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Proceedings of the Combustion Institute 000 (2016) 1–10

www.elsevier.com/locate/proci

Pyrolysis and oxidation of methyl acetate in a shock

tube: A multi-species time-history study
Wei Ren a,∗, King-Yiu Lam b, David F. Davidson b, Ronald K. Hanson b,
Xueliang Yang c
a Department of Mechanical and Automation Engineering, The Chinese University of Hong Kong, New Territories, Hong
Kong
b Department of Mechanical Engineering, Stanford University, Stanford, CA 94305, USA
c Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544, USA

Received 2 December 2015; accepted 15 May 2016

Available online xxx

Abstract

High-temperature methyl acetate (MA) pyrolysis and oxidation were studied behind reflected shock waves
using laser-absorption species time-history measurements of CO, CO2 , OH and H2 O. The shock tube exper-
iments with very dilute fuel mixtures covered a temperature range of 1401–1605 K for MA pyrolysis (0.2%
MA/Ar) and 1423–1674 K for MA oxidation (0.4% O2 , φ = 1), and pressures around 1.5 atm. The dominant
sensitivity of CO2 concentration to MA unimolecular decomposition reactions enabled accurate determina-
tion of the rate coefficient and dissociation branching ratio by monitoring the CO2 time-history during MA
pyrolysis. A recent kinetic mechanism developed by Yang et al. [13] originally for interpreting flow reactor
and low-pressure flame data was adopted to simulate and compare with the current shock tube data. The
measured CO and CO2 time-histories during MA pyrolysis were both well-predicted by the modified Yang
et al. [13] mechanism. A relatively complete description of MA oxidation behavior was given by measuring
CO, CO2 , OH and H2 O time-histories at the same temperature and pressure (1480 K, 1.5 atm). A unique
two-stage CO2 formation during MA oxidation was clearly observed in the measured CO2 time-histories
over the entire temperature range, with the rapid pre-ignition CO2 formation analyzed to be associated with
the initial MA dissociation. Despite the overprediction of MA ignition delay times by 18–40% between 1623
and 1423 K, the kinetic model successfully captures the plateau levels and the peak values of all the measured
species profiles, as well as simulates the characteristic two-stage formation of CO2 observed experimentally.
© 2016 by The Combustion Institute. Published by Elsevier Inc.

Keywords: Shock tube; Laser absorption; Species time-history; Methyl acetate; Pyrolysis and oxidation

1. Introduction

∗Corresponding author. Tel.: +852 39439486. Methyl esters with 1–4 carbon atoms in the
E-mail address: renwei@mae.cuhk.edu.hk, renweithu aliphatic chain are normally selected in combus-
@gmail.com (W. Ren). tion research to understand the chemical kinetics

http://dx.doi.org/10.1016/j.proci.2016.05.002
1540-7489 © 2016 by The Combustion Institute. Published by Elsevier Inc.

Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
http://dx.doi.org/10.1016/j.proci.2016.05.002
JID: PROCI
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2 W. Ren et al. / Proceedings of the Combustion Institute 000 (2016) 1–10
of the ester moiety, a characteristic functional
group of biodiesel components [1–3]. Of these
short-chain methyl esters, methyl acetate (MA) is
the smallest ester containing an alkyl backbone,
showing the lowest reactivity among the C1–C4
methyl esters according to their ignition delay time
measurements [4]. Because of its unique molecular
structure, the combustion study of MA is of par-
ticular interest to the combustion community to
understand and test the chemical kinetic theory.
Only a few chemical kinetics studies of high-
temperature MA pyrolysis and oxidation can be
found in the literature. The very early studies of
MA pyrolysis led to conflicting conclusions that
the dominant reaction pathways were either the
bond-fission reactions to produce CH3 and CO2
[5], or the molecular channels to form methanol
and ketene [6], or both the bond-fission and molec-
ular channels with equal importance [7]. These
seeming discrepancies were recently clarified by
the pressure dependency of the MA dissociation
mechanism [8,9]. Peukert et al. [8] investigated
the shock tube pyrolysis of MA at 1194–1371 K
and approximately 0.5 atm using hydrogen atomic
resonance absorption spectrometry. Annesley et
al. [9] implemented the laser schlieren technique to
study MA pyrolysis at 1492–2266 K and pressures
of 60–120 Torr behind reflected shock waves. It
is concluded that the MA dissociation favors the
molecular channels to produce methanol and
ketene at extremely low pressures (10−3 Torr [6]),
rather than the radical channels dominant at
intermediate to high pressures (>30 Torr [5,8,9]).
Such kinetic modeling is consistent with another
shock tube experiment conducted by Farooq et
al. [10] to measure the CO2 concentrations during
MA pyrolysis at 1377–1623 K and approximately
1.5 atm using a laser absorption strategy.
The oxidation of MA with related chemical ki-
netics has been a subject of interest for several re-
search groups. Dagaut et al. [11] performed the first
oxidation study of MA in a jet-stirred reactor (JSR)
at 800–1230 K and 10 atm by measuring molecular
species concentration profiles with probe sampling
and GC analysis. A comprehensive kinetic mecha-
nism was developed in their study to interpret the
experimental data. Another pioneering work con-
ducted by Westbrook et al. [12] proposed a de-
tailed mechanism for a group of four alkyl esters.
That mechanism was validated against speciation
data from fuel-rich, low-pressure, premixed lami-
nar flames [12]. Very recently, Yang et al. [13] devel-
oped a kinetic mechanism with H-atom abstraction
and radical decomposition reactions of MA com-
puted by high-level ab initio and RRKM master
equation calculations. This new model was tested
against experimental data from a flow reactor and a
low-pressure flat flame using molecular-beam mass
spectrometry [13].
Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
http://dx.doi.org/10.1016/j.proci.2016.05.002
[m;June 9, 2016;10:46]
The present work extends the previous shock
tube pyrolysis of MA [10] to a much lower fuel con-
centration to reduce laser-absorption detection un-
certainties associated with temperature variation.
In addition to CO2 , CO time-histories were also
measured to aid understanding of the major de-
composition pathways of MA. Compared to the
previous oxidation studies of MA in a flow reactor
or JSR [11,13], this work extends the MA oxidation
to a shock tube investigation at higher tempera-
tures by monitoring multi-species time-histories in-
cluding OH, H2 O, CO and CO2 . Different from the
combustion characteristics of hydrocarbons and
most oxygenates, a unique two-stage CO2 forma-
tion was observed for the first time during MA oxi-
dation. Detailed kinetic modeling analysis was per-
formed to interpret the new observations and to aid
understanding of the reaction pathways during the
pyrolysis and oxidation of MA.
2. Experimental methods
2.1. Shock tube
All the experiments were performed in the
Stanford Kinetics Shock Tube with a 14.13 cm
inner diameter. Gas temperatures and pressures
behind reflected shock waves were calculated using
standard normal-shock relations and the measured
incident shock speed, with ±1% uncertainty in
temperature over a test time of 2.5 ms. Further
details on this facility are provided elsewhere
[14]. Liquid MA (>99% pure, Sigma-Aldrich)
was frozen and degassed three times to remove
dissolved volatiles. All the test mixtures were
manometrically prepared with argon as the bath
gas in a stainless-steel mixing tank (40 L), heated
uniformly to 50 °C, with an internal magnetically
driven stirrer. A MA concentration of 0.2% in Ar
was used for pyrolysis experiments, and mixtures of
MA/0.4% O2 /Ar with φ = 1 were used for oxidation
experiments. Relatively low fuel concentrations
were employed to reduce the temperature variation
during pyrolysis and oxidation processes. Several
mixtures of 300–400 ppm MA/Ar were previously
confirmed by multipass laser absorption using a
He–Ne laser [15]. The measured MA concentra-
tions were consistent with the values estimated
from the manometrical preparation within ±5%.
Considering the MA concentrations of 0.114–0.2%
used in this work, the manometrically prepared
mixtures warrant a high accuracy.
Side-wall pressure measurements utilized a
Kistler 601B1 PZT located 2 cm from the shock
tube end wall. A properly designed driver insert was
employed to eliminate the non-ideal dP/dt effect so
that near-ideal, constant-volume performance was
obtained to simplify the kinetic interpretation of
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shock tube data [16]. Two representative pressure
profiles measured during MA pyrolysis (1444 K
and 1.61 atm) and oxidation (1442 K and 1.63 atm)
are depicted in the Supplementary Fig. S1. Nearly
constant pressure traces were observed for both re-
active systems within the test time of approximately
2.5 ms.
2.2. Laser absorption diagnostics
Species-specific, time-revolved and non-
intrusive laser absorption spectroscopy (LAS)
was used for species detection behind reflected
shock waves. In LAS, the fractional transmis-
sion through the test gas inside the shock tube
is determined by Beer’s law: I/I0 = exp(−σ ni L),
where I0 and I are the incident and transmitted
laser intensity, respectively; σ (cm2 /mol) is the
known gas absorption cross-section, ni (mol/cm3 )
is the number density of the absorbing species,
and L(cm) is the optical path length. Multi-species
measurements of COx and Hx O were conducted in
the present study and briefly described here.
In MA pyrolysis experiments, CO and CO2 were
measured using two quantum cascade lasers (QCL)
near 4.6 μm and 4.2 μm, respectively. A fixed-
wavelength direct-absorption strategy was imple-
mented to detect the peak absorbance of the
CO line centered at 2193.36 cm−1 [17]. This mid-
infrared CO sensor enables ppm-level detectivity
over the temperature range of 1000–1800 K in
shock tube experiments. The CO2 diagnostic em-
ployed an external-cavity QCL to measure the peak
absorbance of a fundamental vibrational transition
at 2390.52 cm−1 . The absorption coefficient of this
CO2 transition was experimentally characterized,
providing a detection limit of 5 ppm for most high-
temperature shock tube experiments [18,19].
In oxidation experiments, H2 O and OH diag-
nostics were employed to supplement the COx diag-
nostics, to provide a more thorough description of
the oxidation behavior. The H2 O concentration was
measured using a DFB laser at 2550.96 nm within
the ν 3 -fundamental vibrational band. This absorp-
tion sensor has been well characterized previously
[20] and achieves a minimum H2 O detection sen-
sitivity of 25 ppm at 1400 K and 1.5 atm for a path
length of 15 cm. UV laser absorption of OH radical
was measured using the frequency-doubled output
of a narrow-linewidth ring dye laser near 306.7 nm,
overlapping with the well-characterized R1 (5) ab-
sorption line in the OH A–X (0,0) band [21]. A
minimum detectable OH concentration of approx-
imately 0.5 ppm could be readily achieved using a
common-mode-rejection detection scheme.
3. Results and discussion
A total of 17 reflected shock experiments
were performed to record the concentration time-
Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
http://dx.doi.org/10.1016/j.proci.2016.05.002
[m;June 9, 2016;10:46]
3
histories of COx and Hx O during the pyrolysis and
oxidation of MA. The pyrolysis experiments cov-
ered a temperature range of 1401–1605 K and pres-
sure of approximately 1.5 atm for a mixture of 0.2%
MA diluted in argon. The oxidation experiments
covered the similar temperature (1423–1674 K) and
pressure range, with 0.114% MA and 0.4% oxygen
(φ = 1) diluted in argon. The highly dilute mixtures
result in negligible temperature variation during
fuel pyrolysis and oxidation, and hence no signifi-
cant variation in the absorption cross-sections [22].
3.1. Methyl acetate pyrolysis
Fig. 1 presents the simultaneous measurement
of CO2 and CO time-histories during MA pyrolysis
along with the measurement uncertainties. The ma-
jor contributions to the measurement uncertainties
include temperature (±1%) and absorption coeffi-
cient (±3–5%), and the detailed uncertainty anal-
ysis can be found elsewhere [19,23]. At the highest
temperature of 1605 K, the CO2 and CO plateau
concentrations were measured to be 1130 ppm and
1440 ppm, respectively, recovering more than 92%
of the O-atoms in the reacting system. By com-
paring the formation rates at the early times, the
CO2 time-histories reached the plateau levels sig-
nificantly faster than that of CO. Detailed kinetic
modeling was then performed to interpret these ex-
perimental data for MA pyrolysis.
The high-temperature MA pyrolysis pathways
are governed by its unimolecular decomposition
and H-atom abstraction reactions. Basically, there
exist three major competing pathways of MA uni-
molecular dissociation including two bond-fission
channels, MA ↔ CH3 + CH3 + CO2 (Rxn. (1))
and MA ↔ CH3 OCO + CH3 (Rxn. (2)), as well as
one molecular channel, MA ↔ CH3 OH + CH2 CO
(Rxn. (3)) via a four-centered transition state [8]. Of
these reactions, the C–O bond scission leading ul-
timately to two methyl radicals and one CO2 (Rxn.
(1)) is a dominant decomposition pathway [9].
The Yang et al. [13] mechanism was used to sim-
ulate the pyrolysis experimental data. Fig. 2 de-
picts the CO2 sensitivity coefficient at 1444 K and
1.61 atm during the pyrolysis of 0.2% MA/Ar. The
time-history profile of CO2 is found to be almost
only sensitive to the three unimolecular decompo-
sition channels, with the dominant sensitivity to
the MA bond-fission reaction (Rxn. (1)). Consid-
ering that the branching ratio of Rxn. (2) is much
smaller compared with that of Rxn. (1) and the
CH3 OCO radical dissociates almost dominantly to
CH3 + CO2 [24], the contribution of Rxn. (2) can
be effectively included in Rxn. (1). The increasing
slope of CO2 concentration at early times is a direct
measure of the rate coefficient of Rxn. (1), while
the plateau CO2 concentration at later times reflects
the branching ratio of k1 /(k1 + k3 ). Therefore, k1
can be extracted by the best fit to the experimental
data at the early times, and k3 is adjusted to fit the
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4 W. Ren et al. / Proceedings of the Combustion Institute 000 (2016) 1–10

Fig. 1. Comparison of the measured (solid line) and simulated (dashed line, modified Yang et al. [13] mechanism) concen-
tration time-histories for (a) CO2 and (b) CO during the pyrolysis of 0.2% MA/Ar.

Fig. 2. CO2 sensitivity at 1444 K and 1.61 atm during the pyrolysis of 0.2% MA/Ar.

Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
http://dx.doi.org/10.1016/j.proci.2016.05.002
JID: PROCI
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W. Ren et al. / Proceedings of the Combustion Institute 000 (2016) 1–10 5

Fig. 3. Sample k1 rate coefficient determination using the mixture of 0.2% MA/Ar at 1444 K and 1.61 atm.

Fig. 4. Arrhenius plot of experimental k1 from the current work and Sulzmann et al. [5], along with the master equation
calculations from Peukert et al. [8] and Annesley et al. [9]. The rate coefficient k1 = 3.7 × 1076 T−17.3 exp(−6.16 × 104 /T,
K) s−1 given by least-squares fit (solid line) to experimental data is adopted in the modified Yang et al. [13] mechanism.

plateau. This set of experiments thus enables not
only measurement of the primary decomposition
channel but provides a relatively complete picture
of the dissociation kinetics of MA.
Simulations using the best-fit rate coefficient
(k1 ) as well as its variation by ±50% are plotted
in Fig. 3 for comparison. The Arrhenius plot for
the rate coefficients of k1 are illustrated in Fig. 4,
along with the shock tube data from Sulzmann et
al. [5] using infrared emission at 4.25 μm and UV
absorption at 216 nm, and the recent theoretical
calculations conducted by Peukert et al. [8] and
Annesley et al. [9]. The rate coefficients measured
in the present study agree with the measurements
by Sulzmann et al. [5] within the data scatter. The
current experimental results also fall between two
other recent studies conducted by Peukert et al.
[8] and Annesley et al. [9]. The current rate values
of Rxn. (1) are provided in the Supplementary Ta-
ble S1. The rate coefficient of the other dissociation
channel (k3 ) obtained from the present experiment
is about 3–4 times larger than both the theoretical
predictions [8,9], however, it is consistent with flow
reactor experiments of Yang et al. [13], in which it
was increased by a factor of 4 to fit the experimen-
tal data of CH3 OH and CH2 CO. The modified MA
sub-mechanism is provided in the Supplementary
material and the model predictions are also plotted
in Fig. 1 for comparison.
The sensitivity coefficient of CO is also ana-
lyzed at the same experimental condition as that
for CO2 (Supplementary Fig. S2). The unimolec-

Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
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6 W. Ren et al. / Proceedings of the Combustion Institute 000 (2016) 1–10

Fig. 5. Reaction flux analyses for MA pyrolysis and oxidation. Pyrolysis condition: 0.2% MA/Ar, 1444 K, 1.61 atm, 30%
fuel consumption; oxidation condition: 0.114% MA and 0.4% O2 in Ar, φ = 1, 1480 K, 1.5 atm, 30% fuel consumption. The
numbers with and without parentheses are in the cases of pyrolysis and oxidation, respectively. Dashed arrows represent
several successive elementary reactions.

ular decomposition of MA (Rxn. (1)) and the
H-abstraction from the acetyl-methyl group of
MA by CH3 have strong positive sensitivities. The
methyl–methyl recombination reactions to form
ethane and H + C2 H5 also affect the simulation
significantly with negative sensitivity for the ethane
channel and positive sensitivity for the H + C2 H5
channel. To obtain the best fit to experimental
data while keeping methyl–methyl recombination
rates unchanged, the H-abstraction rate of MA
by CH3 from the acetyl-methyl group has to be
increased by a factor of approximately 4 from the
theoretical prediction by Tan et al. [25], which is
already a factor of 2 or higher than that of Peukert
et al. [8]. This large discrepancy suggests the need
for further investigation of MA + CH3 reactions
either experimentally or theoretically to complete
our understanding of MA kinetics. Although the
rate coefficients for methyl–methyl recombination
reactions are well established, some uncertainty
over the temperature range in the present study still
exists [26] and may affect the CO time-histories.
It should be noted that the measured CO and
CO2 plateau concentrations at the highest tem-
perature cannot complete the O-atom balance.
Another 5–8% of the O-atoms may exist in the sys-
tem as H2 O that is produced via the H-abstraction
by OH radical. During MA pyrolysis, the OH
radical is merely produced from the decomposition
of CH3 OH, an intermediate of MA dissociation
(Rxn. (3)). Hence, the uncertainty of CH3 OH
kinetics may also account for the discrepancies of
the CO data as shown in Fig. 1(b).
The reaction flux analysis explored using the
Yang et al. [13] mechanism is schematically pre-
sented in Fig. 5, for the case at 1444 K and 1.61 atm
and t = 70 μs, corresponding to 30% fuel consump-
tion. It is observed that more than 45% of MA
breaks down via bond-fission reaction (Rxn. (1))
yielding two methyl radicals and one CO2 . Another
unimolecular elimination reaction (Rxn. (3)) con-
sumes another 33% of MA to produce methanol
and ketene, which decompose eventually to yield
CO. The H-abstraction reactions (by H and CH3 )
from the methoxy-methyl group consume 14.2% of
MA to produce a CH3 COOCH2 radical, followed
by β-scission to yield CH3 CO and CH2 O. There-
fore, during MA pyrolysis, CO2 is mainly formed
via MA bond fission (Rxn. (1)), while the unimolec-
ular elimination (Rxn. (3)) and H-abstraction reac-
tions of MA contribute mainly to the final CO pro-
duction.
3.2. Methyl acetate oxidation
The complete time-history data of MA oxida-
tion are provided in the Supplementary Fig. S3
along with the model predictions using the modi-
fied Yang et al. [13] mechanism. Fig. 6(a) depicts
typical measurements of four species time-histories
from three separate shock wave experiments at a

Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
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W. Ren et al. / Proceedings of the Combustion Institute 000 (2016) 1–10 7

Fig. 6. (a) Shock tube measurements and (b) simulations using the modified Yang et al. [13] mechanism for MA oxidation
at a nominal initial condition: 1480 ± 7 K, 1.5 atm, MA/0.4% O2 /Ar (φ = 1). The error bars for CO2 and OH data are too
small to show up on the graph.

nominal temperature of 1480 (±7) K and pressure
of 1.5 atm. A representative pressure trace recorded
along with the species measurements is shown at
the bottom panel of Fig. 6(a). Two-stage CO2 for-
mation was observed during MA oxidation at the
present experimental condition. In the pre-ignition
region, CO2 is formed at a much faster rate than
any other species to reach a plateau level (610 ppm)
at approximately 400 μs, which persists until the
ignition happens. Starting at the time of approxi-
mately 800 μs when the ignition happens, the CO2
concentration rises again at a similar formation
rate as the early-time formation while CO was con-
sumed rapidly after achieving a maximum concen-
tration of 0.24% prior to the ignition. H2 O and OH
radical concentrations reached plateau levels of
0.23% and 200 ppm, respectively, after the ignition
and remained unchanged within the experimental
time.
The four simulated species time-histories at
the same experimental conditions (1480 K and
1.5 atm) were plotted in Fig. 6(b) using the mod-
ified Yang et al. [13] mechanism. In general, the
model captures well the temporal shapes of all
the species concentration profiles. For example, the
simulated post-ignition OH, H2 O plateau level and
CO peak value are in excellent agreement with the
measurements within a difference of 5%. This is
mainly because these values are strongly controlled
by the thermochemistry-determined quasi-steady-

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tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
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Fig. 7. Comparison of the measured and calculated first-stage CO2 formation during MA oxidation.
state product concentrations while not sensitive to
the chemical kinetics.
The two-stage behavior of the CO2 formation
is also accurately captured by the modified Yang
et al. [13] mechanism. In particular as shown in
Fig. 7, the model accurately predicted the first-
stage CO2 formation over the entire temperature
range of 1433–1674 K. Different from the previ-
ously observed two-stage MA oxidation at lower
temperatures (800–1050 K) probably caused by
the MA + HO2 /O2 reactions [13], the sensitivity
analysis of CO2 concentration (Supplementary
Fig. S4) indicates that the early-time CO2 for-
mation at high temperature is mostly sensitive to
the MA unimolecular decomposition (Rxn. (1)).
However, the current MA mechanism overpredicts
the ignition delay times especially at lower temper-
atures. If the ignition delay times are defined as the
period of time till the CO concentration reaches
its peak value, the model overpredicts the ignition
delay times by 40% at 1423 K and 18% at 1623 K,
despite the only perfect agreement at a higher
temperature of 1666 K; see the Supplementary
Fig. S5.
Sensitivity analyses of these species concentra-
tions at the same experimental conditions (1480 K,
1.5 atm) and t = 100 μs, corresponding to 50% MA
consumption, are summarized in Fig. 8. Only the
top 15 reactions are shown in the sensitivity plot.
The MA unimolecular decomposition (Rxn. (1))
shows the largest positive sensitivity for all four
species, and is thus greatest in promoting the over-
all reactivity. This bond-fission reaction produces
one CO2 and two methyl radicals, leading to the
initiation of the radical pool. The chain branching
reaction, H + O2 ↔ O + OH (Rxn. (4)), has the
next-largest positive sensitivity coefficient during
MA oxidation. Another reaction that shows a high
Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
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[m;June 9, 2016;10:46]
positive sensitivity coefficient is the chemically
activated reaction CH3 + CH3 ↔ H + C2 H5 (Rxn.
(5)). This reaction of methyl radicals generates
a hydrogen atom and an ethyl radical, which are
more reactive than methyl radicals, and thus accel-
erate the overall reaction rate. The recombination
reaction of methyl radicals to produce C2 H6
(CH3 + CH3 ↔ C2 H6 , Rxn. (6)), a competing
pathway with Rxn. (5), shows the largest negative
sensitivity coefficient, thus inhibiting the overall
reaction rate. Considering CH3 is the major radical
produced during the MA initiation reactions, the
species concentrations (OH, H2 O and CO) show
a modest sensitivity to a series of methyl-related
secondary reactions (Rxns. (10)–(14)) as shown in
Fig. 8.
It is interesting to see that the H-abstraction
reactions from fuel by H-atom show little impact
on the overall reactivity of MA oxidation. Hy-
drogen atoms are primarily generated from the
methyl–methyl biomolecular reaction (Rxn. (5));
note that the formed ethyl radical immediately
takes the subsequent dissociation path to pro-
duce one more H-atom. This reaction competes
with the methyl–methyl recombination reaction
(Rxn. (6)), and the H-abstraction reactions from
MA by CH3 forming CH3 COOCH2 (Rxn. (7))
and CH2 COOCH3 (Rxn. (8)) radicals. The pro-
duced MA radicals take the subsequent decompo-
sition paths to form relatively stable molecules like
CH2 CO + CH3 OH and CH2 O + CH3 CO. In addi-
tion to the chain-branching reaction with O2 (Rxn.
(4)), the formed H-atom reacts actively with ketene,
a major intermediate produced from MA uni-
molecular elimination (MA ↔ CH3 OH + CH2 CO,
Rxn. (3)), to form the relatively inactive methyl
radical through the vibrationally excited acetyl
(CH2 CO + H ↔ CH3 + CO, Rxn. (9)).
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Fig. 8. Sensitivity to species concentrations: 0.114% MA/0.4% O2 /Ar (φ = 1), 1480 K, 1.5 atm, and t = 100 μs (50% MA
consumption).
A reaction flux analysis, outlined in Fig. 5,
was carried out for 0.114% MA and 0.4% O2
in Ar (φ = 1), 1480 K, 1.5 atm, and at the time
when 30% fuel is consumed. The reaction proceeds
basically in a similar way as the pyrolysis (also
presented in Fig. 5), except for the contribution
of the OH radical to the overall reactivity. The
rate coefficients of the H-abstractions from MA
by OH were recently investigated by Lam et al.
[15] behind reflected shock waves using UV laser
absorption, and calculated by Tan et al. [25] using
high-level ab initio quantum chemistry approaches
and transition state theory. Therefore, besides the
MA sub-mechanism, the current overprediction of
the ignition delay times by the modified Yang et al.
[13] mechanism is likely caused by the secondary
reactions especially related to the methyl radicals,
which are the major intermediate species in the
pyrolysis/oxidation system and appear with modest
sensitivities to affect the overall reactivity.
4. Conclusions
We studied the pyrolysis and oxidation of MA
in a shock tube by employing very dilute fuel
mixtures and multi-wavelength laser absorption
diagnostics. CO2 and CO, two major pyrolysis
products, were measured simultaneously over the
temperature range of 1401–1605 K and pressure
around 1.5 atm. Flux and sensitivity analyses
were performed to interpret the CO/CO2 data
Please cite this article as: W. Ren et al., Pyrolysis and oxidation of methyl acetate in a shock
tube: A multi-species time-history study, Proceedings of the Combustion Institute (2016),
http://dx.doi.org/10.1016/j.proci.2016.05.002
[m;June 9, 2016;10:46]
9
during MA pyrolysis. The rate coefficient of the
dominant MA unimolecular dissociation channel
(MA ↔ CH3 + CH3 + CO2 , Rxn. (1)) and its
branching ratio was determined, showing good
agreement with previous experimental and theoret-
ical studies, but with less scatter and dependency
on other reactions. A relatively complete picture of
MA oxidation was depicted by providing radical
and molecular time-history information of OH,
H2 O, CO and CO2 at a nominal temperature and
pressure (1480 K, 1.5 atm). The modified Yang
et al. [13] mechanism captures well the temporal
shapes of all the species concentrations regarding
the profile plateau levels and peak values. The ob-
served two-stage formation of CO2 in the present
study was also accurately predicted by the modified
Yang et al. [13] mechanism. The early-time rapid
formation of CO2 was established to be due to the
MA unimolecular decomposition channel (Rxn.
(1)). Although rather successful, the current kinetic
model still needs slight revision to account for the
existing overprediction of the ignition delay times
by 18–40% over 1623–1423 K.
Acknowledgments
This work was supported by the Combustion
Energy Frontier Research Center funded by the
U.S. Department of Energy, Office of Science, Of-
fice of Basic Energy Sciences under Award Num-
ber DE-SC0001198. Wei Ren acknowledges sup-
JID: PROCI
ARTICLE IN PRESS
10 W. Ren et al. / Proceedings of the Combustion Institute 000 (2016) 1–10
port by National Natural Science Foundation of
China (11502222).
Supplementary materials
Supplementary material associated with this ar-
ticle can be found, in the online version, at doi:
10.1016/j.proci.2016.05.002.
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