Fuel 365 (2024) 131179

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Chemical kinetic study of gasoline surrogate with ammonia on combustion:

Iso-octane modeling
Zechang Liu a, b, Xu He a, b, *, Guangyuan Feng a, b, Chengyuan Zhao a, b, Xiaoran Zhou a, b,
Zhi Wang c, Qingchu Chen c
a
School of Mechanical Engineering, Beijing Institute of Technology, Beijing 100081, China
b
Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081, China
c
School of Vehicle and Mobility, Tsinghua University, Beijing 100084, China

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

Keywords: To facilitate the transition towards a carbon–neutral society, it is necessary to undertake comprehensive research
iC8H18/NH3 on the utilization of ammonia in gasoline engine applications. In the present work, a new chemical kinetic
Laminar burning velocity mechanism for iso-octane/ammonia (iC8H18/NH3) was proposed and widely validated with the experiment data
Kinetic model
of ignition delay time (IDT) and laminar burning velocity (SL ). The iC8H18 model of Cai [Combust. Flame, 162,
Flame chemistry
2015] and NH3 model of Zhang [Combust. Flame, 234, 2021] was chosen as the based model, and they con­
nected through the chemical coupling between the iC8H18 and the NH2 chemistry. In addition, the influence of C-
N interaction on the prediction ability of iC8H18/NH3 model was also analyzed and found that the H-abstraction
reaction between NH2 and iC8H18 is the key reaction affecting the IDT and SL of mixture. Present work was also
focused on the chemistry kinetic of iC8H18/NH3 mixture. The reaction pathway analysis shows that the addition
of NH3 slightly enhanced the H-abstraction reaction of iC8H18 in tertiary site (cC8H17) and slightly inhibited the
H-abstraction reaction of primary site (aC8H17, bC8H17, and dC8H17). In the end, the mole fraction of NO in
iC8H18/NH3 flames is analyzed. The results show that NH3 addition increased the concentration of NO, but with
the gradual increase of equivalence ratio, the increasing trend of NO concentration gradually decreases. A higher
equivalence ratio can be selected to effectively control the increase of NOx concentration. Through the analysis
of NO formation and reduction reaction pathway, it was found that NH3 addition increases the mole fraction of
NH2 radical, the NO formation pathway was stronger than NO reduction pathway due to the sufficient OH
radical, and finally leading to the increase of NO concentration. However, with the increase of equivalence ratio,
the concentration of NH2 radical exceeds OH, and the number of OH is insufficient in satisfying the NH3-related
NO reaction pathway, resulting in a decrease of the influence of NH3 addition on NO concentration.

ammonia (NH3) offers a notable advantage over hydrogen owing to its

superior energy density. Taking into account the lower heating value
1. Introduction
loss, the overall energy requirements for producing and delivering
ammonia to end-users are estimated to be lower than those for trans­
The combustion of fossil fuels leads to substantial emissions of pol­
porting liquid hydrogen. However, in comparison to conventional hy­
lutants, giving rise to a range of environmental and health issues. As a
drocarbons, the practical utilization of ammonia does come with certain
result, there has been a growing focus on the exploration of hybrid
drawbacks. These drawbacks encompass a slower laminar flame speed,
power devices, innovative combustion techniques, cleaner alternative
higher ignition energy requirements, limited chemical reactivity, and
fuels, and sustainable energy solutions. This encompasses advancements
increased emissions of nitrogen-based pollutants. Previous research has
in storage technology as well [1–8].
suggested using flame enhancement (including hydrogen [10,11],
In recent years, hydrogen has gained significant attention as an
various hydrocarbon fuels like methane [12–17], dimethyl ether [17], n-
efficient and environmentally friendly energy source. However, the
heptane [18,19], aromatic hydrocarbons [14,15], and such oxygen-
inherent physical and chemical properties of hydrogen present chal­
containing fuels as dimethoxymethane (DMM) [16] and methanol
lenges related to safety, storage, and transportation [9]. In contrast,

* Corresponding author.
E-mail address: hhexxu@bit.edu.cn (X. He).

https://doi.org/10.1016/j.fuel.2024.131179
Received 21 November 2023; Received in revised form 9 January 2024; Accepted 6 February 2024
Available online 15 February 2024
0016-2361/© 2024 Elsevier Ltd. All rights reserved.
Z. Liu et al.
Nomenclature
SL Laminar flame speed
P Initial pressure
Ti Initial temperature of SL
XNH3 ammonia mole fraction
IDT Ignition delay time
φ Equivalence Ratio
T Initial temperature of IDT
[20]) as a viable approach to overcome these hurdles in ammonia
combustion. In the context of gas-turbine power generation, methane
(CH4) has been extensively explored as a flame enhancement fuel and
numerous studies have been dedicated to this area of research [12–16].
When considering the transition towards a carbon-free society, it’s
crucial to acknowledge that the exploration of ammonia as a potential
fuel in internal combustion engines (ICE), especially in the context of
gasoline engine applications, remains relatively limited.
One vital problem is that the exhaust temperature of gasoline engine
is high⋅NH3, as a nitrogen-containing fuel, when used in the field of
gasoline engine, may cause external pollutant emission. For NOx after
treatment, currently, the most effective methods involve employing
three-way catalytic (TWC) converters coated with rhodium (Rh), plat­
inum (Pt), and palladium (Pd), and selective catalytic reduction (SCR)
converters based on small-pore zeolites (Cu/SSZ-13) [21]. Grannell et al.
[22] examined the efficacy of employing a TWC for mitigating pollut­
ants in an ammonia-gasoline engine, but lean-burn must be absolutely
avoided. They suggest that the TWC can proficiently convert CO, HC,
NH3, and NO, maintaining an air–fuel ratio within the range of stoi­
chiometric and slightly rich conditions of 0.2 %. In addition, for lean
combustion scenarios, the study of Qi et al. [23] pointed out that the
most substantiated and efficient approach currently verified involves the
use of ammonia slip catalyst (ASC). This catalyst selectively oxidizes
unburned or secondarily produced NH3 in the exhaust, converting it into
benign N2. Therefore, the challenge of pollutant emissions from
ammonia-gasoline blended fuels can be mitigated by employing the
TWC and ASC methodologies.
Meanwhile, it’s important to note that the composition of base gas­
oline can vary significantly due to diverse crude oil sources and various
processing techniques employed in its production. Therefore, re­
searchers adopted surrogate fuels for the research of gasoline, such as n-
heptane, iso-octane, and toluene [24–32]. In recent years, TRF (n-hep­
tane, isooctane, and toluene) has been considered the most suitable
surrogate fuel of gasoline, and many experimental studies on the
laminar burning velocity of TRF were conducted under different initial
conditions [33–39].
However, it is also should note that within the composition of gas­
oline, iC8H18 stands out as one of the major constituents and plays a
critical role in determining the fuel’s octane rating, which reflects its
resistance to detonation. As a result, studying the behavior of mixtures
containing iC8H18 and NH3 serves as a fundamental investigation, laying
the groundwork for more complex gasoline/NH3 blends. Moreover,
gasoline is a highly complex mixture that comprises a wide range of
hydrocarbon compounds. By initially focusing on the reaction between
single components, such as iC8H18, the complexity of the problem is
reduced. This simplification makes it more feasible to gain a compre­
hensive understanding of the fundamental chemical reaction kinetics
and mechanisms involved in these interactions. Such research is vital for
advancing our knowledge of ammonia’s potential as an alternative fuel
in the context of gasoline engines as we work towards a sustainable,
carbon-free future. Limited research has been conducted on the funda­
mental combustion properties of iC8H18/NH3 blends. Liu et al. [40]
explored the impact of NH3 addition on various aspects, including knock
2
Fuel 365 (2024) 131179
suppression, combustion characteristics, thermal efficiency, and emis­
sion performance of gasoline. Zhang et al. [41] measured the IDT of
iC8H18/NH3 mixtures in the rapid compressed machine (RCM) and
developed a simplified mechanism for iC8H18/NH3 blends. However,
their study shows that the simplified mechanism struggled to accurately
capture the IDT trend. Furthermore, Lubrano et al. [18] examined the SL
and chemical kinetic characteristics of n-heptane/NH3 and iC8H18/NH3
mixtures. They utilized the CRECK model [42], but our previous study
[43] found that CRECK model tended to overestimate the SL .
In summary, there remains a lack of widely validated kinetic
mechanism for iC8H18/NH3 mixture that accounts for various combus­
tion properties such as SL, IDT, and stable species concentrations. It is
crucial to advance our understanding of the combustion behavior of
these blends and their potential as alternatives in ICE. Therefore, the
objectives of the present study are threefold: (1) developing a new ki­
netic mechanism for iC8H18/NH3 mixtures, ensuring that it accurately
reproduces experimental data; (2) conducting an in-depth analysis of the
flame chemistry of iC8H18/NH3 blends to shed light on how the intro­
duction of NH3 affects the combustion behavior of iC8H18; (3) investi­
gating the influence of NH3 addition on the concentration of NO and
provide a detailed examination of the chemical kinetics responsible for
NO emissions.
2. Modeling
2.1. Kinetic modeling
In this study, the chemical kinetics model is composed of three key
components: the TRF (Toluene Reference Fuel) mechanism representing
gasoline surrogate fuel, an NH3 mechanism, and the chemical coupling
between the iC8H18 and the NH2 chemistry. Detailed mechanisms and
thermodynamic, transport data can be accessed in the supplementary
materials.
The TRF mechanism employed in this study adopts a recently opti­
mized model by Cai and Pitsch [44], in which the rate rules assigned by
Curran et al. [45] were calibrated to match the IDT for iC8H18 in [46],
which limits the agreement of the model to a broader set of target data.
The Cai model has been subjected to comprehensive validation to ensure
its accuracy and reliability.
In the context of the ammonia mechanism, several kinetic models for
ammonia combustion have emerged in recent years, each aimed at
elucidating the oxidation of ammonia as a primary fuel component.
These models, as referenced in the literature, include the works of Han
et al. [47], Mei et al. [48], Stagni et al. [49], Okafor et al. [12], Wang
et al. [15], Glarborg et al.[50], Zhang et al. [51], and Dai et al. [52],
Shrestha et al. [53], Konnov et al. [54]. They have been developed to
capture the intricacies of ammonia combustion and its associated re­
actions. In a comparative study by Yin et al. [55], various NH3 models
were assessed for their performance concerning SL , IDT, and the con­
centration of stable species. The results revealed that the model pro­
posed by Zhang et al. [51] exhibited superior performance, leading to its
selection as the NH3 sub-model in the present study. Furthermore, for
the interaction mechanisms involving NH3 and C1-C2 species, the
mechanism from Glarborg et al. [50] was adopted and integrated into
the present model.
One of the key objectives of this study is to establish a chemical
coupling between the iC8H18 and the NH2 chemistry, including H-
abstraction reactions between NH2 and alkanes or alkenes. H-abstrac­
tion reactions (R1-R4) play a significant role in influencing the IDT and
the concentrations of species in iC8H18/NH3 mixtures. It’s noteworthy
that, as of now, there haven’t been any reported reaction rate constants
available in the literature for reactions R1-R4. In previous studies, Mebel
et al. [56] calculated the reaction rate constants for the primary and
tertiary H-abstraction reactions of NH2 with iso-butane (i-C4H10) using
the G2M energy, molecular, and transition state parameters within the
framework of transition state theory with tunneling corrections. The rate
Z. Liu et al.
constants for reactions R1-R4 were estimated by unifying the reactions
of iC8H18 and i-C4H10 to the correct degeneracy level, and then
employing the rate constant analogy estimation using K2 = K1 (d1 d2 1.5
) , K2,
K1 and d2, d1 are the rate constants and chemical degeneracy of iC8H18
and i-C4H10, respectively. Subsequently, rate constants for reactions R1-
R4 were scaled to complete the experiment data, and the final rate
constant of R1-R4 are shown in Table 1. Although the IDT is highly
sensitive to reactions R1-R4, the sensitivity of the pre-exponential factor
is relatively small. Therefore, uncertainties associated with the analogy
method are expected to have small impact on model predictions [57].
Furthermore, to enhance the accuracy of the model, H-abstraction
reactions for small alkanes/alkenes were incorporated from the work of
Thoren et al. [57]. Yin et al. [58] developed a mechanism for C3H8/NH3
mixtures and validated it using experimental data on species concen­
trations. The H-abstraction reactions of C3H8 attacked by NH2 radicals
related reactions were also integrated into the current mechanism to
ensure a comprehensive and reliable representation of the chemistry
involved.
In the present work, the NOx of TRF/NH3 mixture also needs to be
discussed. Recently, Fang et al. [59] established a coupled chemical
kinetics model for TRF/NOx based on IDT experimental data of iC8H18/
NO. This model includes a subset of reactions such as the H-abstraction
of iC8H18 attached by NO or NO2 (R5-R8). These reactions are also
incorporated into the present model.
iC8H18 + NO/NO2 = aC8H17 + HNO/HONO
iC8H18 + NO/NO2 = bC8H17 + HNO/HONO
iC8H18 + NO/NO2 = cC8H17 + HNO/HONO
iC8H18 + NO/NO2 = dC8H17 + HNO/HONO
Fig. 1 shows the main reaction schemes described in the current ki­
netics model. It includes typical high-temperature and low-temperature
reactions of iC8H18, as well as interactions between NH3 and fuel spe­
cies. The main high-temperature reaction pathway is shown in the green
box, and the main low-temperature reaction pathway is shown in the
blue box. The red arrow indicates the crossed reactions between NH3
and iC8H18.
In addition, previous studies have demonstrated the vital role of
transport characteristics in the simulation of flame propagation, along
with the substantial uncertainty associated with transport parameters
[60,61]. Conventional methods currently employed for estimating
transport characteristics commonly rely on the utilization of the 12–6
Lennard-Jones (LJ) potential, computed through the implementation of
combination rules for similar molecular pairs [62]. However, it has been
highlighted by Paul and Warnatz [63] that the repulsive potential of LJ
(12–6) tends to be consistently steeper than the actual potential, thereby
resulting in inaccurate determination of the temperature-dependent
transport properties. In recent years, certain studies have utilized ab
initio potentials for calculating the transport properties of classical
collision pairs (such as H-O2, H2O-H, H-CO, etc.) [64]. Under typical
flame temperatures, these calculations reveal a substantial deviation
from the conventional 12–6 Lennard-Jones (LJ) potential computations,
thereby highlighting the enhanced diffusion characterization of small
entities such as OH, O, and H. Building upon the aforementioned
Table 1
The main added and updated reactions in the chemical kinetic model. The rate
constants are in the form of k = A Tn exp (− Ea/(RT)). Units are mole (mol),
centimeter (cm), Kelvin temperature (K), second (s), and calorie (cal).
No Reaction k n Ea Source
R1 iC8H18 + NH2 = aC8H17 + NH3 1.02E + 02 3.61 3342 pw
R2 iC8H18 + NH2 = bC8H17 + NH3 1.05E + 01 3.61 3342 pw
R3 iC8H18 + NH2 = cC8H17 + NH3 9.69E + 02 3.16 1925 pw
R4 iC8H18 + NH2 = dC8H17 + NH3 0.19E + 01 3.61 3342 pw
Fuel 365 (2024) 131179
investigations, a recent study conducted by Jasper et al. [65] employed
first-principle calculations to develop a novel transport database
explicitly tailored for direct integration into Chemkin. Konnov et al. [66]
incorporated this comprehensive database into a kinetic model of H2
combustion and observed significant enhancements in the model per­
formance due to the utilization of updated transport properties. Given
the fact that the H2-O2 oxidation mechanism constitutes a crucial aspect
influencing the flame velocity of hydrocarbon fuels, we also adopted the
new transport properties of Konnov model [66] in our present model.
2.2. Simulation setup
In this study, a steady-state one-dimensional laminar premixed
flame, propagating freely, was simulated utilizing the Chemkin Pro
software [67]. The computational domain was established with a length
of 10 cm, employing a maximum of 500 grid points. The adaptive grid
was controlled based on the solution gradient and curvature, with the
control parameters set at 0.1 and 0.1, respectively. The simulation
incorporated the Soret effect and utilized mixture-averaged transport
models. The computation of IDT was conducted using the Close Ho­
mogeneous Batch Reactor module within the Chemkin Pro software. The
shock tube was treated as a zero-dimensional adiabatic reactor charac­
terized by constant volume. The ignition point is defined as the time
when the initial temperature rises by 400 K. Additionally, the oxidation
simulation of the jet-stirred reactor was performed using the Perfectly
(R5) Stirred Reactor (PSR) module available in the Chemkin Pro software
[31,68].
(R6)
(R7) 3. Results and discussion
(R8) 3.1. Ignition delay time validation
To effectively demonstrate the performance of the current kinetic
mechanism, it is essential to validate it against experimental IDT data for
iC8H18/NH3 mixtures. In Fig. 2, IDT measurements for a 20 mol%
iC8H18/80 % NH3/O2/N2/Ar mixture, conducted by Zhang et al. [41],
are presented. These experiments covered a temperature range of T =
630–840 K, pressure range of P = 15–20 bar, and equivalence ratio ϕ =
1.0. The experimental measurement error is within 15 %. The solid line
in Fig. 2 represents the numerical results obtained from the present
model. For comparative purposes, we also compared two other kinetic
mechanisms: the Zhang model [41] and the Fang model [59]. The Zhang
model combines the iso-octane model developed by Curran et al. [45]
with the ammonia model from Glarborg et al. [50], though it doesn’t
consider C-N cross reactions. On the other hand, the Fang model is
specifically designed for iC8H18/NOx interactions and includes C-N cross
and NH3-related reactions but excludes the NH2 + iC8H18 reactions.
It is evident that both the Zhang and Fang models tend to exhibit
certain limitations. They generally underestimate the IDT experimental
data at T = 710–770 K while overestimating it at temperatures below
710 K and it failed to capture various trends of the experimental data. In
contrast, the present model, while still underestimating the experi­
mental data at P = 15 bar, reasonably captures the overall IDT trend.
The current model’s underestimation of experimental values may pri­
marily stem from two reasons: (1) lack of experimental data on reactor
volume history. Zhang et al. [41] did not provide experimental data on
the volume history of the RCM. Our simulation directly adopts an iso­
choric reactor, which introduces a difference compared to the actual
experimental conditions. It is important to note that the use of an iso­
choric reactor in simulations might not fully capture the complexities
introduced by the dynamic volume changes in the actual experimental
setup. The lack of information on the volume history hampers the
model’s ability to accurately account for heat losses and other volume-
related effects; (2) the present model’s underestimation of experi­
mental data may be caused by Cai model’s underestimation of experi­
mental data of iC8H18-air flame.
3
Z. Liu et al. Fuel 365 (2024) 131179

Fig. 1. Ic8H18/NH3 reaction pathway diagram in the present model. The main high-temperature reaction path is shown in the green box, and the main low-
temperature reaction path is shown in the blue box. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)

Fig. 2. The idt data of 20 % iC8H18/80 %NH3 mixture at T = 630–800 K, P = 15–20 bar, ϕ=1.0. Symbol: experiment data of Zhang et al. [41]; Solid line: present
model; Dash line: Fang model; Dot line: Zhang model.

To gain further insights into the behavior of the present model, Fig. 3
presents numerical results from the Cai model for the IDT of iC8H18/air
mixtures at T = 640 K- 900 K. And the experiment data were obtained
from the studies of Atef et al. [69]. Notably, the Cai model demonstrates
an underestimation of the IDT of pure iC8H18/air mixtures.
Another important purpose of the present study is to investigate how
the C-N cross-reaction affect the iC8H18/NH3 mixture, and to provide
guidance for the development of reduced mechanisms. Fig. 4 shows the
sensitivity analysis of the iC8H18/NH3 mixture at P = 15 bar, ϕ = 1.0, T
= 646 K (a) and 795 K (b). First, it can be seen that R1632: NH3 + OH =
NH2 + H2O reaction has the largest negative sensitivity coefficient at all
temperatures, because R1632 is the main NH3 consumption reaction,
consuming a large number of OH radicals and inhibiting ignition. In
addition, at the T = 646 K, R1533: NH2 + HO2 = H2NO + OH can
promote ignition, because R1533 forms H2NO at low temperature, and
then the overall reaction activity is improved by the rapid oxidation of
H2NO →HNO→ NO [49]. It is interesting to note that R2337: iC8H18 +
NH2 = cC8H17 + NH3 and R2335: iC8H18 + NH2 = aC8H17 + NH3 have
opposite sensitivity in the T = 795 K. This is mainly because the H-
abstraction from the primary site (aC8H17) increases the overall reac­
tivity, while the H-abstraction from the tertiary site (cC8H17) decreases
reactivity due to the lack of low temperature chain branching paths and
the production of relatively inactive alkenes [69], so the sensitivity of
the H-abstraction of iC8H18 attacked by NH2 at different sites is also
different.
In conclusion, in C-N cross-reactions, only R2337 and R2335 showed

4
Z. Liu et al. Fuel 365 (2024) 131179

the above analysis of C-N cross interaction on IDT is effective in all

temperature zones.

3.2. Laminar burning velocity validation

In this section, the validation of the present kinetic model for iC8H18/
NH3, is presented. For iC8H18/NH3 mixtures, the SL considered in the
validation varies over ranges of initial temperature, pressure, and
equivalence ratio.

3.2.1. Model validation against the SL data of iC8H18/NH3 mixtures

Fig. 6 compares the measured SL of iC8H18/NH3-air mixtures at P = 1
atm, XNH3 = 0–70 %, and Ti = 400 K (a) and 470 K (b) with the simulated
results from the present model. Ti is different from T shown above, Ti
represents the initial temperature of SL , and T represents the initial
temperature of IDT. It is apparent that the model closely predicts the
measurements forXNH3 = 0–70 % in all of ϕ with high fidelity within the
bounds of experimental uncertainty. This shows that the present model
(model I) can effectively capture the SL of iC8H18/NH3 mixtures at
Fig. 3. IDT profiles of iC8H18 measured experimentally at the UCONN RCM
facility and the corresponding simulations. Solid lines represent simulations
different initial temperature and XNH3 .
using the Cai model. For SL measurements, the spherical flame technique has been widely
considered a highly reliable method, particularly for examining flames
at high pressures. Therefore, the SL of iC8H18/NH3 mixtures at P = 2–4
significant sensitivity coefficients to IDT. In order to more clearly
atm and XNH3 = 0–50 % was validated with the kinetic model (model I).
explain the influence of C-N cross-reaction on IDT, we divided the
As depicted in Fig. 7, the present model (model I) accurately captures
mechanism into three parts: model I: NH3 reactions + iC8H18 reactions
the measured SL at ϕ = 0.8 and 1.0 within the experimental uncertainty,
+ all C-N cross-reactions; II: NH3 reactions + iC8H18 reactions + R1-R4
while slightly underestimating the measured SL at ϕ = 1.2. This may be
reactions; III: NH3 reactions + iC8H18 reactions and removed all the C-N
attributed to the fact that, with the increase of initial pressure, the flame
cross-reactions. The contrast between the different mechanisms can
surface begins to exhibit cellular instability, leading to a higher value of
illustrate the effect of the different C-N cross-reaction on IDT. In addi­
measured SL . In general, the present model can well capture experi­
tion, it should be noted that the experimental data of IDT for iC8H18/
mental data under high pressure.
NH3 by Zhang et al. [41]. was mainly in the middle and low tempera­
Although there are some discrepancies between the simulation and
ture, and the influence of C-N cross-reaction on IDT at high temperature
experimental data for the iC8H18 and NH3 binary blends, the present
was not clear. As shown in Fig. 5, the effect of C-N interaction on the
model accurately captures the experimental trends, demonstrating its
middle and low temperature region is obviously greater than that on the
potential in characterizing flame kinetics and serving as a foundation for
high temperature region, and the effect on IDT in the high temperature
further improvements.
region is basically negligible. Fig. 5 compares the numerical calculation
In addition to IDT, the influence of C-N cross reaction on flame ve­
results obtained by mechanisms I, II, and III of iC8H18/NH3 mixture at P
locity should also be discussed here to guide the development of
= 15 bar, T = 650 K-1100 K, ϕ= 1.0. It can be seen that the C-N inter­
simplified mechanisms. In a previous study by Han et al.[70], it was
action reaction significantly shortens the IDT of the mixture. The
indicated that the influence of C-N cross-reactions on the SL of NH3 bi­
mechanisms I and III both can capture the changing trend of IDT well,
nary mixture could be disregarded. However, Han’s research only
indicating that only the H-abstraction reaction between NH2 and iC8H18
considered the interaction between NH3 and small molecules of C1-C2,
needs to be included in the construction of the reduced mechanism and
without taking into account the impact of the chemical coupling set

Fig. 4. The sensitivity analysis of 20 % iC8H18/80 %NH3 mixture at T = 646 K (a) and 795 K (b), P = 15 bar andϕ = 1.0.

5
Z. Liu et al.
Fig. 5. The idt data of 20 %iC8H18/80 %NH3 mixture at T = 630–800 K, P =
15 bar, ϕ = 1.0. Symbol: experiment data of Zhang et al. [41]; Solid line: model
I; Dash line: model III; Dash dot line: model II.
between NH2 and hydrocarbon fuels. Therefore, in Fig. 8, we compared
the simulated result of models I, II, and III for the SL of iC8H18/NH3
mixtures under different conditions. We divided the mechanism into
three parts: I: NH3 reactions + iC8H18 reactions + all C-N cross-
reactions; II: NH3 reactions + iC8H18 reactions + R1-R4 reactions; III:
NH3 reactions + iC8H18 reactions and removed all the C-N cross-
reactions. It can be observed that, although C-N cross-reactions do
have an effect on SL , given the experimental errors associated with
laminar flame speeds themselves, this particular influence can be
considered negligible.
3.3. iC8H18/NH3 flame chemistry
3.3.1. Chemical effect of NH3
Reaction path analysis enables a more quantitative tracking of
iC8H18 oxidation and how NH3 addition influences the oxidation routes
of iC8H18, further elucidating the kinetic effect. The results of a primary
reaction pathway analysis of iC8H18/NH3 at Ti = 400 K, P = 1 bar, XNH3 =
Fig. 6. TheSL of iC8H18/NH3-air mixtures measured in constant-volume method at ϕ = 0.8–1.3, P = 1 atm and Ti = 400 K (a) and 470 K (b). Symbols are
experimental data from our previous work [43]. Solid lines show the numerical results for the present model (model I).
6
Fuel 365 (2024) 131179
30–50 % and ϕ = 1.0 are shown in Fig. 9. The percentage of a species
consumed by a specific route is also indicated on each arrow. The red,
and blue colors indicate XNH3 = 50 %, and 30 %, respectively.
The main iC8H18 high-temperature reaction pathway can be
concluded as: RH → R →β-scission products → fragment. The initial
oxidation of iC8H18 by H-abstraction reaction plays a crucial role in the
overall reaction path. In the H-abstraction reactions, the formation of
cC8H17 is the predominant pathway due to the lower bond energy of
cC8H17. H-abstraction is mainly attacked by H radicals.
With NH3 addition, the reaction pathways for iC8H18 oxidation
remain unaltered, while their relative importance is altered. It is inter­
esting that, as ammonia was added, the proportion of aC8H17, bC8H17
and dC8H17 formation channels in the H-abstraction reaction slightly
decreased, but the proportion of cC8H17 reaction channels increased.
This reaction path is the main channel of iC8H18 consumption, which
seems to indicate that the addition of NH3 introduces a large number of
NH2 radicals to participate in the H-abstraction reaction of iC8H18, and
promotes the initial oxidation. And then, cC8H17 rapidly generates iC4H8
and tC4H9 through beta-sicission in the subsequent high-temperature
reaction, and these species consume the active free radicals, thereby
reducing SL , so this may be one of the reasons why the addition of NH3
reduces the flame speed of iC8H18/NH3 mixture.
Fig. 10 (a) and (b) show the NH3 reaction paths ofXNH3 = 30 % (a)
and 70 % (b) atϕ = 1.0 (black) and 1.3 (red), respectively. It can be seen
that the primary oxidation consumption of NH3 is mainly through the H-
abstraction reaction of OH to generate NH2. In order to better explain
the subsequent reaction path of NH2, it is divided into five pathways: (i)
it combines with HO2 to generate H2NO, and H2NO is then converted
into HNO and finally to generate NO; (ii) Combined with iC8H18 to
generate NH3; (iii) Combined with NO to generate NNH or directly
generate N2; (iv) converted to NH, and then, NH is then combined with
NO/CH3 to form N2O/CH2NH, N2O is converted to N2 in subsequent
reactions, and CH2NH is further converted to HCN; (v) combined with O
to generate HNO and finally converted to NO.
Firstly, the influence of XNH3 on reaction pathway was analyzed. In
the comparison between Fig. 10 (a) and (b), it can be found that atφ =
1.0 %, the main channel of NH2 radical consumption is (ii), (iv) and (v),
in which the reaction channel (iv) accounts for the largest proportion
(57.1 %). With the increase of XNH3 , the reaction channel (i) (6.82 %
− 5.16 %) and (v) (26.1 % − 22.3 %) decreased and channel (v)
increased (57.1 %-59.6). In general, the proportion of each channel is
Z. Liu et al. Fuel 365 (2024) 131179

Fig. 7. TheSL of iC8H18/NH3/air mixture measured in constant-volume method for ϕ = 0.8–1.2, Ti = 400 K and P = 2 atm (a) and P = 4 atm (b). Symbols are
experimental data from our previous work [43]. Solid lines show the numerical results from the present model (model I).

basically unchanged.
Secondly, the influence of equivalence ratio on NH3 reaction
pathway was analyzed. When the XNH3 = 70 % and ϕ = 1.0–1.3, it can be
found that NH3 generation is still mainly through the H-abstraction re­
action of OH to NH2 (94.4 %-94.8 %) with the ϕ increase from 1.0 to 1.3.
However, with the increase of the ϕ, the proportion of (iv) in reaction
channels increased, and the proportion of channels (v) and (i) decreased
rapidly. NH2-NH-N2 becomes the main path of NH3 consumption at high
ϕ. In addition, it should also be noted that as the ϕ increases, the pro­
portion of the reaction path where NH combines with CH3 to form
CH2NH also increases, which is an important reaction path for NOx
generation in hydrocarbon fuels.

3.3.2. Stable species concentration validation

Fig. 8. TheSL data of iC8H18/NH3 mixture at Ti = 400 K, P = 1 bar, ϕ = 1.0.
Symbol: experiment data; Solid line: model I; Dash line: model II; Dash dot line:
model III.
Ammonia contains a nitrogen atom in its molecule; therefore,
ammonia combustion may result in the production of large quantities of
nitric oxides through fuel NOx chemistry [71]. Comprehending the
oxidized and reduced states of NO can assist in overcoming the chal­
lenges of high fuel NOx production in iC8H18/NH3 mixtures.
So far, no experiments have been carried out on the species con­
centration of iC8H18/NH3 mixture, and the discussion in the present
model is mainly carried out through the kinetic model, so it is necessary
to verify the concentration of NO to fully illustrate the validity of the
discussion. Considering that the construction of the mechanism is based
on the stratification theory, it is also valid to verify the species

Fig. 9. Reaction pathway analysis of ic8H18 for Ti = 400 K, P = 1 bar, XNH3 = 30–50 % and ϕ = 1.0.

7
Z. Liu et al. Fuel 365 (2024) 131179

Fig. 10. Reaction pathway analysis of nh3 for Ti = 400 K, P = 1 bar, XNH3 = 30–70 % and ϕ = 1.0 and 1.3.

concentration based on the existing experimental data on H2/NH3, and (1a)NH3 ̅̅̅̅̅→ NH2 ̅̅̅̅→ H2NO ̅̅̅̅̅→ HNO ̅̅̅̅̅→ NO;
+OH,H,O +HO2 +H,O,OH +H,O,OH

C3H8/NH3. Figs. 11 and 12 shows the species concentration distribution

(2a)NH3 ̅̅̅̅̅→ NH2 ̅̅̅̅̅→ NH ̅̅̅→ NO; (3a)NO2 → NO + OH(4a)
+OH,H,O +OH,H,O +O2 +H
of C3H8, NH3, H2 and NO in JSR at different initial conditions. In general,
the current mechanism can better capture the changing trend of species CH3 ̅̅̅̅̅̅̅→ NO.
+HNO,NO2

concentration, especially the prediction of NO concentration. And the main reduction of NO are as follows:
(1b) NO ̅̅̅̅→ NO2 + OH；(2b) NH ̅→ N2O；(3b) R10:NH2 + NO
+HO2 +NO
3.3.3. Effects of NH3 blending on NOx concentration
= NNH + OH and R11:NH2 + NO = N2 + H2O. R10 and R11 are the
In Fig. 13, the mole fraction of NOx (NO + NO2 + N2O) is displayed
dominant NO reduction step under all conditions, especially in lean
for iC8H18/NH3 mixtures at Ti = 400 K, P = 1 bar, and XNH3 = 0–70 %.
flames.
As expected, NH3 addition increases the NOx mole fraction of iC8H18/
Based on the ROP analysis of NO, it can be concluded that channels
NH3 mixtures. However, it can be observed that in the case of a rich-
(3a) and (1b) are the primary generation and consumption reactions of
flame, as ϕ increases, the sensitivity of NOx concentration to XNH3
NO. In addition, in the NO generation channels (1a)-(3a), various steps
gradually decreases. For example, at XNH3 = 50 % and XNH3 = 70 %, the
such as the initial decomposition of NH3, the rapid conversion of NH2 to
NOx mole fraction has almost the same value as that at ϕ = 1.3. This
NO via different pathways, and the conversion of NO2 to NO all require
indicates that increasing the blending ratio while increasing the equiv­
H, O, OH radicals. Furthermore, Miller et al.’s research [72] indicates
alent ratio can effectively reduce NOx concentration. Additionally, as
that NO reduction is promoted by the influence of the radical pool
observed from the graph, NO is the predominant species in NOx, with
concentration, which is affected by the branching ratio α = K10/(K10 +
concentrations of species such as N2O and NO2 significantly lower than
K11) and the residence time of NNH. Therefore, in summary, active
that of NO. Consequently, the ensuing discussion will primarily focus on
radicals such as H, O, OH, and NH2 are crucial species influencing NO
the concentration of NO.
concentration and need to be further discussed.
In this section, we aim to elucidate kinetic insights into the signifi­
Due to the nonlinear variation in NO concentration with increasing
cant variation of NO concentration. Through the analysis of the rate of
equivalence ratio, the discussion is divided into two parts. Fig. 14 il­
production (ROP) of NO, the main kinetic reaction pathway of NO was
lustrates the mole fractions of H, O, OH, and NH2 radicals for ϕ = 1.0 (a)
determined. The relevant paths of NO can be divided into NO generation
and 1.3 (b), withXNH3 = 0–70 %. From Fig. 14(a), it can be observed that
pathway and NO reduction pathway.
as the XNH3 increases, the concentrations of H, O, and OH radicals
The main pathways of NO generation are as follows:
gradually decrease, while the NH2 radical increases. Glarborg et al. [50]

Fig. 11. The stable species concentration for c3H8/NH3 mixture in JSR atϕ = 1.0, P = 1 atm, τ=1s and XC3H8 = 20 % (a) and 50 % (b). Symbol: the experiment data
[55]; Line: present model.

8
Z. Liu et al.
Fig. 12. The stable species concentration for h2/NH3 mixture in JSR atϕ = 1.0, P = 1 atm, τ=1s and XH2 = 30 % (a) and 10 % (b). Symbol: the experiment data [51];
Line: present model.
Fig. 13. The mole fraction distribution of nox for ic8H18/NH3 mixture at Ti =
400 K, P = 1 atm and XNH3 = 0–70 %.
pointed out that the concentration of NO formed is determined by the
competition between NH2 and NO (reduction pathway) or reactions
with the radical pool (generation pathway). Therefore, the increase in
NO concentration with increasing XNH3 indicates that the NO generation
pathway is faster than its reduction pathway. This might be attributed to
the fact that at low equivalence ratios, although the NH2 radical con­
centration increases, OH radicals remain the most abundant radicals in
the free radical pool. The abundant presence of OH can provide the
requirements for the initial oxidation of NH3 to generate NH2 and the
conversion of intermediate species like HNO to NO.
From Fig. 14(b), it can be seen that an increase in XNH3 still leads to a
decrease in the concentrations of H, O, OH, and other radicals, while the
NH2 radical concentration increases. However, atXNH3 = 50 %, NH2
exceeds OH radical concentration, becoming the most abundant radical
in the pool. In the initial oxidation of NH3, a substantial amount of OH is
required. The remaining OH radicals may not be sufficient to meet the
demands of reactions (1a)-(3a). This weakening of reaction pathways is
evident in our earlier analysis of NH3 reaction pathways that with the
increase of XNH3 , the percent of these reaction channels decreases.
9
Fuel 365 (2024) 131179
Consequently, with an increasing equivalence ratio, the sensitivity of NO
to the mole fraction of NH3 decreases.
The analysis above regarding NO suggests that compared with H, O
and NH2 radicals, OH appears to be the most critical radical influencing
NO concentration. To further illustrate the impact of radicals on NO
concentration, Fig. 15 displays the relationship between the maximum
NO concentration in the iC8H18/NH3-air flame and the maximum OH, H,
and NH2 radicals. It is evident that, under all XNH3 , H and NH2 radicals
are not particularly sensitive to NO concentration. NO concentration is
relatively sensitive to OH concentration, but with increasing NH3 con­
tent, the sensitivity of NO to OH concentration decreases (R2: 0.98 →
0.96). This decrease is likely mainly due to the rapid increase in NH2
radicals, resulting in an insufficient supply of OH radicals to meet the
overall NO reaction demands. Therefore, it can be concluded that at
lower mixing ratios, OH radical concentration is the primary active
species influencing NO concentration. Effective control of NO concen­
tration can be achieved by regulating the relative quantities of NH2 and
OH radicals.
4. Conclusions
Present study introduces a novel mechanism for iC8H18/NH3 mix­
tures, building upon the iC8H18 model by Cai and the NH3 model by
Zhang. These models are interconnected through chemical coupling
between iC8H18 and NH2 chemistry. The newly developed chemical ki­
netic model has undergone extensive validation using literature data for
iC8H18/NH3, encompassing laminar burning velocity, ignition delay
time, and stable species concentrations. Overall, our kinetic model
demonstrates a robust ability to predict laminar burning velocity for
iC8H18/NH3, well within experimental uncertainties. An in-depth anal­
ysis of C-N interaction reactions reveals that the H-abstraction reaction
between NH2 and iC8H18 is pivotal, significantly impacting ignition
delay time. This insight serves as a practical guide for constructing a
reduced mechanism.
Another focus of this study involves analyzing the flame chemistry of
iC8H18/NH3. Our findings highlight that the addition of NH3 primarily
affects the laminar burning velocity of iC8H18/NH3 mixtures through
chemical effects⋅NH3 enhances the H-abstraction reaction of iC8H18 in
tertiary sites (cC8H17) while inhibiting the same reaction in primary sites
(aC8H17, bC8H17, and dC8H17), resulting in a decrease in active H, O, and
OH radical concentrations and subsequently reducing flame velocity.
Additionally, NH3 addition increases the concentration of NO, but
Z. Liu et al. Fuel 365 (2024) 131179

Fig. 14. The mole fractions of h, o, oh and nh2 in iC8H18/NH3-air mixtures for Ti = 400 K, P = 1 atm, XNH3 = 0–70 % and ϕ = 1.0 (a) and 1.3 (b).

Fig. 15. The relationship between the concentration of no and h (a), oh (c), nh2 (b) radicals for iC8H18/NH3 mixture at P = 1 bar and Ti = 400 K.

10
Z. Liu et al.
with an escalating equivalence ratio, the rate of increase in NO con­
centration gradually diminishes. This phenomenon is closely tied to the
balance of active radicals between OH and NH2 in the fuel. When suf­
ficient OH free radicals are available, NH3 addition leads to increase NO
concentration. However, at high equivalence ratios, where the OH
concentration is inadequate to meet the demands of NH2 consumption
and generation, the impact of NH3 addition on NO concentration be­
comes limited. Importantly, for iC8H18/NH3 mixtures, selecting a higher
equivalence ratio proves effective in controlling the increase of NO
concentration.
CRediT authorship contribution statement
Zechang Liu: Writing – review & editing, Writing – original draft,
Methodology, Investigation. Xu He: . Guangyuan Feng: Data curation.
Chengyuan Zhao: Formal analysis, Data curation. Xiaoran Zhou: Data
curation. Zhi Wang: Funding acquisition. Qingchu Chen: 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.
Acknowledgment
The research was financially supported by the National Natural
Science Foundation of China (Grant No. 52376092) and the Ningbo
Major Research and Development Plan Project (Grant No.2022Z151).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2024.131179.
References
[1] Ma X, Ma Y, Wang Z, Mao J, Liu H, Su F, et al. Optical study on multi-time ignition
mixed-mode combustion with gasoline and PODE. Fuel 2023;335:126910.
[2] Ding H, Zhao J, Zhang Z, Xu K, Fu L, He X. A numerical study on the interaction of
droplet collisions and air flow impact in cross-impinging spray. Energy 2023;277.
[3] Zhao J, Fu L, Ding H, Bai B, Zhang D, Liu J, et al. Numerical simulation of working
process and gas-liquid interaction mechanism of air assisted nozzle. Int J
Multiphase Flow 2023;164.
[4] Zhao J, Ding H, Fu L, Bai B, Zhang D, Liu J, et al. Energy analysis and research on
injection control parameter influence mechanism of air assisted spray system. Fuel
2023;346.
[5] Ma Y, Cui L, Ma X, Wang J. Optical study on spray combustion characteristics of
PODE/diesel blends in different ambient conditions. Fuel 2020;272:117691.
[6] Zhang W, Zhang Z, Ma X, Awad OI, Li Y, Shuai S, et al. Impact of injector tip
deposits on gasoline direct injection engine combustion, fuel economy and
emissions. Appl Energy 2020;262:114538.
[7] Kamil M, Ramadan KM, Olabi AG, Al-Ali EI, Ma X, Awad OI. Economic, technical,
and environmental viability of biodiesel blends derived from coffee waste. Renew
Energy 2020;147:1880–94.
[8] Liu F, Liu Z, Sang Z, He X, Sjöberg M, Vuilleumier D, et al. Numerical study and
cellular instability analysis of E30-air mixtures at elevated temperatures and
pressures. Fuel 2020;271:117458.
[9] Kojima Y, Yamaguchi M. Ammonia as a hydrogen energy carrier. Int J Hydrogen
Energy 2022;47(54):22832–9.
[10] Wang S, Wang Z, Elbaz AM, Han X, He Y, Costa M, et al. Experimental study and
kinetic analysis of the laminar burning velocity of NH3/syngas/air, NH3/CO/air
and NH3/H2/air premixed flames at elevated pressures. Combust Flame 2020;221:
270–87.
[11] Shrestha KP, Lhuillier C, Barbosa AA, Brequigny P, Contino F, Mounaïm-
Rousselle C, et al. An experimental and modeling study of ammonia with enriched
oxygen content and ammonia/hydrogen laminar flame speed at elevated pressure
and temperature. Proc Combust Inst 2021;38(2):2163–74.
11
Fuel 365 (2024) 131179
[12] Okafor EC, Naito Y, Colson S, Ichikawa A, Kudo T, Hayakawa A, et al. Experimental
and numerical study of the laminar burning velocity of CH4–NH3–air premixed
flames. Combust Flame 2018;187:185–98.
[13] Okafor EC, Naito Y, Colson S, Ichikawa A, Kudo T, Hayakawa A, et al.
Measurement and modelling of the laminar burning velocity of methane-ammonia-
air flames at high pressures using a reduced reaction mechanism. Combust Flame
2019;204:162–75.
[14] Lubrano Lavadera M, Pelucchi M, Konnov AA. The influence of ammonia on the
laminar burning velocities of methylcyclohexane and toluene: An experimental and
kinetic modeling study. Combust Flame 2022;237.
[15] Wang D, Wang Z, Zhang T, Zhai Y, Hou R, Tian Z-Y, et al. A comparative study on
the laminar C1–C4 n-alkane/NH3 premixed flame. Fuel 2022;324.
[16] Elbaz AM, Giri BR, Issayev G, Shrestha KP, Mauss F, Farooq A, et al. Experimental
and kinetic modeling study of laminar flame speed of dimethoxymethane and
ammonia blends. Energy Fuels 2020;34(11):14726–40.
[17] Yin G, Li J, Zhou M, Li J, Wang C, Hu E, et al. Experimental and kinetic study on
laminar flame speeds of ammonia/dimethyl ether/air under high temperature and
elevated pressure. Combust Flame 2022;238.
[18] Lubrano Lavadera M, Han X, Konnov AA. Comparative effect of ammonia addition
on the laminar burning velocities of methane, n-heptane, and iso-octane. Energy
Fuels 2020;35(9):7156–68.
[19] Dong S, Wang B, Jiang Z, Li Y, Gao W, Wang Z, et al. An experimental and kinetic
modeling study of ammonia/n-heptane blends. Combust Flame 2022;246.
[20] Wang Z, Han X, He Y, Zhu R, Zhu Y, Zhou Z, et al. Experimental and kinetic study
on the laminar burning velocities of NH3 mixing with CH3OH and C2H5OH in
premixed flames. Combust Flame 2021;229.
[21] Koebel M, Elsener M, Kleemann M. Urea-SCR: a promising technique to reduce
NOx emissions from automotive diesel engines. Catal. Today 2000;59(3):335–45.
[22] Grannell S, Assanis D, Gillespie D, Bohac S. Exhaust Emissions From a
Stoichiometric, Ammonia and Gasoline Dual Fueled Spark Ignition Engine. 2009.
[23] Y. Qi, W. Liu, S. Liu, W. Wang, Y. Peng, Z. Wang, A review on ammonia-hydrogen
fueled internal combustion engines, eTransportation 2023;18.
[24] H. Chu, L. Xiang, X. Nie, Y. Ya, M. E.J. Gu, Laminar burning velocity and pollutant
emissions of the gasoline components and its surrogate fuels: a review. Fuel 2020;
269:117451.
[25] Zhang C, Chen L, Ding S, Xu H, Li G, Consalvi J-L, et al. Effects of soot inception
and condensation PAH species and fuel preheating on soot formation modeling in
laminar coflow CH4/air diffusion flames doped with n-heptane/toluene mixtures.
Fuel 2019;253:1371–7.
[26] Zhou L, Xiong G, Zhang M, Chen L, Ding S, de Goey LPH. Experimental study of
Polycyclic Aromatic Hydrocarbons (PAHs) in n-Heptane laminar diffusion flames
from1.0 to 3.0bar. Fuel 2017;209:265–73.
[27] Liang S, Li Z, Gao J, Ma X, Xu H, Shuai S. PAHs and soot formation in laminar
partially premixed co-flow flames fuelled by PRFs at elevated pressures. Combust
Flame 2019;206:363–78.
[28] Chu H, Ren F, Xiang L, Dong S, Qiao F, Xu G. Numerical investigation on
combustion characteristics of laminar premixed n-heptane/air flames at elevated
initial temperature and pressure. J Energy Inst 2019;92(6):1821–30.
[29] Dong W, Hu J, Xiang L, Chu H, Li Z. Numerical investigation on combustion
characteristics of laminar premixed n-heptane/hydrogen/air flames at elevated
pressure. Energy Fuel 2020;34(11):14768–75.
[30] Dong W, Jin T, Qiu B, Chu H. Effects of carbon dioxide on the combustion
characteristics of the laminar premixed n-heptane/air flames at elevated pressures.
J Energy Inst 2021;99:127–36.
[31] Xu H, Liu F, Sun S, Zhao Y, Meng S, Chen L, et al. Flame attachment and kinetics
studies of laminar coflow CO/H2 diffusion flames burning in O2/H2O. Combust
Flame 2018;196:147–59.
[32] Hu X, Yu Z, Chen L, Huang Y, Zhang C, Salehi F, et al. Morphological and
nanostructure characteristics of soot particles emitted from a jet-stirred reactor
burning aviation fuel. Combust Flame 2022;236:111760.
[33] Zhang S, Lee TH, Wu H, Pei J, Wu W, Liu F, et al. Experimental and kinetic studies
on laminar flame characteristics of acetone-butanol-ethanol (ABE) and toluene
reference fuel (TRF) blends at atmospheric pressure. Fuel 2018;232:755–68.
[34] Sileghem L, Alekseev VA, Vancoillie J, Van Geem KM, Nilsson EJK, Verhelst S,
et al. Laminar burning velocity of gasoline and the gasoline surrogate components
iso-octane, n-heptane and toluene. Fuel 2013;112:355–65.
[35] Liu F, Liu Z, Sang Z, He X, Liu F, Liu C, et al. Kinetic study of the effects of hydrogen
blending to toluene reference fuel (TRF)/air mixtures on laminar burning velocity
and flame structure. Fuel 2020;274:117850.
[36] Di Lorenzo M, Brequigny P, Foucher F, Mounaïm-Rousselle C. Validation of TRF-E
as gasoline surrogate through an experimental laminar burning speed
investigation. Fuel 2019;253:1578–88.
[37] Liao Y-H, Roberts WL. Laminar flame speeds of gasoline surrogates measured with
the flat flame method. Energy Fuel 2016;30:1317–24.
[38] Hu E, Xu Z, Gao Z, Xu J, Huang Z. Experimental and numerical study on laminar
burning velocity of gasoline and gasoline surrogates. Fuel 2019;256:115933.
[39] He X, Liu Z, Jiang H, Liu F, Yang Q, Jiang Z, et al. The reduction in laminar burning
velocity and Markstein length extrapolation uncertainty for TRF-air mixtures. Fuel
2023;335:127052.
[40] Liu S, Lin Z, Zhang H, Lei N, Qi Y, Wang Z. Impact of ammonia addition on knock
resistance and combustion performance in a gasoline engine with high
compression ratio. Energy 2023;262.
[41] Zhang R, Liu W, Zhang Q, Qi Y, Wang Z. Auto-ignition and knocking combustion
characteristics of iso-octane-ammonia fuel blends in a rapid compression machine.
Fuel 2023;352.
Z. Liu et al.
[42] http://creckmodeling.chem.polimi.it/menu-kinetics/menu-kinetics-detailed-
mechanisms.
[43] Liu Z, He X, Jiang Z, Feng G, Zhao C, Yang Q. Study on the laminar combustion
characteristics and kinetic of IC8H18/NH3 premixed flames. Fuel 2024;356:
129633.
[44] Cai L, Pitsch H. Optimized chemical mechanism for combustion of gasoline
surrogate fuels. Combust Flame 2015;162(5):1623–37.
[45] Curran HJ, Gaffuri P, Pitz WJ, Westbrook CK. A comprehensive modeling study of
iso-octane oxidation. Combust Flame 2002;129(3):253–80.
[46] Fieweger K, Blumenthal R, Adomeit G. Self-ignition of S.I. engine model fuels: A
shock tube investigation at high pressure. Combust Flame 1997;109(4):599–619.
[47] Han X, Wang Z, He Y, Liu Y, Zhu Y, Konnov AA. The temperature dependence of
the laminar burning velocity and superadiabatic flame temperature phenomenon
for NH3/air flames. Combust Flame 2020;217:314–20.
[48] Mei B, Ma S, Zhang Y, Zhang X, Li W, Li Y. Exploration on laminar flame
propagation of ammonia and syngas mixtures up to 10 atm. Combust Flame 2020;
220:368–77.
[49] Stagni A, Cavallotti C, Arunthanayothin S, Song Y, Herbinet O, Battin-Leclerc F,
et al. An experimental, theoretical and kinetic-modeling study of the gas-phase
oxidation of ammonia. React Chem Eng 2020;5(4):696–711.
[50] Glarborg P, Miller JA, Ruscic B, Klippenstein SJ. Modeling nitrogen chemistry in
combustion. Prog Energy Combust Sci 2018;67:31–68.
[51] X. Zhang, S.P. Moosakutty, R.P. Rajan, M. Younes, S.M. Sarathy, Combustion
chemistry of ammonia/hydrogen mixtures: Jet-stirred reactor measurements and
comprehensive kinetic modelling, Combust Flame 2021;234.
[52] Dai L, Gersen S, Glarborg P, Levinsky H, Mokhov A. Experimental and numerical
analysis of the autoignition behavior of NH3 and NH3/H2 mixtures at high
pressure. Combust Flame 2020;215:134–44.
[53] Issayev G, Giri BR, Elbaz AM, Shrestha KP, Mauss F, Roberts WL, et al. Combustion
behavior of ammonia blended with diethyl ether. ProCombust Inst 2021;38(1):
499–506.
[54] Konnov AA. Implementation of the NCN pathway of prompt-NO formation in the
detailed reaction mechanism. Combust Flame 2009;156(11):2093–105.
[55] Yin G, Xiao B, Zhan H, Hu E, Huang Z. Chemical kinetic study of ammonia with
propane on combustion control and NO formation. Combust Flame 2023;249.
[56] Mebel AM, Lin MC. Prediction of absolute rate constants for the reactions of NH2
with alkanes from ab initio G2M/TST calculations. Chem. A Eur. J. 1999;103(13):
2088–96.
[57] Thorsen LS, Jensen MST, Pullich MS, Christensen JM, Hashemi H, Glarborg P, et al.
High pressure oxidation of NH3/n-heptane mixtures. Combust Flame 2023;254.
12
Fuel 365 (2024) 131179
[58] Yin G, Xiao B, Zhan H, Hu E, Huang Z. Chemical kinetic study of ammonia with
propane on combustion control and NO formation. Combust Flame 2023;249:
112617.
[59] Fang R, Saggese C, Wagnon SW, Sahu AB, Curran HJ, Pitz WJ, et al. Effect of nitric
oxide and exhaust gases on gasoline surrogate autoignition: iso-octane experiments
and modeling. Combust Flame 2022;236.
[60] Mishra MK, Yetter R, Reuven Y, Rabitz H, Smooke MD. On the role of transport in
the combustion kinetics of a steady-state premixed laminar CO + H2 + O2 flame.
Int. J. Chem. Kinet. 1994;26(4):437–53.
[61] Esposito G, Chelliah HK. Effect of binary diffusion and chemical kinetic parameter
uncertainties in simulations of premixed and non-premixed laminar hydrogen
flames. Combust Flame 2012;159(12):3522–9.
[62] Dagdigian PJ. Combustion simulations with accurate transport properties for
reactive intermediates. Combust Flame 2015;162(6):2480–6.
[63] Paul P, Warnatz J. A re-evaluation of the means used to calculate transport
properties of reacting flows. Symp (Int) Combust 1998;27(1):495–504.
[64] Dagdigian PJ, Alexander MH. Exact quantum scattering calculations of transport
properties for the H2O–H system. J. Chem. Phys. 2013;139(19):194309.
[65] Jasper AW, Kamarchik E, Miller JA, Klippenstein SJ. First-principles binary
diffusion coefficients for H, H2, and four normal alkanes + N2. J. Chem. Phys.
2014;141(12):124313.
[66] Konnov AA. Yet another kinetic mechanism for hydrogen combustion. Combust
Flame 2019;203:14–22.
[67] Kee R, Grcar J, Smooke M, Miller J, Meeks E. PREMIX: a fortran program for
modeling steady laminar one-dimensional premixed flames. Sandia Rep 1985;143.
[68] Li G, Yang W, Tay KL, Yu W, Chen L. A reduced and robust reaction mechanism for
toluene and decalin oxidation with polycyclic aromatic hydrocarbon predictions.
Fuel 2020;259:116233.
[69] Atef N, Kukkadapu G, Mohamed SY, Rashidi MA, Banyon C, Mehl M, et al.
A comprehensive iso-octane combustion model with improved thermochemistry
and chemical kinetics. Combust Flame 2017;178:111–34.
[70] Han X, Wang Z, He Y, Zhu Y, Cen K. Experimental and kinetic modeling study of
laminar burning velocities of NH3/syngas/air premixed flames. Combust Flame
2020;213:1–13.
[71] Valera-Medina A, Xiao H, Owen-Jones M, David WIF, Bowen PJ. Ammonia for
power. Prog Energy Combust. Sci. 2018;69:63–102.
[72] Miller JA, Klippenstein SJ. Theoretical considerations in the NH2 + NO reaction.
J Phys Chem A 2000;104:2061–9.