Fuel Vol. 76, No. 13, pp.

1277-1282, 1997
© 1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
ELSEVIER Plh S0016-2361(97)00106-3 0016-2361/97 $17,00+0.00

Effects of particle size, heating rate

and pressure on measurement of
pyrolysis kinetics by
thermogravimetric analysis

Veronika Seebauer, Josef Petek and Gernot Staudinger

Institut for Verfahrenstechnik, Technical University Graz, Inffeldgasse 25, A-8010 Graz, Austria
(Received 22 October 1996; revised 24 April 1997)

Experiments using varied particle size, heating rate and pressure with a high-volatile bituminous coal were
undertaken to determine possible effects of these experimental parameters on coal pyrolysis experiments. The
results show that secondary reactions can influence the results to a large extent. For the particle size in particular it
is established that the optimum is not a bed of very fine particles, since detailed gas analysis by FT-i.r.
spectroscopy reveals a clear trend in the composition of the product gas which can be related to secondary tar
cracking in the bed. Furthermore, it is concluded that vapour pressure equations cannot be used directly to describe
the evolution of tar. © 1997 Elsevier Science Ltd.

(Keywords: coal pyrolysis kinetics; thermogravimetric analysis; secondary reactions)

Thermogravimetric analysis (t.g.a.) is widely used to
determine the rate of decomposition reactions occurring in
solid fuels under the action of heat. Several publications 1-4
have reported mass loss data obtained at constant heating
rate, often combined with detailed gas analysis of the
volatiles. The results of such measurements often form the
basis for determining kinetic parameters which are used in
more or less elaborate models for the pyrolysis of coal,
biomass or other solid fuels 5-8.
Experimental techniques used by other authors for the
investigation of pyrolysis are the wire-mesh reactor, various
kinds of entrained-flow reactor such as the drop-tube
reactor, fluidized beds or fixed beds. Each method has
certain advantages and limitations 9.
The advantages of a t.g.a, experiment are the accurate
measurement of the sample temperature and the possibility
of combination with an extensive gas analysis system.
However, due to the large sample mass needed to achieve
good quality in gas analysis, such experiments risk being
influenced by the operating parameters of particle size,
heating rate and pressure.
The present paper aims at elucidating the effects of these
parameters on the pyrolysis of coal and compares the
findings with models of vapour-liquid equilibrium for tar.
EXPERIMENTAL
The rmogravimetric analyser ( t.g.a. )
The t.g.a, works in the temperature range up to 1100°C
and pressures up to 4 MPa. As shown in Figure 1, the
sample is suspended by a microbalance located above an
electrically heated reactor. To protect the balance from the
hot product gases, its housing is flushed with a separate gas
flow. Nitrogen is used for both the gas flow through the
balance and the reactor sweep gas. These are both controlled
by mass flow controllers. The gas stream from the reactor
including the product gas is mixed with the balance flush
and flows through a high-pressure filter to precipitate the
condensable substances which are summarized by the term
'tar'. Because of the filter temperature of 15°C, water is not
condensed. The cylindrical sample basket, - 9 mm in
diameter and 30 mm long, is made of Incoloy 800 wire
mesh. The temperature of the sample is measured by a
thermocouple placed upstream, a few millimetres beneath
the sample basket. The main characteristics of the t.g.a, are
summarized in Table I and a more detailed description of its
design and operation is given elsewhere 10.¿~.
Gas analysis
The composition of the uncondensable pyrolysis products
was analysed by Fourier transform infrared (FT-i.r.)
spectrometry and thermal conductivity hydrogen analysers.
A spectrometer with a long-path minicell (path length
1.8 m) was used. The F/'-i.r. range between 4000 and
400 cm -I was scanned with a resolution of 1 cm -I in the
single-scan mode. Focus was placed on the quantitative
analysis of the main components, namely carbon monoxide,
carbon dioxide, methane, ethane, ethene, propane and
propene.
Since one experiment yields up to 350 spectra, a quick but
accurate method to determine the correlation of the
measured spectra with the actual concentrations had to be
developed. Specific problems arose from the fact that the
gas concentrations were rapidly changing and that certain

Fuel 1997 Volume 76 Number 13 1277

Measurement of pyrolysis kinetics by thermogravimetric analysis: V. Seebauer et al.

balanceflush (N2)

samplelock 4======1

coolant expansionvalve

sample holder ~ I1,111,11 Iill i H t° ga~analysia

in the reaet°r i ~ H
coo,an

reactor flush (N2) I ~ high-pressure

filter

Figure 1 Schematic of the thermogravimetric analyser (t.g.a.)

Table 1 Characteristics of the thermogravimetric analyser was connected to the system to check the validity of the F r -
i.r. data.
Temperature -< 1 IO0°C
Pressure - 4 MPa Samples
Heating rate 2 - 6 0 K min -~
Sample mass ~1 g The fuel investigated was Westerholt (Germany) high-
Reactor sweepgas 2 . 4 L m i n -~ N2(s.t.p.) volatile bituminous coal, the proximate and ultimate
Balance flush 1.2 L min -r N2 (s.t.p.) analyses of which are shown in Table 3. The coal samples

Table 2 Gas species analysed by FT-i.r. spectroscopy

Wavenumber (cm -t) Range 1 (ppmv) Range 2 (ppmv) Comment
CO 2172 600 6000
CO2 617 -- 3200 at high concentrations
CO2 668 315 -- at low concentrations
CH4 3086 1030 5200 influenced by other hydrocarbons
C2H6 2895 500 5200 influenced by CH4, C3H8, C3H6
C 2H 4 949 140 1500 influenced by C3H6
C 3H 8 2967 380 1500 influenced by CH 4, C2H 6, C3H6
C3H6 912 140 1500 influenced by C 2H4
H zO 1844 -- --

species interact in the absorption spectra. The spectra were
evaluated by the application of calibration curves obtained
with special gas mixtures and from dilution series of single
gases. The peak height at a wavenumber significant for the
gas species considered was filtered from the multifile
containing the complete record of the spectra over time. In
some cases the peak height was influenced by the presence
of one or more other gases, so that special algorithms had to
be used to deconvolute the spectra. The relation between
absorption and concentration was not linear in all cases.
Table 2 gives an overview of the gases analysed by FF-i.r.
spectroscopy. Since symmetric molecules consisting of two
atoms are not infrared-active, the gas stream also flowed
through two thermal conductivity hydrogen analysers. Two
devices were used so as to cover a wide range of
concentration with good resolution at low concentrations.
The data obtained had to be corrected for sensitivity to water
and hydrocarbons. In addition, a carbon monoxide analyser
were crushed in a mortar, sieved into fractions between 100
and 2000/zm and dried for 2 h at 105°C in an oven.
RESULTS AND DISCUSSION
Effect of particle size
To investigate the influence of particle size the following
parameters were kept constant: pressure 0.1 MPa; final
temperature 1000°C; heating rate 5 K min -~ started at
100°C. The particle size was varied in five fractions
between 100 and 2000/~m. A cylindrical particle with a
diameter of 9 mm and a length of 25 mm, referred to as the
'single particle' was also pyrolysed for comparison.
The total volatile yield was calculated from the mass loss
in the t.g.a. 'Detected gases' are the sum of CO, CO2,
methane, ethane, ethene, propane, propene and hydrogen.
'Tar + water' is the difference between the total volatiles
and detected gases.

1278 Fuel 1997 Volume 76 Number 13

 Measurement of pyrolysis kinetics by thermogravimetric analysis: V. Seebauer et al.

Table 3 Proximate and ultimate analyses (wt% daf) of Wester- 0,12

holt coal ~ I00-125~m
Moisture" 2.4
Ash h 3.4 0,09 +400-500 pm r ~/7~\
Volatiles 40.4 E ~ 8oo_1ooo~Jm ]
Fixed C 59.6 O
o
C 85.0 "5 0,06
H 5.6
O 6.7
N 1.53
S 1.15 o 0,03

"As-received basis n,'

bDry basis
0,00
0 200 400 600
Temperature (°C)
800 1000

4%
[] 100-12s.m Figure 3 Effect of particle size on formation of CO
[I l i j200-2 0.m
/I I I 11 illl j 8OO-lOOOpm 40/0 I
t111 Ililll =16oo-2ooo,m,, I I r-~l~ r-12 K/rain
[] Single particle
o /I il HEll ~-~ m3 K/rain

/l|il IIlll 120 K/rain I

;~%11111 d~ Ii1111 , 4 o K/min : I~
0% , ~ : : ' : ' ', , ; /111 /II!11 1ffll60K/min Ili~

Figure 2 Effect of particle size on yields of gaseous components 1°/

0% lillllllll
o
. .
~
. .
~ ~
.E
rlillm]
~
, --~i --' [i~S
~
, i'ililM
~
Q.
,

No significant differences in total volatiles, detected

gases or tar + water were found between the different
milled fractions. All showed a similar value of - 3 2 wt% daf
total volatile yield. For the single particle, the total volatile
yield was much higher, namely 37 wt%; in this case the
detected gases decreased and tar + water increased
dramatically. Closer examination of the evolved gases
showed differences between the size fractions (Figure 2):
CO, CO; and H2 decreased with increasing particle size,
whereas methane, ethane and propane increased.
The initial porosity of the single particle was - 4 vol.%
and therefore the residence time of the product gas in the
pores was less than in the voidage of the bed, which was in
the range 48-63 vol.% (fraction 100-125 #m, 63 vol.%;
200-250/~m, 57 vol.%; 400-500/~m, 53 vol.%; 800-
1000 #m, 49 vol.%; 1600-2000/~m, 48 vol.%). The differ-
ences in bed porosity between the smaller fractions were
much more pronounced than between the larger fractions.
According to the theory of secondary reactions, the tar is
cracked during transport in the pores of the coal particles,
leading to the formation of CO, methane and soot. Therefore
less tar and more CO and methane should be observed for
larger particles, with longer pores. However, the opposite
was observed. On the other hand, cracking of the tar can also
take place within the fixed bed, in the voids between the
particles. The larger the particles, the higher is the apparent
density and the lower the bed porosity. Hence the larger the
particles, the shorter is the residence time of the tar in the
bed. The single particle shows the highest ultimate yield
because the tar is swept away by the flushing gas
immediately and there is no time for secondary reactions
on the hot surface of the particle.
Figure 3 shows the evolution of CO versus temperature,
Figure 4 Effect of heating rate on yields of gaseous components
revealing a sequence of three significant peaks. The curve is
reduced in height with increasing particle size and
decreasing void space. The single particle shows the
lowest rate of CO formation. Thus the formation of CO
can be directly related to the bed porosity, which seems
to play an important role in the secondary reactions of the
tar.
Effect of heating rate
To investigate the effect of heating rate, the 400-500 #m
size fraction was used at a pressure of 0.1 MPa with a
temperature range of 100-1000°C. A restriction in experi-
ments at high heating rates is the minimum time interval of
32 s between two FT-i.r. measurements. At 60 K min -1 the
whole evolution curve of a gas species consists of only 30
data points, which causes inaccuracies in the evaluation, but
the weight signal is registered separately every 2 s by the
t.g.a.
The yield of volatiles increases with increasing heating
rate, but because of the small range of heating rates applied
the differences in ultimate yield are low. According to
Gibbins-Matham and Kandiyoti 12 the increase in total
volatile yield is mainly due to enhanced tar production.
The reason for this behaviour is the existence of two
competing reactions both consuming the 'metaplast' phase:
tar evaporation and char formation. The higher the heating
rate, the less time is available for tar cracking and
consequently the more tar and the less methane are
produced.

Fuel 1997 V o l u m e 76 N u m b e r 13 1279

Measurement of pyrolysis kinetics by thermogravimetric analysis: V. Seebauer et al.

0,20 0,20
-*- 2 K/min f-t ~0.1 MPa 1
3 K/min ~. ~. 0,16 ~ 0 . 4 MPa /
0,16 o~
J~
--~'1 MPa L
E~
E~ - - 20 K/min ~ 2 MPa I
'5 v 0,12 3 ~ o,12
._~~
) 0,0,
3 MPa I
._~ ~, ~ 4 MPa j
) §o,o6 Z:2::: ,
rr 0,04
(~
tic 0,04

0,00
0,00 r ----
0 200 400 600 800 1000
200 400 600 800 100 Temperature (°C)
Temperature (°C)
Figure 8 Effect of pressure on formation of methane
Figure 5 Effect of heating rate on formation of methane

3,0
+0.1 MPa 1
2,5
40%

30%
4-
~ 2,0 "-04Pa/ I
-,,-1 MPa
~ 2 MPa
~3MPa
h
/
/
=o'O
~ 1,5
4 MPa ]

3,5 1,0
~20%
0,5
,,,,% ~ ~.
10% 0,0
200 400 600 800 1000
Temperature (°C)
0% Figure 9 Effect of pressure on formation of tar + water
Total volatiles Detected gases Tar + water

Figure 6 Effect of pressure on total yields

the kinetic parameters and the available time. Since
pyrolysis experiments at higher heating rates have a shorter
reaction time (between 100 and 1000°C), the product
4%
evolution (which does not occur instantaneously) is shifted
El0.1 MPa
to higher temperatures.
/ " 0 ' 4 MPa
3% In those cases where the rates of formation of a gas
species did not differ even though different heating rates
l~mill~ I:m mill / • 2 MPa were used, heat transfer limitation in the experimental
2% system is the most probable reason.

t]m[Illl [ N4MPa
"o

Effect of pressure
1%
The effect of pressure is the most distinct: it had strong
influence on the yields of total volatiles, detected gases
0%
[j 11111,lU =milL,I| 1=111,E,Hilll, r~,.~, I!H 1=11,~, tl I=111 and tar -t- water (Figure 6). The total volatile yield
o ~ ~ ~ ~ ~ ~ ~: decreased by - 2 0 % , from 37 to 30 wt% daf. The tar +
0 ~ ~ 0a

n o_
Figure 7 Effect of pressure on yields of gaseous components
In this investigation the sum of gases formed remained
more or less constant, but a shift between the species could
be observed (Figure 4): hydrocarbons and hydrogen
decreased with increasing heating rate, whereas CO2
increased.
As an example of the effect of heating rate on the
evolution of all pyrolysis product gases, the evolution of
methane is shown in Figure 5, where a shift in the peak
towards higher temperatures can be observed. This shift can
be explained by the reaction kinetics: the amount of product
formed depends on the concentration of the reacting agent,
water fraction showed an even more distinct dependence,
since the detected gases slightly increased with increasing
pressure.
Pressure exerts the greatest influence on those compounds
which according to Solomon et al. 13 are related to cross-
linking reactions of the metaplast. Such reaction products
are CO2 and methane, which increase with pressure, as can
be seen in Figure 7. In contrast, ethane, ethene, propene
and H2 decreased, while CO remained more or less
constant. Solomon et al. 13 define two sorts of cross-linking
reactions. Low-temperature cross-linking takes place
between 200 and 450°C and is related to the formation of
CO2 and water. Moderate-temperature cross-linking occurs
between 450 and 600°C, associated with the formation of
methane.
The formation of methane is shown in Figure 8 as a

1280 Fuel 1997 Volume 76 Number 13

 Measurement of pyrolysis kinetics by thermogravimetric analysis: V. Seebauer et a l.
function of pressure. At different pressures the peaks start at
approximately the same temperature of 350°C, but with
increasing pressure the formation of methane takes a longer
time and becomes more pronounced at higher temperatures.
A possible explanation for this behaviour is that at higher
pressures the tar evaporation is suppressed and thus cross-
linking reactions yielding methane gain importance.
Propane showed the same trend as methane.
The other hydrocarbons investigated did not show a
relation to cross-linking reactions, because they appeared at
the same temperature, independent of pressure. Furthermore
the yield of e.g. ethane decreased in approximately the same
ratio as the tar + water yield was reduced (Figure 9), so the
formation of ethane was proportional to the tar production.
This was also true for ethene and propene, which showed
the same behaviour as ethane.
Comparing the formation of methane and tar + water, it is
evident that methane and also propane originate from
sources other than tar and the other hydrocarbons.
Comparison with models of vapour-liquid equilibrium of
tar
To describe the effects of heating rate and pressure on the
ultimate tar yield and on the composition of the condensable
pyrolysis products, several models for coal pyrolysis
contain mechanisms which consist of the following steps:
• thermal degradation of the coal structure yielding macro-
molecules or clusters of different size ('bridge-breaking',
'metaplast formation'),
followed by the competing steps of
• evaporation of the resulting small and medium-sized
molecules determined by vapour-liquid equilibria
and
• condensation of the fragments to form large highly aro-
matic structures ('cross-linking', 'char formation').
Fletcher et al. ~4 give a summary of several models ~5-17,
applying a vapour pressure equation of the form:
PV = e~ e x p ( - ~8(MW)7-) (1)
where pv denotes the vapour pressure of tar molecule i
(atm), MW is the molecular mass (g mol -j) and T is the
temperature (K). The constants or, ~ and 3' given by the
authors concerned are listed in Table 4. Fletcher et al.
showed that their model (FGP) performed best in compar-
ison with measured values of vapour pressures of narrow-
boiling fractions of coal liquids and with the boiling points
of organic compounds at different pressures, while other
equations turned out to be fitted statistically to yield the
measured molecular weight distribution of the tar. Therefore
further comparison focuses on the FGP constants.
Figure 9 shows the rate of formation of the tar + water
fraction (calculated from the volatiles evolution measured
by the weight loss and the amount of gases detected in the
gas analysers) in the pressure range 0.1-4 MPa. With
increasing pressure a clear decrease in the total yield of this
fraction can be observed, but also a slight shift in the onset
of evolution and in the peak position towards lower
temperature. Yet the overall temperature range in which
the evolution of tar 4- water takes place remains
approximately the same, i.e. between 300 and 600°C.
If the mechanism for the evolution of tar were simply the
evaporation of molecules of different sizes from a liquid
phase, an increase in pressure should result in a shift in the
Table 4 Constants in the vapour pressure equation (Equation (1))
given by different authors
oe (atm) • 7
Unger and Suuberg 15 5756 255 0.586
Niksa 16 69.2 1.6 1
Niksa and Kerstein 17 296077 200 0.6
Fletcher et al. ~4 (FGP) 87 060 299 0.59
4 MPa
0.1 MPa
0.04 MPa
0.001 MPa
0 100 200 300 400 500 600 700
Molar weight (g/mole)
Figure 1O Molecular size range of tar tractions reaching the
indicated vapour pressure in the temperature range 300-600°C,
calculated from Equation (1)
stage of evolution towards higher temperatures. According
to the FGP equation a molecule of size 500 g m o l - 1reaches
a partial pressure of 0.01 atm at a bulk pressure of 1 atm at a
temperature of 458°C, whereas the same partial pressure at
40 atm (i.e. a vapour pressure of 0.4 atm) is reached at
677°C. On the other hand, tar contains a large fraction of
components with a molecular mass < 200 g mo1-1 which
already develop a considerable vapour pressure at tempera-
tures well below 300°C.
In Figure 10 the size range of molecules is shown which
according to Equation (1) reach a certain vapour pressure--
4, 0.1, 0.04 and 0.00l M P a - - i n the temperature range 300-
600°C. As the composition of the boiling fraction changes
dramatically with pressure, the trend which was found in
Figure 9, i.e. that the tar evolution decreases with increasing
pressure but remains at the same temperature location
(between 300 and 600°C at a heating rate of 5 K min-I),
cannot be explained by a simple evaporation mechanism.
Therefore other mechanisms have to be included which
help to resolve these discrepancies. It is obvious that at first,
tar precursors have to be formed before any tar can evolve.
Kinetic models that include the breaking of bridges in the
molecular structure of the coal or simply the formation of
'metaplast' succeed in the description of the onset of tar
evolution, since the kinetic parameters of these scission
mechanisms determine the evolution of substances of low
molecular mass.
A more complex mechanism has to be invoked to explain
the fact that the peaks of the evolution of tar shift to lower
temperature with increasing pressure and that tar evolution
ends at -600°C, independent of the bulk pressure.
Reactions among the molecules in the mobile phase which
combine the aromatic structures of the tar precursors to form
char represent the most probable mechanism that gives rise
to the phenomena observed at different pressures and
heating rates. At higher pressures these so-called 'cross-
linking' reactions lead to a higher char yield since the tar
precursors are kept in the mobile phase for longer and at
Fuel 1997 V o l u m e 76 N u m b e r 13 1281
Measurement of pyrolysis kinetics by thermogravimetric analysis: V. Seebauer et al.
higher temperature, so that more char is formed. On the
other hand the bridge-breaking mechanism takes place in a
more interconnected structure, so it can only produce
smaller fractions which evaporate at lower temperature.
High heating rates cause the evaporation of larger fragments
before the cross-linking reactions become effective, and
thus the total volatile yield and in particular the tar yield are
very sensitive to the heating rate.
However, a major problem remains with the mechanisms
described above: neither the process of bridge-breaking nor
the cross-linking reactions can be directly quantified in
pyrolysis experiments, since only the overall process of the
gas and tar evolution can be recorded. Of course,
experimental data on e.g. solvent swelling of the coal and
char or the molecular weight distribution of the tar can give
considerable information about the amount of cross-linking
or bridge-breaking, but in the end it is the total volatile yield
of the pyrolysis experiment that is decisive. Furthermore, it
must be considered that the more parameters a model
combines, on the one hand the easier it is to conform with
experimental results, but on the other hand the more difficult
it is to verify the assumptions concerning a single step in the
sequence of mechanisms.
CONCLUSIONS
The main conclusion to be drawn from this study is that
t.g.a, experiments alone cannot be used to derive kinetic
parameters for pyrolytic reactions. Although such experi-
ments offer the possibility of very precise analysis of the
evolving non-condensable gases, it is evident that there are
large effects of the bed of particles. For example, the use of
smaller particles led to a higher extent of secondary
reactions, i.e. lower tar yields and higher yields of the
gases produced by cracking reactions (e.g. carbon dioxide,
methane). Nevertheless, the information about the composi-
tion of the primary pyrolysis products (although it may be
altered to a certain extent by secondary reactions) still
constitutes a basic fact for the modelling of pyrolysis
reactions. It is suggested that the use of a single particle in a
t.g.a, experiment at low heating rates leads to gas analysis
data which are less influenced by secondary reactions.
Future work will be dedicated to the combination of t.g.a.
results with data for other reactor types.
From the data on the effect of pressure, it must be
concluded that the vapour pressure equations cited above
cannot be directly used to describe the evolution of tar as a
function of pressure and heating rate. Actually the models
1282 Fuel 1997 Volume 76 Number 13
using such vapour pressure equations always link the tar
evolution to other reactions in the metaplast phase, such as
bridge-breaking or cross-linking, or to overall assumptions
concerning mass transport (entrainment of large molecules).
Since the parameters of these processes are not experimen-
tally accessible and thus represent only a fit to the actual
outcome of the experiment, the authors suggest deriving
directly a simple kinetic model for the evolution of tar and
the formation of char with the parameters heating rate and
pressure.
ACKNOWLEDGEMENTS
This work was supported by the Austrian Science Founda-
tion FWF (Project No. S06803) and the Austrian Federal
Ministry of Science and Transport.
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