Eq. (12).
Accordingly, two-step kinetic analysis using the Friedman method and subsequent analysis with the experimental
master plots can be universally applied to the kinetic rate
data recorded under isothermal, linear nonisothermal, and
controlled transformation rate mode conditions, as it was
demonstrated for the thermal decomposition of indium(III)

(a) 6
7
8
1.0

9
0.8
2.1
2.2

0.6
2.3

T
2.4
1
/k
2.5
K
1

(b)
Ea/(kJ/mol)

kinetic equation in differential form derived by Akahira in

1928 [17].
 
da
Ea
ln
18
lnAf a 
dt
RT

1533

c
ea

lr

na

0.2
2.6 0.0

tio

0.4

o
cti

Fr

125

100

75

50
0.0

0.2

0.4

0.6

0.8

1.0

Fractional reaction

Fig. 5 Friedman plots for the thermal decomposition of sodium

hydrogencarbonate (a) and the a-dependence of the Ea value
evaluated from the slope of the Friedman plots (b)

hydroxide [58], monohydrocalcite [59], sodium hydrogencarbonate [14], and so on. The systematic kinetic
approach to a process under different heating conditions
results in covering a wide region of kinetic information in
the three-dimensional coordinates of kinetic analysis, ln
(da/dt) vs. T-1 vs. a, as shown in Fig. 6 for the thermal
decomposition of SHC. The universal kinetic analysis of
data in a wide temperature region enabled by the different
temperature change modes results in reliable regression
lines of the isoconversional plots when the process is the
ideal single-step reaction and/or indicates the range of
appropriate experimental conditions for the measurement
of the kinetic rate data.
In general, the differential kinetic rate data are more
sensitive to noise and indicate lower S/N ratio in comparison with the integral rate data. The situation does not
affect the typical kinetic analysis of the differential kinetic
rate data recorded by modern thermoanalytical instruments; however, it should be considered when processes in
which physical quantities change very little during the
course of the reaction, e.g., a mass-change of several
10 lg. In such cases, kinetic analysis by an integral method
is preferred to obtain reliable results. The integral isoconversional method was only applied to the kinetic rate data

123

1534

N. Koga

nonisothermal
isothermal
CRTA

In[(d /dt )/

min1]

3
4
5
6
2.2

1.0
2.3

0.8
0.6

2.4

T
1
/k
K

0.2
2.6

0.0

ctio

0.4

2.5

a
l re

ion
act

Fr

Fig. 6 Kinetic rate data for the thermal decomposition of sodium

hydrogencarbonate recorded under isothermal, linear nonisothermal,
and controlled transformation rate mode conditions

recorded under isothermal and linearly increasing temperatures using the above formalism, but the integral method
applicable to the data under any temperature profiles can be
formalized using Eq. (12). Vyazovkin proposed an integral
isoconversional method universally applicable to the data
under any temperature profile using the nonlinear least
squares analysis [60], where the Ea value at a fixed a can be
optimized by minimizing the following function.
n X
n
X
hi
;
19
UEa
h
i1 j6i j
where the subscripts i and j represent the ordinal numbers
of two series of data points with different temperature
profiles. Accordingly, the isoconversional relationship can
be estimated from the kinetic rate data under any temperature profiles using either the differential method of
Friedman or the integral method of Vyazovkin.

Complex reaction processes

Influence of additional factors
We have to remember that the above kinetic relationships
formalized by Ozawa are applicable only to ideal kinetic
processes that satisfy the single-step approximation and to
the kinetic rate data that are not influenced by factors other
than temperature and conversion. In practice, however, we
sometimes encounter the a-dependent variation of Ea as a
result of the isoconversional analysis. It is easily understood that many heterogeneous processes that are studied
by thermal analysis and subsequently subjected to kinetic
analysis may not be always described by the fundamental

123

kinetic equation, Eq. (4), which is empirically derived and

theoretically validated by an extension of the kinetic theory
for ideal homogeneous reactions.
Even if the process is approximated as a single-step
reaction regulated by a single rate-limiting step, the overall
rate behavior may be influenced by many factors other than
temperature and conversion. Therefore, the real process is
better described by the following equation [42, 6163].


da
Ea
A exp 
f aaa; t; T; P; b; . . .;
20
dt
RT
where a(a,t,T,P,b,) is a function accommodating such
parameters in the kinetic equation. An example of
successful formalization of the accommodation function
is seen in reversible solidgas reactions such as the thermal
decomposition of calcium carbonate, where the influence
of the partial pressure of the evolved gas, P, should be
taken into account by introducing the following
accommodation function [6466].
aP; P0 T 1 

P
;
P0 T

21

where P0 is the equilibrium pressure of the evolved gas and

depends on temperature. Another example is crystal growth
from pre-existing nuclei. When the temperature range for
nucleation is separated from that of growth and the
nucleation rate is of the order of the temperature
scanning rate, the number of pre-existing nuclei for
crystal growth changes depending on b in nonisothermal
runs. For applying the isoconversional method to such
processes, the change in the number of pre-existing nuclei
has to be taken into account. This problem was first pointed
out by Matsushita and Sakka in the application of the
Kissinger method to glass crystallization [67], and later,
was rigorously formalized in the integral isoconversional
method by Matsushita et al. [68] and in the differential
isoconversional method by Ozawa [69]. Furthermore, Koga
and Sestak [70, 71] suggested that the scanning rate during
glass formation has to be considered similarly and the
change in the number of pre-existing nuclei has to be
considered in constructing the experimental master plots
for the growth process. The accommodation function for
such processes can be expressed by [72]
ab; m



bc bh 1=m
;
bc bh

22

where bc, bh, and m are the cooling rate during the glass
formation process, heating rate of the as-produced glass for
crystallization, and the dimension of crystal growth,
respectively.
Even in the case in which an accommodation function
need to be considered in the fundamental kinetic equation,

Ozawas kinetic method for analyzing thermoanalytical curves

the isoconversional plot can be directly applied when the

contribution from the accommodation function to the
overall reaction rate remains constant among the series of
the kinetic rate data under different temperature conditions.
The thermal decomposition of solids with significant particle size distribution is a typical example [43, 73, 74]. The
kinetic model function f(a) for contracting geometry-type
reactions is usually formalized for the reaction of a single
particle; therefore, the sample particles must be uniformly
sized and simultaneously reacted to meet the ideal conditions based on the fundamental kinetic equation. The
thermal decomposition of solids with significant particle
size distribution can be considered as parallel reactions of
different size reactant particles, where the fractional reaction of the respective reacting particles is distributed during
the course of the overall reaction. Even in this case, the
slopes of the isoconversional plots at different overall
fractional reaction a and the Ea values at different a are
constant, because the distribution function does not change
among the series of the kinetic rate data under different
temperature conditions at a fixed overall a. However, the
accommodation function in relation to the particle size
distribution should be exactly considered in the experimental master plots and in fitting the kinetic model function based on the reaction of a single particle.
Similarly, the ideal isoconversional relationship is
established in several other cases when the sample and
reaction conditions for measuring the kinetic rate data were
regulated to maintain the value of the accommodation
function constant among the series of the kinetic rate data.
For example, the accommodation functions in Eqs. (21)
and (22) can be set to unity or a constant when the kinetic
rate data are measured under high vacuum and after
annealing to saturate the pre-existing nuclei, respectively.
The successful control of the contribution from the
accommodation function is a criterion in thermal analysis
for appropriate sample and measuring conditions to obtain
reliable Ea values. However, in many cases, the control of
the value of accommodation function is not easy and the
value changes with the applied measuring conditions for
recording the series of the kinetic rate data, resulting in
variations of the calculated Ea value with a. In many
practical kinetic studies, the sample and measuring conditions required to study are far from the ideal conditions for
the kinetic study. In view of the fundamental kinetic
equation, the calculated Ea values and a-dependent variation are superficial because of the application of the over
simplified kinetic model assumed when formalizing the
equation. The rigorous solution is a more detailed kinetic
modeling of the process, but the formalism of the appropriate accommodation function and quantitative measurement of the parameters in the accommodation function are
not always possible. Then, the calculated Ea values and

1535

a-dependent variation are taken as empirical kinetic results

that require correlation analysis. The situation is the same
or more complex for the kinetic approach to the isothermal
relationship, i.e., the time- and/or conversion-dependent
change in the reaction rate, because the reactant solids are
not always well-shaped and uniformly sized particles and
the reaction geometry sometimes changes as the reaction
advances [75]. The kinetic analysis is completed when the
isoconversional and isothermal relationships are satisfactorily described with meaningful physico-chemical and/or
physico-geometrical explanations. In this sense, the kinetic
analysis of solid-state reactions by thermal analysis is
challenging even if the reaction process is approximately a
single-step reaction.
Empirical kinetic approach to the complex reactions
The complexity of the kinetic analysis for overlapping
multistep reactions is easily understood. The rate behavior
of partially overlapping independent kinetic processes is
expressed as [7680]


n
da X
Ea;i

ci Ai exp 
f i ai
dt
RT
i1

23

with
n
X

ci 1

and

i1

n
X

c i ai a

24

i1

where the subscript i indicates the i-th reaction and ci is the

fractional contribution of the i-th reaction to the overall
reaction. In practical processes, the accommodation function
in Eq. (20) have to be considered for the respective component reactions. Further complications are caused by the
interactions among the component processes in concurrent
and consecutive reaction processes. It is also suggested that
the heterogeneous nature of the reaction processes makes the
rigorous kinetic approach more difficult than the kinetic
analysis based on the n-th order treatment in homogeneous
reactions [81]. Thus, the kinetic approach to such complex
multistep solid-state reactions is also part of the history of the
kinetic analysis of thermoanaytical curves.
The overlapping nucleation and growth processes are
considered as an example. The nucleation and growth
processes in the solid state are different kinetic processes
where nucleation is a necessary condition for growth of
nuclei. Under isothermal conditions, the random nucleation
and subsequent growth process is described by the wellknown JohnsonMehl [82]Avrami [8385] equation.
 ln1  a Ztn ;

25

where Z and n, respectively, are the rate constant and the

so-called Avrami exponent related to the nucleation rate

123

1536

N. Koga

law, dimension of nucleus growth, and the rate law of

linear growth. However, the extension of the kinetic
process to nonisothermal conditions have to be carried
out by considering the temperature dependence of the rate
constants j(T) and m(T) for nucleation and growth,
respectively, which are expressed as
jT j0 hn T

26

mT m0 hg T

27

where the subscripts n and g indicate the processes of

nucleation and growth, respectively. h(T) is a temperaturedependent function usually expressed by the Arrhenius
exponential term and the subscript 0 indicates the preexponential term. Ozawa derived the following kinetic
equation for nucleation and growth process under
nonisothermal conditions [86].
Z

m
 ln1  a gj0 mm
hn s hg t  hg s ds;
28
0
where g, m, and t are the geometric factor, dimension of
nucleus growth, and the nucleation time, respectively.
Although Eq. (28) is difficult to directly apply to thermoanalytical curves, the following equation can be derived by
assuming a constant heating or cooling rate b [86].

conditions, many other types of practical kinetic processes

require further rigorous physico-chemical modeling and
mathematical formalization for the ideal kinetic solution
[93, 94]. It is apparent that such ideal kinetic approach is
not easy in many cases because the processes are complex.
As a possible solution, various empirical kinetic parameters
and functions have been introduced into the analytical form
of the kinetic equation for better describing the overall rate
behavior [95]. In view of the isoconversional relationship,
the application of non-Arrhenius-type temperature dependence is a possible extension to the empirical kinetic
description [96]. The change in the Ea value with a is also
accepted in redefining the value as a variable [97100].
Then the variation of Ea is taken as the empirical result
caused by a variation of the kinetic behavior in a manner of
complex reaction scheme. In this line, the a-dependant
change in variable Ea has been a subject to the analysis for
modeling the complex reaction process [101, 102]. However, it must be suggested that the a-dependent change in
Ea also results from the deviation of the measured kinetic
rate data from the ideal conditions [103]. For the isothermal relationship, the physico-geometrical kinetic model is
extended to empirical kinetic models with non-integral

29

where v(T) is the temperature integral term obtained by

assuming b as a constant. It should be noted that the
Avrami exponent appears as an exponent of b. Taking the
logarithm of Eq. (29), we obtain [86]
30

According to Eq. (30), by reading data points at a fixed

T from a series of kinetic rate data at different b, the plot of
log[-ln(1 - a)] versus logb is a straight line as shown in
Fig. 7 for the crystallization of AMAG at different b
recorded by DSC. The slope of the plot corresponds to the
Avrami exponent n and the constancy of the n value at
different temperatures can be confirmed. The above theory
enables us to determine the Avrami exponent from a series
of nonisothermal kinetic rate data at different b, but the
complete solution for the kinetics of the random nucleation
and subsequent growth under nonisothermal conditions has
not been achieved yet [87, 88]. Contributions of the true
activation energies for nucleation and growth, En and Eg, to
the superficial value of apparent activation energy for the
overall crystallization process obtained by applying a
simple kinetic equation for the single-step reaction has
been analyzed theoretically [8992].
As well as we have seen for random nucleation
and subsequent growth processes under nonisothermal

123

1.0
0.8
0.6

/K min1

0.4

10

0.2
0.0
500

510

520

530

T/K

(b)

0.5

0.0

log[In(1 )]

log ln1  a log vT  n log b

Fract. crystallization

(a)
vT
 ln1  a n ;
b

0.5

T/K
1.0

510
515

1.5

520

2.0
0.0

0.2

0.4

0.6

0.8

1.0

log [ /(K min1)]

Fig. 7 Kinetic analysis for the crystallization of magnesium acetate

anhydrate glass: a the kinetic rate data and b plot of log[- ln(1 - a)]
against logb

Ozawas kinetic method for analyzing thermoanalytical curves

and/or fractal dimensions of reaction interface advancement [4446]. The empirical kinetic model function with
several kinetic exponents is also a powerful tool for the
better mathematical description of the isothermal relationship [104, 105], e.g., the well-known SestakBerggren
model [47]: f(a) = am(1 - a)n[-ln(1 - a)]p. For multistep reactions, further additional parameters are introduced
for deconvoluting the kinetic rate data to each component
process [7679]. In empirical kinetic analysis with many
variables, good curve fitting is obtained by mathematical
optimization procedures using the non-linear least squares
analysis. The optimized empirical kinetic parameters are
applied to predict the overall kinetic behavior of the process within the limitations of the performed kinetic analysis
and further the lifetime of the material. For the purpose of
empirical curve fitting, we may ultimately arrive at
sophisticated fitting of thermoanalytical curves using
mathematical models that are not necessarily connected to
the mechanism and kinetics of the process [106, 107].
However, apart from the practical usefulness of the
empirical kinetic parameters, understanding the rate behavior based on the reaction mechanism is an essential purpose
of the kinetic analysis of chemical reactions. By increasing
the number of parameters and extending the restriction of
each parameter in the empirical kinetic approach, it becomes
difficult to exactly interpret the physico-chemical meaning
of each empirical parameter, because of the extended
meaning and mutual interaction of the respective empirical
parameters. Thus, it is always required to evaluate the
physico-chemical meaning of the empirical parameters with
reference to the original meaning in the fundamental kinetic
models and equations. The theory of nonisothermal kinetics
of solid-state reactions established by Ozawa plays an
important role as part of the theoretical fundamentals even in
advanced kinetic approaches to complex reactions.

Prospective for kinetic analysis by thermal analysis

As revealed in this review, the kinetic analysis of the solidstate reactions by thermal analysis has progressed by
complementary developments and/or advancements of
thermoanalytical techniques, methodology of kinetic calculation, and kinetic theory of heterogeneous process [13].
The advancements of thermal analysis and computation
technique in the last 50 years were significant. For example, the sample size for TG could be reduced from several
hundred mg to several mg or less. A large flexibility of the
temperature variation profile is accomplished as one of the
characteristics of modern thermal analysis [108] as is seen
for SCTA [12] and modulated-temperature measurements.
A sophisticated process control with a small sample size
achieved in SCTA largely improved the reliability of the

1537

measured kinetic rate data for thermal decomposition of

solids [57, 109113] as was expected at first developed
[114, 115]. Application of temperature modulation to DSC
[116, 117] revealed novel kinetic features of the chemical
and physical processes in polymer [118122].
The application of modulated-temperature TG to the
kinetic study of thermal decomposition processes has also
been proposed [123]. Ozawa found a characteristic of the
kinetic rate data recorded under modulated-temperature
conditions as suitable for the kinetic analysis of a certain
type of process [124]. The kinetic rate data cover the isoconversional relationship at different a and the isothermal
relationship by a single thermoanalytical run, which enable
the multi-step kinetic calculation in the single-run method.
He also demonstrated a novel application of modulatedtemperature TG to relaxation phenomena observed in
solidgas system as exemplified by the oxygen non-stoichiometry of YBa2Cu3O7-d superconductor [125]. The
suggestion on the usefulness of the modulated-temperature
TG is one of the messages left by Ozawa [126].
We learn much from Ozawa, who spent his life working
on kinetic analysis by thermal analysis. In addition to the
well-known methodology of kinetic analysis, i.e., Ozawa
method, he largely contributed to the foundation of kinetic
theory in heterogeneous system, especially for nucleation
and growth process, and to the developments of thermoanalytical techniques such as heat-flux DSC [8], modulated-temperature DSC [127130], and evolved gas
analysis [131]. On the basis of such fundamental researches, he applied thermal analysis to various practical processes in polymer [132134], oxide superconductor
[135139], latent heat storage materials [140], and so on.
His works, covering a wide field of thermal analysis, tell us
that the complementary advancements of thermoanalytical
technique, methodology of kinetic calculation, and kinetic
theory of the process are required for further progress of
the kinetic analysis by thermal analysis, which will be
achieved by close corporation of the specialists in the
respective subjects.

Conclusions
Measurements of the kinetic rate data in chemical processes, particularly in the solid state, were one of the
potential applications of thermal analysis since it was first
developed. With the advancement of thermoanalytical
techniques, kinetic analysis using thermoanalytical data has
increased their practical usefulness. In the historical process, the traditional kinetic analysis of processes under
isothermal conditions was extended to nonisothermal
condition. On the basis of the earlier work of Kujirai and
Akahira that used TG, Ozawa established the theory of

123

1538

nonisothermal kinetic analysis as a multistep procedure via

consecutive steps to the isoconversional relationship by
isoconversional plots and to the isothermal relationship by
experimental master plots drawn by formalizing the generalized time h. Ozawas kinetic method is based on rigorous theoretical considerations; therefore, further
extension to the kinetic theory under any temperature
profiles was enabled. Now, we have a robust theory of
kinetic analysis for ideal single-step kinetic process in solid
state under any temperature conditions.
Kinetic theory should be further extended to complex
reaction processes influenced by factors other than those
considered in the fundamental kinetic equation and consisting of multi-step reactions. In practice, however, the
rigorous theoretical modeling of complex processes is not
necessarily successful, and various empirical functions and
parameters are introduced to the kinetic equation for better
fitting of the experimental rate data. The determined
empirical kinetic parameters are useful to predict the overall
rate behavior under comparable conditions to the measured
rate data. However, the physico-chemical meaning of each
kinetic parameter becomes difficult to interpret. To keep the
meaning of such empirical parameters as kinetic parameters,
it is always required to evaluate the meaning with reference
to the fundamental kinetic theory established by Ozawa.
Although the kinetic analysis of the complex solid-state
reactions is largely challenging, it is apparent from the history of the progress of thermoanalytical kinetics that further
progress will be accomplished by close corporation of the
specialists in thermoanalytical technique, methodology of
kinetic calculation, and kinetic theory of the solid-state
reactions, by which we would like to contribute to the
materials science as an important tool to characterize and
control the reaction processes.
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