Journal of Analytical and Applied Pyrolysis

63 (2002) 303– 325

www.elsevier.com/locate/jaap

Kinetic modeling of thermal decomposition of

natural cellulosic materials in air atmosphere
N.A. Liu a,*, Weicheng Fan a,
Ritsu Dobashi b, Liusheng Huang c
a
State Key Laboratory of Fire Science, Uni6ersity of Science and Technology of China, Hefei,
Anhui 230026, People’s Republic of China
b
Department of Chemical System Engineering, School of Engineering, the Uni6ersity of Tokyo,
7 -3 -1 Hongo, Bunkyo-ku, Tokyo 113, Japan
c
Department of Computer Science and Technology, Uni6ersity of Science and Technology of China,
Hefei, Anhui 230026, People’s Republic of China

Received 22 February 2001; accepted 28 May 2001

Abstract

The wood and leaf samples of eight species are examined by non-isothermal means to
determine the mass loss kinetics of the thermal decomposition with linear temperature
programming in air atmosphere. A simple kinetic description, named in this work as ‘First
Order Pseudo Bi-component Separate-stage Model (PBSM-O1)’, is developed based on the
experimental results and integral analysis method. The model assumes that the mass loss
process of any wood or leaf sample consists of three steps. The first step corresponds to the
water evaporation, and the subsequent two mass loss steps are mainly due to two major
pseudo components. The two pseudo components decompose respectively at two separate
temperature regions, other than at the global temperature region as used in the previous
developed models by other authors. The global mass loss rate of the sample is looked on as
controlled respectively by the reactions of the two components respectively during the lower
and higher temperature ranges. The kinetics of the two components are found to abide by
the first order equation, which gives the best fits to the experimental data compared with
other model functions. The advantages of PBSM-O1 are discussed by comparing it with
other kinetic models. PBSM-O1 is additionally validated by the reasonable agreement
between the experimental and calculated results. © 2002 Elsevier Science B.V. All rights
reserved.
Keywords: Cellulosic materials; Thermal decomposition; Mass loss; Kinetic modeling

* Corresponding author. Tel.: + 86-551-360-6419; fax: +86-551-360-1669.

E-mail address: liunai@ustc.edu.cn (N. Liu).

0165-2370/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0165-2370(01)00161-9
304 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

1. Introduction

The kinetics of biomass thermal decomposition is important in the context of

thermochemical conversion processes aimed at the production of energy and
chemical products. Biomass is also frequently implicated in fire incidence. On the
fire triangle of heat, fuel and oxygen, the rate of mass loss due to thermal
decomposition determines the available fuel. To a lesser extent, the mass loss rate
also determines the heat release rate, since the heat release rate in the fire can be
modeled by the product of the heat of combustion and the mass of fuel burned.
Additionally, a range of practical problems such as the self-heating of cellulosic
materials and the role of inorganic salts as fire retardants for timber, is associated
with the biomass mass loss processes.
The thermal decomposition of biomass involves a high number of different
reactions due to the chemical complexity. This complexity has led researchers to
study biomass constituents separately. The kinetics and mechanism of the thermal
decomposition of biomass components, especially those of cellulose, have been
studied at varying levels of detail by a great number of investigators [1– 7], and
detailed reviews due to Milosavljevic and Suuberg [8], Antal and Varhegyi [9], and
Antal et al. [10] can be referred to. Global kinetics has also been used successfully
to describe the pyrolysis of lignin and hemicellulose (for which xylan is often used
as a representative) [11– 13].
As for the biomass itself, inspection of the literature reveals that the apparent
mass loss kinetic models developed so far fall into two types: (1) ‘pseudo single-
component overall model (PSOM)’ [14–16], which regards the biomass as consist-
ing of a single pseudo component, and uses its solid– gas reaction kinetics during
the overall temperature range to describe the biomass mass loss kinetics. (2) ‘pseudo
multi-component overall model (PMOM) [3,17,18]’, which looks on the biomass as
consisting of multiple pseudo components. Each pseudo component in PMOM
represents a single real component or a mixture of several real components, and the
biomass decomposition is modeled by the superposition of the overall decomposi-
tions of these components. The word ‘overall’ in the names of the two models
represents the common ground shared by them, i.e. each pseudo component
involved in the two models is considered to decompose in the whole temperature
interval.
The mass loss of biomass is controlled by its main components, i.e cellulose,
hemicellulose and lignin, and in general the mass loss kinetics may change as the
temperature increases. However, it’s obvious that PSOM cannot reflect the possible
change in mass loss kinetics. In contrast, PMOM can reveal this kind of kinetic
variation. In recent years PMOM has been used successfully to describe the mass
loss processes of almond shells [3,18], pine and eucalyptus woods [17], and other
wood species [19]. It seems that almost all the studies led to good agreements
between experimental and calculated mass loss curves. The success of this model
justifies the idea that the mass loss properties of a lignocellulosic material can be
regarded as some kind of weighted average of the pyrolytic properties of the
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 305

individual constituents. Nevertheless, two limitations involved in PMOM cannot

be overlooked. First, due to the global definition of each pseudo component, the
overall mass loss kinetic parameters for biomass itself cannot be achieved. In
fact, only the sets of kinetic parameters respectively corresponding to the in-
volved independent reactions can be calculated by PMOM [17]. However, the
kinetic parameters of biomass itself, if available, would play important roles in
practice. Secondly, optimization computation is used in PMOM to obtain the
kinetic parameters [17]. However, it’s well known that for any objective function
(OF) with several parameters to be determined, in mathematics there may be
even infinite sets of parameters able to meet the demand of the error of OF, and
thus the obtained parameters are most likely to be short of kinetic significance.
In this work, non-isothermal experiments have been performed with the leaf
and wood samples in air atmosphere. The kinetic analysis is carried out by
means of the integral method. The basic aim of the present work is to propose
an improved simple and accurate kinetic description suitable for biomass mass
loss behavior in air under relatively low heating rate (10 °C min − 1 for the
present work). The mass loss behaviors of wood and leaf are also compared
qualitatively based on experimental observations. This work is carried out as a
part of a study on the behavior of bulk biomass in fire, and the low heating rate
kinetics can be used in the formulation of the smoldering combustion as well as
the behavior of the interior of the bulk samples in fire, where heating rates are
comparable with that used in this work.

2. Experimental

The raw materials used in the investigation were respectively the wood and
leaf of fir, banana shrub, tea tree, waxberry, holm oak, heath, masson pine and
nanmao collected from Qimen forest zone of China (Table 1). These materials
were first cut and then ground, thereby the average particle size was specified to
be approximately 40 mm. The grains of the sample were evenly distributed over
the open sample pan of 5 mm diameter, loosely, with the initial amounts of the
samples all kept to be 10 mg or so. The depth of the sample layer filled in the
pan was about 0.5 mm. Thermal decomposition was observed in terms of the
overall mass loss by using a STA 409C Thermobalance. Temperature calibration
of TGA was carried out with special concern, since in this device the thermocou-
ple was not in direct contact with the sample. An air stream was continuously
passed into the furnace at a flow rate of 60 ml min − 1 (at normal temperature
and atmospheric pressure). The temperature was increased to 750 °C at a rate of
10 °C min − 1. The heating rate of this order is generally considered able to
ensure that no temperature gap exists between the sample and its surroundings
[20]. In order to test the transport effect under this heating rate and sample
mass condition, we especially carried out the experiments using the masson pine
as an example with different sample masses for which the least being 4 mg and
306 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

the most being 10.6 mg. The result indicated that the TG curves for different
masses differed from each other only around the upper edge of the domain of
evaluation, at temperatures starting around 500 °C. We regarded one of the
curves as a benchmark curve and evaluated the fit of any other curve (e.g. the
jth curve) relative to this benchmark curve according to the following expression:
 Nj
fit (%) = % [wji −wbi ]2/Nj
0.5
(1)
i=1

where w is the mass percentage, the subscript b refers to the benchmark curve,
and Nj is the number of points on the jth curve. Acceptable agreements were
achieved with the most fit being only 2.6, indicating that the effect of the
transport processes is low. This may be partly due to the low heating rate
employed in this study. The sample mass loss percentage and its temperature
were recorded continuously as a function of heating time. From the sample
mass –loss percentage, the normalized mass–loss ratio of a sample can be deter-
mined and plotted versus the sample temperature as the TG curve. The DTG
curve can then be calculated by differentiating the mass–loss ratio with respect
to time or temperature.

Table 1
Features of the thermogravimetric curves for wood and leaf samples in air

Sample Symbola Tm1 Tm2 T90% Moisture Volatile Ash

(°C)b (°C)b (°C)c (%) (%) (%)

Fir LF 332 460 484 8.0 80.6 11.4

WF 312 442 452 12.6 81.0 6.4
Banana shrub LB 300 492 499 5.5 80.6 13.9
WB 300 460 472 8.7 85.1 6.2
Tea tree LT 312 496 520 9.5 81.5 9.0
WT 312 480 472 13.5 85.5 1.0
Waxberry LW 316 472 482 9.7 81.1 9.2
WW 308 448 462 8.7 86.3 5.0
Holm oak LHO 320 492 503 10.2 85.1 4.7
WHO 304 484 496 10.5 85.6 3.9
Heath LH 292 452 468 10.8 80.7 8.5
WH 276 436 457 10.2 83.5 6.3
Masson pine LMP 320 472 481 10.3 81.9 7.8
WMP 312 456 466 12.2 86.6 1.2
Nanmao LN 303 472 482 9.9 88.4 1.7
WN 302 472 504 13.8 85.2 1.0

a
The initials ‘L’ and ‘W’ in this column denote leaf sample and wood sample respectively.
b
Temperatures of DTG peaks (for each sample there are two peaks).
c
Temperature at 90% mass loss of the original sample.
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 307

3. Results and discussion

3.1. Characteristics of biomass mass loss cur6es

For each sample two runs were performed with the same experimental condi-
tions, and the experiment reproducibility were verified by reasonable agreement
between the two obtained mass loss curves. Fig. 1 presents the superimposed TG
and DTG curves of the biomass samples. In the present work, DTG is used to
determine the characteristic temperatures such as the temperature of maximum
mass loss rate, the initial decomposition temperature and the final decomposition
temperature. Table 1 shows data from these thermograms. All samples subjected
to experiments in air are found to give the same general shape for the TG-DTG
curves. The evaporation of sorbed water occurring in the temperature range of
100–180 °C constitutes an approximately 10% mass loss for all the leaf and
wood samples. Following the water evaporation, the first major mass loss due to
decomposition begins slowly and accelerates rapidly in the temperature range of
290–340 °C. A second major mass loss follows the first one and reaches an
overall mass loss of more than 90%.
Compared with the condition of nitrogen, the air atmosphere seems to be a
more complex condition due to the presence of oxygen. Oxygen enhances the
decomposition of the material at low temperatures, and when the temperature
reaches high enough, oxygen is likely to promote the combustion of the char
residue generated in the early stages of the solid decomposition, thereby combus-
tion and pyrolysis may coexist. Nevertheless, the results under nitrogen atmo-
sphere can be used as reference when we examine the thermal decomposition in
air atmosphere at lower temperatures, since during this temperature range pyrol-
ysis generally plays a major role in the overall mass loss compared with oxidiza-
tion.
In nitrogen, it is well known that mass loss of small biomass sample at low to
moderate heating rates usually evidences two distinct DTG peaks, respectively
associated with hemicellulose and cellulose pyrolysis. For example, Font et al.
[18] investigated the thermal decomposition of almond shells at 10 °C min − 1
under nitrogen, resulting in two not completely separate DTG peaks, with one
centering at around 310 °C and the other centering at around 368 °C. Two
peaks in nitrogen were also reported by many other authors. However, when the
experimental condition (e.g. the heating rate) changes, the two peaks sometimes
merge into one very broad peak, and less often three peaks may be obtained
[9,16,17,21]. No matter how many peaks may be observed, they have been
determined to be ascribed to the pyrolysis of hemicellulose and cellulose, accom-
panied by lignin pyrolysis, which generally occurs slowly over a very broad
range of temperatures [9]. In the present analysis we compare the peak tempera-
tures for nitrogen atmosphere, which were reported in the above cited literatures,
with those for air atmosphere as indicated in Table 1. Comparison indicates that
the first peak temperature in air is comparable with that in nitrogen, whereas
308 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

Fig. 1. Experimental TG and DTG curves for wood (---) and leaf ( —) samples.
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 309

the second peak in air shifts to a higher temperature. For instance, the second
peak temperature of 368 °C in the work of Font et al. [18] is obviously much
lower than those obtained in this work (Table 1). It can be inferred from this
comparison result that the first DTG peak in air is largely due to the pyrolysis
of hemicellulose and cellulose, and in part due to that of lignin, while the second
DTG peak occurring at high temperatures is affected by oxidization in a consid-
erable degree. Both wood and leaf share this characteristics.
On the other hand, the mass loss behavior of wood differs from that of leaf in
view of the several observations to be highlighted as follows:
1. As shown in Fig. 1, during the major part of the experimental temperature
range, the mass loss fraction of the wood sample is found bigger than that of
leaf for each species at all times, indicating that as a whole wood has a more
rapid mass loss rate than leaf.
2. We take the temperatures of the two DTG peaks, i.e. Tm1 and Tm2, as well as
the final decomposition temperature Tf, as the measures of the thermal stabil-
ity. These characteristic quantities have been generally considered to be rela-
tive reliable criteria for thermal stability, and have been widely adopted in
literature (e.g. Sohoni and Mark [22]; Atabe et al. [23]; Rao et al. [24]). Due
to the irregular shape of the DTG curves, it’s difficult to determine the
temperature Tf accurately. We take the temperature at 90% of overall mass
loss in place of Tf. Inspection into these characteristic temperatures (as listed
in Table 1) reveals that in general the thermal stability of wood sample is
lower than leaf sample.
3. As indicated in Table 1, the ash yield from wood decomposition is found to
be lower than leaf decomposition in all cases, implying the difference between
the chemical constituents of leaf and wood.

3.2. Kinetic model of the mass loss process

Generally, the thermal decomposition of biomass can be expressed by the

equation
A (solid)“ B (solid) +C (gas)
The irreversibility is promised by the condition of well-controlled air stream,
which carries the volatile away as soon as it forms, so that the reverse reaction
would not occur. The calculation of kinetic parameters is based on the assump-
tion that the mass loss due to the reaction can be described by the following
rate equation:
dh A
= exp( − E/RT)d T (2)
f(h) i
where h is the mass loss fraction, i the heating rate, E the activation energy, A
the pre-exponential factor, and R the gas constant. T is the absolute tempera-
ture. The specific form of f(h) represents the hypothetical model of the reaction
mechanism. Many kinds of mechanisms have been found to control different
310 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

kinetic mass loss processes, and the corresponding forms of the function f(h) as
well as the derivations were frequently stated in literature [25,26]. As for the
Arrhenius equation involved in Eq. (2), its applicability to solid-state reactions
has long been the subject of intense debate. Galwey and Brown [27] presented a
theoretical justification for the application of the Arrhenius equation to the
kinetics of solid state reactions, and it has now been recognized that this empiri-
cal equation can represent the experimental rate data as function of temperature
accurately for both homogeneous and heterogeneous reactions [28,29].
Published methods of deriving kinetic parameters from TG data center about
Eq. (2) itself or its integral form, respectively referred to as differential and
integral methods. The emphasis in these methods is on finding a way to plot the
data so as to provide a rapid visual assessment of the form of f(h) as well as
the kinetic parameters E and A. For the integral method, a function g(h) is

&
defined as
dhh
g(h) = (3)
0 f(h)

&
and thus
T
A
g(h) = exp( − E/RT) d T (4)
i T0

where T0 is the initial temperature. The temperature-containing integral has no

exact solution, and therefore analytical approximations or numerical solutions
should be used to evaluate the integral. In fact, many of the present available
kinetic methods differ from each other just due to their respective different
approximations of the temperature-containing integral [30–32]. Using the ap-
proximation proposed by Coats and Redfern [30], the following equation can be

 n 
achieved:

ln
g(h)
=ln
AR
1−
2RT n −
E
(5)
T2 iE E RT
Especially for a reaction that satisfies f(h)= (1− h)n, where n is the order of
reaction,

Á
à −ln(1 −h) n=1
g(h) = Í1 −(1 −h)1 − n (6)
à n"1
Ä 1 −n
In general, the term 2RT/E is much less than unity for the thermal decomposi-
tion of polymer materials. A plot of ln[g(h)/T 2] against 1/T should result in a
straight line of slope −E/R for the correct reaction mechanism, as underlies the
method to find the suitable model function g(h) (or f(h)) of global pyrolysis
kinetics. As soon as the form of g(h) is obtained, the apparent activation energy
E and the frequency factor A can be calculated from the straight line in the light
of Eq. (5).
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 311

In what follows the basic idea underlying the kinetic model would be interpreted.
As previously shown, after the evaporation of sorbed water, the pyrolysis occurring
in the lower temperature range leads to the first DTG peak, while another DTG
peak is due to the pyrolysis and oxidization occurring simultaneously in the higher
temperature range. This result suggests that the prevailing reaction mechanism
changes depending on the temperature regions. Further observations of Fig. 1
indicate that the two main mass losses appear nearly separate in almost all the
cases. According to these evidences, we consider that the sample subjected to
experiment can be regarded as being formed of two independent pseudo compo-
nents, which decompose respectively in two separate temperature regions. In other
words, in the framework of the present kinetic model, one of the pseudo-compo-
nents is assumed to decompose in the lower temperature range, and when the
decomposition of it ends, the other component begins to decompose until some
high temperature value reaches. In terms of this idea, a two-stage model consisting
of two independent reactions occurring respectively in the lower and higher
temperature ranges is proposed to describe the biomass mass loss kinetics. The
model differs from PSOM and PMOM in that the pseudo components involved in
the latter two models are all defined in the whole temperature range. As noted
previously, the global definitions of the pseudo-components are in fact the origin of
the main limitations for PMOM. In contrast, the present model takes into account
the experimental fact that the two main mass losses behave nearly separately, and
accordingly defines two pseudo components to decompose respectively in two
separate temperature ranges, other than in the whole temperature range. The mass
loss kinetics of the two pseudo components defined separately as such are consid-
ered able to represent the global mass loss behavior. Theoretically, the present
kinetic model doesn’t deny the global characteristics for the decomposition of real
components, but try to propose a simplified formulation (compared with PMOM)
for the decomposition temperature ranges of the pseudo components involved in
the model, based on available experimental evidences. In terms of these features,
the present kinetic model is referred to as ‘Pseudo Bi-component Separate-stage
Model (PBSM)’.
In the model, the temperature corresponding to the minimum in the DTG curve
is regarded as the point of separation between two mass loss stages [33]. In this way
the initial and residue solid mass fractions corresponding to the two separate
reactions are defined respectively in the definite lower and higher temperature
ranges, as indicated in Fig. 2, and accordingly the global mass loss kinetics can be
expressed as

Áw10 −w1 d h1
w10 Bw Bw1
d h Ãw10 −w2 d T
=Í (7)
d T Ãw20 −w2 d h2
w1 =w20 B wB w2
Äw10 −w2 d T

and
312 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

Fig. 2. Illustration of definitions involved in the present new kinetic model.

Ád h1 A1
à d T = i exp( − E1/RT)f1(h1) w10 B wB w1
Í (8)
Ãd h2 = A2 exp( − E /RT)f (h ) w = w B wB w
Äd T i 2 2 2 1 20 2

where w is the mass percentage of solid, and the subscripts 0 and refer to the
initial and residual amounts respectively, and the subscripts 1 and 2 respectively

Table 2
Kinetic model functions f(h) and corresponding g(h) usually employed for the solid state reactions

Model g(h)= kt f(h) = (1/k)(dh/dt)

Reaction order
O0 h 1
O1 −ln(1−h) 1−h
O2 (1−h)−1 (1−h)2
O3 (1−h)−2 (1−h)3
Phase boundary controlled reaction
R2 1−(1−h)1/2 2(1−h)1/2
R3 1−(1−h)1/3 3(1−h)2/3
Diffusion
D1 h2 1/2h
D2 (1−h)ln(1−h)+h [−ln(1−h)]−1
D3 [1−(1−h)1/3]2 3/2(1−h)2/3[1−(1−h)1/3]−1
D4 (1−2h/3)−(1−h)2/3 3/2[(1−h)−1/3−1]−1
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 313

correspond to the pseudo components 1 and 2. Table 2 shows the basic model
functions usually employed for the kinetic study of solid state reactions. Using
the experimental mass loss curves, the functions shown in Table 2 are substituted
into Eq. (5) respectively to see if any one of them gives good linearity with
regard to this equation. The values of hi (i= 1, 2) are calculated in terms of the
definition indicated in Fig. 2 at each mass loss temperature interval, hereby the
corresponding values of ln[gi (hi )/T 2] are obtained for each attempted form of
gi (hi ). A regression analysis with ‘the least squares method’ is employed in the
analysis for each temperature region. The form of gi (hi ) (i= 1, 2) giving a
straight line with the highest correlation coefficient is considered to be the func-
tion of the model representing the mass loss kinetics for the samples under
study. The values of E and A are then obtained from the slope and intercept of
the line, respectively.
Following the above procedures, it is found that the first order function leads
to good linearity with regard to Eq. (5) for all the wood and leaf samples
without exception. Fig. 3 indicates that plots of ln[− ln(1− hi )/T 2] against 1/T
show very good linearity. The correlation coefficient r provides a good quantita-
tive criterion for the validity of the kinetic model. Table 3 indicates that the
linear regressions have acceptable correlation coefficients r values. The kinetic
parameters (i.e. A and E values) calculated from these plots are also summarized
in Table 3.
In order to verify the model function of first order still further, we compare
this model function with other functions listed in Table 2. Due to space con-
straint, we only take the sample of fir (LF and WF) as an example for the
present discussion. With different functions used, Figs. 4 and 5 show the plots of
ln[g(h)/T 2] 1/T for the samples of LF and WF with the kinetic scheme of
PBSM. Similar plots are obtained for other samples, and the presentation of
these plots is omitted here. It can be seen from Figs. 4 and 5 that for the model
functions based on ‘order’ of reaction, the plots for the functions of O2 and O3
bend down greatly, while the plot for O0 bends up slightly. It is the function of
O1 that shows the best linearity. Therefore it can be concluded that the model
function of first order (O1) is the best ‘reaction order ’ function for the descrip-
tion of biomass mass loss kinetics. Besides O1, the functions such as D3 and R3
also seem to result into relatively good linearity. In order to make a further
inspection into the different functions, the correlation coefficients corresponding
to these plots are calculated and listed in Table 4 for comparison, and several
observations can be achieved as follows:
1. Only the model function of O1 leads to correlation coefficients higher than
0.99 for all the samples under investigations, with the minimum value of
0.9911 (WH) and the maximum value of 0.9991 (LHO).
2. For all the samples examined, the model functions of O1, R2, D2 and D4
result in maximum correlation coefficients of 0.9991, 0.9993, 0.9991 and
0.9995, respectively. However, it can be seen that the latter three values all
correspond to the second mass loss stage of the sample LB, for which the
first mass loss stage leads to relatively low correlation coefficients of 0.9847,
314 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

Table 3
Kinetic parameters for mass loss of the leaf and wood samples by PBSM-O1

Sample Mass loss Temperature Activation Frequency r FitTG FitDTG

temperature range for energy E factor (%) (%)
range (°C) regression (°C) (kJ mol−1) A (min−1)

LF 172–380 200–370 72 4.8×105 0.9968 0.7 5.5

380–516 390–510 133 7.1×108 0.9961
WF 184–380 220–370 82 3.7×106 0.9962 1.5 7.0
380–496 390–490 136 2.7×109 0.9973
LB 196–372 210–372 69 3.7×105 0.9969 0.7 8.6
372–540 410–520 94 6.7×105 0.9938
WB 182–370 210–372 80 3.5×106 0.9964 1.3 6.1
370–520 390–510 113 2.9×107 0.9940
LT 168–410 170–368 52 5.2×103 0.9936 0.7 5.9
410–576 430–540 131 1.6×108 0.9973
WT 190–360 220–352 99 2.5×108 0.9982 0.7 4.9
360–500 382–490 94 1.2×106 0.9966
LW 172–360 220–352 67 2.3×105 0.9982 1.3 5.7
360–516 370–510 122 1.5×108 0.9930
WW 180–380 220–360 96 1.1×108 0.9946 0.6 6.9
380–520 400–510 124 2.2×108 0.9948
LHO 168–380 190–370 69 3.0×105 0.9990 0.6 6.0
380–536 390–530 108 6.9×106 0.9971
WHO 184–380 200–370 83 6.3×106 0.9961 1.5 7.7
380–576 390–570 87 2.0×105 0.9926
LH 164–380 170–370 63 1.0×105 0.9968 1.1 8.3
380–500 390–490 202 1.1×1014 0.9961
WH 192–360 210–350 96 2.1×108 0.9957 1.4 5.3
360–500 372–490 113 4.8×107 0.9911
LMP 192–400 229–389 66 1.1×105 0.9959 1.2 7.8
400–544 421–520 137 1.2×109 0.9983
WMP 180–359 219–352 84 9.5×106 0.9973 0.9 5.9
359–500 380–490 102 5.0×106 0.9994
LN 162–378 200–372 67 1.3×105 0.9965 0.6 5.4
378–499 397–490 161 6.7×1010 0.9974
WN 180–379 201–372 72 5.8×105 0.9983 0.8 4.5
379–550 398–527 93 4.6×105 0.9971

0.9804 and 0.9850 respectively for the functions of R2, D2 and D4. This
indicates that in fact none of the three models is suitable for describing the
global biomass mass loss behavior. On the other hand, the 0.9991 for the
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 315

Fig. 3. Plots of ln[ −ln(1 − h)/T 2] against the 1/T for the leaf and wood samples.

function O1 corresponds to the first mass loss stage of LHO, for which the
second mass loss stage leads to a correlation coefficient of 0.9971, also higher
than 0.99.
316 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

3. For all the samples, the mean value of the correlation coefficients by the model
function of O1 can be easily calculated from Table 4 to be 0.9964, which is
higher than the corresponding values for other models.
These evidences on one hand imply that the model PBSM-O1 can be used to
describe the mass loss behaviors for all the wood and leaf samples within acceptable
accuracy. On the other hand, it’s obvious that with the kinetic scheme of PBSM,
the function of O1 has superiority over other functions listed in Table 2. For these

Fig. 4. Plot of ln[g(h)/T 2]  1/T for the sample of LF by PBSM.

 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 317

Fig. 5. Plot of ln[g(h)/T 2] 1/T for the sample of WF by PBSM.

reasons, it can be concluded that the model of PBSM-O1 is a most reasonable

model to describe the biomass mass loss kinetics.
Let us collate the main points of the model PBSM-O1, which is illustrated in Fig.
6. The model assumes that the mass loss process of any wood or leaf sample
consists of three steps. The first step corresponds to the water evaporation, and the
subsequent two mass loss steps are mainly due to two major pseudo components.
The two components react respectively at two separate temperature regions, both
abiding by the first order kinetics. The global mass loss rate is looked on as
controlled respectively by the reactions of the two components respectively during
the lower and higher temperature ranges.
318 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

Table 4
Correlation coefficients of the plots of ln[g(h)/T 2] 1/T by PBSM

Model function Correlation coefficients r

LF WF LB WB
O0 0.9868 0.9852 0.9737 0.9447 0.9622 0.9955 0.9635 0.9751
O1 0.9968 0.9973 0.9962 0.9973 0.9969 0.9938 0.9964 0.9940
O2 0.9769 0.9675 0.9938 0.9841 0.9708 0.9656 0.9771 0.9375
O3 0.9416 0.9319 0.9765 0.9624 0.9282 0.9383 0.9371 0.8980
R2 0.9948 0.9968 0.9874 0.9798 0.9847 0.9993 0.9833 0.9963
R3 0.9963 0.9983 0.9910 0.9879 0.9904 0.9984 0.9889 0.9986
D1 0.9891 0.9873 0.9777 0.9525 0.9691 0.9964 0.9692 0.9797
D2 0.9935 0.9942 0.9850 0.9707 0.9804 0.9991 0.9792 0.9912
D3 0.9968 0.9985 0.9923 0.9892 0.9920 0.9986 0.9905 0.9988
D4 0.9949 0.9963 0.9878 0.9783 0.9850 0.9995 0.9834 0.9952
LT WT LW WW
O0 0.9780 0.9852 0.9801 0.9792 0.9868 0.9686 0.9922 0.9506
O1 0.9936 0.9973 0.9982 0.9966 0.9982 0.9930 0.9987 0.9990
O2 0.9960 0.9675 0.9897 0.9868 0.9811 0.9380 0.9977 0.9620
O3 0.9875 0.9318 0.9644 0.9680 0.9533 0.8847 0.9901 0.9302
R2 0.9873 0.9968 0.9916 0.9919 0.9961 0.9891 0.9963 0.9859
R3 0.9898 0.9983 0.9945 0.9943 0.9977 0.9930 0.9973 0.9935
D1 0.9826 0.9873 0.9825 0.9828 0.9893 0.9730 0.9931 0.9589
D2 0.9874 0.9942 0.9890 0.9899 0.9945 0.9842 0.9956 0.9765
D3 0.9918 0.9985 0.9952 0.9951 0.9981 0.9938 0.9977 0.9943
D4 0.9890 0.9963 0.9914 0.9921 0.9961 0.9885 0.9964 0.9840
LHO WHO LH WH
O0 0.9874 0.9844 0.9748 0.9362 0.9699 0.9656 0.9848 0.9576
O1 0.9991 0.9971 0.9953 0.9978 0.9961 0.9926 0.9957 0.9911
O2 0.9805 0.9645 0.9937 0.9725 0.9947 0.9771 0.9975 0.9904
O3 0.9463 0.9271 0.9743 0.9501 0.9728 0.9423 0.9912 0.9731
R2 0.9961 0.9968 0.9867 0.9816 0.9852 0.9825 0.9912 0.9784
R3 0.9979 0.9984 0.9901 0.9904 0.9895 0.9869 0.9929 0.9837
D1 0.9897 0.9870 0.9783 0.9530 0.9753 0.9682 0.9865 0.9632
D2 0.9944 0.9941 0.9846 0.9728 0.9832 0.9779 0.9902 0.9747
D3 0.9983 0.9987 0.9914 0.9923 0.9914 0.9878 0.9937 0.9856
D4 0.9960 0.9964 0.9872 0.9812 0.9862 0.9817 0.9915 0.9789
LMP WMP LN WN
O0 0.9667 0.9548 0.9907 0.9982 0.9800 0.9934 0.9812 0.9753
O1 0.9959 0.9983 0.9956 0.9978 0.9965 0.9974 0.9983 0.9971
O2 0.9962 0.9746 0.9776 0.9823 0.9847 0.9847 0.9794 0.9873
O3 0.9800 0.9485 0.9469 0.9583 0.9542 0.9636 0.9440 0.9669
R2 0.9844 0.9860 0.9955 0.9931 0.9906 0.9975 0.9928 0.9907
R3 0.9891 0.9925 0.9961 0.9958 0.9932 0.9980 0.9956 0.9939
D1 0.9730 0.9616 0.9920 0.9819 0.9835 0.9940 0.9844 0.9798
D2 0.9820 0.9778 0.9947 0.9901 0.9890 0.9967 0.9904 0.9881
D3 0.9910 0.9934 0.9965 0.9964 0.9943 0.9981 0.9963 0.9948
D4 0.9854 0.9844 0.9956 0.9928 0.9911 0.9974 0.9928 0.9909

For each sample, the left column corresponds to component 1, while the right column corresponds to
component 2.
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 319

Fig. 6. Schematic illustration of the new kinetic model (PBSM-O1).

The temperature ranges for the two main mass loss stages and those for
regression calculations are reported respectively in the second and the third
columns of Table 3. Outside these regions for regression, appreciable deviations are
found to exist for the plots of ln[− ln(1− h)/T 2] against the reciprocal of T. The
reason may be that in each temperature interval, the mass loss process is controlled
most predominantly by the first order kinetics, whereas in the intermediate range,
i.e. at the temperatures from the end of the first range to the beginning of the
second range, the two first order kinetics for the two temperature ranges may take
effect together. Additionally, it is also found that in the initial 15% stages (from
room temperature to about 210 °C, as indicated in Table 3) first order kinetics is
not obeyed. This result agrees well with several previous investigations of the
pyrolysis of cellulose, for which the initial stage of the pyrolysis was found not to
follow a first-order reaction law as well [34]. This kind of deviation may be due to
the remarkable impact of secondary reactions on the overall mass loss for which the
subsequently controlling kinetic step accounts for only a small proportion during
the initial stage.
In comparison with the model of PSOM, PBSM-O1 in some degree reflects the
variation of the mass loss kinetics with the sample temperature, and therefore is a
more reasonable description for biomass mass loss kinetics. Compared with
PMOM, PBSM-O1 has several remarkable advantages as follows: (1) PBSM-O1
allows us to determine the kinetic parameters for the overall mass loss process of
biomass. Overall kinetic parameters are very useful in developing the models to
describe the biomass combustion process, in which pyrolysis and oxidization play a
major role. In addition, overall kinetic parameters may be used to evaluate some
other characteristics (e.g. the thermal stability) of the sample. (2) Optimization
computation is not required in PBSM-O1, and therefore the difficulty and limita-
tion due to the characteristics of multi-extrema of the objective function don’t exist
in PBSM-O1.
Although the achieved kinetic parameters differ from each other, it is found that
these parameters fit the kinetic compensation effect (KCE) very well, i.e. for either
component 1 or 2, the kinetic parameters as a result of sample changes satisfy the
linear relationship between ln A and E. The linear relationships are determined by
linear regression analysis as follows (Fig. 7):
320 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

Component 1 ln A = −3.0334( 90.3724)+ 0.2262(9 0.0048)E r= 0.9968

Component 2 ln A = −2.5444( 90.5375)+ 0.1727(9 0.0043)E r= 0.9957
where E is expressed in kJ mol − 1 and A in min − 1.

3.3. Verification of PBSM-O1 by reconstruction of the mass loss data

Once a kinetic model is developed to describe the mass loss behavior, the
reliability of it should be verified with care by means of different methods. In fact,
for the PBSM-O1 developed in the present work, the good linearity of the plot of
ln[ −ln(1− h)/T 2] against 1/T itself is a direct verification of the model. Further
verification may be realized by comparing the experimental and calculated mass
loss plots versus temperature. However, this is not a convincing method to test the
model, since as indicated by Flynn and Wall [35], different sets of kinetic parame-
ters may lead to mass loss curves close to each other. To solve this issue, Agrawal
[36] suggested that both the TG and DTG curves resulted from the experiment and
calculation should be fully compared, and the satisfactory agreements between
them may be looked on as an acceptable justification of the model. Varhegyi et al.
[37] also pointed out that the quantitative characterization of the fit should not be
based on a single quantity, and the fit of DTG curves should be calculated since it
reflects better the similarities or differences in the peak shapes. With this suggestion
in mind, in the present work, the obtained apparent kinetic parameters are first
substituted into Eq. (4) to obtain the calculated TG curves. The exact value of the
temperature integral is calculated numerically by using the 1/3rd Simpsons rule.
The calculated TG curve is then substituted into Eq. (2) leading to the calculated
DTG curve. In the formation of the calculated curves, the relatively narrow
transition region between the two mass loss processes is not taken into account,
since in the kinetic sense, the mass loss during the transition region is controlled
simultaneously by the two first order kinetic reactions corresponding to the two
mass loss processes, and no simple kinetic equation may be achieved to describe the

Fig. 7. Compensation plot of kinetic parameters from all samples.

 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 321

Fig. 8. Comparison of the experimental and theoretical TG-DTG curves for the leaf and wood samples
of fir (LF and WF).

mass loss behavior during this region. The temperatures used in the calculations are
those listed in the third column of Table 3, with the temperatures in the transition
region omitted. The weak smoothness of the DTG curves during the transition
region is merely due to the method of graphic construction. In fact, if we used the
temperature values listed in the second column of Table 3, non-continuity may be
observed in the transition region for both the TG and DTG curves.
By comparing the calculated and experimental TG-DTG curves, the kinetic
model may be further tested and verified. Representative plots of comparison are
presented in Fig. 8 for the fir leaf (LF) and fir wood (WF) samples. Similar plots
322 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

are obtained for other samples, and so omitted here for the limitation of space. The
fit for each calculated curve can be evaluated in terms of the following expression
that was suggested and successfully employed by the authors such as Varhegyi

 
[37– 39] and Orfao [17]:
N
fit (%) =100 % [X calc
i −X exp 0.5
i ] /X
highest
(9)
i=1

where X calc
i and X exp
i represent the calculated and experimental data (sample mass
or DTG), N is the number of points on the experimental curve, and X highest is the
highest absolute value of the experimental curve. It should be clarified that the way
to utilize this expression here differs little from that used in the above-cited
literature. In the literature this expression was used in the optimization computa-
tion in order to find out the optimal parameter set, whereas the present study uses
it to testify the kinetic description, which has been obtained by other indirect means
(i.e. the Coats and Redfern method). The fit values are listed in the last two
columns of Table 3. The results show that the experimental and calculated TG
curves have excellent agreements for all the samples, while comparison of the
experimental and calculated DTG curves results in worse fit. According to the
points clarified in literature [37,40], the worse fit may be due to (a) the systematic
errors of the thermal analysis. During the calculation of the experimental DTG
curves by differentiation algorithm, we first used the smoothing method to filter out
the random experimental errors involved in the TG curves. However, the remaining
non-random errors cannot be removed. This kind of systematic error can be
enlarged by the numerical differentiation computation. (b) the error resulted from
the smoothing calculation. As indicated by Varhegyi and Till [40], a compromise
must be found between the effective removal of the various experimental error
components and the distortion of the curves by too strong smoothing. However, in
practice this compromise is difficult to be achieved. With these two kinds of errors
in mind, the fitDTG values obtained can be looked on as reasonable.

4. Conclusions

In the present low heating rate experimental condition, the mass loss of either
wood or leaf exhibits three obvious steps as the temperature increases. The first step
of 10% mass loss is due to water evaporation. The second step results from the
pyrolysis of hemicellulose and cellulose. The pyrolysis of lignin contributes partly to
the second and third steps, and the third step is largely affected by oxidation.
For each species, compared with the leaf sample, the wood sample has the lower
thermal stability as a whole, as well as a higher and a lower DTG peaks respectively
in the lower and higher temperature ranges. In addition, the ash yield from wood
decomposition is lower than leaf decomposition in all cases, implying the difference
between the chemical constituents of leaf and wood.
A simple kinetic scheme, i.e. PBSM, consisting of two pseudo components that
react respectively in the lower and higher separate temperature ranges is suitable to
 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325 323

describe the mass loss behaviors of biomass samples. PBSM differs from the
existing models in that the pseudo components involved in the existing models
were defined to react in the global temperature range, while the two pseudo
components in PBSM are assumed to react in two separate temperature ranges.
This model carries certain remarkable advantages over existing models.
With the kinetic scheme of PBSM, the model function of first order gives the
best fits to the experimental data compared with other model functions. This
result suggests the possibility that ‘first order’ reflects the real mechanism. How-
ever at present there is no direct evidence that this is so, and we merely regard
this rate law as providing the best engineering fit to the data. The mechanism
resulting into the present rather accurate kinetic characterization for biomass
thermal decomposition remains to be an important topic of the future work. The
mass loss processes of both wood and leaf are considered to be reasonably
modeled by the kinetic model PBSM-O1 (O1 means ‘first order’) as described by
the following expression:

Á d h1 A1
(w − w10) = (w1 − w10) exp( −E1/RT)(1 −h1) w10 Bw Bw1
d w à 1 dT i
=Í (10)
dT Ã d h2 A2
(w − w20) = (w2 − w20) exp( − E2/RT)(1 −h2) w1 =w20 Bw Bw2
Ä 2 dT i

For each pseudo component, the kinetic parameters E and A for different
samples satisfy the KCE relationship.

Acknowledgements

This work was sponsored by National Natural Science Foundation of China

under Grants 59876039 and 59936140, the National Key Basic Research (973)
Program of China ‘Dynamics of Fire and its Control’, and the China– Greece
Joint Project ‘Investigation on the Characteristics of Forest Fire in the Early
Stage and Its Control Technique’. N. A. Liu was supported by the National
High Performance Computing Foundation of China and the Resource and Envi-
ronmental Scientific Base of USTC. Thanks are due to Professor Liu Zhenhai
and Li Xingui for their great help in the preparation of this paper.

Appendix A. Nomenclature

A apparent pre-exponential factor (min−1)

E apparent activation energy (kJ mol−1)
n apparent reaction order
324 N.A. Liu et al. / J. Anal. Appl. Pyrolysis 63 (2002) 303–325

r correlation coefficient
R gas constant (kJ K−1 mol−1)
T absolute temperature (K)
T0 initial decomposition temperature (K)
Tm1, Tm2 the temperatures of the DTG peaks (K)
Tf final decomposition temperature (K)
w sample mass percentage
w0 initial sample mass percentage
w residual sample mass percentage
h mass loss fraction
i heating rate (K min−1)

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