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org/EF Review

Flammability Limits: A Comprehensive Review of Theory,

Experiments, and Estimation Methods
Andrés Z. Mendiburu,* João A. Carvalho Jr., and Yiguang Ju
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ABSTRACT: Flammability limits play an important role in combustion research,

industrial applications, and fire safety. This article provides a comprehensive review of
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recent developments in the fundamental understanding of flammability limits and their

experimental determination as well as estimation methods for pure fuels and fuel mixtures.
The article begins with a discussion of the importance and challenges of determining
flammability limits. It then presents the theoretical, computational, and experimental
methods available to understand the mechanism of flammability limits and to quantify
them. The experimental setups using cylindrical and spherical vessels to determine the
flammability limits are discussed. The effects of buoyancy, thermal radiation, and flame
stretch are examined. The relationship between the fundamental flammability limits and
the extinction limits of stretched flames via strain and radiation is presented. The effects of
initial temperature, pressure, mixtures of different fuels, and diluents are examined, and
available estimation methods are presented. Finally, the flammability limits of renewable
and alternative fuels are addressed and strategies for estimating the flammability limits of
these fuels are presented.

1. INTRODUCTION temperature and pressure conditions. Similarly, the UFL is

The purpose of this review article is to present the state of the art
in the study of flammability limits of premixed flammable gas
mixtures. Flammability limits are the concentration limits
beyond which a flame fails to propagate. The flammable
mixtures studied in this review are formed by homogeneous
premixing of a gaseous fuel and an oxidizer. In most cases, the
oxidant is air (actually, it is the O2 present in air), but other
oxidants can also be used to determine the flammability limits of
a mixture.
In the presence of an ignition source, a planar and unstretched
flame can form and propagate freely in a fuel−oxidizer mixture if
the mixture is within the fundamental flammability limits
(FLs);1,2 otherwise no flame propagation is possible. The
fundamental FLs are determined for certain standard initial
conditions of temperature and pressure. The FLs of a fuel−air
mixture at certain initial conditions Ti and pi should depend only
on the composition of the mixture and not on experimental
configurations. There are two fundamental FLs: a lower
flammability limit (LFL) for a lean fuel−air mixture and an
upper flammability limit (UFL) for a rich fuel−air mixture. The
FLs are generally expressed as fuel concentrations in the fuel−air
mixtures. The FLs measured in a laboratory experiment often
depend on the experimental configurations and flame
geometry.2 Therefore, the fundamental FLs must be appropri-
ately extrapolated from the observed FLs to the planar and
unstretched flame conditions.
The LFL is defined as the leanest composition of the fuel−air
mixture below which a flame will not propagate under certain
defined as the richest composition of the fuel−air mixture above
which a flame fails to propagate under certain temperature and
pressure conditions. Therefore, the FLs are important for the
application of safety measures in industry to prevent the
formation of flammable mixtures in locations where an ignition
source may be present. The formation of flammable mixtures
can occur in different ways and in different applications.
As aforementioned, the FLs of a mixture are temperature and
pressure dependent. Thus, if one of these parameters is varied
while the other is held constant, the values of the FLs will also
change. It can be observed that an increase in the initial
temperature, while the initial pressure remains constant,
decreases the value of the LFL and increases the value of the
UFL. In other words, less fuel is needed on the lean side and less
oxidizer is needed on the rich side to sustain flame propagation.
On the other hand, increasing the initial pressure while
maintaining the initial temperature leads to an increase in the
UFL. Experimental observations have not clearly demonstrated
the effect of initial pressure on the LFL; in most cases it appears
Received: October 24, 2022
Revised: February 6, 2023

© XXXX American Chemical Society https://doi.org/10.1021/acs.energyfuels.2c03598

A Energy Fuels XXXX, XXX, XXX−XXX
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to be very weak. The effects of temperature and pressure on FLs
are discussed in detail in section 6.
Another important problem is the determination of the FLs of
a mixture of two or more fuels with an oxidizer. For example,
adding hydrogen to natural gas can improve flame stability3 and
combustion efficiency.4 Therefore, the fuel mixture of hydrogen
and natural gas could improve the combustion process in some
applications. However, due to safety concerns, it would be
necessary to determine the FLs of this fuel mixture. The FLs of
fuel mixtures can be determined experimentally or estimated by
the law of Le Chatelier.5 A comprehensive validation of this law
has recently been carried out, taking into account the available
experimental data.5 This law will be discussed later in this article.
The FLs also depend on the composition of the oxidant
present in the fuel−oxidant mixture. As an example, consider the
difference between pure oxygen and air, which is the high
concentration of nitrogen in the latter and its absence in the
former. Likewise, air can be said to be further diluted by adding
more nitrogen or another type of diluent such as carbon dioxide,
water vapor, or helium, to name a few possibilities. These
mixtures are studied in the literature as fuel−diluent−oxidant
mixtures. Under certain temperature and pressure conditions,
the addition of diluents results in an increase in the LFL and a
decrease in the UFL.
Furthermore, the burning limits of a mixture can be
significantly changed by flame stretch.1 Therefore, it is
important to understand the relationship between the burning
limits of a stretched flame and the fundamental FLs. In addition,
for low temperature combustion of fuels such as n-alkanes,
alcohols, and ethers, the flammability limits of a cool flame can
differ significantly from those of a hot flame for the same
mixture.6 A transition from cool flame to hot flame can change
the FLs of a hot flame. Therefore, it is also important to
understand the differences between the FLs of cool and hot
flames for the same mixtures. A review of the dynamics of cool
flames has recently been published.6 Therefore, only a brief
discussion is provided in the Supporting Information.
Some examples of the importance of the FLs for practical
applications can be listed. For instance, in nuclear reactors,
mixtures of combustible gases rich in hydrogen can form and
come into contact with the hot walls of the reactor.7 Nuclear
waste stored in underground tanks can also produce flammable
mixtures.8 In addition, the introduction of renewable fuels into
the energy matrix leads us to consider fuel mixtures involving
gaseous fuels such as hydrogen and ammonia,9−11 and also
liquid fuels involving blends of biodiesel12 and ethanol,13,14
among others. In either case, a flammable mixture could form
and FLs must be known for safe operation.
Some of the fuels mentioned are already present in industrial
processes, such as mixtures of carbon monoxide and hydrogen
produced during the reforming of fossil fuels.15 Ammonia is used
in the polymer industry as a source of nitrogen and hydrogen
and at high temperatures in the nitration process for hardening
steel.16 Due to the need to replace chlorofluorocarbons, various
gas mixtures are used in cooling processes. For example,
chlorofluorocarbons have been replaced by hydrofluorocarbons,
hydrofluoroethers, and mixtures of hydrofluorocarbons with
hydrocarbons.17,18
Further evidence of the importance of FLs for practical
applications is the tragic accident of Trans World Airlines Flight
800, which crashed into the Atlantic Ocean on July 17, 1996.
The cause was determined to be an explosion in the center wing
fuel tank due to the ignition of a flammable fuel−air mixture that
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had formed there.19 Therefore, FLs are of great importance for
the adoption of safety measures in the application of alternative
aviation fuels. Moreover, understanding the chemical kinetic
mechanisms of alternative aviation fuels20 is necessary for the
development of theoretical models for the prediction of FLs.
Despite the importance of FLs, few reviews have been
published on this topic. As far as the authors are aware, the most
recent were published in 2001 by Ju et al.,2 in 2012 by Coronado
et al.,21 and in 2022 by Qi et al.22 In the case of the article by Ju et
al.,2 the focus was on the theoretical developments up to 2001,
while Coronado et al.21 focused on the experimental methods to
determine FLs for aerospace applications. In the recent article by
Qi et al.22 the flammability limits of gases at elevated
temperatures and pressures were reviewed. This article, on the
other hand, aims to be comprehensive by including discussions
on the theoretical developments, experimental procedures, and
estimation methods that enable the understanding and
determination of flammability limits.
Thus, the objective of this article is to review the state of the
art in the study of flammability limits using a comprehensive
approach by addressing the following topics:
• the definition and existence of fundamental FLs
• theoretical approaches to the determination of FLs
• experimental methods for determining the FLs
• the available estimation methods to determine the FLs in
air under reference conditions
• the effects of initial temperature and pressure conditions
• the effect of adding diluents to the fuel and oxidant
mixture
• the estimation of FLs of fuel mixtures according to Le
Chatelier’s law
• the FLs of renewable and alternative fuels and future
perspectives
2. THE THEORY OF FLAMMABILITY LIMITS
In an earlier review on FLs, Lovachev et al.23 adopted the
following definition for a flammable mixture: “We propose to
define a gaseous mixture as flammable per-se at a stated
temperature and pressure if, and only if, it will propagate flame
indefinitely, the unburnt portion of the mixture being
maintained at that temperature and pressure”.
From this definition, the FL can be defined as follows:23 “The
flammability limits of a gaseous mixture, at a determined
temperature and pressure, are the leanest and richest
compositions for which the mixture can be considered as
flammable.” As Ju et al.1 have pointed out, the fundamental FLs
of a mixture at a given pressure and temperature can only be
defined for the propagation limit of a planar unstretched flame,
which is governed only by the chemistry of the fuel−oxidant
mixture and the thermal radiation. Therefore, a definition of the
fundamental FLs can be stated as follows: The fundamental
flammability limits of a gaseous mixture, at a determined
temperature and pressure, are the leanest and richest
composition for which a planar unstretched flame can propagate
through the mixture. As will be seen later, the experimental
determination of FLs does not consider planar flames in most
cases.
It is known that for a given mixture there are two extinction
limits for a stretched premixed flame, namely the stretch
extinction limit at a high stretch rate, at which the characteristic
burning time becomes longer than the flow residence time, and
the radiation extinction limit at a low stretch rate, at which the
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Figure 1. Schematic representation of the flammability limits of the ethanol−air mixture. Experimental data from Zabetakis.24
heat loss by radiation becomes comparable to the chemical heat
release from the flame.1 It should be noted that these extinction
limits should not be confused with the fundamental flammability
limits. It is interesting to point out that, in the review by Ju et al.,2
they used the general term “combustion limits” instead of the
classical flammability limits defined for premixed flames. The
fundamental flammability limits, as well as the associated
extinction limits for premixed flames, are discussed in this review
article. Hereafter, the fundamental flammability limits will be
referred to simply as flammability limits. The combustion limits
with nonzero flame stretch will be referred to as the extinction
limits.
FLs are usually expressed as the percent mole fraction of fuel
in the gas mixture. FLs are then expressed as shown in eq 1:
nF
FL = · 100%
nF + nox
where nF and nox are the numbers of moles of fuel and oxidant,
respectively. The FL could also be expressed in terms of the
equivalence ratio (ϕ). However, this is not a common practice in
fire safety regulations. For example, the FLs of the ethanol−air
mixture are shown schematically in Figure 1, with experimental
data taken from the work of Zabetakis.24
A first interpretation of the FLs can be achieved by an analysis
of the energy, mass, and species conservation equations,
considering a freely propagating, one-dimensional, planar
flame with some simplifying assumptions:
(i) The heat capacities and thermal conductivities are
independent of temperature and composition.
(ii) The process is at steady state.
(iii) The Lewis number is unity: Le = k/ρcpD = 1.
(iv) The combustion reaction can be represented by a one-
step kinetic reaction.
(v) The heat losses by radiation are represented by a single
term, L.
(vi) The temperature profile is linear.
The above assumptions are compatible with the Shvab−
Zeldovich formulation in one dimension,25−28 which is shown in
eq 2.
Ä ÉÑ
d ÅÅÅÅ Ñ
cp dT ÑÑÑÑ
d d
mS
dx ( cp dT + ) dx ÇÅ
ÅÅ D
dx ( ÖÑ
) at x = δ/2:
0
= hf, i f Wi (2)
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Some of the above assumptions need explanation. Note that
the goal of this formulation is to obtain a simple relationship
between the heat released by the reaction, the mixture
properties, the heat losses, and the laminar flame speed.
Therefore, the assumptions of a one-step reaction and a linear
temperature profile are reasonable. Furthermore, it is not
necessary to assume a thermal radiation model to understand
the relationship between the above parameters.
The assumption that cp is independent of temperature can be
justified by the definition of the mean of a function, i.e., cp =
(∫ TTbu ∑Yicp,i)/(Tb − Tu). In a mixture where one species is
d
strongly present in excess, the cp value can be considered
independent of the composition in such cases. Note that the
Lewis number for stoichiometric methane−air mixtures without
and with some degree of dilution by argon, nitrogen, and carbon
dioxide is close to unity.29 The Lewis number for methane−air
(1)
mixtures with a ϕ value between 0.7 and 1.5 at 100 kPa and 293
K was calculated by the authors to be close to 1.09. The
assumption Le = 1 is often used to simplify the mathematical
formulation, since it implies that k/ρcp = D.26
Applying the assumptions and introducing the heat loss term,
the following expression is obtained:
dT k d2T 1 L
mS = hf,0i iWi +
dx cp dx 2 cp cp (3)
The mixture composition can be either lean or rich. In the first
case, complete combustion is assumed, while in the second case
incomplete combustion is considered. By using these two
limiting cases, a simplified relationship for FLs can be derived.
The summation term on the right-hand side of eq 3 represents
the volumetric heat release rate, and for a complete combustion
reaction can be expressed as ω̇ fWfΔhC. Therefore, the total
combustion heat release rate is related to the fuel consumption
rate (ω̇ f), the fuel’s molecular weight (Wf), and the fuel’s heat of
combustion (ΔhC). The expression is substituted into eq 3, and
integration is performed by applying the boundary conditions
and variable substitution shown below:
at → −∞:
T = Tu and dT /dx = 0 (4)
T = (Tb + Tu)/2 and dT /dx = (Tb Tu)/ (5)
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Using L̅ and f to represent the mean values of heat loss and for ξ → +∞:
fuel consumption rate, respectively, denoting the flame thickness d
by δ, and applying the variable substitution, then eq 3 can be = 0, =0
integrated, and the expression shown in eq 6 is obtained: d (11b)
The dimensionless variables and parameters are shown in eqs
1 ijjj L hC yz
zz 2 mS k 12−18. In those expressions, ω̇ A,b is species A’s consumption
j f Wf z (Tb Tu) + (Tb Tu)
2 jj cp 2cp zz 2 cp rate at the adiabatic flame temperature (Tb) and at the initial
k { mass fraction of fuel (YA,u) in kmol/(m3·s). The parameter kb is
=0 (6) the thermal conductivity at Tb, and Lb is the heat loss rate at Tb
where ṁ S is the mass flux rate. The expression shown in eq 6 is a per unit volume.
quadratic equation; therefore, a real solution is possible only if T Tu
the inequality shown in eq 7 is true. = dimensionless temperature
Tb Tu (12)
ij L hC yz
cp(Tb Tu)(mS)2 8k jjjj f Wf z
zz 0 ij cp SL yz
j cp 2cp zz = expjjj xzzz dimensionless coordinate
k { (7)
k k { (13)
The mass flux rate can be related to the laminar flame speed by YA
ṁ S = ρuSL. Rearranging eq 7, the expression shown in eq 8 is = dimensionless mass fraction of A
obtained. YA,u (14)

ij L hC yz hC A,bWAk b
1 8k jj zz = dimensionless heat release
SL j f Wf z
cp(Tb Tu) jj cp 2cp z z (Tb Tu)(cp SL)2
u k { (8)
(15)
The above expression provides an estimate of the minimum
k A WA
value for the laminar flame speed at which FLs are found. The = dimensionless reaction rate
key parameter is the balance between the heat losses due to kb A,bWA (16)
thermal radiation and the heat release rate. Note that both are
negative. This result is consistent with experimental observa- kL
= dimensionless heat loss
tions of a nonzero laminar flame speed at FLs. Thus, the k bL b (17)
condition for the existence of FLs is heat loss by thermal
radiation from the flame to the surroundings. Note that the Lb
K= ratio of heat loss to heat release
assumption of a linear temperature profile allowed the A,bWA hC (18)
integration of eq 3, which is not so easily performed when an
exponential profile is adopted. The results of more detailed The parameter K represents the ratio between the heat loss to
investigations are presented in the next section. Although eq 8 the surroundings at the adiabatic flame temperature (Lb) per
was obtained for a lean mixture, a similar expression would be unit volume and the heat release rate of the combustion reaction
obtained for a rich mixture, with the main difference in the value at the adiabatic flame temperature (ω̇ A,bWAΔhC) per unit
of ΔhC. Another theoretical relationship for the flammability volume. To understand the parameter λ, it is first necessary to
limit of a planar flame is given by Ju et al.2 in their review. Some notice that the flame thickness is equal to δ ∼ kb/cpṁ S. Then, λ is
more rigorous theoretical analyses have also been developed to the ratio between the heat release rate of the combustion
explain and predict FLs. Sections 2.1−2.3 discuss some reaction per unit area (ΔhCω̇ AWAkb/cpṁ S) and the rate of
important aspects of these theories. Due to the nature of this sensible enthalpy transport by convection per unit area cpṁ S(Tb
article, full formulations are not provided. − Tu). Considering that A is the fuel, Spalding30 showed that, for
2.1. Theoretical Developments with One-Step Chem- a type of reaction characterized by eqs 19 and 20, there is a
ical Kinetics. Spalding30 used a one-dimensional approach to critical value of K, above which there are no real values of λ.
develop a theory about the FLs. In his analysis, a one-step Thus, the critical values KC and λC define the FL.
reaction was considered in the form shown in eq 9. n
= (19)
A+B C (9)
l
o m
for >1
o
Starting from the one-dimensional energy and species =m
o
o 0 for 1
conservation equations,28 it is possible to model the problem n (20)
by the dimensionless equations in eqs 10 and 11, subject to the The solution obtained by Spalding shows the relationship
boundary conditions shown in eqs 11a and 11b. between λ, K, and θ as a function of n and m, which typically take
d2 values in the ranges 6−15 and 1−5, respectively.30 The simple
= ( +K ) results given in eqs 21 and 22 can be used to plot the graphs
d 2 2
(10)
depicted in Figure 2 by varying θ between 0.005 and 1.
d2 (n + 1)(n + 2)
= =
d 2 2
(11) 2 n+2 (21)

for ξ = 0: 2 n+ 2 m
K= (1 )
= 0, =1 (11a) (n + 1)(n + 2) (22)

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Energy & Fuels
Figure 2. Results for λ and K as functions of θ according to eqs 21 and
22.
The critical values θC, λC, and KC are given by eqs 23−25. In
addition, the theory proposed by Spalding can be used to
determine the critical value of the laminar flame speed (SL,C),
given in eq 26.
n+2 m
C =
n+3 m (23)
2 n+2 m
KC = C It is worth noting that Hertzberg37−40 published four
(n + 1)(n + 2)(n + 3 m) (24)
(n + 1)(n + 2) (n + 2)
C = C conductive−convective heat loss, radiative heat loss, and flow
2 (25)
1 k bL b
SL,C =
cp (Tb Tu)K C C (26)
Although this theory explains the relationship between heat
release and heat loss at the FL, it is not directly applied to
determine the fuel mole fraction at the FLs. However, the value
of SL,C can be estimated as follows: At the LFL the properties of
the mixture can be approximated by those of air (cp = 1004 J/kg·
K, ρ = 1.169 kg/m3, kb = 0.100 W/m·K31). As given by
Spalding,30 the exponent m of the dimensionless heat losses χ =
θm varies from 1 to 5. A larger value of m means that the heat
losses due to thermal radiation are more important than those
due to thermal conduction. Moreover, the exponent n of the
dimensionless reaction rate φ = αθn varies between 6 and 15.
Therefore, the values of m = 8 and n = 2 are within the intervals
recommended by Spalding.
In previous work, the authors determined the Tb value at
initial conditions of 298 K and 101 kPa for 120 hydrocarbons at
LFL,32 273 oxygenated compounds at LFL,33 115 hydrocarbons
at UFL,34 and 208 oxygenated compounds at UFL.35 It is
noticeable that the mean value of Tb at the LFL is 1548 K and
that at the UFL is 1067 K, with standard deviations of 107 and
147 K, respectively. Therefore, the assumption of Tb = 1500 K
for a mixture at the LFL is reasonable. Following Spalding, Lb =
0.4186 J/cm3·s, and assuming Tb = 1500 K, m = 8, and n = 2, eq
26 gives the value SL,C = 1.342 cm/s.
Another theoretical approach was developed by Williams,36
who applied a one-dimensional formulation including a heat loss
term. In this theory, the heat loss rate is given by the expression
shown in eq 27.
L the fuel (LeF), and the Lewis number of the oxidant (LeO). Also,
K=
hCYf,umS,ad 2cp (27)
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where the mass fraction of fuel at the initial condition and the
mass flow rate for the adiabatic conditions are represented by Yf,u
and ṁ S,ad, respectively. Considering the heat loss term at the
flame temperature of the nonadiabatic flame (Lb), the limit
condition given in eq 28 is obtained.
2 2
1 mS,ad RcpTb
= 2L b
e Ea (28)
where Ea and e are the activation energy and Euler’s number,
respectively. The limit condition can also be written as shown in
eq 29, which represents the decrease in the mass burning rate
due to the decrease in flame temperature or the increase of heat
loss.
ij m yz
2
jj S zz = exp[ Ea /RTf ]
jj zz
k mS,ad { exp[ Ea /RTb] (29)
36
Williams suggested that a first approximation for the FL can
be obtained by varying ṁ S,ad while holding constant the other
parameters in eq 28 in order to establish the limit conditions.
Then, a critical value of exp[−Ea/RTb] can be identified due to
its proportionality with ṁ S,ad. The lower and upper flammability
limits would be represented by the critical values of exp[−Ea/
RTb].
interesting papers in the 1970s−1980s dealing with various
phenomena related to FLs, such as natural convection,
gradients. Hertzberg found that the limiting velocity of the
laminar flame at the LFL is between 6 and 8 cm/s.37
2.2. The Relationship between Extinction Limits and
Fundamental FLs. More detailed analyses of premixed flames
subject to heat losses, flame curvature, different reaction orders,
and transport properties can be found in early studies by Joulin
and Clavin,41 Buckmaster,42 and Mitani43 in the 1970s.
However, the relationship between flame extinction limits and
the fundamental flammability limits was still not clear.
Beginning in the 1980s, research on combustion in micro-
gravity44 sparked renewed interest in the study of combustion
limits. Analytical and experimental studies showed that, in
addition to flame chemistry, flame extinction can be influenced
by the coupling between flame stretch and thermal radia-
tion.1,45−47 To understand the coupling effect of flame stretch
and radiation on flame extinction and FLs, Ju et al.48 applied an
asymptotic analysis to include this effect. The results showed
that the stretch and radiation extinction limits are the two
solutions of eq 30.
2
1 2CLeF jij Ta zyz ji T zy
= jjj zzz expjjjj a zzzz
ae (YO YF LeO/LeF ) k Tf { k Tf { (30)
where
2
WF( + 1)YF
C= 3
2 0vO LeF (31)
The stretch rate at the radiation extinction limit (ae) is related
to the dimensionless concentrations of the fuel (Y̅ F) and the
oxidant (Y̅ O), the dimensionless flame temperature (T̅ f), the
dimensionless activation temperature (T̅ a), the Lewis number of
in the above equations, κ is a geometric coefficient of the
stretched flame, κ0 is the frequency factor of the reaction, vO is
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the stoichiometric coefficient of the oxidant, ρ is the density, and
YF∞ is the initial mass fraction of the fuel. As such, the solution of
eq 30 gives the extinction limits of a stretched flame as a function
of the fuel concentration at different Lewis numbers of fuel or
oxidizer.48
As can be seen in Figure 3, there are two extinction branches
for each fuel concentration. The upper one shows the stretch
Figure 3. Effect of Lewis number of fuel on the flammability limit.
Reproduced with permission from ref 48. Copyright 2000 Elsevier.
extinction limit, and the lower one is the radiation extinction
limit. As the fuel concentration decreases, these two branches
merge, defining the burn limit of a stretched premixed flame.
Note that this burn limit is different from the fundamental FL. It
can also be seen that, as the Lewis number of the fuel decreases
(increases), the stretched flame extinction limit, the radiation
extinction limit, and the burn limit of a stretched flame are
expanded (narrowed). Therefore, for a stretched flame the flame
burn limit will be affected by the Lewis number of the mixture,
flame stretch, and radiation, all of which are coupled together.
However, in the formulations in eqs 30 and 31 the relationship
between the fundamental flammability limit and the burn limits
of stretched flames was still unknown. For example, it was
unclear whether the burn limit of a stretched flame shown in
Figure 3 would extend to the fundamental flammability limit. To
answer this question, computational1 and analytical49,50 efforts
were made to understand the flame extinction limits of a
stretched flame subjected to radiation at near zero stretch rate.
The analytical relationship50 between the normalized mass
burning rate (m), normalized flame location (ηf), flame stretch
(a), normalized Lewis number deviation from unity (l), and
flame temperature change (pf), due to stretch and heat losses
before (H−) and after (H+) the flame front, is given as
a standard flammability limit.
= e pf /2 , m= f
2a
2 f g1 (32)
ij 1
1 yzzz 2H + 2
pf = ljjjj 2
z+ gg
j 2 f
g1 zz a f 12
k {
H ijjj I1 yzz
+ jj g3 + zzz
a j g1 z
k { (33)
where gi and I1 are integral functions of flame location. In the
limit of zero stretch rate, that is, ηf → ∞ and a → 0, eq 33
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reduces to eq 30. At low fuel concentration (YF = 0.029) below
the flammability limit, the flame can exist in a narrow range of
stretch rate bounded by a radiation extinction limit and a
stretched extinction limit. The results of eqs 32 and 33 for flame
location as a function of flame stretch at LeF = 0.9 at different fuel
concentrations (YF) are shown in Figure 4. Note that Figure 4a
has a different scale than the other three diagrams in Figure 4.
Figure 4. Flame location as a function of flame stretch for LeF = 0.9 at
different fuel concentrations (YF) predicted by the analytical solution in
eqs 32 and 33.
It is seen that, at a normalized fuel mass fraction, YF = 0.029,
below the standard flammability limit, there is a stretched flame
island bounded by a radiation extinction limit at a low stretch
rate and a stretch extinction limit at a high stretch rate [Figure
4a]. Outside these two limits there is neither a flame with a lower
stretch rate nor a flame with a higher stretch rate than these two
limits. This result is consistent with Figure 3.
However, as the fuel concentration is increased close to the
standard flammability limit, YF = 0.0295, a new weak flame island
appears at very low stretch rates [Figure 4b]. This weakly
stretched flame is located very far from the stagnation point of
the counterflow flame. Therefore, both the weakly stretched
flame and the normal stretched flame can exist below the
At the fuel concentration at or slightly above the standard
flammability limit, YF = 0.0296, Figure 4c shows that the weakly
stretched flame island expands rapidly toward zero stretch rate.
At this time, the weakly stretched flame can be extended to zero
stretch rate, i.e., the planar and unstretched flame. Therefore,
when the Lewis number is below unity, only the extinction limit
of the weakly stretched flame can be extrapolated to the standard
flammability limit, while this is not possible for the normally
stretched flame.
When the fuel concentration is above the flammability limit,
YF = 0.03, the island of the weakly stretched flame is further
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extended to a higher stretch rate and merges with the island of near the FLs. The flammability exponents calculated by Wang et
the normal stretched flame [Figure 4d]. Only under this al.52 for the LFL and UFL of CH4/SG mixtures in air were
condition can the weakly stretched flame smoothly transition always different from unity. Therefore, the condition established
into the normally stretched flame by increasing the stretch rate, by Law and Egolfopoulos51 to find the FLs was not satisfactory
and conversely, a normally stretched flame can smoothly when applied to these experimental data.
transition into an unstretched flame by decreasing the stretch Two modified flammability exponents were proposed by
rate. As such, eqs 32 and 33 and Figure 4 provide a clear Liang and Law.53 In their study, Liang and Law found that, in
relationship between the normal stretched flame and the addition to competition for radicals between branching and
unstretched planar flame via a weakly stretched flame near the termination reactions, there is also competition for intermediate
flammability limit. This analytical result was validated by species involving four other competing reactions. Therefore,
numerical simulations. The relationship between the extinction they proposed two alternative modifications of the flammability
limits of weakly and normal stretched flames and the standard exponent. In the first modification of the flammability exponent,
flammability limit at different Lewis numbers is presented in shown in eq 37, two groups of competing reactions are
section 2.3. considered, while in the second modification, shown in eq 38,
2.3. Theoretical Developments with Detailed Chem- three groups of competing reactions were considered.
ical Kinetic Mechanisms. 2.3.1. Theoretical Developments ÄÅ ÉÑ
Å Ñ
lnÅÅÅÅwT2 + wB2 w +T w ÑÑÑÑ
( )
w
with Detailed Chemical Kinetic Mechanisms and without
Heat Losses. This section begins with the work of Law and ÅÇ T B ÑÖ
b( ) = ÅÄÅ ÑÉÑ
Egolfopoulos,51 in which it was concluded that for the lnÅÅÅÅwB2 w +B w ÑÑÑÑ
( )
w
propagation of a one-dimensional planar flame near the FL ÅÇ T B Ñ Ö (37)
there is a condition in which the rate of a particular chain- ÅÄÅ ÑÉ
branching reaction is equal to that of a corresponding chain-
termination reaction. Therefore, the flame can be extinguished
lnÅÅÅÅwT1 + wB1
ÅÇ ( wT2
) + w ( )(
wT2 + wB2
wB2
B1 w + w
T2 B2
wT
wT + wB )ÑÑÑÑÑÑÖ
c( )= ÄÅ ÉÑ
Å
by any perturbation of the balance of these chain-branching and
chain-termination processes.51 They determined the dominant
lnÅÅÅÅwB1
ÅÇ ( )( )ÑÑÑÑÑÑÖ
wB2
wT2 + wB2
wB
wT + wB

branching and termination reactions for the propagation of (38)

52
premixed methane−air flames using a detailed chemical kinetic In their article, Wang et al. used the refined flammability
mechanism. They then represented the net rate of the dominant exponent from eq 37 to determine the FL numerically. The
branching reaction by its maximum value, wB, and the net rate of comparison between the experimental and calculated FLs for
the corresponding termination reaction by wT. Considering the CH4/SG mixtures in air is shown in Figure 5. Although the
equivalence ratio ϕ, the following expressions were proposed.
B( ) T( )
wB and wT (34)
The relationship between these net rates is then wT ∼ wBα(ϕ),
and this allows the definition of the flammability exponent α(ϕ)
= αT(ϕ)/αB(ϕ). Therefore, the FLs are expected to be found at a
limiting ϕFL that satisfies the relationship shown in eq 35.
( FL
)= T( FL )/ B( FL ) =1 (35)
From the expressions in eqs 34 and 35, and from the
relationship assumed for α(ϕ), the flammability exponent can be
represented as shown in eq 36.
(ln wT)/ (ln ) (ln wT)
a( )= =
(ln wB)/ (ln ) (ln wB) (36)
A predictive determination of the FLs consists of solving the
adiabatic one-dimensional flame propagation model, for differ-
ent values of ϕ, using detailed chemical kinetic mechanisms.
Then, a sensitivity analysis is performed to identify the dominant
chain-branching and chain-termination reactions to determine Figure 5. Comparison of results obtained with the flammability
the exponent αa(ϕ). Finally, the condition α(ϕFL) = 1 is used to exponent and the modified flammability exponent for the FL of CH4/
find the value of the FLs by identifying ϕFL. SG mixtures in air. Reproduced with permission from ref 52. Copyright
Following this approach, Wang et al.52 investigated the lower 2021 Elsevier.
LFL and UFL of methane (CH4) in air with the addition of a
combustible gas (SG) and nitrogen (N2), where the SG was a
mixture of ethane (C2H6), ethylene (C2H4), carbon monoxide modified exponent showed better agreement than the
(CO), and hydrogen (H2) in a ratio of 5:1:1:1. Experiments unmodified one, the authors noted that large absolute errors
were performed at atmospheric pressure and temperature, and were observed between the calculated and experimental FLs.
the FLs were determined for different volumetric concentrations This error could be due to the fact that, in addition to chain-
of the SG and N2, respectively. The authors performed a branching reactions, other important chain-propagation reac-
sensitivity analysis of the mass burning rate and identified the tions must also be considered, since they also contribute
competing chain-branching and chain-termination reactions significantly to the overall reaction rate from chain branching to
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Figure 6. Theories of flammability limits involving detailed chemical kinetics with radiative heat losses. (a) Inflection point for a nonadiabatic
methane−air flame at 1 atm and comparison with the adiabatic flame. Reproduced with permission from ref 54. Copyright 1992 Elsevier. (b)
Maximum flame temperature as a function of stretch rate. Reproduced with permission from ref 1. Copyright 1997 Cambridge University Press. (c)
Fundamental flammability limit found as the extension to zero stretch of weak flames. Reproduced with permission from ref 57. Copyright 1999
Cambridge University Press.

equilibrium. Therefore, even with the modified flammability
exponent, it was not possible to accurately determine the FLs.
2.3.2. Theoretical Developments with Detailed Chemical
Kinetic Mechanisms and with Thermal Radiation Heat
Losses. In a second article, Law and Egolfopoulos54 made a
modification to the PREMIX55 routine in order to include heat
losses due to thermal radiation, which in turn were calculated
using the expression given in eq 39.
qr = 4 bKP(T 4 T 4)
where
KP = pCO K CO2 + pH O K H2O + pCO K CO + pCH K CH4
2 2 4
point was not observed in the adiabatic case. It was concluded
that the fundamental flammability limit is explained by the
effects of competition between chain-branching and chain-
termination reactions and radiative heat losses. The flame speed
and temperature at the inflection point were 2.3 cm/s and 1375
K, respectively. Note that the flame speed is of the same order of
magnitude as that determined using Spalding’s theory.
Using the criterion developed in their earlier work [α(ϕFL) =
(39) 1], Law and Egolfopoulos found an equivalence ratio ϕLFL =
0.502, which is close to the value obtained by considering the
inflection point (ϕLFL = 0.493). Thus, in the specific case of
methane, the concepts of flammability exponent (α) and

(40)
The Stefan−Boltzmann constant is represented by σb, while
KP and pi are the Planck mean absorption coefficient and the
partial pressure of the radiating species i, respectively. Then they
determined the mass flux (ṁ S) for different ϕ’s under adiabatic
and nonadiabatic conditions and found that in the latter case an
inflection point for methane−air flames was reached at ϕLFL =
0.493, which is close to the experimental value of the LFL for
methane in air [Figure 6a]. On the other hand, this inflection
inflection point were shown to provide similar LFL values. The
predominant chain-branching and chain-termination reactions
for the methane−air lean flames at 1 atm are shown in reactions
R1′ and R2′. Here H represents the hydrogen atom, O2
represents oxygen, OH represents the hydroxyl radical, HO2
represents the hydroperoxy radical, and M represents a third
body (any chemical species).
H + O2 OH + O chain branching (R1′)

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Figure 7. (a) Schematic of the flammable region for normally stretched flames and weakly stretched flames (WSF) and projected G-shaped
flammability limit diagram for Le < Lecr. (b) The G-shaped flammability limit diagram of methane/air mixture with Le = 0.97 < Lecr. (c) The K-shaped
flammability limit diagram of propane/air mixture with Le > Lecr. Reproduced with permission from ref 57. Copyright 1999 Cambridge University
Press.

H + O2 + M HO2 + M chain termination extinction limit. For a methane concentration of 4.9%, it was
(R2′) shown that at the stretch extinction limit the heat loss due to
Thus, the reactions shown in (R1′) and (R2′) dominate the radiation was less than 1% of the chemical heat release, while this
combustion process at the LFL of one-dimensional methane− loss at the radiation extinction limit was about 25% of the
air planar flames. To understand the coupling effects of flame chemical heat release.
stretch and thermal radiation with detailed chemical kinetic The maximum temperatures reached near the normally
mechanisms, Ju et al.1 numerically investigated the extinction stretched lean premixed flames at different stretch rates are
mechanism of weakly stretched and normally stretched shown in Figure 6b, where the radiation extinction limit is at
premixed methane−air flames with an optically thin radiation point d and the stretch extinction limit is at point c. The
model. The Planck constants of the radiative gases such as water existence of the radiation extinction limit is related to the
(H2O), carbon dioxide (CO2), and CO were derived from the increase in flame volume, which leads to larger radiation heat
statistical narrow-band model.56 The system of conservation losses from the flame.58
equations solved by Ju et al.1 is as follows. The stretch and radiation extinction limits were determined
by Ju et al.1,57 for various equivalence ratios, and the results are
da shown in Figure 6c. The lower burning limit of a stretched flame
=0
dt (41) is the point where the stretch and radiation extinction branches
d dU meet, which is denoted as point B in Figure 6c. The fundamental
+ = 2 G flammability limit is also shown in Figure 6c at point E. Leaner
dt dx (42)
mixtures than that at the fundamental flammability limit can be
d ij dG yz i da y burned if a suitable stretch rate is set, as shown by the branches
L(G) = jj zz G2 + jjj + a 2zzz of the curves AB and FB, which lie to the left of point E in Figure
dx k dx { k dt { (43)
6c. A flame that occurs for a mixture leaner than the fundamental
d ij dT yz
n
dT
n flammability limit is called a sublimit flame,57 and its existence
cpL(T ) = jj zz YVc
i i p,i hi iMi was confirmed by Ronney and Wachman59 in experiments
dx k dx { i=1 dx i=1 under microgravity.
+ qr As discussed later in Figure 7 and shown in Figure 6c, the
(44)
branches of the stretch extinction limit (AB) and the radiation
d
n extinction limit (FB), of normally stretched flames, extrapolated
L(Yi ) = ( YV
i ix ) + i Mi to zero stretch rate, do not lead to the fundamental flammability
dx i=1 (45) limit (E). On the other hand, the extinction limit of the weakly
where L(ϕ) = dϕ/dt + U dϕ/dx, and the boundary conditions stretched flame branch (CE) can be extrapolated to the
are given in eqs 46 and 47. fundamental flammability limit for methane. Similar conclusions
were drawn by Guo et al.60 and confirmed for hydrogen−air
x= L; T = TL ; Yi = YiL ; G=a (46) mixtures61 and methane−hydrogen−air mixtures.62
To better understand the conditions under which extrap-
x = 0; dT /dx = 0; dYi /dx = 0; dG /dx = 0; olation of the extinction limit of the normally stretched flame to
U = 0; a = a0 zero stretch can lead to the fundamental flammability limit,
(47)
computational studies were performed to observe the effects of
1,57
The numerical results obtained by Ju et al. [Figure 6b,c] the fuel Lewis number on the normally and weakly stretched
show the existence of a stretch extinction limit and a radiation premixed flames of CH4−O2−N2−He mixtures.57,63 The Lewis
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Figure 8. Upper flammability limit of benzene with detailed chemical kinetic mechanism, radiative heat losses, and soot emissions. (a) Flammability
limit with sudden drop in laminar flame speed.64 (b) Flammability limit with a sudden drop in temperature.64
number of the mixture was increased by increasing the
concentration of helium (He) in the mixture. The results
showed that for a fuel Lewis number below a critical value, Lecr,
as shown in Figure 7a, the existence of sublimit normally
stretched flames and the near-limit weakly stretched flames
(WSF) lead to a G-shaped flammability limit diagram [Figures
7b and 6c] for lean methane−air mixtures.
Therefore, for Le < Lecr, the stretch extinction limit of the
normally stretched flames cannot be directly extrapolated to
zero stretch rate to obtain the fundamental flammability limit,
and only the stretch extinction limit of the weakly stretched
flames can be directly extrapolated to zero stretch rate to obtain
the fundamental flammability limit. It was also found that Lecr is
greater than unity and depends on the radiation intensity of the
mixture and the product. The higher the radiation intensity, the
higher Lecr will be.
For the lean propane−air mixture with a Lewis number
greater than Lecr, the sublimit normally stretched flames
disappear, as seen in Figure 7c, where the fundamental
flammability limit (E) is to the left of the ABC curve. Note
that this was not the case for the methane−air mixture in Figure
7b. Therefore, the result for the propane−air mixture is a K-
shaped flammability limit diagram [Figure 7c] instead of the G-
shaped diagram obtained for methane−air. Therefore, for Le >
Lecr, the stretch extinction limit of the normally stretched flames
can be directly extrapolated to zero stretch rate to obtain the
fundamental flammability limit, as shown by the extrapolation
CE in Figure 7c.
Another development regarding the determination of FL with
detailed chemical kinetics and radiative heat losses was carried
out by Bertolino et al.64 The most notable innovation of this
work was the inclusion of a soot formation model and a soot
emissivity model to improve the predictions of the UFL. The
FLs were estimated by changing the equivalence ratio until
sudden drops in laminar flame speed (SL) and flame temperature
were achieved, as shown in Figure 8, parts a and b, respectively.
Note that the sudden drop in flame speed occurs at about 3 cm/
s, which again is of the same order of magnitude as the flame
speed according to Spalding’s theory.
The authors validated their work with experimental data for
methanol, benzene, methane, ethane, propane, n-butane, and n-
pentane. The validation included the effects of the type of
oxidant, pressure, temperature, and diluent. Also, Mascarenhas
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et al.65 developed a study that considered detailed chemical
kinetic mechanisms and heat losses by thermal radiation,
without considering the emission from soot molecules at rich
conditions. The calculated and experimental FLs of methane in
air at different initial pressures were compared for validation.
The model proved to be very accurate for determining the LFL.
However, it showed only acceptable accuracy for the
determination of the UFL. Therefore, the comparison of the
works of Bertolino et al. and Mascarenhas et al. shows that the
inclusion of emissions from soot is very important for the
accurate prediction of the UFL.
The theoretical results presented in this section could be
extended to other fuels in air. After decades of development,
there are several detailed chemical kinetic mechanisms for
hydrocarbons, 66,67 hydrocarbons and oxygenated com-
pounds,68,69 and alcohols.70 The new developments in the
detailed chemical kinetic mechanisms for hydrogen71,72 and its
reduced or one-step mechanisms73 are of particular interest
because it is a very important fuel that has many applications
worldwide. In the cases of the United States and Brazil, ethanol
is of great importance since these countries are the first and
second ethanol producers in the world.74 There are detailed
chemical kinetic mechanisms for ethanol,14,75 and also a reduced
chemical kinetic mechanism was developed in 2018.76 Although
much progress has already been made, it is worth noting that
Brown et al.77 have shown that methods for determining
transport properties used in numerical simulations of flame
propagation can still be improved.
A possible approach to extending the results obtained with
detailed chemical kinetic mechanisms would be to obtain one-
step chemical kinetic mechanisms, as has been done in the past
by Westbrook and Dryer.78,79 In their work, Westbrook and
Dryer fitted the parameters used to determine the reaction rates
of the fuels by comparing the calculated laminar flame speeds
with some experimental values. The laminar flame speeds were
plotted against the equivalence ratio, and it was expected that the
projection on the horizontal axis would intersect it at the
flammability limits. The parameters obtained in this way are
presented in some textbooks.26 However, the species in the
products were H2O and CO2, which is unfavorable for the
analysis of rich flames, since the heat release is overestimated in
such cases.
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Figure 9. Schematic representation of the experimental apparatus as presented by Coronado et al.82 Reproduced with permission from ref 82.
Copyright 2014 Elsevier.

Note that, at high CO2 and H2O concentrations, radiation

reabsorption can increase the flame temperature and extend the
flammability limit. Such radiation reabsorption effects have been
demonstrated by computational modeling of CO2-diluted
methane−air and dimethyl ether−air mixtures.56,80

3. EXPERIMENTAL DETERMINATION OF THE

FLAMMABILITY LIMITS
3.1. Description of Experimental Determination of the
FLs by the ASTM Method. In order to provide a better picture
of the experimental determination of FLs, the ASTM E68181
standard is considered. This standard was applied by Coronado
et al.82 for the determination of FLs of anhydrous ethanol and
hydrated ethanol in air at different temperatures and pressures.
A schematic representation of the experimental equipment is
shown in Figure 9. The vessel shown in Figure 9 can be placed in
a heating chamber or a cooling chamber, depending on the
desired initial temperature. The ignition source is located in the
center of the vessel and is supplied by two electrodes 6.44 mm
apart with an ignition voltage of 15 kV and 30 mA.81
The procedure for obtaining FLs begins by bringing the vessel
close to vacuum conditions using a vacuum pump. Then the
mixture is prepared to the desired pressure using the partial
pressure method. A magnetic stirrer is activated for about 2 min
to homogenize the mixture. Finally, the mixture is ignited, and
the flame propagation is recorded by a video camera. The visual
criterion is applied to the recorded videos to determine whether
a mixture is flammable or not.
The visual flammability criterion states that a mixture is
flammable if the flame spreads upward and toward the wall,
forming an arc greater than 90°. This criterion is shown in Figure
10. The fuel concentration in the mixture is varied to determine
two different, but close, fuel concentrations such that one is
flammable and the other is not flammable under the same
pressure and temperature conditions. The FL is determined for
the average of the fuel content of these two mixtures. Therefore,
the smaller the gap between these two compositions, the more
reliable the FL is. Another flammability criterion is the pressure
rise criterion, which classifies a mixture as flammable when the
K https://doi.org/10.1021/acs.energyfuels.2c03598
Figure 10. Visual criterion of flammability as given in the norm ASTM
E681 and presented by Coronado et al.82 Reproduced with permission
from ref 82. Copyright 2014 Elsevier.
internal pressure rise is about 5 or 7% of the initial pressure.
These pressure rise values are specified by the European and
American standards, respectively.21
Two experiments performed by Mendiburu83 in a spherical
vessel with two flammable mixtures near the FLs are shown in
Figure 11. A typical flame near the LFL is shown in Figure 11a,
while a typical flame near the UFL is shown in Figure 11b. It is
clear that both flames meet the visual criterion because the
flames form a 90° arc. However, while the flame near the LFL
expands into a sphere, the flame near the UFL expands into a
hemisphere. This qualitative difference is of great importance
when UFLs are theoretically determined, since the effect of
buoyancy is obvious.
Standards based on the visual criterion consider a vessel that
vents to the atmosphere when the internal pressure increases. In
the ASTM E681 standard, this is accomplished by using a rubber
cap to seal the vessel. This rubber is removed by the internal
pressure of the vessel. Given this venting, which is considered in
the visual criterion, and the small pressure rise considered in the
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Figure 11. Typical flames observed for flammable mixtures. (a) Slightly
above the LFL of anhydrous ethanol in air at 20 kPa and 50 °C. (b)
Slightly below the UFL of hydrated ethanol at 40 kPa and 280 °C.
Experiments performed by Mendiburu.83
pressure rise criterion (5−7%), it can be concluded that flame
propagation at constant pressure is a reasonable approximation
of the experimental conditions. Note that this is not necessarily a
coincidence, since the experimental methods for determining
FLs are intended to mimic a freely propagating flame as much as
possible.
The European standard EN 183984 is also widely used for the
experimental determination of FLs. In this standard, there are
two test methods for determining FLs. The first method is EN
1839(T), which considers a vertical tube with a volume of at
least 1.52 L (D = 8 cm). The flammability criterion in this case
Figure 12. General characteristics of most common experimental equipment used to determine the flammability limits. (a) Experimental works with
cylindrical vessels.4,7,15,16,18,52,97−166 (b) Experimental works with spherical vessels.17,69,82,95,167−226
pubs.acs.org/EF Review
states that a mixture is flammable if, after ignition, the flame
detaches (and spreads) a distance greater than 100 mm from the
ignition source. The second method is EN 1839(B), in which
case a 5 L spherical bomb is used. However, the flammability
criterion used is the pressure rise criterion. A mixture is classified
as flammable when the pressure increases by 5% compared to
the initial pressure.
Note that, in the ASTM E681 standard, FLs are the final
compositions that support flame propagation. This is
determined as the average fuel concentration between two
successive compositions, one showing no flame propagation and
the other showing flame propagation. On the other hand, the EN
1839 standard defines the FL as the fuel concentration for which
no flame propagation can be supported, and which follows the
last concentration that supports flame propagation. Therefore,
slightly different values for the FLs are to be expected when
different standards are used. This last statement is confirmed in
the work of Schröder and Molnarne,85 who compared four
different methods for determining the FLs of several fuels. As an
example, let us consider the FLs of CH4 in air. The LFL of CH4
was 4.3% using EN 1839(T), 4.9% using EN 1839(B), and 3.8%
using ASTM E681. On the other hand, the UFL of CH4 was
16.8% using EN 1839(T), 16.9% using EN 1839(B), and 16.9%
using ASTM E681.85
In most experimental tests to determine FLs, the composition
of the combustion gases is not measured.86 The reason for this is
that the main focus is to determine whether or not the mixture is
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flammable. This is a limitation for theoretical modeling of FLs
and for determining the difference between normal flame
propagation at the UFL and propagation of a cool flame (see the
Supporting Information).
There are several compilations of experimental data on FLs.
The most complete would be that of the Design Institute for
Physical Properties (DIPPR Project 801).87 However, there are
also some free online sources,88−90 and some handbooks
covering various properties along with FLs are also avail-
able.91−94 These sources may be sufficient for many applications.
However, to develop theoretical models, experimental con-
ditions are also of interest.
3.2. Analysis of the Available Experimental Data. As
mentioned earlier, there are several standard experimental
methods for determining FLs. For example, Coronado et al.21
compared the methods of the German Institute for Stand-
ardization (DIN 51649-1) and the European standards [EN
1839(T), EN 1839(B)]. On the other hand, Kondo et al.95 used
the American Society of Heating, Refrigeration and Air
Conditioning Engineers (ASHRAE) method and Schröder
and Molnarne85 compared four experimental methods for
determining FLs (as mentioned earlier). These methods are
given by the EM 1839(T), ASTM E681-01, and DIN 5164-1
standards and gave similar values of the FL for hydrogen,
methane, ethylene, and ammonia.
It is not the aim of this article to provide a detailed description
of existing standard methods for the experimental determination
of the FLs; interested readers may wish to consult the work of
Coronado et al.,21 Schröder and Molnarne,85 and Britton.96 The
goal of this section is to provide a general insight into the
experimental determination of the FLs. Since the experimental
procedure of the ASTM E681 standard has already been
presented, the evolution of the experimental determination of
FLs will now be discussed to show that researchers are currently
still using different approaches. The most commonly used
experimental configurations are cylindrical and spherical vessels.
As can be seen in Figure 12, the use of these devices began a
century ago. The experimental works cited in Figure 12 are
presented in more detail in Table S1. Some of these works have
determined FLs at various initial temperatures and pressures,
taking into account diluents or fuel mixtures. For another
compilation, see Table S2. In this table, the emphasis is on
experimental work in which the FLs were determined with
vessels of different volumes and/or geometries. As observed in
Figure 12, there are 73 works in which cylindrical vessels were
used,4,7,15,16,18,52,97−166 62 works in which spherical vessels were
used,17,69,82,95,167−226 and 10 works in which both geometries
were used.3,227−235 Compilations of experimental data are also
available.8,24,236−246
The articles listed in Table S2 allow us to evaluate the effects
of geometry on FLs. Based on the hypothesis that larger vessels
would reduce the heat lost to the walls, it was expected that
larger tube diameters would result in larger flammability ranges.
However, this hypothesis is at odds with several experimental
results. For example, Burgoyne and Williams-Leir247 determined
the FLs of CO, C2H4, cyclohexane (C6H12), and hexane (C6H14)
in tubes with diameters of 4.8 and 10.1 cm and heights of 152.4
cm. It was observed that the UFLs of C2H4 and C6H14 decreased
with increasing diameter. On the other hand, the LFLs showed
no significant variation with tube diameter. These observations
are confirmed by the results of Takahashi et al.230 for CH4 and
C3H8 in cylindrical and spherical vessels. It was observed that for
a height of 40 cm and a diameter of 5 to 150 cm, the LFL
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increased (slightly) and the UFL decreased with increasing
diameter.
Similarly, Shoshin and De Goey248 observed that the LFL of
CH4 and CH4−H2 mixtures decreased with increasing tube
diameter. Moreover, most CH4−H2 mixtures tested in tubes
larger than 12.3 mm in diameter achieved an LFL that was
independent of tube diameter. Note that the tube diameters
used by Shoshin and De Goey were very small (6 mm to 50.2
mm) compared with other studies. Therefore, it is not surprising
that the LFL was higher for the smaller diameters (6 mm to 12.3
mm). These results may be the cause of the increased flame
surface area due to the rapid formation of the boundary layer in a
narrow tube.
Further analysis of the experimental results shows that for
vessels of the same diameter (5 cm), the flammable range
shrinks with increasing height if the assumed flammability
criterion requires that the flame reach all the way to the top to
consider the mixture flammable. The data of Takahashi et al.230
for methane and propane indicate that there is a critical volume
above which FLs are not significantly affected by geometry, as
shown by the experiments they performed in a vessel of 160 L
volume. On the basis of all these comparisons, Takahashi et
al.230 recommended that cylindrical vessels with a diameter of at
least 20 cm and a height of 60 cm should be used to determine
FLs. The FLs determined in a 12 L spherical vessel using the
visual criterion (90° arc) have values similar to those determined
in the 160 L cylindrical vessel for methane and propane.230 In
addition, Kondo et al.249 compared the results for FLs of
methane obtained with cylindrical vessels of 20 and 40 cm in
height and 10 cm in diameter and recommended the use of the
largest vessel to determine FLs. Thus, they confirmed to some
extent the conclusions of Takahashi et al.230 Glukhov et al.234
found that the FLs of hydrogen, methane, and propane were
consistent at subatmospheric pressure for vessels of 25 and 500
L volumes. In addition, the minimum pressure at which flame
propagation was observed is lower in the work of Glukhov et al.
than in the work of Kuznetsov et al.,250 who used a spherical
vessel of 8.2 L. The idea that there is a critical volume above
which the FLs do not show significant variations can be
confirmed in the work of Zlochower and Green,221 who used
spherical vessels of 20 and 120 L to determine the FLs of
methane. Also, the FLs determined with the 120 L vessel for CO,
C2H4, and propane (C3H8) are similar to those determined by
Kondo et al.184,187 in a 12 L vessel.
The comparison of FLs obtained in cylindrical and spherical
vessels was performed by several authors. For example, Van den
Schoor et al.231 determined the FLs of CH4−H2−air mixtures in
cylindrical (0.84 L) and spherical (4.2 L) vessels. Larger
flammability ranges were obtained with the cylindrical vessel.
Van den Schoor and Verplaetsen3 tested CH4−H2−air mixtures
and found that the UFL tended to be lower when determined in
a spherical vessel (4.2 L) than when determined in a cylindrical
vessel (1.50 L). Goethals et al.227 also observed a narrower
flammability range for toluene when FLs were determined in a
spherical vessel (8.0 L) compared to those determined with a
cylindrical vessel (0.84 L). Markus et al.229 studied the FLs of
methanol (CH3OH) mixed with CH4 and air and found higher
UFLs for a cylindrical vessel (0.8 L) than for a spherical vessel (5
L). Note that Markus et al. used a much higher ignition energy
(70 J) for the tests with spherical vessels than for the tests with
cylindrical vessels (10 J). Therefore, the volume and geometry
were more important than the energy of the ignition source. De
Smedt et al.232 showed that the flammable ranges for methane,
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ethane, propane, and butane determined in a spherical vessel (20 The data in Table 1 show that the FLs depend on the diameter
L) were narrower than those determined in a cylindrical vessel and height of the tube. In addition, the UFLs determined with
(0.84 L). The ignition energies were 10 and 5 J, respectively. downward flame propagation (DFP) are smaller than those
Two possible conclusions can be drawn from these results: (1) determined with upward flame propagation (UFP) due to the
vessels with larger volume yield narrower flammability ranges, buoyancy effect, while those determined with horizontal flame
regardless of the flammability criterion used; (2) experiments propagation (HFP) are intermediate between the two. This type
conducted in cylindrical vessels yield broader flammability of difference in experimental results motivated the determi-
ranges than those conducted in spherical vessels. nation of FLs of some fuels under microgravity conditions, a
Kul et al.218 considered spherical vessels with volumes ranging topic that will be discussed in section 4.
from 3.2 to 21.3 L. They found that the LFL of difluoromethane In their work, Hu et al.103 determined the LFL of H2 in pure
was higher for the smaller vessel (3.2 L) and was the same for O2 with dilution by N2 and CO2 in tube experiments and also
vessels of 5 L and above (within experimental uncertainty). considered two directions of flame propagation, namely UFP
Therefore, in this case, larger vessels did not yield narrower FLs and DFP. The results show that, for DFP, the LFL decreases
for volumes of 5 L and above. The comparison of the UFL of between 8 and 13% when O2 is diluted by CO2. On the other
propane obtained in spherical vessels of 4.2 and 8 L at different hand, for UFP, the LFL decreases between 4 and 7%, also when
initial temperatures (up to 250 °C) and at pressures between 10 O2 is diluted with CO2. A similar behavior is observed for
and 20 bar was performed by Van den Schoor220 using the dilution with N2. The influence of the flame propagation
pressure rise criterion of 1 and 5%, respectively. Since it was direction on the determination of FLs was therefore also
expected that the UFL would not depend on the volume in this demonstrated by Hu et al. In a work by Hertzberg,37 it was found
case, the author stated that the higher pressure rise criterion was that the laminar flame velocity at the limit for horizontal flame
responsible for the lower values of UFL in the 8 L vessel. These propagation is almost twice as high as the limit velocity for
results are in contradiction with conclusion 1. Therefore, upward flame propagation. Therefore, the flammable ranges
conclusion 2 should be further investigated. The larger tend to be larger for UFP than for DFP or HFP. Note that flames
flammability ranges observed in cylindrical vessels suggest that
with HFP develop inverted flame fronts in closed vessels, also
the flammability criterion and the direction of flame propagation
called tulip flames.252,253 It is not clear how this phenomenon
play important roles.
affects the experimental determination of FLs with HFP.
Kul et al.218 used the same flammability criterion and
Again considering the work of Coward and Jones,251 it was
geometry (spherical) in their work and confirmed that there is
shown that the flammability range determined with UFP is
a wall quenching effect that reduces the flammable range for
smaller vessels. Since the cylindrical vessels were always smaller larger than that determined with DFP. The experimental FL
than the spherical ones, the wall quenching effect should have values of various compounds determined with UFP and DFP are
narrowed the flammable ranges, but this was not the listed in Table 2 for comparison. All of the compounds listed in
case.227,229,231,232 This would imply that the flammability Table 2 show some dependence of UFL on the direction of
criterion and the direction of flame propagation are responsible flame propagation, and some of these compounds show strong
for increasing the flammable range in cylindrical vessels. Before
turning to the analysis of the flammability criterion and the Table 2. Flammability Limits of Some Compounds with UFP
direction of flame propagation, it is important to point out that and DFPa
Bolshova et al.213 determined the LFL of methane in air using a upward flame downward flame
spherical vessel and a countercurrent burner and found that the propagation propagation
LFLs were consistent for both methods. LFL UFL LFL UFL
In early studies where FLs were determined using flame compound formula (%) (%) (%) (%)
propagation in vertical and horizontal cylindrical tubes, the hydrogen H2 4.15 75.00 8.80 74.50
ignition source could be at the top, bottom, or center of the tube. methane CH4 5.35 14.85 5.95 13.35
Consequently, the flame would propagate downward, upward, acetylene C2H2 2.60 78.00 2.80 63.50
or in both horizontal directions, respectively. The FLs acetaldehyde C2H4O 4.21 57.00 4.36 12.80
determined with these configurations were reported by Coward propylene C3H6 2.18 9.70 2.26 7.40
and Jones251 for several compounds. Not surprisingly, the methyl ethyl ketone C4H8O 2.05 9.90 2.10 7.40
experimental values obtained under different configurations benzene C6H6 1.45 7.45 1.48 5.55
were in some cases very different. As an example, the FLs of methyl alcohol CH3OH 7.10 36.50 7.65 26.50
methane in air obtained with different experimental config- butylene C4H8 1.70 9.00 1.80 6.25
urations are shown in Table 1. toluene C7H8 1.31 6.75 1.32 4.60
carbon disulfide CS2 1.41 50.00 2.03 34.00
Table 1. Experimental FLs of Methane in Air at Atmospheric ethane C2H6 3.12 14.95 3.26 10.15
Conditions for Different Experimental Configurations251 acetone C3H6O 2.90 12.60 3.15 8.35
ethyl acetate C4H8O2 2.32 11.40 2.37 7.10
direction of flame propagation ethyl alcohol C2H5OH 4.24 18.95 4.44 11.50
pentane C5H12 1.42 8.00 1.48 4.64
tube dimensions upward downward horizontal
hydrogen sulfide H2S 4.30 45.50 5.85 21.30
diameter height LFL UFL LFL UFL LFL UFL ethylene C2H4 3.20 34.00 3.33 15.50
(cm) (cm) (%) (%) (%) (%) (%) (%)
ethyl ether C4H10O 1.93 48.00 2.15 6.15
6.0 200 5.40 14.80 6.00 13.40 5.40 14.30
acetaldehyde C2H4O 4.21 57.00 4.36 12.80
4.0 100 5.50 14.10 6.10 13.30 5.60 13.90
5.0 50 − 15.11 5.80 13.38 5.39 14.28 a
Data from Coward and Jones.251

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dependence. For example, the UFLs of acetaldehyde (C2H4O),
diethyl ether (C4H10O), hydrogen sulfide (H2S), and C2H4
determined with UFP are more than twice as high as the UFLs
determined with DFP. All compounds, except H2, showed a
weak dependence of the LFL on the direction of flame
propagation.
Sometimes a mixture could not propagate at all for DFP. For
example, White254 determined the FLs of ammonia−air
mixtures in tubes 1.5 m long and with diameters of 5.0 and
7.5 cm. It was observed that ammonia−air flames do not
propagate downward at initial temperatures below 70 °C. On
the other hand, Krivulin et al.255 determined the FLs of
ammonia−air mixtures at 25 °C with DFP in a 8 m3 cubic
combustion chamber. Thus, it was possible to measure the FLs
with DFP for ammonia−air mixtures at room temperature using
a large vessel.
There are at least three effects that can cause this increase in
UFL as the flame propagates upward: (1) natural convection
due to buoyancy, (2) preheating by the burned gas, and (3)
Lewis number effect. Natural convection promotes flame
propagation in UFP. However, in DFP, it counteracts flame
propagation. Therefore, natural convection may be responsible
for some differences between UFLs determined with UFP and
those determined with DFP.
Preheating of the unburned mixture by the burned gases in the
experiments could have a greater impact on the difference
between UFLs measured in UFP and DFP experiments. In
addition, Jarosinski et al.256 found that the differences in FLs for
UFP and DFP also depend on the Lewis number (Le) of the
mixture. They determined the value of Le as the ratio of the
thermal diffusivity (α) of the mixture to the mass diffusivity (D)
of the deficient reactant. It was observed that there is a significant
difference between the UFLs for UFP and DFP when the Lewis
number is less than unity (Le < 1). The preferential diffusion of
such mixtures may support UFP. This observation can be related
to the results of the asymptotic analysis of Ju et al.,48 who
showed that the lower flammability limit decreases for lower
Lewis numbers of the fuel (deficient reactant).
The results obtained by Takahashi et al.230 and Coward and
Jones251 raised the question of the flammability limit criterion,
that is, the criterion applied in an experiment to determine
whether a mixture is flammable or nonflammable. In this regard,
Britton96 examined several flammability criteria and stated,
“Although wider flammability limits might be claimed to be
more conservative, it is not the job of a test laboratory to include
safety factors in the test method. Such safety factors should be
included during application of data, not during measurement.”
Lovachev et al.23 pointed out that there is confusion in
experimental determination of FLs and determination of safety
margins against explosions. To date, there is no unified criterion
for the flammability limit. However, the visual criterion and the
pressure rise criterion are the most commonly used. Note that
the temperature rise criterion is useful to determine cool flame
propagation, as applied by Cato et al.128
4. EFFECT OF BUOYANCY AND STUDIES IN
MICROGRAVITY
As shown in section 3, the flame propagation direction affects
the experimentally determined values of FLs, mainly due to the
buoyancy force in normal gravity, which promotes UFP and
opposes DFP. The buoyancy effect in the experiments makes it
difficult to understand the flame dynamics near the limiting
conditions. Since different experimental methods and con-
pubs.acs.org/EF Review
ditions produced different FLs, Jarosinski257 argued in his review
paper that “until now it has been impossible to formulate a
universal theory of extinction limits [in this review FLs] for a
large range of initial and boundary conditions.”
When the experimental environment of microgravity and
detailed kinetic models became available in the 1990s,
researchers used microgravity experiments and numerical
models to try to understand the mechanism of FLs. For
example, the outward propagating spherical flame without
gravity was simulated by Sibulkin and Frendi258 and Lakshmisha
et al.259 with the inclusion of thermal radiation. The predicted
LFL for methane−air was very close to the experimental data.
They also showed that there is no FL for an adiabatic flame.
Therefore, they concluded that heat loss by radiation is the
mechanism that causes the flammability limit. These studies
motivated subsequent computational and experimental inves-
tigations to understand the mechanism of FLs of stretched
flames in a counterflow system with coupling of flame stretch
and thermal radiation.1,2,44−47,57,63,260 As shown in Figure 6, the
findings on the existence of sublimit stretched flames, weakly
stretched flames, and radiation extinction have provided a clear
understanding of the mechanism of FLs through the intricate
coupling between chemistry, flame stretch, and thermal
radiation.
4.1. Flammability Limits in Microgravity. Experimental
determination of FLs under microgravity conditions has the
advantage of isolating the influence of buoyancy from diffusion
and convection processes in the experiments. Extensive studies
of combustion in microgravity have been performed to obtain
FL values that do not depend on gravity and do not depend on
the direction of flame propagation. Mixtures with Le < 1 include
lean hydrogen−air, rich propane−air, and higher hydrocarbon−
air mixtures. In these cases, there is a significant difference
between FLs determined with DFP and with UFP.244 On the
other hand, there are some mixtures with Le > 1, for example, the
rich methane−air and lean propane−air mixtures. In these cases,
the FLs determined with DFP and UFP are almost identical.244
Jarosinski et al.261 studied the flammability limits of propane−
air mixtures under microgravity conditions. The UFL under
microgravity conditions was 8.7% compared to the UFL
determined under normal gravity conditions of 9.5% with
UFP and 6.3% with DFP. Therefore, the UFL for the propane−
air mixture under microgravity conditions is between the UFLs
determined with UFP and DFP. The laminar flame speed of a
propane−air mixture with a propane content of 8.4% was
determined to be about 2.0 cm/s for microgravity conditions
and about 2.3 cm/s for normal gravity conditions.
Pu et al.244 found that the FLs of propane−air mixtures were
almost identical under gravity and microgravity conditions. The
values were 2.2% for the LFL and 9.2% for the UFL. They
attributed the differences to insufficiently sensitive measurement
techniques compared to the work of Jarosinski et al.261 However,
in the work of Jarosinski et al. a nonvisible flame propagation
characterized by a pressure rise was reported for a propane−air
mixture with a propane content of 9.0%. Therefore, the
difference in UFL values is probably related to the flammability
criteria adopted.
Ronney262 studied the effects of transport properties and
chemical kinetics for near-limit flames in microgravity. The
effects of chemical kinetics were evaluated by comparing the
behaviors of mixtures with similar Lewis numbers but different
chemical kinetic mechanisms. The mixtures studied were lean
NH3−air (ammonia−air), rich C3H8−air, and lean CH4−air
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Figure 13. Results of experiments under microgravity for methane−air mixtures. (a) Comparison of LFL under microgravity with those under normal
gravity for different initial pressures. Reproduced with permission from ref 59. Copyright 1985 Elsevier. (b) Stagnation velocity gradient at the
extinction limits (2U/L), for different equivalence ratios under microgravity. Reproduced with permission from ref 264. Copyright 1996 Elsevier.

with Lewis numbers slightly less than unity (Le < 1). In addition, Wachman,59 and Wang et al.,265 among others. Interestingly,
rich NH3−air and lean C3H8−air mixtures were considered the laminar flame speed determined by Wang et al.265 for a
whose Lewis numbers were greater than unity (Le > 1). At methane−air mixture at the LFL of 1.20 cm/s is consistent with
atmospheric pressure, the FLs of NH3−air mixtures in the flame speed theoretically determined by Spalding30 (using
microgravity were between the FLs with UFP and DFP in air properties).
normal gravity. To evaluate the influence of transport processes, 4.2. Flame Balls in Microgravity. One of the most
Ronney262 studied the behaviors of H2−O2−N2 and CH4−O2− important findings in research on combustion under zero gravity
N2 mixtures with different stoichiometries. In these cases, each is Ronney’s flame ball.44 To understand the competing physical
set of these mixtures has similar chemical kinetic mechanisms, processes, Ronney compared the time scales of the various key
while the effective Lewis number was changed by varying the processes in flames. The time scales for chemical reaction
stoichiometry. (tchem), for inviscid buoyant convection (tinv), for viscous
The role of transport processes was then investigated by buoyant convection (tvis), for heat loss by conduction and
comparing mixtures with similar chemical kinetic mechanisms convection to the walls (tcond), and for heat loss by radiation
but different transport properties, such as lean CH4−air (trad) are given in eqs 48−52.
compared to lean C3H8−air and lean NH3−air compared to
tchem
rich NH3−air. From the above comparisons, Ronney262 SL 2 (48)
concluded that transport properties, rather than chemical
kinetics mechanisms, play the most important role in explaining ij d yz
1/2
the behavior of near-limit flames in microgravity. Figure 13a t inv jj zz
jj g zz
shows the lower flammability limits of methane−air mixtures at k { (49)
different initial pressures under normal gravity and microgravity
1/3
conditions. Ronney263 also studied the extinction processes in jij v zyz
microgravity of lean mixtures of CH4 and NH3 and rich mixtures tvis jj 2 zz
jg z
of C3H8, all in air. It was found that for mixtures with Le ∼1 the k { (50)
FLs in microgravity are probably caused by radiative heat losses
from the product gases. d2
tcond
Experiments with premixed methane−air flames in counter- 16 (51)
flow and microgravity were performed by Maruta et al.264 It was p
observed that there are two extinction limits that appear on a trad 4
curve obtained by plotting the stagnation velocity against the 14 b (Tf T 4) (52)
extinction equivalence ratio. Moreover, the upper and lower The comparison of time scales was performed by Ronney for
branches of this curve merge at a point when the equivalence stoichiometric and near-limit flames, and the results of this
ratio is sequentially reduced. The results of the experiments are comparison are shown in Table 3. It can be seen in Table 3 that
shown in Figure 13b. The stagnation velocity gradient is defined buoyancy convection is unimportant for stoichiometric flames,
as 2U/L, where U is the flow velocity at the burner outlet and L is as can be deduced by comparing their time scales with the
the distance between the two tubes. In Figure 13b, the upper chemical reaction time scale (tinv ≫ tchem, tvis ≫ tchem). For flames
part of the curve corresponds to the stretch extinction limit, the near the limit, on the other hand, this relationship is reversed,
lower part corresponds to the radiative heat loss extinction limit, and buoyancy convection is actually very important under
and the inflection point is the flammability limit of a stretched normal gravity conditions (tchem ≫ tinv, tchem ≫ tvis). For flames
flame. near the limit, the time scales for radiation and chemical reaction
Experimental data on laminar flame speeds in zero gravity can are of the same order of magnitude. However, the time scale for
be found in the works of Ronney,262,263 Ronney and buoyant convection is much smaller than that of radiation (trad
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Table 3. Comparison of Characteristic Time Scales of stable. It was Ronney who observed a stable flame ball in a
Combustion Processes for Stoichiometric and near Limit microgravity experiment.
Flamesa A schematic representation of a stationary spherical flame is
shown in Figure 14a. These flames were characterized by a
time scale
radius rf, and the fuel and oxidant were transported by diffusion
stoichiometric near limit from the surroundings into the reaction zone. At the same time,
flame flame
the combustion products and heat are being diffused outward
chemical reaction (tchem) 0.00094 s 0.250 s
from the reaction zone. In experiments conducted by Ronney267
inviscid buoyant convection (tinv) 0.071 s 0.071 s
at the NASA Lewis Research Center in microgravity, he
viscous buoyant convection (tvis) 0.012 s 0.010 s
observed the formation of flame balls for mixtures containing 7%
conduction heat loss to walls (tcond) 0.950 s 1.400 s
H2 in air with an addition of 4% bromotrifluoromethane
radiant heat loss (trad) 0.130 s 0.410 s
a (CF3Br) and characterized by a low Lewis number.
Reproduced with permission from ref 44. Copyright 1998 Elsevier. The small flame balls shown in Figure 14b had a visible radius
that ranged from 2.0 to 4.0 mm (approximately). In another
≫ tinv, trad ≫ tvis). Therefore, the effect of radiation would only study, Ronney et al.268 increased the duration of microgravity
be observable under low gravity experimental conditions. from a time of 2.2 s determined in the work of Ronney267 to a
If there is no convection and the time scales of heat/mass time 10 times longer using aircraft-based experiments. Burning
diffusion and reaction rate become comparable, a stationary velocities observed by Ronney267 in drop tower experiments
flame can exist. The possibility of the existence of stationary ranged from 0.25 to 2.5 cm/s for H2−air mixtures with H2
spherical flames was theoretically predicted by Zeldovich.266 concentrations between 5 and 7.5% (near the LFL). These
However, the theory predicted that an adiabatic flame ball is not burning velocities are of the same order of magnitude as those

Figure 14. Stationary spherical flames and flame balls observed in microgravity. (a) Schematic representation of stationary spherical flame.
Reproduced with permission from ref 44. Copyright 1998 Elsevier. (b) Flame balls observed in drop tower experiments for mixtures of 7% H2 in air
with the addition of 4% CF3Br. Reproduced with permission from ref 267. Copyright 1990 Elsevier. (c) Flame balls observed in aircraft experiments for
mixtures of 3.5% H2 in air. Reproduced with permission from ref 268. Copyright 1994 American Institute of Aeronautics and Astronautics. (d) Flame
balls observed in space shuttle experiments for mixtures of 4.9% H2, 9.8% O2, and 85.3% CO2. Reproduced with permission from ref 269. Copyright
1998 American Institute of Aeronautics and Astronautics.

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Figure 15. Experimental results for counterflow twin H2−air premixed flames, with jet spacing of 1.27 cm. (a) Stability and extinction limits. (b) Near-
planar flames for 8.26% H2 and 60 s−1 strain rate. (c) Wrinkled flames for 8.10% H2 and 110 s−1 stretch rate. (d) Moving tube flames for 6.96% H2 and
60 s−1 strain rate. (e) Stationary twin tube flames for 6.68% H2 and 60 s−1 strain rate.270 and (f) Stationary single tube flame for 6.64% H2 and 60 s−1
strain rate. (a−e) Reproduced with permission from ref 270. Copyright 2000 American Institute of Aeronautics and Astronautics.

predicted by Spalding’s theory. The flame balls were also presented in the work of Ronney et al.,269 where flame balls were
observed in aircraft experiments for various H2−air mixtures formed for mixtures of H2−O2−CO2 and H2−air. The
characterized by low Lewis numbers268 [Figure 14c]. The visible
radius of these flame balls was about 3 mm. Further confirmation maximum duration of the experiments was 500 s, and the
was provided by experiments performed in a space shuttle and flame balls for the H2−O2−CO2 mixture persisted all the time
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Table 4. Comparison of Available Methods for the Determination of FLs in Air at Reference Conditions
reference limit NTot Ncorr NPred AARE (%) R2 type of compound
Methods for the Estimation of the LFL
Albahri274 LFL 472 454 18 4.10 0.9300 several
Albahri275 LFL 543 518 25 2.28 0.9998 several
Bagheri et al.276 LFL 1615 1292 323 15.29 0.9295 several
Frutiger et al.277 LFL 443 − − 11.50 0.9900 several
Gharagheizi278 LFL 1056 845 211 7.68 − several
Gharagheizi279 LFL 1057 846 211 4.62 0.9860 several
Kondo et al.280 LFL 238 − − 18.06 0.8665 several
Lazzús281 LFL 418 328 90 − 0,9865 several
Mendiburu83 LFL 324 243 81 5.32 0.9591 C−H
Mendiburu et al.33 LFL 374 273 101 5.43 0.9752 C−H−O
Pan et al.282 LFL 1038 830 208 5.60 0.9787 several
Rowley et al.283 LFL 509 309 200 10.67 − several
Seaton284 LFL 150 − − 5.13 0.9904 several
Methods for the Estimation of the UFL
Albahri274 UFL 477 464 13 11.80 0.9600 several
Frutiger et al.277 UFL 351 − − 15.90 0.9100 several
Gharagheizi285 UFL 865 693 172 9.56 0.9209 several
High and Danner286 UFL 181 − − 26.40 − several
Kondo et al.280 UFL 238 − − 19.14 0.4197 several
Lazzús281 UFL 418 328 90 7.10 0.9776 several
Mendiburu83 UFL 247 158 89 8.32 0.9202 C−H
Mendiburu et al.35 UFL 208 136 72 8.95 0.9346 C−H−O
Pan et al.287 UFL 579 465 114 19.23 0.7540 several
Seaton284 UFL 141 − − 9.68 0.8862 several

[Figure 14d]. The visible radii of the flame balls were 2.5−4.0
mm (approximately).
Flame balls are more stable when the mixture is near the
flammability limits, where thermal radiation plays a critical role
in stabilizing the flame ball. Flame balls are unstable for mixtures
with a Lewis number close to unity or greater than unity;
therefore, these flames were not observed for lean CH4−air and
C3H8−air mixtures, which have Le numbers of 0.9 and 1.7,
respectively.
These studies have shown that the Lewis number is important
for the formation of the flame ball and for extending the burning
limits. To better understand how flow stretch and flame
curvature affect the burning limits of a fuel at a low Lewis
number, Kaiser et al.270 measured the flame regimes and burning
limits of hydrogen flames in a counterflow slot burner under
normal gravity conditions. Two flame configurations for
premixed H2−O2-N2 flames were tested: (1) the single flame
(premixed gas versus inert gas) and (2) the twin flame
(premixed gas versus premixed gas). Only the results of the
second case are briefly discussed here.
The experiments were performed varying the equivalence
ratio and the global strain rate σst = (Vupper + Vlower)/d, where
Vupper and Vlower are the exit velocities of the upper and lower jets,
respectively, and d is the distance between the nozzles’ exits. As
can be seen in Figure 15a, there are two extinction limits for a
solid fuel composition: one at high σst due to stretch extinction
and another at low σst due to heat loss. For a fixed σst with
decreasing H2 concentration, it was observed that the nearly
planar twin flames [Figure 15b] gradually become wrinkled
flames [Figure 15c] and multiple moving tube flames [Figure
15d]. With even further decrease of the H2 concentration, the
observations show stationary twin tubes [Figure 15e], stationary
single-tube flames [Figure 15f], and finally extinction.
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It is important to note that a stationary single-tube flame was
observed at an H2 concentration as low as 6.11%. This result
clearly shows that flame curvature or flame stretch has extended
the flammable region. A single-tube flame with a higher stretch
could burn much leaner. This observation is consistent with the
predicted G-shaped flammability limit of a stretched flame in
Figure 6.
5. METHODS FOR ESTIMATION OF THE
FLAMMABILITY LIMITS IN AIR AT REFERENCE
CONDITIONS
Several authors have developed methods for the determination
of FLs in air under reference conditions. These methods are
listed here, and their accuracy is compared. However, in this
section, only the methods that have better accuracy are analyzed
in more detail. The estimation methods are of great importance
for industrial applications.
In general, methods for estimating FLs can be divided into
two groups: (1) methods that use quantitative properties of
molecular structure or group contributions together with linear
correlation or neural networks; (2) methods that use calculated
adiabatic flame temperature (CAFT) together with linear
correlation and combustion theory. Note that group contribu-
tion methods are well-established for the determination of
various properties of fluids, as shown in classical hand-
books,271,272 and several authors have applied these methods
to develop correlations for the determination of FLs. On the
other hand, CAFT methods are based on the theory of
equilibrium combustion. In this approach, if the adiabatic
flame temperature is known and equilibrium is assumed, the
composition of the reactants can be calculated.
The available methods for determining FLs are semiempirical,
meaning that a total set of compounds is divided into a
correlation set and a prediction set. The correlation set is used to
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obtain a correlation or train a neural network, and the prediction where the first, second, and third order group contribution
set is used to test the results obtained in the previous step. The factors are accounted for by the terms Cj, Dk, and El, respectively.
accuracy of these methods is evaluated by the absolute value of These terms are provided by Frutiger et al.277 as Supporting
the relative error (ARE), the average value of the relative error Information in their work. Nj, Mk, and Ol are the number of
(AARE), and the squared correlation coefficient (R2), which are occurrences of a given group in the molecular structure. To
determined by eqs 53−55. know how many groups of each order are present in a
|FLcalc FLexp| compound, it is necessary to analyze the 2D structure of the
ARE = · 100% molecule.
FLexp (53) It is interesting to show how this method can be applied to a
N compound. Ethanol is considered as an example. From the
1 CAMEO Chemical Datasheet,88 the experimental LFL and UFL
AARE = AREi
N i=1 (54) of ethanol are 3.3% and 19.0%, respectively. The 2D structure of
the ethanol molecule can be found in ref 288. The groups
SSE observed in the structure are methyl radical (CH3), methylene
R2 = 1
SST (55) (CH2), and OH. Each of the groups exhibits Nj = 1. In the
The sum of squares of the errors (SSE) and the total sum of Supporting Information of Frutiger et al.,277 these are classified
squares (SST) are given in eqs 56 and 57.273 as first order groups; therefore, the terms Mk and Ol are both
N
zero. The values of Cj for the LFL are −0.24, −0.23, and 0.06 for
SSE = (FLcalc, i FLexp, i) each group; on the other hand, the values of Cj for the UFL are
i=1 (56) −1.15, −0.14, and −0.76 for each group.277 The results of
applying eqs 58 and 59 are an LFL of 3.00% and a UFL of
N 2 16.73%. As can be observed, the application of this method is
SST =
N
(FLexp, i)2
( i=1 )
FLexp, i
simple, and the accuracy is good. Frutiger et al.277 provide
i=1
N (57) another sample calculation in their paper and also develop a
method to obtain a 95% confidence interval.
The comparison of the different methods is given in Table 4. There are several group contribution methods similar to the
The total number of compounds considered is NTot, the number one developed by Frutiger et al.277 In general, these methods can
of compounds in the correlation set is Ncorr, the number of
be used without much difficulty to accurately estimate
compounds in the prediction set is Npred, the average of the
relative error of the whole data set, AARE, and the squared flammability limits under reference conditions of temperature
correlation coefficient of the whole data set, R2, are also shown in and pressure.
the Table. 5.2. Calculated Adiabatic Flame Temperature (CAFT)
Most of the methods considered rely on knowledge of the Method for FLs in Air at Reference Conditions. There is
molecular structure of the compound to directly estimate the FL another type of method that assumes that the adiabatic flame
or to find the necessary parameters for estimating the FL. In temperature can be approximated by a correlation283 or by using
some cases, it is also necessary to use the neural network an average value.289 With the use of the value of the adiabatic
developed in the specific work. Frutiger et al.277 reported that flame temperature, the FL can then be calculated by a simple
Gharagheizi,278,279,285 Pan et al.282,287 and Bagheri et al.276 used procedure assuming equilibrium in the combustion products. In
experimental and predicted values in developing their methods. this section, a method that can account for the LFL and UFL of
Therefore, these methods are not recommended. In sections 5.1
C−H and C−H−O compounds is presented. This method is a
and 5.2, methods based on group contribution properties and
another using CAFT are considered. The results presented in synthesis of previous work by Mendiburu et al.32−35 to
Table 4 show that most of the listed methods have R2 determine the FLs of C−H and C−H−O compounds. For
coefficients above 0.90 and AAREs below 20%. simplicity, a C−H compound is one that contains carbon and
5.1. Group Contribution Based Method for FLs in Air at hydrogen atoms in its molecule. A C−H−O compound is
Reference Conditions. The method developed by Frutiger et analogously defined as a compound containing carbon,
al.277 was selected from those presented in Table 4 for its hydrogen, and oxygen in its molecule.
accuracy and consistency, since the authors used only The combustion process is assumed to occur under adiabatic
experimental data to train the model. The structure of the and constant pressure conditions. The nitrogen and excess
compound must be known to determine the first, second, and oxygen are considered inert. In addition, complete combustion
third order group contributions. The FLs are calculated using is assumed in the LFL and the products of combustion are
the expressions presented in eqs 58 and 59. assumed to be in chemical equilibrium in the UFL. There are
ÄÅ É
ÅÅÅ ij yzÑÑÑÑ three possible combustion reactions: one in the LFL and two in
Å j zÑ
LFL = 4.53ÅÅÅexpjjj NC j j + Mk Dk + Ol El zzzÑÑÑ the UFL. These reactions are shown in eqs 60−62.
ÅÅ jj zzÑÑ
ÅÅÇ k j k l {ÑÑÖ (58) combustion reaction at the LFL:
ÄÅ É
ÅÅ i yzÑÑÑÑ
LFL
ÅÅ jj CxCH x HOxO + vair (O2 + 3.76N2)
zÑ
UFL = 129.96ÅÅÅexpjjj NC
j j + Mk Dk + Ol El zzzÑÑÑ xH
ÅÅ jj zzÑÑ xCCO2 + LFL
H 2O + (vair s
vair LFL
)O2 + 3.76vair N2
ÅÅÇ k j k l {ÑÑÖ 2
(59) (60)

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combustion reaction at the UFL, without condensate: or 62], on the compound in question, and on the equilibrium
UFL
constants, Ksc for eq 65 and Kcc for eq 66. The expressions
CxCH x HOxO + vair (O2 + 3.76N2) needed to determine the coefficients are given below.
Coefficients for the reaction without condensate are defined
nCO2CO2 + nCOCO + nH2OH 2O + nH2 H 2
in eqs 68−75.
UFL
+ 3.76vair N2 (61) av = am2 + 2am (68)
combustion reaction at the UFL, with condensate: xH
UFL
bv = 2amn + amxO + 2an (2a + 1)mxC m 2xC
CxCH x HOxO + vair (O2 + 3.76N2) 2
(69)
UFL
nCOCO + nCC + nH2OH 2O + nH2 H 2 + 3.76vair N2 xH
(62) cv = an2 (2a + 1)nxC + (an xC)xO (n xC)
2
In the case of the LFL, the energy conservation equation is + 2xC 2 (70)
used to relate the stoichiometric coefficient of air (vLFL
air ), which is
equal to the number of oxygen moles in the air, to the adiabatic hair,R 2h H 2 2 h H 2O 3.76h N2
flame temperature at the LFL (TLFL). Isolating then vLFL air , one m=
obtains the expression shown in eq 63. hCO hCO2 + h H2O hH2 (71)
s xH xN
hF,R + vair hO2 xChCO2 h h xH
LFL
vair = 2 H 2O 2 N2
n=
hF,R xChCO2 + (2xC xO)h H2O + xO ( 2 )
2xC h H2
hair hair, R (63) hCO hCO2 + h H2O h H2
where the subscript “R” refers to the reactants and all other (72)
enthalpies correspond to the products. The h̅air is defined as a=1 K sc (73)
shown in eq 64, while a similar expression determines h̅air,R. Note
that in order to evaluate the enthalpies of the products, it is UFL xH
necessary to know the value of TLFL. b = 2avair xC(2a + 1) + axO
2 (74)
hair = hO2 + 3.76h N2 (64) i x UFL y
c = xCjjj2xC + H xO 2vair zz
z
In the case of the UFL, the reaction without condensate k 2 { (75)
represents the combustion process and provides the solution
Coefficients for the reaction with condensate are defined in
when there is sufficient oxygen. On the other hand, if there is not
eqs 76−84.
enough oxygen, the reaction with condensate represents the
combustion process and provides the solution. In such cases, the av = am2 2am + 3.76(a 1)m 7.52(a 1) (76)
condensate is represented by carbon graphite (C). It is therefore
necessary to find a solution for both reactions, with and without ix y
condensate. The equilibrium condition is applied by the bv = 2amn + amjjj H xOzzz 2an + (a 1)
k 2 {
homogeneous and heterogeneous water−gas reactions. The
former is used for the reaction without condensate and the latter [3.76(n xO) x H] (77)
for the reaction with condensate. These reactions are shown in
ix y xH
eqs 65 and 66, respectively. cv = an2 + anjjj H xOzzz (a 1) xO
water−gas homogenous reaction: k 2 { 2 (78)

H 2O + CO CO2 + H 2 (65) hair,R 2h H 2 2 h H 2O 3.76h N2

m=
water−gas heterogenous reaction: hCO hCO2 + h H2O hH2 (79)
C + H 2O CO + H 2 (66) xH

The criterion for determining whether or not the solution n=

hF,R xChC xOh H2O + xO ( 2 )hH 2

should contain condensate is that the mole numbers of all hCO hH2 h H 2O hC (80)
species must be positive. In most cases, only one of the reactions
will meet this criterion. However, if both reactions meet the a = 1 + Kcc(p0 /p) (81)
criterion, then the UFL obtained in the reaction with condensate
will be greater than that in the reaction without condensate. xH UFL UFL
b= a xOa + 3.76vair (a 1) 2avair
From the point of view of safety, the first should be preferred to 2 (82)
the second. This criterion was applied by Mendiburu et al.34,35 in ÅÄÅ x
their previous work. By use of the law of conservation of energy c = (1 a)ÅÅÅÅx HvairUFL UFL
+ 3.76xOvair + H xO
and the equilibrium condition, it is possible to obtain a quadratic ÅÇ 2
equation vUFL ÑÉ
air for the two reactions under consideration. UFL 2 Ñ
+ 7.52(vair ) ÑÑÑÑ
UFL 2
av(vair UFL
) + bvvair + cv = 0 (67)
ÑÖ (83)

The coefficients of eq 67 depend on the adiabatic flame xH UFL

nT = nCO + + 3.76vair
temperature in the UFL (TUFL), on the reaction chosen [eq 61 2 (84)

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Table 5. Coefficients for Use with Correlations Shown in Eqs 85 and 86

LFL UFL
C−H C−H−O C−H C−H−O
coefficient
a0 1.4774 1.5101 2.3737 2.5526
a1 1.0186 × 10−2 −6.7195 × 10−3 −2.3822 × 10−1 −1.7112 × 10−1
a2 −2.0090 × 10−3 1.3081 × 10−2 1.2076 × 10−2 −2.9203 × 10−2
a3 6.4563 × 10−2 8.4976 × 10−2 2.8293 × 10−2 −5.8587 × 10−4
a4 1.1814 × 10−2 6.4285 × 10−3 4.6652 × 10−2 −6.1402 × 10−2
a5 − − 9.8788 × 10−4 −4.1708 × 10−3
a6 − − −1.8129 × 10−4 −4.9859 × 10−5
a7 − − 5.2138 × 10−2 −4.9785 × 10−1
a8 − − −1.9116 × 10−1 1.1146 × 10−1
a9 − − 4.3725 × 10−2 −4.3060 × 10−3
a10 − − −2.0102 × 10−2 2.1873 × 10−2
a11 − − −1.3389 × 10−1 −1.6556 × 10−1
N 324 374 247 208
AARE (%) 5.53 5.57 8.46 9.24
R2 0.9608 0.9756 0.9312 0.9318

The ratio of the adiabatic flame temperature in stoichiometric
combustion (Tstq) to TLFL is obtained from eq 85. In the same
manner, the ratio of Tstq to TUFL is obtained from eq 86.
Therefore, the value of Tstq must be calculated beforehand. The
expressions for xi are shown in eq 87, and the values for the
coefficients ai are presented in Table 5.
Tstq
= a0 + a1x1 + a2x2 + a3x3 + a4x4
TLFL (85)
Tstq
= a 0 + a1x1 + a 2x12 + a3x13 + a4x2 + a5x2 2
TUFL
+ a6x2 3 + a 7x3 + a8x32 + a 9x33 + a10x4 + a11x41/2
(86)
0 0
hf,F hf,F
x1 = ; x2 = ; sudden drop in the temperature of the combustion products.
WF xCx H(xO + 1)
WF xC(xO + 1)
x3 = ; x4 =
xCxH(xO + 1) xH (87)
The above correlations are based on the earlier work of
Mendiburu et al.32−35 The original correlations were modified to
obtain two correlations: one for the LFL and one for the UFL.
The accuracy of the method was not significantly affected, as
shown by comparing the values for AARE and R2 reported in
Table 5 with those in Table 4. The value xO = 0 corresponds to
C−H compounds; therefore, (xO + 1) is used in x2, x3, and x4. In
a few cases, the method may converge to two UFL values: one
for the reaction without condensate and another for the reaction
with condensate. In these cases, the two UFL values are close
and the higher value is chosen.
A calculation example for this method is presented by
Mendiburu et al.35 in the Supporting Information of their paper.
Application of the method to the case of ethanol in air under
reference conditions gives an LFL of 3.27% and a UFL of
18.71%. These values are close to the experimental values of
3.3% and 19.0%, respectively.88 It is interesting to note that
Jarosinski et al.256 found that the adiabatic flame temperatures
near the FLs of propane in air are about 150 °C higher than the
experimental temperatures. The present method can be
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implemented in Excel or Matlab to obtain a straightforward
application.
It is important to discuss the relationship between CAFT
methods and the most fundamental methods based on chemical
kinetics and radiative heat losses discussed in section 2. The
methods based only on the competition between chain-
branching and chain-termination reactions cannot be directly
related to the CAFT methods because the latter assume
chemical equilibrium and do not analyze the steps between
reactants and products.51,53,54
Nevertheless, CAFT takes into account some features of the
latest methods, which consider detailed chemical kinetic
mechanisms and radiative heat losses. For example, Bertolino
et al.64 introduced soot formation to determine the UFL. This
feature is introduced in the CAFT method simply by assuming a
reaction containing carbon graphite in the products. In addition,
the method of Bertolino et al. identifies the FLs when there is a
The theory developed by Spalding30 predicts the FLs by
assuming a one-step chemical kinetic reaction and applying
radiative heat losses to a propagating flame. This theory assumes
knowledge of some properties that allow determination of
radiative heat losses. CAFT methods assume infinitely fast one-
step chemical reactions that reach equilibrium and replace
radiative heat losses with knowledge of an approximate adiabatic
flame temperature. These features explain the success of the
simple CAFT methods in practical applications where FLs must
be estimated.
Before concluding this section, a discussion of soot formation
is necessary because it is important to UFL. Soot can be formed
by two mechanisms: by a homogeneous reaction in the vapor
phase or by pyrolysis in the liquid phase. The amount of soot
formed from a fuel depends on several physical parameters,
including the type of flame. In premixed flames, aromatics tend
to form soot the most, followed by alkanes, alkenes, and alkynes.
It is also known that in premixed flames increasing the
temperature reduces the tendency to form soot.27
The sooting limit is defined at the experimental condition that
produces the first luminous continuum radiation on a premixed
flame. The sooting limit of several fuels was measured by
Takahashi and Glassman290 in a specially designed apparatus
using a Bunsen burner. The mass flow rate of the oxidizer was
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Figure 16. Effect of mixture initial temperature on FLs for different compounds in air: (a, b) hydrogen,16,291 (c) dimethyl ether,182 (d) methyl
formate,182 (e−g) ethylene;212,220,291 (h, i) methane.133,291 (a−i) Reproduced with permission from ref 292. Copyright 2017 Elsevier.

kept constant while the mass flow rate of the fuel was increased The above definition can be expressed as ψc = [(xc/2) + (xH/
until the flame emitted a luminous continuum radiation. The 4)]/nO2,exp. As the mass flow rate of the fuel is increased in the
d

critical sooting equivalence ratio (ψc) is defined as the ratio of

experiments, nO2,exp = (ṁ O2,exp/ṁ F,exp)(WF/WO2) then decreases
the stoichiometric number of moles of oxygen required to form d d d

CO and H2O in the products to the experimental number of until the sooting limit is reached. Therefore, lower values of ψc
moles of oxygen per mole of fuel at the sooting limit.290 imply a lower sooting tendency because a higher mass flow rate
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of the fuel was required to find the sooting limit. Following the FLT hC,0 ij hair, T yzz
results of Takahashi and Glassman,290 it is found that at the same jj1 zz
= j
flame temperatures, ψc,ethane > ψc,ethylene > ψc,acetylene. One of the FL0 hC, T + hF, T hair, T jk FL0hC,0 z{ (90)
most important parameters for soot formation in premixed From the experimental observations, it is expected that FLT/
flames is the flame temperature, since an increase in temperature FL0 = 1 ∓ mΔT, where the minus sign (−) corresponds to the
increases the oxidation rate of the soot precursors due to the LFL and the plus sign (+) corresponds to the UFL. Therefore,
attack of OH radicals. In addition, the C/H ratio of the fuel eq 90 can be solved for the slope m. In this expression, ΔT = T −
molecule is also important, as it determines the OH T0.
concentration.
1
ji hC, T hF, T hair, T zyz jij har, T hC, T
6. TEMPERATURE AND PRESSURE EFFECTS ON FLS m = ± jjjj + zz
z
jj1
j
k hC,0 hC,0 { k FL0hC,0 hC,0
The initial temperature and pressure conditions have an
influence on the values of FLs. Therefore, it is necessary to hF, T y
hair, T zz 1
+ zz
evaluate the influence of these parameters. First, the temperature hC,0 z T
effect is considered by giving a general description in section 6.1, { (91)
a discussion of Burgess−Wheeler’s law in section 6.1.1, and a It is reasonable to assume that the term (Δh̅F,T − Δh̅air,T)/hC,0
description of available methods in section 6.1.2. Then, in is small and can be neglected compared to the other terms of eq
section 6.2, the pressure effect is considered. Finally, section 6.3 91. Moreover, the sensible enthalpy of air can be represented by
presents the available empirical equations for determining the an average heat capacity at constant pressure Δh̅air,T = cp̅ ,airΔT.
FLs of some compounds in air at various initial temperatures and Therefore, the expression for the slope can be simplified as given
pressures. in eq 92.
6.1. Temperature Effect on FLs. The effect of the initial
ij hC,0 hC, T yz cp ,air
temperature of the mixture on the FLs is determined m = ± jjjj FL0 1zzzz
experimentally by holding the pressure constant. An example j cp ,air T z FL0hC, T
of such observations is shown in Figure 16. The experimental k { (92)
data shown in Figure 16 are for hydrogen,16,291 dimethyl Substituting eq 92 into eq 90, an expression for the variation
ether,182 methyl formate,182 ethylene,212,220,291 and meth- of the FL with the initial temperature is obtained. The simple
ane.133,291 The results of the estimation method developed by expression shown in eq 93 is the modified Burgess−Wheeler law.
Mendiburu et al.292 are also shown in Figure 16. The
FLT ij hC,0 hC, T yz cp ,air
= 1 ± jjjj 1zzzz
experimental data show that the LFL decreases with the increase
FL0 T
of initial temperature, while the UFL increases with the increase FL0 j cp ,air T z FL0hC, T
of initial temperature. Moreover, the flammability limits vary k { (93)
almost linearly with the initial temperature. As Glassman et al.27 In the methods that use detailed chemical kinetic mechanisms
noted, increasing temperature accelerates chemical reactions; and include radiative heat losses, the extension of the
therefore, it is reasonable that the flammable range increases as flammability range is mainly caused by the increase in reaction
the initial temperature increases. rates of some key reactions. However, in the case of the modified
Assuming that the oxidant is air, the expression in eq 1 can be Burgess−Wheeler law, the assumption that the enthalpies of the
written as FL = 100/(1 + na/nF). From the point of view of the reactants at the FLs are constant can be related to the fact that
ratio of air to fuel (na/nF), this ratio increases in the LFL and some chain-initiation and chain-branching reactions require a
decreases in the UFL as the initial enthalpy of the mixture is certain amount of energy for a flame to propagate.
increased. This means that the reactant in excess can be 6.1.2. Methods for Determination of FLs at Different Initial
increased when the initial temperature is higher because the Temperatures. There are some methods for the determination
chemical reactions are accelerated at a higher initial temperature. of FLs at different initial temperatures and atmospheric pressure.
6.1.1. The Modified Burgess−Wheeler Law. The modified The method of Zabetakis24 follows directly from eq 93. It
Burgess−Wheeler law states the following: “For a flammable gas assumes that the heat released is constant (hC,0 = hC,T) and
the sum of the heat released at the LFL and the sensible corresponds to the heat released by complete combustion of 1
enthalpies of the reactants is constant.”24 The practical mol of fuel (HC). The values of 0.0075 kcal/(mol·K) and 10.4
implications of such a simple law are of great importance for kcal/mol can be assumed for cp̅ ,air and FL0HC, respectively. The
industrial applications. This law can be written as shown in eq expression obtained is shown in eq 94, where the minus sign (−)
88, where the index T refers to the initial temperature, hC,T is the corresponds to the LFL and the plus sign (+) to the UFL.
heat released at T, and K is a constant. FLT
=1 0.000721(T T0)
FLT[( hF, T hair, T ) + hC, T ] + hair, T = K FL0 (94)
(88)
283
The method developed by Rowley et al. uses the expression
Assuming that FL0 is a known flammability limit value at the shown in eq 95 to approximate LFLT.
reference temperature T0, Burgess−Wheeler’s law can be written
as shown in eq 89. (1 ) cp ,F air
LFLT (%) = LFL0 (T T0)
HC (95)
FL0hC,0 = K (89)
where
Dividing eq 88 by eq 89, and rearranging, the expression
cp,F air = LFL0 cp ,F, T0 + (100 LFL0) cp ,air, T0 (96)
shown in eq 90 is obtained.
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Table 6. Comparison of Methods for the Determination of the FLs at Different Initial Temperatures and Constant Pressure
LFL UFL
method N AARE (%) R2 N AARE (%) R2
24
Zabetakis 180 4.82 0.9948 129 5.01 0.9748
Mendiburu et al.292 180 3.25 0.9928 129 3.60 0.9957
Britton and Frurip293 161 4.44 0.9946 − − −
Rowley et al.283 109 4.95 0.9857 − − −
Catoire and Naudet295 140 14.64 0.9003 − − −

= 0.0125xC2 0.779 (97) the fuel and the initial temperature. The adiabatic flame
293
temperatures for the stoichiometric combustion at different
Another method, developed by Britton and Frurip and initial temperatures (Tstq,T) are also needed in this method. The
Britton,294 uses the expression shown in eq 98 to approximate ratio given in eq 106 increases linearly with an increase in the
the LFLT. initial temperature of the mixture.
TLFL,0 T1 * T /TUFL,
Tstq, * T
LFLT = LFL0 UFL, T
= = 1 + kUFL(TT T0)
TLFL,0 T0 (98) * /TUFL,0
*
UFL,0 Tstq,0 (106)
The value of the adiabatic flame temperature in the LFL with
where the subscript “0” refers to the temperature T0. The slope
initial temperature T0 is denoted TLFL,0 and is determined by the
kUFL is approximated by the correlations presented in eqs 107
correlations given in eqs 99−101. Catoire and Naudet295 have
*
and 108. The value of TUFL,T is determined by eq 109.
also developed a method using the correlation shown in eq 102.
for C−H compounds and hydrogen:
hydrocarbons:294
4
ij H yz kUFL = 3.7611 × 10 3.0500 × 10 4I
TLFL,0 = 2181 7.4613jjj sC zzz
j vair z + 2.5988 × 10 6hf,F
° + 2.0798 × 10 8(hf,F
° )2
k { (99)
(107)
C−H−O−N compounds:294
for C−H−O compounds and carbon monoxide:
ij H yz
TLFL,0 = 2290 7.6944jjj sC zzz kUFL = 5.8362 × 10 3
3.8838 × 10 4I
j vair z
k { (100)
6.7817 × 10 5hf,F
° 1.4430 × 10 7(hf,F
° )2
293
C−H−O−Cl compounds: (108)
ij H yz 1
TLFL,0 = 2427 8.3846jjj sC zzz * T
Tstq, ij y
UFL, T z
j vair z * T= jj z
zz
* jj
k { (101) TUFL, z
* /TUFL,0
Tstq,0 k UFL,0 { (109)
s
LFL = 519.957(1 + 5vair ) 0.70936 xC 0.197T 0.51536 (102) Finally, the UFL is determined using the number of moles of
292
Mendiburu et al. have developed methods to estimate the oxygen obtained by eq 110, which was derived by algebraically
FLs at different initial temperatures. In the case of the LFL, a manipulating the energy conservation equation by replacing the
correlation for the slope m is obtained by using a parameter I. excess fuel with an equal mass of air. The molecular weight of air
This parameter is given in eq 103 and relates the molecular used in eq 110 is Wair = 28.96 g/mol, and the UFL is determined
weight of the fuel (WF) to the product of the heat released by UFL = 100%/(1 + 4.76vUFL air ) .
during combustion of 1 mol of fuel (HC) and the number of UFL
vair = [vair s
(WF/Wair)(hair,P hair,R )]
moles of a gaseous fuel−air mixture (nF*) occupying a volume of ÄÅ
12 L at T0. The correlation for the slope at the LFL is given in eq ÅÅÅh xH
ÅÅ F xChCO2 h H O + (WF/Wair)
104. Finally, the LFL is determined by eq 105. ÅÇ 2 2
ÉÑ
Ñ 1
3.76h N2)ÑÑÑÑ
WF s
I= (hair,P hair,R ) + vair (hair,R
*
nF HC (103) ÑÖ (110)
Note that in this method the excess fuel is treated as a heat
mLFL,calc = 8.3959 × 104 + 9.6643 × 10 5I sink. The above methods are compared in Table 6. In another
comparison of the methods for determining the LFL at different
+ 2.6402 × 10 6I 2 + 8.3413 × 10 10
HCI
initial temperatures, Mendiburu et al.292 showed that their
(104) method is more accurate for compounds with xC > 5 and for
LFLT = LFL0[1 mLFL,calc(T T0)] (105)
hydrogen. It was also found that the LFL of ammonia is not
correctly approximated by any of the three more accurate
In the case of the UFL it was assumed that the excess fuel does methods.24,292,293 In the case of the UFL at different initial
not react,292 so the mass of unreacted fuel is replaced by an equal temperatures, the method of Mendiburu et al.292 is more
mass of air in the products. This allows the determination of an accurate.
adiabatic flame temperature at the UFL that is independent of Some articles have considered the adiabatic flame temper-
the global combustion reaction (T*UFL,T) and depends only on ature in the LFL and UFL to be independent of the initial
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Figure 17. Pressure dependence of FLs of methane in air: (a) LFL and (b) UFL. Reproduced with permission from ref 299. Copyright 2016 Elsevier.
Pressure dependence of FLs of natural gas in air: (c) LFL and (d) UFL. Reproduced with permission from ref 300. Copyright 2019 Elsevier.

temperature of the mixture.296−298 This approach has given compounds show nonlinear behavior. The experimental data
good results for lower alkanes; however, the authors have found obtained by Van den Schoor220 are shown in Figure 18 and
that it leads to higher deviations for oxygenated compounds confirm the nonlinearity of the UFLs of methane and natural gas.
(C−H−O). These data show nonlinear behavior for ethane, propane, n-
In another work by Liaw and Chen,297 a method to calculate butane, and ethylene UFLs in air at 200 °C and pressures above
the FLs at different initial temperatures was developed. This atmospheric. In the case of hydrogen, Liu and Zhang109 showed
method was developed for two cases: (1) adiabatic combustion
process and (2) combustion process with radiative heat losses.
The adiabatic approach was found to be more accurate.
Moreover, in this work, the adiabatic flame temperature was
assumed to be constant and the combustion reaction in the UFL
assumes the presence of CO, CO2, H2, and H2O in the products.
However, this type of reaction cannot be satisfied for some
compounds such as ethylene.
6.2. Pressure Effect on FLs. The dependence of FLs on the
initial pressure of the mixture is discussed in this section.
Experimental data show that, for low hydrocarbons, an increase
in initial pressure increases the UFL; however, it has a weaker
effect on the LFL.156,205,212 This behavior is shown in Figure 17
for the cases of methane299 and natural gas.300 The experimental
data presented in Figure 17 confirm the stronger effect of the
initial pressure on the UFL compared to the effect on the LFL. It
can be observed that the data for methane and natural gas show a Figure 18. Flammability limits in air of ethane, propane, n-butane, and
linear behavior of the LFL for different initial pressures. ethylene at 200 °C and pressures above the atmospheric. Data taken
However, the experimental data for the UFLs of these from ref 220.

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that increasing the initial pressure (from 0.1 to 0.4 MPa) leads to
a decrease in LFL and an increase in UFL, with the latter
showing nonlinear behavior.
It is interesting to point out that Coward and Jones251
presented experimental FL values obtained for DFP in a 2 cm
diameter, 50 cm long tube and for different flame propagation
directions in a 5 cm diameter, 50 cm long tube. The results
showed that at low pressures there is convergence of the LFL
and UFL. However, the FLs reported by Coward and Jones251
are limits of flame propagation in a tube of a given diameter
rather than flammability limits.27
In their experimental study, Coronado et al.82 determined the
FLs of anhydrous and hydrated ethanol in air at different
temperatures and reduced pressures in a 20 L spherical vessel.
The LFL and the UFL showed no tendency to converge at low
pressures. There are two works in which the LFLs of some
compounds were theoretically determined at different initial
pressures.301,302 In these works, the adiabatic flame temper-
atures at different pressures were used to estimate the LFL.
Therefore, the method used is similar to that described in
section 5.2.
The phenomenological description of a planar flame,
presented by Law,303 is interesting to explain the behavior of
FLs at different initial pressures. The burning mass flux rate (ṁ S)
is related to the flame thickness (δ), the specific heat capacity
(cp), and the thermal conductivity (k) by the expression shown
in eq 111. In addition, the burning mass flux rate is equal to the
product of the laminar flame speed (sL) and the unburned
mixture density (ρu).
k /cp
mS = sL
u (111)
Then, the mass flux rate can be related to the pressure by eq
112, where the dependence of the reaction rate on pressure is w0b
0
∼ pne−Ta/Tb , where Ta is the activation temperature, n is the
d
reaction order, and Tb is the adiabatic flame temperature.
ÄÅ ÉÑ1/2
ÅÅ i y ÑÑ
ÅÅ n jj kt zz Ta / TbÑ
Ñ
mS ÅÅp jj zz e ÑÑ
ÅÅ jj zz ÑÑ
ÅÅ k cp { ÑÑ
ÅÇ b ÑÖ (112)
The ratio k/cp is insensitive to pressure variations. Therefore,
for reactions of order n = 2, the mass flux rate would be pressure
independent. However, in cases where n > 0 and n ≠ 2,
increasing the pressure would increase the mass flux rate. The
burning mass flux rate (ṁ S) varies inversely with flame thickness
[see eq 111]. Furthermore, for a reaction order of n > 0,
increasing the initial pressure would increase the burning mass
flow rate (ṁ S) and decrease the flame thickness (δ).
Since a thinner flame involves lower heat losses due to the
lower volume of the flame,303 the UFL is expected to increase
and the LFL to decrease at higher pressures. On the other hand,
increasing the pressure leads to an increase in heat loss by
thermal radiation per unit volume due to an increase in the
average absorption coefficient.54 It can be concluded that there
are two competing mechanisms: the decrease in heat losses per
unit volume associated with the decrease in flame thickness at
higher pressures and the increase in heat losses due to thermal
radiation associated with the increasing mean absorption
coefficient at higher pressures.
6.3. Empirical Formulas for FLs at Different Initial
Temperatures and Pressures. The slopes for the linear
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dependence of FLs on initial temperature were obtained by
applying a linear regression to the experimental data from several
articles. The results of this procedure are given in Table S3. Van
den Schoor211 determined the slopes for estimating the UFLs of
some alkanes at different temperatures and initial pressures of
the mixture. A linear relationship is also used to determine the
UFL at different initial temperatures. The coefficients for these
relationships are given in Table S4. Goethals et al.227 established
an empirical equation to determine the change in FLs of toluene
with the initial temperature of the mixture for different initial
pressures. The coefficients are listed in Table S5. Vanderstraeten
et al.204 experimentally studied the change in UFL of methane
with temperature and pressure. The coefficients for their
empirical equations are given in Table S6.
Several experimental articles presented their own empirical
relationships to estimate the effects of initial temperature and
pressure on the FLs of a given compound. The information in
Table S1 gives the references in which the effects of these
variables were determined. The dependence on pressure is
generally logarithmic, as shown in eq 113.
ij p yz
FLp = FL p + a0 lnjjjj zzzz
0 jp z
k 0{ (113)
To the author’s knowledge, there is no simple method
validated with experimental data from different data sets and
multiple fuels that allows the determination of FLs at different
initial pressures. Zabetakis24 established the following empirical
equations for the determination of FLs of natural gas (85−95%
methane and 15−5% ethane) at different initial pressures and
ambient temperatures in air.
LFLp = 4.9 0.71(log p) for 1 680 atm (114)
UFLp = 14.1 + 2.04(log p) for 1 680 atm (115)
In eqs 114 and 115, p0 = 1. LFLp0 = 4.9, UFLp0 = 14.1, a0 =
d d
0.71, and a0 = 2.04, for LFLp and UFLp, respectively. The
experimental data available in the literature can be correlated in
this way.
7. DILUENT GAS EFFECTS ON FLS
The addition of a diluent (or inert) gas to the fuel−air mixture
affects the FL value. Figure 19 shows the behavior of the FLs of
different methane−inert−air mixtures as a function of the
concentration of the diluent gas.24 In Figure 19, the pressure is
atmospheric and the temperature is 25 °C. Diluent gases added
to fuel−air mixtures are sometimes referred to as inert gases.
Note that, strictly speaking, CO2 and H2O are not inert gases.
They can chemically affect the reaction process by promoting or
suppressing the production of radicals. These species can be
nitrogen, carbon dioxide, water vapor, or helium, among others.
The behavior shown in Figure 19 is typical of hydrocarbons (C−
H) and oxygenated compounds (C−H−O) mixed with a
diluent gas in air. As the concentration of the diluent gas is
increased, the LFL increases slightly and the UFL decreases. At a
certain point, called the fuel inertization point (FIP), both limits
are equal. Mixtures in the FIP are generally rich, with some
exceptions (hydrogen for example).
The variation in the FLs is greater for the diluent gases added,
which have higher heat capacities. For example, looking at the
relationship for cp,i shown in eq 116 and comparing it to the
variation in the FLs shown in Figure 19, we find that a greater
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Figure 19. Flammability limits of methane−inert−air mixtures at 1 atm
and 25 °C.24
variation corresponds to the added inert gases with higher values
of cp,i.
cp ,CCl4 > cp ,CO2 > cp ,H2O > cp,N2 > cp ,He (116)
The effect of the diluent gas can be attributed to the fact that
some of the heat released by the combustion process is used to
raise the temperature of the inert species to the flame
temperature. This simple argument can also be used to
understand the effects of the addition of He (helium) on the
LFL. However, in the case of halogenated compounds, the
differences in heat capacities are not sufficient to explain the
behavior shown in Figure 19. Halogenated compounds inhibit
the chain-branching reactions of the H2−O2 system by
catalyzing the recombination of hydrogen atoms to form
molecules and radicals that are relatively less reactive.303
In the case of He, the LFL increases slightly with increasing
He concentration as cp,He > cp,N2. Comparing the dilution by N2
d
with that by He, we find that the latter affects the thermal
diffusivity of the mixture (α = k/ρcp) differently. For example, at
300 K and 1 atm, the densities of N2 and He are 1.1233 and
0.1615 kg/m3, the specific heat capacities are 1.041 and 5.193
kJ/(kg·K), and the heat conductivities are 0.0259 and 0.152 W/
(m·K), respectively.31,304 Therefore He influences the value of
the Lewis number more strongly than N2. According to
Matalon,305 the effective Lewis numbers (Leeff’s) of lean and
rich mixtures can be determined by the expressions given in eqs
117 and 118.
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LeO + (1 )LeF
Leeff,lean =
2 (117)
LeF + (1 + )LeO
Leeff,rich =
2+ (118)
In eqs 117 and 118, Φ̃ ∼ β(1 − ϕ). The Lewis number of the
fuel (LeF) and the Lewis number of the oxidizer (LeO) are
calculated by using the thermal diffusivity of the mixture and the
mass diffusivities of the fuel and oxidizer, respectively. The
equivalence ratio (ϕ) and the Zeldovich number (β) are also
used in eqs 117 and 118. Note that β = Ea(Ta − Tu)/RTb2. Fan et
al.306 calculated the effective Lewis numbers for mixtures of H2−
O2−He and H2−O2−N2 with ϕ = 0.4; for the former the value of
Leeff,lean was 0.60 and for the latter it was 0.57.
Qiao et al.29 studied the flammability limits and laminar flame
speed of methane−air mixtures in microgravity with dilution by
He, argon (Ar), N2, and CO2. They determined the effective
Lewis number as the ratio between the thermal diffusivity of the
mixture and the mass diffusivity of the methane−oxygen pair, as
shown in eq 119. They then calculated the values of the effective
Lewis numbers for mixtures of CH4−air−diluent for different
molar concentrations of the diluent. The results are summarized
in Table 7.
mix
Leeff =
DCH4 O2 (119)
Table 7. Effective Lewis Numbers for CH4−Air−Diluent
Mixturesa
diluent mole concn (%) Leeff
He 0−35 0.99−3.46
Ar 0−48 0.99−0.97
N2 0−35 0.99−0.98
CO2 0−22 0.97−0.89
a
Reproduced with permission from ref 307. Copyright 2010 Elsevier.
Since spherical flames have a positive flame stretch rate when
they propagate outwardly, as in the case of FL experiments, the
effect of the Lewis number can be evaluated by considering the
generalized stretch factor (σ), where the Karlovitz number (Ka)
is also needed.303 The generalized stretch factor takes into
account the chemical and diffusive properties of the mixture
through the first two factors on the right-hand side of eq 120 and
the system dynamics through the third factor (Ka).
ij 1 yz
= jj 1zzzKa
j
j
2 k Leeff z
{ (120)
Therefore, flame speed and temperature decrease for mixtures
with Leeff > 1 and increase for mixtures with Leeff < 1. Thus, in the
case of helium, flame propagation is affected by the stretch effect
by reducing the laminar flame speed and flame temperature as
the effective Lewis number of the mixtures is greater than unity.
According to Glassman et al.27 the chain-termination reaction
(R3) competes with the chain-branching reaction (R1) when
the system is rich. The third body can be an inert species such as
N2, H2O, or CO2. Law and Egolfopoulos51 found that, at
atmospheric pressure for lean methane−air flames, the main
competing reactions were the chain-termination reaction (R2)
and the chain-branching reaction (R1). Nevertheless, the
accuracy of these observations can be tested by performing a
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Figure 20. Flame speed sensitivity analysis for freely propagating methane−air flame near the FLs. (a) CH4 mole concentration of 4.90%; (b) CH4
mole concentration of 15.80%.

sensitivity analysis of the laminar flame speed for methane near
the LFL and near the UFL. The results of this analysis are shown
in Figure 20. The simulations were performed with Cantera
software308 using the GRI3.0309 chemical kinetic mechanisms.
H + O2 OH + O
H + O2 + M HO2 + M
H+H+M H2 + M
The graphs in Figure 20 depict the 10 elementary reactions
that presented the highest absolute values of the sensitivity
coefficient (k/SL)(dSL/dk). The importance of the chain-
branching reaction shown in (R1) is evident. Furthermore, the
effects of N2 and H2O on the LFL are noted by promoting the
formation of the more stable HO2 species by consuming a more
reactive H radical. The recombination reactions shown in (R4)
and (R5) become important chain-termination reactions for the
CH4−air mixture near the UFL.
CH3 + H + M CH4 + M
2CH3 + M C2 H 6 + M
In addition, the chain-propagation reactions (R6)−(R8),
where HCO is the formyl radical, also play a crucial role in H
radical production and heat generation.
CO + OH CO2 + H
HCO + M CO + H + M (R7)
H 2O + O 2OH (R8)
For example, the addition of a diluent gas not only decreases the
(R1)
fuel and oxygen concentrations, but the increase in the third-
(R2)
body coefficient also changes the reaction rates of chain-
termination and chain-propagation reactions [(R2), (R3), and
(R3) (R7)], so the overall reaction rate is varied, resulting in changes
in flame speeds and FLs. When H2O is added, reaction R8
promotes the production of the OH radical. When CO2 is added,
reaction R6 (reverse) suppresses the production of the H
radical, leading to strong chemical effects on flame speeds and
FLs.
The dilution effect causes the inert species to lower the flame
temperature. This effect is stronger in the UFL than in the LFL
because more heat can be released in the LFL. In the case of a
lean mixture, the termination reaction (R2) competes “more
efficiently” with the chain-branching reaction (R1). However,
due to the decreasing temperature, the chain-branching reaction
(R4)
becomes slower. For rich mixtures, the reaction rate of the chain-
termination reaction (R3) becomes greater than that of (R2)
(R5)
because it depends on the hydrogen concentration, which is
expected to be higher for rich mixtures. Therefore, reaction R3
competes “more efficiently” with the chain-branching reaction
(R1), which at the same time becomes slower due to the lower
temperature. As a result of these interactions, the UFL is more
(R6) affected by the addition of diluents than the LFL.
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Another important feature is that the rates of production of H2
and HO2 by the reactions shown in (R3) and (R2), respectively,
increase with increasing concentration of the diluting species. It
is important to note that halogenated compounds follow a
different mechanism that also inhibits the combustion process
(see refs 27 and 303).
In addition, H2O and CO2 have a radiative effect on flames.
This effect can either lower the flame temperature (optically thin
mixtures) or increase the flame temperature (optically thick
mixtures). Guo et al.310 found that the addition of CO2 increases
the optical thickness of the flame because CO2 is able to emit
and absorb radiation. The increase in the heat capacity of the
mixture (due to the addition of CO2) causes the flame
temperature to drop and increases the probability that the
flame will extinguish due to stretch or radiative heat loss.
Therefore, flammability limits are also affected by the addition of
CO2, as has been observed experimentally. The existence of
flammability limits considering radiation reabsorption in
premixed flames was demonstrated by Ju et al.311
It is expected that the addition of a diluting species will cause
incomplete combustion. This is confirmed by Kumar et al.,312
who tested H2−H2O−air mixtures with a hydrogen concen-
tration of 8.0%. They found that the combustion efficiency was
100.0% at 0.0 and 15.0% vapor concentrations; however, at
30.0% vapor concentration, the combustion efficiency was
38.0%.
7.1. Methods for Determining FLs with Added Diluent
Species. Some methods have been developed to determine the
FLs of fuel−diluent−air mixtures at 1 atm and reference
temperature. In most methods, the adiabatic flame temperature
was assumed constant; also, a global reaction was assumed at the
UFL. The fuel−diluent−air mixture presents two independent
concentrations. The fuel molar fraction (FL) and the diluent
molar fraction (Pd) can be considered independent in order to
define a fuel-diluent mixture, characterized by the fuel molar
fraction (yF) defined in eq 121. Therefore, the diluent molar
fraction in the fuel−diluent mixture would be yd = 1 − yF.
FL
yF =
FL + Pd (121)
Chen et al. 313,314
studied the FLs of hydrocarbons in air
diluted with N2 and CO2. They obtained the expression shown
in eq 122, which relates the flammability limit without added
diluent (FL0) to the flammability limit with added diluent (FLd)
by means of a factor identified as ΦFL. They theoretically
determined the values of ΦFL; however, the results were not
entirely satisfactory.
ij 1 yz
1 1 jj 1zzzz
= + FL j
j
FLd/100 FL/100 jy z be used to evaluate the effectiveness of a diluent gas when it is
k F { (122)
313,314
In the calculations of Chen et al., the adiabatic flame
temperature was assumed to be constant and CO2, CO, H2O,
and H2 were assumed to be formed at the UFL. A similar
approach was used by Shu et al.315,316 Note that compounds
with high UFLs would require a condensate (carbon) in the
products to be considered at equilibrium. For example, in the
case of ethylene, the UFL in air is 31.5%186 and the reaction
[without condensate] shown in eq 61 cannot provide a solution
for high UFL values; in these cases, the reaction [with
condensate] shown in eq 62 has been successfully applied.34,35
The assumption of a constant adiabatic flame temperature was
applied by Liaw et al.,317,318 who also evaluated the effect of
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radiative heat losses on the calculations. Surprisingly, they found
that the results obtained with the adiabatic model were more
accurate than those obtained with the nonadiabatic model. Bade
Shrestha et al.319 also applied a constant adiabatic flame
temperature approach. They considered that at the UFL the
oxygen was consumed first to form CO and second to form H2O,
and if any O2 was still available it would react to form CO2 from
the available CO. The same scheme of O2 consumption was
applied in the work of Shu et al.315,316 mentioned earlier. The
main difficulty in applying the CAFT method for fuel−diluent−
air mixtures is the prediction of the UFL, because in this case the
CAFT will not be constant due to the significant variations in the
UFL. Therefore, there is room for further simulations to
investigate the effects of diluent addition on flammability limits.
It is worth noting that Gutiérrez Velásquez et al.320 applied
kriging regression to predict the FLs of hydrated and anhydrous
ethanol. Therefore, dilution with H2O was somehow considered
in this work.
7.2. Empirical Equations to Determine FLs with Added
Diluent Species. Wang et al.321 determined the empirical
values of ΦFL for the determination of the UFL in air of fuels
diluted with N2 or CO2. These empirical values are shown in
Table S7. To evaluate the applicability of the empirical values of
ΦFL together with eq 122, a validation was performed by
considering the UFL of 528 experimental data for fuel−N2−air
mixtures and 208 experimental data for fuel−CO2−air mixtures.
The results show AAREs of 4.53 and 6.07%, respectively, while
the R2 values were 0.9839 and 0.9748, respectively. These results
are also shown in Table S7. The experimental data considered
here are the same as specified in Tables S8 and S9.
Correlations for various fuel−diluent−air mixtures can be
found in the literature. For example, Kondo et al.186,187 obtained
correlations for determining the FLs of some hydrocarbons,
oxygenated compounds, and ammonia diluted with N2 and CO2.
Also, correlations for the determination of the FLs of ammonia
diluted with HFC-134 and HFC-125 were obtained by Kondo et
al.95 In another work, Kondo et al.185 established correlations for
the FLs of isobutane diluted with N2 and CO2. Li et al.136
presented correlations for the determination of the FLs of
methane−N2−air mixtures at low temperatures and 1 atm.
In another work, Li et al.18 presented correlations to
determine the FLs of R-290 and R-152a refrigerants diluted
with 1,1,2,2-tetrafluoroethane (C2H2F4). Zhang et al.193
obtained correlations to calculate the FLs of dimethyl ether
diluted with five different compounds. Molnarne et al.322
investigated the use of a method that assigns a nitrogen
equivalence coefficient to other dilution gases. This method can
used to reduce the flammability range of a compound. The case
of nitrogen was studied in a previous work.85
A simple way to obtain empirical equations for different
compounds is to assume that there is a simple relationship
between the number of oxygen moles on the FL without added
diluent species (vFL air,0), the number of oxygen moles on the FL
with added diluent species (vFL air,d), and a correlation factor kFL, as
performed by Mendiburu et al.323 The expected relationship is
shown in eq 123. Equations 124 and 125 are used to determine
the values of vFL FL
air,0 and vair,d.
FL FL
vair,d = yF vair,0 + yd kFL
(123)
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1 ijj 100 yz 7.3. Methods to Determine the Fuel Inertization Point

FL
vair,0 = j 1zzz
4.76 jjk FL0 z (FIP). It is said that at the FIP both flammability limits are equal.
{ (124) However, the mixture at this point is usually rich (ϕ > 1), which
means that the FIP is actually part of the UFL curve. The
1 ijj 100 yz
FL
vair,d = j 1zzz problem of determining the FIP involves the determination of at
4.76 jjk FLd + Pd z
{ (125) least two unknowns, namely (1) the value of the equivalence
ratio at the FIP (ϕFIP) and (2) the value of the fuel molar fraction
The values of kFL were determined for several fuel−diluent− (yFIP
F ) in the fuel−diluent mixture at the FIP.
air mixtures using experimental data to solve eq 123. It was Shebeko et al.324 assumed that only CO, H2O, N2, and the
found that the dependence of the FL on the type of diluent added inert gas are present in the products. The FIP is obtained
added can be approximated by the average values of kFL as shown assuming that the number of moles of oxygen is exactly that
in eqs 126 and 127. The FIP is part of the UFL curve since it needed to obtain the aforementioned products. However, the
corresponds to a rich mixture (except hydrogen). determination of the fuel molar fraction or of the adiabatic flame
N 1 temperature is not specified. Bade Shrestha et al.319 developed
av 1 an approximation for the fuel molar fraction at the FIP. This
kLFL = kLFL
N i=1 (126) approximation uses empirically determined constants that
measure the influence of the added inert at the LFL (aLFL)
N
av 1 and UFL (aUFL). The equation to be solved is shown in eq 129.
kUFL = kUFL The authors have not provided a method for determining aFL
N i=1 (127) when experimental data are not available for a particular fuel.
323
The values of kav
FL were obtained by Mendiburu et al. for 1
1 i 100 100 yz
different fuel−N2−air and fuel−CO2−air mixtures at 1 atm and = 1 + (aLFL aUFL)jjj + zz
25 °C. The results of this procedure are given in Tables S8 and 1 yFFIP k UFL LFL { (129)
S9. Once the value of vFL air,d is obtained, the FL is determined by
applying eq 128. The accuracy of the empirical approximations Razus et al.325,326 have developed a method that assumes an
is shown in Table 8, where it can be seen that the AARE is less average value of the equivalence ratio on the FIP (ϕav FIP) for the
than 5.0% and the R2 is greater than 0.989. cases of addition of N2, CO2, or H2O. Then, the value of the
yF adiabatic flame temperature at the FIP (TFIP) is approximated by
FL = FL
·100% a linear correlation with the adiabatic flame temperature at the
1 + 4.76vair,d (128) LFL without the added inert (TLFL). Hansen327 and Hansen and
Crowl328 assumed a constant adiabatic flame temperature and
Table 8. Accuracy of Empirical Determination of the FL of assumed that excess oxygen in the products was not converted at
Fuel−Inert−Air Mixtures with Values of kav
FL Obtained from the UFL. In this way, CO2 and H2O could be assumed to be part
Experimental Dataa of the products. An empirical model was fitted with data for 38
compounds diluted with nitrogen. This model showed a low
ARE
value of squared correlation coefficient (R2 = 0.672).
added inert N AARE (%) R 2
≤10% 10−20% >20% Van den Schoor et al.203 experimentally determined the FIP
Lower Flammability Limits points of C2H4−N2−air, H2−N2−air, and C2H4−H2−N2−air.
N2 461 1.45 0.9973 457 6 0 The FIP was approximated by the following considerations: (a)
CO2 170 3.08 0.9895 159 8 3 the LFL does not change with the addition of N2; (b) at the FIP
Upper Flammability Limits the equivalence ratio is equal to unity. However, as shown in
N2 521 3.29 0.9973 487 23 11 Table S8, the equivalence ratios at the FIP points of fuel−N2−air
CO2 201 4.21 0.9959 178 15 8 mixtures are not equal to unity. In a later work, it was found that
a
Adapted from Mendiburu et al.323 this approximation is inaccurate for mixtures containing H2−
CO−N2−air.137
Mendiburu et al.323 proposed a method for determining the
molar fraction of diluent in a fuel−diluent mixture, assuming
As an example, the UFL of an ethanol−CO2−air mixture can that the adiabatic flame temperature at the FIP (TFIP) can be
be determined. The experimental UFL of an ethanol−CO2 determined and used to determine yFIP by assuming a global
mixture in air is 9.5% when the fuel−diluent mixture contains reaction and performing equilibrium calculations as explained
32.2% ethanol and 67.8% CO2. The values kav UFL = 0.3410 and for the CAFT method in section 5.2. The adiabatic flame
vUFL
air,0 = 0.913 are taken from Table S9. Applying eq 123, the value temperatures at the FIP and at the LFL (without diluent) were
vUFL
air,d = 0.256 is determined. Finally, from eq 128, the calculated related as shown in eq 130.
UFL is 9.2%. In this case, the ARE is 3.16%.
It is important to note that, to determine the FLs of a fuel− TFIP
d =
diluent−air mixture, the concentration of the diluent added TLFL (130)
must be kept constant. Therefore, it is easier to use the
concentrations in the fuel−diluent mixture that are derived from Mendiburu et al.323 found that, for the fuel−diluent−air
the actual concentrations in the fuel−diluent−air mixture. mixtures listed in Tables S8 and S9, the θd value ranged from
Although there is a reasonable amount of experimental data on 0.78 to 1.17 and the ϕFIP value ranged from 0.841 to 1.847. The
FLs for fuels diluted with N2 and CO2, data for fuels diluted with exception was H2, for which the ϕFIP values, when the mixtures
H2O are still sparse. Moreover, other diluents have rarely been were diluted with N2 and CO2, were 0.463 and 0.468,
considered in experiments. respectively. The equivalence ratio at the FIP (ϕFIP) is related
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to the mole fraction of fuel at the FIP (yFIP

F ) and to the moles of hd, R hd,P
oxygen at the FIP (vFIP n=
air ) by eq 131. hCO hCO2 + h H2O hH2 (141)
yFFIP i x xO yz
FIP
vair = j
jjxC + H zz Note that the eq 134 can provide two values for yFIP
F , but only
FIP k 4 2 { (131) one of them satisfies the mass balance of the global reaction [eq
In the same article, a correlation was proposed to obtain θd, 133]. The method developed by Mendiburu et al.323 showed
ϕFIP, kav av
LFL, and kUFL, as shown in eq 132.
AAREs of 0.82 and 1.95% for the FIPs of fuel−N2−air and fuel−
CO2−air mixtures, respectively. The Supporting Information of
L = a 0 + a1z1 + a 2z 2 + a3(z1z 2) + a4z12 + a5z 2 2 the original article contains sample calculations for the
application of this method. For a discussion of flammability
+ a6(z1z 2)2 (132) limits in oxygen see the Supporting Information.
where L might be θd, ϕFIP, kav
LFL, or kav
UFL. The zi are given in eq
133. 8. THE FLAMMABILITY LIMITS OF FUEL MIXTURES
LHVi LHVav FLA, i FLA,av Le Chatelier’s law can be used to determine the FLs in air of a
z1 = ; z2 = mixture containing more than one fuel based on the FL data for
SLHV SFL (133)
each fuel. The mathematical expression for this law is very
The LHVav and FLA,av are average values of the lower heating simple and is shown in eq 142.
value and of the flammability limit of the compounds used for
the correlation set. The SLHV and SFL are the standard deviations 1
FLmix = yi
of these variables for the correlation set. Table S10 presents the
coefficients and the values of the averages and standard FLi (142)
deviations necessary to apply the correlation in eq 132. In the
cases of θd and ϕFIP the determination of z2 involves the LFLA,i, There are a total of four different ways to derive Le Chatelier’s
LFLA,av and SLFL for determining z2. Assuming the global law; these are presented by Mashuga and Crowl,329 Carvalho et
reaction shown in eq 134, the necessary equations to apply the al.,330 Chen et al.,331 and more recently by Mendiburu et al.5 The
method are obtained. following can be stated as Le Chatelier’s law: A mixture of N
combustible gases at the FL in air requires a number of moles of
yFFIP CxCH x HOxO + ydFIP Md + vair
FIP
(O2 + 3.76N2) oxygen equal to the weighted sum of the number of moles of
oxygen required by each gas at its respective FL in air, where the
nCO2CO2 + nCOCO + n H2OH 2O + n H2 H 2 mole fractions are the weighting factors. This section briefly
FIP
+ 3.76vair N2 + ydFIP Md presents the derivation of Le Chatelier’s law as given by
(134) Mendiburu et al.5
The value of yFIP
Fis obtained from eq 135, and the required Consider the combustible gases A and B and their mixture,
coefficients are obtained from eqs 136−141. The Keq is from the denoted C. Given the composition of the FLs of A, there are vFL air,A
homogeneous water−gas reaction [eq 65]. moles of oxygen per mole of species A. Assuming an adiabatic
combustion process at constant pressure, that the nitrogen and
av(yFFIP )2 + bvyFFIP + cv = 0 (135) excess oxygen are inert, and applying conservation of energy to
the global combustion reaction for species A, eq 143 is obtained.
a=1 Keq (136) * = vFL
In this equation, the excess oxygen is represented by vair,A air,A
s
s − vair,A. Moreover, in the LFL, vair,A
* > 0 and α = 1. In the UFL,
var,1 * < 0 and α = 0.
however, vair,A
av = am2 + 2 (am xC) + xC[2xC (2a + 1)m]
FIP
xH hA njhj * hO ,A
vair,A
FL A 2
+ xO(am xC) + (xC m) vair,A =
2 (137) 3.76h N2,A (hO2,R + 3.76h N2,R ) (143)
s
var,1 xH For 1 mol of A, FLA can be determined as follows FLA =
bv = 2amn + 2an (2a + 1)nxC + anxO n
FIP 2 100%/(1 + 4.76vFL air,A). This gives the expression shown in eq
(138) 144. In this expression, the heat released in the combustion
process of A is hC,A = h̅0f,A − ∑A njh̅0f,j.
cv = an2 (139)
ÄÅ É
ÄÅ yA jij hC,A + hA ÅÅ
ÅÅÇ n * hO ,A ÑÑÑÑ zyz
hj + vair,A 2 Ñ
ÅÅ = yA + 4.76yA jjjj Ö zzz
s A j
vair,1
m = ÅÅÅÅhF + jj zz
(har,R 3.76h N2 + 2h H2 2h H2O) FLA 3.76h N2,A (hO2,R + 3.76h N2,R ) z
ÅÅ k {
ÅÇ FIP
(144)
xH
h H + xC(2h H2O 2h H 2 hCO2)
2 2 Note that it is always possible to choose the reference
ÉÑ
ÑÑ temperature equal to the initial temperature of the reactants.
+ xO(h H2 h H2O) + (hd,P hd,R )ÑÑÑÑ Thus, writing eq 144 for the combustible gas B, considering the
ÑÑ
ÑÖ initial temperature to be equal to the reference temperature for
1 gases A and B at the FL (∑njΔh̅j = 0), and adding these
(hCO hCO2 + h H2O h H 2) (140) expressions, the relationship shown in eq 145 is obtained.
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Figure 21. Results obtained by applying the law of Le Chatelier to the determination of (a) LFLs of mixtures and (b) UFLs of mixtures. Reproduced
with permission from ref 5. Copyright 2020 Elsevier.

yA yB N
+ = yA FL
var,mix = yv FL
FLA FL B i ar, i
ÄÅ É i=1 (149)
ij h
j C,A
ÅÅ
ÅÅÇ * hO ,A ÑÑÑÑ yzz
n hj + vair,A 2 Ñ
+ 4.76yA jjjj Ö zz + y
A j
zz The above expressions are consistent with Le Chatelier’s law,
jj 3.76h N2,A zz B
although they are formulated in terms of the number of moles of
k {
oxygen at the FLs. In their work, Mendiburu et al.5 compared the
ij h ÅÄÅ É
* hO ,BÑÑÑÑ yzz
j C,B ÅÅ n hj + vair,B FLs calculated according to Le Chatelier’s law with experimental
+ 4.76yB jjjj ÅÇ B j 2 Ñ Ö zz
zz data from Coward and Jones,251 Hustad and Sonju,147 Karim et
jj 3.76h N2,B zz
k { (145) al.,130 Kondo et al.,95,184,185 Shoshin and de Goey,248 White,123
Zhao et al.,99 Wierzba and Wang,133 and Wierzba et al.135 It is
A similar procedure can be applied to C (mixture of A and B) important to note that most experimental data correspond to
to obtain the expression in eq 146. binary mixtures of fuels in air. For ternary mixtures, there were
23 experimental data for LFL and 14 for UFL. No data were
ÄÅ É
ij h
j C,C
ÅÅ
ÅÅÇ n * hO ,CÑÑÑÑ yzz
hj + vair,C found for mixtures of more than three flammable compounds.
2 Ñ
= 1 + 4.76jjjj Ö zz
1 C j The validation results presented in this section are sufficient to
zz
FLC jj 3.76h N2,C zz understand the accuracy of this law. Nevertheless, the lack of
k { data for mixtures (or blends) of three or more fuels is a gap that
(146) should be addressed in future studies of conventional and
Since the gas C is a mixture of the gases A and B (yA + yB = 1), renewable fuels.
the law of Le Chatelier requires that the equality shown in eq 147 A total of 272 experimental data for the LFLs and 217 for the
UFLs were used for validation. The AAREs were 2.76% for the
is fulfilled.
LFLs and 8.28% for the UFLs. The values of R2 were 0.9870 for
ÄÅ É
* hO ,CÑÑÑÑ
the LFLs and 0.8649 for the UFLs. Looking at the results
hC,C ÅÅÅÅ C nj hj + vair,C 2 Ñ
Ç Ö presented in Figure 21, it is clear that Le Chatelier’s law predicts
3.76h N2,C LFLs with great accuracy, while it is only acceptably accurate in
ÄÅ É predicting UFLs. The experimental data used for this validation
ij h Å
jj C,A ÅÅÅÇ A nj hj + vair,A * hO ,A ÑÑÑÑ yzz are listed in Tables S11 and S12.
2 Ñ Ö zz
= yA jjj zzz After an analysis of the above derivation, it can be
jj 3.76h N2,A z
k { hypothesized that Le Chatelier’s law applies to fuels that react
ÄÅ ÉÑ according to their own chemical kinetic mechanisms, as if the
ij h ÅÅ Ñy
jj C,B ÅÅÇ B nj hj + vair,BhO2,BÑÑÑÖ zzz
* other fuels were not present in the mixture. This hypothesis will
+ yB jjj zzz be partially tested in the remainder of this section.
jj 3.76h N2,B zz
k { (147) In their simulations, Bertolino et al.64 used laminar flame
speed as an indicator to identify FLs. Moreover, Liang and Law53
The equality shown in eq 147 is possible only if the reaction assumed that three pairs of competing reactions are relevant in
kinetic paths of A and B are virtually unchanged, even if these FLs. Therefore, the hypothesis can be tested by performing a
compounds react in the same combustible mixture. In such a sensitivity analysis of laminar flame speed and identifying up to
case, the global effect of the reaction kinetic mechanisms is three pairs of competing reactions. It is expected that the three
accounted for by eq 146. Moreover, the global effect can be pairs of major competing reactions identified for each fuel at its
represented in a simpler expression by substituting eq 143 into FLs must have a similar degree of importance (as measured by
eq 147. Thus, eq 148 is obtained. The same procedure can be their sensitivity coefficients) when the fuel mixture at the FLs is
considered.
applied to any number of combustible gases forming a mixture.
Consider the mixtures containing methane, propane, and
In this case, the expression shown in eq 149 is obtained.
dimethyl ether (C2H6O), namely CH4−C3H8−air and CH4−
FL FL FL C2H6O−air. In both cases, Le Chatelier’s law accurately predicts
vair,C = yA vair,A + yB vair,B (148) the LFLs. However, the UFL of CH4−C2H6O−air cannot be
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Figure 22. Flame speed sensitivity analysis for mixtures 50% CH4−50% C3H8−air (mix 1) at the FLs.

Figure 23. Flame speed sensitivity analysis for mixtures 50% CH4−50% C2H6O−air (mix 2) at the FLs.

predicted accurately. The flame speed sensitivity analysis was CH4 + H CH3 + H 2 (R14)
performed using Cantera.308 The relevant elementary reactions
include all the reactions presented so far in this article as well as C3H6 + H C3H5 + H 2 (R15)
the reactions listed below.
8.1. The CH4−C3H8−Air Mixture. In this case, Le C3H8 + H H 2 + i C3H 7 (R16)
Chatelier’s law accurately predicts the FLs of the mixture 50% The results of the flame speed sensitivity analysis are shown in
CH4 + 50% C3H8 (mix 1). The San Diego mechanism67 was Figure 22. It is noticeable that the relative importance of the
used together with Cantera.308 At the LFL, the three main chain- competing elementary reactions is consistent with the
branching (or initiation) reactions are reactions R1, R7, and R6 hypothesis resulting from the derivation of Le Chatelier’s law.
for CH4, C3H8, and mix 1. The main chain-termination (or That is, Le Chatelier’s law is true if the chemical kinetic
recombination) reactions are reactions R2, R9, and R10 for mechanisms of the individual fuels are not affected by the
CH4; reactions R2, R9, and R11 for C3H8; and reactions R2, R9, presence of the other fuels in the mixture. This is confirmed by
R10, and R11 for mix 1. the fact that the main competing reactions of the individual fuels
HCO + O2 CO + HO2 (R9) at the FLs are also very important for the fuel mixture at the FLs.
8.2. The CH4−C2H6O−Air Mixture. In this case, Le
CH3OH + M CH3 + OH + M (R10)
Chatelier’s law accurately predicts the LFL of the mixture 50%
CH4 + 50% C2H6O (mix 2). However, it is inaccurate in
C2H4 + O CH3 + HCO (R11)
predicting the UFL of mix 2. The mechanism developed by Liu
et al.332 was used in conjunction with Cantera.308 At the LFL,
At the UFL, the major chain-branching (or initiation) the major chain-branching (or initiation) reactions are reactions
reactions are reactions R1, R12, and R13 for CH4; reactions R1, R6, and R7 for CH4, C2H6O, and mix 2. The major chain-
R1, R13, and R14 for C3H8; and reactions R1, R13, R14, and termination (or recombination) reactions are reactions R2, R9,
R12 for mix 1. The major chain-termination (or recombination) and R17 for CH4, C2H6O, and mix 2.
reactions are reactions R4, R5, and R14 for CH4; reactions R5, In the UFL, the main chain-branching (or initiation) reactions
R15, and R16 for C3H8; and reactions R5, R15, R4, R12, and are reactions R1, R6, and R18 for CH4 and reactions R20, R21,
R16 for mix 1. and R22 for C2H6O. However, for mix 2, reactions R6, R18, and
R21 are not of the same relative importance as for the individual
CH3 + O2 CH 2O + OH (R12) fuels. The most important chain-termination (or recombina-
tion) reactions are reactions R4, R5, and R14 for CH4 and
C2H3 + O2 CH 2CHO + O (R13) reactions R7, R22, and R23 for C2H6O. However, for mix 2,
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reactions R4, R5, R7, and R14 are not of the same relative flames at the UFL. Note that reactions R19−R22 are reactions
importance as for the individual fuels. that characterize combustion at low temperatures.333 For further
HO2 + OH H 2O + O2 discussion on the chemistry of cool flames, see the Supporting
(R17)
Information.
2CH3 C2H5 + H (R18) Systematic testing of the hypothesis of the applicability of Le
Chatelier’s law requires a sensitivity analysis of the chemical
CH 2OCH 2O2 H + O2 O2 CH 2OCH 2O2 H (R19) kinetics of fuel mixtures for which experimental data are
available (see Tables S11 and S12). However, such a study is
CH3OCH3 + OH CH3OCH 2 + H 2O (R20) beyond the scope of this section and is proposed as a future
research prospect.
CH3OCH 2O2 CH 2OCH 2O2 H (R21)
As Law303 states, Le Chatelier’s law represents the possibility
CH 2OCH 2O2 H 2CH 2O + OH (R22) of a unifying concept for the phenomena of flammability limits.
To overcome the experimental difficulties in the UFL, it would
CH 2O + OH H 2O + HCO (R23) be necessary to perform experiments with UFP and DFP in
microgravity and compare the results. However, such experi-
The results of the flame speed sensitivity analysis are shown in ments would be very complex.
Figure 23. Note that, in this case, some of the competing
elementary reactions that are very important in the UFLs of the 9. FLAMMABILITY LIMITS OF RENEWABLE FUELS
individual fuels have a lower relative importance in the UFL of AND FUTURE PERSPECTIVE
mix 2. This observation is consistent with the fact that Le
Chatelier’s law is not accurate for determining the UFL of mix 2. This section focuses on the FLs of renewable and alternative
Analyzing the available experimental data, the authors have fuels. Knowledge of FLs is important for the safe use of these
shown in a previous work5 that Le Chatelier’s law is accurate for fuels. Up to this point, the theory and estimation methods for
estimating the experimental LFLs and UFLs determined with FLs have been discussed. It is also interesting to discuss
downward flame propagation (DFP). Moreover, higher AREs strategies to establish reliable databases for new fuels by
are observed when Le Chatelier’s law is used to estimate the minimizing the need to conduct new experiments. Therefore,
experimental UFLs determined with spherical flame propaga- estimation methods should be used when possible.
tion (SFP) and with upward flame propagation (UFP). 9.1. The FLs of Emerging Renewable Fuels. The use of
Therefore, the effect of buoyancy is also important for the hydrogen as an energy carrier has become very important for
accuracy of Le Chatelier’s law. Note that, for UFP, buoyancy society. However, production methods334 and storage strat-
promotes flame propagation. Also, for SFP, the formation of the egies335 are still under investigation. Hydrogen can be produced
top half of a sphere is sufficient to classify the mixture as from natural gas336 and biomass,337 among others. Other
flammable (see Figure 11), i.e., buoyancy promotes flame important renewable and alternative fuels include ammonia,
propagation at the UFL for SFP. ethanol, methanol, syngas, and biogas. For aerospace
Looking at experiments with SFP, the fuel mixtures for which applications, there is interest in Fischer−Tropsch isoparaffinic
Le Chatelier’s law shows low accuracy in UFLs are the following: kerosene (FT-IPK), hydroprocessed esters and fatty acids
(HEFA), and synthesized isoparaffins from hydroprocessed
• C2H6O−C2H4, C2H6O−NH3, C2H6O−CO, C2H6O− fermented sugars (SIP). The list of experimental works in which
C3H8−C2H4, C2H6O−C3H8−CO, C2H6O−C2H4−CO, FLs were determined can be found in Tables S1 and S2.
C2H4−NH3, C2H4−C3H6, C2H4−CO, and C2H4− However, Table 10 provides a compilation of the pressure and
C3H8−CO temperature ranges for which experimental FLs are available for
On the other hand, Le Chatelier’s law shows low accuracy for these renewable and alternative fuels.
UFLs in the experiments with UFP for the following: As can be seen in Table 10, the experimental FLs of several
• H2−H2S, H2−C2H4, H2−C3H8, H2−NH3, CH4−C2H2, alternative fuels are available for a wide range of temperatures
and CH4−H2S and pressures. For example, the FLs of hydrogen have been
determined for temperatures between 143 and 673 K and for
As shown in Table 9, some oxygenated fuels such as dimethyl
pressures between 10.1 and 450.3 kPa. On the other hand, there
ether have manifested cool flames near the UFL. Since cool
are fuels for which there is not as much data, such as alternative
flames are characterized by low temperature reactions, Le
aviation fuels and fuel blends. The experimental determination
Chatelier’s law is not expected to give accurate results for
of FLs of liquid fuels is associated with the difficulty of
mixtures containing a fuel with a tendency to develop cool
vaporizing them before testing. Therefore, most of the available
experimental data on alternative aviation fuels are related to
Table 9. Compounds for Which Cool Flames Have Been temperatures of 373 K or higher. Moreover, no experiments are
Reported near or at the UFL in Air available at pressures above 101 kPa.
As discussed in sections 2 and 8, chemical kinetic mechanisms
compound formula UFL (%)
190
are important to perform theoretical studies on FLs. There are
dimethyl ether C2H6O 26.2 comprehensive chemical kinetic mechanisms for alternative
ethyl formate190 C3H6O2 15.7 fuels such as hydrogen, carbon monoxide, ammonia, methanol,
methyl formate190 C2H4O2 22.7 and ethanol. However, to the authors’ knowledge, the chemical
methyl acetate190 C3H6O2 14.0 kinetic mechanisms for hydrogen sulfide, HEFA, FT-IPK, and
acetaldehyde162,190 C2H4O 57.0, 57.0 SIP need further development. In the case of alternative aviation
methylal190 C3H8O2 18.5 fuels, however, these are modeled by fuel surrogates.338 In
ethyl ether162,190 C4H10O 46.0, 48.0 addition to FLs, detonation limits339 and fast flame limits340 are
ethyl nitrite162 C2H5NO2 >50.0 also important for the application of alternative fuels.
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9.2. Estimation of the FLs of Renewable and

4, 7, 16, 105, 111, 115, 123, 130−132, 134, 135, 147, 165, 166, 215, 217, 221, 291
Alternative Fuels. If the FLs are not available for a renewable
fuel at 298 K and atmospheric pressure, it is possible to apply the
methods described in section 5. In the case of the CAFT
method, the data required for its application are the molecular
weight, the enthalpy of formation, and the number of moles of
carbon, hydrogen, and oxygen in the molecule of the fuel. The
implementation of such a method can be done in any
programming language or even in spreadsheet software.
The effect of temperature on FLs can be estimated using the
methods in section 6.1. The simplest method for estimating FLs
15, 105, 122, 130, 133, 137, 141, 159, 202, 221

at different initial temperatures is to use eq 94 derived from the

ref

16, 95, 123, 126, 181, 182, 184, 217, 254

modified Burgess−Wheeler’s law. As observed experimentally,

105, 115, 131, 147, 182, 184, 221, 291

the FLs vary linearly with temperature. Therefore, an improve-

ment to eq 94 is to allow for a variable slope. In the case of the
LFL, this is achieved by using eq 104. However, for the UFL, the

Tables S1 and S2 cite the experimental works used to construct this table. bSyngas presents different compositions involving at least H2 and CO.
improvement is introduced by using a CAFT approach, as
shown in eq 109. To implement these enhancements, the
167, 174, 175, 226

molecular weight of the fuel, the enthalpy of formation, the heat

82, 176, 178, 216
Table 10. Pressure and Temperature Ranges of the Available Experimental Data for the FLs of Several Alternative Fuels

released during combustion per mole of fuel, and the number of

16, 108, 217

moles of fuel and oxidant (for a volume of 12 L at T0) must be

168, 169

123, 140

167, 226
167, 226

174, 175

known.
The effect of added diluents on FLs can be estimated using the
176

methods in section 7. The simplest approach in this case is to use

eq 123 together with the average correlation factor (kav FL) given
pmax (kPa)

by the correlation in eq 132. The fuel inertization point can also

405.3
101.3
101.3
101.3
101.3
101.3
689.4
101.3

101.3
101.3
101.3
101.3

be calculated using eq 131 and the correlation in eq 132, but with

−

different coefficients. In this case, the data required are the lower
heating value and the flammability limit of the fuel without
upper flammability limit
pmin (kPa)

diluent. Note that this method was developed for N2 and CO2
101.3
101.3
101.3
101.3
101.3

101.3
10.1

20.0

50.7
50.7
20.0
20.0

only. However, it can be extended to other diluents.

−

The LFLs of fuel mixtures can be determined by applying Le

Chatelier’s law. As stated in section 8, Le Chatelier’s law is
Tmax (K)

accurate for determining LFLs, but has inaccuracies when used

673.0
873.0
295.0
673.0
573.0
473.0
523.0
292.0

415.0
385.0
465.0
465.0

to determine UFLs. To the authors’ knowledge, there is no other

−

method for determining the FLs of fuel mixtures.

Furthermore, to the authors’ knowledge, there is no method
Tmin (K)
173.0
278.0
295.0
278.0
291.0
373.0
298.0
292.0

450.0
415.0
425.0
425.0

for estimating FLs as a function of initial pressure. Therefore, the

−

FLs of renewable and alternative fuels must be determined

experimentally at different initial pressures.
9.3. Future Perspective for Research on FLs. In
pmax (kPa)
405.3
250.0
250.0
101.3
911.9
101.3
689.4
101.3

101.3
101.3
101.3
101.3
101.3

anticipation of future applications of renewable and alternative

fuels such as hydrogen and ammonia and given the need to
explore the flammability of fuel mixtures, more experimental
lower flammability limit

data are needed on the FLs of mixtures with three or more fuels.
pmin (kPa)
10.1
50.0
50.0
101.3
101.3
101.3
20.0
101.3

40.0
50.7
50.7
20.0
20.0

Le Chatelier’s law has been shown to be very accurate for

determining LFLs. However, it shows inaccuracies in determin-
ing the UFLs of some fuel mixtures.5 In this case, the influence of
the direction of flame propagation needs to be further
Tmax (K)
723.0
873.0
573.0
673.0
573.0
473.0
523.0
373.0

423.0
385.0
385.0
460.0
470.0

investigated, and new experiments on UFLs should include

sampling of the combustion products to determine their
composition.
Tmin (K)

The one-dimensional simulation approach could be improved

143.0
278.0
293.0
143.0
291.0
373.0
273.0
292.0

373.0
415.0
415.0
415.0
415.0

with two different objectives. One objective would be to make it

more realistic by including more detailed schemes for soot
formation and thermal radiation losses to deepen the under-
hydrogen + ammonia

jet fuel + ethanol

standing of the phenomenon. The other objective would be to

a
alternative fuel

Jet A + HEFA
carbon monoxide

Jet fuel + SIP

hydrogen sulfide

make the one-dimensional simulations more practical for the

aviation fuels

prediction of FLs. In this case, the simulation of fuels

FT-IPK
hydrogen

methanol
ammonia

characterized by more complex molecules could be performed

syngasb

ethanol

SIP

by adopting reduced chemical kinetic mechanisms76 or the

approach known as flamelet generated manifolds.341
a

AJ https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
Methods for estimating FLs of pure fuels have shown great
accuracy in determining LFLs and only good accuracy in
determining UFLs. In the development of new estimation
methods for the determination of UFLs, the critical sooting
equivalence ratio (ψc) could be included as one of the relevant
parameters to obtain new correlations for CAFT or directly for
UFL.
There is evidence that some fuels, such as dimethyl ether,
develop cool flames at the UFL.190 In addition, for some fuels,
UFLs determined with UFP are higher than those determined
with DFP.251 Therefore, experimental studies are needed to
clarify the influence of the direction of flame propagation. These
experiments should include sampling the combustion products
at the UFL to determine whether they are typical products of
normal or cool flames. Note that the results of such experimental
studies could affect the methods used to determine the
fundamental flammability limits, which should depend only on
the fuel concentration and not on the experimental config-
uration or flammability criterion.
As far as the authors are aware, there are no two- or three-
dimensional numerical studies of flame propagation near the
flammability limits. That is, the field of flammability limits has
not benefited from recent advances in computational fluid
dynamics and computational capabilities. Such studies could be
useful to understand the influence of wall quenching on FLs,
which in turn could be useful for developing experimental
devices to determine the FLs. In addition, the two- and three-
dimensional simulations could help clarify the role of buoyancy
in experiments. Reduced chemical kinetic mechanisms or
flamelet generated manifolds could also be used for this type
of study.
From this review article, it is also clear that the effect of initial
pressure on FLs needs to be further investigated, not only to
improve the understanding of the phenomenon, but also
because there is no reliable estimation method that takes into
account the effect of pressure on FLs. In addition, the estimation
methods for FLs of fuels with diluents also need to be improved.
Finally, the theoretical approach developed by Spalding30
could be improved by removing some of the considerations he
made in the 1950s. For example, the dimensionless reaction rate
assumed by Spalding was φ = αθn. Therefore, the adoption of an
Arrhenius form for this reaction rate would improve the current
results. In addition, the heat loss term was not explicitly given by
Spalding. It could be written using Planck’s mean absorption
coefficients for optically thin conditions. Then the relationship
between the thermal radiation and the critical value of the heat
loss term could be determined. It is clear that this approach
complicates the search for an analytical solution to the problem.
In case this problem cannot be solved by purely analytical
methods, a mixed approach of analytical and numerical methods
could be an alternative.
10. CONCLUSIONS
The fundamental flammability limits of a planar and unstretched
flame have been distinguished from the extinction limits of a
stretched flame and from measured empirical flammability
limits. Although theoretical studies have shown that the
fundamental flammability limits are determined solely by fuel
chemistry, temperature, pressure, and thermal radiation, the
extinction limits of a flame can be affected by flame geometry,
flame length, and the Lewis number of the mixture. Despite
these differences, the empirically determined flammability limits
of single-component fuels and fuel mixtures are still being
pubs.acs.org/EF Review
measured at various oxygen dilutions and concentrations
because they are important for the safe operation of industrial
applications.
The mechanism of flammability has been studied theoretically
and computationally by asymptotic and numerical methods,
respectively, with detailed and one-step chemical kinetics and
optically thin and thick radiation models in various flame
geometries. These studies have shown that the fundamental
flammability limits are determined by the heat loss of thermal
radiation in the suppression of chain-branching reactions. It has
also been shown that, for a stretched flame, the flammable region
is bounded by a stretch extinction limit and a radiation
extinction limit and may lie outside the region bounded by the
fundamental flammability limits.
There is a critical Lewis number below and above which the
burning limits of a stretched flame and the fundamental
flammability limit can generally be described by a G-curve and
a K-curve, respectively. These curves determine whether the
extinction limits of a stretched flame can be directly extrapolated
to the fundamental flammability limit at zero stretch. At a very
low Lewis number, a flame ball consisting only of diffusion and
thermal radiation can exist well below the fundamental
flammability limit.
Experimental determination of flammability limits is detailed
by several standards, namely DIN 51649-1, EN 1839(T), EN
1839(B), ASHRAE, ASTM E681-01, and others. The most
commonly used test configurations are the vertical tube and
spherical vessel, which have been used for more than a century.
It should be noted that flammability limits depend on the
volume of the vessel up to a critical volume value. For spherical
vessels, for example, there is a slight variation in experimental
flammability limits for volumes of 12 L or more.
Other factors such as the direction of flame propagation also
affect the experimental values of flammability limits. The effect
of buoyancy is evident when upper flammability limits (UFLs)
are determined, especially for upward flame propagation (UFP)
inside tubes. For lower flammability limits (LFLs), there is not
much difference between experimental values determined with
UFP and downward flame propagation (DFP). Experiments
under microgravity conditions have shown that buoyancy can
significantly affect the limits. The UFLs determined under
microgravity conditions are usually somewhere between the
values determined with DFP and UFP.
The methods developed to determine the flammability limits
under reference conditions are generally classified as group
contribution methods and calculated adiabatic flame temper-
ature (CAFT) methods. The latter are most commonly used
because they relate the fundamental theory of equilibrium
combustion to the flammability limits. These methods show
high accuracy in determining the LFL and good accuracy in
determining the UFL. Temperature dependence can also be
estimated using the available methods. However, there is no
available method that accounts for the pressure dependence of
the flammability limits. The effect of diluents such as N2 and
CO2, including the fuel inertization point, can be estimated
using published methods. Nevertheless, the impact of other
diluents such as water vapor or helium need further study.
Experimental flammability limits of several renewable and
alternative fuels are available at various initial temperatures and
pressures. The flammability limits of hydrogen have been
determined experimentally over a wide range of initial
temperatures and pressures. However, the available database
for other renewable fuels is still under development. Alternative
AK https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
aviation fuels are an example of a database under development.
In addition, flammability limits of fuel mixtures may not be
available. In such cases, Le Chatelier’s law may be used.
Although this law is very accurate in determining the LFLs, it is
less accurate in determining the UFLs of fuel mixtures. Available
methods based on the CAFT can also be used to estimate the
flammability limits of renewable and alternative fuels.
In light of the issues discussed in this review, the authors argue
that future studies of flammability limits could incorporate more
realistic Arrhenius-type reactions and radiative heat losses to
promote theoretical developments. To improve the one-
dimensional simulations, it is also suggested that more detailed
mechanisms for soot formation be included. Experimental
determination of flammability limits should include the
determination of product composition and verification of the
UFLs of some fuel mixtures with respect to the inaccuracies of
Le Chatelier’s law in the UFLs. In addition, two- and three-
dimensional simulations could be helpful in understanding the
effects of wall quenching and buoyancy.
Regarding estimation methods, one-dimensional simulations
need to be made more practical to determine the flammability
limits of more complex fuels. This can be accomplished by using
techniques to simplify chemical kinetic mechanisms. Note that
improvement in methods for determining UFLs could be
achieved by including the critical sooting equivalence ratio in the
correlations. In addition, methods for determining flammability
limits at different initial pressures need to be developed and
methods for estimating flammability limits of dilute fuels need to
be improved.
■ ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.energyfuels.2c03598.
List of experimental works for different geometries;
coefficients and information on the use of the main
correlations listed in the review article; compilation of
experimental results for fuel mixtures; flammability limits
with oxygen and cool flame chemistry (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Andrés Z. Mendiburu − Department of Mechanical
Engineering, Federal University of Rio Grande do Sul
(UFRGS), Porto Alegre, Rio Grande do Sul 90050-170,
Brazil; International Research Group for Energy Sustainability
(IRGES), Porto Alegre, Rio Grande do Sul 90050-170,
Brazil; orcid.org/0000-0003-4733-625X;
Email: andresmendiburu@ufrgs.br
Authors
João A. Carvalho Jr. − Department of Chemistry and Energy,
São Paulo State University (UNESP), Guaratinguetá, São
Paulo 12510-410, Brazil; International Research Group for
Energy Sustainability (IRGES), Porto Alegre, Rio Grande do
Sul 90050-170, Brazil
Yiguang Ju − Department of Mechanical and Aerospace
Engineering, Princeton University, Princeton, New Jersey
08544, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.2c03598
pubs.acs.org/EF Review
Notes
The authors declare no competing financial interest.
Biographies
Andrés Z. Mendiburu is a professor at the Federal University of Rio
Grande do Sul (UFRGS), Brazil. He earned his bachelor’s degree in
energy engineering from Santa University (Peru) in 2008 and his Ph.D.
in mechanical engineering from São Paulo State University (Brazil) in
2016. He is interested in deflagrations, detonations, DDT, and
alternative fuels. Andrés coordinates the International Research
Group for Energy Sustainability (IRGES). He is a coauthor of the
book Applied Combustion (in Portuguese).
João A. de Carvalho, Jr., is a professor at the Department of Chemistry
and Energy of São Paulo State University (UNESP). He coordinated
(supervised) several research projects, master’s dissertations, and
doctoral theses. He received his Ph.D. in aerospace engineering from
Georgia Institute of Technology in 1983. João was head of the
Combustion and Propulsion Associate Laboratory of the Brazilian
Space Research Institute (INPE) for 8 years. He is a coauthor of the
book Applied Combustion (in Portuguese).
Yiguang Ju is the Robert Porter Patterson Professor at Princeton
University. He received his bachelor’s degree in engineering
thermophysics from Tsinghua University in 1986 and his Ph.D. degree
in mechanical and aerospace engineering from Tohoku University
(Japan) in 1994. He is an associate editor for AIAA Journal, Proceedings
of the Combustion Institute, and Combustion Science and Technology. He
received the Bessel Research Award from the von Humboldt
Foundation and the 2021 AIAA Propellants and Combustion Award.
■ ACKNOWLEDGMENTS
The authors are grateful to CNPq (Conselho Nacional de
Desenvolvimento Científico e Tecnológico) for supporting this
work through Projects 423369/2018-0 and 308915/2022-4, and
to FAPERGS (Fundação de Amparo à Pesquisa do Estado de
Rio Grande do Sul) for supporting this work through Project
21/2551-0000677-3. The authors would also like to thank the
grant support from DOE BES award DE-SC0021135 and the
ExxonMobil fuel research grant.
■ NOMENCLATURE
a = stretch rate, s−1
e = Euler’s number
Ea = activation energy, kJ/kmol
cp = heat capacity at constant pressure, kJ/kg·K
T = temperature, K
d = characteristic length, m
D = ordinary diffusion coefficient, m2/s
G = combined function of stretch rate and the stream function
h0f,i = enthalpy of formation of the species i, kJ/kg
h̅0f,i = enthalpy of formation of the species i, kJ/mol
h̅i = absolute enthalpy of species i, kJ/mol
Δh̅i = sensible enthalpy of species i, kJ/mol
hC,i = heat released at the combustion process of i, kJ/mol
HC = heat released at the complete combustion of 1 mol of
fuel, kJ
k = thermal conductivity coefficient, W/m·K
KP = Planck’s mean absorption coefficient for species i
l = normalized Lewis number deviation from unity
L = heat losses, kJ/m3
L̅ = mean value of the heat loss, kJ/m3
ṁ S = mass flux rate, kg/m2·s
nF = number of moles of fuel, mol
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Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels pubs.acs.org/EF Review

n*F = number of moles of gaseous fuel which occupies 12 L at HEFA50 = hydroprocessed esters and fatty acids
T0, mole Jet A = Jet A fuel
nox = number of moles of oxidant, mol LFL = lower flammability limit
p = pressure, Pa UFL = upper flammability limit
pi = partial pressure of ith species in a gas mixture, Pa UFP = upward flame propagation
ΔhC = heat of combustion, kJ/kg fuel HFP = horizontal flame propagation
R2 = squared correlation coefficient SIP = synthesized isoparaffins from hydroprocessed fer-
R = radial coordinate, m mented sugars
SL = laminar flame speed, m/s
T∞ = ambient temperature, K
Tb = adiabatic flame temperature, K
■ REFERENCES
(1) Ju, Y.; Guo, H.; Maruta, K.; Liu, F. On the Extinction Limit and
Tf = flame temperature, K Flammability Limit of Non-Adiabatic Stretched Methane−Air
tchem = time scale for chemical reaction, s Premixed Flames. J. Fluid Mech. 1997, 342, 315−334.
tinv = time scale for inviscid buoyant convection, s (2) Ju, Y.; Maruta, K.; Niioka, T. Combustion Limits. Appl. Mech. Rev.
tvis = time scale for viscous buoyant convection, s 2001, 54 (3), 257−277.
tcond = time scale for conduction heat loss to the walls, s (3) Van den Schoor, F.; Verplaetsen, F. The Upper Flammability
trad = time scale for radiation heat loss, s Limit of Methane/Hydrogen/Air Mixtures at Elevated Pressures and
u = axial component of velocity, m/s Temperatures. Int. J. Hydrogen Energy 2007, 32 (13), 2548−2552.
U = axial mass flow rate, kg/s (4) Miao, H.; Lu, L.; Huang, Z. Flammability Limits of Hydrogen-
vair = number of moles of oxygen in the oxidant, mol Enriched Natural Gas. Int. J. Hydrogen Energy 2011, 36 (11), 6937−
6947.
vsair = number of moles of oxygen in oxidant for stoichiometric (5) Mendiburu, A. Z.; Coronado, C. R.; de Carvalho, J. A. Difficulties
reaction, mol on the Determination of the Flammability Limits of Fuel Mixtures by
* = number of moles of oxygen in excess, mol
vair the Law of Le Chatelier. Process Saf. Environ. Prot. 2020, 142, 45−55.
v = radial component of velocity, m/s (6) Ju, Y.; Reuter, C. B.; Yehia, O. R.; Farouk, T. I.; Won, S. H.
Vix = diffusion velocity of species i in the x-direction Dynamics of Cool Flames. Prog. Energy Combust. Sci. 2019, 75, 100787.
Wi = molecular weight of species i, kg/kmol (7) Wierzba, I.; Ale, B. B. Rich Flammability Limits of Fuel Mixtures
w = net rate of reaction, kmol/m3·s Involving Hydrogen at Elevated Temperatures. Int. J. Hydrogen Energy
x = axial coordinate 2000, 25 (1), 75−80.
xC = number of moles of carbon (C) in fuel, mol (8) Pfahl, U. J.; Ross, M. C.; Shepherd, J. E.; Pasamehmetoglu, K. O.;
xH = number of moles of hydrogen (H) in fuel, mol Unal, C. Flammability Limits, Ignition Energy, and Flame Speeds in
H2-CH4-NH3- N2O-O2-N2Mixtures. Combust. Flame 2000, 123 (1−
xO = number of moles of oxygen (O) in fuel, mol 2), 140−158.
yi = mole fraction of species i (9) Rehbein, M. C.; Meier, C.; Eilts, P.; Scholl, S. Mixtures of
Yi = mass fraction of species i Ammonia and Organic Solvents as Alternative Fuel for Internal
Greek Symbols Combustion Engines. Energy Fuels 2019, 33 (10), 10331−10342.
γ = specific heat ratio (10) Siddiqui, O.; Dincer, I. Design and Optimization of a Dual
σb = Stefan−Boltzmann constant (5.670367 × 10−8 W·m−2· Renewable Energy-Based Plant Utilizing Integrated Hydrogen to
Ammonia and Fuel Cell Systems. Energy Fuels 2021, 35 (1), 670−689.
K−4) (11) Valera-Medina, A.; Amer-Hatem, F.; Azad, A. K.; Dedoussi, I. C.;
α(ϕ) = flammability limit exponent De Joannon, M.; Fernandes, R. X.; Glarborg, P.; Hashemi, H.; He, X.;
αt = thermal diffusivity, m2 Mashruk, S.; et al. Review on Ammonia as a Potential Fuel: From
ϕ = equivalence ratio Synthesis to Economics. Energy Fuels 2021, 35 (9), 6964−7029.
φ = dimensionless reaction rate (12) Liu, Z.; Lian, T.; Li, W.; Cao, C.; Xiong, H.; Li, Y. Mini Review of
ρ = density, kg/m3 Current Combustion Research Progress of Biodiesel and Model
δ = flame thickness, m Compounds for Gas Turbine Application. Energy Fuels 2021, 35 (17),
ω̇ i = rate of production of species i, kmol/m3·s 13569−13584.
3 (13) Al Qubeissi, M.; Sazhin, S. S.; Al-Esawi, N.; Kolodnytska, R.;
f = mean value of fuel’s rate of destruction, kmol/m ·s
Khanal, B.; Ghaleeh, M.; Elwardany, A. Heating and Evaporation of
ψc = critical sooting equivalence ratio Droplets of Multicomponent and Blended Fuels: A Review of Recent
χ = dimensionless heat losses Modeling Approaches. Energy Fuels 2021, 35 (22), 18220−18256.
Subscripts (14) Mendiburu, A. Z.; Lauermann, C. H.; Hayashi, T. C.; Mariños, D.
ad = adiabatic J.; Rodrigues da Costa, R. B.; Coronado, C. J. R.; Roberts, J. J.; de
B = chain-branching reaction Carvalho, J. A. Ethanol as a Renewable Biofuel: Combustion
Characteristics and Application in Engines. Energy 2022, 257,
b = burned
No. 124688.
f = fuel (15) Wierzba, I.; Kilchyk, V. Flammability Limits of Hydrogen-
T = chain-termination reaction Carbon Monoxide Mixtures at Moderately Elevated Temperatures. Int.
u = unburned J. Hydrogen Energy 2001, 26 (6), 639−643.
eff = effective (16) Ciccarelli, G.; Jackson, D.; Verreault, J. Flammability Limits of
Abbreviations NH3-H2-N2-Air Mixtures at Elevated Initial Temperatures. Combust.
Flame 2006, 144 (1−2), 53−63.
ARE = absolute value of relative error, % (17) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.;
AARE = average of relative error, % Mizukado, J.; Sekiya, A. Flammability Limits of Olefinic and Saturated
CAFT = calculated adiabatic flame temperature Fluoro-Compounds. J. Hazard. Mater. 2009, 171 (1−3), 613−618.
DFP = downward flame propagation (18) Li, Z.; Gong, M.; Wu, J.; Zhou, Y. Flammability Limits of
FL = flammability limits Refrigerant Mixtures with 1,1,2,2-Tetrafluoroethane. Exp. Therm. Fluid
FT-IPK = Fischer−Tropsch isoparaffinic kerosene Sci. 2011, 35 (6), 1209−1213.

AM https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
(19) National Transportation Safety Board. In-Flight Breakup Over the
Atlantic Ocean Trans World Airlines Flight 800 Boeing 747-131, N93119
Near East Moriches, New York July 17, 1996. Defense Technical
Information Center, August 23, 2000. https://apps.dtic.mil/sti/
citations/ADA388166.
(20) Westbrook, C.; Heufer, K. A.; Wildenberg, A. Key Chemical
Kinetic Steps in Reaction Mechanisms for Fuels from Biomass: A
Perspective. Energy Fuels 2021, 35 (19), 15339−15359.
(21) Coronado, C.; Carvalho, J. A.; Andrade, J. C.; Cortez, E. V.;
Carvalho, F. S.; Santos, J. C.; Mendiburu, A. Z. Flammability Limits: A
Review with Emphasis on Ethanol for Aeronautical Applications and
Description of the Experimental Procedure. J. Hazard. Mater. 2012,
241−242, 32−54.
(22) Qi, C.; Yan, X.; Wang, Y.; Ning, Y.; Yu, X.; Hou, Y.; Lv, X.; Ding,
J.; Shi, E.; Yu, J. Flammability Limits of Combustible Gases at Elevated
Temperatures and Pressures: Recent Advances and Future Perspec-
tives. Energy Fuels 2022, 36 (21), 12896−12916.
(23) Lovachev, L. A.; Babkin, V. S.; Bunev, V. A.; V’Yun, A. V.;
Krivulin, V. N.; Baratov, A. N. Flammability Limits: An Invited Review.
Combust. Flame 1973, 20 (2), 259−289.
(24) Zabetakis, M. G. Flammability Characteristics of Combustible
Gases and Vapors; BM-BULL-627; Bureau of Mines, U.S. Department
of the Interior: 1965; 121 pp. DOI: 10.2172/7328370.
(25) Kuo, K. K. Principles of Combustion, 2nd ed.; John Wiley & Sons,
Inc.: 2005; 732 pp.
(26) Turns, S. R. An Introduction To Combustion: Concepts and
Applications, 3rd ed.; McGraw Hill: New York, 2011; 752 pp.
(27) Glassman, I.; Yetter, R. A.; Glumac, N. G. Combustion, 5th ed.;
Elsevier: New York, 2015; 757 pp.
(28) Date, A. W. Analytic Combustion, 2nd ed.; Springer Nature
Singapore: Singapore, 2020; 405 pp. DOI: 10.1007/978-981-15-1853-
9.
(29) Qiao, L.; Gan, Y.; Nishiie, T.; Dahm, W. J. A.; Oran, E. S.
Extinction of Premixed Methane/Air Flames in Microgravity by
Diluents: Effects of Radiation and Lewis Number. Combust. Flame
2010, 157 (8), 1446−1455.
(30) Spalding, D. B. A Theory of Inflammability Limits and Flame-
Quenching. Proc. R. Soc. London. Ser. A. Math. Phys. Sci. 1957, 240, 83−
100.
(31) Bergman, T. L.; Lavine, A. S. Fundamentals of Heat and Mass
Transfer, 8th ed.; Wiley: 2017; 1046 pp.
(32) Mendiburu, A. Z.; de Carvalho, J. A.; Coronado, C. R. Estimation
of Lower Flammability Limits of C-H Compounds in Air at
Atmospheric Pressure, Evaluation of Temperature Dependence and
Diluent Effect. J. Hazard. Mater. 2015, 285, 409−418.
(33) Mendiburu, A. Z.; de Carvalho, J. A.; Coronado, C. R.;
Chumpitaz, G. A. Determination of Lower Flammability Limits of C−
H−O Compounds in Air and Study of Initial Temperature Depend-
ence. Chem. Eng. Sci. 2016, 144, 188−200.
(34) Mendiburu, A. Z.; de Carvalho, J. A.; Coronado, C. R. Estimation
of Upper Flammability Limits of C-H Compounds in Air at Standard
Atmospheric Pressure and Evaluation of Temperature Dependence. J.
Hazard. Mater. 2016, 304, 512−521.
(35) Mendiburu, A. Z.; de Carvalho, J. A.; Coronado, C. R.
Determination of Upper Flammability Limits of C-H-O Compounds
in Air at Reference Temperature and Atmospheric Pressure. Fuel 2017,
188, 212−222.
(36) Williams, F. Combustion Theory: The Fundamental Theory of
Chemically Reacting Flow Systems, 2nd ed.; The Benjamin/Cummings
Publishing Co., Inc.: 1985; 665 pp.
(37) Hertzberg, M. The Theory of Flammability Limits: Natural
Convection; Bureau of Mines, U.S. Department of the Interior:
Washington, DC, 1976; 19 pp.
(38) Hertzberg, M. The Theory of Flammability Limits: Conductive-
Convective Wall Losses and Thermal Quenching; Bureau of Mines, U.S.
Department of the Interior: Washington, DC, 1980; 31 pp.
(39) Hertzberg, M. The Theory of Flammability Limits: Radiative Losses
and Selective Diffusional Demixing; Bureau of Mines, U.S. Department of
the Interior: Washington, DC, 1982; 42 pp.
pubs.acs.org/EF Review
(40) Hertzberg, M. The Theory of Flammability Limits: Flow Gradient
Effects and Flame Stretch; Bureau of Mines, U.S. Department of the
Interior: Washington, DC, 1984; 41 pp.
(41) Joulin, G.; Clavin, P. Analyse Asymptotique Des Conditions
d’extinction Des Flammes Laminaires. Acta Astronaut. 1976, 3 (3−4),
223−240.
(42) Buckmaster, J. The Quenching of Deflagration Waves. Combust.
Flame 1976, 26 (C), 151−162.
(43) Mitani, T. Asymptotic Theory for Extinction of Curved Flames
with Heat Loss. Combust. Sci. Technol. 1980, 23 (3−4), 93−101.
(44) Ronney, P. D. Understanding Combustion Processes through
Microgravity Research. Symp. Combust. 1998, 27 (2), 2485−2506.
(45) T’ien, J. S. Diffusion Flame Extinction at Small Stretch Rates:
The Mechanism of Radiative Loss. Combust. Flame 1986, 65 (1), 31−
34.
(46) Chao, B. H.; Law, C. K.; T’ien, J. S. Structure and Extinction of
Diffusion Flames with Flame Radiation. Symp. Combust. 1991, 23 (1),
523−531.
(47) Maruta, K.; Yoshida, M.; Guo, H.; Ju, Y.; Niioka, T. Extinction of
Low-Stretched Diffusion Flame in Microgravity. Combust. Flame 1998,
112 (1−2), 181−187.
(48) Ju, Y.; Masuya, G.; Liu, F.; Hattori, Y.; Riechelmann, D.
Asymptotic Analysis of Radiation Extinction of Stretched Premixed
Flames. Int. J. Heat Mass Transfer 2000, 43 (2), 231−239.
(49) Buckmaster, J. The Effects of Radiation on Stretched Flames.
Combust. Theory Model. 1997, 1, 1−11.
(50) Ju, Y.; Minaev, S. Dynamics and Flammability Limit of Stretched
Premixed Flames Stabilized by a Hot Wall. Proc. Combust. Inst. 2002, 29
(1), 949−956.
(51) Law, C. K.; Egolfopoulos, F. N. A Kinetic Criterion of
Flammability Limits: The C-H-O-Inert System. Symp. Combust.
1991, 23 (1), 413−421.
(52) Wang, T.; Liang, H.; Luo, Z.; Su, B.; Liu, L.; Su, Y.; Wang, X.;
Cheng, F.; Deng, J. Near Flammability Limits Behavior of Methane-Air
Mixtures with Influence of Flammable Gases and Nitrogen: An
Experimental and Numerical Research. Fuel 2021, 294, 120550.
(53) Liang, W.; Law, C. K. Extended Flammability Limits of N-
Heptane/Air Mixtures with Cool Flames. Combust. Flame 2017, 185,
75−81.
(54) Law, C. K.; Egolfopoulos, F. N. A Unified Chain-Thermal
Theory of Fundamental Flammability Limits. Symp. Combust. 1992, 24
(1), 137−144.
(55) Kee, R. J.; Grcar, J. F.; Smooke, M. D.; Miller, J. A.; Meeks, E.
PREMIX: A FORTRAN Program for Modeling Steady, Laminar, One-
Dimensional Premixed Flames; Reaction Design: San Diego, CA, 1998.
(56) Ju, Y.; Masuya, G.; Ronney, P. D. Effects of Radiative Emission
and Absorption on the Propagation and Extinction of Premixed Gas
Flames. Symp. (Int.) Combust. 1998, 27 (2), 2619−2626.
(57) Ju, Y.; Guo, H.; Liu, F.; Maruta, K. Effects of the Lewis Number
and Radiative Heat Loss on the Bifurcation and Extinction of CH4/O2-
N2-He Flames. J. Fluid Mech. 1999, 379, 165−190.
(58) Ju, Y.; Guo, H.; Maruta, K.; Niioka, T. Determination of Burning
Velocity and Flammability Limit of Methane/Air Mixture Counterflow
Flames Using Determination of Burning Velocity and Flammability
Limit of Methane/Air Mixture Using Counterflow Flames. Jpn. J. Appl.
Phys. 1999, 38 (2), 961−967.
(59) Ronney, P. D.; Wachman, H. Y. Effect of Gravity on Laminar
Premixed Gas Combustion I: Flammability Limits and Burning
Velocities. Combust. Flame 1985, 62 (2), 107−119.
(60) Guo, H.; Ju, Y.; Maruta, K.; Niioka, T.; Liu, F. Radiation
Extinction Limit of Counterflow Premixed Lean Methane-Air Flames.
Combust. Flame 1997, 109 (4), 639−646.
(61) Guo, H.; Ju, Y.; Niioka, T. Effects of Radiative Heat Loss on the
Extinction of Counterflow Premixed H2-Air Flames. Combust. Theory
Model. 2000, 4 (4), 459−475.
(62) Guo, H.; Smallwood, G. J.; Liu, F.; Ju, Y.; Gülder, Ö . L. The Effect
of Hydrogen Addition on Flammability Limit and NOx Emission in
Ultra-Lean Counterflow CH4/Air Premixed Flames. Proc. Combust.
Inst. 2005, 30 (1), 303−311.
AN https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels pubs.acs.org/EF
(63) Maruta, K.; Ju, Y.; Honda, A.; Niioka, T. Lewis Number Effect on
Extinction Characteristics of Radiative Counterflow CH4−O2−N2−
He Flames. Twenty-Seventh Symp. Combust. 1998, 27 (2), 2611−2617.
(64) Bertolino, A.; Stagni, A.; Cuoci, A.; Faravelli, T.; Parente, A.;
Frassoldati, A. Prediction of Flammable Range for Pure Fuels and
Mixtures Using Detailed Kinetics. Combust. Flame 2019, 207, 120−133.
(65) Mascarenhas, V. J.; Weber, C. N.; Westmoreland, P. R.
Estimating Flammability Limits through Predicting Non-Adiabatic
Laminar Flame Properties. Proc. Combust. Inst. 2021, 38 (3), 4673−
4681.
(66) Simmie, J. M. Detailed Chemical Kinetic Models for the
Combustion of Hydrocarbon Fuels. Prog. Energy Combust. Sci. 2003, 29
(6), 599−634.
(67) The San Diego Mechanism. University of California at San Diego.
https://web.eng.ucsd.edu/mae/groups/combustion/mechanism.html
(accessed 2022-12-16).
(68) Metcalfe, W. K.; Burke, S. M.; Ahmed, S. S.; Curran, H. J. A
Hierarchical and Comparative Kinetic Modeling Study of C1 - C2
Hydrocarbon and Oxygenated Fuels. Int. J. Chem. Kinet. 2013, 45 (10),
638−675.
(69) Rarata, G.; Szymczyk, J.; Wolanski, P. Experiments on the Upper
Explosion Limits of Gaseous Alkanes-Oxygen Mixtures at Elevated
Conditions of T and P in a Spherical Vessel. Trans. Inst. Aviat. 2009,
No. 200, 160−167.
(70) Sarathy, S. M.; Oßwald, P.; Hansen, N.; Kohse-Höinghaus, K.
Alcohol Combustion Chemistry. Prog. Energy Combust. Sci. 2014, 44,
40−102.
(71) Sánchez, A. L.; Williams, F. A. Recent Advances in Under-
standing of Flammability Characteristics of Hydrogen. Prog. Energy
Combust. Sci. 2014, 41, 1−55.
(72) Konnov, A. A. Yet Another Kinetic Mechanism for Hydrogen
Combustion. Combust. Flame 2019, 203, 14−22.
(73) Fernández-Galisteo, D.; Sánchez, A. L.; Liñán, A.; Williams, F. A.
One-Step Reduced Kinetics for Lean Hydrogen-Air Deflagration.
Combust. Flame 2009, 156 (5), 985−996.
(74) Annual World Fuel Ethanol Production. Renewable Fuels
Association. https://ethanolrfa.org/markets-and-statistics/annual-
ethanol-production (accessed 2023-01-26).
(75) Marinov, N. A Detailed Chemical Kinetic Model for High
Temperature Ethanol Oxidation. Int. J. Chem. Kinet. 1999, 31 (3), 183−
220.
(76) Millán-Merino, A.; Fernández-Tarrazo, E.; Sánchez-Sanz, M.;
Williams, F. A. A Multipurpose Reduced Mechanism for Ethanol
Combustion. Combust. Flame 2018, 193, 112−122.
(77) Brown, N. J.; Bastien, L. A. J.; Price, P. N. Transport Properties
for Combustion Modeling. Prog. Energy Combust. Sci. 2011, 37 (5),
565−582.
(78) Westbrook, C. K.; Dryer, F. L. Simplified Reaction Mechanisms
for the Oxidation of Hydrocarbon Fuels in Flames. Combust. Sci.
Technol. 1981, 27 (1−2), 31−43.
(79) Westbrook, C. K.; Dryer, F. L. Chemical Kinetic Modeling of
Hydrocarbon Combustion. Prog. Energy Combust. Sci. 1984, 10 (1), 1−
57.
(80) Chen, Z.; Qin, X.; Xu, B.; Ju, Y.; Liu, F. Studies of Radiation
Absorption on Flame Speed and Flammability Limit of CO2 Diluted
Methane Flames at Elevated Pressures. Proc. Combust. Inst. 2007, 31
(2), 2693−2700.
(81) American Society for Testing and Materials. ASTM E681-09.
Standard Test Method for Concentration Limits of Flammability of
Chemicals (Vapors and Gases); ASTM: 2015. DOI: 10.1520/E0681-
09R15.
(82) Coronado, C. J. R.; Carvalho, J. A.; Andrade, J. C.; Mendiburu, A.
Z.; Cortez, E. V.; Carvalho, F. S.; Gonçalves, B.; Quintero, J. C.;
Velásquez, E. I. G.; Silva, M. H.; et al. Flammability Limits of Hydrated
and Anhydrous Ethanol at Reduced Pressures in Aeronautical
Applications. J. Hazard. Mater. 2014, 280, 174−184.
(83) Mendiburu, A. Study of the Flammability Limits of Hydrocarbons
and Alcohols in Fuel-Air and Fuel-Diluent-Air Mixtures (in Portuguese).
AO
Review
Ph.D. Thesis, Sao Paulo State University, 2016; 272 pp. https://
repositorio.unesp.br/handle/11449/141531.
(84) EN 1839:2017 Determination of the Explosion Limits and the
Limiting Oxygen Concentration (LOC) for Flammable Gases and
Vapours; European Union: 2017.
(85) Schröder, V.; Molnarne, M. Flammability of Gas Mixtures: Part
1: Fire Potential. J. Hazard. Mater. 2005, 121 (1−3), 37−44.
(86) Macek, A. Flammability Limits: A Re-Examination. Combust. Sci.
Technol. 1979, 21 (1−2), 43−52.
(87) Design Institute for Physical Properties. DIPPR Project 801
Database. https://www.aiche.org/dippr (accessed 2023-01-26).
(88) NOAA. Cameo Chemicals. https://cameochemicals.noaa.gov/
search/simple (accessed 2023-01-26).
(89) NCBI. PubChem Compound Database. https://www.ncbi.nlm.
nih.gov/pccompound (accessed 2023-01-26).
(90) ChemicalBook. Chemical Book. http://www.chemicalbook.com
(accessed 2023-01-26).
(91) CRC Handbook of Chemistry and Physics, 97th ed.; Haynes, W.
M., Lide, D. R., Bruno, T. J., Eds.; CRC Press: Boca Raton, FL, 2016;
2641 pp. DOI: 10.1201/9781315380476.
(92) Hazardous Chemicals Handbook, 2nd ed.; Carson, P., Mumford,
C., Eds.; Butterworth Heinemann: London, 2002; 608 pp.
(93) The John Zink Combustion Hand Book; Baukal, C. E. J., Ed.; CRC
Press: 2001; 730 pp.
(94) Bretherick’s Handbook of Reactive Chemical Hazards, 7th ed.;
Urben, P. G., Ed.; Elsevier: 2007; 2682 pp.
(95) Kondo, S.; Takizawa, K.; Tokuhashi, K. Flammability Limits of
Binary Mixtures of Ammonia with HFO-1234yf, HFO-1234ze, HFC-
134a, and HFC-125. J. Fluor. Chem. 2013, 149, 18−23.
(96) Britton, L. G. Two Hundred Years of Flammable Limits. Process
Saf. Prog. 2002, 21 (1), 1−11.
(97) Zhao, F. Inert Gas Dilution Effect on Flammability Limits of
Hydrocarbon Mixtures. Ph.D. Dissertation, Texas A&M University,
2011.
(98) Zhao, F.; Rogers, W. J.; Mannan, M. S. Calculated Flame
Temperature (CFT) Modeling of Fuel Mixture Lower Flammability
Limits. J. Hazard. Mater. 2010, 174 (1−3), 416−423.
(99) Zhao, F.; Rogers, W. J.; Sam Mannan, M. Experimental
Measurement and Numerical Analysis of Binary Hydrocarbon Mixture
Flammability Limits. Process Saf. Environ. Prot. 2009, 87 (2), 94−104.
(100) Zhao, F. Experimental Measurements and Modeling Prediction of
Flammability Limits of Binary Hydrocarbon Mixtures. M.S. Thesis, Texas
A&M University, 2008; 108 pp.
(101) Jones, G. W.; Beattie, B. B. Explosive Properties of Divinyl
Ether. Ind. Eng. Chem. 1934, 26 (5), 557−560.
(102) Jones, G. W.; Miller, W. E.; Seaman, H. Explosive Properties of
Methyl Formate-Air Mixtures. Ind. Eng. Chem. 1933, 25 (6), 694−696.
(103) Hu, X.; Yu, Q.; Sun, N.; Qin, Q. Experimental Study of
Flammability Limits of Oxy-Methane Mixture and Calculation Based
on Thermal Theory. Int. J. Hydrogen Energy 2014, 39 (17), 9527−9533.
(104) Hu, X.; Yu, Q.; Sun, N.; Liu, J. Effects of High Concentrations of
CO2 on the Lower Flammability Limits of Oxy-Methane Mixtures.
Energy Fuels 2016, 30 (5), 4346−4352.
(105) Shang, R.; Li, G.; Wang, Z.; Wang, Z. Lower Flammability Limit
of H2/CO/Air Mixtures with N2 and CO2 Dilution at Elevated
Temperatures. Int. J. Hydrogen Energy 2020, 45 (16), 10164−10175.
(106) Huang, L.; Wang, Y.; Pei, S.; Cui, G.; Zhang, L.; Ren, S.; Zhang,
Z.; Wang, N. Effect of Elevated Pressure on the Explosion and
Flammability Limits of Methane-Air Mixtures. Energy 2019, 186,
115840.
(107) Cui, G.; Yang, C.; Li, Z.; Zhou, Z.; Li, J. Experimental Study and
Theoretical Calculation of Flammability Limits of Methane/Air
Mixture at Elevated Temperatures and Pressures. J. Loss Prev. Process
Ind. 2016, 41, 252−258.
(108) Lesmana, H.; Zhu, M.; Zhang, Z.; Gao, J.; Wu, J.; Zhang, D.
Experimental and Kinetic Modelling Studies of Flammability Limits of
Partially Dissociated NH3 and Air Mixtures. Proc. Combust. Inst. 2021,
38 (2), 2023−2030.
https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
(109) Liu, X.; Zhang, Q. Influence of Initial Pressure and Temperature
on Flammability Limits of Hydrogen-Air. Int. J. Hydrogen Energy 2014,
39 (12), 6774−6782.
(110) Hu, X.; Xie, Q.; Yu, Q.; Liu, H.; Yan, F. Effect of Carbon Dioxide
on the Lower Flammability Limit of Propane in O2/CO2 atm. Energy
Fuels 2020, 34 (4), 4993−4998.
(111) Hu, X.; Xie, Q.; Zhang, J.; Yu, Q.; Liu, H.; Sun, Y. Experimental
Study of the Lower Flammability Limits of H2/O2/CO2Mixture. Int. J.
Hydrogen Energy 2020, 45 (51), 27837−27845.
(112) Wu, X.; Yang, Z.; Wang, X.; Lin, Y. Experimental and
Theoretical Study on the Influence of Temperature and Humidity on
the Flammability Limits of Ethylene (R1150). Energy 2013, 52, 185−
191.
(113) Luo, Z.; Su, B.; Cheng, F.; Wang, T.; Shu, C.; Li, Y. Influences of
Ethane on the Flammable Limits and Explosive Oxygen Concentration
of Methane with Nitrogen Dilution. J. Loss Prev. Process Ind. 2018, 56,
478−485.
(114) Luo, Z.; Liang, H.; Wang, T.; Cheng, F.; Su, B.; Liu, L.; Liu, B.
Evaluating the Effect of Multiple Flammable Gases on the Flammability
Limit of CH4: Experimental Study and Theoretical Calculation. Process
Saf. Environ. Prot. 2021, 146, 369−376.
(115) Wang, T.; Zhou, Y.; Luo, Z.; Wen, H.; Zhao, J.; Su, B.; et al.
Flammability Limit Behavior of Methane with the Addition of Gaseous
Fuel at Various Relative Humidities. Process Saf. Environ. Prot. 2020,
140, 178−189.
(116) Hao, Q.; Luo, Z.; Wang, T.; Xie, C.; Zhang, S.; Bi, M.; Deng, J.
The Flammability Limits and Explosion Behaviours of Hydrogen-
Enriched Methane-Air Mixtures. Exp. Therm. Fluid Sci. 2021, 126,
110395.
(117) Lv, Z.; Yang, Z.; Chen, Y.; Zhang, Y. Experimental Studies on
the Flammability Limit and Burning Velocity of the Mixtures of 2,3,3,3-
Tetrafluoroprop-1-Ene. Fuel 2021, 298, No. 120698.
(118) Jones, G. W.; Kennedy, R. E. Extinction of Propylene Flames by
Diluting with Nitrogen and Carbon Dioxide and Some Observations on the
Explosive Properties of Propylene; RI 3395; Bureau of Mines, U.S.
Department of the Interior: Washington, DC, 1938.
(119) Jones, G. W.; Kennedy, R. E. Extinction of Ethylene Flames by
Carbon Dioxid and Nitrogen. Anesth. Analg. 1930, 9 (1), 6−11.
(120) Muth, W. A. Effect of Pressure on the Flammable Limits of Some
Hydrocarbon-Air Mixtures. Ph.D. Dissertation, Iowa State University,
1963; 248 pp. DOI: 10.31274/rtd-180813-1904.
(121) Zabetakis, M. G.; Scott, G. S.; Jones, G. W. Limits of
Flammability of Paraffin Hydrocarbons in Air. Ind. Eng. Chem. 1951, 43
(9), 2120−2124.
(122) Heffington, W. M.; Gaines, W. R.; Renfroe, D. A. Flammability
Limits of Coal-Derived Low-BTU Gas Mixtures Containing Large
Amounts of Inert Gases. Combust. Sci. Technol. 1984, 36 (3−4), 191−
197.
(123) White, A. G. VIII. Limits for the Propagation of Flame in
Inflammable Gas-Air Mixtures. Part II. Mixtures of More than One Gas
and Air. J. Chem. Soc. Trans. 1925, 127, 48−61.
(124) Zhao, Y.; Ting, W.; Xihong, L. Experimental Studies and
Estimates of the Explosion Limit of Some Environmentally Friendly
Refrigerants. Combust. Sci. Technol. 2005, 177 (3), 613−626.
(125) Jones, G. W.; Kennedy, R. E. Prevention of Butadiene-Air
Explosions by Addition of Nitrogen and Carbon Dioxide; RI 3691; Bureau
of Mines, U.S. Department of the Interior: 1943.
(126) Rolingson, W. R.; MacPherson, J.; Montgomery, P. D.;
Williams, B. L. Effect of Temperature on the Upper Flammable Limit
of Methane, Ammonia, and Air Mixtures. J. Chem. Eng. Data 1960, 5
(3), 349−351.
(127) Mishra, D. P.; Rahman, A. An Experimental Study of
Flammability Limits of LPG/Air Mixtures. Fuel 2003, 82, 863−866.
(128) Cato, R. J.; Gilbert, W. H.; Kuchta, J. M. Effect of Temperature
on Upper Flammability Limits of Hydrocarbon Fuel Vapors in Air. Fire
Technol. 1967, 3 (1), 14−19.
(129) Cui, G.; Li, Z.; Yang, C. Experimental Study of Flammability
Limits of Methane/Air Mixtures at Low Temperatures and Elevated
Pressures. Fuel 2016, 181, 1074−1080.
pubs.acs.org/EF Review
(130) Karim, G.; Wierzba, I.; Boon, S. Some Considerations of the
Lean Flammability Limits of Mixtures Involving Hydrogen. Int. J.
Hydrogen Energy 1985, 10 (2), 117−123.
(131) Karim, G. a.; Wierzba, I.; Boon, S. The Lean Flammability
Limits in Air of Methane, Hydrogen and Carbon Monoxide at Low
Temperatures. Cryogenics 1984, 24 (6), 305−308.
(132) Terpstra, M. A. Flammability Limits of Hydrogen-Diluent
Mixtures in Air. M.S. Thesis, The University of Calgary, 2012; 72 pp.
DOI: 10.11575/PRISM/26185.
(133) Wierzba, I.; Wang, Q. The Flammability Limits of H2-CO-
CH4Mixtures in Air at Elevated Temperatures. Int. J. Hydrogen Energy
2006, 31 (4), 485−489.
(134) Wierzba, I.; Ale, B. B. Effects of Temperature and Time of
Exposure on the Flammability Limits of Hydrogen-Air Mixtures. Int. J.
Hydrog. EnergyInternational J. Hydrog. Energy 1998, 23 (12), 1197−
1202.
(135) Wierzba, I.; Harris, K.; Karim, G. Effect of Low Temperature on
the Rich Flammability Limits in Air of Hydrogen and Some Fuel
Mixtures Containing Hydrogen. Int. J. Hydrogen Energy 1992, 17 (2),
149−152.
(136) Li, Z.; Gong, M.; Sun, E.; Wu, J.; Zhou, Y. Effect of Low
Temperature on the Flammability Limits of Methane/Nitrogen
Mixtures. Energy 2011, 36 (9), 5521−5524.
(137) Van den Schoor, F.; Norman, F.; Vandermeiren, K.;
Verplaetsen, F.; Berghmans, J.; Van den Bulck, E. Flammability Limits,
Limiting Oxygen Concentration and Minimum Inert Gas/Combustible
Ratio of H2/CO/N2/Air Mixtures. Int. J. Hydrogen Energy 2009, 34
(4), 2069−2075.
(138) Yu, X.; Yu, J.; Ji, W.; Lv, X.; Yan, X. A Research on Flammability
Limits of the Refrigerant HCFC-22/Air Mixtures at Elevated Pressures.
J. Loss Prev. Process Ind. 2019, 61, 89−93.
(139) Li, P.; Liu, Z.; Li, M.; Huang, P.; Zhao, Y.; Li, X.; Jiang, S.
Experimental Study on the Flammability Limits of Natural Gas/Air
Mixtures at Elevated Pressures and Temperatures. Fuel 2019, 256,
No. 115950.
(140) Li, P.; Li, M.; Liu, Z.; Zhao, Y.; Qian, X.; Huang, P. Effect of
High Temperature and Sulfur Vapor on the Flammability Limit of
Hydrogen Sulfide. J. Clean. Prod. 2022, 337, 130579.
(141) Li, R.; Liu, Z.; Li, P.; Li, M.; Zhao, Y. Investigation on the
Flammability Limit and Limiting Oxygen Concentration of N2-Diluted
H2/CO/Air Mixtures at High Temperature and Pressure. Fuel 2022,
308, No. 121955.
(142) Koshiba, Y.; Hasegawa, T.; Kim, B.; Ohtani, H. Flammability
Limits, Explosion Pressures, and Applicability of Le Chatelier’s Rule to
Binary Alkane - Nitrous Oxide Mixtures. J. Loss Prev. Process Ind. 2017,
45, 1−8.
(143) Koshiba, Y.; Takigawa, T.; Matsuoka, Y.; Ohtani, H. Explosion
Characteristics of Flammable Organic Vapors in Nitrous Oxide
Atmosphere. J. Hazard. Mater. 2010, 183 (1−3), 746−753.
(144) Koshiba, Y.; Nishida, T.; Morita, N.; Ohtani, H. Explosion
Behavior of N-Alkane/Nitrous Oxide Mixtures. Process Saf. Environ.
Prot. 2015, 98 (3), 11−15.
(145) Koshiba, Y.; Hasegawa, T.; Ohtani, H. Numerical and
Experimental Study of the Explosion Pressures and Flammability
Limits of Lower Alkenes in Nitrous Oxide Atmosphere. Process Saf.
Environ. Prot. 2018, 118, 59−67.
(146) Mohler dos Santos, C. C.; Zanoelo, E. F. Flammability Limits of
Iso-Butanol/Iso-Octane/n-Heptane Blends. Fire Saf. J. 2017, 88, 40−
44.
(147) Hustad, J. E.; Sonju, O. K. Experimental Studies of Lower
Flammability Limits of Gases and Mixtures of Gases at Elevated
Temperatures. Combust. Flame 1988, 71 (3), 283−294.
(148) Ohtani, H. Flammability Limits of Silane/Perfluorocarbon/
Nitrogen Mixtures. J. Loss Prev. Process Ind. 2004, 17 (5), 381−383.
(149) Ohtani, H. Experimental Study on Flammability Limits of
Perfluorocarbons in a Fluorine Atmosphere. J. Loss Prev. Process Ind.
2004, 17 (5), 377−379.
AP https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels pubs.acs.org/EF
(150) Ohtani, H.; Horiguchi, S.; Urano, Y.; Iwasaka, M.; Tokuhashi,
K.; Kondo, S. Flammability Limits of Arsine and Phosphine. Combust.
Flame 1989, 76 (3−4), 307−310.
(151) Scott, B. G. S.; Kennedy, R. E.; Spolan, I.; Zabetakis, M. G.;
Stanley, G. Flammability Characteristics of Ethylene; Bureau of Mines,
U.S. Department of the Interior: Washington, DC, 1965.
(152) Jones, G. W.; Spolan, I.; Kennedy, R. E. Effect of High Pressures
on the Flammability of Natural Gas-Air-Nitrogen Mixtures; Bureau of
Mines, U.S. Department of the Interior: Washington, DC, 1949.
(153) Huang, L.; Wang, Y.; Zhang, L.; Su, Y.; Zhang, Z.; Ren, S.
Journal of Loss Prevention in the Process Industries Influence of
Pressure on the Flammability Limits and Explosion Pressure of Ethane/
Propane-Air Mixtures in a Cylinder Vessel. J. Loss Prev. Process Ind.
2022, 74, No. 104638.
(154) Naegeli, D. W.; Weatherford, W. D. Practical Ignition Limits for
Low Molecular Weight Alcohols. Fuel 1989, 68 (1), 45−48.
(155) Crescitelli, S.; Russo, G.; Tufano, V. The Influence of Different
Diluents on the Flammability Limits of Ethylene at High Temperatures
and Pressures. J. Hazard. Mater. 1979, 3 (2), 167−175.
(156) Payman, W.; Wheeler, R. V. The Effect of Pressure on the Limits
of Inflammability of Mixtures of Paraffin Hydrocarbons with Air. Chem.
Soc. J. 1923, 123, 426−434.
(157) Marmentini Vivas, B. M.; Zanoelo, É . F. An Experimental
Investigation of Flammability Limits and Autoignition Temperatures of
Petrofuels and Biofuels in a Tubular Burner. Combust. Sci. Technol.
2011, 183 (12), 1433−1444.
(158) Hu, X.; Yu, Q.; Sun, Y. Effects of Carbon Dioxide on the Upper
Flammability Limits of Methane in O2/CO2 atm. Energy 2020, 208,
No. 118417.
(159) Jaimes, D.; McDonell, V. G.; Samuelsen, G. S. Lean
Flammability Limits of Syngas/Air Mixtures at Elevated Temperatures
and Pressures. Energy Fuels 2018, 32 (10), 10964−10973.
(160) Bee, A.; Börner, M. Laminar Burning Speeds and Flammability
Limits of CH4/O2Mixtures With Varying N2 Dilution at Sub-
Atmospheric Conditions. Combust. Sci. Technol. 2021, 1−20.
(161) Furno, A. L.; Martindill, G. H.; Zabetakis, M. G. Limits of
Flammability of Hydrazine-Hydrocarbon Vapor Mixtures. J. Chem. Eng.
Data 1962, 7 (3), 375−376.
(162) White, A. G. CXLVIII.�Limits for the Propagation of Flame in
Vapour−Air Mixtures. Part I. Mixtures of Air and One Vapour at the
Ordinary Temperature and Pressure. J. Chem. Soc., Trans. 1922, 121,
1244−1270.
(163) White, A. G.; Price, T. W. CXXXVIII. The Ignition of Ether-
Alcohol-Air and Acetone-Air Mixtures in Contact with Heated
Surfaces. J. Chem. Soc. Trans. 1919, 115, 1462−1505.
(164) Holmstedt, G. S. The Upper Limit of Flammability of Hydrogen
in Air, Oxygen, and Oxygen-Inert Mixtures at Elevated Pressures.
Combust. Flame 1971, 17 (3), 295−301.
(165) Le, H.; Liu, Y.; Mannan, M. S. Lower Flammability Limits of
Hydrogen and Light Hydrocarbons at Subatmospheric Pressures. Ind.
Eng. Chem. Res. 2013, 52 (3), 1372−1378.
(166) Le, H.; Nayak, S.; Mannan, M. S. Upper Flammability Limits of
Hydrogen and Light Hydrocarbons in Air at Subatmospheric Pressures.
Ind. Eng. Chem. Res. 2012, 51 (27), 9396−9402.
(167) Li, A. Flammability Limits of Alternative Aviation Fuels. M.S.
Thesis, Purdue University, 2016; 86 pp.
(168) Chang, Y. M.; Lee, J. C.; Chen, J. R.; Liaw, H. J.; Shu, C. M.
Flammability Characteristics Studies on Toluene and Methanol
Mixtures with Different Vapor Mixing Ratios at 1 Atm and 150°C. J.
Therm. Anal. Calorim. 2008, 93 (1), 183−188.
(169) Chang, Y. M.; Hu, K. H.; Chen, J. K.; Shu, C. M. Flammability
Studies of Benzene and Methanol with Different Vapor Mixing Ratios
under Various Initial Conditions. J. Therm. Anal. Calorim. 2006, 83 (1),
107−112.
(170) Chang, Y.; Lee, J.; Wu, S.; Chen, C.; Shu, C. Elevated Pressure
and Temperature Effects on Flammability Hazard Assessment for
Acetone and Water Solutions. J. Therm. Anal. Calorim. 2009, 95 (2),
525−534.
AQ
Review
(171) Flasinska, P.; Fraczak, M.; Piotrowski, T. Explosion Hazard
Evaluation and Determination of the Explosion Parameters for Selected
Hydrocarbons C6 - C8. Cent. Eur. J. Energ. Mater. 2012, 9 (4), 399−
409.
(172) Wen, P. J.; Shu, C. M.; Chang, Z. C.; Chen, S. C.; Shyu, M. L.
Effects of Initial Pressure on the Flammability Limit of OX-Air Mixture
with 20-L-Apparatus. In The 17th Annual Conference of Asia Pacific
Occupational Safety & Health Organization; APOSHO: 2001; pp 443−
465.
(173) Bai, C.; Liu, N.; Zhang, B. Experimental Investigation on the
Lower Flammability Limits of Diethyl Ether/n-Pentane/Epoxypro-
pane-Air Mixtures. J. Loss Prev. Process Ind. 2019, 57, 273−279.
(174) Barbosa, J. A.; Coronado, C. J. R.; Tuna, C. E.; Silva, M. H.;
Mendiburu, A. Z.; Carvalho, J. A.; de Andrade, J. C. Experimental
Determination of Lower Flammability Limits of Synthesized Iso-
Paraffins (SIP), Jet Fuel and Mixtures at Atmospheric and Reduced
Pressures with Air. Fire Saf. J. 2021, 121, 103276.
(175) Barbosa, J. A.; Coronado, C. J. R.; de Andrade, J. C.; Tuna, C. E.;
Silva, M. H.; Carvalho Junior, J. A.; Mendiburu, A. Z. Experimental
Determination of Upper Flammability Limits of Synthesized Iso-
Paraffins (SIP), Jet Fuel and Their Mixtures with Air at Atmospheric
and Sub-Atmospheric Pressures. Process Saf. Environ. Prot. 2022, 160,
102−115.
(176) Rios Escalante, E. S.; Rodriguez Coronado, C. J.; de Carvalho, J.
A., Jr. A Detailed Experimental and Numerical Assessment of the
QAV−1/Anhydrous Ethanol Blends in Their Lower Flammability
Limits. Fuel 2022, 311, No. 122531.
(177) Qin, S. H.; Sun, X. X.; Lin, W. C.; Shu, C. M.; You, F.; Ho, S. C.
Experimental and Computational Approaches for CH4 and C2H4
Flammability Zones. Energy Fuels 2017, 31 (9), 9950−9956.
(178) Gibbon, H. J.; Wainwright, J.; Rogers, R. L. Experimental
Determination of Flammability Limits of Solvents At Elevated
Temperatures and Pressures. IChemE Symp. Ser. 1994, 134, 1−12.
(179) Fu, W.; Zhang, K.; Wu, J. Flammability Limits of Benzene,
Toluene, Xylenes from 373 to 473 K and Flame-Retardant Effect of
Steam on Benzene Series. Process Saf. Environ. Prot. 2020, 137, 328−
339.
(180) Chen, Q.; Yan, J.; Chen, G.; Zhao, Y.; Shi, Y.; Zeng, Z.; Pan, Q.
Experimental Studies on the Flammability of Mixtures of Dimethyl
Ether. J. Fluor. Chem. 2015, 176 (1), 40−43.
(181) Kondo, S.; Takizawa, K.; Tokuhashi, K. Effects of Temperature
and Humidity on the Flammability Limits of Several 2L Refrigerants. J.
Fluor. Chem. 2012, 144, 130−136.
(182) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K. On the
Temperature Dependence of Flammability Limits of Gases. J. Hazard.
Mater. 2011, 187 (1−3), 585−590.
(183) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.; Sekiya,
A. Flammability Limits of Five Selected Compounds Each Mixed with
HFC-125. Fire Saf. J. 2009, 44 (2), 192−197.
(184) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.; Sekiya,
A. A Study on Flammability Limits of Fuel Mixtures. J. Hazard. Mater.
2008, 155 (3), 440−448.
(185) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.; Sekiya,
A. Flammability Limits of Isobutane and Its Mixtures with Various
Gases. J. Hazard. Mater. 2007, 148 (3), 640−647.
(186) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.
Extended Le Chatelier’s Formula and Nitrogen Dilution Effect on the
Flammability Limits. Fire Saf. J. 2006, 41 (5), 406−417.
(187) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.
Extended Le Chatelier’s Formula for Carbon Dioxide Dilution Effect
on Flammability Limits. J. Hazard. Mater. 2006, 138 (1), 1−8.
(188) Kondo, S.; Urano, Y.; Takizawa, K.; Takahashi, A.; Tokuhashi,
K.; Sekiya, A. Flammability Limits of Multi-Fluorinated Compounds.
Fire Saf. J. 2006, 41 (1), 46−56.
(189) Kondo, S.; Takizawa, K.; Takahashi, A.; Tokuhashi, K.
Measurement and Numerical Analysis of Flammability Limits of
Halogenated Hydrocarbons. J. Hazard. Mater. 2004, 109 (1−3), 13−
21.
https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
(190) Kondo, S.; Takahashi, A.; Tokuhashi, K. Experimental
Exploration of Discrepancies in F-Number Correlation of Flammability
Limits. J. Hazard. Mater. 2003, 100 (1−3), 27−36.
(191) Rowley, J. R.; Rowley, R. L.; Wilding, W. V. Experimental
Determination and Re-Examination of the Effect of Initial Temperature
on the Lower Flammability Limit of Pure Liquids. J. Chem. Eng. Data
2010, 55 (9), 3063−3067.
(192) Yang, Z.; Wu, X.; Tian, T. Flammability of Trans-1, 3, 3, 3-
Tetrafluoroprop-1-Ene and Its Binary Blends. Energy 2015, 91, 386−
392.
(193) Zhang, K.; Meng, X.; Wu, J. Flammability Limits of Binary
Mixtures of Dimethyl Ether with Five Diluent Gases. J. Loss Prev. Process
Ind. 2014, 29 (1), 138−143.
(194) Tian, H.; Wu, M.; Shu, G.; Liu, Y.; Wang, X. Experimental and
Theoretical Study of Flammability Limits of Hydrocarbon−CO2M-
ixture. Int. J. Hydrogen Energy 2017, 42 (49), 29597−29605.
(195) Wu, M.; Shu, G.; Chen, R.; Tian, H.; Wang, X.; Wang, Y. A New
Model Based on Adiabatic Flame Temperature for Evaluation of the
Upper Flammable Limit of Alkane-Air-CO2Mixtures. J. Hazard. Mater.
2018, 344, 450−457.
(196) Zhai, R.; Yang, Z.; Feng, B.; Sun, S. Effect of Environmental
Condition on the Flammability Limits of Two Isomers of
Tetrafluoropropene. Combust. Flame 2019, 207, 295−301.
(197) Azatyan, V.; Shebeko, Y.; Bolod’yan, I.; Shebeko, A.; Navtsenya,
V.; Tomilin, A. Concentration Limits of Flammability of H2-N2-O2-
Inhibitor Mixtures. Russ. J. Phys. Chem. B 2008, 2 (4), 568−574.
(198) Zhai, R.; Yang, Z.; Zhang, Y.; Lv, Z.; Feng, B. Effect of
Temperature and Humidity on the Flammability Limits of Hydro-
carbons. Fuel 2020, 270, No. 117442.
(199) Zhong, Q.; Huang, Y.; Zhao, H.; Wang, X.; Zhang, Y.; Shen, J.
Experimental Study on the Influence of Trifluoroiodomethane on the
Flammability of Difluoromethane and Propane. Int. J. Refrig. 2022, 135,
14−19.
(200) Wu, X.; Zhang, X.; Tang, F.; Xu, S.; Dang, C.; Sun, D.
Flammability Inhibition Effects of R227ea, R125, R134a, and R744 On.
Int. J. Refrig. 2022, 134 (2), 55−63.
(201) Askari, M. H.; Ashjaee, M. Experimental Measurement of
Laminar Burning Velocity and Flammability Limits of Landfill Gas at
Atmospheric and Elevated Pressures. Energy Fuels 2017, 31 (3), 3196−
3205.
(202) Grune, J.; Breitung, W.; Kuznetsov, M.; Yanez, J.; Jang, W.;
Shim, W. Flammability Limits and Burning Characteristics of CO−
H2−H2O−CO2−N2Mixtures at Elevated Temperatures. Int. J.
Hydrogen Energy 2015, 40 (31), 9838−9846.
(203) Van den Schoor, F.; Norman, F.; Tangen, L.; Sæter, O.;
Verplaetsen, F. Explosion Limits of Mixtures Relevant to the
Production of 1,2-Dichloroethane (Ethylene Dichloride). J. Loss Prev.
Process Ind. 2007, 20 (3), 281−285.
(204) Vanderstraeten, B.; Tuerlinckx, D.; Berghmans, J.; Vliegen, S.;
Van't Oost, E.; Smit, B. Experimental Study of the Pressure and
Temperature Dependence on the Upper Flammability Limit of
Methane/Air Mixtures. J. Hazard. Mater. 1997, 56 (3), 237−246.
(205) Kondo, S.; Takahashi, A.; Takizawa, K.; Tokuhashi, K. On the
Pressure Dependence of Flammability Limits of CH2 = CFCF3,
CH2F2 and Methane. Fire Saf. J. 2011, 46 (5), 289−293.
(206) Jia, Z.; Pan, Y.; Yang, L.; Liu, Y.; Jiang, J. Journal of Loss
Prevention in the Process Industries Lower Flammability Limits of
Flammable Ternary Organic Mixtures: Synergistic Behavior. J. Loss
Prev. Process Ind. 2020, 66, No. 104173.
(207) Liaw, H. J.; Li, Z. H. Mathematical Model for Describing the
Influence of Initial Pressure on the Flammability Limits of Light
Hydrocarbons at Subatmospheric Pressures. J. Loss Prev. Process Ind.
2022, 77 (1), No. 104776.
(208) Azatyan, V.; Shebeko, Y.; Bolod'yan, I.; Navtsenya, V. Effect of
Diluents of Various Chemical Nature On Flammability Limits of Gas
Mixtures. Combust. Explos. Shock Waves 2006, 42 (6), 708−714.
(209) Shebeko, A.; Shebeko, Y.; Zuban’, A.; Navtsenya, V.; Azatyan, V.
Influence on Fluorocarbons Flammability Limits in the Mixtures of H2-
N2O and CH4-N2O. Russ. J. Phys. Chem. B 2014, 8 (1), 65−70.
pubs.acs.org/EF Review
(210) Van den Schoor, F.; Verplaetsen, F.; Berghmans, J.
Experimental and Numerical Study of the Influence of Pressure and
Temperature on the Flammability Limits of Combustible Gases in Air.
In European Combustion Meeting 2007; European Union: 2007; pp 1−7.
(211) Van Den Schoor, F.; Verplaetsen, F. The Upper Explosion Limit
of Lower Alkanes and Alkenes in Air at Elevated Pressures and
Temperatures. J. Hazard. Mater. 2006, 128 (1), 1−9.
(212) Craven, A. D.; Foster, M. G. The Limits of Flammability of
Ethylene in Oxygen, Air and Air-Nitrogen Mixtures at Elevated
Temperatures and Pressures. Combust. Flame 1966, 10 (2), 95−100.
(213) Bolshova, T. A.; Bunev, V. A.; Knyazkov, D. A.; Korobeinichev,
O. P.; Chernov, A. A.; Shmakov, A. G.; Yakimov, S. A. Dependence of
the Lower Flammability Limit on the Initial Temperature. Combust.
Explos. Shock Waves 2012, 48 (2), 125−129.
(214) Burgess, M. J.; Wheeler, R. V. CCXXVIII. The Lower Limit of
Inflammation of Mixtures of the Paraffin Hydrocarbons with Air. J.
Chem. Soc. Trans. 1911, 99, 2013−2030.
(215) Zhang, K.; Luo, T.; Li, Y.; Zhang, T.; Li, X.; Zhang, Z.; Shang, S.;
Zhou, Y.; Zhang, C.; Chen, X.; et al. Effect of Ignition, Initial Pressure
and Temperature on the Lower Flammability Limit of Hydrogen/Air
Mixture. Int. J. Hydrogen Energy 2022, 47 (33), 15107−15119.
(216) Zhang, K.; Gao, W.; Li, Y.; Zhang, Z.; Shang, S.; Zhang, C.;
Chen, X.; Sun, K. Journal of Loss Prevention in the Process Industries
Lower Flammability Limits of Ethanol, Acetone and Ethyl Acetate
Vapor Mixtures in Air. J. Loss Prev. Process Ind. 2022, 74, No. 104676.
(217) Zhang, K.; Shang, S.; Li, X.; Gao, W. Lower Flammability Limits
of NH3/H2Mixtures under Different Initial Temperatures and Initial
Pressures. Fuel 2023, 331 (P2), 125982.
(218) Kul, I.; Gnann, D. L.; Beyerlein, A. L.; DesMarteau, D. D. Lower
Flammability Limit of Difluoromethane and Percolation Theory. Int. J.
Thermophys. 2004, 25 (4), 1085−1095.
(219) Bui-pham, M. N.; Lutz, A. E.; Miller, J. A.; Desjardin, M.;
O’Shaughnessey, D. M.; Zondlak, R. J. Rich Flammability Limits in
CH3OH/CO/Diluent Mixtures. Combust. Sci. Technol. 1995, 109 (1−
6), 71−91.
(220) Van den Schoor, F. Influence of Pressure and Temperature on
Flammability Limits of Combustible Gases in Air. D.Ing. Thesis,
Katholieke Universiteit Leuven, 2007; 209 pp.
(221) Zlochower, I. A.; Green, G. M. The Limiting Oxygen
Concentration and Flammability Limits of Gases and Gas Mixtures. J.
Loss Prev. Process Ind. 2009, 22 (4), 499−505.
(222) Wang, Y.; Qi, C.; Ning, Y.; Lv, X.; Yu, X.; Yan, X.; Yu, J.
Experimental Determination of the Lower Flammability Limit and
Limiting Oxygen Concentration of Propanal/Air Mixtures under
Elevated Temperatures and Pressures. Fuel 2022, 326, 124882.
(223) Qi, C.; He, M.; Ning, Y.; Chen, S.; Yan, X.; Wang, Y.; Yu, X.; Yu,
J. Experimental Measurement and Theoretical Prediction for Lower
Flammability Limits of Ternary Hydrocarbon Mixtures. Process Saf.
Prog. 2022, 41 (3), 581−590.
(224) Akram, M. Z. Study of Hydrogen Impact on Lean Flammability
Limit and Burning Characteristics of a Kerosene Surrogate. Energy
2021, 231, 120925.
(225) Gomez Casanova, C. A.; Othen, E.; Sorensen, J. L.; Levin, D. B.;
Birouk, M. Measurement of Laminar Flame Speed and Flammability
Limits of a Biodiesel Surrogate. Energy Fuels 2016, 30 (10), 8737−
8745.
(226) Li, A.; Vozka, P.; Mastrean, A.; Kilaz, G.; Qiao, L. Lean
Flammability Limits of Alternative Aviation Fuels. Fire Saf. J. 2019, 108,
102851.
(227) Goethals, M.; Vanderstraeten, B.; Berghmans, J.; De Smedt, G.;
Vliegen, S.; Van’t Oost, E. Experimental Study of the Flammability
Limits of Toluene−Air Mixtures at Elevated Pressure and Temperature.
J. Hazard. Mater. 1999, 70 (3), 93−104.
(228) Shebeko, Y.; Tsarichenko, S.; Korolchenko, A.; Trunev, A.;
Navzenya, V.; Papkov, S.; Zaitzev, A. Burning Velocities and
Flammability Limits of Gaseous Mixtures at Elevated Temperatures
and Pressures. Combust. Flame 1995, 102 (4), 427−437.
AR https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
(229) Markus, D.; Schildberg, H.-P.; Wildner, W.; Krdzalic, G.; Maas,
U. Flammability Limits of Premixed Methane/Methanol/Air Flames.
Combust. Sci. Technol. 2003, 175 (11), 2095−2112.
(230) Takahashi, A.; Urano, Y.; Tokuhashi, K.; Kondo, S. Effect of
Vessel Size and Shape on Experimental Flammability Limits of Gases. J.
Hazard. Mater. 2003, 105 (1−3), 27−37.
(231) Van den Schoor, F.; Hermanns, R. T. E.; van Oijen, J. A.;
Verplaetsen, F.; de Goey, L. P. H. Comparison and Evaluation of
Methods for the Determination of Flammability Limits, Applied to
Methane/Hydrogen/Air Mixtures. J. Hazard. Mater. 2008, 150 (3),
573−581.
(232) De Smedt, G.; De Corte, F.; Notelé, R.; Berghmans, J.
Comparison of Two Standard Test Methods for Determining
Explosion Limits of Gases at Atmospheric Conditions. J. Hazard.
Mater. 1999, 70 (3), 105−113.
(233) Heinonen, E. W.; Tapscott, R. E.; Crawford, F. R. Methods
Development for Measuring and Classifying Flammability/Combustibility
of Refrigerants. Final Report; U.S. Department of Energy: 1994; 93 pp.
DOI: 10.2172/114574.
(234) Glukhov, I. S.; Shebeko, Y. N.; Shebeko, A. Y.; Zuban, A. V.
Journal of Loss Prevention in the Process Industries An Investigation of
Flammability Limits of Gaseous Mixtures at Reduced Pressures. J. Loss
Prev. Process Ind. 2020, 66, 104195.
(235) Yu, X.; Yan, X.; Ji, W.; Luo, C.; Yao, F.; Yu, J. Effect of Super-
Ambient Conditions on the Upper Explosion Limit of Ethane/Oxygen
and Ethylene/Oxygen Mixtures. J. Loss Prev. Process Ind. 2019, 59,
100−105.
(236) Knyazkov, D. A.; Bolshova, T. A.; Shvartsberg, V. M.;
Gerasimov, I. E.; Shmakov, A. G.; Korobeinichev, O. P. Effect of
Inhibitors on Flammability Limits of Dimethyl Ether/Air Mixtures.
Proc. Combust. Inst. 2019, 37 (3), 4267−4275.
(237) Li, S.; Zhang, Y.; Qiu, X.; Li, B.; Zhang, H. Effects of Inert
Dilution and Preheating Temperature on Lean Flammability Limit of
Syngas. Energy Fuels 2014, 28 (5), 3442−3452.
(238) Ale, B. J. M.; Bruning, F.; Koenders, H. A. A. The Limits of
Flammability of Mixtures of Ammonia, Hydrogen and Methane in
Mixtures of Nitrogen and Oxygen at Elevated Temperatures and
Pressures. J. Hazard. Mater. 1981, 4 (3), 283−289.
(239) Crowl, D. A.; Louvar, J. F. Chemical Process Safety, 2nd ed.;
Prentice Hall PTR: 2002; 625 pp.
(240) Kuchta, J. M. Investigation of Fire and Explosion Accidents in the
Chemical, Mining, and Fuel-Related Industries: A Manual; Bulletin 680;
Bureau of Mines, U.S. Department of the Interior: 1985; 84 pp.
(241) Liao, S. Y.; Jiang, D. M.; Huang, Z. H.; Cheng, Q.; Gao, J.; Hu,
Y. Approximation of Flammability Region for Natural Gas-Air-Diluent
Mixture. J. Hazard. Mater. 2005, 125 (1−3), 23−28.
(242) Liao, S. Y.; Cheng, Q.; Jiang, D. M.; Gao, J. Experimental Study
of Flammability Limits of Natural Gas-Air Mixture. J. Hazard. Mater.
2005, 119 (1−3), 81−84.
(243) Liao, S. Y.; Jiang, D. M.; Cheng, Q.; Gao, J.; Hu, Y.
Approximations of Flammability Characteristics of Liquefied Petro-
leum Gas−Air Mixture with Exhaust Gas Recirculation (EGR). Energy
Fuels 2005, 19 (1), 324−325.
(244) Pu, Y.; Hu, J.; Jarosinski, J. Experimentally Determined Flame
Properties near Flammability Limits Under Gravity and Microgravity
Conditions. Combust. Sci. Technol. 2009, 181 (12), 1431−1442.
(245) Liekhus, K. J.; Zlochower, I. A.; Cashdollar, K. L.; Djordjevic, S.
M.; Loehr, C. A. Flammability of Gas Mixtures Containing Volatile
Organic Compounds and Hydrogen. J. Loss Prev. Process Ind. 2000, 13
(3−5), 377−384.
(246) Knyazkov, D. A.; Yakimov, S. A.; Korobeinichev, O. P.;
Shmakov, A. G. Effect of Trimethylphosphate Additives on the
Flammability Concentration Limits of Premixed Methane-Air
Mixtures. Combust. Explos. Shock Waves 2008, 44 (1), 9−17.
(247) Burgoyne, J. H.; Williams-Leir, G. The Influence of
Incombustible Vapours on the Limits of Inflammability of Gases and
Vapours in Air. Proc. R. Soc. A Math. Phys. Eng. Sci. 1948, 193, 525−539.
pubs.acs.org/EF Review
(248) Shoshin, Y. L.; de Goey, L. P. H. Experimental Study of Lean
Flammability Limits of Methane/Hydrogen/Air Mixtures in Tubes of
Different Diameters. Exp. Therm. Fluid Sci. 2010, 34 (3), 373−380.
(249) Kondo, S.; Urano, Y.; Takahashi, A.; Tokuhashi, K.
Reinvestigation of Flammability Limits Measurement of Methane by
the Conventional Vessel Method with AC Discharge Ignition. Combust.
Sci. Technol. 1999, 145 (1−6), 1−15.
(250) Kuznetsov, M.; Kobelt, S.; Grune, J.; Jordan, T. Flammability
Limits and Laminar Flame Speed of Hydrogen−Air Mixtures at Sub-
Atmospheric Pressures. Int. J. Hydrogen Energy 2012, 37 (22), 17580−
17588.
(251) Coward, H. F.; Jones, G. W. Limits of Flammability of Gases and
Vapors; Bulletin 503; Bureau of Mines, U.S. Department of the Interior:
1952; 155 pp.
(252) Mendiburu, A. Z.; Serra, A. M.; Andrade, J. C.; Silva, L. M.;
Santos, J. C.; de Carvalho, J. A. Characterization of the Flame Front
Inversion of Ethanol−Air Deflagrations inside A Closed Tube. Energy
2019, 187, 115932.
(253) Serra, A. M.; Andrade, J. C.; Silva, L. M.; Santos, J. C.; Silveira, J.
C.; de Carvalho, J. A.; Mendiburu, A. Z. Experimental Observation of
Ethanol−Air Premixed Flames Propagating inside a Closed Tube with
High Aspect Ratio. J. Brazilian Soc. Mech. Sci. Eng. 2023, 45 (2), 80.
(254) White, A. G. Limits for the Propagation of Flame at Various
Temperatures in Mixtures of Ammonia with Air and Oxygen. J. Chem.
Soc. Trans. 1922, 121, 1688−1695.
(255) Krivulin, V. N.; Lovachev, L. A.; Kudryavtsev, E. A.; Baratov, A.
N. Flammability Limits Ammonia Air Mixtures (Translated). Fiz.
Goran. i Vzryva 1975, 11 (6), 759−764.
(256) Jarosinski, J.; Podfilipski, J.; Fodemski, T. Properties of Flames
Propagating in Propane-Air Mixtures near Flammability and Quench-
ing Limits. Combust. Sci. Technol. 2002, 174 (1), 167−187.
(257) Jarosinski, J. A Survey of Recent Studies on Flame Extinction.
Prog. Energy Combust. Sci. 1986, 12, 81−116.
(258) Sibulkin, M.; Frendi, A. Prediction of Flammability Limit of an
Unconfined Premixed Gas in the Absence of Gravity. Combust. Flame
1990, 82 (3−4), 334−345.
(259) Lakshmisha, K. N.; Paul, P. J.; Mukunda, H. S. On the
Flammability Limit and Heat Loss in Flames with Detailed Chemistry.
Symp. Combust. 1991, 23, 433−440.
(260) Ronney, P. D. Effect of Chemistry and Transport Properties on
Near-Limit Flames at Microgravity. Combust. Sci. Technol. 1988, 59 (1−
3), 123−141.
(261) Jarosinski, J.; Podfilipski, J.; Gorczakowski, A.; Veyssiere, B.
Experimental Study of Flame Propagation in Propane-Air Mixture near
Rich Flammability Limits in Microgravity. Combust. Sci. Technol. 2002,
174 (9), 21−48.
(262) Ronney, P. D. Effect of Chemistry and Transport Properties on
Near-Limit Flames at Microgravity. Combust. Sci. Technol. 1988, 59 (1−
3), 123−141.
(263) Ronney, P. D. On the Mechanisms of Flame Propagation Limits
and Extinguishment-Processes at Microgravity. Symp. Combust. 1989,
22 (1), 1615−1623.
(264) Maruta, K.; Yoshida, M.; Ju, Y.; Niioka, T. Experimental Study
on Methane-Air Premixed Flame Extinction at Small Stretch Rates in
Microgravity. Symp. Combust. 1996, 26 (1), 1283−1289.
(265) Wang, S. F.; Zhang, H.; Jarosinski, J.; Gorczakowski, A.;
Podfilipski, J. Laminar Burning Velocities and Markstein Lengths of
Premixed Methane/Air Flames near the Lean Flammability Limit in
Microgravity. Combust. Flame 2010, 157 (4), 667−675.
(266) Zeldovich, Y. B. Selected Works of Yakov Borisovich Zeldovich;
Ostriker, J. P., Barenblatt, G. I., Sunyaev, R. A., Eds.; Princeton
University Press: 1992; 479 pp.
(267) Ronney, P. D. Near-Limit Flame Structures at Low Lewis
Number. Combust. Flame 1990, 82 (1), 1−14.
(268) Ronney, P. D.; Whaling, K. N.; Abbud-Madrid, A.; Gatto, J. L.;
Pisowicz, V. L. Stationary Premixed Flames in Spherical and Cylindrical
Geometries. AIAA J. 1994, 32 (3), 569−577.
AS https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels pubs.acs.org/EF
(269) Ronney, P. D.; Wu, M.-S.; Pearlman, H. G.; Weiland, K. J.
Experimental Study of Flame Balls in Space: Preliminary Results from
STS-83. AIAA J. 1998, 36 (8), 1361−1368.
(270) Kaiser, C.; Liu, J.; Ronney, P. D. Diffusive-Thermal Instability of
Counterflow Flames at Low Lewis Number. In 38th Aerospace Sciences
Meeting and Exhibit; AIAA: 2000; pp 1−14. DOI: 10.2514/6.2000-576.
(271) Perry’s Chemical Engineers’ Handbook, 9th ed.; Green, D. W.,
Southard, M. Z., Eds.; McGraw Hill: New York, 2019; 2274 pp.
(272) Poling, B. E.; Prausnitz, J. M.; O’Connell, J. P. The Properties of
Gases and Liquids, 5th ed.; McGraw-Hill: New York, 2001; 803 pp.
DOI: 10.1036/0070116822.
(273) Montgomery, D. C. Design and Analysis of Experiments, 5th ed.;
John Wiley & Sons, Inc.: 2001; 684 pp.
(274) Albahri, T. a. Flammability Characteristics of Pure Hydro-
carbons. Chem. Eng. Sci. 2003, 58 (16), 3629−3641.
(275) Albahri, T. A. Prediction of the Lower Flammability Limit
Percent in Air of Pure Compounds from Their Molecular Structures.
Fire Saf. J. 2013, 59, 188−201.
(276) Bagheri, M.; Rajabi, M.; Mirbagheri, M.; Amin, M. BPSO-MLR
and ANFIS Based Modeling of Lower Flammability Limit. J. Loss Prev.
Process Ind. 2012, 25 (2), 373−382.
(277) Frutiger, J.; Marcarie, C.; Abildskov, J.; Sin, G. Group-
Contribution Based Property Estimation and Uncertainty Analysis for
Flammability-Related Properties. J. Hazard. Mater. 2016, 318, 783−
793.
(278) Gharagheizi, F. Quantitative Structure-Property Relationship
for Prediction of the Lower Flammability Limit of Pure Compounds.
Energy Fuels 2008, 22 (5), 3037−3039.
(279) Gharagheizi, F. A New Group Contribution-Based Model for
Estimation of Lower Flammability Limit of Pure Compounds. J.
Hazard. Mater. 2009, 170 (2−3), 595−604.
(280) Kondo, S.; Urano, Y.; Tokuhashi, K.; Takahashi, A.; Tanaka, K.
Prediction of Flammability of Gases by Using F-Number Analysis. J.
Hazard. Mater. 2001, 82 (2), 113−128.
(281) Lazzús, J. a. Neural Network/Particle Swarm Method to Predict
Flammability Limits in Air of Organic Compounds. Thermochim. Acta
2011, 512 (1−2), 150−156.
(282) Pan, Y.; Jiang, J.; Wang, R.; Cao, H.; Cui, Y. A Novel QSPR
Model for Prediction of Lower Flammability Limits of Organic
Compounds Based on Support Vector Machine. J. Hazard. Mater.
2009, 168 (2−3), 962−969.
(283) Rowley, J. R.; Rowley, R. L.; Wilding, W. V. Estimation of the
Lower Flammability Limit of Organic Compounds as a Function of
Temperature. J. Hazard. Mater. 2011, 186 (1), 551−557.
(284) Seaton, W. H. Group Contribution Method for Predicting the
Lower and the Upper Flammable Limits of Vapors in Air. J. Hazard.
Mater. 1991, 27 (2), 169−185.
(285) Gharagheizi, F. Prediction of Upper Flammability Limit Percent
of Pure Compounds from Their Molecular Structures. J. Hazard. Mater.
2009, 167 (1−3), 507−510.
(286) High, M. S.; Danner, R. P. Prediction of Upper Flammability
Limit by a Group Contribution Method. Ind. Eng. Chem. Res. 1987, 26
(7), 1395−1399.
(287) Pan, Y.; Jiang, J.; Wang, R.; Cao, H.; Cui, Y. Prediction of the
Upper Flammability Limits of Organic Compounds from Molecular
Structures. Ind. Eng. Chem. Res. 2009, 48 (10), 5064−5069.
(288) ChemSpider. http://www.chemspider.com/ (accessed 2023-01-
26).
(289) Vidal, M.; Rogers, W. J.; Holste, J. C.; Mannan, M. S. A Review
of Estimation Methods for Flash Points and Flammability Limits.
Process Saf. Prog. 2004, 23 (1), 47−55.
(290) Takahashi, F.; Glassman, I. Sooting Correlations for Premixed
Flames. Combust. Sci. Technol. 1984, 37 (1−2), 1−19.
(291) White, A. G. XCVI.�Limits for the Propagation of Flame in
Inflammable Gas−Air Mixtures. Part III. The Effects of Temperature
on the Limits. J. Chem. Soc., Trans. 1925, 127, 672−684.
(292) Mendiburu, A. Z.; de Carvalho, J. A.; Coronado, C. R.; Roberts,
J. J. Flammability Limits Temperature Dependence of Pure
AT
Review
Compounds in Air at Atmospheric Pressure. Energy 2017, 118, 414−
424.
(293) Britton, L. G.; Frurip, D. J. Further Uses of the Heat of
Oxidation in Chemical Hazard Assessment. Process Saf. Prog. 2003, 22
(1), 1−19.
(294) Britton, L. G. Using Heats of Oxidation to Evaluate
Flammability Hazards. Process Saf. Prog. 2002, 21 (1), 31−54.
(295) Catoire, L.; Naudet, V. Estimation of Temperature-Dependent
Lower Flammability Limit of Pure Organic Compounds in Air at
Atmospheric Pressure. Process Saf. Prog. 2005, 24 (2), 130−137.
(296) Zlochower, I. A. Experimental Flammability Limits and
Associated Theoretical Flame Temperatures as a Tool for Predicting
the Temperature Dependence of These Limits. J. Loss Prev. Process Ind.
2012, 25 (3), 555−560.
(297) Liaw, H. J.; Chen, K. Y. A Model for Predicting Temperature
Effect on Flammability Limits. Fuel 2016, 178, 179−187.
(298) Wan, X.; Zhang, Q.; Lian, Z. Estimation of the Upper
Flammability Limits of Hydrocarbons in Air at Elevated Temperatures
and Atmospheric Pressure. Ind. Eng. Chem. Res. 2016, 55 (30), 8472−
8479.
(299) Cui, G.; Yang, C.; Li, Z.; Zhou, Z.; Li, J. Experimental Study and
Theoretical Calculation of Flammability Limits of Methane/Air
Mixture at Elevated Temperatures and Pressures. J. Loss Prev. Process
Ind. 2016, 41, 252−258.
(300) Li, P.; Liu, Z.; Li, M.; Huang, P.; Zhao, Y.; Li, X.; Jiang, S.
Experimental Study on the Flammability Limits of Natural Gas/Air
Mixtures at Elevated Pressures and Temperatures. Fuel 2019, 256,
115950.
(301) Wan, X.; Zhang, Q. Numerical Study of Influence of Initial
Pressures and Temperatures on the Lower Flammability Limits of
Oxygenated Fuels in Air. J. Loss Prev. Process Ind. 2016, 41, 40−47.
(302) Wan, X.; Zhang, Q.; Shen, S. L. Theoretical Estimation of the
Lower Flammability Limit of Fuel-Air Mixtures at Elevated Temper-
atures and Pressures. J. Loss Prev. Process Ind. 2015, 36, 13−19.
(303) Law, C. K. Combustion Physics; Cambridge University Press:
New York, 2006; 722 pp.
(304) Borgnakke, C.; Sonntag, R. E. Fundamentals of Thermodynamics,
8th ed.; Wiley: 2013; 894 pp.
(305) Matalon, M. Flame Dynamics. Proc. Combust. Inst. 2009, 32 (1),
57−82.
(306) Fan, A.; Xiang, Y.; Yang, W.; Li, L. Enhancement of Hydrogen
Combustion Efficiency by Helium Dilution in a Micro-Combustor with
Wall Cavities. Chem. Eng. Process. - Process Intensif. 2018, 130, 201−207.
(307) Qiao, L.; Gan, Y.; Nishiie, T.; Dahm, W. J. A.; Oran, E. S.
Extinction of Premixed Methane/Air Flames in Microgravity by
Diluents: Effects of Radiation and Lewis Number. Combust. Flame
2010, 157 (8), 1446−1455.
(308) Goodwin, D. G.; Moffat, H. K.; Schoegl, I.; Speth, R. L.; Weber,
B. W. Cantera: An object-oriented sof tware toolkit for chemical kinetics,
thermodynamics, and transport processes. Zenobo, February 12, 2021.
DOI: 10.5281/zenodo.4527812.
(309) GRI-Mech Home Page. GRIMECH3.0. http://combustion.
berkeley.edu/gri-mech/index.html (accessed 2021-08-30).
(310) Guo, H.; Ju, Y.; Maruta, K.; Niioka, T.; Liu, F. Numerical
Investigation of CH4/CO2/Air and CH4/CO2/O2 Counterflow
Premixed Flames with Radiation Reabsorption. Combust. Sci. Technol.
1998, 135 (1−6), 49−64.
(311) Ju, Y.; Masuya, G.; Ronney, P. D. Effects of Radiative Emission
and Absorption on the Propagation and Extinction of Premixed Gas
Flames. Symp. Combust. 1998, 27 (2), 2619−2626.
(312) Kumar, R. K.; Tamm, H.; Harrison, W. C. Combustion of
Hydrogen-Steam-Air Mixtures near Lower Flammability Limits.
Combust. Sci. Technol. 1983, 33 (1−4), 167−178.
(313) Chen, C. C.; Wang, T. C.; Liaw, H. J.; Chen, H. C. Nitrogen
Dilution Effect on the Flammability Limits for Hydrocarbons. J.
Hazard. Mater. 2009, 166 (2−3), 880−890.
(314) Chen, C. C.; Liaw, H. J.; Wang, T. C.; Lin, C. Y. Carbon Dioxide
Dilution Effect on Flammability Limits for Hydrocarbons. J. Hazard.
Mater. 2009, 163 (2−3), 795−803.
https://doi.org/10.1021/acs.energyfuels.2c03598
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels pubs.acs.org/EF Review

(315) Shu, G.; Long, B.; Tian, H.; Wei, H.; Liang, X. Flame (334) Ishaq, H.; Dincer, I.; Crawford, C. A Review on Hydrogen
Temperature Theory-Based Model for Evaluation of the Flammable Production and Utilization: Challenges and Opportunities. Int. J.
Zones of Hydrocarbon-Air-CO2Mixtures. J. Hazard. Mater. 2015, 294, Hydrogen Energy 2022, 47 (62), 26238−26264.
137−144. (335) Modisha, P. M.; Ouma, C. N. M.; Garidzirai, R.; Wasserscheid,
(316) Shu, G.; Long, B.; Tian, H.; Wei, H.; Liang, X. Evaluating Upper P.; Bessarabov, D. The Prospect of Hydrogen Storage Using Liquid
Flammability Limit of Low Hydrocarbon Diluted with an Inert Gas Organic Hydrogen Carriers. Energy Fuels 2019, 33 (4), 2778−2796.
Using Threshold Temperature. Chem. Eng. Sci. 2015, 138, 810−813. (336) Ehlig-Economides, C. A.; Hatzignatiou, D. G. Energy Analysis
(317) Liaw, H. J.; Chen, C. C.; Chang, C. H.; Lin, N. K.; Shu, C. M. of Low Carbon Hydrogen from Methane and End Use Implications.
Model to Estimate the Flammability Limits of Fuel-Air-Diluent Energy Fuels 2022, 36 (16), 8886−8899.
Mixtures Tested in a Constant Pressure Vessel. Ind. Eng. Chem. Res. (337) Zhou, D.; Li, D.; Yuan, S.; Chen, Z. Recent Advances in
2012, 51 (6), 2747−2761. Biomass-Based Photocatalytic H2 Production and Efficient Photo-
(318) Liaw, H. J.; Chen, C. C.; Lin, N. K.; Shu, C. M.; Shen, S. Y. catalysts: A Review. Energy Fuels 2022, 36 (18), 10721−10731.
(338) Kathrotia, T.; Oßwald, P.; Zinsmeister, J.; Methling, T.; Köhler,
Flammability Limits Estimation for Fuel-Air-Diluent Mixtures Tested
M. Combustion Kinetics of Alternative Jet Fuels, Part-III: Fuel
in a Constant Volume Vessel. Process Saf. Environ. Prot. 2016, 100,
Modeling and Surrogate Strategy. Fuel 2021, 302, 120737.
150−162. (339) Mendiburu, A. A. Z.; Ciccarelli, G.; Carvalho, J. A. DDT Limits
(319) Bade Shrestha, S. O.; Wierzba, I.; Karim, G. A. Prediction of the of Ethanol−Air in an Obstacles-Filled Tube. Combust. Sci. Technol.
Extent of Diluents Concentrations in Flammability Limited Gaseous 2018, 1−16.
Fuel-Diluent Mixtures in Air. Appl. Therm. Eng. 2009, 29 (11−12), (340) Ciccarelli, G.; Chaumeix, N.; Mendiburu, A. Z.; N'Guessan, K.;
2574−2578. Comandini, A. Fast- Flame Limit for Hydrogen/Methane-Air Mixtures.
(320) Gutiérrez Velásquez, E. I.; Coronado, C. J. R.; Quintero Proc. Combust. Inst. 2019, 37 (3), 3661−3668.
Cartagena, J. C.; Carvalho, J. A.; Mendiburu, A. Z.; Andrade, J. C.; (341) van Oijen, J. A.; Donini, A.; Bastiaans, R. J. M.; ten Thije
Cortez, E. V.; Santos, J. C. Prediction of Flammability Limits for Boonkkamp, J. H. M.; de Goey, L. P. H. State-of-the-Art in Premixed
Ethanol-Air Blends by the Kriging Regression Model and Response Combustion Modeling Using Flamelet Generated Manifolds. Prog.
Surfaces. Fuel 2017, 210, 410−424. Energy Combust. Sci. 2016, 57, 30−74.
(321) Wang, T.; Chen, C.; Chen, H. Nitrogen and Carbon Dioxide
Dilution Effect on Upper Flammability Limits for Organic Compound
Containing Carbon, Hydrogen and Oxygen Atoms. J. Taiwan Inst.
Chem. Eng. 2010, 41 (4), 453−464.
(322) Molnarne, M.; Mizsey, P.; Schröder, V. Flammability of Gas
Mixtures. Part 2: Influence of Inert Gases. J. Hazard. Mater. 2005, 121
(A1), 45−49.
(323) Mendiburu, A. Z.; de Carvalho, J. A.; Coronado, C. R. Method
for Determination of Flammability Limits of Gaseous Compounds
Diluted with N2 and CO2 in Air. Fuel 2018, 226, 65−80.
(324) Shebeko, Y.; Fan, W.; Bolodian, I.; Navzenya, V. An Analytical
Evaluation of Flammability Limits of Gaseous Mixtures of Combus-
tible−Oxidizer−Diluent. Fire Saf. J. 2002, 37 (6), 549−568.
(325) Razus, D.; Molnarne, M.; Fuß, O. Limiting Oxygen
Concentration Evaluation in Flammable Gaseous Mixtures by Means
of Calculated Adiabatic Flame Temperatures. Chem. Eng. Process.
Process Intensif. 2004, 43 (6), 775−784.
(326) Razus, D.; Molnarne, M.; Movileanu, C.; Irimia, A. Estimation
of LOC (Limiting Oxygen Concentration) of Fuel-Air-Inert Mixtures
at Elevated Temperatures by Means of Adiabatic Flame Temperatures.
Chem. Eng. Process. Process Intensif. 2006, 45 (3), 193−197.
(327) Hansen, T. J. Estimation of the Flammability Zone Boundaries
with Thermodynamic and Empirical Equations. M.S. Thesis, Michigan
Technological University, 2009; 139 pp.
(328) Hansen, T. J.; Crowl, D. A. Estimation of the Flammability Zone
Boundaries for Flammable Gases. Process Saf. Prog. 2010, 29 (3), 209−
215.
(329) Mashuga, C. V.; Crowl, D. A. Derivation of Le Chatelier’s
Mixing Rule for Flammable Limits. Process Saf. Prog. 2000, 19 (2),
112−117.
(330) Carvalho, J. A.; Mendiburu, A. Z.; Coronado, C. R.; McQuay,
M. Q. Combustão Aplicada; Editora da UFSC: Florianópolis, 2018; 372
pp.
(331) Chen, C. C.; Liu, S. H.; Kang, X. Evaluating Lower Flammability
Limit of Flammable Mixtures Using Threshold Temperature Approach.
Chem. Eng. Sci. 2018, 185, 84−91.
(332) Liu, D.; Santner, J.; Togbé, C.; Felsmann, D.; Koppmann, J.;
Lackner, A.; Yang, X.; Shen, X.; Ju, Y.; Kohse-höinghaus, K. Flame
Structure and Kinetic Studies of Carbon Dioxide-Diluted Dimethyl
Ether Flames at Reduced and Elevated Pressures. Combust. Flame 2013,
160 (12), 2654−2668.
(333) Compton, R. G.; Hancock, G. Low-Temperature Combustion and
Autoignition; Elsevier: New York, NY, 1997; 794 pp.

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Energy Fuels XXXX, XXX, XXX−XXX