Chemical Engineering Science 63 (2008) 567 – 575

www.elsevier.com/locate/ces

The kinetic study of temperature-programmed reduction of nickel oxide in

hydrogen atmosphere
B. Janković ∗ , B. AdnaYević, S. Mentus
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, P.O. Box 137, 11001 Belgrade, Serbia and Montenegro

Received 19 January 2007; received in revised form 9 July 2007; accepted 20 September 2007
Available online 1 October 2007

Abstract
The powder samples of nickel oxide were synthesized by sol–gel procedure. The non-isothermal reduction of nickel oxide using hydro-
gen was investigated by temperature-programmed reduction (TPR) at four different heating rates (2.5, 5, 10 and 20 ◦ C min−1 ). Reaction
kinetics parameters (Ea , ln A) were determined using a few methods: Stationary point (SP), Kissinger, Friedman, Flynn–Wall–Ozawa and
Kissinger–Akahira–Sunose methods. The Málek’s kinetic procedure was used for the determination of the most suitable kinetic model and
calculation of a complete set of kinetic parameters. The kinetic model of the investigated reduction process was determined, and this model
corresponds to the empirical two-parameter Šesták–Berggren equation which gives a more quantitative description. The kinetic triplet obtained
for the investigated process is Ea = 90.8 kJ mol−1 ; ln A = 19.50 (A expressed in min−1 ) and f () = 0.63 (1 − )1.39 . The reliability of kinetics
parameters calculated from TPR data is tested by comparing calculated and experimental non-isothermal data. Comparing both experimental
and calculated rate curves at constant heating rate assessed the adequate consistency of the kinetic triplet. In agreement with the obtained
results, the mechanism of nickel oxide reduction by hydrogen was considered.
䉷 2007 Elsevier Ltd. All rights reserved.

Keywords: Nickel oxide; Reduction; Kinetics; Activation energy; Šesták–Berggren model

1. Introduction nitrate at 400 ◦ C. They approached to the some very important

conclusions: (a) reduction occurs at the interface between NiO
Metal oxides are widely used in many technological applica- and previously reduced Ni; (b) there is an “autocatalytic” effect;
tions, such as coating, catalysis, electrochemistry, optical fibers, (c) there is an induction (i.e., nucleation) period that depends
sensors, etc. (Heinrich and Cox, 1994; Pacchioni, 2000). For on the nature of the sample and temperature; and (d) added
the preparation of active oxide catalysts, the partial reduction water reduces the reduction rate and increases the induction
of nickel oxide under hydrogen at elevated temperatures is the period. Koga and Harrison (1984) reviewed general reactions
effective method for this preparation (Furstenau et al., 1985; between solids and hydrogen and represented the induction
Delmon, 1997; Lescop et al., 2004). In former studies, two process as generation of nickel atoms on the outer surface
different kinetic models have been proposed for the reduction of NiO grains. Following nucleation, Ni clusters grow two-
of metal oxides: (1) nucleation model (Furstenau et al., 1985; dimensionally across the surface until they overlap, at which
Scholz and Langell, 1985) and (2) interface-controlled model point hydrogen rapidly dissociates from Ni and the interface
(Delmon, 1969). The first reported systematic measurements of proceeds quickly into the grain (Koga and Harrison, 1984).
bulk NiO reduction was by Benton and Emmett (1924). These Bandrowski et al. (1962) measured water produced during the
authors measured water formation as an indication of the ex- reduction to generate sigmoidal conversion curves which they
tent of reaction for a sample of NiO made by heating nickel explained with a two-step kinetic model. The first step, reaction
between NiO and hydrogen atoms adsorbed on NiO, predom-
∗ Corresponding author. Tel./fax: +381 11 2187 133. inates in the early part of the reduction and is proportional
E-mail address: [email protected] (B. Janković). to the square root of the hydrogen pressure. The second step
0009-2509/$ - see front matter 䉷 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.09.043
568 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575

is the reaction at the metal–oxide interface between NiO and methods. In addition, the Málek’s (1992) criteria were used to
hydrogen atoms adsorbed on the previously reduced NiO. The confirm that the single-step model can be applied to fit the ex-
above models emphasized the chemical mechanism and kinet- perimental data in the case of NiO reduction. Also, the most
ics of the reduction process, but there was a little uniformity in accurate kinetic triplet (the conversion model, f () and Arrhe-
the physical properties of NiO grains and pellets used. Never- nius parameters) of the investigated process was established,
theless, it was suspected that morphological factors were just as involving the empirical two-parameter Šesták–Berggren (SB)
important as topological properties in determining the course of (Šesták and Berggren, 1971) reaction model.
the reduction. Generally, some authors (Richardson et al., 1994,
2003; Tikekar et al., 2003; Waldbillig et al., 2005) believed
2. Experimental procedure
that NiO reduction is the first-order and the rate has a linear
dependence with the partial pressure of hydrogen. Richardson
2.1. Materials and methods
et al. (1994) conducted a series of experiments using isothermal
H2 consumption and magnetization measurements to determine
The NiO samples were obtained by gel-combustion method
the Ni–O bond rupture (NiO conversion) and the growth of
described elsewhere (Mentus et al., 2005). A green-colored
nucleated Ni atoms, respectively. They found the growth pro-
transparent gel was obtained by drying an aqueous solution of
cess lagged NiO conversion by a time interval that increased
nickel nitrate hexahydrate (Fluka, 99.5%) and citric acid (Fluka,
with decreasing temperature, lower gas flow rates and the pres-
99.5%) dissolved in a mole ratio 1.8:1. This gel was made to
ence of H2 O added to the reducing gas. Rodriguez et al. (2002)
undergo a self-ignition by heating in air up to 300 ◦ C, and an
showed that in experiments with an NiO (1 0 0) crystal and
additional heating of up to 500 ◦ C produced a very fine nickel
NiO powders, oxide reduction is observed at atmospheric pres-
oxide powders. The mean size of nickel oxide particles deter-
sures and elevated temperatures (250–350 ◦ C), but only after
mined from XRD data is dm = 30 nm, and this value overlaps
an induction period. These authors showed that the presence
very well with the data published by Wu et al. (2007).
of O vacancies leads to an increase in the adsorption energy of
H2 and substantially lowers the energy barrier associated with
the cleavage of the H–H bond. Richardson et al. (2003) stud- 2.2. Temperature-programmed measurements
ied the hydrogen reduction of porous bulk NiO particles with
an in situ hot-stage X-ray diffraction (XRD) in the tempera- The experiments were carried out in a TA SDT 2960 device,
ture range 175–300 ◦ C. The results obtained by these authors capable of simultaneous TGA-DTA analysis in the temperature
indicated that reduction in the absence of water added to the range from 25 to 1500 ◦ C. The nickel oxide samples were re-
reducing gas followed several steps: (1) an induction period as- duced directly within the thermobalance, in korund pans, under
sociated with the initial reduction of NiO and the appearance (99.9995 vol%) hydrogen flowing at a rate of 100 mL min−1 ,
of Ni metal clusters; (2) acceleration of the reduction rate as and using various heating rates: 2.5, 5, 10 and 20 ◦ C min−1 ,
the size of the clusters increase and (3) a pseudo-first-order in the temperature range from an ambient one up to 500 ◦ C.
process in which NiO disappeared and Ni appeared in concert The sample mass used for thermogravimetric investigations was
until reduction slowed at a fractional conversion of about 0.8. about 25 ± 0.5 mg. The degree of conversion () of the reduc-
When 2.2 × 10−2 atm of H2 O was added to the reducing gas, tion process is expressed as
induction times increased by approximately a factor of 2 and
m0 − mt
reduction rates decreased, with an apparent activation energy = , (1)
of 126 ± 27 kJ mol−1 . Utigard et al. (2005) investigated the re- m0 − m f
duction kinetics of NiO granules formed by vapor deposition
where m0 , mt and mf refer to the initial, actual and final mass
from a chloride solution, using thermal gravimetry. They re-
of the investigated sample, respectively.
ported that in the temperature range from 400 to 600 ◦ C, the
rate of reduction increased with increasing temperature and in-
creasing hydrogen pressure. Microscopic analysis showed that 3. The calculating methods used to evaluate the kinetics
in this temperature range the reaction followed the shrinking parameters of the reduction process
core model (Utigard et al., 2005). The same authors found that
the activation energy for reduction process have a value of 3.1. Stationary point method
90 kJ mol−1 in the above temperature range.
Bearing in mind a considerable interest relating to the kinet- In the heterogeneous chemical reaction kinetics, function
ics and mechanism of NiO reduction, in this paper, we contin- d/dt = f (T ) (where d/dt is the velocity of process and
ued the investigation to find the best kinetic model describing T is the absolute temperature), which has zero-initial ve-
this process, using the recent theories of heterogeneous kinet- locity, can be observed as a function with local maximum.
ics. In our previous paper (Janković et al., 2007) using the only This maximum appears in the so-called stationary point (SP):
isoconversional Friedman (1963) (FR) method, the invariance S[(d/dt)max ; Tmax ] (Tmax is the temperature at the maximal
of the apparent activation energy of reduction process was es- velocity of process (d/dt)max ), where (d2 /dt 2 ) = 0 (Klarić
tablished in a limited conversion range (0.20 0.60). In et al., 1995). Consequently, SP is defined as a point in which
the present paper, this finding was confirmed by several other the reaction systems, under given conditions, have maximal
 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575 569

reaction velocity. In that case, the following equation is valid: factor and n is the reaction order. Showing that the term
  n(1 − m )n−1 ≈ 1 (for n = 1), Kissinger (1957) found the
d following expression:
= k(T , pj )f (max ), (2)
dt max
 AR Ea
where (d/dt)max is maximal velocity of considered reaction ln 2
= ln − . (7)
or process, k(T , pj ) the temperature and partial pressure de- Tmax Ea RT max
pendent rate constant, f (max ) is a function of the reaction
2 ) versus 1/T
mechanism, max the degree of conversion at T = Tmax and pj From a plot of ln(/Tmax max and fitting to a straight
denotes the partial pressure of the gaseous products. For non- line, the pre-exponential factor A and the apparent activation
isothermal conditions, when the temperature varies with time energy Ea can be calculated from the intercept and slope,
with a constant heating rate (),  = dT /dt, Eq. (2) can be respectively.
written in the following form:
    3.3. Friedman method
d
 = k(T , pj )f (max ). (3)
dT max Friedman (1963) method presents an isoconversional differ-
If Arrhenius dependence of (k(T , pj )) on temperature is ential method, based on the following equation:
supposed, Eq. (3) can be transformed in the following form:    
      d Ea,i
d Ea ln  = ln[Af ()]i − , (8)
 = A exp − f (max ), (4) dT i RT i
dT max RT max

where Ea is the apparent activation energy of the overall pro- where the subscript, i, denotes that the corresponding quan-
cess, whereas A and R are the pre-exponential factor and gas tity is evaluated at a specific value of the degree of conver-
constant, respectively. Since the logarithmic form of Eq. (4) is sion, i . The apparent activation energy, Ea,i , at this specific
    degree of conversion, is evaluated from the slope of the plot
d Ea ln(d/dT )i  versus 1/Ti , known in the literature as the
ln  = ln[Af (max )] − (5)
dT max RT max isoconversional line. In this approach, Ea is expressed as a
function of degree of conversion (). Any change in Ea as the
and from the slope of the dependence between ln[(d/dT )max ] reaction proceeds indicates a change in the rate-limiting step.
and 1/Tmax , it is possible to determine the value of the appar- Budrugeac et al. (2001) have presented some problems concern-
ent activation energy Ea of the investigated process. Method ing the evaluation of the activation energy from non-isothermal
of the SP does not directly enable the calculation of the pre- data for reactions with kinetic parameters dependent on the de-
exponential factor (A). The value of the pre-exponential factor gree of conversion. They have found out that if the activation
(A) can be determined only in the case when the exact math- energy depends on the degree of conversion, FR method, which
ematical form of the function f (max ) is known (Klarić et al., uses directly the equation of the reaction rate, can be used as
1995). Furthermore, by this method we obviously can obtain a recommended procedure. However, this method is known as
only one value of activation energy, the one that can be calcu- being noise sensitive.
lated comparing (d/dt)max at different temperatures and which
corresponds to max (the degree of conversion at T = Tmax ).
3.4. Flynn–Wall–Ozawa method
3.2. Kissinger’s method
The Flynn–Wall–Ozawa (FWO) method (Flynn and Wall,
1966; Ozawa, 1965) is an isoconversional integral method,
Kissinger (1957) method has been used in the literature to
which uses Doyle’s approximation for the temperature integral
determine the apparent activation energy of solid state reactions
p(x)(x = Ea /RT ) (Doyle, 1961a,b), and based on the follow-
from plots of the logarithm of the heating rate versus the inverse
ing equation:
of the temperature at the maximum reaction rate in constant
heating rate experiments. AE a Ea
The apparent activation energy can be determined by ln  = ln − 5.331 − 1.052 , (9)
Rg() RT
Kissinger method without a precise knowledge of the reaction
mechanism, using the following equation:
where g() is the algebraic expression for integral form of the
 AR Ea reaction model. For  = const., ln  versus 1/T obtained from
ln 2
= ln + ln[n(1 − max )n−1 ] − , (6) thermograms recorded at several heating rates yields a straight
Tmax Ea RT max
line whose slope allows evaluation of the apparent activation en-
where  is the heating rate, Tmax and max are the absolute ergy. For x < 20, Doyle’s approximation leads to errors higher
temperature and the degree of conversion at the maximum than 10%. For such cases, Flynn (1983) suggested corrections
mass-loss rate (d/dt)max , respectively. A is the pre-exponential in order to obtain an accurate value for the activation energy.
570 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575

3.5. Kissinger–Akahira–Sunose (KAS) method 4. Results and discussion

This is an isoconversional integral method (Akahira and The temperature-programmed reduction (TPR) curves of
Sunose, 1971) based on the following equation: nickel oxide in hydrogen atmosphere recorded at different
    heating rates (2.5, 5, 10 and 20 ◦ C min−1 ) are shown in Fig. 1.
 AR Ea
ln 2
= ln − . (10) The total mass-change of investigated nickel oxide samples
T Ea g() RT at all considered heating rates is about 21.4%.
For  = const., ln(/T 2 ) versus 1/T obtained from thermo- The conversion (–T) curves of nickel oxide reduction by
grams recorded at several heating rates yields a straight line hydrogen at different heating rates are shown in Fig. 2.
whose slope allows evaluation of the apparent activation en- Table 1 shows the influence of heating rate of considered
ergy. This method is based on the Coats and Redfern (1964) system on the characteristic temperatures of reduction process:
approximation for the temperature integral (for 20 < x < 50). initial temperature (Ti ), inflection temperature (Tp ), final tem-
perature (Tf ) and temperature differences (T = Tf − Ti )
3.6. Málek’s method (M method) (Málek, 1992) (Fig. 1).
The increase in heating rate leads to the increase of Ti , Tp ,
Once the apparent activation energy has been determined, Tf and T values. Dependence of d/dt versus T at different
it is possible to find the kinetic model which best describes heating rates of the considered system is shown in Fig. 3.
the measured set of TA data. It can be shown that for this With increasing heating rate (), the rate of reduction process
purpose it is useful to define two special functions y() and of nickel oxide by hydrogen increased.
z(), which can easily be obtained by simple transformation of The values of temperatures Tmax (Fig. 3) at four different
experimental data. These functions can be expressed as follows heating rates for reduction of nickel oxide in hydrogen atmo-
(Málek, 1992): sphere are shown in Table 2.
2 ) versus (1/T
  Fig. 4 shows the dependence of ln(/Tmax max )
d for the reduction of nickel oxide by hydrogen.
y() = exp(x), (11)
dt The values of kinetics parameters of nickel oxide reduction
  using hydrogen which were determined by SP and Kissinger
d T
z() = (x) , (12) methods are shown in Table 2 (Columns 3,4 and 5,6, respec-
dt 
tively). The values of Ea obtained by the SP and Kissinger
where x =Ea /RT , (x) is an approximation of the temperature methods (Table 2) are higher than the value of Ea obtained by
integral. It was suggested that (x) may be accurately estimated Richardson et al. (2003) (Ea = 85.0 kJ mol−1 (non-isothermal
by means of the fourth rational expression of Senum and Yang
(1977):
(x 3 + 18x 2 + 88x + 96)
(x) = . (13)
(x 4 + 20x 3 + 120x 2 + 240x + 120)
The y() function is proportional to the f () function. Thus
by plotting the y() dependence, normalized within the (0,1)
interval, the shape of the function f () is obtained. The y()
function is therefore characteristic for a given kinetic model
(Málek, 1992), and it can be used as a diagnostic tool for kinetic
model determination. It has been verified that the shape of the
y() function, as well as the maximum m of the y() function
and ∞p of the function z(), can help to choose the best kinetic
model. Knowing the value of the apparent activation energy and
the kinetic model, the pre-exponential factor can be calculated
using the following equation:
xp
A=− exp(xp ), (14)
Tp f  (p )
where f  () is the differential form of the kinetic model
[df ()/d], p is the degree of conversion corresponding to
the maximum on differential rate curve and p is the maximum
of differential rate curve.
The comparison between y() and z() functions may be
used as the criterium of a reaction model in the following sense:
if y() and z() functions notably differ mutually in the shape, Fig. 1. Temperature-programmed curves for nickel oxide reduction process
then one may exclude the assumption of a single-step model. in hydrogen atmosphere at different heating rates.
 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575 571

Fig. 2. The degree of conversion () as a function of temperature (T) for Fig. 3. Experimental (lines) reaction rate curves (d/dt versus T) for the
the reduction of nickel oxide under linearly rising temperature, in hydrogen reduction of nickel oxide by hydrogen at different heating rates.
atmosphere, at the following heating rates: 2.5, 5, 10 and 20 ◦ C min−1 (from
left to right).

(FR) and integral (FWO and KAS) isoconversional methods.

Table 1 Differential method uses the point value of the overall reaction
The influence of heating rate on the characteristic temperatures of reduction rate, while the integral method uses integrals which describe
process of nickel oxide using hydrogen the history of the system. The above differences in determined
values of Ea by FR, FWO and KAS methods can be expected,
 (◦ C min−1 ) Ti (◦ C) Tp (◦ C) Tf (◦ C) T (◦ C)
because FWO and KAS methods involve a systematic error in
2.5 260 285 395 135 Ea that does not appear in the FR method. Thus, the activation
5 275 300 455 180 energies obtained as a function of the degree of conversion
10 285 315 465 180
from the FR methods are more reliable than those obtained
20 300 340 485 185
from the FWO and KAS methods (Vyazovkin, 2001).
The obtained average value of the apparent activation energy
using FR’s method is very close to the values of Ea , which were
TGA for porous powder in loosely packed samples)), which determined in papers of Richardson et al. (2003) (for porous
used Kissinger’s method also. The value of pre-exponential powder in loosely packed samples) and Utigard et al. (2005) (for
factor (A) is about a factor of 10 greater than the value of A nickel oxide granules). From the existing of “plateau” in Fig. 5,
which was obtained by Richardson et al. (2003) (obtained pre- in the wide range of  values, the proof of existing of single-
exponential factor is A = 2.31 × 107 min−1 ). step reaction is evident. The increase of Ea with increasing 
The values of apparent activation energies (Ea ) of the in- for  0.60 (Fig. 5) was possibly designated on the existence of
vestigated reduction process, at different constant values of , parallel independent reaction (Vyazovkin et al., 1992), which
which were determined by FR, FWO and KAS methods, are possessed the higher value of activation energy and whose part
shown in Fig. 5. in the overall process in this range of  increasing.
From Fig. 5 is evident that the values of the apparent activa- From the complex dependence of Ea on , which is indicative
tion energies obtained by FR method are lower than the values of the complex mechanism of nickel oxide reduction, the kinetic
of apparent activation energies obtained by FWO and KAS model of investigated process was determined by applying the
methods. Independent of the calculation procedure used, the Málek’s (1992) procedure. Using the constant value of Ea , an
activation energy is practically constant in the 0.20  0.60 appropriate kinetic law and the pre-exponential factor (A) are
range, with the average values of Ea = 90.8, 97.2 and determined, where y() and z() functions defined above are
96.6 kJ mol−1 calculated by FR, FWO and KAS methods, re- useful for such kinetic analyses. In addition, these functions
spectively. The obtained values of Ea are somewhat different, allow us to check the applicability of the conventional kinetic
and this can be due to the different conception of differential models and to extend these models to the more sophisticated
572 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575

Table 2
The values of Tmax and values of kinetics parameters obtained by Stationary point (SP) and Kissinger methods (K), for reduction process of nickel oxide
using hydrogen

 (◦ C min−1 ) Tmax (◦ C) EaSP (kJ mol−1 ) ln[ASP f (max )], ASP (min−1 ) EaK (kJ mol−1 ) ln AK , AK (min−1 )

2.5 285 88.3 16.68 98.4 18.93

5 300
10 315
20 340

Fig. 5. Dependency of the activation energy (Ea ) on the degree of conver-

Fig. 4. Kissinger plot for the reduction of nickel oxide in hydrogen atmosphere.
sion () determined using Friedman (FR), Flynn–Wall–Ozawa (FWO) and
Corresponding apparent activation energy (Ea ) and pre-exponential factor (A)
Kissinger–Akahira–Sunose (KAS) methods for the reduction of nickel oxide
are given in the insert.
in hydrogen atmosphere.

ones (Koga et al., 1993). Thus, the most reliable kinetic model
can be determined by comparing the y() and z() functions, that the values of m and ∞ p parameters conform to the two-
according to Eqs. (11) and (12). The normalized y() and z() parameter autocatalytic kinetic model of Šesták and Berggren
functions are presented in Fig. 6. (1971).
The shapes of both the y() and (less expressed) the z() plot In some cases, it is convenient to use more flexible empir-
vary somewhat with the variations in heating rate. Namely, as ical kinetic model functions, f (), for the description of the
already noted, the data in Table 3, extracted from Fig. 6, show crystallization processes. The advantage of such an approach
that m (for y() function) and ∞ p (for z() function) depend
is that it is possible to describe experimental TA data even in
on the heating rate. the case when some of the basic assumptions for the validity of
The maxima of y() and z() functions fall into the range the Avrami–Erofe’ev model are no longer held. These models
of 0.27m 0.34 and 0.52 ∞ p 0.54, respectively. These
can also be understood in terms of the accommodation function
variances correspond to the variances in the calculated val- introduced by Šesták (1991), expressing a deviation from the
ues of the apparent activation energies. Consequently, one can ideal case due to a more complex processes. In this respect, it is
conclude that the kinetics of the process under investigation very convenient to use the SB function (Šesták and Berggren,
may not be exactly described by a one single-step reaction 1971):
model, and the calculated values of activation energy are ap- f () = m (1 − )n , (15)
parent values and differ from the actual values. The m val-
ues are lower than ∞ ∞
p values and p exhibits values lower and this is the most popular form of f () for examination of
than 0.632 (a characteristic value for the kinetic model deter- auto-catalyzed chemical reactions. This flexible two-parameter
mination) (Montserrat et al., 1998). From Table 3, it is evident (m, n) SB function, in fact, also includes the Avrami’s (1939,
 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575 573

Table 4
Kinetic parameters evaluated for the reduction of nickel oxide by hydrogen

 (◦ C min−1 ) s m n ln Aa (min−1 )

2.5 0.52 0.77 1.48 19.72

5 0.38 0.46 1.22 19.10
10 0.40 0.60 1.49 19.74
20 0.50 0.69 1.39 19.44

Average 0.45 0.63 1.39 19.50

The kinetic parameters are calculated using Málek’s procedure.

a Activation energy (via Friedman method): 90.8 kJ mol−1 .

Fig. 6. The y() and z() functions calculated by applying Eqs. (11) and (12)
for reduction process of nickel oxide using hydrogen at various heating rates.

Table 3
The values m and ∞ p of the y() and z() functions evaluated for the
reduction of nickel oxide using hydrogen

 (◦ C min−1 ) m ∞
p

2.5 0.34 0.52

5 0.27 0.54
10 0.29 0.53
20 0.33 0.54

1940, 1941) kinetic model. Therefore, the SB kinetic model

can be used for a quantitative description of more complex
crystallization processes involving partially overlapping nucle- Fig. 7. Experimental (lines) and calculated (symbols) rate curves (d/dt
ation and growth phases. The kinetic parameters, m and n in versus T) corresponding to the reduction process of nickel oxide samples in
Eq. (15), are characteristic of a particular crystallization pro- hydrogen atmosphere: () 2.5 ◦ C min−1 ; () 5 ◦ C min−1 ; (•) 10 ◦ C min−1
and (◦) 20 ◦ C min−1 .
cess, although it is rather problematic to find their real physi-
cal meaning. It was shown (Málek et al., 1989), however, that
the physically meaningful values of the parameter m should be
confined in the range: 0 < m < 1. Then the second kinetic exponent (m) is m = s × n. The pre-
The ratio of the kinetic exponents s = m/n (Eq. (15)) can exponential factor A and kinetics exponents n and m were de-
be calculated from the maximum of the y() function (Málek, termined from each heating rate, and their average values were
1992; Málek et al., 1995): used to determine the kinetics model. The obtained results are
m m shown in Table 4.
s= = . (16) Using the following values one can calculate average kinetic
n 1 − m
parameters: Ea = 90.8 kJ mol−1 , ln A = 19.50 (A is expressed
Once the value of s (ratio m/n) is known, the values of the in min−1 ), m = 0.63 and n = 1.39. The obtained value of the
kinetic exponents (m and n) can be obtained using the following activation energy of 90.8 kJ mol−1 represents the apparent ac-
relation (Málek, 1992; Málek et al., 1995): tivation energy in the conversion range of 0.20  0.60.
   Experimental rate curves (full lines) and rate curves (sym-
d Ea
ln exp = ln A + n ln[s (1 − )]. (17) bols) calculated using the kinetic parameters corresponding to
dt RT
each heating rate (Table 4) are compared in Fig. 7.
The kinetic exponent n corresponds to the slope of linear de- A good agreement can be seen between the calculated theo-
pendence of ln[(d/dt) exp(Ea /RT )] versus ln[s (1 − )]. retical curves and those experimentally determined. This means
574 B. Janković et al. / Chemical Engineering Science 63 (2008) 567 – 575

that the two-parameter SB (m, n) model gives a good descrip- Acknowledgment

tion of the NiO reduction process.
Based on the results showed above, it was decided that in- The investigation was partially supported by the Ministry
deed f () = 0.63 (1 − )1.39 is the best conversion function of Science and Environmental Protection of Serbia, under the
because according to Šesták et al. (1973), in case of a system Projects 142025 and 142047 (S. Mentus).
that contains metallic particles, the reduction processes take
place mainly along the border between the oxide and metallic References
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