Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

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Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Levoglucosan formation mechanisms during cellulose pyrolysis

Xiaolei Zhang a, , Weihong Yang a , Changqing Dong b
a
b

Division of Energy and Furnace Technology, Department of Materials Science and Engineering, Royal Institute of Technology, SE-100 44 Stockholm, Sweden
National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

a r t i c l e

i n f o

Article history:
Received 9 November 2012
Accepted 26 September 2013
Available online 8 October 2013
Keywords:
Levoglucosan
Cellulose pyrolysis
Density functional theory

a b s t r a c t
Levoglucosan is one important primary product during cellulose pyrolysis either as an intermediate or
as a product. Three available mechanisms for levoglucosan formation have been studied theoretically
in this paper, which are free-radical mechanism; glucose intermediate mechanism; and levoglucosan
chain-end mechanism. All the elementary reactions included in the pathway of every mechanism were
investigated; thermal properties including activation energy, Gibbs free energy, and enthalpy for every
pathway were also calculated. It was concluded that free-radical mechanism has the highest energy barrier during the three levoglucosan formation mechanisms, glucose intermediate mechanism has lower
energy barrier than free-radical mechanism, and levoglucosan chain-end mechanism is the most reasonable pathway because of the lowest energy barrier. By comparing with the activation energy obtained
from the experimental results, it was also concluded that levoglucosan chain-end mechanism ts better
with the experimental data for the formation of levoglucosan.
2013 Elsevier B.V. All rights reserved.

1. Introduction
The use of biomass or bio-energy offers signicant environmental advantages over fossil fuels; they produce fewer carbon
dioxide emissions and less environmental pollution, and they can
ease the global energy shortage. The technology of pyrolysis is an
efcient way to convert biomass into usable energy, such as char
from conventional slow pyrolysis and liquids or gases from fast
pyrolysis. As the main component of biomass, cellulose pyrolysis
plays an important role in the investigation of biomass pyrolysis. It was reported that several important primary products for
cellulose pyrolysis, such as levoglucosan, glycolaldehyde, and 5hydroxymethylfurfural. Especially, levoglucosan is one important
primary product during cellulose pyrolysis, either as a product
[14] or as an important intermediate for the formation of other
products [511].
Shazadeh et al. [12] reported that cellulose is rst decomposed
into active cellulose without weight loss; the active cellulose can
then be depolymerized into volatiles or polymerized to solid char.
This reaction scheme is known as the BroidoShazadeh model,
where volatiles, including tar (levoglucosan), represent a condensable fraction. The authors concluded that the activation energy
for the formation of volatiles in vacumm is 198 kJ/mol. The activation energy for cellulose primary pyrolysis from Milosavljevic and
Suuberg [13] and Antal et al. [14] are 218 kJ/mol and 228 kJ/mol,

Corresponding author. Tel.: +46 8 790 85 31.

E-mail address: zhxl@kth.se (X. Zhang).
0165-2370/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.09.015

respectively. Capart et al. [15] studied cellulose pyrolysis in nitrogen and concluded that the activation energy is about 202 kJ/mol
for the primary decomposition of cellulose. In the pyrolysis reaction scheme proposed by Banyasz et al. [10], it was concluded that
cellulose can either be transferred into char, tar (levoglucosan), or
gases (hydroxyacetaldehyde, formaldehyde, and CO) via depolymerizing cellulose. The activation energy for tar calculated in the
Banyasz model is 151 kJ/mol. It was also reported that the activation energy of levoglucosan formation from cellulose fast pyrolysis
is about 200 kJ/mol from Mamleev et al.s work [16]. Lin et al.
[17] also proposed that levoglucosan is the rst resulting anhydromonosaccharide, then levoglucosan can undergo dehydration and
isomerization reactions to form other anhydro-monoscaaharides
such as dianhydro--d-glucopyranose, levoglucosenone, and 1,6anhydro--d-glucofuranose.
Mayes and Broadbelt [18] summarized the formation mechanism of levoglucosan from cellulose, levoglucosan can be formed
via glucose intermediate (Fig. 1a); via free-radical mechanism
(Fig. 1b); via ionic mechanism (Fig. 1c). Free-radical intermediate mechanism which was proposed by Pakhomov [19], described
the cellulose chain will break into dehydroglucose diradicals, then
levoglucosan can be formed from these dehydroglucose diradicals. Another radical mechanism for formation of levoglucosan
from cellulose was from Shen and Gus work [20]. Which proposed that levoglucosan radical with one unpaired electron will
be transferred into levoglucosan by reacting with hydroxyl radical.
This mechanism is not representative for levoglucosan formation because the limitation of hydroxyl groups existed in biomass
pyrolysis process. Instead of radical intermediate, ionic mechanism

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X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

Fig. 1. Main mechanisms for the formation of levoglucosan from cellulose pyrolysis.

[21] shows that the cellulose can produce levoglucosan by an

ionic intermediate. Regarding radical cleavage and ionic cleavage,
it is proved that under the gas atmosphere, which is the atmosphere for real biomass gasication, ionic cleavage need quite more
energy than radical cleavage. Thus the ionic cleavage mechanism
will not be considered in this paper. In Irvine and Oldhams work
[22], it was mentioned that levoglucosan can be formed from glucose which was produced by hydration of cellulose chain, this
levoglucosan pathway is called glucose intermediate mechanism
in this paper. There were also many studies [16,2326] mentioned the levoglucosan formation via levoglucosan (LG) chain-end
mechanism (Fig. 1d). Two transglycosylation steps are included in

the LG chain-end mechanism. During the rst transglycosylation

step, a cellulose chain is depolymerized into a levoglucosan-end
intermediate and a short cellulose chain. During the second transglycosylation step, the levoglucosan-end intermediate which is
formed from the rst step will be unzipped into a levoglucosan
molecule, with another levoglucosan-end intermediate formed by
the remaining part. Even Mayes and Broadbelt [18] veried that
LG chain-end mechanism has quite low energy barrier by density
functional theory (DFT). Until now, there is still no systemic comparison for the cellulose decomposition via glucose, or free-radical
intermediate mechanism, or via levoglucosan chain-end mechanism.

Fig. 2. Cellulose homogeneous cleavage at two positions: C1 O position and O C4 position.

X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

21

Fig. 3. Energy illustration and geometries change of free-radical mechanism for LG formation.

In this work, we assessed the cellulose cleavage to form levoglucosan via glucose intermediate, free-radical mechanism, and LG
chain-end mechanism by density functional theory. The detailed
pathways including the geometries and thermal properties of all
the involved structures for these mechanisms will be calculated and
compared. Theoretical comparison under the same level can help to
understand the formation mechanism of levoglucosan formation,
and understand the biomass pyrolysis process further.
2. Computational details
The optimizations of all the geometries (reactants, products, and
transition states) were performed at the DFT/M062X level using the
6-31+G(d,p) basis set. Comparing with the method B3LYP which
was used in our previous work [2730], M062X was proved to be
more accurate than B3LYP in many other studies [18,3133] about
carbohydrates systems. The unrestricted open-shell wave function
was used in all open-shell cases. Calculations were carried out in
the ground state. The transition states were calculated by the TS
method and were conrmed by frequency analysis and intrinsic
reaction coordinate (IRC) calculations, which were performed at
the same basis set of that used for optimizations. The stabilities
of all optimized structures were certied by frequency analysis.
All the stable structures (reactants, intermediates, and products)
have no imaginary frequency, and transition states have exactly one
imaginary frequency. All the calculations were performed by the
program Gaussian 09 [34]. And all of the calculations were carried
out on the high performance computer in PDC at the Royal Institute
of Technology (KTH) in Sweden.
3. Results and discussion
3.1. Free-radical mechanism (M1)
For the free-radical mechanism (as called M1) for levoglucosan
formation during cellulose pyrolysis, the cellulose chain rstly
was decomposed into anhydroglucose radical units (as shown in
Fig. 1b), then this anhydroglucose radical can be transferred into
levoglucosan.

The free-radical can be formed by homogeneous cleavage of a

cellulose chain, where bond breaking of -(1-4)-glycosidic linkage with two electrons separate equally. Two cleavage positions
(C1 O bond and O C4 bond) in cellulose chain are possible, the
relative cleavage pathways are called as C1 O cleavage and O C4
cleavage, respectively. Two types of free-radicals, free-radical A and
free-radical B, can be produced, respectively, as shown in Fig. 2. The
bond energy for these two bonds C1 O and O C4 are 422 kJ/mol
and 426 kJ/mol, respectively, which was calculated by M062X/631+G(3df,2p) after basis set superposition error correction. It can
be seen that breaking of these bonds and forming free-radical needs
quite high external energy, indicating the difculty for levoglucosan formation via free-radical mechanism. It can be seen that
the C1 O bond is slightly weaker than O C4 bond, the probable reason is the C1 O5 bond linked with O is weaker than the
C4 C3 bond on the other side of O atom. The two types of freeradical should be co-existed in the system because of the slightly
difference of the bond energy, only 4 kJ/mol. The free-radical structure A formed from the C1 O bond cleavage will be considered in
the following study, which is supported by two reasons, one is the
slight weakness of C1 O bond than O C4 bond, and another reason is the geometry of free-radical A is easier for the formation of
levoglucosan.
Once the free radical is formed from cellulose chain cleavage,
these radicals can be transferred into levoglucosan. The mechanism for levoglucosan formation from free-radical A was described
detailed in our previous work [27]. As shown in Fig. 3, from freeradical A, rstly there is a hydrogen-donor reaction. A hydrogen
atom H6c transfers from one oxygen atom O1 to another oxygen
atom O. Then, there is a possible reaction because of a strong afnity between the active oxygen atom O1 and the active carbon atom
C1. If there is a bond formed between them, product levolgucosan
can be formed with a bridged structure. For this bridged structure
formation step, the singlet state is more stable than the triplet state,
which veries that there is one bond formed by the two unpaired
electrons from intermediate to form the product. The driving forces
for this pathway are the two unpaired electrons from the oxygen atom O1 and the carbon atom C1. It can be seen that product
levoglucosan is much more stable than the reactant free radical.

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X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

Fig. 5. Two possible positions for the hydrolysis of cellobiosan.

Even the activation energy for the formation of levoglucosan from

free-radical is not so high; however, free-radical mechanism needs
huge external energy due to the homogeneous cleavage of cellulose chain, which is the determining step for the whole free-radical
mechanism.
The geometries of the two transition states in free-radical
mechanism M1-TS1 and M1-TS2 were shown in Fig. 4. Both M1TS1 and M1-TS2 has exactly one imaginary frequency, which is
1717 icm1 for M1-TS1, and 88 icm1 for M1-TS2. The vibration
of M1-TS1 is the stretching of hydrogen atom between two oxygen
atoms. And for M1-TS2, there is a stretching between the atoms of
O1 and C1. M1-TS1 has triplet ground state, and for M1-TS2, the
ground state is singlet, indicated that there are two unpaired electrons during the rst reaction step, the two unpaired electrons form
one bond during the second step.
3.2. Glucose intermediate mechanism (M2)

Fig. 4. Structures of the two transition states during free-radical mechanism. The
unit for bond length is . (a) Transition state M1-TS1, (b) Transition state M1-TS2.

In the glucose intermediate mechanism (as called M2), cellulose

rstly is decomposed into glucose units by hydrolysis, then levoglucosan can be formed from these glucose units by dehydration.
For the hydrolysis step, similar with the two cleavage positions
for the free-radical mechanism, water can react with cellulose at
two possible positions, C1 O bond and O C4 bond as shown in
Fig. 5. In this study, we assumed the process into a cellobiosan reacts

Fig. 6. Energy illustration and geometries change for hydrolysis of cellobiosan for formation of two glucose units.

X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

23

Fig. 9. Structure of the transition state for formation of levoglucosan during dehydration of glucose. The unit for bond length is .

Fig. 7. Structures of two transition states for the hydrolysis of cellobiosan. The unit
for bond length is . (a) Transition state M2-TS1. (b) Transition state M2-TS1 .

with one water molecule to form two glucose units. The energy
illustrations for the reaction at these two positions are shown in
Fig. 6. One water molecule reacts with cellobiosan, and try to break
the bond C1 O and O C4 respectively. Two glucose units can be
produced by both pathways shown in Fig. 6. At position C1 O, one
hydroxyl group from water bonds with C1, and the hydrogen atom
from water bonds with oxygen atom O, simultaneously with the

breaking of C1 O. Similarly, at position O C4 , hydroxyl group and

hydrogen atom from water can form bonds with C4 and oxygen
O, respectively, with the breaking of O C4 bond and formation of
two glucoses. It can be seen that the energy barrier for hydrolysis
at C1 O position is 264 kJ/mol. However, for hydrolysis at O C4
position the energy barrier is 346 kJ/mol, indicating that C1 O is the
possible position for the cleavage of C O bond in cellulose chain by
hydrolysis. The possible reason is the weaker bond of C1 O than
O C4 . However, the C1 O is only 4 kJ/mol slightly weaker than
O C4 , so it can be concluded that the energy difference of C1 O
and O C4 bond is enlarged when reacting with water rather than

Fig. 8. Energy illustration and geometries change for LG formation via glucose intermediate mechanism.

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X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

Fig. 10. Energy illustration and geometries change for levoglucosan formation via LG chain-end intermediate mechanism.

the direct bond breaking, which indicates that the weakness of a

bond can be enlarged during hydrolysis.
The structures for the two transition states for the hydration
of cellobiosan were shown in Fig. 7. Both of these two transition
states have an imaginary frequency, which is 259 icm1 for M2TS1, and 882 icm1 for M2-TS1 . For M2-TS1, the vibrations under
the imaginary frequency are stretching of the C1 O and O H bonds,
with the tendency of new bonds formation between C1 OH and
O H. Compared with M2-TS1 , M2-TS1 is a reasonable transition
state for hydrolysis due to the lower activation energy.
After hydrolysis of cellulose, the glucose unit formed from
hydration of cellulose chain can produce levoglucosan by getting
rid of water. The energy illustration and geometries changes for the
whole glucose mechanism including of the hydrolysis and dehydration steps were shown in Fig. 8. For the hydration of cellulose
chain, only the position C1 O was considered here because the
lower energy barrier than the position of O C4 . For the dehydration step, it can be seen that a hydrogen atom from O1 and a
hydroxyl group from C1 form a water molecule and released further
from glucose, and the remained part is levoglucosan with a bond
formation between O1 and C1. The activation energy for the dehydration step is 227 kJ/mol, compared with the activation energy of
hydrolysis step, 264 kJ/mol, it can be concluded that the hydrolysis step is the rate-determining step for the whole levoglucosan
formation process via glucose intermediate mechanism.
The structure of the transition state for the dehydration from
glucose to levoglucosan was shown in Fig. 9. The imaginary frequency for this transition state is 193 icm1 , with vibration of
stretching between O1 and hydrogen atom, C1 and hydroxyl group.
3.3. LG chain-end mechanism (M3)
Levoglucosan formation via LG chain-end intermediate mechanism (as called M3) happens through two transglycosylation steps,
the formation of the LG chain-end structure intermediate and
the formation of levoglucosan from the LG chain-end structure

intermediate. The energy illustration and geometries change for

LG chain-end mechanism were shown in Fig. 10.
For the formation of LG chain-end intermediate, there is one
transglycosylation elementary reaction. From the structure of M3TS1, we can see that three phenomena are happened during this
elementary reaction: rstly the cleavage of the C1 O bond; secondly one hydrogen atom H6c transfers from O1 to the oxygen O;
and at last a new bond formed by C1 and O1. Similar processes
happen for second step: the formation of levoglucosan from LG
chain-end intermediate. The activation energies for the two steps
are 195 kJ/mol and 182 kJ/mol, respectively. Which showed the rst
step is the rate-determining step.
The structures for the two transition states for LG chain-end
mechanism were shown in Fig. 11. It can be seen that the two transition state has similar bond change. There is a ring-closing process
with a hydrogen shifting. The imaginary frequency for these two
transition states are 431 icm1 and 413 icm1 respectively.
3.4. Comparison of all the calculated mechanisms for
levoglucosan formation
The energy diagrams for the three mechanisms are shown in
Fig. 12, it can be seen that levoglucosan formed from free-radical
mechanism is the most difcult pathway due to the high energy
barrier for the cleavage of the C O bonds in cellulose chain. The levoglucosan formed via glucose intermediate needs lower activation
energy than the free-radical mechanism. However, LG chain-end
mechanism gives the lowest energy barrier. The activation energy
obtained from the experimental results [10,12,35] are also shown
in Fig. 12, it can be seen that the general range for the activation
energy obtained from experiments are 151228 kJ/mol. The energy
barrier for free-radical mechanism can be obtained from the energy
barrier for direct breaking C1 O bond. The energy barrier for freeradical mechanism is quite high, about 422 kJ/mol. The activation
energies for glucose intermediate mechanism and LG chain-end
mechanism are 264 kJ/mol and 195 kJ/mol, respectively. It can be

X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

25

Fig. 11. Structure of two transition states involved in the LG chain-end intermediate mechanism. The unit for bond length is . (a) Transition state M3-TS1. (b) Transition
state M3-TS2.

concluded that the activation energy calculated from LG chain-end

mechanism is the closest with the experimental result.
By comparing the three mechanism and their elementary steps,
the most important thermal properties including activation energy,
energy change, Gibbs free energy change, Gibbs free energy barrier, and enthalpy change were shown in Table 1. The rst column
gives the detailed activation energy for every pathway and elementary step, which is same with what can be obtained from Fig. 12.
The Ea are listed here just for comparison. The second and fth
columns give the thermal energy changes and enthalpy changes
for every pathway and elementary reactions, respectively. It can be
seen that no matter which pathway, there is no big difference for
the global energy change from the reactant cellulose and product
levoglucosan. Take enthalpy for example, the enthalpy change is

106 kJ/mol for free-radical mechanism, 73 kJ/mol for glucose mechanism, and 102 kJ/mol for LG chain-end mechanism. All the thermal
energy and enthalpy change shows that it is an endothermic reaction for the formation of levoglucosan from cellulose. The fourth
column gives the Gibbs energy barrier for all the pathways, it also
shows that LG chain-end mechanism gives lowest energy barrier,
which is same trend which was reected by the activation energy
Ea .
From the calculation for the three mechanisms for levoglucosan formation, it can be seen that the rate-determining step for
free-radical mechanism is the direct breaking of C1 O bond. The
rate-determining step for glucose intermediate mechanism is the
formation of glucose from cellulose chain, which simultaneously
with the breaking of C1 O bond. And for LG chain-end mechanism

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X. Zhang et al. / Journal of Analytical and Applied Pyrolysis 104 (2013) 1927

Fig. 12. Comparison of the energy barrier of experiment and different calculated levoglucosan formation mechanisms.

Table 1
Comparison of activation energy (Ea ), energy change (E), Gibbs free energy change (G), Gibbs free energy change between transition state and reactant (G ), and enthalpy
change (H) for the three mechanisms for LG formation from cellulose. The unit is kJ/mol.
Ea
Free-radical mechaniam (M1)
Step 1: from cellulose to free-radical
Step 2: from free-radical to LG
Glucose mechanism (M2)
Step 1: from cellulose to glucose
Step 2: from glucose to LG
LG chain-end mechanism (M3)
Step 1: from cellulose to LG chain-end intermediate
Step 2: from LG chain-end intermediate to LG

48
264
264
227
195
195
182

for levoglucosan formation, the rate-determining step is the rst

transglycosylation step with the formation of a LG chain-end intermediate and a glucose, which happens with breaking of C1 O at the
same time. So it can be concluded that breaking of C1 O bond is the
rate-determining step for levoglucosan step no matter via which
mechanism. Free-radical mechanism needs more energy because
of the difculty of breaking C1 O bond directly. Glucose intermediate mechanism needs lower energy than free-radical mechanism
because it is easier to break C1 O bond due to the existing of water
molecule in the process. And LG chain-end mechanism needs lowest energy barrier because of it is easiest to break the C1 O bond
by transglycosylation.

E

G

G

H

81
406
325
71
24
47
97
58
39

28
343
315
18
14
4
12
6
6

60
307
307
226
193
193
183

84
409
325
73
24
49
102
60
42

enlarged during the hydrolysis process, the water molecule reacts

at C1 O position gives much lower activation energy than that at
O C4 position, the activation energy difference is about 78 kJ/mol.
The rate-determining step for all these three mechanisms is
the one with breaking of C1 O bond. Free-radical mechanism has
high energy barrier because of the difculty of breaking C1 O bond
directly. C1 O bond can be easier broken when there exist water
molecule to form glucose.
During the three mechanisms for levoglucosan, LG chain-end
mechanism which happens via two transglycosylation steps is the
most reasonable pathway.
Acknowledgments

4. Conclusions
Three mechanisms for levoglucosan formation during cellulose pyrolysis are studied and compared in this work, which are
free-radical mechanism, glucose intermediate mechanism, and LG
chain-end mechanism. Firstly, it was concluded that the formation
of levoglucosan from cellulose is endothermic no matter via which
pathway.
In cellulose chain, C1 O bond is slightly weaker than the bond
O C4 , with an energy difference of 4 kJ/mol. But this trend can be

Financial support from Vetenskapsrdet (Swedish Research

Council) is highly appreciated. One of the authors, Xiaolei Zhang,
would also like to acknowledge nancial support from the Chinese
Scholarship Council (CSC).
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