Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215

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Journal of Analytical and Applied Pyrolysis

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Thermal cracking of 1-n-butyldecalin at high pressure (100 bar)

Darwin A. Rakotoalimanana a , Roda Bounaceur a,∗ , Baptiste Sirjean a , Françoise Béhar b ,
Valérie Burklé-Vitzthum a , Paul-Marie Marquaire a
a
Laboratoire Réactions et Génie des Procédés, UMR 7274, CNRS-UL, Nancy, F-54001, France
b
Total Exploration and Production, Paris La Défense, F-92078, France

a r t i c l e i n f o a b s t r a c t

Article history: The pyrolysis of 1-n-butyldecalin at high pressure (100 bar) was studied in gold sealed tube reactors at
Received 24 May 2016 400 ◦ C. It leads to 4 main chemical families of products in order of predominance: (a) normal alkanes
Received in revised form (methane, ethane, propane and n-butane), (b) bicyclics (decalin and 1-methyldecalin), (c) hydroaromat-
10 November 2016
ics (tetralin and 5-methyltetralin) and (d) diaramatics (naphthalene and 1-methylnaphthalene). This
Accepted 8 December 2016
distribution of products suggests that breaking of side alkyl chain and aromatization reactions should
Available online 10 December 2016
prevail at high pressure and low temperature. Reaction pathways are effectively proposed to account for
the formation of main products. Both normal alkanes (except CH4 and C2 H6 ) and bicyclics should mainly
Keywords:
Butyldecalin
come from C C bond breaking reactions on the side alkyl chain of 1-n-butyldecalin. Methane and ethane
Pyrolysis should come from further decomposition of fuel radicals, including ring opening through beta-scissions
Naphthene given the absence of any C12 and C13 compounds in similar quantities. Both hydroaromatics and diaromat-
High pressure ics are secondary products, which result from aromatization reactions of decalin and 1-methyldecalin. In
Reaction pathways our conditions, 1-n-butyldecalin and n-butylcyclohexane have a similar thermal reactivity. A higher yield
in n-butane was observed in the case of 1-n-butyldecalin. In comparison with the pyrolysis of decalin at
low pressure (≤1 atm) and high temperature (>500 ◦ C), the production of naphthalene and the absence
of any BTX (Benzene, Toluene and Xylene) in detectable quantities is here worth mentioning.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction cyclic model compound i.e. n-butylcyclohexane. It completed other

An estimation of the thermal evolution during geological time
(millions of years) of reservoir oils requires a good knowledge of the
kinetics of the thermal cracking reactions [1] occurring at high pres-
sure (100–1000 bar) and low temperature (150–220 ◦ C). The first
step consists in simulating those reactions at laboratory scale by
studying kinetically the pyrolysis of oils e.g. [2], oil fractions e.g. [3]
or model compounds e.g. [4–8] at high pressure (100–700 bar) but
at higher temperature (300–450 ◦ C) to obtain acceptable reaction
times (from few hours to 1 month).
As petroleum constitutes a very complex chemical system
with hundreds of compounds, it is necessary to firstly elucidate
the chemistry of thermal cracking of each main chemical family
i.e. alkanes e.g. [4,5], aromatics [7,8] and naphthenes e.g. [9,10].
Our previous paper [11] highlighted the lack of knowledge of
the thermal cracking of naphthenes and presented experimental
results of the pyrolysis at 100 bar and around 400 ◦ C of a mono-
∗ Corresponding author.
E-mail address: roda.bounaceur@univ-lorraine.fr (R. Bounaceur).
previous results on alkylcyclohexanes e.g. [9,10] at high pres-
sure (100–400 bar). These studies confirm altogether the inductive
effect of the side alkyl chain of the thermal reactivity of an alkylcy-
clohexane in these conditions. This is also supported by mechanistic
approaches, either via quantum chemical calculations e.g. [12,13]
or free-radical detailed mechanisms e.g. [14,15]. Breaking of side
alkyl chain and aromatization reactions effectively prevail over ring
opening at reservoir conditions, which leads to a large amount of
normal alkanes, as main pyrolysis products alongside with unsub-
stistuted and methylated cyclics in lower quantities.
Tissot and Welte [1] showed the predominance of monocyclic
and also bicyclic compounds among naphthenes in most reservoir
oils. Some examples of compounds are depicted in Fig. 1.
Yet, until now, the literature on the thermal cracking of bicyclic
naphthene only concerns the decalin (Fig. 1) at higher tempera-
ture (≥450 ◦ C) and mostly at atmospheric pressure (oil refining
conditions). Bredael and Rietvele [16] initiated the study of the
pyrolysis of decalin to compare it with tetralin in terms of yields
in benzene, toluene and xylene (BTX) for steam-cracking process.
By operating at 700–950 ◦ C and 0.5 bar in heated quartz reac-
tor, they showed that the thermal cracking of decalin results in

http://dx.doi.org/10.1016/j.jaap.2016.12.001
0165-2370/© 2016 Elsevier B.V. All rights reserved.
 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215 205

Fig. 1. Structure of di- and tricyclic compounds.

a ring opening in these conditions and ultimately leads to large Table 1

Structure of 1-n-butyldecalin (BD).
yields in BTX with an optimum at 900 ◦ C. Virk et al. [17] compared
the pyrolysis of cyclohexane, decalin and perhydrophenanthrene Compound Formula Structure M (g/mol) Densitya
to propose reaction pathways based on free-radical mechanisms
leading to benzene from decalin and perhydrophenanthrene.
Ondrushka et al. [18] studied the pyrolysis of decalin in a BD C14H26 194 0.849
tubular quartz reactor (600–800 ◦ C, 1 bar) and focused on the
formation of olefins (unsaturated hydrocarbons) and particularly
3-methylenecyclohexene to propose some free-radical mecha- a
Determined at 20 ◦ C and 1 bar.
nisms. They also noticed the absence of naphthalene among the
pyrolysis products in their conditions. In supercritical conditions Table 2
(550–750 ◦ C, 2–100 bar), Stewart et al. [19] compared the pyroly- Mass balances of pyrolysis of 1-BD in gold tubes.
sis of n-decane, decalin and tetralin. At 414 bar and between 460
t Charge Gas BD C6+ DCM total Conversion
and 540 ◦ C, decalin mainly leads to the formation of small normal h mg mg/g %
alkanes (ie. methane, propane, propane and butane) but also to
0 100 0 1000.0 0 0 1000.0 0
methylcyclohexene and methylhexahydroindane. They showed a 9 101.7 22.7 902.6 38.4 0 963.7 9.7
tendency of cycle contraction, which turns out to be even more 24 102.0 48.1 821.6 92.5 0.9 963.0 17.8
favored at higher pressure, which was supported by previous 48 77.0 125.8 698.0 144.0 1.5 969.3 30.2
work of Metzger et al. [20]. Yu and Eser [21] proposed decom- 72 77.0 171.2 584.3 207.4 2.6 965.5 41.6
144 52.4 242.9 310.0 421.9 3.1 978.0 69.0
position pathways of decalin based on free-radical mechanisms
to describe the formation of these products and pointed out that
isomerization reactions are significant at high pressure (450 ◦ C,
23–75 bar). configuration isomers (e.g. 2-n-butyldecalin). The properties of BD
Following works aimed at modeling the thermal cracking of are given in Table 1.
decalin at atmospheric pressure to better understand the thermal
cracking and the oxidation at high temperature (>500 ◦ C) of fuel or 2.1. Pyrolysis of 1-n-butyldecalin (1-BD)
jet fuels. Chae and Violi [22] implemented an ab initio approach to
elucidate main decomposition reaction pathways at atmospheric The recently-developed protocol [11] was implemented to
pressure and in the temperature range of 550–1300 ◦ C leading kinetically study the pyrolysis of BD at high pressure (100 bar) and
to BTX compounds. Dagaut et al. [23] proposed semi-detailed 400 ◦ C. The chosen conditions are provided in Table 2.
free-radical mechanism (11,000 reactions) validated at high tem- Pyrolysis experiments were carried out in gold sealed tubes in an
perature (>500 ◦ C) and atmospheric pressure with the results of isobaric and isothermal regime. Given the chemical inertia, ductil-
Zámostný et al. [24] among others. This model was recently adapted ity and malleability of gold material, these reactors appear to be the
by Zhu et al. [25] to account for the results obtained at higher most convenient to kinetic studies of high pressure pyrolysis e.g.
pressure i.e. 20–50 bar. Another smaller detailed free-radical model [6–8,27,28]. A preliminary step consisted in eliminating any pos-
(1774 reactions) was developed by Zeng et al. [26] at atmospheric sible impurities of the walls of the tubes. The tubes were heated
pressure and higher temperature i.e. 650–1230 ◦ C to show that (700 ◦ C) for 1 h, boiled in hydrochloric acid (1N) and finally washed
the formation of monocyclic aromatic hydrocarbons prevails over with distillate water and acetone. The gold tubes were loaded with
the formation of polycyclic aromatic hydrocarbons at these condi- a charge of 50–100 mg and sealed by an ultrasonic welding sys-
tions. tem (Telsonic) in an anoxic environment (i.e. N2 atmosphere) to
The current kinetic study of the pyrolysis of 1-n-butyldecalin avoid any air contamination which would lead to the formation of
at 100 bar provides supplementary insights in better understand- unwanted compounds such as oxygenated hydrocarbons. This step
ing the thermal cracking of naphthenes at high pressure and was effectively realized in a glove box, whose oxygen concentration
low temperature (400 ◦ C). The possible kinetic effect of a second was controlled below 10 ppm.
cycle is here investigated in comparison with n-butylcyclohexane For each experiment, 2–6 tubes were confined into a N2 -
[11]. Besides, comparison with the thermal cracking of decalin pressurized autoclave to apply to the chosen pyrolysis conditions.
at high pressure is also made in this paper. Some reaction path- This autoclave was then placed in a preheated oven, where temper-
ways are proposed to account for the formation of main pyrolysis ature (confidence interval of 1 ◦ C) and pressure (confidence interval
products. of 0.1 bar) were kept constant: real-time values were measured and
recorded. Once the temperature in the autoclave core was stabi-
lized at the chosen value, pyrolysis time was initiated. At the end
2. Material and methods of the pyrolysis time, the hot autoclave was thermally quenched
in a water bath at room temperature (around 20 ◦ C) and then
BD (C14 H26 ) was synthesized by BOC Sciences Creatives slowly depressurized to avoid any possible rupture of the tubes.
Dynamics Inc. (USA). The purity (≥98%) was certified by gas chro- The extracted tubes were eventually checked for any leakage of
matography – mass spectrometer (GCMS). Impurities were mostly products by weighing.
206 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215

Fig. 2. Chromatogram of C6+ HC pyrolysis products at 400 ◦ C, 100 bar and after 144 h.

2.2. Analysis of products Table 3

Main hydrocarbon products at 400 ◦ C and 100 bar.

The same analytical protocol as for the study of the thermal Alkanes
cracking of n-butylcyclohexane at 100 bar [11] was followed to
Methane (C1 ) Ethane (C2 ) n-Propane (C3 ) n-Butane (C4 )
recover and analyze pyrolysis products. For each pyrolysis condi- n-Pentane Isobutane Isopentane
tion, the analysis of the gaseous and liquid products was separated.
Thus, at least 2 tubes were treated. Alkenes

Ethylene Propylene
2.2.1. Gaseous products
The gold tubes were pierced within a closed system. The gaseous Cyclics

products were recovered through a vacuum line equipped with a

vacuum pump leading to a fixed-volume sealed tank. Thanks to a
pressure gauge, the total quantity of gas generated during pyrolysis
was determined before being injected in GC (HP 6890). GC was
equipped with two detectors: a flame ionization detector (FID) for Decalin (D) 1-Methyldecalin (MD) 1-n-Butyldecalin (BD)
C1 -C5 hydrocarbons (HC) and a thermal conductivity detector (TCD)
for non-HC compounds (H2 and N2 in our study). GC was calibrated Hydroaromatics
with a standard gas.

2.2.2. Liquid products

The first step consisted in slowly releasing the gaseous phase
Tetralin (T) 5-Methyltetraline (MT)
while avoiding any loss of the volatile products. The gold tubes
were actually pierced in a glass device filled with a “cold” pen- Diaromatics
tane solution, whose temperature was maintained below 15 ◦ C by
an external dry ice bath. The two following steps corresponded
to two extractions of the first solution containing the tube cut up
(successively with pentane and dichloromethane) under reflux for
1 h followed by a filtration step. Both extraction volumes were Naphthalene (N) 1-Methylnaphthalene (MN)
exactly weighed along the whole process, before and after sam-
pling aliquots for composition analyses, i.e. molecular identification
and quantification. Hydrocarbon compounds soluble in pentane not fully quantified, as pentane corresponds to our main solvent.
were firstly identified by a HP 5973 mass spectrometer Mass Selec- However, gas analysis provided an estimation of a part of C5
tive Detector (MSD) coupled to a GC, and then quantified by a gaseous HC. Furthermore, the processing of the gold tube during
HP 6890 GC FID. Complete setting of both analytical apparatus the experiments (piercing, cutting) could account for some mass
was accurately described in our previous paper [11]. No molecu- loss (estimated to 1 or 2 mg/g).
lar identification of compounds soluble in dichloromethane was
performed, as they correspond to a very minor fraction (Table 2). 3. Results

2.3. Mass balances 3.1. Products

Systematic mass balances were calculated for each experiment
to guarantee a quasi-full recovery of the pyrolysis products. Mean
values corresponding to at least 2 experiments are given in Table 2.
4 fractions were considered in the mass balance: “gas” fraction
(C1 –C5 HC and H2 ), “C6+ ” fraction (C6+ HC soluble in pentane), “BD”
fraction (remaining reactant) and “DCM” fraction (C14+ HC not solu-
ble in pentane but in dichloromethane). It is worth mentioning that
no black solid residue was observed on the walls of the gold tubes in
our pyrolysis conditions contrary to the case of n-butylcyclohexane
[11].
We obtained globally good mass balances (above 96%). Some
uncertainties still remained: C5 hydrocarbon compounds were
Fig. 2 shows an overview of the main pyrolysis products in the
“C6+ ” fraction at 400 ◦ C, 100 bar and after 144 h (conversion of about
70%). It is worth mentioning the quite low number of pyrolysis
products: 6 main products can be distinguished. The products (2)
and (3) could not be identified by mass spectrometer with a suffi-
cient matching percentage. However, structure related compounds
are proposed and are actually quite consistent with decalin related
literature e.g. [16].
The exact structures of the main hydrocarbon products of the
pyrolysis of 1-BD at 400 ◦ C and 100 bar are provided in Table 3.
The “gas” fraction is mostly consisting of normal- and iso-alkanes
alongside with alkenes and hydrogen (not depicted in Table 3).
 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215
100
80
Conversion (%)
60 BCH
40 BD
20
0 two possible pathways for both fuels, which eventually lead to
0 24 48 72 96 120 144
Time (h)
Fig. 3. Conversions at 400 ◦ C and 100 bar of 1-n-butyldecalin (1),
butylcyclohexane (2).
In the “C6+ ” fraction, 3 chemical families are identified: cyclics
(derivatives of decalin), hydroaromatics (derivatives of tetralin)
and diaromatics (derivatives of naphthalene).
The distribution of the products suggests two main reaction
pathways: breakings (in alpha and beta position from the cycle)
of the alkyl side chain and aromatization of the saturated rings. It
is worth emphasizing the presence of naphthalene, which is not
detected (or traces) during the pyrolysis of decalin at higher tem-
perature (>500 ◦ C) and 50 bar. In these conditions, decalin rather
leads to BTX compounds by ring opening [19], which are absent in
our distribution of products.
3.2. Conversion
The conversion of BD was calculated by difference between the
initial load of reactant and its remaining quantity after pyroly-
sis. The initial load reactant was determined by direct weighing
whereas the remaining quantity was obtained by integration of
the corresponding GC peak. Results (mean values) as time func-
tion, at 400 ◦ C and 100 bar, are given in Fig. 3 (lines corresponding
to trends). In the meantime, results are compared with the con-
version of n-butylcyclohexane in the same conditions [11]. At
400 ◦ C and 100 bar, 1-n-butyldecalin is slightly more stable than n-
butylcyclohexane. This small difference could be explained by the
presence of both hydroaromatics and diaromatics, which have an
inhibiting effect on the thermal cracking of normal alkanes [29,30].
Thus, the second cycle seems to have no significant kinetic effect
in comparison with n-butylcyclohexane (BCH) in our experimental
conditions.
3.3. Yields of products
The yields (in molar fraction) of the main pyrolysis products at
400 ◦ C as time function are given in Table 4. Those compounds cor-
respond to the two major fractions “Gas” and “C6+ ”. Fig. 4 depicts
the corresponding curves vs. time of products of the “gas” frac-
tion (methane, ethane, propane and n-butane). Previous results on
pyrolysis of n-butylcyclohexane at 400 ◦ C and 100 bar [11] are also
reported in Fig. 4 to draw a parallel between the two compounds.
In the “gas” fraction at 400 ◦ C, we obtain propane > n-
butane ≈ ethane > methane, in order of predominance. This is
consistent with the presence of unsubstituted and methy-
lated compounds in “C6+ ” fraction. In comparison with n-
butylcyclohexane, the yields of normal alkanes (except for n
butane) are smaller. This difference could suggest that the side
alkyl chain is less subjected to breaking reactions in the case of 1-
n-butyldecalin (Fig. 5). This is actually supported by the calculation
of BDE (Fig. 8): the C C bonds on the side alkyl of 1-n-butyldecalin
are globally stronger than the corresponding C C bonds of n-
207
butylcyclohexane. Concerning the higher yield in n-butane in the
case of 1-n-butyldecalin, a possible explanation could be inferred
from a mechanistic point of view along BDE values of both fuels
(Fig. 8). In a previous paper [15], we showed that normal alka-
nes mainly come from breaking reaction of the side alkyl chain
of n-butylcyclohexane (␤-scission reaction of butylcyclohexyl rad-
ical followed by H-transfer reaction) at 100 bar and around 400 ◦ C.
Thus, an analogy could be made here.
Taking into account the double degeneracy of n-
butylcyclohexane due to its structural symmetry, there are
n-butane. Regarding radical sites of fuel radicals, a slight difference
could be here highlighted. In the case of 1-n-butyldecalin, one of
n-
them corresponds to a radical center on a tertiary carbon, whose
formation is de facto favored, as the corresponding hydrogen atom
is more labile (lower C H bond BDE). However, this is not enough
to explain the clear difference in yield in n-butane. All reaction
pathways such as further decomposition of fuel radical following
ring opening by beta-scission should be also considered (detailed
in next section).
Fig. 6 depicts the corresponding curves vs. time of the
“C6+ ”fraction (decalin, tetralin, naphthalene, 1-methyldecalin, 5-
methyltetralin and 1-methylnaphthalene).
Among the “C6+ ” HC products, unsubstituted compounds prevail
over methylated compounds. We could here infer that dealky-
lation reactions are relatively more significant than breaking
reactions in ␤-position from the cycle. Concerning the unsubsti-
tuted hydrocarbons, we have decalin > tetralin > naphthalene, in
order of predominance. This shows that aromatization reactions
(aromatization of one cycle at a time) are also major degradations
pathways of 1-n-butyldecalin at 400 ◦ C. This is also supported by
the profiles of naphthalene and 1-methylnaphthelene, with a flat
tangent from the diagram’s zero.
3.4. Trends of products organized by chemical family
Balances of chemical families are usually done in petroleum geo-
chemistry. This is illustrated in Fig. 7 for the 1-n-butylcyclohexane
and compared with the case of n-butylcyclohexane. At 400 ◦ C,
we obtained a large amount of normal alkanes (more than 40
molar% after 144 h). In order of predominance, we had then
cyclics > hydroaromatics > diaromatics. This is actually similar to
the case of n-butylcyclohexane at 400 ◦ C, which confirms that both
model compounds have similar chemistry of thermal cracking at
high pressure. Subsequently, the second cycle of 1-n-butyldecalin
does not have any significant effect, in comparison with n-
butylcyclohexane.
4. Discussion
4.1. Bond dissociation energies
Bond dissociation energies (BDE) of 1-n butyldecalin (in the
trans configuration) were computed using Gaussian09 software
[31]. For the C H and C C bonds located outside the decalin bicycle,
the high-level composite CBS-QB3 method [32] was applied. The
bond breaking of C C bonds belonging to the decalin bicycle leads
to the formation of singlet diradicals. To compute the BDE of these
electronic structures, the CBS-QB3’ method, modified for open shell
single biradicals [33], was used. It should be noted that the BDE of
acyclic hydrocarbons is equivalent to the activation energy required
to break the bond because the reverse reaction, i.e., the combi-
nation, is barrierless. In the case of initial C C bond scissions in
cyclic alkanes, the reverse combination of the biradical into the
cycloalkane features a small reaction barrier. Therefore, the energy
208 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215

Table 4
Yields of main products at 400 ◦ C and 100 bar vs. time.

Products

T (◦ C) 400
t (h) 9 24 48 72 144
Conversion (%) 9.7 17.8 30.2 41.6 69.0

“Gas” fraction
H2 3.0 4.9 5.2 4.4 2.6
CH4 1.2 2.6 4.0 5.1 7.0
C2 H6 1.5 3.0 5.8 7.4 10.4
C2 H4 0.0 0.0 0.0 0.0 0.0
C3 H8 2.2 5.2 11.5 13.9 17.1
C3 H6 0.1 0.1 0.1 0.1 0.1
i-C4 H10 0.6 0.2 0.4 1.2 0.4
n-C4 H10 2.1 4.0 8.1 10.2 11.5
i-C5 H12 0.0 0.0 0.1 0.2 0.3
n-C5 H12 0.0 0.1 0.4 0.5 0.6

“C6+ ” fraction
Decalin 1.3 4.1 6.1 8.0 10.8
1-Methyldecalin 0.3 0.8 1.2 1.5 2.0
Tetralin 0.6 1.6 3.0 4.3 8.6
5-Methyltetralin 0.3 0.6 1.6 1.9 4.1
Naphthalene 0.0 0.2 0.7 1.1 3.6
1-Methylnaphthalene 0.0 0.0 0.2 0.4 2.8

N-ALKANES
Methane Ethane
15 15
Mole fracon (%)

Mole fracon (%)

10 10

5 5

0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h)

Propane n-Butane
25 15
Mole fracon (%)

Mole fracon (%)

20
10
15
10 5
5
0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h)
Fig. 4. Profiles of “gas fraction” at 400 ◦ C and 100 bar: BD (1) and BCH (2) (trends in dotted line).

Fig. 5. ␤-scission reactions on n-butylcyclohexane (1) and 1-n-butyldecaline (2) leading to n-butane.
 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215 209

CYCLICS HYDROAROMATICS DIAROMATICS

Decalin Tetralin Naphthalene
15 10 4

Mole fracon (%)

Mole fracon (%)

Mole fracon (%)
8 3
10
6
2
4
5
2 1
0 0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h) Time (h)

1-Methyldecalin 5-Metyltetralin 1-Methylnaphthalene

2.5 5 3

Mole fracon (%)

Mole fracon (%)

Mole fracon (%)

2.0 4
2
1.5 3
1.0 2
1
0.5 1
0.0 0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h) Time (h)

Fig. 6. Profiles of “C6+ fraction” at 400 ◦ C and 100 bar (trends in dotted line).

BD BCH
50 70
60
Mole fracon (%)

Mole fracon (%)

40
Alkanes 50
30 40 Alkanes
Cyclics (no BD)
20 30 Cyclics (no BCH)
Hydroaromacs
20
10 Diaromacs Aromacs
10
0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h)
◦
Fig. 7. Evolution of chemical families versus time at 400 C and 100 bar (trends in dotted lines).

Fig. 8. Bond dissociation energies of 1-n-butyldecalin computed at the CBS-QB3 and CBS-QB3 levels of calculations (see text). (a) C C and (b) C H calculated bond
dissociation energies.
210 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215
required to break the C C bond of the ring is an activation energy
defined as the energy difference between the transition state (TS)
and the reactant [34]. In this study, the BDE leading to biradicals
were calculated as an activation energy (HTS – Hreactant at 298 K).
Fig. 8 presents the results of the BDE calculations.
4.2. Reaction pathways
In a similar way to the case of n-butylcyclohexane [11,15], some
reaction pathways based on free-radical mechanisms are given
here to explain the formation of normal alkanes and main “C6+ ”
products i.e. cyclics, hydroaromatics and diaromatics. The reaction
schemes proposed in this subsection should provide guidelines to
an eventual detailed kinetic modeling of the thermal cracking of
1-n-butyldecalin at high pressure (>50 bar), as the development
of a detailed kinetic model is not the scope of this work. Aside
[15], two previous works of modeling on similar fuels are worth
here being mentioned. Dagaut et al. [23] developed an 11.000
reaction model to describe the decalin oxidation and pyrolysis
between 480 ◦ C and 1080 ◦ C and at 1 and 10 bar. For similar con-
ditions (650–1330 ◦ C, 0,04–1 bar), Zheng et al. [26] also recently
built a model consisting of 1774 reactions to describe decalin
pyrolysis. Out of structure-related point about decalin and 1-n-
butyldecalin (asymmetry and presence of a side alkyl chain), one
clear difference remains: conditions of pressure and temperature
as explained in Bounaceur et al. [35] who studied the pyrolysis
of n-octane at temperature around 400 ◦ C and pressure ranging
from 1 to 1000 bar. The authors clearly explained that, depend-
ing on temperature and pressure range, both the chemistry and
the chemical compounds are different. This is actually illustrated
by the difference of product distribution. Zeng et al. observed
relatively high yields in monoaromatics and polyaroaromatics
whereas these compounds correspond to the small fraction in our
study.
4.2.1. Formation of normal alkanes
n-Butane and n-Propane should mainly come from C C bond
breaking reactions on the side alkyl chain of 1-n-butyldecalin.
More precisely, 1-n-butyldecalin is firstly initiated by H-transfer
reactions, leading to the formation of 14 cyclic radicals (Fig. 9).
Radicals R6 and R5 then undergo respectively C C bond ␤-scission
to form, on the one hand, octalin and n-butane, and on the other
hand, 1-methylenedecalin and n-propane after metathesis. It is
worth mentioning that the side products such as octalin and 1-
methylenedecalin were not detected among pyrolysis products
but constitutes precursors to hydroaromatics and/or diaromatics
(described in later subsections).
Concerning the formation of methane and ethane, such direct
pathways of dealkylation do not seem justified, as no C12 and C13
were observed in significant quantities among pyrolysis products.
Methane and ethane should come from further decomposition of
fuel radicals, including ring opening (Fig. 9) by beta-scission, which
results in the formation of very reactive intermediary radicals (with
an unsaturation). In a similar way to n-butylcyclohexane [15], oth-
ers reactions could occur such as isomerization (intramolecular
relocalization of radical site) or resonance equilibrium (when the
radical site is located near the unsaturation). As already showed
in [15], the resulting “network” of reactions corresponds to a sec-
ondary source of alkanes. We have not detected any compound
with two or more unsaturation as diene or triene. Then, as shown in
Fig. 9, these compounds can react via addition with radicals becom-
ing another source of alkanes or are unresolved compound. For each
pyrolysis condition, 2–4 tubes were heated simultaneously and
analyzed for a better consistency of the experimental results. Glob-
ally, mass balances were mainly were between 96% and 98%, which
is totally satisfying (Table 2). So we can consider that even if these
compounds have not been detected, their concentrations are very
low.
4.2.2. Formation of cyclics
Cyclics should mainly come from C C bond breaking reactions
on the side alkyl chain of 1-n-butyldecalin, as normal alkanes.
More precisely, radicals R2 and R3 (Fig. 9) undergo respectively
C C bond ␤-scission to form, on the one hand, propylene and 1-
methyldecalin, and on the other hand, but-1-ene and decalin after
metathesis (Fig. 10). As in the case of n-butylcyclohexane [15],
alkenes should be quickly consumed by hydrogenation (due to
the presence of H2 in the reaction medium) and addition reac-
tions with other radicals (e.g. alkyl radicals). H2 is effectively
the major gaseous product at the beginning of the reaction and
after 18 h, its molar fraction decreases as a function of time
(Table 4).
Another reaction pathway would be the initiations of 1-n-
butyldecalin by unimolecular C C bonds homolysis, followed by
H-transfer reactions. However, it was previously showed [6] that H-
transfer reactions prevail at high pressure over unimolecular bond
homolysis.
4.2.3. Formation of hydroaromatics
The aromatization pathways of decalin and 1-methyldecalin
leading respectively to tetralin and 5-methyltetralin are similar to
the aromatization pathways of alkylcyclohexanes during the pyrol-
ysis of n-butylcyclohexane at high pressure [11]. Different steps are
depicted in Fig. 11 and include successive reactions of H-transfer
and C H bond ␤-scission. Given the presence of H• and CH3 • in the
reaction medium, we can also assume an interconversion between
unsubstituted and methylated compounds by ipso-addition reac-
tions.
4.2.4. Formation of diaromatics
The formation of diaromatics from hydroaromatics constitutes
the step that follows the aromatization of cyclics into hydroaromat-
ics. Thus, the formation of diaromatics follows the same reaction
pathways as already described in 4.1.2 (Fig. 12).
4.3. Comparison with other studies
4.3.1. Effect of the number of cycles on reactivity
No significant difference was observed between the thermal
conversion of n-butylcyclohexane and 1-n-butyldecalin at 400 ◦ C
and 100 bar. Furthermore, no significant difference was found
between the yields of normal alkanes, except for n-butane, which
is favored in the case of 1-n-butyldecalin.
However, considering the reaction pathways of both n-
butylcyclohexane [11,15] and 1-n-butyldecalin, some differences
could be observed, as 1-n-butyldecalin leads to three tertiary
radicals, whose formation is favored. Two consequences could
be drawn from this point: firstly, it should favor the formation
of n-butane (Subsection 3.3) and also free-radical aromati-
zation reactions. This brings us to another major difference
with n-butylcyclohexane, which quickly forms n-butylbenzene at
400 ◦ C and 100 bar. In the case of 1-n-butyldecalin, neither 5-n-
butyltetralin nor 1-n-butylnaphthalene was observed in the same
conditions.
4.3.2. Conditions high temperature/low pressure
As aforementioned, comparisons of our current results with
other works [17,16,19,21,22] on the thermal cracking of decalin
at high temperature (>500 ◦ C) and low pressure (≈1 bar) empha-
size two major differences. In these conditions, the pyrolysis
of decalin does not produce naphthalene but rather BTX
compounds in high yields. The inverse case is obtained for
 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215 211

Fig. 9. Examples of reaction pathways leading to alkanes.

the 1-n-butyldecalin at 400 ◦ C and 100 bar: no BTX com- 4.4. Application to thermal cracking of reservoir oils
pounds but production of naphthalene in the whole conversion
range. In the context of petroleum geochemistry, both monocyclic
and bicyclic compounds are major compounds among naph-
212 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215

Fig. 10. Reaction pathways leading to 1-methyldecalin and decalin.

Fig. 11. Reaction pathways leading to tetralin and 5-methyltetralin.

thenes in reservoir oils [1]. In Fig. 13, the thermal decomposition
of n-butylcyclohexane (monocyclic model compound) and 1-n-
butyldecalin (bicyclic model compound) are compared in terms of
chemical families (in wt%).
For both compounds, we obtain the same order of predomi-
nance: alkanes > cyclics (either mono- or bi-) > aromatics (either
mono- or diaromatics). However, in the case of 1-n-butyldecalin,
the relative significant production of hydroaromatics is worth men-
tioning, they are known to be inhibitors of the thermal cracking
of normal alkanes [29,30]. Thus, the presence of a second cycle
seems to induce others products i.e hydroaromatics in comparison
with monocyclics at high pressure and low temperature (reservoir
conditions).
4.5. Molecular kinetics model at 400 ◦ C and 100 bar
According to Table 4, we have a constant production as func-
tion of time for all pyrolysis products 400 ◦ C, it is then reasonable
to develop a one-step global stoichiometric reaction model, which
is mainly derived from experimental data. Assuming a first-order
kinetic law, kinetic parameters and stoichiometric coefficients
were numerically optimized according with our experimental data,
which needed to be expressed in weight fraction in this case. The
 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215 213

Fig. 12. Reaction pathways leading to naphthalene and 1-methylnaphthalene.

Fig. 13. Thermal decompositions of n-butylcyclohexane (left) and 1-n-butyldecalin (right).

BD Alkanes
Weight fracon (wt %)

100 16
Weight fracon (wt %)

80 12
Exp
60
Sim 8 C3
40
C1
20 4

0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h)

Alkanes Cyclics
Weight fracon (wt %)
Weight fracon (wt %)

16 16

12 12 D
C4
8 8 MD
C2
4 4

0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h)

Hydroaromacs Diaromacs
Weight fracon (wt %)

Weight fracon (wt %)

6
10
8 4
T N
6
MT MN
4 2
2
0 0
0 24 48 72 96 120 144 0 24 48 72 96 120 144
Time (h) Time (h)

Fig. 14. Comparison between simulated using stoichiometric model (lines) and experimental (dots) profiles of products at 400 ◦ C.
214 D.A. Rakotoalimanana et al. / Journal of Analytical and Applied Pyrolysis 123 (2017) 204–215
optimization was performed with the IFP GeoKin Compositional
software [2], using the method of least squares i.e. minimizing the
function F:

n
F= rk 2 withrk = wk exp − wk sim
k=1
where wk corresponds to the weight fraction of the product k and
n the total number of products. We obtained for our case the fol-
lowing one -step model. The corresponding nomenclature is given
in Table 3.
BD → 2.40C1 + 7.31C2 + 20.28C3 + 20.71C4 + 21.98D + 6.05MD
+10.68T + 6.76MT + 2.51N + 1.02MT
Simulated results (expressed in wt%) of our optimized one-step
model are compared with our experimental at 400 ◦ C in Fig. 14.
Globally, a very good agreement is reached with experimen-
tal data for both degradation of 1-n-butyldecalin and profiles
of products, except the case of hydroaromatics and diaromatics,
where the model starts to diverge after 72 h by underestimat-
ing experimental values. This was expected as these compounds
correspond to secondary products (c.f. Subsection 4.1). Thus, a one-
step reaction could not take into account this aspect. Given this
stoichiometric reaction, a rate constant at 400 ◦ C could be cal-
culated: at 400 ◦ C, we obtained a value of kBD = 1.83 × 10−6 s−1 .
This value can be compared to the case of n-butylcyclohexane
(kBCH = 2.44 × 10−6 s−1 ) [11]. Thus, it confirms that 1-n-butyldecalin
and n-butylcyclohexane have a similar reactivity at 400 ◦ C and
100 bar, while 1-n-butyldecalin still remains slightly less reactive
than n-butylcyclohexane. By assuming the same global activa-
tion energy, we obtained a frequency factor for 1-n-butyldecalin:
A = 5.0 × 1016 s−1 (vs 6.7 × 1016 s−1 for n-butylcyclohexane).
5. Conclusions
In this paper, we investigated the thermal cracking of an
alkylated decalin at high pressure (100 bar) and 400 ◦ C. The exper-
imental and analytical protocols are the same as described in our
previous paper [11], to study the pyrolysis of 1-n-butyldecalin at
400 ◦ C and 100 bar in gold tube reactors in isothermal and isobaric
regime.
At 400 ◦ C and 100 bar, the pyrolysis of 1-n-butyldecalin leads
in order of predominance: small normal alkanes (from C1 to C4 ),
cyclics (decalin and 1-methyldecalin), hydroaromatics (tetralin
and 5-methyltetralin) and diaromatics (naphthalene and 1-
methylnaphthalene). At a conversion of 40% we obtain 51 wt% of
alkanes, 28 wt% of bicyclics, 17 wt% of hydroaromatics and 4 wt%
of diaromatics. In comparison with the pyrolysis of decalin at
atmospheric pressure and high temperature, it is worth mention-
ing both the formation of naphthalene and the absence of any
BTX compounds. Our experimental results showed no significant
difference of thermal reactivity between 1-n-butyldecalin and n-
butylcyclohexane at 400 ◦ C and 100 bar. Thus, a second cycle seems
to have no effect in comparison with n-butylcyclohexane in these
conditions, except for the formation of hydroaromatics.
Reaction pathways based on free-radical mechanisms are pro-
posed to explain the formation of main pyrolysis products. Both
normal alkanes (except methane and ethane) and cyclics should
result from breaking reactions of the side alkyl chain of 1-n-
butyldecalin. The reaction pathway to methane and ethane consists
in decomposition of fuel radical, including ring opening by beta-
scissions, isomerization and resonance equilibrium. The proposed
mechanism are supported by the calculation of BDE of C H and C C
bonds of 1-n-butyldecalin, which could partly explain some differ-
ence compared to pyrolysis of n-butylcyclohexane: C C bonds are
globally stronger in 1-n-butyldecalin than in n-butylcyclohexane.
Hydroaromatics and diaromatics should be formed by successive
aromatization reactions of both saturated cycles of decalin and
1-methyldecalin. Given these free-radical mechanisms, an expla-
nation is provided to account for a higher yield of n-butane in
comparison with n-butylcyclohexane. In the meantime, a one-
step global reaction model was developed at 400 ◦ C and optimized
with the experimental results. This model allowed us to esti-
mate decomposition rate constant of 1-n-butyldecalin at 400 ◦ C:
1.83 × 10−6 s−1 .
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