Fuel 341 (2023) 127676

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Combustion chemistry of ammonia/C1 fuels: A comprehensive kinetic

modeling study
Xiaoyuan Zhang *, Kiran K. Yalamanchi , S. Mani Sarathy
Clean Combustion Research Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: The application of ammonia (NH3) as a fuel could contribute to mitigating global warming and achieving carbon
Ammonia neutrality by mid-century. To enhance the reactivity of NH3 combustion, cofiring NH3 with hydrogen or C1 fuels
Syngas like syngas, methanol and methane is proposed. In previous work, we studied the combustion chemistry of NH3/
Methanol
H2 mixtures using a comprehensive kinetic model. In this work, we expanded our comprehensive kinetic model
Methane
to cover NH3/syngas, NH3/methanol and NH3/methane mixtures. Rate constants of critical cross reactions be­
Kinetic model
tween C- and N-containing species were evaluated based on previous experimental and theoretical studies for
selection and incorporation in the present model. Experimental data for both NOx/C1 and NH3/C1 fuels were
selected from literature to test the present model, including speciation data measured in shock tubes, flow re­
actors, jet-stirred reactors, burner-stabilized flames, and the global parameters like ignition delay times and
laminar flame speeds. The kinetic model validation conditions cover temperatures of 473–2000 K, pressures of
0.04–100 atm, and equivalence ratios of 0.04–116. In general, the present model adequately captures the
selected experimental data. The present model can not only be used to predict the combustion of NH3/C1 fuel
mixtures, but is also capable to predict the mutual interaction of NOx/C1 fuels. It is found that the rate constants
between C-containing species and H2-related radicals are generally faster than (or close to) those between C- and
N-containing species. At high temperatures, H2-related radicals (i.e. H, O, OH) have higher concentrations than
reactive N-related radicals (NH, NH2, NO2). Therefore, under these conditions, C-containing species are more
likely to react with H2-related radicals rather than N-related ones, making the C/N cross reactions less prominent.
However, under low- and intermediate-temperature conditions, the concentrations of H and O radicals become
lower, while those of NH2 and NO2 become higher, making the cross reactions between C- and N-containing
species possible to compete with C/H cross reactions. The present model can be used as the base chemistry model
for NH3/larger hydrocarbon fuels.

1. Introduction
Ammonia (NH3) is an attractive H2 carrier and carbon-free fuel that
has received significant attention in recent years. It can either be con­
verted to H2 for energy supply, or used directly as a fuel, both of which
could contribute to mitigating global warming and achieving carbon
neutrality by mid-century. However, its utilization as direct fuel has two
main concerns: low reactivity and high NOx emissions. Regarding to
these two issues, cofiring NH3 with C-containing fuels is a possible so­
lution. Particularly, small C-containing fuels like syngas, methanol
(CH3OH) and methane (CH4) are cleaner fuels than coal and heavy oils.
Blending these C1 fuels with NH3 can reduce emissions. From the per­
spectives of combustion chemistry, these C1 fuels have much higher
reactivity than NH3 and blending them can enrich the radical pools of
NH3 combustion [1]. In addition, NO can react with small hydrocarbon
radicals (e.g., CH2, CH3, HCCO) to eventually form N2 via reburning
chemistry [2], resulting in lower NOx emissions. A reliable kinetic model
for NH3 and C1 fuels is therefore necessary to understand fuel blending
chemistry and to predict the operation conditions where the lowest NOx
emissions are reached.
Kinetic models for NH3/C1 fuels consist of pure NH3 and C1 fuel
subsets and the interaction mechanisms between C- and N-containing
species. Although C1 models are considered ubiquitous, well-
established, and reliable, recent progress in non-thermal effects [3]
like prompt dissociation, are not fully adopted in widely used core C1
reaction mechanisms [4]. Compared with the C1 subset, the pure NH3

* Corresponding author.
E-mail address: xiaoyuan.zhang@kaust.edu.sa (X. Zhang).

https://doi.org/10.1016/j.fuel.2023.127676
Received 7 December 2022; Received in revised form 31 January 2023; Accepted 1 February 2023
Available online 10 February 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
X. Zhang et al.
submechanism contains larger uncertainties. In our recent modeling
study on NH3/H2, the performance of different comprehensive models
displayed large discrepancies [5]. Earlier combustion chemistry studies
on the interaction mechanism between C- and N-containing species were
mainly motivated by the reburning process. In the modeling studies of
Miller and Glarborg [6,7], cross reactions between N- and C-containing
species (up to C2) were considered. These studies are important building
blocks for the further development on C/N interaction chemistry
[2,8–14]. Among these studies, the most recent and comprehensive
modeling study is from Glarborg et al. [2], which was developed based
on their previous studies over the past 30 years and widely adopted by
recent literature modeling work on NH3/hydrocarbon fuels [15–17].
Nevertheless, recent theoretical calculations [1,18–20] on the cross re­
actions between C- and N-containing species provide chances to further
improve the C/N interaction mechanism. On the other hand, most pre­
vious chemical kinetic models for NH3/syngas [21,22], NH3/CH3OH
[1,23] and NH3/CH4 [15,24–26] focused on specific combustion con­
ditions and limited experimental targets for model validation.
Comprehensive kinetic models for NH3/C1 fuels, which are validated
against experimental data covering chemically reacting flows at various
temperatures, pressures, and equivalence ratios in various reactors, are
scarce.
In this work, a comprehensive kinetic model for NH3/syngas/
CH3OH/CH4 is proposed based on our ongoing modeling studies for pure
NH3 [5] and small hydrocarbon fuels [27–32]. Rate constants of critical
cross reactions between C- and N-containing species were evaluated
based on previous experimental and theoretical studies. The proposed
model is validated against previous experimental data for both NH3/C1
fuels and NOx/C1 fuels, covering wide temperature, pressure and
equivalence ratio conditions. The role of C/N cross reactions under
different conditions is discussed based on the present model.
2. Model development
2.1. Pure ammonia and pure C1 fuels
The starting kinetic models for NH3 and C1 fuels (i.e. syngas, CH3OH
and CH4) were taken from our previous modeling studies [5,27–32]. The
C1 fuel models were developed hierarchically and adopted the same
hydrogen mechanism as the NH3 model; therefore, they were merged
together. Our recent NH3 model [5] has been tested against compre­
hensive experimental data for pure NH3, NH3/H2, H2/NO, H2/N2O,
NH3/NO, NH3/NO2 mixtures; it can reproduce the validation targets
over a wide range of pyrolysis and oxidation conditions. The original C1
fuel models have incorporated recent progress in non-thermal effects [3]
like prompt dissociation and termolecular reactions. The CH3OH subset
was taken from our previous modeling work on formaldehyde (CH2O)
and CH3OH [29], which was comprehensively tested against both
speciation data and global combustion parameters under wide com­
bustion conditions. The CH4 subset includes both C1 and C2 chemistry.
The high-temperature oxidation mechanism of CH4 was taken from our
previous modeling studies on CO/CH4 [30] and ethylene (C2H4) [27], in
which experimental targets obtained under intermediate- and high-
temperature conditions were selected to test the model. The low-
temperature oxidation mechanism of CH4 was adopted from our
modeling studies on acetaldehyde (CH3CHO) [28] and propanal
(C2H5CHO) [32], in which the low-temperature chemistry of CH3 and
C2H5 was visited.
Recent theoretical calculation study from Klippenstein et al. [33]
revisited the reaction of HO2 + HO2, and found that besides the triplet
product channel R1, the singlet product channel to HO3 + OH plays an
important role in leading to the formation of O2 and two OH radicals, i.e.
R2. Klippenstein et al.’s calculation results for R1 and R2 were adopted
in the present model.
HO2 + HO2 = H2O2 + O2 (R1)
2
Fuel 341 (2023) 127676
HO2 + HO2 = OH + OH + O2 (R2)
To better predict CH3OH oxidation under high-pressure and low-
temperature conditions, the rate constant of R3 was updated based on
the estimation from Burke et al. [34]. To better predict the flame
propagation and ignition of CH4, the rate constants of R4 and R5 were
updated from Troe et al. [35] and Srinivasan et al. [36], respectively.
CH3OH + HO2 = CH2OH + H2O2 (R3)
CH3 + H(+M) = CH4(+M) (R4)
CH4 + O2 = CH3 + HO2 (R5)
In addition, the reactions in Chebyshev format were replaced by Troe
format, and rate constants with a negative pre-exponential factor were
refitted and replaced by positive ones. The re-fitting uncertainties are
within 10 % under combustion related conditions. This modification
ensures facile application of the present model into various simulation
software. Since the rate constants of R1-R5 were updated, selected
validation targets for pure fuels were used to re-examine the model
performance, as found in subsequent sections of this paper.
For the NH3 subset, the rate constants of isomerization and decom­
position reactions of HONO radical (i.e. R6-R9) were updated based on
recent theoretical calculations by Chen et al [37]. They identified a well-
skipping product channel, i.e. R8, which was not found in previous
theoretical work by Rasmussen et al. [10], and which was missing in our
previous NH3 model [5]. The rate constants of R8 are comparable with
those of R7 at 1 atm, and 3–5 times lower than R7 at 100 atm.
NO2 + H = NO + OH (R6)
OH + NO = HONO (R7)
OH + NO = HNO2 (R8)
HNO2 = HONO (R9)
Bimolecular reactions of HONO isomers with H atom (i.e. R10-R15)
were updated based on theoretical calculations in [19]. According to
their calculation results, at atmospheric pressure, R10, R11 and R12 are
competitive for the consumption of HONO at high-temperatures, while
R13 is dominant amongst R13-R15 for the consumption of HNO2 over
the whole temperature range. These modifications on HONO/HNO2
have negligible influences on the predictions of NH3 oxidation. As seen
from Figs. S1-S6 in the Supplementary material, the present model well
predicts speciation data in H2/NO oxidation.
HONO + H = NO2 + H2 (R10)
HONO + H = HNO + OH (R11)
HONO + H = NO + H2O (R12)
HNO2 + H = NO2 + H2 (R13)
HNO2 + H = HNO + OH (R14)
HNO2 + H = NO + H2O (R15)
2.2. Interactions between N- and C1-containing species
Important radicals/intermediates in ammonia oxidation, such as
NH2, NO and NO2, can react with C1 fuels and their related radicals.
Reburning chemistry between C1 species and NO is the basis for un­
derstanding NH3/C1 chemistry, since NO is one of the most important
intermediate/product in ammonia oxidation. NO has a relatively high
concentration and has a radical character, indicating that the reactions
with NO could be competitive. NO is easily oxidized to NO2 via R16,
converting HO2 to OH in the process.
X. Zhang et al. Fuel 341 (2023) 127676

NO + HO2 = NO2 + OH (R16) CH2O + NO2 = HCO + cis/trans-HONO (R24)

NO2 is an unusual intermediate in NH3 oxidation, which exhibits a

high affinity, since every atom in the molecule has a radical character.
The reactions related to NO2 play an important role in NH3/hydrocarbon
oxidation under low and intermediate temperatures [1,15,26]. Besides
nitrogen oxides, NHi radicals can also react with C1 species. These re­
actions could play an important role in determining global combustion
parameters at low and intermediate temperatures [1] and in predicting
speciation profiles [15]. In this work, the original interaction mecha­
nism between N- and C-containing species, including kinetic, thermo­
dynamic and transport data, was adopted from Glarborg et al. [2].
Important cross reactions between C- and N-containing species were
revisited in this work, with full consideration of more recent studies.
2.2.1. Interaction mechanism between N-containing species and CO subset
Since CO and CO2 are relatively stable molecules, only a few radicals
are reactive enough to attack them. Recently, Kroupnov et al. [38]
theoretically studied R17 and reported both forward and reverse rate
constants. They also compared their results with literature data. It was
found that their computed rate constants match well with those
measured at intermediate and high temperatures [39,40], while they are
10 times higher than earlier measurements at 500 K [41]. Since we
focused on combustion related conditions, where the rate parameter
accuracy at intermediate and high temperatures are more important
than 500 K, the computed result from [38] was adopted in the present
model.
CO + NO2 = CO2 + NO (R17)
Poskrebyshev et al. [42] theoretically investigated the reaction be­
tween NH2 and CO, as well as the decomposition of NH2CO to HNCO and
H. The computed rate constant for R18 at 300 K and 1 atm is 1.3×106
cm3/mol/s, which is several orders of magnitude lower than common
addition reactions. Therefore, it was not incorporated in the present
model. The addition-elimination reaction of NH2 + CO can lead to the
formation of HNCO and H (i.e. R19), which transfers NH2 to more
reactive H atom and varies the radical pool. Therefore, it was incorpo­
rated in this model with a rate constant taken from Baulch et al. [43], in
which the reverse rate constant of R19 was evaluated. CO2 has two
double bonds and is more stable than CO. Its reactions with N-containing
radicals like amines were reviewed in previous work [25]. Similar to CO,
the reactions between N-containing radicals and CO2 are too slow to be
of importance under combustion related conditions.
NH2 + CO = NH2CO (R18)
NH2 + CO = HNCO + H (R19)
The interaction mechanism between HCO and NOx mainly includes
R20-R23. Details on the kinetic parameter evaluation can be found in
the Supplementary material.
HCO + NO = HNO + CO (R20)
HCO + NO2 = NO + CO2 + H (R21)
HCO + NO2 = HONO + CO (R22)
HCO + NO2 = HO + NO + CO (R23)
CH2O + NO2 = HCO + HNO2 (R25)
CH2O + NH2 = HCO + NH3 (R26)
Besides R24 and R25, Wu et al. [18] also investigated the kinetics of
CH3OH + NO2 theoretically. Their computed global rate constant lies
between previous measurements [45,46]. Similar to previous theoretical
calculations by Xiao et al. [47], they found the branching channels to
CH2OH formation are more important than CH3O formation. However,
branching ratios amongst the product channels display large discrep­
ancies between Wu et al. [18] and Xiao et al. [47]. According to Wu et al.
[18], the channels to CH2OH + cis-HONO and R28 are dominant at 300
to 2000 K. In contrast, the results from Xiao et al. [47] show that the
product channels to CH2OH + cis-HONO and CH2OH + trans-HONO are
dominant. In this model, we adopted the more recent theoretical cal­
culations by Wu et al. [18] to describe the kinetics of CH3OH + NO2,
since they adopted a more advanced theoretical calculation method,
including proper treatments of quantum tunneling effects and partition
functions.
CH3OH + NO2 = CH2OH + cis/trans-HONO (R27)
CH3OH + NO2 = CH2OH + HNO2 (R28)
CH3OH + NO2 = CH3O + cis/trans-HONO (R29)
CH3OH + NO2 = CH3O + HNO2 (R30)
The reaction between CH3OH and NH2 was theoretically investi­
gated in a recent modeling work on NH3/CH3OH [1]. According to this
study, R31 and R32 are the main product channels. R33 has a much
higher energy barrier and is not important. Interestingly, according to Li
et al. [1], the rate constant of R32 is roughly-two times faster than that of
R31 at 1000 K, which shows an opposite trend to the H-abstraction re­
actions of CH3OH by other radicals, such as H, O, OH and HO2 [29].
Based on their PES calculations, the energy barrier of R32 is only 1 kJ/
mol higher than that of R31. However, R32 has a looser transition state
than R31, making k32 faster than k31. More experimental data are
required to confirm these theoretical results [1]. Due to the limited
studies on the kinetics of CH3OH + NH2, the theoretical calculations
from Li et al. [1] were adopted for R31-R33.
CH3OH + NH2 = CH2OH + NH3 (R31)
CH3OH + NH2 = CH3O + NH3 (R32)
CH3OH + NH2 = NH2OH + CH3 (R33)
CH2OH is a dominant intermediate radical in CH3OH oxidation [29].
It can combine with NOx species to proceed R34-R36, and react with NHi
via R37-R40. Details on the kinetic parameter review and selection are
available in the Supplementary material. Note that although the inter­
action reactions between N-containing species and CH2OH were incor­
porated in the present model, they are not competitive with R41 due to
much higher concentrations of O2 compared to N-containing species and
comparable rate constants between R41 and R34-R40.
CH2OH + NO = HNCO + H2O (R34)
CH2OH + NO2 = CH2O + HONO (R35)

CH2OH + NO2 = CH2O + HNO2 (R36)

2.2.2. Interaction mechanism between N-containing species and CH3OH
subset CH2OH + NH2 = CH2O + NH3 (R37)
Since CH2O is the most important intermediate in CH3OH oxidation, CH2OH + NH2 = NH + CH3OH (R38)
the reactions between CH2O and N-containing species, i.e. R24-R26,
were revisited. Their rate constants were taken from Wu et al. [18] CH2OH + NH2 = HCOH + NH3 (R39)
and Li et al. [44]. Details on the rate constant evaluation can be found in
CH2OH + NH2 = CH2NH2 + OH (R40)
the Supplementary material.

3
X. Zhang et al.
Fig. 1. Comparison of the rate constant of CH4 + NH2 = CH3 + NH3 (R45).
Symbols [50–53] and lines [52,55–58] represent measured and theoretical
calculation values.
CH2OH + O2 = CH2O + HO2 (R41)
For the methoxy radical (CH3O), its bimolecular reactions are less
competitive than unimolecular decomposition reaction, i.e. R42.
Therefore, the interaction mechanism between N-containing species and
CH3O are not important. Nevertheless, we still incorporated the inter­
action reactions between N-containing species and CH3O in the present
model for completeness. The reaction pathways and rate constants were
adopted from previous modeling studies [2,48].
CH3O (+M) = CH2O + H (+M) (R42)
2.2.3. Interaction mechanism between N-containing species and CH4 subset
H-atom abstraction reactions from CH4 by NO2 can lead to three
product channels, i.e. R43-R44. Review on the rate constants of these
reactions before 2008 can be found in [11].
CH4 + NO2 = CH3 + cis/trans-HONO (R43)
CH4 + NO2 = CH3 + HNO2 (R44)
According to a recent study at a high level of theory [49], the rate
constant of CH3 + cis-HONO is the largest, while R44 is the smallest. The
Glarborg 2018 model [2] adopted the computed rate constants for R43-
R44 from [49] without distinguishing cis-HONO and trans-HONO.
Duplicate reactions were defined in the model for cis-HONO and trans-
HONO channels. To simplify the mechanism, recently, Fuller et al. [19]
assumed that cis-HONO and trans-HONO were lumped into a single
species. Transition state theory (TST) calculations for the direct H-
abstraction performed in [49] were redone with a single HONO isomer
that systematically treats the cis-/trans- conversion as a hindered inter­
nal rotation in both the reactant and transition state. Their computed
overall rate constant for CH4 + NO2 is within a factor of two compared
with that obtained from [49]. In the present model, the rate constants for
R43 and R44 were taken from [49].
The H-atom abstraction reaction from CH4 by NH2 (R45) is another
chain-propagation reaction in NH3/CH4 oxidation.
CH4 + NH2 = CH3 + NH3 (R45)
The rate constants for R45 from different sources are compared in
4
Fuel 341 (2023) 127676
Fig. 1. Demissy et al. [50] evaluated the rate constant of R45 experi­
mentally by flash photolysis using laser resonance absorption detection
of NH2. The temperature range covers 300–520 K. Hack et al. [51]
studied R45 in an isothermal discharge flow system over the tempera­
ture range of 743–1020 K, extending previous work [50] to intermediate
temperatures. At high temperatures, the measured rate constants by
Song et al. [52] are 3 times higher than those measured by Hennig et al.
[53] over 1600–2100 K. Both experiments were conducted in shock
tubes. In the experimental study of Hennig et al. [53], NH2 was formed
by the thermal decomposition of hydrazine and its concentration was
measured by laser absorption. In contrast, Song et al. [52] used
methylamine to generate NH2, and the NH2 decay was measured using a
frequency modulation (FM) absorption technique, which can achieve
much lower detection limit compared with direct laser absorption. Be­
sides these measurements, Yu et al. [54] theoretically studied R45 and
obtained both the forward and reverse rate constants over 300–2100 K.
Their computed forward rate constant is in reasonable agreement with
previous measurements from [51,53] over intermediate and high tem­
peratures, while overpredicting the rate constant measured at 300 K
from [50] by a factor of 10. Mebel et al. [55,56] also computed the rate
constant of R45. In contrast, their calculation results agree well with the
measured results at low temperatures [50], while overpredicting the
measured rate constants at intermediate [51] and high temperatures
[52,53]. More recent theoretical calculations on R45 were performed by
Siddique et al. [57] at the CBS-QB3 level. Their computed results agree
well with the measured results of [50] at low temperatures and those of
Song et al. [52] at high temperatures, while overpredicting the mea­
surements of Hack et al. [51] by a factor of 4 at intermediate tempera­
tures. Song et al. [52] not only performed an experimental study, but
also performed theoretical calculations. They computed the rate con­
stants of R45 over 300–2100 K, which well predict the measured rate
constants [50–52] over 300–2084 K. In the present model, we adopted
the rate constant from the theoretical calculations of Song et al. [52],
albeit large uncertainties remain for the rate constant of R45 at high
temperatures.
For the reactions between CH3 and NHi, multiple reaction channels
are possible, including H-atom abstraction, recombination, and
addition-elimination reactions, i.e. R46 and R47. Dean and Bozzelli [48]
performed theoretical calculations to identify possible reaction chan­
nels, and obtained rate constants based on QRRK theory. Their results
were adopted in the present model.
The sub-mechanism of CH3NH2 was taken from a recent kinetic
modeling work from Glarborg et al. [20], where the rate constants of
critical reactions were computed theoretically.
CH3 + NH = CH2NH + H (R46)
CH3 + NH2 = CH3NH2 (R47)
The reaction between CH3 and NO2 can proceed via a dispropor­
tionation reaction (i.e. R48) or combination reaction (i.e. R49). A study
by Glarborg et al. [59] evaluated k48 at 1180 K by adjusting this
parameter in the mechanism to match measured NO2 profiles. In com­
bination with low temperature data, they suggested the k48 decreases
slightly with temperature. Wollenhaupt et al. [60] measured the rate
constant of R48 using LIF detection of CH3O over 233–356 K.
Temperature-independent rate constants over this range were reported,
which agree (within 16 %) with those evaluated by Glarborg et al. [59].
At high temperatures, the measured k48 by Srinivasan et al. [61] is 50 %
higher than that from Glarborg et al. [59]. In the present model, the
value from Glarborg et al. [59] was adopted. For R49, recent modeling
work from Sahu et al. [62] evaluated its rate constant at various tem­
peratures and pressures. They recommended to adopt the theoretical
results from [63], which better match measurements [63,64] at various
pressures compared to values from [59] and [65]. Therefore, Sahu
et al.’s recommendations, i.e. theoretical results from [63], were adop­
ted in this model. Studies on the reactions related to nitromethane
X. Zhang et al.
Fig. 2. Comparison of the rate constant of CH3O2 + NO = CH3O + NO2 (R52).
Symbols and lines represent measured [68–72] and theoretical calculation/
evaluation values [73–76], respectively.
chemistry are limited and important kinetic parameters available in the
literature are decades old. Further work is required in this area to
improve the understanding of nitromethane pyrolysis and combustion.
CH3 + NO2 = CH3O + NO (R48)
CH3 + NO2 = CH3NO2 (R49)
For the kinetics of CH3 + NO, Miller et al. [66] computed the global
rate constant of CH3 + NO over 1000–2500 K, which is close to previous
shock tube measurements [67]. They concluded tentatively that the
radical channel R51 should be dominant, which is in disagreement with
the measurements by Henning [67]. Similar to the Glarborg 2018 model
[2], we assumed an equal contribution for R50 and R51 in the present
model, and the global rate constant from Miller et al. [66] was adopted.
More studies on the branching ratio are required in the future.
CH3 + NO = HCN + H2O (R50)
CH3 + NO = H2CN + OH (R51)
A number of experimental studies on the kinetics of CH3O2 + NO are
available at low temperatures (200–400 K) and low pressures [68–72].
According to theoretical calculations [73], R52 is the dominant reaction
channel at 300–1500 K and 0.01–100 atm.
CH3O2 + NO = CH3O + NO2 (R52)
Atkinson et al. [74,75] reviewed previous studies and recommended
k52 over ~200–400 K, as seen from Fig. 2. In the two review studies, the
rate constants of R52 at 300 K are the same, while the temperature-
dependencies are different. The measurements from Villalta et al. [69]
generally lie between those evaluated by Atkinson et al. [74,75].
Measured results for k52 at temperatures higher than 430 K are not
available. Nguyen et al. [73] reported computed rate constants of R52 at
300–1500 K and 0.01–100 atm. Interestingly, k52 is nearly temperature-
independent at 300–430 K, which is inconsistent with previous negative-
temperature dependent trends observed [69,70,74,75]. At higher tem­
peratures, the computed k52 has an obvious positive-temperature
dependent trend. More experimental studies under higher tempera­
tures are desired to confirm their calculations. In this work, we adopted
the measurements from Villalta et al. [69] for R52.
3. Model validation
To test the reliability of the present model, experimental data for
5
Fuel 341 (2023) 127676
both NOx/C1 and NH3/C1 fuel mixtures were selected for validation. The
validation targets are summarized in Table 1, including speciation data
measured in shock tubes, flow reactors, jet-stirred reactors (JSRs),
burner-stabilized premixed flames and the global parameters like
laminar flame speeds and ignition delay times. The temperature, pres­
sure and equivalence ratio conditions cover 473–2000 K, 0.04–100 atm
and 0.04–116, respectively. Two criteria are followed for choosing
experimental validation data: 1) the data cover as wide combustion
conditions as possible; and 2) the experiments adopt state-of-art
methods with quantified experimental uncertainties. Simulations were
performed with Chemkin-Pro software [77]. We followed the same
simulation methods used in our previous study on NH3/H2 [5], and
details can be found in [5]. Before performing simulations, the collision
limit compliance was checked based on the online tool developed in our
previous work [78] over 500–2500 K. The reactions that exceed collision
limits are mainly C2 related reactions at 500 K or above 2000 K, which is
beyond the normal combustion relevant conditions. These reactions are
not important in the present NH3/C1 systems, and will be evaluated in
our future modeling study on NH3/C2 mixtures. The model files,
including kinetic, thermodynamic and transport data, are available in
the Supplementary material. In this section, comparisons between the
experimental targets and the predicted results by the present model are
presented. In addition, the simulated results by Glarborg 2018 model [2]
are also included for comparison, since this is the most recent and
comprehensive NH3 co-firing model, including NH3-syngas, NH3-
CH3OH and NH3-CH4 subsets, and this model has served as the base
model for many other recent models, especially for the C/N interaction
mechanism.
3.1. Global parameters
3.1.1. Laminar flame speeds
Laminar flame speeds are helpful to examine the high-temperature
model, especially reactions involving H atoms. Experimental measure­
ments for laminar flame speeds of NH3/C1 fuels are available in the
literature [21,23,82,83,101], covering wide unburned temperature,
pressure and equivalence ratio conditions. Under some conditions, more
than one set of experimental data are available [82,101,102], which is
helpful to check the reliability of the experimental data. Fig. 3 presents
the comparison between the measured and predicted laminar flame
speeds of stoichiometric NH3/syngas/air, NH3/CH3OH/air and NH3/
CH4/air at unburned gas temperature of 298 K. The experimental data
show that with increasing content of C1 fuels, the laminar flame speeds
are increased. The enhancement effects of syngas are the strongest,
followed by CH3OH and CH4. This trend is well captured by the present
and the Glarborg 2018 model [2]. However, the present model can
better predict the laminar flame speeds of NH3/C1 fuels under conditions
with low C1 fuel concentration. Under these conditions, the pure NH3
mechanism becomes more important. The present model adopted the
subset of NH3 from our previous model [5], which has a better perfor­
mance than the Glarborg 2018 model [2] in predicting laminar flame
speeds for pure NH3 and NH3/H2 mixtures [5].
Fig. 4 presents the measured and predicted laminar flame speeds
across wide equivalence ratio conditions and unburned gas temperature
of 298 K. For the NH3/syngas/air and NH3/CH4/air cases, as seen from
Fig. 4a and c, the present model can reasonably predict the experimental
data under various unburned pressures, while the Glarborg 2018 model
[2] can only reasonably predict NH3/CH4/air mixtures. For the pre­
dictions of NH3/CH3OH/air mixtures, the present model better predicts
the pure CH3OH/air case than the Glarborg 2018 model [2]. Both the
present and Glarborg 2018 models [2] can reasonably predict cases with
CH3OH contents of 60–80 %. With lower CH3OH contents, the present
and Glarborg 2018 models underpredict and overpredict the laminar
flame speeds, respectively. Additional validations against laminar flame
speeds of NH3/CO/air, NH3/syngas/air, NH3/CH3OH/air, NO/CH4,
NO/CH4/O2/N2, NO/CH4/O2/Ar, NH3/CH4/air can be found in Figs S7-
X. Zhang et al. Fuel 341 (2023) 127676

Table 1
A list of validation data for the present model.
Fuel Method Mixture T (K) P (atm) ϕ Refs

H2-NO JSR H2/NO/O2/N2 700–1150 1–10 0.1–1.0 [79]

Flow reactor H2/NO/O2/N2 802 10 0.25 [80]

CO-NO Flow reactor CO/H2O/O2/NO/N2 850–1400 1 1.24–1.68 [81]

CO-NH3 Flame speed CO/NH3/air 298 1 0.7–1.7 [82]

Flame speed CO/NH3/air 298 1–5 0.7–1.5 [83]
Flow reactor CO/NH3/H2O/O2/NO/N2 775–1300 1 N/A [84]

CO/H2-NO JSR CO/H2/O2/NO/N2 800–1400 1 0.1–2.0 [85]

Flow reactor CO/H2/O2/NO/NO2/N2 600–900 20–100 0.06 [10]

CO/H2-NH3 Flame speed CO/H2/NH3/air 298 1 0.7–1.6 [22]

Flame speed CO/H2/NH3/air 298 1–5 0.7–1.6 [83]
Flame speed CO/H2/NH3/air 298 1–10 0.7–1.5 [21]

CH3OH-NOx JSR CH3OH/O2/H2O/NO/N2 700–1100 10 0.3–1.0 [86]

JSR CH3OH/O2/H2O/NO2/N2 700–1100 10 0.3–1.0 [86]
JSR CH3OH/O2/NO/N2 550–1000 10 1.0 [87]
Flow reactor CH3OH/O2/H2O/NO/N2 700–1450 1 0.068–2.7 [88]

CH3OH-NH3 Ignition delay CH3OH/O2/Ar/N2 845–1100 40 0.5–2.0 [1]

Flame speed CH3OH/air 298–448 1 0.7–1.8 [23]

CH4/NO Flow reactor CH4/O2/NO/Ar 473–973 6 0.7–2.1 [89]

Flow reactor CH4/O2/NO/N2/CO2 1173–1773 1 0.125–1.4 [12]
Flow reactor CH4/O2/NO/N2/H2O 800–1250 1 0.12 [90]
JSR CH4/O2/NO/Ar 650–1200 1 0.5–2 [91]
JSR CH4/O2/NO/N2 800–1150 1 0.1 [92]
JSR CH4/O2/NO/N2 800–1150 10 0.5–1.0 [93]
Burner-stabilized flame CH4/NO/O2/N2 400–1800 0.05 0.95 [94]
Flame speed CH4/NO/air 298 1 0.4–1.8 [16]
Flame speed CH4/O2/NO/N2/Ar 298 1 0.6–1.5 [95]

CH4/NO2 Shock tube CH4/NO2/He/Ar 1213–1913 1 0.5 [96]

JSR CH4/O2/NO2/Ar 650–1200 1 0.5–2 [91]
Flow reactor CH4/O2/NO/NO2/N2 598–898 20–100 0.04–116 [11]
Flow reactor CH4/O2/NO2/N2/H2O 800–1250 1 0.12 [90]
Ignition delay CH4/O2/NO2/N2/Ar 901–1650 15–30 1.0 [62]
Ignition delay CH4/O2/NO2/Ar 1016–1981 5–16 1 [97]

CH4/NH3 Flow reactor CH4/NH3/NO/NO2/O2/Ar 730–1035 1 N/A [98]

Flow reactor CH4/NH3/O2/He 1200–2000 1 1 [26]
Flow reactor CH4/NH3/O2/N2 973–1773 1 0.13–1.55 [25]
JSR CH4/NH3/O2/He 600–1200 1 0.5–2.0 [26]
Ignition delay CH4/NH3/air 1369–1804 2–5 0.5–2 [99]
Ignition delay CH4/NH3/O2/N2/Ar 900–1100 20–40 0.5–2 [100]
Flame speed CH4/NH3/air 298 1–5 0.6–1.6 [101]
Flame speed CH4/NH3/air 298 1–5 0.7–1.3 [102]
Flame speed CH4/NH3/air 298 1 0.7–1.5 [82]
Burner-stabilized flame CH4/NH3/O2/N2 400–1800 0.05 0.95 [94]

Fig. 3. Laminar flame speeds of stoichiometric (a) NH3/syngas/air, (b) NH3/CH3OH/air and (c) NH3/CH4/air at unburned gas temperature of 298 K. Symbols are
measurements from [21,23,82,83,101]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

6
X. Zhang et al. Fuel 341 (2023) 127676

Fig. 4. Laminar flame speeds of (a) NH3/syngas/air, (b) NH3/CH3OH/air and (c) NH3/CH4/air at unburned temperature of 298 K. Symbols are measurements from
[22,23,82,83,101,102]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

Fig. 5. Ignition delay times of stoichiometric NO2/CH4/O2/Ar/N2 mixtures at (a) 5 atm, (b) 10 atm, (c) 16 atm, (d) 15 atm and (e) 30 atm. Symbols are mea­
surements from [62,97]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

Fig. 6. Ignition delay times of (a-c) NH3/CH3OH/O2/Ar/N2 mixtures at 40 atm, (d-f) NH3/CH4/O2/Ar/N2 mixtures at 20 and 40 atm. Symbols are measurements
from [1,100]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

7
X. Zhang et al.
Fig. 7. (a-b) Mole fractions of CO in the atmospheric flow reactor oxidation of CO/H2O/O2/N2 with and without NO; Mole fractions of (c) NH3 and (d) NO in the
atmospheric flow reactor oxidation of NH3/H2O/O2/NO/N2 with and without CO. Symbols are measurements from [81,84]. Solid and dashed lines are the simulation
results by the present and Glarborg 2018 models [2], respectively.
S21 in the Supplementary material. In general, the present model can
reasonably predict these experimental targets and has a marginally
better performance than the Glarborg 2018 model [2].
3.1.2. Ignition delay times
Ignition delay times measured in shock tubes are helpful to examine
the intermediate- and high-temperature oxidation mechanism, while
those obtained in rapid compression machines (RCMs) are valuable for
validations at low and intermediate temperatures. Fig. 5 presents the
comparison between measured and simulated ignition delay times for
NO2/CH4 mixtures. The ignition delay data shown in Fig. 5(a – c) were
obtained from a shock tube study at various pressures and doping ratios
[97]. Both the present and Glarborg 2018 models [2] can capture pure
CH4 oxidation behavior over 5–16 atm. With increasing content of NO2,
the present model slightly underpredicts ignition delay times. Compared
with the Glarborg 2018 model [2], the present model shows better
performance. The ignition delay time data shown in Fig. 5(d and e) were
taken from RCM measurements [62]. Both models can reasonably pre­
dict pure CH4 cases at 15 and 30 atm, while the present model better
captures NO2/CH4 mixture cases, especially at higher pressures and
lower temperatures.
Fig. 6(a – c) presents the comparison of ignition delay times of NH3/
CH3OH mixtures between measurements and simulations. The experi­
mental data were obtained in an RCM with varying CH3OH contents and
equivalence ratios [1]. With increasing CH3OH content, the ignition
occurs at lower temperatures, indicating CH3OH blending can enhance
ignition reactivity of NH3. The present model can reasonably predict the
ignition delay times of both pure CH3OH and NH3/CH3OH mixtures. In
contrast, the Glarborg 2018 model [2] fails to predict these data. The
deficiency of the Glarborg model [2] in predicting the ignition delay
8
Fuel 341 (2023) 127676
times of NH3/CH3OH mixtures is mainly due to the CH3OH subset, since
it fails to predict the ignition delay times of pure CH3OH. Sensitivity
analysis for pure CH3OH mixture at ϕ = 1.0, Pc = 40 atm and Tc = 850 K
was performed based on both the present and Glarborg model [2], as
seen from Fig. S22 in the Supplementary Material. It shows that R3
(CH3OH + HO2 = CH2OH + H2O2) plays a dominant role in promoting
the ignition in both models. The rate constant of R3 updated in this
model is around 5.5 times higher than that in the Glarborg model [2],
which can explain the large prediction discrepancies between the pre­
sent and Glarborg model [2]. Fig. 6(d – f) presents the comparison be­
tween the measured and predicted ignition delay times for NH3/CH4
mixtures. The experimental data were taken from RCM measurements
[100]. With increasing CH4 content, the ignition reactivity is enhanced.
Both the present and Glarborg 2018 models [2] can reasonably predict
this experimental data, although the present model has better perfor­
mance under some cases. Additional validations against the ignition
delay times measured in shock tubes can be found in Figs. S23-S24 in the
Supplementary material. It shows that both models perform quite well.
3.2. Speciation data
3.2.1. NH3/NO/syngas
To further constrain the present model, speciation profiles of fuels,
intermediates and products were also selected to test the present model.
Fig. 7(a and b) presents the measured and predicted mole fraction
profiles of CO in the flow reactor oxidation of CO/NO/H2O/O2/N2
mixtures [81]. Both the measured and predicted results show that
blending NO results in higher temperature windows for CO conversion.
Both the present and Glarborg 2018 models [2] can reasonably capture
the experimental data. Fig. 7(c and d) presents the validation results
X. Zhang et al.
Fig. 8. Mole fractions of (a) CH3OH, (b) CH2O, (c) CO and (d) CO2 in the JSR
oxidation of CH3OH/NO/O2/N2 mixture at 10 atm, ϕ = 1.0 and τ = 1 s.
Symbols are measurements from [87]. Solid and dashed lines are the simulation
results by the present and Glarborg 2018 models [2], respectively.
against the speciation data measured in flow reactor oxidation of CO/
NH3/NO/H2O/O2/N2 mixtures [84]. Both the present and Glarborg
2018 models [2] can accurately capture the effects of CO blending on the
conversion of NH3 and NO, while the present model has better pre­
dictions in capturing NO conversion temperature windows. Additional
validations against speciation data measured in high-pressure flow re­
actors and JSRs are provided in Figs S25-S30 in the Supplementary
material. In general, the present model can adequately predict these
experimental data.
3.2.2. NH3/NO/Ch3oh
Model validations against speciation data in the oxidation of pure
CH3OH are presented in Figs S31 and S32 in the Supplementary mate­
rial. Compared with the Glarborg 2018 model [2], the present model can
better capture the temperature windows of CH3OH conversion in at­
mospheric flow reactor oxidation, and better predict the yield of CH2O
Fig. 9. Mole fractions of (a) CH4, (b) NO2, (c) NO, (d) CH2O, (e) CO and (f) CO2 in the JSR oxidation of CH4/NO/O2/Ar mixtures at 1 atm and τ = 1.5 s. Symbols are
measurements from [91]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.
9
Fuel 341 (2023) 127676
in high-pressure JSR oxidation. The validation results against the
speciation data in the oxidation of CH3OH/NOx/O2/N2 mixtures are
presented in Fig. 8 and Figs. S33-S40 in the Supplementary material. In
general, the predicted results between the present and Glarborg 2018
models [2] are close, both of which can reasonably capture the experi­
mental data.
3.2.3. NH3/NOx/Ch4
Figs. 9 and 10 present the measured and predicted speciation data in
the JSR oxidation of CH4/NO/O2/Ar and CH4/NO2/O2/Ar mixture,
respectively. Compared with the Glarborg 2018 model [2], the present
model can better predict the temperature windows of fuel conversion
and the yields of products. Additional validation results against the
speciation data measured in flow reactors, JSRs, shock tubes and pre­
mixed flames can be found in Figs S41-S51 in the Supplementary ma­
terial. In general, the present model has similar performance with the
Glarborg 2018 model [2] against the speciation data obtained at low and
atmospheric pressures, while can better predict the yields of products in
the flow reactor oxidation at high pressures [11], as seen from Fig. S43
in the Supplementary material.
Figs. 11 and 12 present the speciation data measured in the JSR
oxidation of NH3/CH4/O2/He mixtures at fuel-lean and fuel-rich con­
ditions, respectively. Compared with the Glarborg 2018 model [2], the
present model can better predict the temperature windows of fuel con­
version and the yields of products, especially under fuel-lean condition.
The over-predicted reaction rates shown in Fig. 11 by the Glarborg
model [2] are mainly due to the deficiency of NH3 subset. In our pre­
vious study [5], it was shown that the Glarborg model [2] greatly over-
predicts the NH3 conversion under lean conditions, since the rate con­
stant of the chain-termination reaction, i.e. NH2 + HO2 = NH3 + O2, is
largely under-estimated. Additional validations against the speciation
data measured in flow reactors and burner-stabilized flames are pre­
sented in Figs S52-S59 in the Supplementary material. In general, both
the present and Glarborg 2018 models [2] can reasonably capture these
experimental data.
4. Discussion
When blending C1 fuels in NH3 combustion, C1 fuel molecules and
their radicals can either react with H2-related radicals like H, O, OH and
X. Zhang et al. Fuel 341 (2023) 127676

Fig. 10. Mole fractions of (a) CH4, (b) NO2, (c) NO, (d) CH2O, (e) CO and (f) CO2 in the JSR oxidation of CH4/NO2/O2/Ar mixtures at 1 atm and τ = 1.5 s. Symbols
are measurements from [91]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

Fig. 11. Mole fractions of (a) NH3, (b) NO, (c) C2H6, (d) CH4, (e) CO and (f) CO2 in the JSR oxidation of CH4/NH3/O2/He mixture at 1 atm, ϕ = 0.5 and τ = 1.5 s.
Symbols are measurements from [26]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

Fig. 12. Mole fractions of (a) NH3, (b) NO, (c) C2H6, (d) CH4, (e) CO and (f) CO2 in the JSR oxidation of CH4/NH3/O2/He mixture at 1 atm, ϕ = 2.0 and τ = 1.5 s.
Symbols are measurements from [26]. Solid and dashed lines are the simulation results by the present and Glarborg 2018 models [2], respectively.

10
X. Zhang et al.
Fig. 13. Sensitivity analysis results of the present model for stoichiometric 50 % NH3/50 % C1 fuels/air under (a-c) Tu = 298 K, Pu = 1 atm and (d-e) Tc = 850 K, Pc
= 40 atm. C/N interaction reactions are highlighted with red color. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)
HO2, or react with N-containing species like NH, NH2, NO and NO2.
Therefore, the C/H and C/N interaction reactions could be competitive.
To study the role of cross reactions between C- and N-containing species,
sensitivity analyses were performed for the NH3/syngas, NH3/CH3OH
and NH3/CH4 mixtures under both flame and autoignition conditions, as
seen from Fig. 13. The results show that the C/N interaction reactions
are not sensitive under flame conditions, while they can be sensitive
reactions under autoignition conditions. To explain the sensitivity ana­
lyses results, rate constants of C/N interaction reactions are compared
with those between C-containing species and H2-related radicals, as seen
from Fig. 14. Meanwhile, the critical radical pools of stoichiometric
NH3/C1 fuel oxidation under typical flame and ignition conditions are
compared in Fig. 15. The peak mole fractions of H, O, OH, HO2, NH,
NH2, NO, NO2 are predicted by the present model under flame propa­
gation and ignition conditions.
In NH3/syngas oxidation, the most important C/H cross reaction is
11
Fuel 341 (2023) 127676
R53. This reaction has a much higher rate constant than the C/N
interaction reactions (i.e. CO + NH2 = HNCO + H and CO + NO2 = CO2
+ NO), as seen from Fig. 14a. Besides, OH radical has much higher
concentration than NH2 and NO2, indicating the C/H cross reaction R53
plays a dominant role in NH3/syngas oxidation compared with C/N
cross reactions.
CO + OH = CO2 + H (R53)
In NH3/CH3OH oxidation, the H-abstraction reactions of CH3OH by
H2-related and N-related radicals are important chain-propagation re­
actions and are responsible for CH3OH conversion. Their rate constants
are compared in Fig. 14b. It is found that the H-abstraction reactions of
CH3OH by H2-related radicals (i.e. H, O, OH, black lines in Fig. 14b) are
more than one order of magnitude higher than those by N-related rad­
icals (i.e. NH2, NO, NO2, red lines in Fig. 14b), while the concentration
levels between H2-related radicals and N-related radicals are in the same
X. Zhang et al.
Fig. 14. Rate constants comparison between selected C/H and C/N cross reactions. The rate constants are taken from the present model.
Fig. 15. Predicted radical pool distributions in the oxidation of stoichiometric 50 % NH3/50 % C1 fuels under typical (a) flame (unburned temperature of 298 K,
pressure of 1 atm) and (b) ignition (850 K, 40 atm) conditions.
order of magnitude (see Fig. 15). Therefore, for the CH3OH related re­
actions, C/N interaction reactions can hardly compete with C/H cross
reactions in NH3/CH3OH oxidation. As seen from Fig. 13e, the sensi­
tivity coefficients of H-abstraction reactions of CH3OH by NH2/NO2 are
two orders of magnitude smaller than that by HO2. The rate constants of
CH2OH related reactions are not compared, since the contribution of
R41 (CH2OH + O2 = CH2O + HO2) is dominant compared with the re­
actions between CH2OH and radicals in NH3/CH3OH oxidation [1].
In NH3/CH4 oxidation, the rate constants of H-abstraction reactions
of CH4 by H2-related and N-related radicals are compared in Fig. 14c.
Similar to NH3/CH3OH oxidation, the concentrations between H2-
related radicals and N-related radicals are in the same order of magni­
tude (see Fig. 15), while the rate constants of CH4 + H2-related radicals
are much higher than those of CH4 + N-related reactions (see Fig. 14c),
making the C/N cross reactions less competitive. Unlike CH2OH radical,
CH3 radical has multiple important consumption pathways. As seen
from Fig. 14d, the rate constant of R4 (CH3 + H(+M) = CH4(+M)) is in
the same order of magnitude with R47 (CH3 + NH2 = CH3NH2), and the
concentrations between H and NH2 in NH3/CH4 oxidation are close
under ignition condition (see Fig. 15b). Therefore, R47 could be
competitive with R4 under ignition conditions. In addition, under
ignition conditions, HO2 and NO2 become important radicals. The
concentration of NO2 is much higher than HO2 in the oxidation of NH3/
CH4 mixture (see Fig. 15b), while the rate constants between CH3 + HO2
12
Fuel 341 (2023) 127676
= CH3O + OH and R48 (CH3 + NO2 = CH3O + NO) are close, indicating
the C/N interaction reaction R48 could play an important role under
ignition conditions. This analysis can explain the reactions between CH3
and NO2 become sensitive reactions under ignition conditions, as shown
in Fig. 13.
In summary, the rate constants of C/H cross reactions are generally
faster than (or close to) those of C/N ones in NH3/C1 systems. Under
flame conditions, H2-related radicals (i.e. H, O, OH) have generally
higher concentrations than reactive N-related radicals (NH, NH2, NO2).
Therefore, under these conditions, C-containing species are more likely
to react with H2-related radicals rather than N-related ones, making the
C/N cross reactions less competitive. This can explain the conclusions
drawn in previous studies under flame propagation conditions [23]—
the cross reactions between C- and N-containing species are insignifi­
cant. In contrast, under low- and intermediate-temperature conditions, i.
e. typical ignition conditions, the concentrations of H and O radicals
decrease, while those of NH2 and NO2 increase, thereby making C/N
interaction reactions possible to compete with C/H reactions.
5. Conclusions
In this work, a comprehensive kinetic model for NH3/syngas/
CH3OH/CH4 was proposed based on our ongoing modeling studies for
pure NH3 and small hydrocarbon fuels. Critical cross reactions between
X. Zhang et al.
C- and N-containing species were evaluated based on previous experi­
mental, modeling and theoretical calculation studies. The proposed
model was tested against previous experimental data for both NH3/C1
and NOx/C1 fuels, covering temperatures of 473–2000 K, pressures of
0.04–100 atm, and equivalence ratios of 0.04–116. In general, the pre­
sent model adequately predicts all the selected validation targets.
Compared with the previous Glarborg 2018 model [2], the present
model can better predict laminar flame speeds and ignition delay times
obtained in RCMs. The present model can not only be used to predict the
combustion of NH3/C1 fuel mixtures, but is also capable to predict the
mutual interaction of NOx/C1 fuels. It is found that the rate constants of
critical C/H cross reactions are generally faster than (or close to) those of
C/N cross reactions. Under flame conditions, H2-related radicals (i.e. H,
O, OH) have higher concentrations than reactive N-related radicals (NH,
NH2, NO2). Therefore, under these conditions, C-containing species are
more likely to react with H2-related radicals rather than N-related ones,
making the C/N cross reactions less competitive. However, under low-
and intermediate-temperature conditions, the concentrations of H and O
radicals become lower, while those of NH2 and NO2 become higher,
making cross reactions between C- and N-containing species possible to
compete with C/H cross reactions. The present model can be used as the
base chemistry subset for NH3/larger hydrocarbon fuels.
CRediT authorship contribution statement
Xiaoyuan Zhang: Conceptualization, Methodology, Validation,
Data curation, Writing – original draft. Kiran K. Yalamanchi: Meth­
odology. S. Mani Sarathy: Writing – review & editing, Funding
acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
This paper is based on work supported by the Saudi Aramco Research
and Development Center FUELCOM3 Program under Master Research
Agreement Number 6600024505/01. FUELCOM (Fuel Combustion for
Advanced Engines) is a collaborative research undertaking between
Saudi Aramco and KAUST, intended to address the fundamental aspects
of hydrocarbon fuel combustion in engines, and develop fuel/engine
design tools suitable for advanced combustion modes. This work is also
supported by King Abdullah University of Science and Technology
(KAUST) with funds allocated to the Clean Combustion Research Center.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2023.127676.
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