international journal of hydrogen energy xxx (xxxx) xxx

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Investigation of influence of detailed chemical

kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation

Bing Liu, Guo-Qiang He, Fei Qin*, Jian An, Shuai Wang, Lei Shi
Science and Technology on Combustion, Internal Flow and Thermal-structure Laboratory, Northwestern
Polytechnical University, Xi'an Shaanxi 710072, PR China

article info abstract

Article history: Five detailed hydrogen combustion chemical kinetics mechanisms coupled with a partially
Received 8 October 2018 stirred reactor (PaSR) combustion model were applied with large eddy simulation (LES) to
Received in revised form study the influence of detailed mechanisms on supersonic combustion in a model scramjet
24 December 2018 combustor. The LES predictions of five detailed mechanisms for velocity, temperature, and
Accepted 1 January 2019 combustor wall pressure show reasonable agreement with experimental results. Exam-
Available online xxx ining the effects on the distributions of temperature and species in supersonic combustion
reveals that the supersonic flame structure is affected by detailed mechanisms. The
Keywords: different detailed mechanisms have a strong influence on the combustion efficiency, vol-
Detailed chemical kinetics mecha- ume of the subsonic region, and subsonic combustion heat release rate in the combustor.
nism Moreover, the total heat release in the computational domain for the five detailed chemical
Hydrogen combustion kinetics mechanisms is quite different. The subsonic combustion is dominant in the
Large eddy simulation combustor for all detailed mechanisms. An analysis of the important reactions for H2O,
Supersonic combustion HO2, and OH is performed, revealing the reasons for differences in temperature and spe-
Partially stirred reactor combustion cies distributions among the different detailed mechanisms in the combustor.
model © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

been viewed as superior to hydrocarbon fuels at high flight

Introduction
There is a trend in future civil and military aircraft develop-
ment toward hypersonic vehicles, in which the scramjet is
regarded as the most suitable power device because of its high
specific impulse. For scramjet engines, supersonic combus-
tion is the key enabling technology in maintaining high-Mach-
number flight. Typically, the length of the combustion
chamber is meter-scale and the residence time of air and fuel
is measured in milliseconds [1]. Therefore, there is a need for
effective mixing and injection strategies and for fuels with
shorter ignition delay times. For decades, hydrogen fuel has
Mach numbers owing to its wide flammability limit, shorter
ignition delay time, and minimum ignition energy [2].
Because of the complexity and high cost of ground tests as
well as restrictions on available measurements, computa-
tional fluid dynamics (CFD) is playing an increasingly impor-
tant role in this research area. Accurate simulation of
supersonic combustion requires good turbulence, combustion
models and chemical kinetics mechanism [3]. Recently, su-
personic combustion of hydrogen has often been numerically
simulated by utilizing global reactions or detailed chemical
kinetics mechanisms.

* Corresponding author.
E-mail address: qinfei@nwpu.edu.cn (F. Qin).
https://doi.org/10.1016/j.ijhydene.2019.01.005
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
2 international journal of hydrogen energy xxx (xxxx) xxx

Huang et al. [4e6] studied a hydrogen-fueled model
scramjet combustor by combining large eddy simulation (LES),
a partially stirred reactor (PaSR) combustion model, and a
detailed chemical kinetics mechanism consisting of nine
species and 27 steps [7]. The results of LES matched well with
experimental data, including mean axial velocity and tem-
perature. The results revealed that the flame is stabilized by
auto-ignition rather than flame propagation. Fureby et al. [8]
investigated supersonic combustion in the same model
scramjet engine using the LES-PaSR model, a two-step global
mechanism [9], and a seven-step reduced mechanism [10].
The global reaction could not calculate reasonable ignition
delay time and heat release rate values. The best agreement
was obtained between LES results for the seven-step reduced
mechanism and experimental data. It was also shown that a
combination of the combustion model with the multi-step
chemical reaction mechanism is necessary for simulating
the complex physical process of supersonic combustion.
Jachimowski et al. [11] studied the influence of chemical
mechanisms on supersonic combustion. It was found that the
ignition delay time was primarily controlled by chain
branching and propagation reactions. Furthermore, it was
reported that the HO2 reactions were key in the mechanism,
and the reaction rate of HO2 significantly affected the pre-
diction of the heat release rate. Davidenko et al. [10] examined
three reduced mechanisms and a detailed chemical kinetics
mechanism for the supersonic combustion of hydrogen/air
based on a steady-state simulation. It was found that reduced
mechanisms could predict experimental data reasonably well.
However, it was also reported that reduced mechanisms
cannot correctly predict the ignition delay time and heat
release rate. Kumaran et al. [12] numerically investigated su-
personic combustion using a detailed chemical kinetics
mechanism consisting of nine species and 37 reactions [13]
and the SpalarteAllmaras turbulence model [14]. The re-
sults, which were compared with earlier results using a single
global reaction, showed that detailed chemical kinetics
mechanisms predicted higher and wider heat release than
what was predicted by the global reaction. It was also shown
that detailed chemical kinetics mechanisms could predict
details of the supersonic combustion process such as induc-
tion distance. Huang et al. [15] employed two chemical ki-
netics mechanisms to evaluate the effects on supersonic
combustion of hydrogen/air based on the Reynolds-averaged
NaviereStokes (RANS) equations and the two- and seven-
step chemical kinetics mechanisms. The chemical kinetics
mechanisms had a slight effect on overall supersonic diffu-
sion combustion performance.
Many global reactions and detailed chemical kinetics
mechanisms for hydrogen combustion have been widely used
in supersonic combustion simulation, and there are reason-
able agreements between experiment and simulation [16e30].
From the above studies, reduced and global chemical kinetics
mechanisms are suitable for evaluating overall scramjet en-
gine performance, and detailed chemical kinetics mechanism
can provide more detailed information for optimum design
and improvement of the combustor [31]. Large eddy simula-
tion coupled with detailed chemical kinetics mechanism can
provide an in-depth understanding of detailed features of
supersonic combustion. However several different detailed
chemical kinetics mechanisms for hydrogen/air are available,
such as those proposed by Burke et al. [32], Li et al. [33], Saxena
et al. [34], Marinov et al. [7], and Fureby et al. [35]. To choose
among these, it is important to investigate the influence of
different detailed chemical kinetics mechanisms on large
eddy simulation of supersonic combustion.
The present work aims at validating and comparing five
detailed chemical kinetics mechanisms to simulate

Fig. 1 e Schematic of (a) the model scramjet combustor [8] and (b) the 3-D computational domain.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
 international journal of hydrogen energy xxx (xxxx) xxx 3

Table 1 e Inflow conditions.

Mach number Velocity (m/s) Temperature (K) Static pressure (kPa) O2 H2 N2 H2O
Air 2 730 340 100 0.232 0.0 0.736 0.032
Hydrogen 1 1200 250 100 0.0 1.0 0.0 0.0

supersonic combustion in a model scramjet [8]. The five

detailed chemical kinetics mechanisms include those pro-
posed by Burke et al. [32], Li et al. [33], Saxena et al. [34],
Marinov et al. [7], and Fureby et al. [35]. Large eddy simulation
(LES) with a partially stirred reactor (PaSR) combustion model
is used to investigate the influence of detailed mechanisms on
hydrogen-fueled supersonic combustion, which is imple-
mented in an Open-Source Field Operation and Manipulation
(OpenFOAM) [36] solver. The simulation results are analyzed
and discussed.
Computational methodology
The filter was applied to conservation of mass, momentum,
energy, and species in the NaviereStokes equations based on
local grid size; then the governing equations for supersonic
combustion, which were solved by OpenFOAM [36], were ob-
tained. The partially stirred reactor (PaSR) combustion model
[37] was employed to model turbulenceechemistry interac-
tion. Applicability of the PaSR combustion model to super-
sonic combustion has been validated in several studies
[38e42]. More about the combustion model and turbulence
model can be found in our previous work [4e6].
An implicit second-order total-variation-diminishing
(TVD) RungeeKutta scheme for temporal integration [43] and
a nominally fourth-order TVD convective scheme were used.
The orthogonal part was calculated by a fourth-order central
difference scheme and the non-orthogonal part was con-
ducted by surface interpolation of variable gradients. The CFL
number was not more than 0.5, corresponding to a time step
of 2
107 s.
Computational configuration and flow condition
Fig. 1 shows a schematic of (a) the combustor of the model
scramjet [8] and (b) the 3-D computational domain. The
combustor consisted of a single-sided expansion channel and
a wedge-shaped flame holder. H2 was injected through a row
of 15 holes at the base of the flame holder. The diameter of the
holes was 1 mm and the distance between adjacent holes was
2.4 mm.
Because the combustor was symmetrical in the width di-
rection, three fuel holes were included in the computational
domain of this paper to reduce calculation cost and ensure the
3D-effects due to the interactions of the fuel plumes. Three
structured grids with 6.0 million (Grid-1), 12.0 million (Grid-2)
and 19.0 million (Grid-3) cells respectively were used for large
eddy simulation to verify the grid resolution. The regions
around the shear layers and near the walls of strut were
refined to ensure good resolution. Inflow conditions for the air
and hydrogen are listed in Table 1.
Results
Comparison of detailed chemical kinetics mechanisms
In this study, five detailed chemical kinetics mechanisms
were chosen to simulate supersonic combustion. A brief
introduction to these mechanisms follows.
Burke et al. [32] presented an updated hydrogen/oxygen
detailed chemical kinetics mechanism based on Li et al. [33],
which consists of nine species and 19 elementary reactions. It
was introduced to eliminate the discrepancies between
experimental results and numerical simulations in high-
pressure flames. The mechanism was examined against the
previous validations considered by Li et al. [33] and validations
from recent studies. The detailed mechanism was employed
for investigating turbulenceechemistry interactions in a
ramp-stabilized supersonic hydrogen/air diffusion flame [44],
and numerical simulation results were consistent with
experimental values.
A comprehensive hydrogen/oxygen detailed chemical ki-
netics mechanism was presented by Li et al. [33] based on the
study of Mueller et al. [45]. The detailed mechanism consists
of nine species and 19 elementary reactions. The modified
mechanism was validated against a wide range of experi-
mental data including shock tubes, flow reactors, and laminar
premixed flames. Findings demonstrated that the detailed
mechanism is comprehensive and has good predictive ability
for different experimental systems. Jin et al. [46] conducted a
direct numerical simulation of a three-dimensional super-
sonic turbulent jet flame in a heated coflow using a detailed
mechanism.
Saxena et al. [34] developed a detailed mechanism con-
sisting of nine species and 21 elementary reactions for the
combustion of hydrogen and carbon monoxide. Some modi-
fications were applied to rate parameters for elementary re-
actions in the mechanism for hydrogen. Reasonable
agreement was obtained with experimental results, including
laminar flame speed, diffusion flame extinction conditions,
Table 2 e Detailed chemical kinetics mechanisms for
hydrogen/air.
Mechanism Number of Number of
species reactions
Burke et al. [32] a 9 19
Li et al. [33] a 9 19
Saxena et al. [34] b 9 21
Marinov et al. [7] c 9 20
Fureby et al. [35] 9 22
a
He and Ar were deleted.
b
CO, CO2, and HCO were deleted and N2 was added.
c
He was deleted.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
4 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 2 e Comparison of (a) laminar flame speed results (p ¼ 1.0 atm, T ¼ 298 K), (b) adiabatic flame temperature results,
(c) ignition delay time results (p ¼ 1.0 atm), (d) ignition delay time results (p ¼ 4 atm), (e) OH mass fraction (p ¼ 1 atm), and
(f) H2O mass fraction (p ¼ 1 atm), and experimental results from Refs. [48,49].

Fig. 3 e Main reaction pathways for (a) T ¼ 1000 K and (b) T ¼ 1800 K (Numbers correspond to the order of the legend in
Fig. 2, and the numbers represent the absolute rate of production from reactant to product).

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
 international journal of hydrogen energy xxx (xxxx) xxx
Table 3 e Schmidt numbers of species [8].
Species H2 O2 N2 H2O OH HO2 H2O2 H O
Schmidt 0.29 0.76 0.75 0.6 0.51 0.7 0.7 0.1 0.2
number
and ignition delay time. Coclite et al. [17] presented a nu-
merical simulation of non-premixed supersonic hydrogen/air
combustion using a detailed mechanism. The simulation re-
sults agreed well with experimental data such as temperature,
velocity, and species distribution.
Marinov et al. [7] applied a detailed chemical kinetics
mechanism for hydrogen/air consisting of nine species and 20
elementary reactions. Ignition delay time, laminar flame
speed, and species distribution were validated successfully.
Huang et al. [4,5] simulated supersonic combustion in the
model scramjet based on a detailed mechanism and simula-
tion results were validated against experimental velocity and
temperature.
Fureby et al. [35] developed an optimized detailed mecha-
nism for hydrogen/air using flame temperature, ignition delay
time and laminar flame speed as targets. The detailed mech-
anism is able to reproduce the experimental results of ignition
delay time at the lowest temperatures and crossover region
satisfactorily. The detailed mechanism has been successfully
applied in large eddy simulation, and the results were in good
agreement with the experimental data [47,48]. The five
detailed chemical kinetics mechanisms for hydrogen/air used
in this study are listed in Table 2.
Fig. 2 compares the experimental results and predictions
(calculated by Cantera [50]). For laminar flame speed, as seen
in Fig. 2a, five detailed mechanisms are in reasonable agree-
ment with the experimental data. Concerning adiabatic flame
temperature, OH mass fraction, and H2O mass fraction, as
seen in Fig. 2b, (e) and (f), the predictions of five detailed
mechanisms are similar, with the maximum error at around
stoichiometric ratio. Regarding ignition delay time at 1 atm,
Fig. 2c, the results of all mechanisms above 1000 K are similar,
but there is a large deviation below 1000 K. The predictions of
Li et al. [33] are larger than others in the crossover region. The
Fig. 4 e Comparison of calculated results of three grids with experimental data [8].
Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
5
results of Fureby et al. [35] are smaller than others when
temperature is less than 1000 K. For 4 atm, Fig. 2d, the pre-
dictions of Fureby et al. [35] show a higher precision in the
crossover region, and the satisfactory results at the lowest
temperature also are shown.
The reaction pathway of the detailed mechanisms is
analyzed as well. Fig. 3 illustrates the main reaction pathways
from H2 to H2O under different conditions (T ¼ 1000 K and
T ¼ 1800 K) based 0-D Closed Homogeneous Reactor Model.
One can see that, reactions H2þO]OH þ H and OH þ H2 ¼
H þ H2O are the most important channel for contributing to
H2 consumption, and reactions H2þO]OH þ H and
H þ HO2¼OH þ OH are the most important channel for
contributing to OH production. From Fig. 3a, the absolute rate
of production from reactant to product in the mechanism of
Fureby et al. [35] is larger than other detailed mechanisms,
and the absolute rate of production from reactant to product
in the mechanism of Marinov et al. [7] is smaller than other
detailed mechanisms. As the temperature increases, as
shown in Fig. 3b, the absolute rate of production from reactant
to product in the five detailed mechanisms changes greatly. It
should be noted that the reaction rates of these five detailed
mechanisms in reaction pathways are different.
In the present simulation, the Prandtl number was
assumed to be constant at 0.7 [51]. The Schmidt numbers of
species [8] are shown in Table 3 (the Schmidt numbers for HO2
and H2O2 were assumed to be 0.7).
Comparison of the large eddy simulation results with
experimental results
Fig. 4 shows the predictions and experimental [8] time-
averaged velocity results of the non-reacting case are
compared at three cross sections with different grids. The
accuracy of simulation results increases with the number of
grids. The predictions with Grid-2 (6.0 million grid cells) are
reasonable qualitatively and quantitatively. Considering the
complexity of the supersonic combustion, the calculated re-
sults are in overall good agreement with experimental data.
Consequently, the following calculations are performed based
on the Grid-2 (6.0 million grid cells).
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 5 e Comparison of experimental results [8] with the time-averaged temperature and velocity at three cross sections
obtained from five detailed chemical kinetics mechanisms.

Fig. 6 e Comparison of the time-averaged (a) bottom wall pressure and (b) axial velocity at the centerline obtained from five
detailed chemical kinetics mechanisms compared with experimental results [8].

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
 international journal of hydrogen energy xxx (xxxx) xxx 7

In Fig. 5, the predictions and experimental [8] time-

averaged temperature and velocity results are compared at
three cross sections of the combustor. It is evident from Fig. 5
that the predicted results of the five detailed chemical kinetics
mechanisms show reasonable agreement with experimental
data for three cross sections and that the results are very
similar. The predicted temperatures of Fureby et al. [35] agree
well with experimental data for three cross sections. It is
observed that the predicted velocities of the five detailed
chemical kinetics mechanisms show reasonable agreement
with experimental values, but the error is large for X ¼ 78 mm.
The bottom wall pressure and the axial velocity
(Y ¼ 25 mm) of the simulations are compared with the
experimental results, as shown in Fig. 6. Fig. 6a shows the
pressure at the bottom wall of the combustor. The simulation
results of the five detailed mechanisms are similar, qualita-
tively predicting the pressure peaks at the bottom wall caused
by reflected shock waves. However, according to Ref. [8], the
simulations and experiments are not well matched, possibly
because of insufficient boundary layer resolution. Fig. 6b
shows a relatively consistent trend between simulations and
experimental velocity for Y ¼ 25 mm. The simulations
underestimated the velocity behind the flame holder; this
resulted because the recirculation region of the simulation is
shorter than that in the experiment.
Fig. 7 shows the comparison of the LES results (contours of
OH and gradients of density) with experimental results [52] (OH-
PLIF and schlieren). All the LES results are qualitatively consis-
tent with the experimental results, but there are still some
differences, which may be caused by insufficient boundary
layer resolution. The simulation results of Burke et al. [32] and Li
et al. [33] are similar, and the results of other three detailed
mechanisms are similar, which are caused by the reaction
process of chemical reaction mechanisms, as shown in Fig. 3.
The previous study [35] indicated that the ignition delay
time below 1000 K affects the flame stabilization of the
combustor. Therefore, based on the above results and previ-
ous studies [47,48], the mechanism of Fureby et al. [35] is more
suitable for the simulation of supersonic combustion, but
supersonic combustion can also be reasonably simulated by
using the other four detailed chemical kinetics mechanisms.
The influence of the above detailed chemical kinetics mech-
anisms on supersonic combustion shows some differences
upon detailed examination, as shown in Figs. 3 and 7, which Fig. 7 e Comparison of the LES results (contours of OH
are further investigated in the next section. and gradients of density) with experimental results [52]
(OH-PLIF and schlieren).
Influence of five detailed chemical kinetics mechanisms

Fig. 8 illustrates (a) instantaneous temperature and (b) time-
averaged temperature profiles. The sizes of high-
temperature regions of the combustor are distinct. Using the
mechanisms of Saxena et al. [34], Marinov et al. [7] and Fureby
et al. [35], they seem to be longer and wider than the regions
obtained using the mechanisms of Burke et al. [32] and Li et al.
[33]. The high-temperature regions of Burke et al. [32] and Li
et al. [33] seem to be similar, and those of Marinov et al. [7],
Saxena et al. [34] and Fureby et al. [35] have the same trend.
According to Fig. 8a, the chemical kinetics mechanisms
clearly affect the flame structure. Fig. 8b shows that the lift-off
heights are almost the same.
Fig. 9 represents the (a) instantaneous and (b) time-
averaged H2O profiles for five detailed chemical kinetics
mechanisms. From Fig. 9a, the regions with high H2O mass
fractions using the mechanisms of Burke et al. [32] and Li et al.
[33] are smaller than the regions obtained using the mecha-
nisms of Saxena et al. [34], Marinov et al. [7] and Fureby et al.
[35]. As mentioned above, the flame structures are also influ-
enced by detailed chemical kinetics mechanisms. From
Fig. 9b, the Burke et al. [32] and Li et al. [33] mechanisms
produce a similar region with a high H2O mass fraction, and
the regions produce using the Saxena et al. [34], Marinov et al.
[7] and Fureby et al. [35] mechanisms are similar.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 8 e (a) Instantaneous temperature and (b) time-averaged temperature profiles for five detailed chemical kinetics
mechanisms.

OH is the important intermediate radical in hydrogen
combustion [53]. The instantaneous OH profiles for five
detailed chemical kinetics mechanisms are shown in Fig. 10a.
It can be seen that the OH profiles produced using the Saxena
et al. [34], Marinov et al. [7] and Fureby et al. [35] mechanisms
are more disperse than those produced using the Burke et al.
[32] and Li et al. [33] mechanisms. Fureby et al. [8] divided the
supersonic combustion in this scramjet model into three re-
gions: (1) the induction region, where turbulence affects the
mixing and combustion process; (2) the transitional region,
which is controlled by large-scale coherent flow structures,
convective mixing, air entrainment, and exothermicity; and
(3) the turbulent combustion region with large-scale coherent
structures and mixing, as shown in Fig. 10b. It is observed that
the induction region of the five detailed chemical kinetics
mechanisms is almost same, because the mechanisms' igni-
tion delay times are quite similar, as mentioned in Fig. 2. The
transition regions produced using the Saxena et al. [34], Mar-
inov et al. [7] and Fureby et al. [35] mechanisms are larger than
those produced using the Burke et al. [32] and Li et al. [33]
mechanisms, but the turbulent combustion regions using
the Saxena et al. [34], Marinov et al. [7] and Fureby et al. [35]
mechanisms are smaller than those obtained using the
Burke et al. [32] and Li et al. [33] mechanisms.
Fig. 11 represents the (a) instantaneous and (b) time-
averaged HO2 profiles for five detailed chemical kinetics

Fig. 9 e (a) Instantaneous and (b) time-averaged H2O profiles for five detailed chemical kinetics mechanisms.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
 international journal of hydrogen energy xxx (xxxx) xxx 9

Fig. 10 e (a) Instantaneous and (b) time-averaged OH profiles for five detailed chemical kinetics mechanisms.

mechanisms. HO2 mainly exists at the recirculation region The combustion efficiency hc [54] was calculated according
and shear layer. From Fig. 11a, the regions with high HO2 mass to the following equation:
fractions using the five detailed mechanisms exist at the shear Z
layer. From Fig. 11b, the previous four detailed mechanisms ðAðxÞrgas uYH2 dA m_ H2;x
have more HO2 than the last detailed mechanism in the hc ¼ 1  ¼1 (1)
m_ H2;in m_ H2;in
recirculation region, and the previous three detailed mecha-
nisms have more HO2 than the other two detailed mecha- where m_ H2;x is the hydrogen mass flow rate at a given section
nisms in the shear layer. and m_ H2;in is the total injected hydrogen mass flow rate. The

Fig. 11 e (a) Instantaneous and (b) time-averaged HO2 profiles for five detailed chemical kinetics mechanisms.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
10 international journal of hydrogen energy xxx (xxxx) xxx

about 95% (obtained using the mechanism of Fureby et al.

[35]). The minimum combustion efficiency is about 90% (ob-
tained using the mechanism of Li et al. [33]). According to the
degree of combustion efficiency, the sequence of mechanisms
in decreasing order is: Fureby et al. [35], Saxena et al. [34],
Marinov et al. [7], Burke et al. [32], and Li et al. [33]. The overall
trend of combustion efficiency is also confirmed by the dis-
tribution of the H2O mass fraction from Fig. 9.
A statistical calculation was conducted to give quantitative
heat release rate values. The heat release rate was calculated
with the following equations [55]:
Z
HRRtot ¼ ShdV (2)

Z
Fig. 12 e Combustion efficiency obtained from the five HRRsub ¼ Shsub dVsub (3)
detailed chemical kinetics mechanisms.

hsub ¼ HRRsub =HRRtot (4)

where HRRtot is the total heat release rate of the computational

domain, Sh is the heat release rate per unit volume, V is the
Table 4 e Heat release for the five considered
mechanisms. volume of the computational domain, HRRsub is the heat
release rate of a given subsonic combustion region, Shsub is the
Mechanisms Vsub (m3) HRRsub HRRtot hsub (%)
heat release rate per unit volume of a given subsonic region,
(KJ/s) (KJ/s)
Vsub is the volume of the given subsonic region, and hsub is the
Burke et al. [32] 9.33E-6 16.0 21.5 74.4
subsonic combustion contribution coefficient. Table 4 lists the
Li et al. [33] 8.41E-6 17.5 23.3 75.1
Saxena et al. [34] 1.19E-5 27.9 34.4 81.1
results of calculations for the combustor and the contribution
Marinov et al. [7] 1.31E-5 26.8 35.0 76.6 coefficients of subsonic combustion for the five mechanisms.
Fureby et al. [35] 1.32E-5 18.2 24.4 74.6 It is apparent from Table 4 that the volumes of subsonic re-
gions using the Saxena et al. [34], Marinov et al. [7] and Fureby
et al. [35] mechanisms are larger than those obtained using
combustion efficiency values hc of the five detailed chemical the Burke et al. [32] and Li et al. [33] mechanisms, which is also
kinetics mechanisms are shown in Fig. 12. It is clear that the confirmed by Fig. 10a. The reason for this may be that the
combustion efficiency values obtained using the Saxena et al. longer and wider high-temperature regions of the Saxena
[34], Marinov et al. [7] and Fureby et al. [35] are larger than et al. [34], Marinov et al. [7] and Fureby et al. [35] results lead to
those obtained using the Burke et al. [32] and Li et al. [33] a more disperse heat release rate distribution, as shown in
mechanisms downstream of the combustor. At the combus- Figs. 8b and 10b, resulting in lower Mach numbers down-
tion chamber exit, the maximum combustion efficiency is stream of the combustor. However, HRRsub in the Burke et al.

Fig. 13 e Reaction rates of H2O in H2þOH]H2O þ H at three cross sections.

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
 international journal of hydrogen energy xxx (xxxx) xxx 11

Fig. 14 e Reaction rates of OH in HO2þH]OH þ OH at three cross sections.

Fig. 15 e Reaction rates of OH in H2þO]OH þ H at three cross sections.

[32], Li et al. [33] and Fureby et al. [35] mechanisms are very
similar, while HRRsub in the Saxena et al. [34] and Marinov et al.
[7] mechanisms are larger, so is HRRtot . Subsonic combustion
dominates in the combustor for the five detailed mechanisms
with contribution coefficients of 74.4%, 75.1%, 81.1%, 76.6%,
and 74.6%, respectively. Thus, it is concluded that detailed
chemical kinetics mechanisms have a strong influence on the
heat release rate distribution in scramjet combustors.
The H2þOH]H2O þ H, H2þO]OH þ H, and HO2þH]
OH þ OH for the five detailed chemical kinetics mechanisms
in 3-D large eddy simulations, which are the important re-
actions (as mentioned in Fig. 3), are compared at three given
cross sections. As shown in Figs. 13e15, the reaction rates of
H2O in H2þOH]H2O þ H using the mechanisms of Saxena
et al. [34], Marinov et al. [7] and Fureby et al. [35] are obviously
larger than those obtained using the Burke et al. [32] and Li
et al. [33] mechanisms. Similarly, the reaction rates of OH in
HO2þH]OH þ OH and H2þO]OH þ H using the mechanisms
of Saxena et al. [34], Marinov et al. [7] and Fureby et al. [35] are
clearly larger than those using the Burke et al. [32] and Li et al.
[33] mechanisms. This explains why the distributions of spe-
cies are different.
Conclusions
In this study, large eddy simulation and the PaSR combustion
model were used to investigate the influence of five detailed

Please cite this article as: Liu B et al., Investigation of influence of detailed chemical kinetics mechanisms for hydrogen on supersonic
combustion using large eddy simulation, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.01.005
12 international journal of hydrogen energy xxx (xxxx) xxx
chemical kinetics mechanisms on supersonic combustion in a
model scramjet, including the mechanisms of Burke et al. [32],
Li et al. [33], Saxena et al. [34], Marinov et al. [7], and Fureby
et al. [35]. Reasonable agreement between the experimental
data and LES predictions using the five detailed mechanisms
for the time-averaged temperature, velocity, and wall pres-
sure is obtained. The most suitable for the simulation of su-
personic combustion among them is the mechanism of
Fureby et al. [35]. By studying the distribution of temperature
and species produced using the five detailed mechanisms, it is
found that the distribution of temperature and species ob-
tained using the Saxena et al. [34], Marinov et al. [7] and Fureby
et al. [35] mechanisms are longer and wider than those ob-
tained using the mechanisms of Burke et al. [32] and Li et al.
[33]. This means that detailed mechanisms have great influ-
ence on supersonic flame structure even if they can reason-
ably predict the ignition delay time and laminar flame speed.
The combustion efficiency values and heat release rate of the
LES simulations are also analyzed. The sequence of proposed
mechanisms in decreasing order of combustion efficiency is
Fureby et al. [35], Saxena et al. [34], Marinov et al. [7], Burke
et al. [32], and Li et al. [33]. The volumes of the subsonic re-
gions for the Saxena et al. [34] Marinov et al. [7] and Fureby
et al. [35] mechanisms are larger than those for the Burke et al.
[32] and Li et al. [33] mechanisms, and HRRsub in the Burke et al.
[32], Li et al. [33] and Fureby et al. [35] mechanisms are very
similar, while HRRsub in the Saxena et al. [34] and Marinov et al.
[7] mechanisms are larger, so is HRRtot . Subsonic combustion
dominated in the combustor for the five detailed mechanisms,
with contribution coefficients of 74.4%, 75.1%, 81.1%, 76.6%,
and 74.6%, respectively. The reaction rates for H2þOH]
H2O þ H, H2þO]OH þ H, and HO2þH]OH þ OH using the
Saxena et al. [34], Marinov et al. [7] and Fureby et al. [35]
mechanisms are larger than those using the Burke et al. [32]
and Li et al. [33] mechanisms, which results in different dis-
tributions of temperature and species. In conclusion, in order
to obtain more accurate LES results, more parameters of
detailed chemical kinetics mechanism remain to be verified in
CFD.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (contract no. 91541110 and
51606156).
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